Resin composition

A resin composition comprising PA1 (a) 40 to 80% by weight of a resin comprising PA2 an oligomer having a number average molecular weight of 900 to 3,000 in terms of polystyrene equivalent obtained by gel permeation chromatography and having two or more terminal (meth)acrylate groups and PA2 an unsaturated polyester, and PA1 (b) 20 to 60% by weight of methyl (meth)acrylate monomer.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a resin composition providing fast curing and 
being distinguished in crack resistance when used according to the resin 
transfer molding (which will be referred to as RTM or R-RIM in the 
following) which is one of the molding methods of fiber reinforced 
thermosetting plastics (which will be referred to as FRP in the 
following). 
2. Prior Art 
RTM features in that it permits low pressure, low temperature molding so 
that the equipment investment such as mold and press costs can be reduced. 
However, it has difficulties in productivity and moldability. 
To satisfy these requirements, a resin composition distinguished in curing 
performance or of fast curing and in resistance to cracking is required. 
As such resin composition, an unsaturated polyester resin composition is 
cited in EP-A-234692 laid open on January 13, 1987. It is a polymeric 
composition comprising an unsaturated polyester, styrene and/or acrylate 
monomer and a compound having a (meth)acrylate group. However, such 
composition was intended for improvement of the odor of the unreacted, 
volatile unsaturated monomer (such as styrene) in the molded product and 
had thus difficulties in that the compound having the (meth)acrylate group 
was of a low molecular weight comprising no hydroxyl group so that if the 
curing time (time from addition of a hardener to maximum heat generation 
for hardening) were accelerated, the gelling time (time from addition of 
the hardener to loss of fluidity) would be extremely reduced, resulting in 
gelation occurring during the process of injection or cracking occurring 
in the molded product. To prevent cracking, a thermoplastic resin such as 
poly(vinyl acetate) or polystyrene was blended to the unsaturated monomer 
solution of an unsaturated polyester, or the content of the unsaturated 
acid in the unsaturated polyester was reduced, for adjustment of the 
concentration of cross-links. However, prevention of cracking with such 
method had the curing time extremely extended or the mechanical strength 
of the molded product greatly reduced. Thus, both productivity and 
moldability were hardly satisfied simultaneously. 
SUMMARY OF THE INVENTION 
As the results of intensive research with view to obtaining a resin 
composition which would satisfy both fast curing and moldability 
simultaneously, the present inventors have completed a resin composition 
distinguished in fast curing performance and crack resistance in molding 
by dissolving in methyl (meth)acrylate monomer a mixture of an unsaturated 
polyester and an oligomer of a particular molecular weight with a terminal 
of (meth)acrylate group, said mixture being dissolved in methyl 
(meth)acrylate monomer. 
Therefore, the present invention provides a fast curing and crack resistant 
resin composition comprising (a) 40 to 80% by weight of a resin comprised 
of an oligomer of a number average molecular weight of 900 to 3,000 in 
terms of polystyrene equivalent obtained by gel permeation chromatography 
(GPC) with the terminal being two or more (meth)acrylate groups and an 
unsaturated polyester and (b) 20 to 60% by weight of methyl (meth)acrylate 
monomer.

DETAILED DESCRIPTION OF THE INVENTION 
The unsaturated polyester which can be used in the present invention refers 
to an unsaturated polyester which contains 20 to 70% by weight of an 
unsaturated dibasic acid and is obtainable through reaction between an 
acid component containing a saturated polybasic acid, if desired, and a 
polyhydric alcohol component in an equivalent proportion of 1:1. If the 
unsaturated dibasic acid is less than 20% by weight, the curing 
performance is degraded, and if it is greater than 70% by weight, the 
crack resistance is deteriorated. Examples of such unsaturated dibasic 
acid component constituting the unsaturated polyester include well-known 
and generally used .alpha.,.beta.-unsaturated dibasic acids such as maleic 
acid, fumaric acid, itaconic acid, citraconic acid, metaconic acid and 
chlorinated maleic acid or anhydrides thereof. 
Among the unsaturated dibasic acids, maleic anhydride is preferred. 
Examples of the saturated polybasic acid component which can be used 
concurrently in the present invention together with the unsaturated 
dibasic acids, if desired, include generally known and conventionally used 
saturated acids or anhydrides or esters thereof such as phthalic acid, 
phthalic anhydride, tetrahydrophthalic anhydride, 
cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic anhydride, isophthalic 
acid, terephthalic acid, dimethylterephthalic acid, mono-chlorophthalic 
acid, dichlorophthalic acid, trichlorophthalic acid, chlorendic acid (Het 
acid), tetrabromophthalic acid, sebacic acid, succinic acid, adipic acid, 
glutaric acid, pimelic acid, trimellitic acid and pyromellitic acid. 
Examples of the alcohol component of the unsaturated polyester include 
listed generally known and conventionally used polyhydric alcohols such 
as, for example, ethylene glycol, diethylene glycol, triethylene glycol, 
polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene 
glycol, polypropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 
1,4-butylene glycol, neopentyl glycol, hexylene glycol, octyl glycol, 
trimethylolpropane, glycerine, pentaerythritol, ethylene oxide or 
propylene oxide additive of hydroquinone, ethylene oxide- or propylene 
oxide-adduct of bisphenol A, hydrogenated bisphenol A and tricyclodecane 
dimethylol. Of these, propylene glycol is particularly preferred. 
The oligomer having a terminal of (meth)acrylate group which can be used in 
the present invention is a compound, which is preferably in the form of a 
straight chain and has hydroxyl groups as side chains, the compound having 
(meth)acrylic acid, hydroxy(meth)acrylate or glycidyl (meth)acrylate 
introduced to the molecular chain, its side chains or both terminals of 
the main chain and containing 10% by weight or more or, more preferably, 
20 to 40 % by weight, based on the weight of the oligomer, of 
(meth)acrylate group 
##STR1## 
The number average molecular weight of the oligomer containing the 
(meth)acrylate group which can be used in the present invention 
corresponds to polystyrene equivalent measured according to GPC method, 
which is practically acceptable and used for convenience's sake although 
it would not always indicate accurate number average molecular weight of 
the polymer 900 to 3,000, and preferably 1,000 to 2,800. When the 
molecular weight is less than 900, the molded product which can be 
obtained has tackiness and is inferior in tensile strength and other 
physical properties, and when it is greater than 3,000, the molded product 
is apt to produce foams and take much time for molding, resulting in 
decrease of the productivity. 
The oligomer of the present invention specifically refers to epoxy 
acrylates and polyester acrylates, preferably epoxy acrylates. 
Such epoxy acrylate is an epoxy acrylate obtainable by reaction of a 
polyepoxide (epoxy resin) with an .alpha.,.beta.-unsaturated monobasic 
acid in an equivalent proportion of 1:2. That is, it refers to an epoxy 
acrylate having a main chain of polyepoxide and both terminals of a 
(meth)acrylate group, respectively. 
Representative examples of the polyepoxide (epoxy resin) include 
condensation products of polyphenols and (methyl)epichlorohydrin. For the 
polyphenols, there may be listed bisphenol A, 
2,2'-bis(4-hydroxyphenyl)methane (bisphenol F), halogenated bisphenol A, 
resorcinol, tetrahydroxyphenylethane, phenol novolak, cresol novolak, 
bisphenol A novolak and bisphenol F novolak. There may also be listed 
epoxy compounds of the alcohol ether type obtainable from polyols such as 
ethylene glycol, butane diol, glycerine, polyethylene glycol, 
polypropylene glycol and alkylene oxide-adduct of bisphenols, and 
(methyl)epichlorohydrin; glycidyl amines obtainable from anilines such as 
diaminodiphenylmethane, diaminophenylsulfon and p-aminophenol, and 
(methyl)epichlorohydrin; glycidyl esters based on acid anhydrides such as 
phthalic anhydride and tetrahydro-or hexahydro-phthalic anhydride; and 
alicyclic epoxides such as 3,4-epoxy-6-methylcyclohexylmethyl and 
3,4-epoxy-6-methylcyclohexyl carbonate. Compounds having a bisphenolic 
skeleton are preferred. 
For the .alpha.,.beta.-unsaturated monobasic acids, acrylic acid and 
methacrylic acid are representative. 
The number average molecular weight of the epoxy acrylate is preferably 900 
to 2,500, or more preferably 1,300 to 2,200. If the number average 
molecular weight is less than 900, the molded product has tackiness and is 
inferior in the physical properties, and if it is greater than 2,500, the 
molded product is apt to form foams and take much time for molding, 
resulting in degradation of the fast curing performance and thus in 
decrease of the productivity. 
The unsaturated polyester acrylate having (meth)acrylate groups at the 
terminals which can be used in the present invention refers to an 
unsaturated polyester acrylate having an unsaturated glycidyl compound 
added to an unsaturated polyester obtainable through reaction of an acid 
component containing a saturated polybasic acid or its anhydride, if 
desired, an unsaturated polybasic acid or its anhydride with an alcohol 
component in an equivalent proportion of 2:1, or an unsaturated polyester 
acrylate having an unsaturated glycidyl compound added to an unsaturated 
polyester containing a carboxyl group at each terminal. 
Examples of the unsaturated glycidyl compound constituting a component of 
the polyester include those that are generally known and conventionally 
used such as glycidyl esters of unsaturated monobasic acids of acrylic 
acid and methacrylic acid such as, for example, glycidyl acrylate and 
glycidyl methacrylate. For such unsaturated glycidyl compound, glycidyl 
methacrylate is preferred. 
Examples of the dibasic acid component include any generally known and 
conventionally used saturated acids or their anhydrides or esters such as, 
for example, phthalic acid, phthalic anhydride, tetrahydrophthalic 
anhydride, cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic anhydride, 
isophthalic acid, terephthalic acid, dimethylterephthalic acid, 
monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, 
chlorendic acid (Het acid), tetrabromophthalic acid, sebacic acid, 
succinic acid, adipic acid, glutaric acid, pimelic acid, trimellitic acid 
and pyromellitic acid. Isophthalic acid is preferred. 
As the unsaturated polybasic acid or anhydride thereof to be used jointly, 
if desired, there may be listed generally known and conventionally used 
.alpha.,.beta.-unsaturated polybasic acids such as maleic acid, fumaric 
acid, itaconic acid, citraconic, metaconic acid and chlorinated maleic 
acid, or anhydrides thereof. 
Examples of the alcohol component of the polyester acrylate include 
polyhydric alcohols which are generally known and conventionally used such 
as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene 
glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 
polypropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 
1,4-butylene glycol, neopentyl glycol, hexylene glycol, octyl glycol, 
trimethylolpropane, glycerine, pentaerythritol, ethylene oxide- or 
propylene oxide-adduct of hydroquinone, hydrogenated bisphenol A and 
tricyclodecane dimethylol. Glycols of rigid structure having a bisphenol 
skeleton are particularly preferred. 
The number average molecular weight of the unsaturated polyester acrylate 
is preferably 1,500 to 3,000, or more preferably 1,800 to 2,800. When the 
number average molecular weight is less than 1,500, the molded product may 
have teckiness or be degraded in tensile strength and other physical 
properties, and when it is greater than 3,000 the mold is apt to produce 
foams and take much time for molding, resulting in degradation of the fast 
curing performance and decrease of the productivity. When only an oligomer 
the terminal of which is a (meth)acrylate group is used as a resin, the 
molded product may be distinguished in fast curing, injection 
characteristic and crack resistance, but it may be inferior in physical 
properties such as tensile strength and tensile elasticity which may be 
required depending on its application. 
According to the present invention, the weight based mixing proportion of 
the unsaturated polyester (a) and the oligomer containing terminal 
(meth)acrylate groups (b) is: (a):(b)=5:95 to 95:5, and preferably 20:80 
to 80:20. When the unsaturated polyester is less than 5 parts by weight, 
sufficient tensile strength and modulus of elasticity are not obtainable, 
and when it is greater than 95 parts by weight, the curing characteristic 
is degraded. 
The resin component used in the present invention, 40 to 80% by weight, and 
preferably 50 to 70% by weight. When it is less than 40% by weight, the 
curing characteristic is degraded, and the resin flowing out of the molded 
product has its surface remaining to be tacky, and when it is greater than 
80% by weight, the viscosity increases to extend the molding time or 
decrease the cross-linking density, resulting in degradation of the 
tensile strength and other physical properties. 
In the present invention, said resin is used preferably in an amount of 30 
to 50% by weight dissolved in 20 to 60% by weight of methyl 
(meth)acrylate. This is also important as stated above. Use of methyl 
(meth)-acrylate is particularly important for obtaining the fast curing 
characteristic (molding time, about 3 minutes). However, any other vinylic 
monomer may be used jointly in such a small amount that the effect of the 
invention will not be impaired. 
The resin composition of the present invention may contain various 
additives such as a thickener, coloring agent, reinforcing agent, filler, 
curing catalyst, curing accelerator, curing retarder, internal lubricant 
and/or low shrink agent, if desired. 
The thickener should be such that it chemically bonds with the hydroxyl and 
carboxyl groups and ester bonds contained in the resin to form linear or 
partially cross-linking bonds and thus increase the molecular weight and 
the viscosity of the unsaturated polyester resin, and as such thickener, 
there may be listed diisocyanates such as toluene diisocyanate, metal 
alkoxides such as aluminum isopropoxide and titanium tetrabutoxide, oxides 
of divalent metals such as magnesium oxide, calcium oxide and beryllium 
oxide, and hydroxides of divalent metals such as calcium hydroxide. The 
amount of use of the thickener is normally 0.2 to 10 parts by weight, and 
preferably 0.5 to 4 parts by weight per 100 parts by weight of the resin 
composition. Also, there may be used a small amount of highly polar 
substance such as water as an auxiliary thickener, if desired. 
As a coloring agent, any of the conventional organic and inorganic dyes and 
pigments can be used. However, such a coloring agent which is 
distinguished in heat resistance and transparency and does not impede 
curing of the unsaturated polyester and terminal (meth)acrylate group 
containing oligomer, is preferred. 
For the reinforcing agent used in the present invention, fiber glass may be 
cited generally. However, organic fibers of Vinylon, polyester, phenol, 
poly(vinyl acetate), polyamide and poly(phenylene sulfide) and inorganic 
fibers of asbestos, carbon fiber, metal fiber and ceramic fiber, may 
cited. These may be in the forms of strand, knit and nonwoven fabric, 
planar or solid. The reinforcing agent is not limited to such fibers, and 
plastic foams such as polyurethane foam, phenol foam, vinyl chloride foam 
and polyethylene foam; hollow hardened products of glass and ceramics, and 
solids, molded products or honeycomb structures of metals, ceramics, 
plastics, concrete, wood and paper, can also be used. 
Example of the filler include calcium carbonate powder, clay, alumina 
powder, silica, talc, barium sulfate, silica powder, glass powder, glass 
beads, mica, aluminum hydroxide, cellulose filament, quartz sand, river 
sand, white marble, marble scraps and crushed stone. Of these, glass 
powder, aluminum hydroxide and barium sulfate are particularly preferred 
in that they provide semi-transparency in curing. 
To accelerate the curing, a metal compound may be added to the resin 
composition, if desired, and for such metal compound, metal compound 
accelerators used generally for unsaturated polyester resins are used. 
Their examples include cobalt naphthonate, cobalt octonate, divalent 
acetylacetone cobalt, trivalent acetylacetone cobalt, potassium hexoate, 
zirconium naphthonate, zirconium acetylacetonate, vanadium naphthonate, 
vanadium octonate, vanadium acetylacetonate and lithium acetylacetonate, 
and combinations thereof. Also, such accelerator may be used in 
combination with any other conventional accelerators such as amines, 
phosphorus containing compounds, and .beta.-diketones. 
The amount of addition of such curing accelerator is subject to adjustment 
with the gelling time, but it is preferably 0.0001 to 0.12 part by weight 
as a metal component per 100 parts by weight of the resin composition. In 
the case of molding at a medium temperature or higher (40.degree. C. or 
higher), this curing accelerator may be used or omitted. 
Examples of the curing catalyst include such compounds which act on the 
unsaturated polyester or terminal (meth)-acrylate group containing 
oligomer, including azo compounds such as azoisobutyrlonitrile and organic 
peroxides such as tertiary butyl perbenzoate, tertiary butyl peroctoate, 
benzoyl peroxide, methyl ethyl ketone peroxide, acetoacetic ester peroxide 
and dicumyl peroxide. The catalyst is used in an amount of 0.1 to 4 parts 
by weight, or preferably 0.3 to 3 parts by weight, per 100 parts by weight 
of the resin composition. 
Redox curing agents such as acetoacetic ester peroxide/cobalt naphthenate 
and benzoyl peroxide/dimethyl p-toluidine are particularly preferred. 
For the curing retarder, there may be listed hydroquinone, 
toluhydroquinone, tertiary-butylcatechol and copper naphthenate, and such 
compound is preferably used in an amount or 0.0001 to 0.1 part by weight 
per 100 parts by weight of the resin composition. 
For the internal lubricant, there may be listed the conventional higher 
fatty acids and higher fatty acid esters such as stearic acid and zinc 
stearate and alkyl phosphoric esters. Such lubricant can be used in a 
proportion of normally 0.5 to 5 parts by weight per 100 parts of the resin 
composition. 
For the low shrinkage agent, there may be listed such thermoplastic resins 
as homopolymers or copolymers of lower alkyl esters of acrylic or 
methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl 
methacrylate, methyl acrylate and ethyl acrylate, and monomers of styrene, 
vinyl chloride and vinyl acetate; copolymers of at least one of said vinyl 
monomers and at least one of monomers comprising lauryl methacrylate, 
isovinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl acrylate 
or methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, 
methacrylic acid and cetylstearyl methacrylate; and further cellulose 
acetate butyrate and cellulose acetate propionate, polyethylene, 
polypropylene and saturated polyesters. These may be added, if desired for 
particular use, so long as the effect of the invention is not impaired. 
The resin composition of the present invention may be cured with heat with 
various peroxides added or by ultraviolet ray or any other active light 
with various photo sensitive agents added and is fast curing and 
distinguished in mechanical strength. 
The resin composition according to the present invention is of a viscosity 
of preferably 3 poise or less at 25.degree. C. But, it is not always 
required to be 3 poise or less at room temperature. So long as the effect 
of the invention is achieved, it may have the viscosity reduced to 3 poise 
or less by heating or otherwise at the time of injection to the mold. This 
viscosity allows injection to the R-RIM molding machine with ease. If the 
viscosity is greater than 3 poise, much time is required for injection, 
and so the productivity is decreased. 
According to the present invention, the molded product is produced by 
dividing the resin composition into two parts, adding a curing agent 
(peroxide) to one part (component A) and an accelerator to the other 
(component A'), circulating these two components A and A' in separate 
lines respectively under a high pressure (injection pressure) of 
preferably 5 to 200 kg/cm.sup.2 or more preferably 80 to 150 kg/cm.sup.2, 
and injecting them in a short time of preferably 0.1 to 30 seconds or more 
preferably 0.5 to 20 seconds into a mold having a reinforcing agent 
charged and maintained at a mold temperature of preferably 10.degree. to 
80.degree. C. or more preferably 40.degree. to 70.degree. C. and a mold 
pressure of preferably 5 to 100 kg/cm.sup.2 or more preferably 20 to 50 
kg/cm.sup.2. 
According to the invention, molding is performed at a molding temperature 
of 80.degree. C. or less (mold temperature). If molded at a temperature 
higher than 80.degree. C., the methyl (meth)acrylate monomer is subject to 
evaporation to produce air bubbles in, or voids on the surface of, the 
molded product, resulting in cracking, and so such temperature is not 
desirable. 
Also, according to the invention, the molded product has a reinforcing 
agent charged before it is locked and has the composition injected. Here, 
according to the prior art in which the reinforcing agent was added to the 
composition before injection, it was difficult to provide a high strength 
as the reinforcing agent was of a fibrous form. Also, according to the 
conventional RTM, when a reinforcing agent in the form of long filaments 
was used, if the injection time is reduced, it was caused to flow on 
account of the high viscosity of resin composition so that the mechanical 
strength was not evenly distributed, resulting in a product of poor 
quality. According to the present invention, such problem is eliminated, 
and a uniform molded product having a high mechanical strength can be 
obtained. 
The number average molecular weight specified in the invention refers to 
that value of GPC (gel permeation chromatography) which is determined 
under the following condition of measurement. 
GPC: Product of Japan Analytical Industry, Model LC-08 
Column: SHODEX A-804+A-803+A-802+A-801 (product of Showa Denko) 
Solvent: THF (tetrahydrofuran) 
Standard sample for calibration curve: Polystyrene (product of Toso) 
Detector: Differential refractometer (product of Japan Analytical Industry) 
The resin composition of the present invention may be cured with heat with 
various peroxides added or by ultraviolet ray or any other active light 
with various photo sensitizers added, and the cured molded product has 
very little foam and an excellent mechanical strength. 
The resin composition of the present invention is distinguished in fast 
curing characteristic and crack resistance and is very excellent for RTM. 
EXAMPLE 
Now, the present invention will be described in detail with reference to 
reference examples and examples. It should be noted that the "parts" in 
the following show the parts by weight. 
Reference Example 1 
(Preparation of unsaturated polyester [PE-1]) 
Heating, dehydrating and condensating 540 g of maleic anhydride and 460 g 
of 1-2 propylene glycol in an inert gas at 220.degree. C. for 10 hours, 
there was obtained a condensation product giving an acid value of 30. To 
this, 0.15 g of hydroquinone was added, and the mixture was cooled to 
120.degree. C. Then, this solid was dissolved in 600 g of methyl 
methacrylate monomer, and there was obtained an unsaturated polyester of 
non-volatile component 60.2%, viscosity 3.8 poises (at 25.degree. C.) and 
acid value 18.6 with the content of unsaturated dibasic acid at 59.9% by 
weight. 
Reference Example 2 
(preparation of unsaturated polyester [PE-2]) 
Heating, dehydrating and condensating 237 g of maleic anhydride, 358 g of 
phthalic anhydride and 405 g of 1-2 propylene glycol in an inert gas at 
220.degree. C. for 10 hours, there was obtained a condensation product 
giving an acid value of 28. To this, 0.15 g of hydroquinone was added, and 
the mixture was cooled to 120.degree. C. Then, this solid was dissolved in 
390 g of methyl methacrylate monomer, and there was obtained an 
unsaturated polyester of solid component 70.1% viscosity of 4.0 poises (at 
25.degree. C.) and acid value of 17 with the content of unsaturated 
dibasic acid at 26% by weight. 
Reference Example 3 
(Preparation of unsaturated polyester [PE-3]) 
Heating, dehydrating and condensating 152 g of maleic anhydride, 459 g of 
phthalic anhydride and 389 g of 1-2 propylene glycol in an inert gas at 
220.degree. C. for 10 hours, there was obtained a condensation product 
giving an acid value of 25. To this, 0.15 g of hydroquinone was added, and 
the mixture was cooled to 120.degree. C. Then,. this solid was dissolved 
in 600 g of methyl methacrylate monomer, and there was obtained an 
unsaturated polyester of solid component 60%, viscosity 6.2 poises (at 
25.degree. ) and acid value 15 with the content of unsaturated dibasic 
acid at 16.6% by weight. 
Reference Example 4 
(preparation of unsaturated polyester [PE-4]) 
Heating, dehydrating and condensating 540 g of maleic anhydride and 460 g 
of 1-2 propylene glycol in an inert gas at 220.degree. C. for 10 hours, 
there was obtained a condensation product giving an acid value of 29. To 
this, 0.15 g of hydroquinone was added, and the mixture was cooled to 
120.degree. C. Then, this solid was dissolved in 600 g of styrene monomer, 
and there was obtained a styrene type unsaturated polyester having a resin 
solid component of 59.8%, viscosity of 6.2 poises (at 25.degree. C.) and 
acid value of 16.5 with the content of unsaturated dibasic acid at 59.9% 
by weight. 
Reference Example 5 
(Preparation of epoxy acrylate [AC-1]) 
Introducing in a three-necked flask provided with a thermometer, stirrer 
and cooler 1,850 g of EPICLON.RTM. 850 (epoxy resin product of Dainippon 
Ink & Chemicals, Inc) obtained through reaction of bisphenol A with 
epichlorohydrin with an epoxy equivalent of 185 (equivalent to 10 epoxy 
groups), 860 g of methacrylic acid (equivalent to 10 carboxyl groups), 
1.36 g of hydroquinone and 10.8 g of triethylamine, the mixture was heated 
to 120.degree. C. and allowed to react at the same temperature for 10 
hours, and there was obtained liquid epoxy acrylate with an acid value of 
3.5, epoxy equivalent of 15,000 or more and color number of 2. Then, 
dissolving this epoxy acrylate in 2,217 g of methyl methacrylate monomer, 
there was obtained 4,920 g of epoxy acrylate of the non-volatile component 
at 55%, acid value at 2, viscosity at 2 poises at 25.degree. C. and (meth) 
acrylate group content in the solid at 31.4% by weight. 
Reference Example 6 
(Preparation of unsaturated polyester acrylate [AC-2]) 
Heating, dehydrating and condensating 166 g (1 mol) of isophthalic acid and 
152 g (2 mols) of 1-2 propylene glycol in an inert gas at 220.degree. C. 
for 10 hours, there was obtained a reaction product having a solid 
component of an acid value of 5. Then, it was cooled to 100.degree. C. 
Next, 196 g (2 mols) of maleic anhydride was charged, and through heating, 
dehydration and condensation at 200.degree. C. for 5 hours, there was 
obtained a reaction product having a solid component of an acid value of 
254. To this, 0.15 g of hydroquinone was added, and the mixture was cooled 
to 140.degree. C. Next, 284 g (2 mols) of glycidyl methacrylate was 
charged, and through reaction at 140.degree. C. for 10 hours, there was 
obtained a solid reaction product of an acid value of 10. Dissolving this 
unsaturated polyester acrylate in 508 g of methyl methacrylate monomer, 
there was obtained 1,270 g of an unsaturated polyester acrylate with a 
non-volatile component of 60.5%, viscosity of 0.5 poise at 25.degree. C., 
acid value of 6.1 and the acrylate group content in the solid at 23.4% by 
weight. 
Reference Example 7 
(Preparation of styrene type epoxy acrylate [AC-3] 
Introducing in a three-necked flask provided with a thermometer, stirrer 
and cooler 1,850 g of EPICLON.RTM. 850 (epoxy resin product of Dainippon 
Ink & Chemicals, Inc) obtained through reaction of bisphenol A and 
epichlorohydrin with each other with an epoxy equivalent of 185 
(equivalent to 10 epoxy groups), 860 g of methacrylic acid (equivalent to 
10 carboxyl groups), 1.36 g of hydroquinone and 10.8 g of triethylamine, 
the mixture was heated to 120.degree. C. and allowed to react at the same 
temperature for 10 hours, and there was obtained liquid epoxy acrylate 
with an acid value of 3.5, epoxy equivalent of 15,000 or more and color 
number of 2. Dissolving this solid in 1,800 g of styrene monomer, there 
was obtained 4,500 g of styrene type epoxy acrylate of a non-volatile 
component of 60.3%, acid value of 2.1, viscosity of 10 poises at 
25.degree. C. with the methacrylate group content in the solid at 31.4 5 
by weight. 
Reference Example 8 
(Preparation of unsaturated polyester acrylate ([AC-4]) 
Heating, dehydrating and condensating 133 g (0.8 mol) of isophthalic acid, 
76 g (1 mol) of 1,2-propylene glycol, and 324 g (1 mol) of ethylene oxide 
2 mol adduct of bisphenol A in an inert gas at 220.degree. C. for 9 hours, 
there was obtained a solid product of an acid value of 3. This was cooled 
to 100.degree. C. Then, charging 147 g (1.5 mols) of maleic anhydride, and 
heating, dehydrating and condensating at 200.degree. C. for 6 hours, there 
was obtained a solid product of an acid value of 37. To this, 0.16 g of 
hydroquinone was added, and the mixture was cooled to 140.degree. C. Next, 
85 g (0.6 mol) of glycidyl methacrylate was charged, and through reaction 
at 140.degree. C. for 6 hours, there was obtained a solid product of na 
acid value of 10. This unsaturated polyester acrylate was dissolved in 456 
g of methyl methacrylate monomer, and there was obtained 1,088 g of an 
unsaturated polyester acrylate product of a non-volatile component of 
60.2%, acid value of 6, viscosity of 20 poise at 25.degree. C. with the 
acrylate group content in the solid at 7.2% by weight. 
Reference Example 9 
(Preparation of epoxy acrylate [AC-5]) 
Using 5,000 g of EPICLON.RTM. 1050 of an epoxy equivalent of 500 in place 
of EPICLON.RTM. 850 in Reference Example 5, 860 g of methacrylic acid, 
2.93 g of hydroquinone and 21.6 g of triethylamine, a solid epoxy acrylate 
product was obtained as in Reference Example 5. Dissolving this epoxy 
acrylate in 4,975 g of methyl methacrylate monomer, there was obtained 
10,835 g of epoxy acrylate of a non-volatile component of 55%, acid value 
of 2, viscosity of 2.8 poises (25.degree. C.) with the (meth) acrylate 
group content at 14.7% by weight. 
Characteristics of the resin compositions obtained in Reference Examples 1 
through 9 are shown in Table 1. 
TABLE 1-1 
__________________________________________________________________________ 
Resin (1-17) 
Charge compositions (A-K) 
A B C D E F G H I 
__________________________________________________________________________ 
Unsaturated polyester 
Reference 
460 540 901 
Example 1 
PE-1 
Reference 
405 358 
237 913 
Example 2 
PE-2 
Reference 
389 459 
152 916 
Example 3 
PE-3 
Reference 
460 540 900 
Example 4 
PE-4 
Terminal (meth)acrylate group containing oligomer 
Reference 1850* 
860 
2710 
Example 5 
AC-1 
Reference 
152 166 196 
284 762 
Example 6 
AC-2 
Reference 1850* 
860 
2710 
Example 7 
AC-3 
Reference 
76 
324 
133 147 
85 632 
Example 8 
AC-4 
Reference 5000** 
860 
5860 
Example 9 
AC-5 
__________________________________________________________________________ 
A 1,2Propylene glycol 
B Ethylene oxide (2 mols) adduct of bisphenol A 
C Isophthalic acid 
D Orthophtalic anhydride 
E Maleic anhydride 
F Glycidyl methacrylate 
G *EPICLON .RTM. 850 
**EPICLON .RTM. 1050 
H Methacrylic acid 
I Total of resin solid component 
TABLE 1-2 
______________________________________ 
Change 
Composition Characteristics (L-Q) 
J K L M N O P Q 
______________________________________ 
Unsaturated Polyester 
Reference 
600 60.2 18.6 3.8 59.9 2250 
Example 1 
PE-1 
Reference 
390 70.1 17 4.0 26 1892 
Example 2 
PE-2 
Reference 
600 60 15 2.8 16.6 1950 
Example 3 
PE-3 
Reference 600 59.8 16.5 6.2 59.9 2250 
Example 4 
PE-4 
Terminal (meth)acrylate group containing oligomer 
Reference 
2217 55 2 2 31.4 918 
Example 5 
AC-1 
Reference 
498 60.5 6.1 0.5 23.4 1952 
Example 6 
AC-2 
Reference 1800 60.3 2.1 10 31.4 1487 
Example 7 
AC-3 
Reference 
456 60.2 6 20 7.2 3363 
Example 8 
AC-4 
Reference 
4975 55 2 2.8 14.7 2400 
Example 9 
AC-5 
______________________________________ 
J Methyl methacrylate monomer 
K Styrene monomer 
L Resin solid component (%) 
M Acid value (mg .multidot. KOH/g) 
N Viscosity (poise at 25.degree. C.) 
O Content of unsaturated dibasic acid (%) in solid component 
P Content of (meth)acrylate groups (%) in solid component 
Q Number average molecular weight 
EXAMPLE 1 
As Example 1, the resin VE-1 obtained in Reference Example 1, acetoacetic 
ester peroxide (PERCURE SA, product of Nippon Oil & Fats Co., Ltd.) and 6% 
cobalt naphthenate were compounded in a proportion shown in Table 2. The 
results are shown in Table 2. Examples 2 to 5 and Comparative Examples 1 
to 7 were carried out similarly to Example 1. Measurement of the 
characteristics was made according to the methods shown below. 
Curing performance: Obtained from a torque-time curve at 50.degree. C. with 
CURELASTOMETER III (product of Japan Synehetic Rubber Company) used. 
Viscosity: Stationary flow viscometer at 25.degree. C. (REOMETER IR-200, 
product of Iwamoto Seisakusho Co., Ltd.) 
RTM molding test: charging a preforming mat adjusted to a glass content of 
30% by weight to a 600.times.800 mm box type electro-formed nickel/copper 
mold with epoxy resin backing, the mold was locked at 20 kg/cm.sup.2. 
Injection of the resin into the mold was made with an injector, Model 
IP-6000 of Applicator Co., used, and the duration from the time of start 
of the injection to the time of the resin flowing out of the clearance on 
the opposite side was taken as the injection time and shown as such. 
As seen from Table 2, the resin compositions of the present invention were 
distinguished in the fast curing performance, crack resistance, tensile 
strength, tensile modulus of elasticity and Barcol hardness. 
TABLE 2-1 
______________________________________ 
Resin composition 
(Parts by weight) 
(A-B) Curing Agent (C-F) 
A B C D E F 
______________________________________ 
Example 
1 PE-1 70 AC-1 30 1.0 0.2 -- -- 
2 PE-1 70 AC-1 30 -- -- 3.0 0.3 
3 PE-2 10 AC-2 90 1.0 0.2 -- -- 
4 PE-2 50 AC-2 50 1.0 0.2 -- -- 
5 PE-1 60 AC-5 40 1.0 0.2 -- -- 
Comparative 
Example 
1 PE-3 60 AC-1 40 1.0 0.2 -- -- 
2 PE-1 100 -- 1.0 0.2 -- -- 
3 PE-1 70 AC-3 30 1.0 0.2 -- -- 
4 PE-4 15 AC-3 85 1.0 0.2 -- -- 
5 PE-1 50 AC-4 50 1.0 0.2 -- -- 
6 PE-1 70 Trimethyl- 1.0 0.2 -- -- 
olpropane 
trimetha- 
crylate 30 
7 PE-1 50 Trimethyl- 1.0 0.2 -- -- 
olpropane 
trimetha- 
crylate 50 
______________________________________ 
A Unsaturated polyester resin (I-A) 
B Terminal (meth)acrylate group containing oligomer (I-B) 
C Acetoacetic ester peroxide 
D 6% Cobalt naphthenate 
E 50% Benzoyl peroxide 
F Dimethylpara-toluidine 
TABLE 2-2 
______________________________________ 
Molding Conditions 
(G-J) Results (K-O) 
G H I J K L M N O 
______________________________________ 
Example 
1 3.0 100 30 300 .circle. 
.circle. 
13.1 1200 47 
2 3.0 120 30 300 .circle. 
.circle. 
13.5 1250 45 
3 1.2 90 18 300 .circle. 
.circle. 
12.5 1150 47 
4 1.8 130 21 300 .circle. 
.circle. 
12.7 1010 46 
5 2.9 105 30 300 .circle. 
.circle. 
13.3 1238 46 
Compara- 
tive 
Example 
1 2.3 900 25 1500 x x 10.0 870 35 
2 3.8 810 35 1500 x x 12.8 1000 36 
3 3.0 1200 27 1500 x x 10.5 950 39 
4 10 600 90 1500 .circle. 
x 13.0 1100 40 
5 12 600 122 1500 .circle. 
x 10.9 900 38 
6 1.0 1200 15 2400 .circle. 
x 8.2 600 35 
7 0.7 1800 10 2400 .circle. 
x 7.6 550 32 
______________________________________ 
G Viscosity at 25.degree. C. (poise) 
H Cure characteristic at 50.degree. C. (seconds) 
I Injection time (second) 
J Molding time (second) 
K Crack resistance* 
L Curing** 
M Tensile strength (kg/mm.sup.2) 
N Tensile modulus of elasticity (kg/mm.sup.2) 
O Barcol hardness 9341 
Judgment criteria 
*Cracking .circle.: No cracking x: Cracking 
**Barcol hardness .circle.: 45 or higher x: 45 or less (undercure) 
Reference Example 10 
(Preparation of unsaturated polyester acrylate [PEA-1]) 
Heating, dehydrating and condensating 166 g (1 mol) of isophthalic acid and 
152 g (2 mols) of 1-2 propylene glycol in an inert gas at 220.degree. C. 
for 10 hours, there was obtained a condensation product with a solid 
component of an acid value of 5. This was cooled to 100.degree. C. Then, 
charging 196 g (2 mols) of maleic anhydride and through heating, 
dehydration and condensation at 200.degree. C. for 5 hours, a solid of an 
acid value of 254 was obtained. To this, 0.15 g of hydroquinone was added, 
and the mixture was cooled to 140.degree. C. 
Next, charging 284 g (2 mols) of glycidyl methacrylate, and reacting at 
140.degree. C. for 10 hours, a solid of an acid value of 10 was obtained. 
Dissolving this solid in 508 g of methyl methacrylate monomer, there was 
obtained 1,270 g of an unsaturated polyester acrylate of a non-volatile 
component, 60.5%; viscosity, 0.5 poise at 25.degree. C.; acid value, 6.1; 
and acrylix double bond content in the solid component, 6.3%. 
Reference Example 11 
(Preparation of styrene type unsaturated polyester acrylate [PEA-2]) 
Dissolving a similar solid of acid value 10 to that in Reference Example 1 
in styrene monomer, there was obtained a styrene type unsaturated 
polyester acrylate of a non-volatile component, 60%; viscosity, 10 poises; 
acid value, 6.2; and acrylic double bond content in the solid component, 
6.3%. 
Reference Example 12 
(Preparation of unsaturated polyester acrylate [PEA-3]) 
Heating, dehydrating and condensating 166 g (1 mol) of isophthalic acid, 76 
g (1 mol) of 1-2 propylene glycol and 324 g (1 mol) of ethylene oxide 2 
mol additive of bisphenol A in an inert gas at 220.degree. C. for 15 
hours, there was obtained a solid of an acid value of 5. This was cooled 
to 100.degree. C. Then, charging 196 g (2 mol) of maleic anhydride and 
through reaction at 200.degree. C. for 6 hours, a solid having an acid 
value of 163 was obtained. To this, 0.2 g of hydroquinone was added, and 
the mixture was cooled to 140.degree. C. Next, 284 g (2 mols) of glycidyl 
methacrylate was charged and reacted at 140.degree. C. for 10 hours. A 
solid having an acid value 8 was obtained. This solid was dissolved in 683 
g of methyl methacrylate monomer, and there was obtained 1,683 g of an 
unsaturated polyester acrylate of a non-volatile component, 61%; 
viscosity, 2 poises at 25.degree. C.; acid value, 5.8; and acrylic double 
bond content in the solid component, 4.8%. 
Reference Example 13 
(Preparation of unsaturated polyester acrylate [PEA-4]) 
Heating, dehydrating and condensating 166 g (1 mol) of isophthalic acid, 76 
g (1 mol) of 1-2 propylene glycol and 324 g (1 mol) of ethylene oxide 2 
mol additive of bisphenol A in an inert gas at 220.degree. C. for 15 
hours, a solid of an acid value of 4 was obtained. This was cooled to 
100.degree. C. Then, 147 g (1.5 mols) of maleic anhydride was charged and 
heated, hydrated and condensated at 200.degree. C. for 6 hours. A solid 
having an acid value of 85 was obtained. To this, 0.16 g of hydroquinone 
was added, and the mixture was cooled to 140.degree. C. Next, 142 g (1 
mol) of glycidyl methacrylate was charged for reaction at 140.degree. C. 
for 10 hours, and a solid having an acid value of 8 was obtained. This 
solid was dissolved in 546 g of methyl methacrylate monomer, and there was 
obtained 1,365 g of an unsaturated polyester acrylate of a non-volatile 
component, 61.5%; viscosity, 4 poises at 25.degree. C.; acid value, 4.9; 
and acrylic double bond content in the solid component, 2.9%. 
Reference Example 14 
(Preparation of unsaturated polyester acrylate [PEA-5]) 
Heating, dehydrating and condensating 133 g (0.8 mol) of isophthalic acid, 
76 g (1 mol) of 1-2 propylene glycol and 324 g (1 mol) of ethylene oxide 
(2 mol) adduct of bisphenol A in an inert gas at 220.degree. C. for 9 
hours, there was obtained a solid having an acid value of 3. Then, 147 g 
(1.5 mols) of maleic anhydride was charged and heated, dehydrated and 
condensated at 200.degree. C. for 6 hours, and a solid having an acid 
value of 37 was obtained. To this, 0.16 g of hydroquinone was added, and 
the mixture was cooled to 140.degree. C. Next, 85 g (0.6 mol) of glycidyl 
methacrylate was charged and reacted at 140.degree. C. for 6 hours, and a 
solid having an acid value of 10 was obtained. Dissolving this solid in 
456 g of methyl methacrylate monomer, there was obtained 1,088 g of an 
unsaturated polyester acrylate of a non-volatile component, 60.2%; acid 
value, 6; viscosity, 20 poises at 25.degree. C.; and acrylic double bond 
content in the solid component, 2.0%. 
Reference Example 15 
(Preparation of epoxy acrylate [VE-1]) 
Charging into a three-necked flask provided with a thermometer, stirrer and 
cooler 1,850 g of EPICLON.RTM. 850 (epoxy resin product of Dainippon Ink & 
Chemicals, Inc.) obtained through reaction of bisphenol A with 
epichlorohydrin with an epoxy equivalent of 185 (equivalent to 10 epoxy 
groups), 860 g of methacrylic acid (equivalent to 10 carboxyl groups), 
1.36 g of hydroquinone and 10.8 g of triethylamine, the mixture was heated 
to 120.degree. C. and allowed to react at the same temperature for 10 
hours, and there was obtained a liquid epoxy acrylate having an acid value 
of 3.5, epoxy equivalent of 15,000 or more and color number of 2. Then, 
dissolving this epoxy acrylate in 1,800 g of methyl methacrylate monomer, 
there was obtained 4,510 g of an epoxy acrylate of a non-volatile 
component, 60%; acid value, 2; viscosity, 2 poises at 25.degree. C.; and 
acrylic double bond content in the solid component, 8.9%. 
Reference Example 16 
(Preparation of epoxy acrylate [VE-2]) 
Charging into a reaction vessel similar to that in Example 15, 1,300 g of 
EPICLON .RTM. 725 (epoxy resin product of Dainippon Ink & Chemicals, Inc.) 
obtained through reaction of a polyhydric alcohol with epichlorohydrine 
with an epoxy equivalent of 130 (equivalent to 10 epoxy groups), 860 g of 
methacrylic acid (equivalent to 10 carboxyl groups), 1.34 g of 
hydroquinone and 10.7 g of triethylamine, they were allowed to react at 
110.degree. C. for 8 hours, and there was obtained 2,160 g of an epoxy 
acrylate having an acid value of 5. Dissolving this epoxy methacrylate in 
1,440 g of methyl methacrylate monomer, there was obtained 3,600 g of an 
epoxy acrylate of a non-volatile component, 61 2%; acid value, 3; 
viscosity, 0.5 poise; and acrylic double bond content in the solid 
component, 11%. 
Reference Example 17 
(Preparation of styrene type epoxy acrylate [VE-3] 
A similar solid to that in Example 15 was dissolved in styrene monomer, and 
a styrene type epoxy acrylate of a non-volatile component, 59.8%: 
viscosity, 10 poises at 2520 C.; and acrylic double bond content in the 
solid component, 8.9%. 
Reference Example 18 
(Preparation of epoxy acrylate [VE-4]) 
Charging into a reaction vessel similar to that in Reference Example 15, 
7,400 g of EPICULON.RTM. 3050 (product of Dainippon Ink & Chemicals, Inc.) 
obtained through reaction of a polyhydric alcohol with epichlorohydrin 
with an epoxy equivalent of 740 (equivalent to 10 epoxy groups), 860 g of 
methacrylic acid, 5.1 g of hydroquinone and 41.3 g of trimethylamine, they 
were allowed to react at 140.degree. C. for 12 hours, and there was 
obtained 8,260 g of an epoxy acrylate having an acid value of 5.3. 
Dissolving this epoxy acrylate in 5,507 g of methyl methacrylate monomer, 
there was obtained 13,760 g of an epoxy acrylate of a non-volatile 
component, 60.5% ; acid value, 3.2; viscosity, 20 poises; and acrylic 
double bond content in the solid component, 2.9%. 
Reference Example 19 
(Preparation of epoxy acrylate [VE-5]) 
The same procedures as in Reference Example 15 were repeated except that 
the proportion of the resin component to methyl methacrylate was changed 
as shown in Table 3-2. 
TABLE 3-1 
______________________________________ 
Charge Composition (I) (A-I) 
A B C D E F G H I 
______________________________________ 
Epoxy -- -- -- -- -- 185 130 740 -- 
equiva- 
lent 
Poly- 
ester 
acry- 
late 
PEA-1 166 152 -- 196 284 -- -- -- -- 
PEA-2 166 152 -- 196 284 -- -- -- -- 
PEA-3 166 76 324 196 284 -- -- -- -- 
PEA-4 166 76 324 147 142 -- -- -- -- 
PEA-5 133 76 324 147 85 -- -- -- -- 
PEA-6 166 76 324 196 284 -- -- -- -- 
Epoxy 
acry- 
late 
VE-1 -- -- -- -- -- 1850 -- -- 860 
VE-2 -- -- -- -- -- -- 1300 -- 860 
VE-3 -- -- -- -- -- 1850 -- -- 860 
VE-4 -- -- -- -- -- -- -- 7400 860 
VE-5 -- -- -- -- -- 1850 -- -- 860 
______________________________________ 
A Isophthalic acid 
B 1-2 Propylene glycol 
C Ethylene oxide (2 mols) adduct of bisphenol A 
D Maleic anhydride 
E Glycidyl methacrylate 
F EPICLON .RTM. 850 
G EPICLON .RTM. 725 
H EPICLON .RTM. 3050 
I methacrylic acid 
TABLE 3-2 
__________________________________________________________________________ 
Solvents (I):(II) 
(II) Proportion 
Characteristics 
(J-K) (w %) (M) 
(N-R) 
J K L M N O P Q R 
__________________________________________________________________________ 
Polyester 
acrylate 
PEA-1 
763 
508 
-- 60.5:39.5 
60.5 
6.1 
0.5 
22.3 
1405 
PEA-2 
763 
-- 508 
60:40 60 6.2 
10 22.3 
1405 
PEA-3 
1010 
683 
-- 61:39 61 5.8 
2 16.8 
1952 
PEA-4 
819 
546 
-- 61.5:38.5 
61.5 
4.9 
4 10.4 
2680 
PEA-5 
653 
435 
-- 60.2:39.8 
60.2 
6 20 7.8 
3663 
PEA-6 
1010 
433 
-- 70:30 70 6.9 
3 16.8 
1952 
Epoxy 
acrylate 
VE-1 2710 
1800 
-- 60:40 60 2 3 31.4 
1487 
VE-2 2160 
1440 
-- 61:39 61.2 
3 0.5 
39.3 
807 
VE-3 2710 
-- 1800 
59.8:40.2 
59.8 
1.9 
10 31.4 
1487 
VE-4 8260 
5507 
-- 60.5:39.5 
60.5 
3.2 
20 10.3 
2690 
VE-5 2710 
3300 
-- 45:55 45 1.8 
0.5 
31.4 
1487 
__________________________________________________________________________ 
J Total of resin solid component 
K Methyl methacrylate monomer 
L Styrene monomer 
M (a):(b) Proportion (w %) a: Resin b: monomer 
N Nonvolatile component (%) 
O Acid value (mg .multidot. KOH/g) 
P Viscosity (poise at 25.degree. C.) 
Q Acrylate group content (w %) 
R Number average molecular weight 
Characteristics of the resin compositions obtained in Reference Examples 10 
through 18 are shown in Table 3. 
Examples 6 through 13; Comparative Examples 8 through 16 
As Example 6, the resin PEA-3, 100 parts by weight, obtained in Reference 
Example 12, was divided into two parts, each in 50 parts by weight. To one 
part of the resin, 6 parts by weight of 50% benzoyl peroxide was added, 
and to the other, 0.6 part by weight of dimethyl-para-toluidine was added, 
as shown in Table 4, and each resin solution was circulated to a four 
mixing head RIM injector under a pressure of 150kg/cm.sup.2 and was 
injected to an aluminum mold having charged thereto a preforming mat 
preadjusted to a glass content of 50 % by weight, maintained at a mold 
temperature of 50.degree. C. and locked under a pressure of 20kg/cm.sup.2, 
and thus a mold product was obtained. Physical properties of the mold 
product thus obtained are shown in the same table. 
Examples 7 through 10 and Comparative Examples 8 through 16 were carried 
out similarly to Example 6. Determination of the properties was made 
according to the following methods. 
Curing performance: Obtained from a torque-time curve at 40.degree. C. with 
CURELASTOMETER II (product of Japan Synthetic Rubber Company) used. 
Viscosity: Stationary flow viscometer at 25.degree. C. (REOMETER IR-200, 
product of Iwamoto Seisakusho Co., Ltd.) 
Injection time and molding test: Charging a preforming mat adjusted to a 
glass content of 50% to a 50.times.100.times.0.3 cm aluminum mold, the 
mold was locked under 20kg/cm.sup.2. Injection of the resin into the mold 
was made under an injection pressure of 150kg/cm.sup.2 with a four mixing 
head RIM injector, product of Krauss-Maffei, used, and the duration from 
the time of start of the injection to the time of the resin flowing out of 
the clearance on the opposite side was taken as the injection time and 
shown as such. 
Forming and tackiness: By visual observation. 
Physical properties: JIS Designation K-6911. 
TABLE 4-1 
______________________________________ 
Curing agents 
Resin compositions 
(A to D) 
(in parts) A B C D 
______________________________________ 
Example 
6 PEA-3 100 3 0.3 -- -- 
7 PEA-4 100 3 0.3 -- -- 
8 VE-1 100 3 0.3 -- -- 
9 VE-1 100 -- -- 1.0 0.15 
10 PEA-3 30 VE-1 70 3 0.3 -- -- 
11 PEA-6 100 3 0.3 -- -- 
12 VE-5 100 3 0.3 -- -- 
13 VE-1 50 PE-1 50 3 0.3 -- -- 
Comparative 
Example 
8 PEA-1 100 3 0.3 -- -- 
9 PEA-2 100 3 0.3 -- -- 
10 PEA-5 100 3 0.3 -- -- 
11 VE-2 100 3 0.3 -- -- 
12 VE-3 100 3 0.3 -- -- 
13 VE-4 100 3 0.3 -- -- 
14 Acrylurethane 
100 3 0.3 -- -- 
oligomer 
15 Hydroxyl group 
100 (Note) 
containing 
acryl oligomer/ 
Polyisocyanate, 
solution type 
16 VE-2 100 1.5 0.2 
______________________________________ 
A 50% Benzoyl peroxide 
B Dimethylpara-toluidine 
C Acetoacetic ester peroxide 
D 6% Cobalt naphthenate 
(Note) 
(1) 6% Cobalt naphthenate: 0.1 (part) 
(2) Dibutyltin-dilaurate: 0.1 
(3) Tertiary butyl perbenzoate: 2.6 
(4) Diphenylmethane diisocyanate: 51.1 
__________________________________________________________________________ 
Molding 
conditions 
(E and F) 
Results (G-N) 
E F G H I J K L M N 
__________________________________________________________________________ 
Example 
6 50 150 
2 1'40" 
13" 
3'00" 
No No 12.0 
1300 
7 50 150 
3 2'00" 
18" 
3'00" 
No No 13.2 
1450 
8 70 150 
2 1'30" 
10" 
3'00" 
No No 15.0 
1500 
9 50 150 
2 1'10" 
13" 
3'00" 
No No 15.3 
1500 
10 50 150 
2 1'30" 
13" 
3'00" 
No No 15.5 
1480 
11 50 150 
3 3'00" 
30" 
5'00" 
No No 10.8 
1200 
12 50 150 
0.5 
3'30" 
7" 
7'00" 
No Yes 
12.8 
1050 
13 50 150 
2.3 
1'40" 
25" 
3'00" 
No No 16.0 
1580 
Comparative 
Example 
8 50 150 
1.2 
1' 40" 
10" 
3'00" 
No Yes 
11.2 
1000 
9 50 150 
10 11'40" 
30" 
15'00" 
(*) 
Yes 
9.2 
800 
10 50 150 
20 20'00" 
30 25'00" 
(*) 
Yes 
12.9 
1100 
11 50 150 
0.5 
3'20" 
7" 
5'00" 
** Yes 
7.5 
880 
12 50 150 
10 8'20" 
30" 
10'00" 
No Yes 
12.1 
1200 
13 50 150 
20 15'30" 
30" 
3'00" 
(*) 
Yes 
13.8 
1400 
14 50 150 
0.7 
1'40" 
9" 
3'00" 
No Yes 
13.2 
806 
15 50 150 
5 1'30" 
15" 
3'00" 
*** 
No 7.2 
800 
16 100 
150 
2.3 
1'00" 
7" 
7'00" 
# No 15.1 
1300 
__________________________________________________________________________ 
E Mold temperature (.degree.C.) 
F Injection pressure (kg/cm.sup.2) 
G Viscosity at 25.degree. C. (poise) 
H Cure characteristic at 50.degree. (min, sec) 
Molding time at 50.degree. (min, sec) (below I-N) 
I Injection time (sec) 
J Molding time (min, sec) 
K Mold product foaming 
L Burr tackiness 
M Tensile strength (kg/mm.sup.2) 
N Tensile modulus of elasticity (kg/mm.sup.2) 
* Improper impregnation 
** Much cavity 
*** More or less foaming 
# Much foaming with cracking partially 
As seen from Table 4, Comparative Examples 8, 10, 11 and 13 using an 
unsaturated polyester acrylate or epoxy acrylate out of the range of the 
number average molecular weight of the present invention were inferior in 
the fast curing performance, moldability, foaming performance, tackiness 
and tensile strength and other physical properties. Comparative Examples 9 
and 12 using a styrene monomer in place of the methyl methacrylate monomer 
were inferior in fast curing performance, tackiness and physical 
properties. On the other hand, according to the manufacturing method of 
mold under the present invention, the products were all distinguished in 
the fast curing performance, non-tackiness, non-foaming and fast 
moldability.