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US 20220243051AI
(19) United States
(12) Patent Application Publication (io) I ub. No.: US 2022/0243051 A1
KOCHI et al. (43) Pub. Date: Aug. 4, 2022

(54) PRKPRII('ND I(IBKR-RI I ~ 1(ORCKD lay-up device, when such a device is used with the aim of
COMPOSITK MATKRLAI. pmducmg a fiber-reinfiirced composite material having a
high toughness and impact resistance
(71) Applicant. TORAY Industries, Inc., Tokyo (JP) A prepreg compusing ihc componmim [A] to [E] oven
below. mceiuig the requirements (i) to (ni) given below, and
(72) Inventors: Shin]i KOCIH. Iyo- un (JP): Daisuke servmg to produce a cured pmduct having a reinfiircing fiber
KIDO. Iyo- un (JP); Aya layer defined as the reuion ranging froni 8% to 92/8 depth
KOMORIYsu lyo-gun (JP) from the surface in the thickness direction that contains a
first epoxy resin composition in which 90 mass % or more
(73) Assignee: TORAY Industries, Inc.. Tokyo (JP) of the componeiu [A] exists. and two surface resin layers
each dclined as the region ranging from either surface io a
(21) Appl. No 17/621),311
ilcptll of 8% exclusive ill ilia illlckllcss dirac(loll illa( coll(sill
a second epoxy resin composition in which 85 niass % or
(22) PCT Filed Jun. 30, 2020
nxire of the coniponent [I i] exisig
(86) PCT Noc PCT/JP2020/025662 (i) the second epoxy resin composition includes the com-
ponmits [B] to [E] of which thc component [C] accounts
sj 371 (c)(1), for 8 to 24 parts by mass relauve io 100 parts by mass of
(2) Date. Dec. 17, 2021 the second epoxy resin con)position,
(ii) the second epoxy resin composition has a stomge elastic
(30) Foreign Application Priority Data modulus (i'n the range of 1.0xlo to 3 Oxlo" Pa when
Jul 5, 2019 (JP) 20i9-125901
measured ai 25'. mid an angular fretiuency of 3.14
rad/s. and
Publication Classification (iii) plies of the prepreg laid up afier bein left to stand for
24 hours at room temperature show a peel stren thof 0.1
(51) Int. CL N/mm or more at 33" C.,
CVSL 63/00 (200G.OI) [AJ a carbon fiber,
CVSJ 5/24 (200G.OI) [B] an epoxy resin containing the components [bi] and [b2]
(52) IJ.S. CL spccilied below,
CPC ............... CVSL 63/VV (2013.01): CVSJ 5/24 [biJ a di- or less-functional epoxy resin containing. in a
(2013 Ol); ('08/ 2463/00 (2013.01); ('08/. niolecule, at least one ring stmcture having four- or
2205/025 (2013.01); (Y)8/ 236i3/00 (2013.01), more-membered rin and a glycidyl amine group bonded
(Y)8/. 2205/035 (2013 0 1) to a ring structure,
[b2] a iri- or morc-funcuonal epoxy resui.
(57) ABSTRACT
[C] a thermoplastic resin with a iveight-avemge molecular
'I'he pmblem is solved by the present invention, which aims weight of 2.000 to 30.000 g/mol,
to provide a prepre that allows continuous laying-up of [l)J diaminodiphenyl sulfone.
prepreg layers wlule preventin the reinforcing, fibers or the [E] particles having a volume-avemge particle size of 5 to 50
matrix resin from being partly deposited on the automated pm md insoluble in the component [B]

2
!
Patent Application Publication Aug. 4, 2022 US 2022/0243051 A1
US 2022/024305 [ A[ Aug. 4, 2022

PREPREG AND FIBER-REINFORCED in workability, Patent docunlent 2 discloses a method for

COMPOSITE MATERLLL reducrng ihc iackincss of ihc prcttrcg by usulg a matrix resin
having a high viscosity.
'I'I I('I IN i CA I. III II.D
I
PRIOR ARI'OCUMI:N1 S
[000)J 'the present invention relates to a prepreg that
shoivs a high processabihty in an automated lay-up device Patent Documents
and serves to pmduce a cured product with a high tougluless [(R)05J Patent document I )apanese Unexainined Patent
and high inlpact strength and also relates to a pmducrion Publication (Kokai) No. 2010-229211
ntcihtx! (hclclor.
[0006J Patent document 2 )apanese Unexamined Patent
Publication (Kokai) No. HEI 09-194GI I
13A('K(iR(BIN I )
AR'I'0002]
I'iber remfbrced composite materials made of rein-
SUMMARY OF INVENTION

forcing fibers such as glass fiber. carbon fiber, and aramid Problems to bc Solved by the Invention
fiber. and cured pmducts of thermosetting resins such. as
unsantrated polyester resin, vinyl ester resin. epoxy resin, [0007] The prepreg dcscribcd in Paicut document I falls io
phCnol rt:S1n. C)"Illa(C cstcl ICSill. alai blSntrl)Cllludc liwlll, have a sulliciently reduced tackulcss, aud Ii cannot be said
have 1 erv good nlcchrllui al plopcl iles such rls high slrcnglh that the proposed automated lay-up device has a sufficiently
and elastic modulus and are high in heat resistance and inlproved pmcessability. On the other hand, the prepreg
corrosion resistance, although light in weight, and therefore, described in Patent document 2 is too low In tackiness,
they have been applied in many fields including, the nlanu- resultulg in insufilclent adhesiveness between prepreg lay-
facturing of aircraft members, spacecraft members. autorno- ers
bile members, ship members. civil engineering and con- [0008] Thus. the problem is solved by the present inven-
struction maicnals, and sporiulg goods. In particular. fiber tion, which aims to provide a prepreg that allows continuous
reinforced composite ma(coals incorporaling conlimious Ltying-up of prepreg layers rvhile preventing the reinforcin
fibers have been used in applications requiring high perfor- libera or ihc mainx resin from being partly deposited on ihe
mance. ivhere carlxm fiber. which is high in specitic strength auiomairxl lay-up dcvicc. when such B device is used with
and specific elastic modulus. is often adopted as reinforcing the aim of producing a hier-reinforced composite material
fiber while epoxy resin, wlfich have ood mechanical prop- having a high toughness and impact resistance.
erties and hi+ heat resistance and chemical resismnce and
cml achier c strong adhesion to carbon liber, ls often used as Means of Solvulg the Problmns
matrix resin.
[0009] To solve the aforementioned problem, thc prcscnt
[0003] In recent years. industries for manufacturing large invention is configured as descnbed below
sized composite materials including those fbr aircraft cnnl- [0010J (I) A prepreg including the conlponents [AJ to [I I]
monly adopt such methods as ATL (automated tape layup) given below,
and AFP (automated fiber placement) in order to Lsy up meeting the requirements (i) to (iii) given below, and
prepreg layers using an automated lny-up device because serving to produce a cured product that incorpomttes
ihC)'dll IICBICv C B hlghCI plixlUC(lvll)'hdn IBC Inllxl hl)'-up
method. In particular, the AFP method is suitable Ibr pro- a reinforcing fiber layer defined as the region rangin from
ducing parts containing a relatively Ltr e number of curved 8% to 92%v depth from the surface in the thickness direction
faces such as aircraft fuselage and can realize high-yield and contauung a Iirsi epoxy resul composiuon ul wluch 90
material production. and accordingly. this method has been turlss % ol Illolc of ihe ctnuponcni [A] cxfiis, Bnd
frequently adopted in recent years. In the AFP method. about two surface rcsul layers ouch defined as the region rangulg
ten to several tens of slit tape prepre s with widths of 3 to from either surface ro a depth of 8%s exclusive in the
13 mm, wluch arc prepared by cuuing a prcptreg mto a tluckness direction and containing a second epoxy resin
(ape-like shape ul the direction of'hc reulforcmg fibers, arc composition in wluch 85 mass % or more of the component
passed between guide rolls. collected on 'I nlachine head, [E1 exists.
and laid up on a base In this step. as the guide rolls and the (i) the second epoxy resin composition includes the com-
slit tape prepregs abrade each other, the matrix resin con- ponents [B] io [E] ol'wiuch the component [C] accounts Ibr
tained in the slit tape prepregs tends to adhere ro the guide 8 io 24 parts by mass rclanve io 100 parts by nuiss of thc
rolls and cause the problem of a decrease in productivity. second epoxy resin composition,
Pdicn( document I dcscnbcs a pre)trcg and a production (il) the second epoxy resin composition has a storage elastic
method thcrcfbr whereul a high handleabihty rmd process- modulus G'n the ran e of I Ox)0 to 3 Oxlfi Pa rvhen
ability are achieved and composites rvith good mechanical measured at 25', and an anguLtr frequency of 3.14 mtd/s,
pmperties can be pmduced as a result of appropriately Burl
controlling the viscosity and glass transition temperature of (ili) plies of the prepreg laid up afier bein left to stand for
the epoxy resin composition existing on both surfaces of the 24 hours rn an cnvlrotunmli Bra tempcraturc of'25 2'. and
prepreg and also controlling the viscosity of the epoxy resin a lumudlty ol'50 5% RH show a peel strength of 0.1 N/mm
conlposl lion cxlsihlg ill ihc ihlckllcss-directional ccnlix pot- or nlorc Bi 35 C.,
ion. [AJ a carbon fiber,
[0004J I'urrhennore, for the purpose of optimizing the [13J an epoxy resin containing the components [bi J and [b2J
tackiness properties of the prepreg and irnpnlving the nlold- specified belorv,
US 2022/024305 [ A[ Attg. 4, 2022

[bl] a di- or less-hnictional epoxy resin containing. in a stnictures to decrease the free volume, making it possible to
&lx&loci&le. Sileast onc ru&g strUc&U&e hdvulg Ii&U&- 0& n&ore- produce a cured product luw ing the advantage of maintain-
&no&nbcrcd ring aud a glyc&dyl anunc group bonded to a ring iug a high clast&c modulus.
structure. [0019] Epoxy rcsu&s uselbl as the component [bi] include
[b2] a tri- or more-functional epoxy resin, N,N-diglycidy1-4-phenoxy mulu&c, N,N-d&glycxly1-4-(4-
[C] a thermoplastic resin havings weight-avers e molecular mcthylphenoxy) an&lute, N.N-diglyc&dy1-4-(4-&crt-butylphc-
vveight of 2,000 to 30.000 g/mol, noxy) aniline, and N,N-diglycidyl-4 (4-phenoxyphenoxy)
[D] diaminodiphenyl sulfone, and 'l &u 0 f& C.
[E] particles hav &ng a volume-average Ivdr&iclc s&zc ol' to 50 [0020] In many cases, these epoxy rcs&ns cau bc produccxI
iun dnd insoluble in the component [B]. by addmg epichlorohydrin to a phenoxyanilme derivative
[tlt)l IJ According to a preferred embodiment of the and cyclizing it ivith an alkali compound Specifically,
prepreu of the present invention, the component [C'J con- usable phenoxyaniline derivatives include 4-phenoxyani-
tained accounts for 8 to 20 parts by mass relative to 100 parts line. 4-(4-methylphenoxy) aniline. 4-(3-methylphenoxy)
by mass of the second epoxy resin composition. and accord- amluic, 4-(2-methylphcnoxy) amino, 4-(4-cihylphenoxy)
in to another preferred embodiment, the second epoxy resin amluic, 4-(3-ethylphcnoxy) iuul&nc, 4-(2-ethylphcnoxy) iuu-
compos&uon has a storage clast&c modulus G'n thc ran e of 1&ne, 4-(4-propylphcnoxy) iuul&nc, 4-(4-ter&-buiylphenoxy)
1.0x10'o 1.0xlfis Pa when measured at 25'. and an ambne, 4-(4-cyclohexylphenoxy) an&line. 4-(3-cyclohex-
angular frequency of 3.14 rad/s. ylphenoxy) aniline, 4-(2-cyclohexylphenoxy) anihne. 4 (4-
[0012J (2) a fiber reinforced composite material produced methoxyphenoxy) aniline, 4-(3-methoxyphenoxy) aniline,
by curing the prepreg 4-(2-methoxyphenoxy) aniline. 4-(3-phenoxyphenoxy) ani-
luic. 4-(4-phcnoxyphenoxy) amlinc. 4-[4-(iufiuoromcihyl)
Advuntagix&us Efii:cts of ihe lnvenuon phcnoxy] &Online, 4-[3-(inlluoromethyl) pheuoxy] a&ulmc,
[0013] The use of a prepreg according to the present 4-[2-(tnfiuoromethyl) phm&oxy] a&ulinc, 4-(2-naphthyloxy-
invention ensures good lfigh slit tape processability and phenoxy) aniline. 4-(I-naphthyloxyphenoxy) anilme, 4-[(1,
splmuig property &n the process of producing a tiber rc&n- lubiphenyl-4-yl)oxyJ miiline. 4-(4-nitrophenoxy) aniline,
forcixi compos&ic matcnal with a high impact rcs&stance and 4-(3-nitrophenoxy) aniline. 4-(2-nitrophenoxy) aniline,
interlayer iou luiess by means of an automated lay-up 3-n&tro-4-aminophenyl phenyl ether, 2-nitm-4-(4-nitrophe-
device noxy) a&uhnc. 4-(2,4-duuirophmioxy) an&linc. 3-&uiro-4-phc-
noxy anilu&c, 4-(2-chiorophcnoxy) a&ulinc. 4-(3-cldorophc-
13RII.I'IIS('RIPI'ION Ol'l Ill DRAY&IN(IS noxy) aniline. 4-(4-chlorophcnoxy) an&lu&c, 4-(2,4-
dichlorophenoxy) aniline, 3-chloro-4-(4-chion&phenoxy)
[0014] FIG. I Tlus &s a schematic vww showm a test for ambne, and 4-(4-chloro-3-tolyloxy) aniline.
ihc dcpos&i&on ol rcsul fUzz o&1 illc pa&11 h&le thdi
&1&casll&l&lg
[IR)21] Commercial epoxy resu& products useful as the
occurs as a slit prepreg &s abraded cmnponent [biJ include Denacol (registered trademark)
EX-731 (glycidylphthalimide. manufactured by Nagase
DESCRIPTION OF PREFERRED Che&uteX Corporation), OPP-CI (o-phenylphenylglycidyl
I:MI3ODI Ml &N'IS
ether. manufactured by Sanko Co.. Ltd.), CIAN (N-digly-
[0015] From the viewpoint of specific stren th and spe- c&dyl anilu&c, manulbcturcd by N&ppon ICayaku Co., Lid.).
cdic clasuc modulus, &t &s csseniml Ior thc component [A] and TOREP (registered tradmuark) A-204E (diglyc&dyl-p-
used for the present u&vm&t&on to bc carbon liber. Prefi:rred phenoxy aniline, manufactured by 'lousy I&ine ( hemicals
types of such carbon hber include, but not limited to. pitch ('o. I td.)
carbon tiber and acrylic carbon fiber. of which acrylic carbon [0022] The component [b2] &s a tn- or morc-funct&onal
fiber is more preferred. epoxy resin, tlmt is, a compou&id that has three or more
[0016] As thc form of carbon liber, tw&stcd yama, epoxy groups in a molecule. 'I'he use of such an epoxy resin
untwisted yama, non-iw&sied yama ur thc like can be us&Uk as the co&nponent [b2J serves to produce a cured pmduct
ln particular, un&wisted yarns and non-twisted yarns are having a high gLsss transition temperature, hi h elastic
preferred because filan&ents are oriented in parallel to ensure modulus, etc.
a good balance between moldability and strength properties [0023] Examples of the component [b2] include glycidyl
of resulting fiber-re&nforced composite materials. amine type tri- or more-functional epoxy resins. glycidyl
[0017] The component [B] used Ii&r ihe present invm&tion ether type tri- or nu&re-functional epoxy resins, and amino-
is an epoxy resin that contains the components [b I J and [b2J. phcnol type iri- or more-limcuomil epoxy rcs&ns. Of ihcsc,
[0018] The component [bl] is a di- or less-hinctional duun&nod&phcnylmcil&anc type epoxy rcs&ns and amuiophe-
epoxy'csu& contauung. u& i»1&olccURX at least inlc ting nol type tri- or more-hmctional epoxy resms are preferred
structure havu&g lour- or morc-mcmbcred rmg a&xl a ly- because they have a ood balance among physical proper-
c&dyl aminc group bonded io a rm structure. Duc to a ties.
an&aller nuniber of glycidyl gmups, which are functional [l)024J Examples of lycidyl amine type tri- or more-
gmups, such an epoxy resin oives a cured product w&th a functional epoxy resins that are preferred as the component
large plastic deformation capacity because the cross-linking [b2] include diaminodiphenylmethane type epoxy resins,
density is controlled moderately durin curing. On the other diaminodiphenyl sulfone type epoxy res&ns, metaxylenedi-
hand, a lower cross-hniong dens&iy leads to ihe d&sadvaniage anunc type epoxy resins. IB-bisam&nomethyl cyclohcxane
ol'a decreased clasuc modulus. However, smce m such an type cpox)'eau&s, a&id &socyzlnU&dic tvpc cpoxv rcsh&s.
epoxy resin, thc nng structures bonded io glyc&dyl amu&e Conunercia1 products of ihcsc epoxy rcs&ns u&cludc Arald&ie
mups are in a hung state like peniLsnts in the molecule, (registered trademark) MY720, Araldite (registered trade-
spaces in the crosshnked stn&cture are filled with these riag mark) MY721, Araldiie (registered traden&ark) MY9512,
US 2022/024305 [ A[ A)fg. 4, 2022
3

Araldite (re istered trademark) MY9663 (all manufactured [00Z9] For the present invention, the component [B] may
by Huntsman Corporation), SUMI-EPDXY (registered contaui epoxy resins other )han thc components [bl] and
tradcmarl ) ELM434 (numulhctured by Sunutomo Chemical [b2] unless they impair )hc prefi:rrixl cllhcts of thc uivcntion.
('o . I,td ), ipotohto (registered trademark) YI 1-434 (nianu-
I Such epoxy resins other than the components [b1 J and [b2J
factured by NIPPON Slligl. ( hemical k. Material ('o., are preferably glycidyl ether type di-functional epoxy resins
Ltd.), and jER (registered trademark) 604 (manufactured by produced from a phenol as precursor. Examples of these
Mitsubishi Chemical Corporation). epoxy resins include so-called bisphenol type epoxy resins
[I)l)25] Exaniples of glycidyl ether type tri- or niore-
such as bisphenol A type epoxy resin resins. bisphenol F
functional epoxy reams that are preferred as the component type epoxy resin resins. and bisphcnol S type epoxy resin
res ills.
[b2] include such epoxy resins as phenol novolac type epoxy
resins, orthocresol novolac type epoxy resins. tris-hydroxy- [0030] Commermal products of bisphcnol A type epoxy
phenylmethane type epoxy resins. and tetm-phenyiol ethane remns that can bc used as such c7toxy resuis other than the
type epoxy resins Coriuncrcial pmduc1s ol these epoxy components fbi] and [b2] include )ER (rcgwtcrcd trade-
resuis uicludc D.E.N. (rcgistcrcd trademark) 431, D.E.N. mark) 825, jER (registered trademark) 827, )I:R (registered
(re istered tmdemark) 438 (both manufactured by I'he Dow trademark) 828, j)i)3 (registered tradeniark) 834. jib)3 (reg-
('hen)ical Company), jl:R (registered trademark) 152 istered trademark) 1001, jER (registered trademark) 1004,
(manufactured by Mitsubishi Chemical Corporation), jER (registered trademark) 1004AF. jER (registered trade-
EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd ), marl ) 1007 (ali manufactured by Mitsubishi Chemical Cor-
EPICLON (registered trademark) N-660 (manufactured by poration). EPICLON (rcgistcred trademark) 850 (manufac-
DIC). Tactix (regwtcrcd tmdcmark) 742 (manufacturixl by tured by DIC Corporation), Epotohto (regwtcrcd trademark)
Huntsman Corporation), )ER (regis)areal trademark) 103 IS YD-128 (manufactured by NIPPON S J'I:lil. ('hemical 8:
(manufactured by Mitsubishi ('hemical ( orporation), and Materia Co, I,td.), D E R. (registered tradeniark) 331. and
I:PICI ON (registered trademark) IJP-7200 (mamifactured D.E R. (re istered trademark) 332 (both manufactured by
by DIC). The Dov: Chemical Company).
[)N)3IJ Commercial products of bisphenol I'ype epoxy
[0026] Examples of mninophcnol type in- or morc-func- resins that can be used as such epoxy resins other than the
tional epoxy resins that am preferred as the component [b2J
components [bl] and [b2] include jER (registered trade-
include triglycidylation products of p-aminophenol, ni-ami- mark) 806, jER (rcgtstcrtx) tmdcmark) 807, )ER (rcgistcrcd
nophenol, p-aminocresol, trdluoromethyl hydroxyamline, tradcnuirk) 1750 (all manufacturtx) by Mitsubishi Chemical
hydroxyphenyl aniline, methoxyhydroxyaniline. butylhy- Corporation), EPICLON (registered trademark) 830 (mmiu-
droxyaniiine, and hydroxynaphthyl aniline. Commercial factured by D)C). and ipotohto (registered tmdemark)
I
products of these epoxy resins include SUMI-EPDXY (reg- YDli-170 (inanufactured by NIPPON S1 Jilil, ('hemical 8:
istered uadcmark) ELM120. SUMI-EPDXY (rcgistcred Matenal Co., Ltd.).
tradeniark) I II,M)00 (both manufactured by Suniitonio
[)N)32J Commercial products of bisphenol 8 type epoxy
( hemical Co, I,td ), MY0500. Araldite (reaistered trade-
resins that can be used as such epoxy resins other than the
mark) MY0510 (both manufactured by Huntsman Corpom-
components [bl] and [b2] include EPICLON (re istered
tion), and jER (registered trademark) 630 (manufactured by
trademark) EXA-1514 (manufactured by DIC).
Mitsubishi Chemical Corporation).
[0033] For the component [B]. the incorpomtion of both
[00Z7J It is prefemble for these epoxy resins used as the an epoxy resin showing fluidity at an appmpriate tempera-
contponent [b2] to have 3 to 4 functional groups in a ture and an epoxy resin showing no fluidity at an appropriate
molecule. If the number of these functional groups is in tlus tcmpcrature is clfectivc for fluidity control of the nmtrix
r;mgc. )hc ma)ox resin tends to form cured products having remn during heat-cunng of the resulting prcprcg. Thc lhiidity
sullicicntly high heat rcswuuicc and clasuc modulus cmitrol of the matrix resin serves to appropriately adjust the
[0028] Furthermore, it is prefbmble that the component degree of impregnation of reinforcing fibers with the matrix
[bi] account for 20 to 50 parts by mass while the component resin and it is also effective for pmducing a prepreg having
[b2] account for 50 to 80 parts by mass relauvc to die total desired degrees of tackiness and drapability.
qumiuty, which accounts I'or 100 parts by mass, of the [l)034J I he component [('J is a thernioplastic resin having,
component [B]. Thc rcsui tends to have a sufliciently high a weight-average molecular wei ht of 2.000 to 30.000
elastic modulus when the component [bi J accounts for 20 g/mol. The weight-average molecular weight referred to
parts by mass or more relative to the total quantity, which herein means a weight-average molecular weight measured
accounts for 100 parts by mass, of the component [B], and by gcl permeation cluomatogmphy and converted in tcnns
the resin tends to have a sufficiently hi h glass transition of polystyrmic. Thc incorporation of thc component [C],
tempcraturc mid clastic modulus when it accounts lor 50 which has a weight-average molecular weight of 2,0()0
perm by mass or less rclativc to the total quantity, wluch 8/mol or inore. serves to pmduce a cured resin with an
accounts for 100 parts by mass, of thc compoiwnt [B]. improved tougluiess and a prepreg with a decreased tacki-
liurthermore. it tends to have a sufficientl high heat resis- ness. Furthermore. the incorporation of the component [C],
tance and good inecbanical property when the compoiient which has a wei ht-average niolecular weight of 30,000
[b2] accounts for 50 parts by mass or more relative to the g/iiiol ol liss, serves to plevelit )lie lnatnx riwiii fl olll liavlllg
total quantity, which accounts for 100 parts by mass, of the all excessively'llgll viscosltv illld prixlucc a priprcg liavlllg
component [B], and it tmids to form a cured ream havuig a a high handleability.
sulliciently high elongation percentage and tougluicss when [0035] The componmit [C] is prefi:rably soluble ui the
thc component [b2] accounts Rir 80 parts bv mass or less component [B] from the viewpoint of obtmnuig a liber-
relative to the total quantity. which accounts for 100 parts by reinforced coinposite material with good niechanical pmp-
niass, of the coniponent [l3J. erties and a niatrix resin with a desired viscosity 1'he
US 2022/024305 [ A] Aug. 4, 2022

expression "soluble in in the component [Bj" used herein mark) (manufactured by Victrex): polysulfone products
mc;ms ihat Ihcrc exists a Icmpcraiure region whcreul a include UDEL (registered Iradnnark) (manuf wiured by
honlogcnciius phase is fonncd when nllxlng thc conlpolu:ni Solvay Spimialtics Polymers). and polyvinyl pyrrolidone
[('1 mid the component [IIJ and subsequently heating and pmducts include I uviskol (registered trademark) (manufac-
stirring thenl I lere, the expression "a homogeneous phase is tured by 13ASF)
formed" means that there is a state wherein phase separation [0043] As the component [C]. cxamplcs ol'other prcfctrcxi
is not found by visual observation. As long Bs a homoge- thermopLlstic resins that are soluble in the component [13]
neous phase can be formed m a particular temperature mnge, include those thermoplastic resins having polyaryl ether
sc)taratton may occur ul other icmpcraiurc re iona. For backbones. The use of such B thermoplastic ream having a
example. sc)tamfion may occur ai 23'. 11' homogcnimus polyaryl ether backbone serves to control the tackiness of
phase is fornled at 120" (')issolution inay be confirnled by the resulting prepreg, control Ihc fiuidiiy ol'hc matnx resin
the following method Specifically, in the case where the dunng heat-cunng of the prcprcg. and provide a tough liber
component [C] is obtained in a powdery foml, the pov.der reulforccd composite ma(coal tstthout impairulg Ihe heat
is mixed in the component [B] and the mixture is maintained resistance or elastic modulus
for several hours. for example 2 hours, at B consmnt tem- [0044] Examples oi'uch a thennoplasuc resin havulg a
peral urc that is lower Ihan Ihc glass Iransi lion I cmp era! urc of polyaryl ether backbone and sen ing favorably as thc com-
thc component [B] while measuring thc chimgcs in viscosity. ponent [CJ include polysulfone, pol)phenyl sulfone,
it cml be decided that the component [CJ is soluble m the polyethersultime, polyetherinlide, polyphenylene ether,
epoxy resin if the viscosity increases by 5% or nxlre front polyether ether ketone. and polyether ether sulfone. and
that of the component [13J alone heated at the same constant these thermoplastic resins having polyaryl ether backbones
temperature. may bc used sulgly or as a combulation of iwo or more
[0036] Furthermore, it is prclbmble thai a thermoplastic thereof. To ensure a lugh heal resistance, ul panicular, Ihe
resin contaming a fiulctional group having hydnlgen bond themloplastic rcsul luoing a polyaryl ether backbone prel-
formin property be used as the component [('J because it is enlbly has a olass transition temperature ('I 0) of at least 150"
expected to work efi'ectively for strengthening the adhesion
between the component [A] and the component [B].
('r more, more prefenlbly 170" ('r more If the glass
transition temperature of the thermoplastic resin having a
Examples of such a functional roup havilig hydrogen bond polyaryl ether skeleton is more than 150" C., moldings
formmg property include alcoholic hydruxyl groups, ianidc produced Ihcrelbom tend io be resistant to thcnnal dciiimla-
bonds. sulfonyl groups, and carboxyl groups. tion.
[0037] Examples of the component [C] having Bn alco- [0045] The terminal functional group in the thermoplastic
holic hydroxyl group include polyvinyl acetal resins such as remn lraving a polyaryl cthcr backbone is preii:rably a
polyvinyl fomlal and polyvmyl butymll as weil as pol)w Inyl hydroxyl group, carboxyl group. (biol group, anhydnde, etc.
alcohol mid phenoxy rcsuts. because they can react lvith a catioil-polynlerixable com-
[0038] Examples of the component [C] having Bn alnide pound. ('Onuuercial pmducts of thermoplastic resin having
bond include polyanudc. polyimide, polyamidemudc. and such a terminal functional group. having a polyaryl ether
poll'vins'I p)xolldonc. bacl bone. and bavin a weight-avera e molecular weight of
[0039] Examples of the component [C] having B suifonyl 2.000 to 30,000 g/moi include Sumika Excel (re istered
group include polysulfone and polyethcrsuii'one. tradcnuirk) PES3600P (manufactured by Sumiiomo Chemi-
[0040] Examples of the component [C] having a carboxyl cal Co., Lid.) and Vtrantagc (regisicrcd trademark)
roup include polyester, polyamide, and polyamideimide. VW-10700RFP (manufactured by Solvay Specialties Poly-
Thc carboxyl group may be located in thc prulcipal chmn mers) as well as copolynler ohgomers of polyethersulfone
and/or al a chain cnd. and polyether ether sultime as described in Published .Iapa-
[0041] Of the above ones, the polyamide, polyimide, and nese Transiation of PCT International Publication JP 2004-
poiv'suliiinc iuav colltalll, in lhcil pllnclpal chBins. lin ether 506789. They also include Uitem (registered trademark)
bund or a funcuonal group such as carbonyl group. In thc 1040 (maluifaciured by SABIC), tshtch is a conunercial
polyalnide. the nitrogen atom in the amide group nlay have product oi'polyethcnmide. An oligomer as refi:rrcd io herein
a substituent is a polymer composed mainly of a Iinitc number, commonly
[0042] As the component [C], extunples of conmlcrcial 10 to 100, of monomers bonded to each other In particular,
thenuoplastic resin pmducts that are soluble in the compo- the use of polysulfone or polyether sulfone is preferable
nent [13J and contain a functional group having hydrogen from the viewpoint of the solubility in the components [B],
bond formmg property include the following. Commercial heat resistance, solvent resistance, and touglmess improve-
polyvinyl acetal resin pmducts include Mowital (registered nlcni.
trademark) (manufactured by Kuraray Co .. Ltit) and vulylcc [0046] Thc component [D] is ihanunodiphnlyl sulfilne.
(rcgisicred trademark) K (manul'aciured by JNC), polyvulyl Thc component [D] is a curing agnlt for thc component [B]
alcohol rcsul products include Denks Poval (rcgistcred and it is a conlpound having an active hydrogen tint can
tradenlark) (nlanufactured by Denka ('ompany I.inuted), react with an epoxy group isomers of diaminodiphenyl
polyuunide resin products mclude Macnlmelt (registered sulfone inciude 3,3udiaminodiphenyl sulfone and 4.4ndi-
trademark) (mamifactured by Henkei) and AmiLln (regis- aminodiphenyl sulfone, of which 4.4udiaminodiphenyl
tered trademark) CM4000 (manufactured by Toray Indus- sulfone is preferred from the vieivpoint of storage stability.
tncs. Inc.). polyimidc products ulclude Ultcm (registered [0047] Commernal products of diaminodiphcnyl sulfone
tradcmarl ) (manufacturixl by SABIC), Aurum (registered include SEIKACURE S (manufacturcxt by Wakayama Sciha
tradcmarl ) (manufacturcxt by Mitsui Chemicals. Inc.). and Kogyo Co., Lid.), MDA-220 (manufactured by Mitsui
Vespel (registered trademark) (manufactured by l)u Pont), ('henucals, Inc.), and 3,)ul)AS (manufactuied by Mitsui
Pl:EK polynler products mclude Victrex (reaistered trade- ('henncals, Inc )
US 2022/024305 [ A[ Aug. 4, 2022

[0048] Here, it is desirable for the total quantity of by. for instance, transmission electron micmscopy. the ther-
diiuninodiphcnyl sullbne of the component [D] to be such moplastic particles ol thc componmit [E] in Ihc cured epoxy
thai thc number of moles ol'active hydrogen contmncd ui the remn do not undergo substanual sluulkage from their ongi-
niolecule is I 05 to 2 0 times, preferably I I to I g times, and nal size with clearly defined interfaces maintained between
still preferably I 2 to I 5 times, as large Ss the number of the thermoplastic particles of the component [)1J and the
moles of epoxy groups contained in the entire second epoxy matrix resin. In this instance. the components of the second
resin composition. If the number of moles of active hydro- epoxy resin composition described later in Example I can be
gen is only less than 1.05 times as large as the number of used as components of the epoxy resin composition other
moles of epoxy groups contauied ui the enure second epoxy than the particles ol'hc component [E]. Howcvcr. other
resin comp os i u on, the resulting cured product can bc hi gh in coulpollcuts Illa)'llso bc ilscd Unless dlssoliltioll cllarBcici-
cross-linkin density. possibly leading to a resin with a istics are changed
decreased elongation percentage. If it is inure than 2.0 times, [0053] The volume-average particle size of the particles of
on the other hand. the heat resistance tends to decrease the component [E] is 5 to 50 iun. Prefemsb)y 7 to 40 iun. and
significantly while the viscosity of the the second epoxy morc prcfcrably 10 to 30 0m. The range may be bctwcen any
resin composition tends to increase, possibly making of thc aforcmcnttoncxI upper limits and miy of the aforc-
prepreg preparation difiicult. ulclltloiied lower liiuitw A iiiiUulc-average piatlclc size
[0049] Only onc type of diaminodiphcnyl sulfone or a controlled at 5 pm or niore selves to prevent the component
combuiation ol' plurahty of types thcrcof may be usu! Bs [I:J contained in the second epoxy resin composition exist-
the component [DJ. in in the surface resin layer of the prepreg according to the
[0050J In addition. a cunng agent other than diaminodi- present invention described later from etting into the
phenyl sulfone may be used in coinbination unless good bundles of thc carbon libera Ol'lu: component [4] Bnd allow
efi'acts of the present invention are impaired. Examples of them to stay in lhe uitcrldyer rcsui layer ln the resulting liber
such a curing agent other than diaminodiphenyl sulfone reuiforccd composite nuiu:rial. whcrcus a volume-average
include dianunodiphenyl ether, diaminobcnzophcnouc, particle size contmlled at 50 iuu or less serves to form a
dicymidiamidc, amuiobcnzoic acul caters. vanous iulhy- surface resin layer of the matrix resin with an appmpriate
drides. phenol novolac resins, cresol novolac resins, poly- thickness on the prepre surface and. in addition, ensure that
phenol con)pounds. imidazale derivatives, aliphatic anlines, a fiber reinforced composite material having a good open
tetramethyl uanidme, thiourea-added amines„methyl hexa- uioilc (uuidc I) Iutcrlil)'cl Ildc/Urc toilghucss (Gi,) Is
hydrophthalic anhydride. Other similar carboxylic anhy- obtained and that the carbon liber of the component [ J4 has
drides. carboxylic acid hydrazide. carboxylic acid amide, an appropnatc volume content.
polymcrcaptan, boron triliuoride ethylanunc complex, and [0054] For example, the niaterial of the particles of the
other similar Lewis acid complcxcs. Part of the component component [E] may be a themlosettlng resin. thermoplastic
[13] and the component [DJ may be reacted prelinunarily resin. or a mixture thereof, of which the use of a thermo-
before adding them to prepare a composition In some cases, plastic resin as primary component Is dcslrablc from thc
this method can serve effectively for viscosity adjustment vicwpouit ol'providing a liber reinfiirccd composite matcnal
and storage stability improvement in preparing an epoxy v ith a high impact resistance. Ilere, particles that incorpo-
resin composition. mate, as primary component, a thermoplastic iesin as referred
[0051] The addition of a curing accelerator may also be to herein mean those particles in wlfich the thermoplastic
cfibcui e for promoting the reaction between thc epoxy resin resin accounts for the largest propoition by mass and they
dnd thc cunng agent. Examples of such a curin accelerator may be thermoplastic resin particles formed only of the
include urea compounds, ternary amines and salts thereof, tilCIllloplaStlC l csin.
imidazole and salts thereof, triphenyl phosphine and denva- [13055J I ixamples of the thenuoplastic resin of the com-
tives thereof. metal carboxylates. Lelvis acid~. Broensted ponent [I! J include polyamide. polyamideiniide, polyethere-
acids, and salts thereof. Of these, the use of a urea compound therketone. polyetherketoneketone. polyester, polypropyl-
is preferred fmm the viewpoint of the balance between its ene. and polyphenylenesultide. of which polyamide is
StoldgC Sniblllt)'lii Cdtalv)IC dblhtv. Iu palticUIBI; thC Colll- particularly prclbrable as particle material bccdusc it scrvcs
bination of a urea compound and a dicymidiarmde of to produce a fiber reinforced composite matenal with a lugh
diaminodiphenyl sulfone is preferred impact resistance. Ol'he various polyumide panicle nmie-
[0052J 'the component [IIJ used for the present invention rials, furthermore. polyamide 12. polyamide 6, polyamide
is particles that have a volunie-average particle size of 5 to 11, polyamide 66, and polyamide 61/12 copolymer are pref-
50 pm and are insoluble in the component [B]. Here. to erable. In addition, it is preferable for the particles contain-
determine the volume-average particle size. particles ing a thermoplastic resin as primary component to be. for
dccountuig for a mass concentration of 9% are dispersed in cxiunplc, a polyamide polymer modllicd with an epoxy
dispersion mcdnun and lhc volume-average di unclcr is compound into a semi-IPN structure bccausc such a polymer
calmilated from mcasurcmeuts taken by laser diiiracllon/ can rcalizc a dcsirablc sucngth of adhesion to an epoxy resin
scattering particle size distnbution measuring equipnlent composition I iere, IPN stands for interpenetrating polyiner
(preferably I.A-750, manufactured by I IOI&IBA, I,td ). Tv 0 network, which is a kind of polymer blend stnlcture gpe-
measurements were taken and their avera e w:as adopted. clfically. crossiinked polymers are used as blend compo-
Here. the expression "being insoluble in the componem [B]** nents and the dissimilar crossiinked polymers are partially or
mc;ms ihat when au epoxy rcsui composition prepared by Iiilly entangled to fomi a multiple network stniclure. A
dispersing paruclcs ol'hc componcni [E] m a composition smni-IPN has a multiple ac)work formed ol'roas baked and
contaiiung the components [B], [C]. mid [D] is heat-curcvk straight-chain polymers. Scum-IPN thermoplastic resin par-
the particles of the compioaent [)1J substantially do not ticles can be produced by, for example. dissolvmg a ther-
dissolve in the coniponent [13] and that in observations made nxiplastic resin and a themiosetting resin in a common
US 2022/024305 [ A[ Aug. 4, 2022

solvent, mixing them uniformly, and perfomling reprecipi- v hich accounts filr 100 parts by mass. If the content is in tlfis
tauon. Thc usc of purticlcs of an epoxy rcsui and a senu-IPN range, thc value ol''t room tnupecdturc can bc improvcxf
polyamidc scrvcs to produce a prcprcg havuig a high heat dnd lllc prcprcg sUriacc cdn bc Iullllstcd 10 Bn Bpploputuc
resistance and lugh impact resistance tackiness Furtheuuore, the time period in which a desirable
[0056J Useful comniercial pmducts of such polyamide tackiness is maintained (which is occasionally referred to as
particles include SP-500, SP-10. 'I'lf-l, 311-2. 'I'oraypearl tack life) can be prolonged. In the case of the first epoxy
(registered trademarl ) TN. (all manufactured by Tony resin composition, as long as it contains epoxy resins. there
Industries. Inc.). Orgasol (registered trademark) 1002D, are no limitations on the chenlical structures of the epoxy
Orgdsol (rcgistcred trademark) 2001UD, Orgasol (rcgistcred resins existing ln Ihc conlposlnoll alai 11 ls 1101 ncccswliy 10
trademark) 2001EXD, Orgasol (rc ustcred tradnnark) contain the component [E] as In tlu: case ol'hc almond epoxy
2002D, Orgasol (registered trademark) 3202D, Orgasol I'csin colrlposttioli
(reuistered tradenlark) 3501D. and Orgasol (registered [0060] The prepre according to the present invention is a
tradenlark) 35021) (all manufactured by Arkema) combination of an epoxy resul composition and carbon
[0057] In regard to the shape of such therinoplastic resin libera The prepreg according to thc prcsnlt ulvcntion Is
particles. they may be spherical. nonsphericnl, porous, preferably produced by the hot-melt process to ensure the
needle-like, whisker-like. flaky, or porous, of which spheri- developnlent of the advantageous effect of the mvention
cal particles arc preferable bcca use sphcucal partmlcs do not The hot-melt process is a solvent-free technique designed
work Io deteriorute thc epoxy resui*s flow property and can for the impre nation of carbon fibers with an epoxy resin
nlaintain hi h carbon hber impregnating pmperh, and the composition that is heated to decrease its viscosity. The
degree of delamination caused by klcal iinpact is further hol-melt process cml bc carried out by some ibifercnl
reduced in drop impact (or local impact) test of fiber proccdurcs Includuig a procedure in which a matux resin
reinforced composite material so that. in the case where a heated to decrease the viscosity is used filr direct impreg;
stress is applied to the fiber reinforced composite matenal nation of carbon fiber: and a procedure in which release
after undcrgoiug thc unpact test thcrc will bc a dcmreased paper sheets laid with resin film are prepared by coatin
number of'elanunatiou pans that result Ibom Ihc local release paper sheets etc, lvith a matrix resin and then used to
impact to act as starting points of destruction attributed to cover either or both surfaces of a carbon fiber sheet, fol-
stress concentration. thereby making it possible to obtain a lowed by applying heat and prcssure to nlsurc thc impreg-
fiber reinforced composite material having a high impact nation ol the carbon liber sheet with the matux rcsui. The
resistance. above procedures are generally intended to provide sheet-
[0058] Furthermore, the component [E] is not dissolved in like prepregs, but a carbon fiber strand may be directly
the nlatrix resin during the curin step and therefore can inunersed in an epoxy resin composition having a decreased
exhibit a better moihficdtion cffccu Thc fniturc that Ihcy are viscosity to provide tape-like or thread-like prepregs.
noi dissolved duuug Ihe curing step is also cfli:ctiic for [0061J In the prepreg according to the present invention,
nlaintaining fluidity of the resin during the curing step and 90 nlass % or more of the component [AJ exists in the
improving Ihe impregnating property reinforcing fiber layer. Furthermore, as described above. the
[0059J In a cured pmduct produced from the prepreg first epoxy resin composition may or may not contain the
according to the present invention. the reinforcing fiber layer component [E[. but it is necessary that 85 mass % or more
defined as the region rangin from 8% to 92% depth fmm of thc component [E] exist in thc surface resin layers. II'lus
Ihe surface in Ihc thickness dirimtion conlams a Iirst epoxy stnlchilc ls rcalizixk iin intel ld)'cl rcslll layer with lnclcdscd
resin composition in wluch 90 mass io or morc of thc toughness can be formed between the reinforcing fiber
conlpollcnt [A] exists, Bnd lllc Iw0 sllrlacc rcsill 111)'cia ciich layers in the resulting hber reinforced composite material.
defined as the region ranyng fmm either surface to a depth
of 8"!s exclusive in the thickness direction contain a second [0062] A cross sccuon ol'hc prcprcg according io thc
present invention can bc obscrvixl by, I'or cxtunple, thc
epoxy resin composition in which 85 mass 'is or more of the
component [E] exists. Here, the feature of the prepreg is method described belolv Specifically. a prepreg is inter-
specified in tenne of Ilm "cured product produced there- posed beuveen two polytetrafluoroethylene resin plates bav-
from". Thc reuson for Ihts is as dcscubcd below. When a in smooth surfaces and brouvght into stmn contact with
cured product is produced Ibom thc prepreg accordm to the them, and then the tempemsture is increased gmsdually so as
to reach the curing tcmpcraturc in scvni days to ensure
present invention, there are two surface resin layers each
dehned as the region ranging fmm either surface to a depth gclation and cuung, linis producing a cured prepreg plate.
of 8!s exclusive measured in the thickness direction and a This cured prc7trcg plate is obscrvcd at a magnification of
reinforcing fiber layer defined as the re ion mnging from 8% 200 or more under. for example, a digital micmscope
VI IX-5000 (manufactured by Keyence ('orporation)
Io 92% depth from Ihc surface measured in Ihc Iluckncss
dircchon. Here, tlm cxprcssion '*when d curn! product is [0063] Thc proportion oflhc component [E] that exists can
produced" Is rcflcrs to the fact that observation is performed bc determined by, for example, the method dcsunbcd beluw.
after curiim a prepreg specimen by gradual heating front In a cmss-sectional photo raph obtained fmm cross-sec-
room temperature to cause slow reaction because it is tional observation of a prepreg„ its proportion is calculated
difficult to observe a cross section of a prepre when it is in from the totai area occupied by the component [E] in the
the uncured state. The reinforcing fiber layer contains the entire prepreg and the area occupied by the component [E]
Iilst cpoxv'iutll conlposltion while Ihc sill pace lcsln flyer iu a particular region. Here, thc total arcs occupied by Ihe
contains Ihc second epoxy resin composilion. It is csscnlial component [E] can bc dcternuncd by taloug a cross-sec-
Ihtu Ihc sccilnil cpoxv resin conlposltloll contains Ihc colll- tional photogldph Bllil cUItlng CUI thc portions ol Illc colll-
ponents [l3J to [IIJ, with the component [(:1 accounting filr ponent [I I] using a generally knov n inlage analysis method
8 to 20 parts by mass relative to the total quantity thereof, In the case where it is difficult to distinguish the component
US 2022/024305 [ A[ Aug. 4, 2022

[E] dispersed in the resin in the photograph, the method of Here. room temperature represents an environment in which
staimng thc component [E] can be adopted. Ilm Iempcraturc Is 25 2 C. and tlm humidity Is SO 5% RH.
[0064] As a good method to localize the component [E] in [0070] From Ihc viewpoint of tlm proccssablbty ul Ihe
the surface resin layer. there is a two stage impregnation
process that consists of prcpanng a resin Iilm-coaled relcasc epoxy resin composition to have a viscosity at 85" ('f
remn Iilm prcparauon step, it is preferable Ibr thc almond
10
paper sheet (hcrclnaficr occasionally referred to simply as to 300 Pa s. It is nlore preferably 20 to 200 Pa s and still
resin film) composed of a piece of release paper etc. coated more preferabiy 30 to 100 Pa s. The mange may be between
with an epoxy resin composition of the components [HJ to any of the aforementioned upper limits and any of the
[DJ, applyin such a resin film-coated release paper sheet to aformncntioncd lower lunits. If the viscosity at 85'. is 10
either or both surfaces of a carbon tiber sheet with the resin Pa s or morc. II tends Io serve suihclcntly Io prcvcnt the resin
film facing the carbon fiber sheet, heating and pressing them from Ilowing out when a Idcl of resin Iilm-coated relcasc
to mlpregnate the carbon liber with the epoxy rcsul compo- paper sheets is pressed to from a prepreg If the viscosity at
siuon Io provide a primary prcpreg, dnd then applyin a 85" ('s 300 Pa s or less. it tends to serve filr the pmduction
resin film produced front the second epoxy resin cmuposi- of a Iilm lvith a unifornl thickness wlfile ensuring good
tion composed of the components [13J to [I:J to each surface impregnating property in impregnatin the reinforcin
of the printery prepreg by the same procedure as for the libera
above primary prepreg prepamtion. follolved by an impre- [0071] The viscosity at 25'. 85'. or as rcfctrixl Io
nation step as required, to provide a prepre . Here. the herein is determined by taking mcasurcmcnts using a
pnmary prcpreg may bc wound up once mxl then unwound dynamic viscoelasticity measuring apparatus (for example
wiulc applying a rcsul Iilm oi'he second cptlxv lesnl ARI.8, nmnufactured by I'A Instnlments) equipped lvith
composition or impregnating the prepreg with it, or the parallel plates, lvhich is operated in the auto-stmsin mode
preparation of a primary prepreg by impregnating the carbon under the conditions of a measurement onset tempemsture of
fiber with the hrst epoxy resin composition may be lnune- 20" C., a parallel plate diameter of 40 mm. a parallel plate
diately followed by applying a resin fihn of the second gap of I nun, an angular frcqucncy of 3.14 md/s, and B
epoxy resin composition or impregnating the prepre with it. tcmperaturc ramp rate OI'.7'./nun to give a temperaturc-
[0065J I'or the epoxy resm composition (I) containing the viscosity curve, fmm which the viscosity at 25" ('r 85'
conlponents [B] to [E] in the surface resin Lsyer, it is is read.
necessary that the component [Cj accounts for 8 to 24 parts [0072J Alternatively, the prepre according to the present
by mass relative to 100 parts by mass ol'he epoxy resin invention may be produced in a single stage impregnation
composition (I). If the component [C] accounts Ibr 8 to 24 step, Instead of the two stage nnpregnation step described
pilrm bv'nass, lt selves lo plcvcnl lhc rcshl iroln shlghlg nl above For example, resin films of the second epoxy resin
the reinfilrcing fiber layer, allow the resulting prepreg to are prcparcxI Iirst, and then these resul Iilms arc applmd Io
have a surface with a long tack life, and realize the produc- either or both surfaces oi' carbon liber shcct, followed by
tion of a material v ith high tougluless. heatin mid pressing them to allow the carbon fibers to be
[0066J I'urthennore, the second epoxy resin composition inlpregnated selectively tvith the components [13J to [DJ
has a storage elastic modulus (I't 25" (1 is in the range of contained in the second epoxy resin composition. thereby
1.0x10 to 3.0x10'a. preferably 1.0x1 0'o 1.0x10'a. If providin a prepreg in vvhich the Iirst epoxy resin compo-
the storage elastic modulus Ci's in this range. it serves to sition is contained in the reinforcin hber layer while the
sufiiciently prevent the epoxy resin composition contained second cptixv rival ctlmpositloll Is coiluunixl ul Ihc sulfacc
in Ihc sit tape prcprcg I'rom adhering Io thc guide roll during rcsnl kly'cl. Ill this ills(BIlctm slnct: Ihc conlponcnt [E] has B
Ihc nnplt:Incus'I(loll of Ihc Bulolndtcd lav-op lnclhod. volume-average particle size in the range of 5 to 50 pm, the
[0067] The stomsge elastic modulus 6't 25" C. referred to component HIJ is prevented from getting into the bundles of
carbon fibers of the component [A]. tints pmviding a prepre
herein is detennincd by Biking mcasurcments using a
having a reinforcing fiber Layer composed of the component
dynamic tiscoclasnclty mcasunng apparatus (Ibr cxiunple
[A] and the first epoxy resin composition, which contains the
ARIISL manufactured by TA Instruments) equipptxI v ith
components [B] Io [D]. but is substantially I'rcc of Ihe
parallel plates. which is operated in the auto-strain nlode
component [E], imd two surface resin layers formed oi'he
under the conditions of a measmement onset tempemlture of second epoxy resin composition. which contains the com-
10" C.. a pamllel pLate diameter of 8 nml, a parallel plate gap
ponents [13J to [IIJ. wherein the filmier layer is interposed
of I mm„an angular frequency of 3.14 md/s. and a tem- between the latter Llyers.
perature ramp rate of I 7'ynun Io give a 0'urve. from
wluch thc Ct'alue at 25'. Is read. It ls noted that the value [0073] For the prepreg accordin to the present Invention,
the carbon hber areal weight is preferably 100 to 1,000 /m'.
of (I'ead at any tentpemsture on the (I'urve i ~ referred to
as (I't that tenlperature If the carbon liber areal weight is 100 g/m'r morc, it lends
to serve to rcducc Ihe number of plies to bc stacked to reahzc
[0068] I iere, measurements of the (I'f a second epoxy a rcquircd tluckncss when moldulg a liber reulibrccd com-
resin composition are valid only when the components [HJ posite material. In addition, if the carbon fiber areal weight
to [Ej contained therein have definite structures and account is I,O(8) g/m'r less, it tends to serve to obtain a tiber
for definite proportions reinforced composite nlaterial having a hi h drapability. The
[0069] Furthermore, it is necessary that plies of the fiber content by mass is preferably 40 to 90 mass %. and
prcprcg Bccordlng Io Ihc prcsclll lllvclllloli thBI alc IBld up more prcfi:rably 50 to 80 mass %s. Thc range may be betweml
alter being left Io stand ior 24 hours BI room temperature dny'f thC BfoICIOCB(ltlliCd llppCI 111111m Bnd aliv OI lhC
show a peel strength of 0.1 N/nun or morc BI 35'. If tlus aioremcntioncd lower lunits. II it is ln Ihw range, void
is realized. a sutficient adhesiveness can be achieved in the generation in the nloldings tends to be depressed to al iov: the
splicing step in which prepreg plies are pasted together. carbon fiber to show its ood mechanical pmperties
US 2022/024305 [ A[ Aug. 4, 2022

[0074] Regarding the structure of the prepreg accord&ng to [0089] Component [('] &Thermoplastic Resin&
thc presm&t invent&on, &t may bc c&ther a onc d&rect&onal liber [0090] milan&age (rcgistcred trademark) 10700
prepreg or a woven fabnc prcprcg. [polycthcrsulfonc. manui'ectured by Solvay Spiwialtics
[0075J 'I he prepreg according to the present invention can Polymers, wc&ght-average molecular wc&ght 21,000
be processed into tapes or threads by dividing it to a requ&red 8/mol)
&vidth by a generally knov n method. Such tape-like or [0091J Suniika Excel (re istered trademark) PIIS5003P
tlu end-like prepreg plies can be laid up suitably by using an (polyethersulfone. nimnifacnired by Sumitonio (qiemi-
auton&ated lay-up device cal Co.. Ltd., wei ht-average molecular weight 47,000
[00'76] Cult&ng of a prcprcg can be aclucved by usu&g a
g/n&ol)
gcncrally known cutter Exiunples thereof u&elude cemented [0092] Component [D) &Curing Agm&t&
carbide blade cutter, ultmssonic cutter. and round blade
cutter [0093] SEIKACLIRE-8 [4,4mdiam&nod&phenyl sulff&ne,
nuu&uihcturcd by SEIKA Corporut&on)
[0077] The fiber reinforced composite material according
to the present invention can be produced by Layin up plies [0094J 3,3ODAS 13,3mdian&inodiphenyl sulfone, manu-
of the prepreg accordin to the present invention in an factured by Mitsui Chemicals„ inc ) Component [E]
appropnatc R&nn and heat&ng them to cure the rcsu&. It &s &particles insoluble in epoxy resin and containing
prefcrablc to press them dunng tlm moldu&g step Ibom the thcnnoplastic &eau& as primary con&poncnt&
vie&vpoint of depressing the formation of voids and obtain- [0095J I'oraypearl [registered trademark) 'I'N [poly-
ing a uniformly cured product I Jere, the application of heat mnide pmticles. nianufactured by 'lonny Industries,
and pressure can be carried out by using a generally kniown Inc., average particle size 13 Iun)
metlu&d such as autoclave molding method. press molding [0096] Orgasol [rcg&stcrcd trademark) 1002D [poly-
metlu&d. bag molding method, wrapping tape method. and mnide part&clcs. manuibctured by Arkcma, average
ultcrnal prcssuic n&olduig n&clhod. particle size 21 I&u&)
[00'78] F&bcr rc&nibrced composite matenals produced by
[0097] (I) Measurement of Avemsge Particle Size of the
the above molding methods preferably have glass transition
tenipemtures in the range of 1(X)" ('o 250" (2 fron& the
Component [E[
[0098] To detcrmu&e thc average part&cle s&zc Of the com-
vie&vpoint of pmcessability of the molded materials in
post-treatment steps. In the case of aircraft members. in ponent [I IJ, particles accounting for a &ve&ght concentmstion
particuLsr, the glass tmnsition temperature is preferably in of 9% are dispersed in a dispersion medium and the volu&ne-
thc rm&gc of 170'. to250'. in order to penuit thc&r average diameter is calculated fmm measurements taken by
Laser diffraction/scattering particle size distribut&on measur-
applmat&on to members for usc at high tcmpcraturcs.
in equipment (LA-750, manufactured by HORIBA, Ltd.).
EXAMPLES Two mcasurcments werc taken I'rom a spccuncn and their
average was adopted.
[00'79] The present invention w&11 now bc illus&ra&cd &n [IIU99J (2) Preparation of 1&poxy Res&n (:on&position
dctml w&0& refbrcncc to cxmnples, but &t should bc under-
stood that the invention is not construed as being limited [0100] In a kneader, epoxy resins of the components [b I]
thereto Preparation and evaluation of prepreg samples in an [b2] and a thcrmoplasuc resu& 01'lm component [C] w erc
these examples v ere performed in an atmosphere main- added accord&ng to thc 1&sm of components m&d proportions
tained at a temperature at 23" C. 2" C. and a relative given in I'shies I to 2 and heated up to 160" (2 while
hun&idity of 50% unless othenvise specified.
kneading, followed by stirring for I hour to ensure that the
[0080] Component [A] &Carbon Fiber& component [(:1 is dissolved &0 prov&de a transparent viscous
liquid. Tlus liquid was allo&ved to cool to 70" C. while
[0081] Toruyca [rcg&stcred trademark) T8000-24K
(carbon fiber havmg 24,0()t) filaments„ tensile strength knead&n and then a curing agent of the component [D) was
of 5.9 (ipa, tensile modulus of 2')4 (ipa, and tens&le added, followed by addi&&onal knead&ng to provalc a Iirst
elongat&on of 2 0%. manufactured by 'Ibmsy Industries, epox)'csu& con&pos&t&on.
Inc.) [IIIUIJ then, the component [('J was dissolved in the
[00821 Component [B1 &Epoxy Resin& components [b I] and [b2] and cooled to 70" C. to prepare a
[0083] [bl] &d&- or less-I'unct&onal epoxy rcsu& con&au&ing, viscous liquid and the con&ponent [E] was add thereto,
in a molecule. at least onc nng stnicture havu&g lour- or fi&llowcd by adding lhc component [D] to provide a almond
more menibered nng and also containing a glycidyl amine epox)'eau& con&pos&t&on [cpoxv'csu& con&posit&on [I)) that
gmup bonded to a ring stn&cture- contau&s thc component [E].
[OU84[ TORI:P freg&&tered trademark) A-2041: [dmly- [(1102J (3) Evaluation of Storage l&lastic Modulus (I'f
cidyl-N-phenoxy aniline. manufactured by Toray Fine Epoxy Resin Composition
('hemicals Co., Ltd.) [0103] Thc a&cond epoxy resin compos&tion was sct in a
[OU85J (IAN [N-diglyc&dyl aniline, ma&n&factured by dynam&c v&scoclasucity measuring apparatus [ARES-G2.
Nippon Kayahu ('0, I,td ) manufactured by I'A Instnunents) equ&pped with flat parallel
[0086] [b2] &tri- or more-functional epoxy resin& plates v ith a dianieter of 8 mm as upper and lower mea-
[0087] jI!IZ [reg&stered trademark) 630 [triglycidyl-p- suring Iig members in such a manner that the epoxy resin
aminophenol, manufactured by Mitsubishi Chen&ical composition specimen was interposed between the upper
Corporation. epoxy equivalent weight 98 g/eq) and lower Iig mcmbcrs spaced by a d&stance of 0 5 mm, and
[0088] Aruld&tc [rcgistcrcd trademark) MY72I (tet- n&casurcu&cuts werc tal cn u& the tora&on mode [mcasunng
raglycidyl &ham&nod&phcnylmethanc, manulbctured by frixpicncy 1.6 Hz) over a mcasunng tempcraturc mngc of
I luntsinan ( orpomst&on. epoxy equivalent &veight 112 5 10': to 60" ('vhile increasing the ten&perature at a rate
u/eq) of I 5" ('/min from 10''o 60''
US 2022/024305 [ A[ Aug. 4, 2022

[0104] (4) Preparation of Prepreg Accordin to the same procedure. the total area occupied the
[0105] In the follov in examples, prepreg samples v.ere component [E] existing ui the surface resin layer, i.c., Ihe
prepared as described below. Silicone was spread unifomily region other than Ihc reinliircing liber layer, mid thc total
over sheets ol'elcasc paper and the first epoxy resin area occupied by the compnnent [I:J existing across the
composition or the second epoxy resui composition (epoxy entire prepreg thickness ivere determined and the pniportion
resin composiuon (I)) prcparcd in Ihe above par i raph (2) to of the component [E] existing in the surface resin layer to
prepare first resin finis and second resin fihns A layer of that existing across the entire prepre tluckness was calcu-
carbon fibers armnged unifiirmly ('I'SOO(i-24K, manufac- lated.
tured by Toray Industries, Inc.) was sandwiched between [0110] (7) ivaluation of Peel Strength of Pmpreg
I

nvo first resin films and heated under pressure using a press
roll io provide a primary prepreg contaiiung a carbon liber [0111] Thc prcprcg samples prcparcd in each example and
layer unprcgimtcd with thc lirst epoxy resin composition colllpilld tivc cxaillplc. w itis olio surface covered w i11i I cled sc
(Ctirboii flbcI'rixll WCIglit 145 giclll, icsiii Colin:lit 23 6 paper, v ere cut in such a nianner that the direction of the
niass %). Subsequently. both release paper sheets v ere reinforcing fibers coincided ivith the length direction of each
peeled ofl'i hen, the primary prepreg was sandv iched prepreg sample, to provide test samples with a size of 50
between nvo second resin fihns and heated under pressure mmx200 mm or 30 mmx150 nun.
using a press mll to provide a prepre impre Bated with both [0112] A prepreg sample with a size of 50 nunx150 nun
the first epoxy resin composition and the second epoxy resin was fixed to a stainlesssteel plate with a size of 50 mmx f 50
composition (carbon liber areal wei lu 145 g/m', resin nunxl.S nun iiuckncss using double-sided tape In tlus
content 34. 0 mass %) Subsequently. one of the release paper
. instance, fixation was pcrfomicd in such a manner tlmt thc
sheets ives peeled otf At this point. the resulting prepreg had prepreg surface not covered ivith release paper was in
only one surface covered with release paper. contact v ith the double sided tape. 1 hen, the release paper
[0106] (5) Evaluation of Average Tluckncss of Prepreg v as removed, ivith the 10 mni end portion nieasured in the
[0107] The prcprcg sample prepared ui each example and leach direction of the prepreg sample left covered with the
colllpdrdtlvc cxtllllplc wds saildwiclicd bctwccii Iwo piiiy'- release paper. to prepare a lower side measurement sample.
tetrafhioroethylene resin plates with smonth surfaces and
[0113] Then. a prepreg sample with a size of 50 mmx200
bain ht intn close contact, and then the temperature was mm was put on the lower side measurement sample in such
increased gradually over 7 days up to 150" (', thereby a mmmer thai it w Bs held w iih the rclcaac paper-covcrml sale
curing the resin to pmduce a plate-like cured product The
up, ilmt i1 was aligned with Ihc rclcasc paper-frcc cnd of Ihe
resulting plate-like cured product was cut in such a manner lower side measurenient saniple, and that the direction of the
thai a cross section of Ihe carbon liber of thc componen1 [A]
was exposed. and ilmn Ihe exposed cmss scmIion was pol- reinforcing fibers in each prep reg sa nip le were parallel to the
length direction
ished 'I'he polished cmss section ives photographed at a
niagnitication of 200 or more under a digital micniscope [0114] In additinn. the Iwo prepreg samples were left to
(VIIX-5000, manufactumd by Keyence Cnrporation) in stand for 5 minutes in a chaniber maintained at a inunidity
such a manner that the top and bottom faces of the prepreg of 25% RH and a tempemture 35" C. and, v bile keeping
svere included the field of view. In the cross-sectional them in the chamber. pasted together under a load of 100 N
photograph, Ihc ilucknes sea of thc surface rcsui layer and thc applied by using a stninlcss steel press roll having a diameter
rcinlbrcuig liber layer werc measured dt five pouits and thc of 30 nun and a width ol'5 mm moved at a speed of SOO
suni of the average surface resin layer thickness and the mm/nnn to prepare a measurement sample
avera e reinforcing fiber layer thickness was adnpted as the [0115] The pccl sirmigth of the preprcg was measured by
avera e thickness of the prepreg 90" peeling test according to )IS K 0237 (2009) "I'est
[0108] (6) Evaluation for the Proportions of the Compo- method for pressure sensitive adhesive tapes and pressure
nent [A] and the Component [E] Existing in the Prepreg*s sensitive adhesive sheets'*. For each measurement sample
Surface Resin Layer Ranging from Each Surfhce of the prepared above, the end portion of a prepre squeezed out of
Prcprcg the stainless siccl plate was lixed Io a digital force gauge
[0109] In thc photogmph ol' cured product used to (ZTA-500N, manufactured by Imadn Co., Lid.) and Ihe
deicrmuie tiu: average prepreg Iluckness by Ihc procedure sample was left to stand for 5 minutes in a chamber (SH-642,
described in the paragraph (5). a line that passes the thrnugh- manufactured by ispec ( orp.) maintained at a humidity of
I

thickness center of the reinforcing fiber layer and is sub- 25% RI I and a tempemture 35" ('ubsequently. while in the
stantially parallel to the boiuidaries between the reinforcing chamber. the digital force gauge was pulled up at an an le
fiber layer and the surface resin layers is drawn first, of 90" to the stainless steel piste at a speed of 150 mm/min
followed by drawing two lines tlmt arc parallel io Ihc above using a linear slider (manufactured by Oriental Motor Co.,
CCilICr litle, CBCli SpaCCd 111 illc IliickllCSS ill CCiioii BW By'lolll Lid.) to separate Ihe prcprcg plies from each other. Thc
Ihe center linc by 42% of the avcmgc prepreg Iluckncss mcasurmncnts taken from the lira( 25 nun long portion alter
deterniined by the procedure described in the paragraph (5). the start nf separation were omitted and the measurements
in this way, the region ranging over 42% of the tntal depth taken from the next 30 mm ion portion were averaged,
front the center line of the reinforcing fiber layer toward followed by dividing the avera e by 50 mm to calculate the
each surface, i.e.. the region of the reinforcing fiber layer. Is peel stren th (unit: N/mm) at 35'. Here. it is noted that
idcntificd. Tiu:n, thc total arcs occupied by Ihe component each prcqtrcg cui to Ihc spccificd size was lcl't to stand liir 24
[A] existing in this region mid the toial area occupied by the hours ai room icmpcraiure (in mi enviromnent mauitained ai
component [A] existing acmss Ihc entire prcprcg Iluckncss a tcmpcraturc of a 25 2'. and a humidity ol'50 5% RH),
were determined and the pmportion of the componmit [AJ with the surface carrying a polyethylene film pasted thereon,
existing in the reinforcing fiber layer was calculated. prior to use.
US 2022/024305 [ A] Aug. 4, 2022
10

[0116] (8) Measurement of Deposition of Resin/Fuzz on provide a prepreg tape having a width of 3.2 mm in the
Path Line (Evaluation of Slit Tape Processability) direction perpendicular to the reinfiircing libera. A 2.S kg
[t)117J A prepreg sample was passed at a constant speed weight was fixed to one end oi'he prcprcg tape, and thc tape
through a path narrower than the width of the prepreg carrymg the weight was put over a roll with a diameter of
sample so that both edges of the prepreg sample were 25 4 mm. 1'hen, the spliced portion was moved back and
abraded. wlule the amount of resitdfttzz coming off from the forth 10 times on the roll, and the test piece v as rated to be
prepreg was nu:asured to simulate thc adherence of resin to acceptable v:hen it ives free of rupture after the 10 back-
an automated lay-up device, thcrcby cvaluatuig thc prcprcg and-forth motions.
pmcessability of the autoniated Lsy-up inethod [t)127J (11) Measuring Method fiir Open Mode (Mode I)
[0118] This evaluation employed a bobbin stand to supply Interlayer Fracture Toughness (Ci„.) of Fiber Reinforced
a prcprcg. guide rolls to allow thc prepreg to tmvel through Composite Material
a predetermined route, cyhndrical staudess steel blocks with
a diameter ol'20 mm to Ibmi a path narrower than thc width [t)128J First, 12 plies of the prepreg prepared in each
of the preprea, and a wind-up machine to take up the exaniple and comparative example were laid up with the
prepre . carbon fibers contained in them aligned in the same direc-
[0119] As illustrated ui FIG. 1, pairs oi'tmnlcss steel tion. md a film ply which was PTFE film v ith a thickness
blocks with a gap ol'6.1 mm bctw ceo thc paired blocks were of 0.01S nun liilded in hall'was placed bctwccn the 6th ply
placed at six positions spaced at inicrvals oi'00 nun ui the and thc 7th ply to worl to cause uutial cmcking Thc laid-up
prepre 's traveling direction, and the prepreg, prepared in prcprcg plica werc wrapped with a nylon film without
each exaniple and comparative example was slit to a width leavmg gaps, heated in mi autoclave up to 180" C at a
of 6.35 nun and caused to travel over a distance of 1,000 m temperature ramp rate of 1.5" ('imin. and cured by heating,
at a speed of 10 nt/min. The weight of material that adhered and pressin for 2 hours at a temperature of 180" C, under
to thc block surfaces during thc traveluig of thc preprcg was a pressure of 700 kPa. Apiece having a width of 25 nun and
mensurmi using an clcctronic balance. a length of 250 nun, whcrcin thc carbon liber direction (0')
is dc)iced as thc length dircmtion. warn cut out and a block
[01ZOJ Based on the results obtained, a sample was rated
as A to D according to the following four smge critenon It (with a length of 2S nuu, made ol'luminum) designed to
ives rated as A v hen the weight was 250 m or more. B apply a pin load was adhered to an end (the end of the
when it w as less than 275 mg. C when it was 27 S mg or morc filni-containing ha) fl of the test piece according to .)IS K
and less tluui 300 mg, or D when it was 300 mg or more. 7086 (1993). A white paint was spread over both surfaces of
the test piece to ensure clear observation of the process of
[01Z I J (9) Measurement of Deposition of Resin/liuzz on
('utter BLsdes (Evaluation of Slit Tape Processability) cracking, and test was carried out usin an Instron type
uiuvcrsal (cater (mamifacturcd by instron Corporation)
[0122] A prcitrcg was cut conunuously mid thc amount of
according to Appcixlix I oi'IS K 7086 (1993). Thc cross-
adhered resin,'fuzz on the cutter blade was measured to
head speed v,as 0.5 mmimin before the length of cracking,
simulate the adherence of resin to an automated lay-up
reached 20 min and increased to I mnv'nim after it reached
device. thereby evaluating the prepreg processability of the
20 mm. The open mode (niode I) interlayer fracture tough-
autoniated lay-up method.
ness (G,„) was calculated from the load, displacement, and
[0123] A prcitrcg prepared ui each example mid compara-
size of cracking according to JIS K 708(i (1993). Measure-
tive exmnple and slit to a width of 6.35 mm ives cut 500
ments werc taken Ibom 5 test pieces and their avcmgc was
times continuously using the same position of a shear-cut
adopted to represent their G„.
type slitter made of an alloy (SKD11), which cmisisted
mainly of a movable blade moving back and forth and a [0129] (12) Measurement of Compression Stren th after
fixed blade. The weights of the movable blade and fixed Impact (CAI) of Fiber Rcmforccd Composite Matcnal
blade were mermurcd on an elcctroiuc balance before and [t)13()J Stacks of plies of the prepreg prepared in each
after the witting test run and thc weight ol'he resin/fuzz example and comparative example v ere prepared. Each
adhered to the cutter blades was calculated fmm the differ- stack had a structure of [+45 "/0'/ — 45'/90" ] where 0" means
ence in weight of the blades between before and after the the length dircm) i on oi'hc carbon libera in the prcprcg. Tlu ac
cutting test nin such stacks, contauung a total of 12 phcs, werc piled up to
[0124] Based on thc results obtauicd, a siunple was rated fiirm a preliminary lamiruite mid then such lamiimtcs were
as A to D according to the Rillowing four stage critcnon It laid up syinmetrically to tiirm a quasi-isotropic preliminary
was rated as A when the weight was less than 3 5 mg. B lanunate containing a total of 24 plies 'I'he resulting quasi-
when it was 3.5 nig or niore and less than 7 mg, ('hen it isotropy preliminary laminate is as placed in an autoclave,
was 7 mg or more and less than 10 5 ma, or I) when it was and under a pressure of 0.(i MPa. it was heated from room
10.5 tng or more. tcmperaturc to a tcmperaturc of 180'. at a rate of 1.7'.
[01Z5J (10) I ivaluation of Spliceability pcr nunutc and cured Ibr 2 hours at a tempcraturc of 180'.
[0126] A prcprcg prepared ui each example and compara- to pmvide a liber rcinlbrced composite matcnal. From thc
tive example was cut to provide two sheets each measuring resulting fiber reinforced composite matenal, a rectangular
800 mm in the reinforcing fiber direction and 152.4 mm in test piece ivith a length of 150 mm and a width of 100 inm
the direction perpendicular to the reinforcing fibers and v as cut out, and a drop impact of 6.7 I per mm thickness of
these prepreg test pieces were laid up one on the other in the test piece was applied to the center of the test piece
snail il ltlaliilci'llat tile rclllforcillg iibcm 111 tllcill Werc according to JIS K 7089 (1996). followed by measurin the
alignmi ui parallel and that they ovcrlappcd by 40.0 10 0 remdual comprcssivc strmigth tmcording to JIS K 7089
mm. Then. a load ol'50 kg was apphed to the overlap (1996). Six mes surcmmim werc takmi and their average was
portion at 27" (1 so that they are integrated under the adopted to represent the compression strength after impact
pressure 'I'he integrated prepreg test piece was cut to (('AI) (MVa)
US 2022/024305 [ A[ Aug. 4, 2022

Example I moles of epoxy groups in the second epoxy resin composi-

[0131] A Iirst epoxy resin composition mid B second cpoxv
tion. Thc storage elasuc modulus G'i 25'. of ilm siwond
resin compost(ion werc prepared from the components epoxy resin composition was 1.8x10'u, and the component
[('J in the second epoxy resin composition accounted for 15
specified in the column under llxainple I in 'I'able l. 'the
nlass %.
number of mules of active hydrogen in the second epoxy
resin composition v as 1.08 times as large as the number of [0136] Using thc lira( and second epoxy resin composi-
moles of epoxy groups in the second epoxy resin composi- tions described above. a prepreg was prepared in the saine
tion. The storage clastic modulus G'l 25'. of the second v ay as in ixample I. In the resulting prepreg, 94 nlass % of
I

epoxy resin composition was I.OX I 0 'a, mid die component the component [A] existed in the reinforcing tiber layer and
97 mass % of the component [E] existed in the surface resin
[C] in the scwond epoxy resin composition accounted for 20
nlass %s la)'cr. hl icnus of dcposluon of rcslll/Iuzz dining shl tape
processing, lurihcrmorc. ii was mtcd as C in thc path lute i est
[0132] In addition, usin TORAYCA (registered trade-
and B ln thc cutter blade test. but served snit ~ Ihctonly ul shi
mark) T800G-24K as the component [A] and also usulg the
lllst cpoxv lcsln conlposltlon Bnd ihc second epoxy rcsnl tape production It had a peel stren th of 0.1 N/mm after
composiuon prepared nbovc, a prc7treg was produced by the standing for 24 hours at mom tempemsture and it was pnlved
to be acceptable in the splicing test. The carbon fiber
pmcedure described in the above pamlgraph (4). In the
resulting prepreg, 96 mass % of the coinponent [AJ existed composite material had an interlayer fracture toughness
in the reinforcin hber layer (ranging from 8'is to 92% depth ((I, ) of 525 1/m'nd a compression stren th after impact
(CAI) of 368 MPu.
from the surface) and 98 mass % of the component [E]
existed in ihc surface resin layer (ranging from either surface
lixample 4
io a depth ol'8'!o exclusive) In addiiion, in the evaluation ln
terms of deposition of resin/fuzz on ihe pail lute and cutter [0137] A lirsi epoxy resin composition and a second epoxy
blade durin slit tape processing, it was mlted as A for both resin cnmposition were prepared from the components
evaluation items, showing lugh slit tape processabihtv. It specified in the cnlumn under I.xample 4 in Table I 'Ihe
had a peel stren th of 0.2 N/mm after standing for 24 hours number of moles of active hydro en in the second epoxy
at room temperature and suffered no rupture after moving resin composition was 1.08 times as large as the number of
back and forth 10 times on ihe roll ul ihc splicing test, moles of epoxy groups in the second epoxy resin composi-
proving that lt was acceptable. Thc carbon tiber composite tion. Thc storage elasuc modulus G'i 25'. of ilm siwond
ma/anal had au interlaycr fracture touglmcss (Gs) of 621 epoxy resin composition was I.OX I O'u, and the component
.Iim and a compression strength after impact (CAi) of 330 [('J in the second epoxy resin composition accounted for 10
Mpa. both heing satisfactorily high nlass %.
[0138] Using thc lira( and second epoxy resin composi-
lixatnpie 2 tions described above. a prepreg was prepared in the saine
[0133] A lirst epoxy resin composiiion mid a scwond epoxy v ay as in ixample I. In the resulting prepreg, 92 nlass % of
I

resul composiuou werc prcparcd from ihe components the component [A] existed in the reinforcing tiber layer and
specihed in the column under Iixample 2 in 'I'able l. The 95 mass % of the component [E] existed in the surface resin
munber of moles of active hydnlgen in the second epoxy Layer. In terms of deposition of resin/fuzz on the path line
resin composition was 1.02 times as large as the nunlber of and cutter blade dunng sht tape processulg, lurthennore, ii
moles of epoxy groups in the second epoxy resin composi- was raiixl as C in boih tests, but served satisfactorily in shi
tion. The storage elastic modulus G't 25" C. of the second tape production It had a peel stren th of 0.1 N/mm after
epoxy rcsul composition was 9.8XI0'a, mid the componmli standing for 24 hours at mom tempemsture and it was pnlved
[C] in the sixoud epoxy resin composilion accounled for 15 to be acceptable in the splicing test. The carbon fiber
iu 'isa composite material had an interlayer fracture toughness
[0134] Using the first and second epoxy resin composi- ((IOO) of 560 1/m'nd a compression strength after impact
tituts described above„a prepreg was prepared in the same (CAI) of 378 MPu.
way as ln Example 1. In thc resuliulg prcprcg. 97 mass % of
ihe component [A] existed ul ihe rcullorculg liber layer and lixample 5
96 mass % of the component [EJ existed in the surface resin [l)139J A first epnxy resin composition and a second epoxy
layer In addition. in ternls of deposition of resin/fuzz on the resin composition ilare prepared from the components
path line and cutter blade during slit tape processing. it was specified in the colunm under Example 5 in Table 1. The
rated as A. showing good quality. It had a peel strength of 0 2 number of moles of active hydrogen in the second epoxy
N/nuu afier standin for 24 hours at room temperature and rcsul composition v'as 0.89 tunes as lurgc as thc number of
ii was provtxl to bc acccptablc in thesplmulg leal The
carbon liber composite matcnal had an uucrlayer fracture
tou hness ((I, ) of 675.1/nl and a compression strength after
tion he storage elastic modulus
I (I't
0'a,
25" ('f
nlolcs of cpoxv gloups nl ihc second epoxy rcsnt conlposi-
the second
epoxy resin compnsition ives I Ox I and the component
impact (('AI) of 365 Mpa, both being satisfactorily high. [C] ul the second epoxy resin composition accounted for 8
mass '!w
lixatnpie 3
[0140] Usin the first and second epoxy resin composi-
[0135] A lirst epoxy resin composiiion mid a scwond epoxy tions dcscnbcd abol c. a prcprcg was prcparix! in the same
resul composiuou werc prcparcd from ihe components way as in Example 1. In thc rcsulung prcprcg. 95 mass % of
specified in thc column under Example 3 in Table 1. The the component [A] cxtstedI in thc reinforcing fiber layer and
munber of moles of active hydnlgen in the second epoxy 96 mass % of the component [ilJ existed ln the surface resin
resin composition was 1.14 times as large as the nunlber of layer. In addition, in tenne of deposition of resin/fuzz during
US 2022/024305 [ A[ A)tg. 4, 2022
12

slit tape processing„ it v as rated as A in the path line test and number of moles of active hydro en in the second epoxy
C m the cutterblade test, showing oodquahty. 11 had speal remn composition was 1.08 tunes as large as the number of
strength of 0.1 N/nun after standing for 24 hours at room molcs ol epoxy groups ul the second epoxy resin composi-
temperature and it was pnlved to be acceptable in the tion. 111e storage elastic nloduius(I't 25" ('. of the second
splicing test. 'I'he carbon fiber colnposite material had an epoxy resin conlposition ives 3.2x10 Pa, and the component
interlayer fracture tougluless (CI, ) of 589 I/ms and a com- [C] in the second epoxy resin composition accounted for 15
pression strength after impact (('AI) of 366 MPC. mass "!s.
[f)146J 1)sing the first and second epoxy resin composi-
Example 6 tions described above. a prepreg v, as prepared in the same
v ay as in Example I. In the resulting prepreg. 98 macs '/s of
[0141] A lirst epoxy resin composiiion mid a scmond epoxy
resin composition lvere prepared from the components the component [A] cxtstcxi in thc reinforcing fiber layer and
specihed in the column under Iixample 6 in 'I'able 1. 1he 98 mass % of thc component [E] existed ul thc surface resin
number of moles of active hydrogen in the second epoxy la)'cr. In tellus of dcposluon of rcsul/fuzz iliulng shl tape
resin conlposition was 0.96 times as large as the number of pmcessing, fulthennore, it ives rated as 13 in both the path
moles of epoxy groups In thc second epoxy resin compos&- line and cutter blade tests. showmg good quality It had a
uon. The storage clasuc modulus G't 25'. Cl'he second peel strennb of 0.2 N/mm after standing for 24 hours at
room temperature and it was proved to be acceptable in the
epoxy rcsul composition was 2.9x101 Pa, mid the componmlt
[Cj in the second epoxy resin composition accounted for 15
sphculg test. The carbon fiber composite material had an
nl 'isa iuterlaycr Ibacturc touglulcss (Cia ) of 651 J/ms tmd a com-
pression strength aficr unpact (CAI) of 369 MPa.
[0142] Usulg thc lirst and second epoxy resin compos&-
(tous dcscnbcd ubovc, a prepreg was prcqtarcd m the stunc
lixample 9
way as In Example 1. In thc resultulg prcprcg. 94 mass % of
the component [AJ existed In the reinfbrcina fiber layer and [f)147J A first epoxy resin conlposition and a second epoxy
97 mass % of the component [EJ existed in the surface resin resin composition were prepared from the components
layer. In addition. in terms of deposition of resin/fuzz during specified in the column under Example 9 in Table 1. The
slit tape processing. it was msted as I3 in both the path line number of moles of active hydro en in the second epoxy
and cutter blade tests, showulg good qualily. Ii llad a peel resin composition was 1.08 times as large as the number of
strength of 0.2 N/nun after standing for 24 hours at room molcs ol epoxy groups ul the second epoxy resin composi-
tcmpcraiurc and it was provcxI io bc acceptable m the tion. Thc storage elasuc modulus G'i 25'. of tlm almond
splicing test. 'I'he carbon fiber colnposite material had an epoxy resin conlposition ives 3.0x10 'a, and the component
interlayer fnlcture toughness (()00) of 5')0 .I/ms and a [('J in the second epoxy resin composition accounted for 24
conlpression strength after impact (CAI) of 372 MPa. nlass %.
[f)148J 1)sing the first and second epoxy resin composi-
Example 7 tions described above. a prepreg was prepared in the salne
[0143] A lirst epoxy resin composiiion mid a scmond epoxy v ay as in Example I. In the resulting prepreg. 93 macs '/s of
resin composition lvere prepared from the components the component [A] existed in the reinforcing fiber layer and
specihed in the column under Iixample 7 in 'I'able 1. 1he 98 mass % of the component [E] existed in the surface recin
munber of moles of active hydnlgen in the second epoxy layer. In addition, in tcmls ol'deposition of ream'fuzz dunng
resin conlposition was 1.08 times as large as the number of sht lapc proccssulg, 11 was rated as A ul both Ihc path lute
moles of epoxy groups In the second epoxy resin composi- and cutter blade tests. showing ood quality It had a peel
uon. The storage clasuc modulus G't 25'. Cl'he second strength of 0 I N/nun after standing fbr 24 hours at room
epoxy rcsul composition was 3.0x101 Pa, mid the componmlt temperature and it was proved to be acceptable in the
[Cj in the second epoxy resin composition accounted for 15 sphculg test. The carbon fiber composite material had an
nl 'isa interlayer fracture foun~less (CIOO) of 689 J/m'nd a
[0144] Using the first and second epoxy resin composi- compression strength after Imptmt (CAI) of 375 MPS.
ttous dcscnbcd ubovc, a prepreg was prcqtarcd m the stunc
I:xampie 10
way as In Example 1. In thc resultulg prcprcg. 95 mass % of
the component [AJ existed In the reinfbrcina fiber layer and [f)149J A first epoxy resin composition and a second epoxy
96 mass % of the component [EJ existed in the surface resin resin composition ilare prepared from the components
layer. In terms of deposition of resin/fuzz duriilg slit tape specified in the colunm under Example 10 in Table I. The
processing, hirthermore. it was rated as C: in both the path number of moles of active hydrogen in the second epoxy
line and cutter blade tests, but served satisfactorily in the rcsul composition v'as 1.99 )uncs as lurgc as thc number of
processing. It had a peel strength of 0.2 N/nuu after standulg
for 24 hours at room tcmpcrature and It was provu! to be
acceptable in the splicing test 'I'he carbon fiber composite
tion he storage elastic modulus
I (I't 25" ('f
nlolcs of cpoxv glonps ul thc second epoxy rcsut coulpilst-
the second
epoxy resin composition lvas 3 Ox10 Pa, and the component
nlaterial had an interlayer fmcture touglmess (GOO) of 655 [C] in the second epoxy resin composition accounted for 13
.Ilm and a compression strength after impact (CAi) of 346
mass '!v.
MPa.
[0150] Usin the first and second epoxy resin compoci-
tlons dcscnbcd abol c. a prcprcg was prcparlx! in the same
Example 8
way as in Example 1. In thc rcsulung prcprcg. 97 mass % of
[0145] A lirst epoxy resin composiiion mid a scmond epoxy the component [A] cxtstcxi in thc reinforcing fiber layer and
resin composition lvere prepared from the components 97 mass % of the component [ilJ existed In the surface resin
specihed in the column under Iixample 8 in 'I'able 1. 1he layer. In addition, in terms of deposition of resin/fuzz during
US 2022/024305] A] Aug. 4, 2022
13

slit tape processino. it was rated as A in both the path line

and cutler blade lasts, showuig good qualily. 11 lmd a peel
strength of 0.1 N/nun after standing for 24 hours at ruom
temperature and it was pnlved to be acceptable in the
splicing test. 'I'he carbon fiber coinposite material had an
interlayer fracture toneless (6100) of 600 J/ms and a
conipression strength after impact (CAI) of 370 MPa.

Comparative Example I
[0151] A lirst epoxy resin composiiion mid a scmond epoxy
resin compositioil ivere prepared from the compoileilts
specihed in the column under ('oinparative example I in
Table 2. The number of moles of active hydrogen in the
second epoxy resin composition was 1.08 times as large as
the mimber of'oles of epoxy groups ul thc second epoxy
('f
Table 2. The number of moles of active hydrogen in the
second epoxy resin composition was 1.08 times as large as
the number of'molcs of epoxy groups ui thc second epoxy
resin conlposition. The storage elastic nlodulus (1't 25"
the second epoxy resin conlposition ives 3.0x10'm and
the component [Cj in the second epoxy resin composition
accounted for 18 mass %. Using the tirst and second epoxy
resin compositions described above„a prepre v as prepared
iu lhc slane way as m Example I In the resulung prc7treg.
93 mass % of the component [A] cxmlcd in the rcinforculg
fiber layer In addition. significant deposition of resin/fizz
on the path line and cutter blade occurred during slit tape
processing. making the processing impossible. It had a peel
stren&h of 0 N/mm after standing for 24 hours at room
temperature and it succeeded in only tss o of the ten test nina
resin compositiou. The ~ longe clastic modulus G't 25'. iu lhc sphcing teal, provuig llml il was unacceptable. The
carbon fiber composite maicnal had an inlcrlayer fracture
of the scmond epoxy rcsui composiiion was 4.0x10 Pa. and
toughness ((is ) of 615.1/m and a compression strength after
the component [('J in the second epoxy resin composition
inipact (CAI) of 238 Mpa. The absence of the component
accounted for 7 mass %.
[EJ resulted in a very large decrease in ('Al
[0152] Usuig thc lirst and second epoxy resin compos&-
uorm dcscnbcd ubovc, a prepreg was prc7tarcd m the siunc Comparative Example 4
way as in Example 1. In thc resulluig prcprcg. 95 mass % of
the component [AJ existed in the reinfilrcinu tiber layer and [0155] A first epoxy resin composition ands second epoxy
96 mass % of the component [11J existed in the surface resin resin composition were prepared from the components
layer. In addition, significant deposition of resin/fuzz on the specified in the column under Comparative exmnple 1 in
path line and cutter blade occurred during slit tape process- 1'able 2. 'Ihe number of mules of active hydrogen in the
ing, making the processing impossible. 11 lmd a peel strength second epoxy resin composition was 2 24 times as large as
of'0 N/mm after standing filr 24 hours al room temperature the number of moles of epoxy gmlups in the second epoxy
slid li succcixlcd ill only'hrcc of lhc 0:ll lcsl rillls ht lllc rcsui composition. Thc storage elastic modulus Ci't 25'.
splicing test, proving that it w:as unacceptable '1'he carbon of lhc second epoxy resin composition was 5.0x10 Pa. and
*

fiber composite matenal had an interhsyer fracture toughness the component [CJ in the second epoxy resin coinposition
(6100) of 301 J/ms and a compression strength after impact accounted for 16 nlass %. Usinu the hrst and second epoxy
(CAI) of 360 MPS. resin compositions described above, a prepreg was prepared
in the same way as in Example l. In the resulting prepreg,
Comparative Example 2 95 mass '!o of the coniponent [A] existed in the reinforcin
liber layer and 98 mass % of'he componnit [E] existed in
[(1153J A first epoxy resin composition and a second epoxy the surfhcc resin layer. In addition. in tcnns of deposiuon of
resin compositioil ivere prepared from the compoileilts resin/fuzz on the path line and cutter blade during slit tape
specihed in the column under ('oinparative example 2 in pmcessing, it v,as rated as 13. showing good quality. I loiv-
Table 2. The number of moles of active hydrogen in the ever, it lmd a peel strength of 0 N,'nlm after standing filr 24
second epoxy resin composition was 0.89 times as large as hours at room temperature and it succeeded in only two of
the mimber of'oles of epoxy groups ul thc second epoxy the ten test runs in the splicin test. proving that it was
resin compositiou. The ~ longe clastic modulus G't 25'. unacceptable. The carbon liber composite material lmd an
of the second epoxy resin composition was I 2xl fio Pa. and iulerlaycr fracture louglmcss (CiOO) of'54 J/m and a
the component [('J in the second epoxy resin composition compression strength after impact (('Al) of 361 Mpa.
accounted for 10 mass %. Using the first and second epoxy
resin compositions described above. a prepre was prepared Comparative Example 5
in the same way as in Example l. In the resultin prepre,
95 mass '!o of lhc component [A] existed m lhe remforcing
[0156] A first epoxy resin composition ands second epoxy
resin composition were prepared from the components
liber layer and 97 mass % of'hc componnlt [E] existed in
the surface resin layer In addition, in terms of deposition of specified in the column under Comparative exmnple 5 in
resinifuzz on the path line and cutter blade during slit tape Table 2. The number of nioles of active hydro en in the
second epoxy resin composition was I 09 times as large as
pmcessinu. it was rated as A in both tests, sholving good
thc number of molcs of'poxy groups in lhc second epoxy
quality. However. it had a peel strength of 0 N/nun after 25'.
rcsui composition. Thc storage elastic modulus Ci't
standing for 24 hours at room temperature and it succeeded
ill univ five of tile tell lest runs ill lhc sphclllg test, plovlllg
of lhc second epoxy resin composition was 3.Sx10 Pa. and
*

the component [CJ in the second epoxy resin coinposition

thai 11 was unacceptable. Thc carbon liber composite mate-
rial had an interlayer fracture toughness ((1„) of 715 .I/ms accounted for 25 nlass %. Usinu the hrst and second epoxy
and a compression strength after impact (('Ai) of 372 Mpa.
resin compositions described above, a prepreg was prepared
in the same way as in Example l. In the resulting prepreg,
('omparative I ixample 3
93 mass % of thc componnil [A] existed in thc reinforculg
liber layer and 98 mass % of'he componnit [E] existed in
[0154] A lirst epoxy resin composiiion mid a scmond epoxy the surfhcc resin layer. In addition. in tcnns of deposiuon of
resin compositioil ivere prepared from the compoileilts resin/fuzz on the path line and cutter blade during slit tape
specihed in the column under ('oinparative example 3 in pmcessing, it was rated as A in both tests, showing good
US 2022/0243051 A1 AT[g. 4, 2022
14

quality. However, it had a peel streilgth of 0 N/nmt after that tt was unacceptable. The carbon fiber composite mate-
standing I'or 24 hours ai room temperature and lt succeeded rial had an utter[eyer frucdurc tougluless [Cia) of 634 J'm
in only llucc of Ihc ten iesi runs in thc sphcuig les(, proving and a compression sumlgth after impact [CAJ) ol'374 Mpu.
TABLE [

Example Ex.unple Example Txtunple Extunple

I fust «pox ''csul coulpcs t ou I 4

2 . ecol)6 epos& resin co)spot)(ion I 2 I

' 2 I 2 I 2

coniponcnt fB[ ti ly idyl-4-phenoxv snit uie SD Il yfi 1() 3') 3. 31 35

(TOREP n, A. (14E)
)5 6 ul dyl .« I n !GAI& pa
gb dy(p:uu ph r I (ilRM 6301 6')
t'.u)

1821 ( 65 6&
terr:igl cidci dismmndiphen& lmethane part5 65 60
(A)tlute'Y7 I)
c rnponent fC[ pnlyerhersulfnne (vnnit( e m lt17(ID) pfiits 'I 52 1 45 I 4( 35 7 35 2u
pa t'
PI 85001PI
cnnipnncnt [D) 4 4 - tiaminodiphca& I suifnne parts 6D 60 OD 61! Ofi 60 60 6)I 41 45
(SEIKACURE X S)
co)It'cut'CV- 3,'! d tun nod pherivl sulfone B.3 DAS pfilts
mpo mnt b I I p.u) 9(l ul 90
pnlcunidc particles lotnysnl n. 100 Dl 'art5

of ompoucrit [C) 01 maui couiposition ulilss

I f)8 10 I 14 I (m t) 89
I fl lt) 98 10 18 1)I I t) IIB It) 10
5ccou(f rc5!II coulp05)tloll
chuacterst s pioport 00 nf cons)onent fhf ex stag u»emfoi n ~ miss
f prepre man layer iansng linin 85 to 9 'epth
prnportion nf cnmp nant [Ei ca)sting m thc res)on nisse 96
rsngmp froui othe) siufi c of prep)as to
85 lex lusvej deptli ntlu guess dre ton
02 01 01
s((t:p I p ytm 217 295
proce555( il!tv ot c aiuat n IA:2 0 B 00 to 270 A C C
ms Il.'fuzz C 75 to 300, D ul(I 1
utter bltde iu 22 5 7 97 9(
C 7)) to Iil D l(10 oruinrcl ('II)l ('oni)
munbcr f times of successful apl) me tuuc5 I re 10 10)l i& li) 10 0
eyalunt on ( 10 t mes. x unsuccessful

6 I 6) &60
fiber ion forced CAI MPS 3 3 tl 365 :7tl
comp ate
matenal

Exunplc Example Essa)pic Exnnplc Exnnplc

I firsf cpoxi I'csin coulpositiou 6 9 II I

I I - I 2 I 2 I

coniponcnt fB[ ti ly idyl-4-phenoxv snit uie 30 31 35 3') 3. 31 35

ITOREP m A 2( 14EI
8, d gl dyl sn)ne (GA.B parts 'I

1821 ( gb dy(p:uu ph r I (ilRM 6301 p.u) 65 65 6 6& 6 6& 61 6 6

terr:igl cidci dismmndiphen& lmethane part5
)Araiditc 8 My 211
c rnponent fC[ pnlyerhersulfnne (vnnit( e m lt17(ID) parts 'I
45 45 I 4( 35 80 35 45
pa
PI 85001PI

'f)
t'arts

cnnipnncnt [D) 4 4 - tiaminodiphca& I suifnne 6D 60 Ofi 6() 61) 111

(SEIKACURE X S)
co)It'cut'CV- 3,'! d tun nod pherivl sulfone B.3 DAS& Pfilts 6( 6() 60 60
mpo mnt b I I p.u) 9(l 91
pnlcunidc particles lotnysnl n. 100 Dl part5
of ompoucrit [C) 01 maui couiposition uiilss 18 I 5

II 9 tj I 08 I 08 I (m I 99
10 . 1)I t) ill 30 10
5ccou(f rc5!II coulp05)tloll
US 2022/0243051 A1 A)hg. 4, 2022
15

TABLE [-continued
94 9
of preprc rclufolclug Icslu layci lauolllg front

from prcpm siu face

97 ng ng 9
thcl'l
cx aullg u I'hc Icgou lang ug flolll c

ckness d rect on
Ll f) 2 01 I) I

51 I''flpc depos ton path I ue ul 270 07 1(O (16

pl * ss b ll) f )ul m(( -'O,B 2)ou 27. B A

('O
les a!fuzz 7( tn 31)(l D 3IIA
C
cuttcl tlsdc ulg 45
evaluar nn IA less than I . B. 3 ( to C B
70 6 70to it)(,D li! oimnre)
number of runes ot'suc essful spl n tunes 10111) ill 10 I 0, IL) IL) Ifl
cvaluatinn (. I 0 times. x: uusu essfid

clttractcristi s of uitCrla) Cr t'r «tulC IOualmeaa (Ga) I'Ill 9(1 65 6 I 669 600
( (I M P. 7 346 69 .' (

coulp05!I'c

TABLE 2
Corn Com C0m C0m Cnm
Pal'Rtl 'c psr.'itl 'c pRI.'I'l 'C PWiltl C parat» c
casu)pic csaulplc exalnplc ex uuplc cxlulplc
I firs't epoxy'c5ul cnulposlunu I 2 4 5

I - I 2 I I 2 I

compnaenr [B] [bl] b, V dlyc d 14 phenos, an lute puts 3( 3 35 3( )5 ( 3( 'I( 3( 'I(

(TOREP % A 04E)
B-diglycid) I sailmc (GAV I piu't5
[b2] toplycidyl-p-anuaophcaol IiER Zl 6301 PRI't5 65 65
tctraglccidyl dmmuiodiphenl(ntcthsne piu't5 65 b.
IAraldite 7 MY! I)
.
mpo «nt I('I Poll Ih . Il» tmrmt;Pa.g 107(IA) pi ts
p.ut 5 61)
I'I S ili) I')
crop n p ut. 611 6t) 4 45 ol! Au )( I 2 I 6tl 6I
(SEBCACI RE m ()
'I3' nnuind pheny( su)tone (3.1 DAS p.lrts
nmp nant [F] polyun de ptut les (Toiml)eall m TV) pilrts go 90
polytun de ptut les (Onmsol m too D) p.lrts
cnatcat nf cmnpnnent [C] ui rc. ui colnpositfnn Ill.'15 5

munbcr of niolcs of actus hvdlngcnonuubcr of molcs of cpoxv moup I tlg O 69 I I.ig 2 24 I 09

ph simii propeltics nf stole c cllstic niodulus ". ' G't Pa 4D x 12 x ID" IA' 105 35 10
lil'6

P Pl

pmportonofcompnnent[f[exstng athemgon mass 07

ian u)g from e the& surtls e f ptepre to
ga (axe)us e) depth n th ckness duect on
peel strength lafiei st.induig for 4 hours) h mm 0 0 fl
slit tape deposition path luis ntg 2A 57 I 0
procc55:lb!!ltt nf e lhtation (A '2((l B 2 il tn 2 . C unpnssiblc A anpnssible B
IO5uiffuzz 7 tn Sotl D. AO I
. nl Shul I Il

('ll 10 D )05 rm 1
A

IA
rnp (sib)

2!10 I I I)
evaluar nn I I I I ames. x: iuisu essful 'R X
once 01 niore)
ch.ua rei st s f uireilaye fri tuie roighriess (Gal f) I 71 61 (54 6'!4
f)her rem fni cad CAI 3 6f) 37 236 '!61 '!74
cnulpns!I'c
ulster!id
US 2022/024305] A] Aug. 4, 2022

EXPLANATION OF NIIMERAI S [bi] a di- or less-functional epoxy resin containinfq in a

molcculc. at least onc ring structure having lmir- or
[0157] 1. prepreg
nlorc-nlcnlbcILSI ting and a gly'cldyl anunc group
[0158] 2. block
bonded to a rin structure,
I A prepreg comprising the components [AJ to [I'IJ given
beloiv. [b2] a tn- or more-liinctional epoxy resin,
nteeting the requirements (i) to (iii) given below. and [C] a thermoplastic resin with a wei ht-avera e molecular
serving to produce a cured product having weight of 2.000 to 30.000 g/mol,
a rcinlorcing liber layer delincd as thc region ranging [D] diaminodiphenyl suifone„
from 8% to 92% depth from Ihe surface ut the tluckness 0JJ particles having a volume-average particle stxe of 5 to
face(lou that conulhls II fnsn L'poxv Icsul conlposltlou 50 lun and insoluble in the component [B]
in v hich 90 mass % or more of the component [AJ 2 A prepreg as set forth in claim l. wherein the compo-
exists. and two surface resin layers each detined as the nent [(:1 accounts for 8 to 20 parts by mass relative to 100
region rangin from either surface to a depth of 8% parts by mass of the second epoxy resin composition.
exclusive in the thickness direction that contain a 3 A prepreg as set forth in either claim 1, wherein the
second epoxy resin composition ut winch 85 mass % or second epoxy resin composition has a storage elastic modu-
morc of thc componmtt [E] exists, lus Ci't thc range ol'1.0x10'o 1.0xl 0 Pa when measured
(I) thc sccorid cpox) Icsul conlposltlLut htchldes thc at 2S" C. and an angular lbcqumtcy of 3.14 rad/s.
components [l3J to [I!J of which the component [(:J 4 A prcprcg as sct forth in claim 1. wherein thc compo-
accounts for 8 to 24 pans by mass relative to 100 parts nent [biJ accounts for 20 to 50 parts by mass and the
by mass of the second epoxy resin composition. component [b2] accounts for 50 to 80 parts by mass relative
(ii) the second epoxy resin composition has a stomge to the total quantity, which accounts for 100 part~ by mass,
clastic modulus Ci'n tlm range of 1.0x10 to 3.0x10 of the component [Bj.
Pa when mcasurcd at 25'. Snd an angular lbequmtcy
5 A prepreg as set forth in claim 1. wherein the number
of 3.14 rad/s, and of molcs of active hydrogen contained In thc component [D]
(iii) plies of the prepreg laid up after being left to stand fbr is I.OS to 2 0 times as large as the number ol'mules ol'epoxy
24 hours at mons temperature show a peel strength of
gmups contained in the second epoxy resin composition
0.1 N/nun or more at 35" C..
6 A fiber reinforced composite material produced by
[A] a carbon fiber„
curing a prepreg as set forth in claim I
[B] an epoxy resin contatnutg the components [bl] and
[b2] speci lied below, i t t t