JP2961610B2 - Method for producing resin composition and molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fiber-reinforced thermosetting plastic (hereinafter referred to as FRP).
Resin injection molding (hereinafter referred to as “resin transfer molding (RTM)”).
The present invention relates to a resin composition having excellent high-speed curability and crack resistance when used for R-RIM, and a method for producing a molded article using the same.

(Prior art)

Since RTM (R-RIM) can be molded at low pressure and low temperature, it has the feature that it can reduce capital investment such as die and press charges. However, there are problems in productivity and moldability.

[Problems to be solved by the invention]

That is, in order to satisfy these requirements, a resin composition having high-speed curability and excellent crack resistance is required. However, unsaturated polyester resin compositions according to the prior art, for example, Japanese Unexamined Patent Publication No.
A polymerizable composition comprising an and / or acrylate monomer and a compound having a (meth) acrylate group is described. However, the purpose is to improve the odor of the unreacted volatile unsaturated monomer (styrene and the like) of the molded product, and since the compound having a (meth) acrylate group has a low molecular weight and does not have a hydroxyl group, the curing time ( If the time from the addition of the curing agent to the maximum curing heat generation) is increased, the gel time (the time from the addition of the curing agent to the loss of fluidity) becomes extremely short, causing gelation during injection or cracking of the molded product. There was a problem that occurred. Therefore, to prevent cracking, for example, blending a thermoplastic resin such as polyvinyl acetate or polystyrene with an unsaturated monomer solution of unsaturated polyester, or lowering the unsaturated acid content in unsaturated polyester,
The crosslink concentration is adjusted. However, if cracks are prevented by these methods, there is a problem that the curing time becomes extremely long and the mechanical strength of the molded product is reduced, that is, it is not possible to satisfy both productivity and moldability at the same time. Was.

[Means for solving the problem]

The present inventors have conducted intensive studies on resin compositions capable of simultaneously satisfying both high-speed curability and moldability. As a result, unsaturated polyesters and oligomers having a specific molecular weight with a (meth) acrylate group at the molecular end are shown. By dissolving this mixture in a (meth) acrylic acid methyl ester monomer and using it, a resin composition excellent in high-speed curability and crack resistance and a method for producing a molded product thereof have been completed. That is, the present invention relates to (I) a (meth) acrylate group having a number average molecular weight of 900 to 3,000 in terms of polystyrene obtained by a GPC measurement method and having two or more molecular terminals, Oligomers selected from epoxy acrylates and / or unsaturated polyester acrylates having an amount of meth) acrylate groups of 10% by weight or more, and unsaturated polyesters having a molecular weight of less than 370 per double bond (not dicyclopentadiene). Resin consisting of
50-70% by weight (II) methyl methacrylate monomer
A resin composition comprising 30 to 50% by weight and having a viscosity (25 ° C.) of 3 poise or less, and a resin composition having a viscosity (25 ° C.) of 3 poise or less (I) obtained by a GPC measurement method. Number average molecular weight of 900 to 3
000 and the terminal of the molecule is two or more (meth) acrylate groups, and the amount of the (meth) acrylate group is 10
50 to 70% by weight of a resin composed of an oligomer selected from epoxy acrylate and / or unsaturated polyester acrylate having a molecular weight of not less than 370% by weight and an unsaturated polyester having a molecular weight of less than 370 per double bond (not dicyclopentadiene). And (II) a resin composition comprising 30 to 50% by weight of a methacrylic acid methyl ester monomer is poured into a mold previously filled with a reinforcing material, and molded at 80 ° C. or less. It provides the law.

〔Constitution〕

The unsaturated polyester of the present invention refers to an unsaturated dibasic acid.
20 to 70% by weight, and if necessary, an acid component containing a saturated polybasic acid and a polyhydric alcohol component in an equivalent ratio,
The term refers to an unsaturated polyester obtained by a one-to-one reaction. If the amount of the unsaturated dibasic acid is less than 20% by weight, the curability will be poor, and if it is more than 70% by weight, the crack resistance will be poor. Examples of the unsaturated dibasic acid component constituting the unsaturated polyester include known and commonly used α, β-unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, metaconic acid and chlorinated maleic acid. There are acids or their anhydrides.

In addition, maleic anhydride is preferable as the unsaturated dibasic acid.

The saturated polybasic acid component which can be used in combination if necessary includes, for example, phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, cis-3-methyl-4-cyclohexene-
Cis, cis-1,2-dicarboxylic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalic acid, monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, heptic acid, tetrabromophthalic acid, sebacic acid, succinic acid, adipic acid Known and commonly used saturated acids such as glutaric acid, pimelic acid, trimellitic acid, and pyromellitic acid, or anhydrides or esters thereof can be used.

Examples of the alcohol component of the unsaturated polyester include 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, glycerin, pentaerythritol, ethylene oxide or propylene oxide adduct of hydroquinone, EO or PO adduct of bisphenol A, hydrogenated bisphenol A and known polyhydric alcohols such as tricyclodecane dimethylol. Particularly, propylene glycol is preferred.

The oligomer having a (meth) acrylate group at the molecular end of the present invention is a resin preferably having a straight chain and having a hydroxyl group as a side chain, and is composed of (meth) acrylic acid or hydroxy (meth) acrylate, or glycidyl (meth) acrylate. ) A compound in which an acrylate is derived from the molecular main chain, its chain or both ends of the main chain. Is contained in an amount of 10% by weight or more, preferably 20% by weight to 40% by weight.

The number average molecular weight of the (meth) acrylate group-containing oligomer of the present invention is equivalent to a polystyrene-equivalent value obtained based on a GPC (abbreviation for gel permeation chromatography) measurement method, and is not necessarily a true number. Although it does not show the average molecular weight, it is shown by a convenient GPC measurement method. Its value is between 900 and 3000, preferably between 1000 and 2800. If the molecular weight is less than 900, the resulting molded product may have tackiness or the like, or the physical properties such as tensile strength may be inferior.If the molecular weight is more than 3000, the foaming property of the molded product, and the molding time may be long, resulting in poor productivity. It will be.

The oligomer of the present invention specifically refers to epoxy acrylate and polyester acrylate, and is preferably epoxy acrylate.

The epoxy acrylate is an epoxy acrylate obtained by reacting a polyepoxide (epoxy resin) with an α, β unsaturated monobasic acid in an equivalent ratio of 1: 2. That is, it refers to an epoxy acrylate in which the middle of the main chain is polyepoxide and both ends have a (meth) acrylate group.

Typical examples of the polyepoxide (epoxy resin) include a condensate of a polyhydric phenol ring and (methyl) epichlorohydrin. Examples of the polyhydric phenols include bisphenol A and 2,2′-bis ( 4-hydroxyphenyl) methane (commonly known as bisphenol F),
Examples include halogenated bisphenol A, resorcinol, tetrahydroxyphenylethane, phenol novolak, cresol novolak, bisphenol A type novolak, and bisphenol F type novolak. Alcohol ether type epoxy compounds obtained from polyols such as ethylene glycol, butanediol, glycerin, polyethylene glycol, polypropylene glycol, alkylene oxide adducts of bisphenols and (methyl) epichlorohydrin; diaminodiphenylmethane, diaminophenylsulfone,
Glycidylamine obtained from anilines such as p-aminophenol and (methyl) epichlorohydrin; various glycidyl esters based on acid anhydrides such as phthalic anhydride, tetrahydro or hexahydrophthalic anhydride; and 3,4- Alicyclic epoxides such as epoxy-6-methylcyclohexylmethyl and 3,4-epoxy-6-methylcyclohexylcarbonate. Those having a bisphenol skeleton are preferred.

Typical examples of the α, β unsaturated monobasic acid include acrylic acid and methacrylic acid. The number average molecular weight of the epoxy acrylate is preferably from 900 to 2500, more preferably from 1300 to 2200. If the number average molecular weight is less than 900, the resulting molded product may have adhesiveness or physical properties may be inferior, and if the number average molecular weight is greater than 2500, foamability of the molded product,
Also, the molding time is long, the high-speed curability is poor, and the productivity is also poor.

The unsaturated polyester acrylate having a (meth) acrylate group at the molecular terminal of the present invention is a saturated polybasic acid or an anhydride thereof, and if necessary, an acid component containing an unsaturated polybasic acid or an anhydride thereof and an alcohol component are equivalent. Unsaturated polyester obtained by reacting to have a ratio of 2 to 1, ie,
It refers to an unsaturated polyester acrylate obtained by adding an unsaturated glycidyl compound to an unsaturated polyester containing a carboxyl group at both ends of the molecule.

Examples of the unsaturated glycidyl compound which is one component of the polyester include known and commonly used compounds such as glycidyl esters of acrylic acid and unsaturated monobasic acid of methacrylic acid, such as glycidyl acrylate and glycidyl methacrylate. . Incidentally, glycidyl methacrylate is preferred as such an unsaturated glycidyl compound.

Examples of the dibasic acid component include phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, cis-3-methyl-
4-cyclohexene-cis, cis-1,2-dicarboxylic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalic acid, monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, heptic acid, tetrabromophthalic acid, sebacic acid, succinic acid Known and commonly used saturated acids such as acid, adipic acid, glutaric acid, pimelic acid, trimellitic acid, and pyromellitic acid, or anhydrides or esters thereof can be used. Preferably, isophthalic acid is good.

Unsaturated polybasic acids or anhydrides which may be used in combination as needed include known and commonly used α, β-unsaturated acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, metaconic acid and chlorinated maleic acid. There are polybasic acids or their anhydrides.

As the alcohol component of the polyester acrylate, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 4-butylene glycol, neopentyl glycol, hexylene glycol, octyl glycol, trimethylolpropane, glycerin, pentaerythritol, ethylene oxide or propylene oxide adduct of hydroquinone, EO or PO adduct of bisphenol A, hydrogenated bisphenol A, tri Known and commonly used polyhydric alcohols such as cyclodecane dimethylol are exemplified. Particularly, a rigid glycol having a bisphenol skeleton is preferable.

The number average molecular weight of the unsaturated polyester acrylate is
It is preferably from 1500 to 3000, more preferably from 1800 to 2800. If the number average molecular weight is less than 1500, the molded product obtained will have tackiness or poor physical properties such as tensile strength, and if it is more than 3000, the foaming property of the molded product and the molding time will be long, and high speed curing The productivity becomes poor, and the productivity also worsens.

In the present invention, the mixing weight ratio of the unsaturated polyester (a) and the oligomer (b) having a molecular terminal (meth) acrylate group is (a) :( b) = 5: 95 to 95: 5, preferably 20: 80-80: 20. If the amount of the unsaturated polyester is less than 5 parts by weight, sufficient tensile strength and elastic modulus cannot be obtained, and if it is more than 95 parts by weight, there is a problem that the curing property is deteriorated.

The resin in the present invention is 50 to 70% by weight. If the amount is less than 50% by weight, the curability deteriorates, and the surface of the resin flowing out of the mold remains sticky forever. However, the molding time is prolonged, and the crosslink density is not sufficiently increased, resulting in poor physical properties such as tensile strength.

In the present invention, the resin is dissolved and used in 30 to 50% by weight of methacrylic acid methyl ester. This point is also important as described above. The use of methacrylic acid methyl ester in the present invention is particularly important for obtaining high-speed curability (molding time: about 3 minutes). However, it does not prevent the use of other vinyl monomers in a small amount so as not to impair the effects of the present invention.

If necessary, the resin composition of the present invention may contain a thickener, a coloring agent, a reinforcing material, a filler, a curing catalyst, a curing accelerator, a curing retarder, an internal release agent, a low-shrinking agent, and the like. good.

As a thickening agent, a hydroxyl group, a carboxyl group, an ester bond, or the like of the resin is chemically bonded to form a linear or partial cross-link, thereby increasing the molecular weight and increasing the viscosity of the unsaturated polyester resin. Having, for example, diisocyanates such as toluene diisocyanate,
Examples thereof include metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy; 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 the thickener used is usually 0.2 to 10 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the resin composition. If necessary, a small amount of a highly polar substance such as water can be used as a thickening aid.

As the colorant, any of conventionally known organic and inorganic dyes and pigments can be used. Among them, heat resistance and transparency are excellent, and curing of unsaturated polyester and oligomer having a molecular terminal (meth) acrylate group is remarkably hindered. Those that do not are preferred.

As the reinforcing material used in the present invention, glass fibers are generally mentioned, and in addition, organic fibers such as vinylon, polyester, phenol, polyvinyl acetate, polyamide, and polyphenylene sulfide, asbestos, carbon fibers, metal fibers, and ceramics. Inorganic fibers such as fibers are also included. Its shape is strand, knitted fabric,
It is a nonwoven fabric of a flat and three-dimensional shape. Further, as the reinforcing material, not limited to fibers, polyurethane foam,
Plastic foams such as phenol foam, vinyl chloride foam and polyethylene foam; cured products of hollow bodies such as glass and ceramic; solids such as metal, ceramic, plastic, concrete, wood and paper, molded products, and honeycomb-shaped structures And the like.

Fillers include calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose thread, silica sand, river sand, cold water stone, marble waste,
Known materials such as crushed stones may be mentioned, and among them, glass powder, aluminum hydroxide, barium sulfate and the like are preferable because they impart translucency upon curing.

As the curing accelerator, a metal compound is added as necessary. Examples of such a metal compound include cobalt naphthonate, cobalt octonate, divalent acetylacetone cobalt, trivalent acetylacetone cobalt, potassium hexoate, Zirconium naphthonate, zirconium acetylacetonate, vanadium naphthonate, vanadium octonate, vanadium acetylacetonate, vanadyl acetylacetonate, metal compound accelerators generally used in unsaturated polyester resins such as lithium acetylacetonate are used. They may be used in combination, or may be used in combination with other accelerators such as amines, phosphorus-containing compounds, and β-diketones.

The addition amount of such a curing accelerator is appropriately adjusted depending on the gelation time, but preferably, the resin composition 100
0.0001 to 0.12 parts by weight based on parts by weight. In the case of molding at a medium temperature or higher (40 ° C. or higher), this curing accelerator may or may not be used.

The curing catalyst acts on an unsaturated polyester or an oligomer having a terminal (meth) acrylate group, for example, an azo compound such as azoisobutyronitrile, tertiary butyl perbenzoate, tertiary butyl peroctoate, or benzoyl. Organic peroxides such as peroxide, methyl ethyl ketone peroxide, acetoacetate peroxide, and dicumyl peroxide, etc., can be used. Based on 100 parts by weight of the resin composition, 0.1 to 4 parts by weight, preferably 0.3 to 4 parts by weight. Used in the range of 3 parts by weight.

Preferred are redox curing agents such as acetoacetic ester peroxide-cobalt naphthenate and benzoyl peroxide-dimethyl paratoluidine.

Examples of the curing retarder include hydroquinone, toluhydroquinone, tertiary butyl catechol, and naphthenic steel, and are preferably used in an amount of 0.0001 to 0.1 part by weight based on 100 parts by weight of the resin composition.

Examples of the internal release agent include stearic acid, higher fatty acids such as zinc stearate, higher fatty acid esters, and conventionally known compounds such as alkyl phosphate esters. It can be used in a ratio of 0.5 to 5 parts by weight.

The low-shrinking agent is a thermoplastic resin, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, lower alkyl esters of acrylic acid or methacrylic acid such as ethyl acrylate, styrene, vinyl chloride, and acetic acid. Homopolymers or copolymers of monomers such as vinyl, at least one of the vinyl monomers, lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxylalkyl acrylate or methacrylate, acrylonitrile, methacrylonitrile , Acrylic acid, methacrylic acid, cetyl stearyl methacrylate, at least one copolymer of monomers, cellulose acetate butyrate and cellulose acetate propione DOO, polyethylene, polypropylene, saturated polyester. These may be added if necessary without deteriorating the effects of the present invention, depending on the application.

The present invention can be cured by heating with various peroxides added, or can be cured with actinic rays such as ultraviolet rays with various photosensitizers added, It is hardened and has excellent mechanical strength.

The resin composition used in the present invention preferably has a viscosity of 25.
It has a viscosity of less than 3 poise at ° C. However, the composition is not necessarily required to be 3 poise or less at room temperature. When the composition is injected (or injected) into a mold, the viscosity can be reduced to 3 poise or less by means such as heating, and the effect of the present invention can be achieved. Good. This viscosity is due to the fact that, when injected (or injected) into an R-RIM molding machine, the injection (or injection) is very easy. If the viscosity is higher than 3 poise, the injection (or injection) step requires time, and the productivity is reduced.

In the method for producing a molded article of the present invention, the composition is divided into two parts, and a curing agent (peroxide) is added to one of the two parts (A component).
On the other hand, an accelerator is added (A 'component), and the two components of AA' are added to each other in a separate line under high pressure (injection pressure), preferably 5
Injection (injection) for a short time, preferably 0.1 to 30 seconds, particularly preferably 0.5 to 20 seconds, while circulating at ~ 200 kg / cm ² , particularly preferably 80-150 kg / cm ² , with the reinforcement filled mold It is carried out in a mold at a temperature of preferably 10 to 80 ° C, especially 40 to 70 ° C, and a mold pressure of preferably 5 to 100 kg / cm ² , especially 20 to 50 kg / cm ² .

In the present invention, molding is performed at a molding temperature (mold temperature) of 80 ° C. or less. However, if molding is performed at a temperature higher than 80 ° C., methacrylic acid methyl ester monomer is likely to be vaporized. This is unfavorable because it easily causes cracks.

Further, in the present invention, the mold is filled with the reinforcing material, then the mold is closed, and the composition is injected (or injected) to be molded. This is performed by putting the reinforcing material into the composition and injecting (or injecting). In the related art, high strength physical properties could not be obtained because a short fiber reinforcing material was used. Furthermore, conventional RTMs use long fibers as reinforcement, but if the injection time is shortened, the reinforcement will flow more easily due to the high-viscosity resin composition, resulting in non-uniform mechanical strength distribution, and only defective molded products will be obtained. Because he couldn't.
In the present invention, since there is no such a problem, a uniform molded product having high mechanical strength can be obtained.

The number average molecular weight defined in the present invention refers to a value measured under the following measurement conditions of GPC (gel permeation chromatography).

GPC: Nippon Kagaku Kogyo Co., Ltd. LC-08 type Column: SHODEX A-804 + A-803 + A-802 + A-801 (Showa Denko) Solvent: THF (Tetrohydrofuran) Calibration curve preparation standard sample: Polystyrene (Tosoh product) Detection Machine: pointing refractometer (manufactured by Nippon Kagaku Kogyo Co., Ltd.) The present invention can be cured by heating with various peroxides added thereto, or can be UV-cured with various photosensitizers added. And the like, and it can be cured by actinic rays, and the cured molded product has excellent mechanical strength with very few bubbles.

〔effect〕

INDUSTRIAL APPLICABILITY The present invention has excellent high-speed curability and crack resistance, and is therefore extremely excellent as a resin composition for RTM.

Hereinafter, the present invention will be described in more detail with reference to examples. Note that “parts” indicates parts by weight.

Reference Example-1 [Preparation of unsaturated polyester (PE-1)] 540 g of maleic anhydride and 460 g of 1-2 propylene glycol were heated and dehydrated and condensed in an inert gas stream at 220 ° C for 10 hours to obtain an acid value of 30. Was. Hydroquinone 0.
15 g was added and cooled to 120 ° C. Next, this solid content was dissolved in 600 g of methyl methacrylate monomer to obtain an unsaturated polyester having a nonvolatile content of 60.2%, a viscosity of 3.8 poise (at 25 ° C.), an acid value of 18.6 and an unsaturated dibasic acid content of 59.9% by weight. Was.

Reference Example-2 [Preparation of unsaturated polyester (PE-2)] Maleic anhydride (237 g), phthalic anhydride (358 g) and 1-2 propylene glycol (405 g) were mixed in an inert gas stream at 220 ° C for 10 days.
Heat dehydration condensation was carried out to obtain an acid value of 28. 0.15 g of hydroquinone was added thereto and cooled to 120 ° C. Next, this solid content was 390 g of methacrylic acid methyl ester monomer.
Dissolved in, resin solid content 70.1%, viscosity 4.0 (at 25 ℃),
An unsaturated polyester having an acid value of 17 and an unsaturated dibasic acid content of 26% by weight was obtained.

Reference Example-3 [Preparation of unsaturated polyester (PE-3)] 152 g of maleic anhydride, 459 g of phthalic anhydride and 389 g of 1-2 propylene glycol were mixed at 220 ° C in an inert gas stream at 10 ° C.
Heat dehydration condensation was carried out to obtain an acid value of 25. 0.15 g of hydroquinone was added thereto and cooled to 120 ° C. Next, the solid content of methacrylic acid methyl ester monomer 600 g
To obtain an unsaturated polyester having a resin solid content of 60%, a viscosity of 2.8 (at 25 ° C.), an acid value of 15, and an unsaturated dibasic acid content of 16.6% by weight.

Reference Example-4 [Styrene type unsaturated polyester (PE-4)
Preparation of maleic anhydride 540 and 1-2 propylene glycol 4
60 g of the resulting product was heated and dehydrated and condensed at 220 ° C. for 10 hours in a stream of inert gas to obtain an acid value of 29. 0.15g of hydroquinone
And cooled to 120 ° C. Next, this solid content was dissolved in 600 g of a styrene monomer to obtain a resin solid content of 59.8% and a viscosity of 6.
2 Poise (at 25 ℃), unsaturated dibasic acid content of acid value 16.5 5
9.9% by weight of a styrene-type unsaturated polyester was obtained.

Reference Example-5 [Preparation of Epoxy Acrylate (AC-1)] In a three-necked flask equipped with a thermometer, a stirrer, and a condenser, "Epiclon 85" having an epoxy equivalent of 185 obtained by the reaction of bisphenol A and epichlorohydrin was added.
0 "[Epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.]
1850 g (equivalent to 10 epoxy groups), 860 methacrylic acid
g (equivalent to 10 carboxyl groups), 1.3 of hydroquinone
6 g and 10.8 g of triethylamine were charged and heated to 120 ° C., and the reaction was continued at the same temperature for 10 hours to obtain an acid value of 3.5.
Thus, a liquid epoxy acrylate having an epoxy equivalent of 15,000 or more and a color number of 2 was obtained. This epoxy acrylate was dissolved in 2217 g of methacrylic acid methyl ester monomer to obtain a nonvolatile content of 55%, an acid value of 2, a viscosity of 2 poise at 25 ° C., and a content of (meth) acrylate group in solid content of 31.4% by weight.
4920 g of the resulting epoxy acrylate was obtained.

Reference Example-6 [unsaturated polyester acrylate (AC-
2) Preparation of 166 g (1 mol) of isophthalic acid and 152 g (2 mol) of 1-2 propylene glycol at 220 ° C. in an inert gas stream.
The product was heated and dehydrated and condensed for an hour to obtain a solid having an acid value of 5. This was cooled to 100 ° C. Next, maleic anhydride 196
g (2 mol) was charged and heated and dehydrated and condensed at 200 ° C. for 5 hours to obtain a solid having an acid value of 254. Hydroquinone
0.15 g was added, and the mixture was cooled to 140 ° C. Next, 284 g (2 mol) of glycidyl methacrylate was charged and reacted at 140 ° C. for 10 hours to obtain a solid having an acid value of 10. This unsaturated polyester acrylate is converted to methacrylic acid methyl ester monomer 50.
Dissolved in 8g, nonvolatile content 60.5%, viscosity 25 ° C, 0.5 poise,
1270 g of an unsaturated polyester acrylate having an acid value of 6.1 and an acrylate group content in the solid content of 23.4% by weight was obtained.

Reference Example-7 [Styrene-type epoxy acrylate (AC-
Preparation of 3)] In a three-necked flask equipped with a thermometer, a stirrer, and a condenser, “Epiclon 85” having an epoxy equivalent of 185 obtained by the reaction of bisphenol A and epichlorohydrin was prepared.
0 "[Epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.]
1850 g (equivalent to 10 epoxy groups), 860 methacrylic acid
g (equivalent to 10 carboxyl groups), 1.3 of hydroquinone
6 g and 10.8 g of triethylamine were charged and heated to 120 ° C., and the reaction was continued at the same temperature for 10 hours to obtain an acid value of 3.5.
Thus, a liquid epoxy acrylate having an epoxy equivalent of 15,000 or more and a color number of 2 was obtained. This solid content was dissolved in 1800 g of styrene monomer to obtain a nonvolatile content of 60.3% and an acid value of 2.
1. 4,500 g of a styrene-type epoxy acrylate having a viscosity of 25 ° C. and 10 poise and a methacrylate group content of 31.4% by weight in a solid content was obtained.

Reference Example-8 [unsaturated polyester acrylate (AC-
Preparation of 4)] 133 g (0.8 mol) of isophthalic acid, 76 g (1 mol) of 1,2 propylene glycol and 324 g (1 mol) of an adduct of bisphenol A with 2 mol of ethylene oxide are heated at 220 ° C. for 9 hours in an inert gas stream. By dehydration condensation, a solid having an acid value of 3 was obtained. This was cooled to 100 ° C. Next, 147 g (1.5 mol) of maleic anhydride was charged and heated and dehydrated and condensed at 200 ° C. for 6 hours to obtain a solid having an acid value of 37. 0.16 g of hydroquinone was added thereto and cooled to 140 ° C. Next, 85 g (0.6 mol) of glycidyl methacrylate was charged and reacted at 140 ° C. for 6 hours to obtain a solid having an acid value of 10. This unsaturated polyester acrylate is dissolved in 456 g of methacrylic acid methyl ester monomer to obtain a nonvolatile content of 60.2%, an acid value of 6, and a viscosity of 25 ° C.
At 20 poise, and the acrylate group content in the solid content 7.
1088 g of a 2% by weight unsaturated polyester acrylate were obtained.

Reference Example 9 [Preparation of Epoxy Acrylate (AC-5)] Same as Reference Example 5 except that instead of Epicron 850 of Reference Example 5, 5000 g of Epicron 1050 having an epoxy equivalent of 500, 860 g of methacrylic acid, 2.93 g of hydroquinone, and 21.6 g of triethylamine were used. To obtain a solid epoxy acrylate. This epoxy acrylate was dissolved in 4975 g of methacrylic acid methyl ester monomer to obtain 10835 g of an epoxy acrylate having a nonvolatile content of 55%, an oxidation of 2, a viscosity of 2.8 poise (25 ° C.), and a (meth) acrylate group content of 14.7% by weight. .

Table 1 summarizes various properties of the resin compositions obtained in Reference Examples 1 to 9.

Example-1 As Example-1, the resin VE-1 obtained in Reference Example-1, acetoacetate ester peroxide (Percure SA, manufactured by NOF Corporation) and 6% cobalt naphthenate were blended in the proportions shown in Table 2. . The results are shown in the same table. Examples 2 to 5
In the case of Comparative Examples 1 to 7, the same method as in Example 1 was used. In addition, the measurement of various performances is based on the following method.

硬化 Curability: Determined from a torque-time curve at 50 ° C by Curastometer III (manufactured by Nippon Synthetic Rubber Co., Ltd.).

○ Viscosity: steady flow viscometer at 25 ° C (Rheometer manufactured by Iwamoto Seisakusho)
IR-200) RTM molding test: A preforming mat adjusted to have a glass content of 30% by weight was charged into a 600 × 800 mm box forming electroform, and then clamped at 20 kg / cm ² . The mold was injected into the mold at a pump pressure of 6 kg / cm ² using an IP-6000 type injector manufactured by Applicator. At that time, the time from the start of the injection to the time when the injected resin liquid flowed out from the clearance on the opposite side was shown as the injection time.

As is clear from Table 2, the composition of the present invention was excellent in high-speed curability, crack resistance, tensile strength, tensile modulus and Barcol hardness.

Example 6 100 parts by weight of PE-1 and AC-1 (50:50, weight ratio) of Example 4 were divided into two parts of 50 parts by weight, and one part was added with 6 parts by weight of 50% benzoyl peroxide, and the other part was added. 0.6 parts by weight of dimethyl paratoluidine was added to the mixture, and each resin solution was mixed in a four-mixing-head type RIM injector (KRAUSS-MAFFEI) to 150 parts.
was circulated at a pressure of kg / cm ^2, glass content in advance 50 wt%
A preforming mat prepared so as to obtain a mold temperature of 50
The resin liquid was filled into an aluminum mold at a temperature of ²⁰⁰ ° C. and clamped at a pressure of 20 kg / cm ² to inject (inject) the resin liquid to obtain a molded product.

The viscosity of the resin liquid is 1.8 poise (25 ° C), the curing property (50 ° C) is 130 seconds, the injection time is 28 seconds, and the molding time is 3
00 seconds.

The molded product had no cracks (made of crack resistance: ○), had good curability (curability: ○), had no stickiness of burrs, and had a tensile strength of 15.3 kg / mm. ^2. Tensile modulus was 1480 kg / mm ² and Barcol hardness was 47.

The curability, viscosity and physical properties were the same as those described above. Injection time was as follows. A 50 × 100 × 0.3 (cm) aluminum mold was charged with a preforming mat having a glass content of 50%, and the mold was clamped at 20 kg / cm ^2.
The time from the start of the injection at the injection pressure of g / cm ² until the resin flowed out from the clearance on the opposite side was measured.

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Claims (3)

(57) [Claims] (I) a polystyrene-equivalent number average molecular weight obtained by a GPC measurement method of from 900 to 3,000,
And an oligomer selected from epoxy acrylates and / or unsaturated polyester acrylates having two or more (meth) acrylate groups at the molecular end and having an amount of (meth) acrylate groups of 10% by weight or more, Resin consisting of unsaturated polyester having a molecular weight of less than 370 (not dicyclopentadiene type) 50 to 70% by weight (II) Methyl methacrylate monomer 30 to 50% by weight Is 3 poise or less. (2) a polystyrene-equivalent number average molecular weight of 900 to 3,000, which has a viscosity (25 ° C.) of 3 poises or less and which is obtained by a GPC measurement method, and has two or more molecular terminals. An oligomer selected from an epoxy acrylate and / or an unsaturated polyester acrylate, which is a meth) acrylate group and the amount of the (meth) acrylate group is 10% by weight or more, and an unsaturated polyester having a molecular weight of less than 370 per double bond (Not dicyclopentadiene resin) 50-70% by weight (II) A resin composition consisting of 30-50% by weight of methacrylic acid methyl ester monomer is poured into a mold previously filled with a reinforcing material. Molding at 80 ° C. or lower. 3. The resin composition according to claim 1, wherein the oligomer is a linear resin having a hydroxyl group as a side chain.