TW548285B - Radical curing resin composition, method for producing the composition and molded product comprising the composition - Google Patents

Abstract

This invention is to obtain a quick-curing resin composition capable of sufficiently exerting inherent air curability of a dicyclopentenyl group-having resin composition and coloring little after being cured. The radical curable resin composition comprises a terpolymer (C) and a monomer (D) copolymerizable with (C) component, in which the terpolymer (C) is obtained by reacting, at a specific ratio, a reaction product (A) of a specific ratio of dicyclopentadiene and maleic acid with an epoxy resin (B) having 2 epoxy groups. Another radical curable resin composition comprises 100 pts.wt. (meth)acrylic syrup composition (E), 5-150 pts.wt., e.g. a specific terpolymer (G) obtained by reacting the reaction product of dicyclopentadiene and maleic acid with (B) component and, if necessary, 5-50 pts.wt. of, e.g. a vinyl ester resin (I).

Description

548285 V. Description of the invention (1) " ~ 1 " The present invention relates to a radical-curable resin composition, a method for producing the same, and a molded article made of the composition. More specifically, the present invention relates to a radically curable resin composition suitable for various fields such as fiber-reinforced plastic (FRP), lining (1 ining), injection molding, and coatings for gluing, a method for producing the same, and the composition. Manufactured molded products. Unsaturated polyacetic acid resins, ethylene resins, etc. are representative of so-called free radical curable resins. They can be used in a wide range of properties by using a variety of characteristics based on the raw materials used and the type and amount of polymerized monomers. field. However, radically curable resins have so-called anaerobic hardening properties that hinder polymerization due to oxygen in the air. There have been many studies to overcome this property, but no satisfactory solution has been found. Therefore, the vinyl ester resins of (meth) and acryloyl radicals and the radical curable resins using alkyl (meth) acrylate polymerizable monomers have strong anaerobic hardening properties, resulting in incomplete hardening and large amounts. The uncured monomers are not compatible. It is said that if dicyclopentyl (Uicyclopentenyi) is introduced into the skeleton of the radically curable resin, some degree of air-hardening i can be expected. In the case of resin, the problem of coloration during the production of resin (main Zri) The knot-chain transfer reaction will hinder the sclerosis of the sclerosis, thus causing the problem of slowing down the sclerosis rate. Block w2i! Ί) Acrylic resin composition is widely used in residential products due to its transparency, weather resistance, and excellent performance; it is widely used in residential plastics; rubber coatings and liners for outdoor products; Wave board, tablet, etc. τ Even in the conventional acrylic resin composition

548285

5. Description of the invention (2) The base curable resin composition 'still has a strong anaerobic hardening property, and it has the disadvantage that it cannot fully exert its performance by blocking the air and being unable to harden. If it is used in combination with conventional ally 1 ether compounds, etc., the radically hardenable (meth) acrylic resin can increase the air hardenability to some extent, but it is likely to cause allyl properties. The reaction of stopping the hydrogen atom should react with the chain transfer reaction, so the hardening reaction speed is slowed down, and it is difficult to complete the reaction. It is difficult to complete the reaction. When used in combination with a cyclopentyl ~ diluted unsaturated polyester containing a double bond with propylene group In the case of resins, it can improve air hardening properties. Unsaturated polyester resins containing a double-bonded dicyclopentenyl group having a propylene group have a high degree of coloration (yellow), and the discoloration resistance is also deteriorated. The fumaric acid α%, unsaturated-unsaturated double bond contained in the ester resin is difficult to copolymerize with (fluorenyl) acryloyl. Therefore, if used in combination, the overall discoloration of the resin composition, In view of the foregoing, an object of the present invention is to provide a resin composition having a dicyclopen tadiene (dicyclopen tadiene) that fully utilizes the original air-hardening property of the resin composition, and at the same time reduces the fast-hardening property of coloring after hardening. Resin group Manufacturing method and a molded article using the resin composition. The object of the present invention is to provide excellent transparency, weather resistance, and discoloration, and to ensure necessary molding even by an open mold (open mo 1 d) method. A radically curable resin composition having sufficient air-hardening properties for workability and moldability, and a molded article using the resin composition. The inventors have discovered that by combining a dicyclopentenyl group with a cis-form; Coexistence of a saturated double bond and a polymerizable monomer can significantly improve air hardenability and change rate, and at the same time, the reaction temperature when introducing a dicyclopentenyl group into the resin skeleton

Page 5 548285, description of the invention, below 17 0 c, and reacted in the presence of a metal ion blocking agent, the moon can prevent the oxidation of dicyclopentenyl in the reaction, and can obtain a tree with less color 'And completed the present invention. That is, the present invention is

(1) A product (A) reacted by a ratio of dicyclopentadiene 1.0 mol to maleic acid 0.8 to 2 mol, and an epoxy compound having two or more epoxy groups (B) 3 mol copolymer obtained by reacting 1 mol of the carboxyl group contained in the reaction product (a) and the epoxy group of the epoxy compound (B) at 0. 8 to 0. 98 mol. (C) A radical-curable resin composition obtained by dissolving in a polymerizable monomer (D) copolymerizable with the ternary copolymer (c) (Invention 1 (2) The radical-curability according to Invention 3 A resin composition in which the polymerizable monomer (D) contains an aliphatic polymerizable monomer as an essential component (Invention 2),

(3) A product (A) 'reacted with a ratio of 1.0 mole of dicyclopentadiene to 0.8 mole of maleic acid and 2 mole of maleic acid, and an epoxy compound (B) having two or more epoxy groups ) After reacting at a molar ratio of 1 mol of carboxyl group contained in the reaction product (A) and epoxy group (B) of 0.8 to 0.98 mol to obtain a 3-membered copolymer (C), The modified tertiary copolymer (c) obtained by addition reaction of the nitroxy group and the polybasic acid anhydride contained in the obtained tertiary copolymer is dissolved in a copolymer which can be copolymerized with the modified tertiary copolymer (q). The radically curable resin composition obtained by polymerizing the body (D) (Invention 3), (4) The radically curable resin composition according to Invention 3, wherein the polymerizable monomer (D) contains a fat A family polymerizable monomer is an essential component

2066-4592-PF (N) .ptd

548285

5. Description of the invention (4) (Invention 4), (5) A method for producing a radically curable resin composition, including: (1) In the presence of a metal ion blocking agent, a bicyclic The product (a (2) · epoxy compound (b) with 2 or more epoxy groups) reacted in the ratio of dipentyl 1 · 〇mol and maleic acid 0.8 ~ 1 · 2 mol in order to counteract the problem. The ternary copolymer (c) obtained by reacting 1 mol of the carboxyl group contained in the raw material (A) and the epoxy group of the epoxy compound (b) in a ratio of 0.8 to 9.8 mol and the following;

(3) Dissolving the obtained 3-membered copolymer (C) in a polymerizable monomer (D) (Invention 5) which can react with the 3-membered human body, " 3 (6) as the free radical of Invention 5 In the method for producing a curable resin composition, in i, a part or all of the polymerizable monomer (D) used for dissolving the ternary copolymer (C) in the reaction product (A) and the epoxy compound ( β) The reaction is performed in the presence of a reaction to obtain a ternary copolymer (Invention 6), (7) The method for producing a radically curable resin composition according to Invention 5, wherein the polymerizable monomer (D) Those containing an aliphatic polymerizable monomer as an essential component (Invention 7),

(8) The method for producing a radically curable resin composition is at 170, in the presence of a metal ion blocking agent. 〇Bicyclic dipenta

1. The product (A) reacted at a ratio of 〇mol and maleic acid 0.8 ~ h 2 mol is contained in the reaction product with the epoxy compound (B) U having 2 or more epoxy groups. 1 mol of carboxyl group and epoxy group of epoxy compound (B)

548285 V. Description of the invention (5) ~ " After the reaction of the ternary copolymer (c) obtained by the ratio of 0.8 to 098 moles, (3) · The ternary copolymer (C) contained in the obtained The modified ternary copolymer is obtained by the addition reaction of the hydroxyl group and polybasic acid anhydride, meaning (4). The modified ternary copolymer is dissolved in a polymerizable monomer that can react with the modified ternary copolymer. (D). σ — (9) The method for producing a radically curable resin composition according to Invention 8, wherein a part or all of the polymerizable monomer (D) used for dissolving the ternary copolymer (C) is in The reaction product (a) is present when reacting with the epoxy compound (B) and reacts to produce a ternary copolymer (Invention 9) ^ (1 0) The method for producing a radical curable resin composition according to Invention 8 'Where the polymerizable monomer (D) contains an aliphatic polymerizable monomer as an essential component (Invention 10), (1 1) a radical curable resin composition composed of a (meth) acrylic acid slurry (E) 100 parts by weight, the number-average molecular weight obtained by adding the reaction product (F) of dicyclopentadiene and maleic acid to the epoxy compound (B) having two or more epoxy groups 800 ~ 250,000 ternary copolymer (G) and / or the modification obtained by the addition reaction of the hydroxyl group contained in the ternary copolymer with maleic anhydride or a polybasic anhydride containing maleic anhydride The ternary ternary copolymer (heart) is composed of 5 to 150 parts by weight (Invention 1U, (1 2)) The radical hardening as described in Invention 11. The resin composition further includes a polymerizable monomer (H) 5 to 2000 parts by weight (Invention 12), (1 3) The radically curable resin composition according to Invention 11, wherein the component (E) is Contains co-polymers of fluorenyl acrylic acid with alkyl fluorenyl acrylate

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The carboxyl group contained in the polymer is formed with an unsaturated glycidyl compound (Invention 1 3), (14) The radically curable resin composition according to Invention 11, which is derived from the (G) component and / or (Gi) The translocation rate of the maleic acid unit to the fumaric acid unit contained in the component is 70% or less (Invention 4), (15) a radical curing resin composition, which is composed of (meth) acrylic acid The slurry composition (E) is 100 parts by weight, plus the reaction product (F) of dicyclopentadiene and maleic acid, and is obtained by reacting with an epoxy compound (B) having two or more epoxy groups. Ternary copolymer (G,) having a number average molecular weight of 800 to 250,000, and / or the hydroxyl group contained in the ternary copolymer and a maleic acid needle or a polybasic acid anhydride containing maleic anhydride Modified 3-membered co-hydrate (5) to 150 parts by weight of the addition reaction, and 5 (5) of the hydroxyl group contained in the vinyl ester resin (I) and ethyl acetate resin (!) ~ 40% of modified vinyl ester resin (Ιι) obtained by addition reaction with maleic acid Xin and / or succinic anhydride (5) to 50 parts by weight (Invention 丨5), (1 6) The radically curable resin composition according to the invention 15, further comprising a polymerizable monomer (H) 5 to 200 parts by weight (invention 16), (1 7) as the invention 5 In the above-mentioned radically curable resin composition, the component (E) is a composition containing a reactant of a carboxyl group contained in a copolymerization of fluorenyl acrylic acid and fluorenyl alkyl acrylate with an unsaturated epoxypropyl compound ( Invention 17), (18) The radically curable resin composition according to Invention 15, wherein the maleic acid unit contained in the (G) component and / or (Gi) component is prepared as maleic acid Unit indexing rate is below 70% (invention 18),

2066-4592-PF (N) .ptd-page 9 548285 V. Description of the invention (7) (1 9) Invented by the first 1, 2, 3, 4, 11, 1 2, 1 3, 1 4, 1 The molded article manufactured by the radically curable resin composition according to item 5, 1, 6, 7 or 18 ° The radically curable resin composition according to the present invention 1 is characterized in 〇mol and the maleic acid 0.8 ~ 1.2 Moore reaction product (A), and the epoxy compound (B) with two or more epoxy groups to the reaction product (A) The ternary copolymer (c) obtained by reacting 1 mol of the carboxyl group and the epoxy group of the epoxy compound (b) at a ratio of 0.8 to 0.98 mol is dissolved in the ternary copolymer (C) Polymerized monomer. The radically curable resin composition of the third aspect of the present invention is a product (A) formed by the reaction of di-ene 1.0 mole with maleic acid 0.8 to 1.2 mole, and a ring having two or more epoxy groups. The oxygen compound (β) is a ternary copolymer obtained by reacting 1 mol of the carboxyl group contained in the reaction product (A) and the epoxy group of the epoxy compound (β) is 0.8 to 0.98. c) Afterwards, it is obtained by adding the aminooxy group contained in the polymer to polyacid test liver addition reaction? The Bayou copolymer (Cl) is obtained by dissolving in a polymerized monomer (D) copolymerizable with the modified 3-member copolymer (Q). According to the present invention, the radically curable resin composition of the present invention 1 and the base-curable tree curable composition of the present invention are used in a three-way copolymerization, in which the meta-polymer (Cl) and the polymerizable monomer (D) are used together, ( The residual monomers of the material are reduced, and the weather resistance is also excellent. Good quality, hardening and other excellent properties, in the presence of metal ion blocking agent M8285 V. Description of the invention

Γ Seeking hetero (C) or modified ternary * polymerization (Cl) field The aforementioned polymerizable monomer (D), if it is an essential component, is from 为 to ^ contains an aliphatic polymerizable monomer The point of view is better. & The above-mentioned excellent hardenability and weather resistance are produced by the production method of the radical hardening method 5 of the present invention. The resin composition is produced by, for example, the radical curing of the present invention 3, the production method of the present invention 8, and the like. The resin composition is by way of example. The manufacturing method of invention 5 firstly produces a product in which the dicyclopentadiene l Q mole and maleic acid are reacted at a ratio of 0.8 to 1.2 moles in the presence of a metal blocking agent. (A), the obtained reaction product (A) and the epoxy compound (B) having two or more epoxy groups, so that 1 mole of the radical of the reaction product (A) and the epoxy compound (b) The epoxy group was reacted at a ratio of 0.8 to 0.98 moles to produce a ternary copolymer (epoxy maleamine resin) (C). Thereafter, the produced ternary copolymer (C) is dissolved in a polymerizable monomer (D) that can be copolymerized with the ternary copolymer (C) to produce a radically curable resin composition. This makes it possible to prevent dicyclopentadiene and maleic acid from reacting in the presence of a metal blocking agent, thereby preventing the overall reaction system from being colored. And 'because the reaction temperature is below 170 ° C, it can prevent coloring and limit the cis-type α, ling-unsaturated double bond derived from maleic acid to be transposed to the trans-type α, /?- The unsaturated double bond is the minimum. In addition, because it is reacted with dicyclopentadiene 1.0 mole and maleic acid 0.8 ~~: L 2 mole, the dicyclopentadiene maleic acid can be obtained.

2066-4592-PF (N) .ptd Page 11 548285 V. Description of the invention (9) 'e Monoester. In addition, because the reaction product (a) has a molar ratio of 1 mol to the carboxyl group of the reaction product (a) and the epoxy group of the epoxy compound (B) has a molar ratio of 0.8 to 0.98 molar, the strength of the cured product can be obtained. The basic properties such as heat resistance, chemical resistance, etc. are fully utilized. Therefore, since the obtained ternary copolymer (C) is dissolved in a polymerizable monomer to form a radical-curable resin composition, excellent air-hardening properties are also maintained. The aforementioned metal ion blocking agent can prevent the oxidation of the dicyclobutenyl group when the reaction product of dicyclopentadiene and maleic acid is obtained, even if the resin composition has a (Hazen) number of 2000 or less, It can also be reduced to a Hazen number of 10,200 or even 10,000. At the same time, the storage stability is also significantly improved, and because it can ensure that the conventional radical-curing resin group containing dicyclopentadienyl group is well-known A large amount of polymerization inhibiting agent ί 3 t used for practical storage stability is used to reduce the occurrence of an appropriate effect without adversely affecting hardening. As a result of using the aforementioned metal ion blocking agent, the time for the complete completion of the chemical increase greatly, and can be reduced to promote hardening: more = the amount of monomer is below m, or even 0.8 weight; :: 0.6% by weight or less, and a hardened product (such as a molding port) having good properties and discoloration resistance can be obtained. & Ιί The blocking agent is not particularly limited as long as it is a compound having a conventional metal ion: lock- '. For example, mule blockade-

Caminocarbon) and agricultural chemicals, (alkenyl) phosphate and the glutamin acid, the salts of N-amination, (3) N-amination (Asparagin acid) and 548285 V. Description of the invention (ίο) These salts, (4) cold-diacetone inducer, (5) phenone inducer, etc. The detailed descriptions are shown below. These can be used alone or in combination of two or more. (1) The amine carbonic acid is preferably an amine carbonic acid having three or more carboxyl groups and its salts from the viewpoint of metal blocking ability. Specific examples include nitrilo tri acetic acid, ethylene diaminetetra acetic acid, diethylene triaminepenta acetic acid, triethylene tetramine hexaacetic acid ), Cyclohexene-1,2-diaminetetraacetic acid, N-hydroethylethyl diamine triacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid, ethylene diamine tetrapropionic acid, N-alkane -N, -carboxymethylaminodibutyric acid (aspar agin acid), N-lipenyl-N'-carboxymethylaminosuccinic acid, and alkali metal salts, alkaline earth metal salts, ammonium salts, etc. Amine salts, etc. (2) Examples of the monoalkyl phosphate, monoalkenyl ester, and the salts thereof include lauryl phosphoric acid and stearic acid phosphoric acid. (3) Examples of N-acylated glutamic acid, aminoaminosuccinic acid, and the salts thereof include, for example, commercially available amisohft HS-11, GS- 11 etc. (4) Examples of the cold-diketone inducer include acetylacetone and benzoylacetone. — (5) The phenone inducer may include, for example, pentoxin and thoracin. , 1 Among the aforementioned metal ion blocking agents, from the resistance of the good to have three bismuth Qi Xi ## 丁丁 耆 色 〖生生 点 彡, I am more carboxyl-containing amine I and its salts, of which Preferably

548285 V. Description of the invention (11) Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexanoacetic acid, cyclohexyl-1,2-diaminetetraacetic acid, N-hydroethylethyl ethylene Amine triacetic acid and its salts. The amount of the metal ion blocking agent used is 5 to 500 ppm, and more preferably 10 to the total amount of dicyclopentadiene and maleic acid (the amount of maleic acid when using maleic anhydride). 100 ppm, particularly preferably 15 to 50 ppm. When the amount of the metal ion blocking agent exceeds 50 ppm, it is made into a radical-curing resin composition (epoxy maleimide (ma 丨 eimi de) resin composition) and mixed with the resin composition to have a latex effect. When a hardening agent such as an organic peroxide is added to harden the radical, the added metal compound is trapped in the remaining metal ion blocking agent, and it is easy to hinder the radical hardening. If it is less than 5 ppm, it tends to be difficult to obtain a sufficient color reduction effect. The reaction between monocyclopentadiene and maleic acid can be carried out by, for example, dripping water in dicyclopentadiene and maleic anhydride. Furthermore, the reaction ratio of dicyclopentadiene to maleic acid is mol, and more preferably 1.0 to mol. When the reaction ratio of dicyclopentadiene to mol of maleic acid exceeds ·· 2 mol, the viscosity of the epoxy compound added in the subsequent step, (B), and the overall system of the system suddenly increase, and it becomes easy to harden. =, In the case of less than 0, ·, 8 moles, the maleic acid produced by dicyclopentadiene is increased by 1 $ ', which tends to reduce the 3-membered copolymer (epoxy maleimide on the month = The hardening reactivity of the resulting resin composition, the chemical resistance of the hardened product, and the basic properties of the green strength are degraded. The reaction of 1% pentadiene with maleic acid is described in丨 7 〇 ^ Following

548285 V. Description of the invention (12) line, usually 90 ~ 140 ° C, it is preferably 100 ~ 120 ° C for stable formation of single lipid. After completion of the above-mentioned reaction, the temperature is raised to 15 5 to 16 5 ° C after 0.5 to 2 hours, and the reaction is completed by maintaining the temperature to 0.5 to 2 hours. The produced reaction product (A) usually has characteristics such as an acid value of 200 to 290. The epoxy compound (B) that reacts the reaction product (A) is an epoxy compound having two or more epoxy groups in one molecule, and is, for example, a bisphenol A epoxy resin (commercial products are, for example, Manufactured by She 1 1 Chemical Co., Ltd. under the trade names of epicoat 828, epicoat 1001, and epicoat 1004, manufactured by Asahi Kasei Industries Co., Ltd. under the trade names of AER-664H, AER-331, and AER-337, and trade names of Dow Chemical Co., DER 330, D. Ε · R66 0, D · Ε · R · 64, manufactured by Toto Kasei Co., Ltd. under the trade names Epitote YD-127, Epitote YD-901, Epitote YDB-400, etc.) Acid (phenol novolak) type, o-phenol novolac type, bisphenol A novolac type, bisphenol F novolac type, brominated phenol novolac type, napht hoi novolac type phenolic epoxy resin, etc. (its market Examples of products sold are Dainippon INK Chemical Industry Co., Ltd.'s trade name EPICL0N N-665, Dow Chemical Co., Ltd. trade names DEN · 431, DEN · 438, Shell Chemical Co., Ltd. trade names epicoat 152, epicoat 154, Asahi Chiba ( Stock) manufacturing trade name EPN1138, Toto Kasei (share ) Manufactured under the trade name Epitote YDCN-704, etc.); Benzene-type bifunctional epoxy resin, epoxy-propyl ester of a polyvalent alcohol having a valence of 2 or more, preferably 2 to 3, such as neopentyl glycol diepoxy Propyl ester, polyethylene glycol bicyclo

2066-4592-PF (N) .ptd Page 15 548285

Oxypropyl s, polypropylene glycol dioxo propylene oxide, etc .; more than 2 valence is preferred < 2 = radical, trimethylolpropane triglycidyl ester, such as benzene dioxane Formic acid, divalent dibasic acid, trivalent or higher polyvalent carbonic acid propyl esters, etc., and propyl esters and adipic acid diepoxy resins represented by the general formula: 3 Rings with a dicyclopentadiene skeleton

(In the formula, R represents a hydrogen atom, a tooth atom, a nitrogen chain, a branched or cyclic alkyl group, a carbon number, and a carbon number of 1 to 10; a ^ group, a straight integer of 1 to 3, and a repeating unit n represents. ~ 5, alkoxy or phenyl, m represents the range of 15, and the average n integer of the repeating unit 11 and λ is on average 0 ~ 1% limonene = epoxide of phenol adduct, dicyclopentane Ethylene emulsion of diene naphthol adducts (for example, dicyclopentadiene resin (Mitsui Chemical Co., Ltd. product name: DPR-500, etc.) is reacted with epoxy resin by ordinary methods Shuyue said that commercially available products are, for example, Daiichiben I κ κ Chemical Co., Ltd. (trade names EPICLON HP-720 0, EPICRON HP-7200, etc.). These can be used alone or in combination of two or more. Proportion when the reaction product (A) is reacted with the epoxy compound (b)

The epoxy compound (B) is 1 mole of the carboxyl group contained in the reaction product (A).

2066-4592-PF (N) .ptd Page 16 548285 V. Description of the invention (14) The mounting oxygen is 0.8 ~ 0. 98 mole, from the stability of the reaction and hardened

In terms of basic performance, it is preferably 0.9 to 9595 moles. When the epoxy group contained in the reaction product (A) is less than 08 mol, the basic properties such as the strength of the hardened material are easily deteriorated. On the contrary, the strength is higher than 98 mol. Occasion 'Responsiveness to viscosity increase during the reaction is prone to cause gel incompatibility. 2. The reaction of the epoxy compound (B) with the aforementioned reaction product (A) of dicyclopentadiene and maleic acid is a reaction between an epoxy group and an enemy group. 13G or less, from the viewpoint of stability, it is better to score below 120. The lower limit is preferably 80 or more in terms of economics in which the reaction time is stopped within a certain time. The above reaction is carried out under the conditions, but as in the case of the present invention 6 described later, the reaction may be carried out in the presence of an associative early body (D). The specific examples of the esterification catalyst include tertiary amines such as difluorenylbenzylamine and triamine; and bismuth such as trimethylbenzyl ammonium gas compounds: bismuth, lithium lice, Inorganic salts such as chromium chloride; 2_ethyl_4_methylimidazole; Scale salts such as methyltriethylphosphonium chloride compounds, diethylethylphosphonium chloride compounds, benzylmethyldiphenylphosphonium chloride compounds, bromide compounds, etc .; secondary amines; tetrabutylurea; three Triphosphine 丄 tritoiyi phosphine; triphenyl isochronous, but the soil is not limited to this one. These can be used alone or in combination of two or more. The number average molecular weight of the produced ternary copolymer (C) is 8000 2500 ′, more preferably 850,000 to 150,000, and the weight average molecular weight is

2066-4592-PF (N) .ptd Page 17

548285 V. Description of the invention (15) '-20000' is more preferably 30000 ~ loooo, the acid value of the solid content is 3 ~ 20, more preferably 3 ~ 15, especially 5 ~ 丨 5 and The epoxy compound (b) is reacted to obtain the desired ternary copolymer (C). When the number average molecular weight is less than 800 ', the heat resistance of the molded product of the resin composition produced using the ternary copolymer (c) is insufficient, and when it exceeds 250,000, the reaction time increases, and the ternary copolymer ( C) The viscosity is increased, and gelation occurs and the coloring occurs.

Furthermore, the product (A) having a reaction ratio of 1.0 mol of dicyclopentadiene and 0.8 mol to 1.2 mol of maleic acid used in Invention 1 and an epoxy compound having two or more epoxy groups (B) a ternary copolymer obtained by reacting the epoxy group of the carboxyl group 1 mole 'epoxy compound (B) contained in the reaction product (a) at a ratio of 0.8 to 0.98 mole (C), usually the reaction product (F) of dicyclopentadiene and maleic acid used in Invention 11, and reacted with an epoxy compound (B) having two or more epoxy groups to obtain a number average molecular weight of 8 〇〇 ～ 2500 The 3-membered copolymer (G) is a 3-membered copolymer, and does not become the reaction product (F) of dicyclopentadiene and maleic acid used in Invention 11 and has more than 2 Epoxy-based epoxy compounds (B \ reactions are ternary copolymers having a number average molecular weight of 800 to 2500 ternary copolymers (g) outside the range. The aforementioned ternary copolymers (C) and copolymerizable The polymerizable monomer (D) 1 is a ternary copolymer (C) dissolved in the manufacture, and the viscosity is adjusted. At the same time, it is used as a ternary copolymer (c) during hardening. The formation of copolymerizable components. When the copolymerizable polymerizable monomer (D) contains an aliphatic polymerizable monomer, Guyi and the allyl type contained in the dicyclopentadienyl group are twofold. key

Page 18

548285 V. Description of the invention (16) The β 14 monomer (D) containing the aforementioned alicyclic ring contained in the β 14 monomer (D) which is a preferred combination is 5% by weight or more, and is 5% by weight. The allyl 2-bond contained in the monoalkenyl group and the copolymerizability derived from the acid and α, / 3-unsaturated 2-double bond are preferred. The family polymerizable monomer is: The "weight" type u-unsaturated double bond and methacryloyl group are preferred, and it is easy to bond. It is preferred. Specific examples of the aforementioned aliphatic polymerizable monomer include (meth) acrylic acid. (Meth) acrylic acid, (meth) acrylic acid, ($) acrylic acid, (fluorenyl) acrylic acid, (meth) acrylic acid 2 monoethylhexyl, (meth) acrylic acid lauryl Cyclohexyl (meth) acrylate, Hydroxyethyl (meth) acrylate, 2-Hydroxypropyl (meth) acrylate, 2-Hydroxybutyl (meth) acrylate, 4-Hydroxy (meth) acrylate 4- Hydroxybutyl, (fluorenyl) amine acrylate, propylene oxide (meth) acrylate, ethylene propylene di (meth) propionate, diethylene oxide propylene di (fluorenyl) acrylate, Di (fluorenyl) acrylates such as neopentyl ethylene glycol di (fluorenyl) acrylate; trimethylolpropane tri (meth) acrylate, trihydroxymethylethane tri (meth) acrylate , Glycerol tri (fluorenyl) acrylate, pentaerythritol tetra (meth) acrylate, diquaternary hydrazone Tetraol hexa (fluorenyl) acrylate and three or more (meth) acrylic monomers such as (fluorenyl) acrylic monomers; glycerol diallyl adipate, dilute polypropyl Formic acid (acetal), allyl ester of fluorenyl glyoxal alkyl urea, etc. Especially methyl methacrylate is used

2066-4592-PF (N) .ptd Page 19 548285 V. In the description of the invention (17), it can give high performance, " '" The comonomer can be used alone as a product, which is better. . The above-mentioned aliphatic polymerizable polymerizable monomers are used in combination of two or more kinds. The fat / responsiveness. The combination of both can adjust the surface hardness and specific examples of the monomers other than the anti-polymerizable monomer (D). It can be proclaimed that the aliphatic polymerizable monomer is (toluene :), p ~ ter Butadiene such as styrene, ethylene f styrene styrene, p-f-based acetophenene, a-methylstyrene, P-chlorinated styrene-based monomer and di-, sub-styrene, diethylene Benzene and other phthalic acid vinegar, tri-propyl cyanide; original purpose, di-propyl propyl isopara LI :::, etc. 100 parts by weight of the polymerizable monomer ternary copolymer (c) and the polymerizable copolymer (C) (using ratio, 5 to 200 parts for the ternary (D), more preferably 10 to 1 ^) Ii) When the content of the polymerizable monomer is less than 5 parts: the second ring & part. Polymerizable monomer ⑴ Insufficient heavy-bonding reaction 'Exceeds stone =, = Allyl type 2 contained is not sufficiently gas hardenable. UU. In the case of osmium, it is easy to produce the above-mentioned reaction product (A) and the three-component ternary copolymer (Cl) by air. It is necessary to see the following: "body") and a modifier. Specific examples may include (hydrOquinone), methylhydroquinone, Yiqing hydroquinone, 2,5-di + butyl hydroquinone, benzene paraben, dibutylamine, butyl 2066-4592- PF (N) .ptd Page 20 548285 V. Description of the invention (18) (benzoquinone), t-butylcatechol, catechol, ^ _Caifen, nitrophenol, 2, 4-Di-t- butyl methophenone (phenol), 4-hydroxyl, di-t_ butyl nitryl (nitroxyl), ^ hydroxy_2,2,6,6_tetramethylpiperidine (piperidine) , 1-hydroxy-2, 2, 6, 6-tetramethylpiperidine-4_yl monoacetate, 2,3,6,6-tetramethylpiperidine_4_yl_2_ethyl Hexanoic acid ester, hydroxy-2, 2, 6, 6-tetramethylpiperidine-4-yl-stearate, but not limited to the above. These can be used alone or in combination of 2 More than one kind of use.

In order to obtain practical storage stability while maintaining the hardening reactivity and inhibiting the coloration of the hardened material, the polymerization inhibiting dose is preferably within 500 ρ_. The radical curable resin composition is produced, for example, by the aforementioned method of the present invention 5. The dicyclopentadienyl group and the cis α, θ-unsaturated double bond and the coexistence of the polymerizable monomer I can Significantly improve the air hardenability and harden the reaction temperature when the resin f frame leads to dicyclopentene: alkenyl group; below c, and because it reacts in the presence of a metal ion blocking agent, it can prevent the reaction -瑷 Λ —, knees and stained resin 2 Less colored resin. "Emulsification of 戍 -synthesis" and can be obtained .... The ternary copolymer (c) used in the present invention 5 is adjusted by reacting ternary mound = medium = addition reaction with polybasic acid. Modified 3-component copolymerized α 1 with the ratio of # group and carboxyl group, can be dispersed into pigment and polymerizable monomer;}: mesh, g, and anhydrous silica A 鎞 Do from +

Page 21

548285

ί Mouth !! Improves dispersion and so on. In addition, when the polybasic acid anhydride is maleic anhydride, if it is processed afterwards, ^ ^ ^ The hardening reactivity of the radical-curable resin composition obtained by Thienan will be light and light & l # ^ 巧巧The radical resistance of the molded product of the radical curable resin composition is used to improve the composition and curing reactivity of the two radical curable resins obtained in the present invention 5, and to increase the heat resistance of the molded product of the composition, which is most derived from polymerization. The maleic acid is cis-α, 10,000-unsaturated bond,: d is added to cis-α, / 9-unsaturated bond, by the hydrogen contained in the ternary copolymer (C) The addition of, for example, maleic anhydride to an oxy group results in a modified ternary copolymer (q) having a cis a, yS-unsaturated bond. In addition, the addition of maleic anhydride can reduce the proportion of the inverse a-saturation and unsaturated bond formed in the aforementioned reaction of dicyclopentadiene and maleic compound. When the ratio of inverse a, stone-unsaturated bonds is increased, the discoloration resistance of a molded article using the radical-curable resin composition of the present invention 5 is reduced, so inverse a, / 5-unsaturated bonds That is, the translocation rate of the fumaric acid unit is preferably 70% or less, more preferably 30% or less, and most preferably 20% or less. Relative to the amount of the hydroxyl group when the ratio of the hydroxyl group to the enemy group of the ternary copolymer (c) is adjusted based on the hydrazine addition reaction in the ternary copolymer (C), The amount of polybasic acid anhydride varies depending on the purpose of the modified ternary copolymer (G) to be manufactured. 'It cannot be generalized, but in general, it is 0.05 to 1 mole of hydroxyl polybasic acid anhydride. 1 () Mohr, more preferably 0.05 to 0.4 Moore ', but from the viewpoint of the "" ratio of the azepine group concentration to the carboxyl group concentration after the reaction, it is most preferably 0.1 to 0.4 Moore. Examine the addition reaction of the hydroxyl group contained in the aforementioned ternary copolymer (C)

2066-4592-PF (N) .ptd Page 22 548285 V. Description of the invention (20) " " " 1- Basic acid anhydride reaction conditions are generally in the absence of a catalyst, or a level 3 amine, In the presence of reaction catalysts such as grade 3 Θ, fluorinated bell, grade 4 ammonium salt, grade 4 phosphonium salt, conditions such as 20 ° to 120 ° C are used, but it is not limited to this case. In the case where the hydroxyl group addition reaction in the ternary copolymer (C) is multiplied with an acid anhydride to increase the hardening reactivity and increase the heat resistance of the molded product, '5 to 5 of the hydroxyl group is preferred 40% addition reaction of maleic anhydride, in this case 'neither coloring, but by the inverse α, cold-unsaturated bond (α, / 3-unsaturated double bond of fumaric acid) There is almost no indexing for comparison, and the low temperature is 20 ~ 120. 〇Reaction, can get modified ternary copolymer (Ci). The polybasic anhydride is described. Among the aforementioned maleic anhydrides, for example, spherical anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid, and fluorenyltetrahydrobenzenedifluorene. Acid anhydride, 3,6-methyl bridge (611 (1101116 seven 1 ^ 16116) tetrahydrophthalic anhydride, methyl methyl bridge tetrahydrophthalic anhydride, tetrabromobenzenedicarboxylic anhydride, trimellitic anhydride acid anhydride), etc. These may be used singly or in combination of two or more kinds. The aforementioned ternary copolymer (dagger) has a number average molecular weight of 800 or more, more preferably 850 or more, and particularly preferably It is 860 or more and 3,000 or less, more preferably 250,000 or less, and particularly preferably 2,000 or less, especially 15,000 or less, such as 80 () to 3000, more preferably 800 to 2500, and particularly preferably 850 to 2000, more preferably from 850 to 1500, weight average molecular weight from 2000 to 2000 (), more preferably from 25 to 100, and the acid value of the solid content is from i to 5 5, more preferably i 5 to 5 5, particularly preferably 20 to 50. The manufacturing method of the present invention 8 is 3 yuan of the manufacturing method of the present invention 5.

548285

The copolymer (c) is replaced with a modified ternary copolymer (c is produced in the same manner as the production method of the present invention 5. Modified ternary copolymerization) and the proportion of the polymerizable monomer (D) is used. The copolymerization (c) is 100 parts, and the polymerizable monomer (D) is preferably 5 to 20 parts-10 to 150 parts. | Ling Ling is the manufacturing method of 6 or 9 of the present invention. As in the case of 5 or 8 of the present invention, firstly, in the presence of a metal ion blocking agent, firstly make dipentadiene h 0 Mo at 170 ° C or less. Ratio of ear to maleic acid 0.8 ~ 1.2 Molar = product (A), and the obtained reaction product (A) and epoxy compound (B) having two or more mounting oxygen groups, The ternary copolymer (c) was produced by reacting the carboxyl group of 1 mol of the reaction product (A) with an epoxy compound of 0.8 mol in order to produce a ternary copolymer (c). At this time, polymerizability was obtained. The epoxy group reacts with a carboxyl group in the presence of the monomer (D). The effect of reacting dicyclopentadiene with maleic acid in the presence of the aforementioned metal ion blocking agent is at a reaction temperature of 170. 〇 The effect of the following reaction, the effect of the reaction of dicyclopentadiene 1.0 mol and maleic acid ratio of 0.8 ~ 1.2 mol 'on the carboxyl 1 mol epoxy compound of the reaction product (A) ( b) The effect of the ratio reaction of epoxy groups of 0.8 to 0.89 mole is the same as the effect in the case of the present invention 5 or 8. The difference is that the reaction product (a) and the epoxy compound (B) can be reacted in the present invention 5 or 8 without a polymerizable monomer (D) to obtain a ternary copolymer ( C) In the present invention 8, in order to react a polybasic acid anhydride, in the present invention 6 or 9, these reactions must be performed in the coexistence of a polymerizable monomer (D). Therefore, the viscosity of the reaction system decreases and the reaction The base concentration decreases and the reaction proceeds slowly.

2066-4592-PF (N) .ptd Page 24 548285 V. Description of the invention (22) When the reaction product (A) and the epoxy compound (B) are reacted, the polymerizable monomer It (D) The amount refers to a portion of the polymerizable monomer (D) used to dissolve the ternary copolymer or modified 3 = copolymer (Q) = ^, so that it is in the reaction product (A) and the epoxy compound The reaction of (β) = L exists and the reaction proceeds. It is also possible to obtain a ternary copolymer (C), but 1: it is easy to control the progress of the reaction, and for the reaction product (A) and epoxy 2 (B) The total amount of 100 polymerizable monomers (D) is preferably 10 to bu, and more preferably 15 to 35. Anyone can also use the radical-curable resin composition manufactured by the invention 6 or 9 to make the total amount of the 2 monomers (D) in the 2T port 14 coexist when the reaction product (A) and the epoxy port β) react. The polymerizable monomer (d) that is used to make the composition of radically curable resin satisfies the aforementioned range and uses a part of the polymer "raw: body", and the remaining can be mixed afterwards. A hemp! ^ Can be obtained A light-colored free resin composition with excellent air-hardening properties and hardening properties. The radical-hardening properties of the present invention :: tree: can be mxr, ethylene resin, amine resin (methyl sulfonate or two or more) The artificially hardened tree that is made of rare materials such as ^ refers to one thing. You " ^ / As a hardening resin with work hardening, the side lining (1; V is used for FRP molding materials, injection molding In areas such as molding materials for molding, nV ": inflammatory", etc., which require a beautiful bathtub and washing mr 7ic r ^ water pipe for untreated rolling hardening and hardening, = smoke (reSln pipe , Shop clothes, temples, f, can be applied to a wide range. ^ ^ Month of the present invention 1 1 radical curable resin composition and

2066-4592-PF (N) .ptd Page 25 548285 V. Description of the invention (23) The radically curable resin composition of 15 according to the present invention.

The composition of 11 of the present invention is composed of a (meth) acrylic acid-based slurry new product (E) 'plus a reaction product (F) of dicyclopentane and maleic acid and having two or more rings Oxide epoxy compound (b) is a ternary copolymer (G) having a number average molecular weight of 80 0 to 2500 and / or a hydroxyl addition reaction of maleic anhydride contained in the ternary copolymer or A radically curable resin composition composed of a modified ternary copolymer (Gi) containing a polybasic acid anhydride of maleic anhydride. When the composition of the present invention 11 is hardened, a reaction between cis-type α, / 5 -unsaturated bonds derived from maleic acid and a (meth) acrylic group is caused, and the chuanbei-type α, / 3 -unsaturated bonds are added. It reacts with an allyl double bond of dicyclopentadienyl group, so it has fast hardening property. For example, the mold opening method can ensure necessary forming workability and sufficient air hardening property. . Moreover, a hardened | cured material (for example, a molded article) which has favorable transparency, weather resistance, and discoloration resistance is obtained. The (meth) acrylic-based slurry composition (E) may be, for example, polymethyl (meth) acrylate, polyethylene methyl acrylate, methyl methacrylate / methacrylate copolymer, or the like. (Meth) acrylic polymer dissolved in (meth) acrylic acid ester monomer of methyl methacrylate (meth) propylene-based slurry composition (E1), meth (fluorenyl) acrylate, ethyl ( Fluorenyl) acrylate, n-propyl (meth) acrylate, η-butyl (meth) acrylate, t-butyl (meth) acrylic acid g, (meth) acrylamide, (Methenyl) Acrylonitrile or a mixture of one or two or more of them is appropriately polymerized to obtain a (meth) acrylic-based slurry composition (E2).

P.26 548285 V. Description of the invention (24) S. Single ϊ: Ϊ 2 group) propylene polymer is dissolved in (fluorenyl) acrylic acid. Can di (f-based) acrylic acid be used? In the case of the liquid composition (E1), two: the plant Δκ D body is put into the monomer, for example, 30 Λ is mixed by mixing at 60 ° C to dissolve the polymer in the monomer, and the polymer is mixed The proportion of the entire car is 7-8. % By weight, more preferably 2. ~ 4. weight%. ) Polymerized to obtain a (meth) acrylic-based slurry composition (E2 # 代 I: 物 盘: 1 as in the molecule and using a chain transfer agent with a thiol group :) Tian :, organic peroxide or coupling A polymerization initiator of a nitrogen compound polymerizes (meth) propylene-based monomers in a block. Describing the compounds of the generation, it was prepared ★ 同 # ίΛ ϋΐ ^, ν ^ ^ Bamboo, which is the polymer in the reaction mixture: = = Effect. By adding a thio compound, specific examples of compounds that can be very equal include, for example, η-dodecylthiol m-based thioglycolic acid, thioglycolic acid-based vinegars, ^ knife The compound or the like having two or more thiol groups is not particularly limited. This # can be used alone or in combination of two or more. ::: Dimethyl) Acryl-based monomer (hereinafter referred to as monomer component) or a mixture of monomers (hereinafter referred to as monomer composition) may be added according to the type of the thio compound and the monomer composition The combination of the knife or the early body composition is not particularly limited, and it is preferably 0.01 to 2% by weight. ^ Specific examples of the polymerization initiators just mentioned are, for example, benzyl peroxide, lauryl peroxide, lauryl peroxide, ketone peroxide, t —Butylperoxy-2-ethylhexyl_: Bu ^ 美

548285 V. Description of the invention (25), octyl ester, t-butylperoxybenzene f acid, hydroperoxide, dicumenyl peroxide, bis (4-butylene, cyclohexane perdicarbonate Organic peroxides such as esters; 2, 2, oxyhexyl) peroxyazo-2, 4-di-f-4_f-valeronitrile and other iso-isobutenes and 2-benzene are limited to these compounds. These grasses are not even, compounds, etc., but are not used. It may be used in combination of two or more types. There is no particular limitation on the aforementioned monomer component or monomer composition. I. The amount of the initiator added The reaction conditions for carrying out the aforementioned block polymerization are not particularly limited, and it is possible to use: ::: Temple reaction, etc., to make the green body component or monomer composition. It is partially polymerized), from the viewpoint of obtaining the first stage (= medium = method (that is, the point of matter is better.)) The polymerization of the acrylic liquid composition (E) in the acrylic liquid slurry composition Body into

The method is to replace a partially polymerized monomer with A and replace the 'by the aforementioned method == component or monomer composition object component, and then by copolymerizing the copolymer; a person reacts with a carboxyl-containing copolymeric compound, and Manufacture of carboxyl group and unsaturated propylene oxide). (Meth) acrylic-based slurry composition (E3 The aforementioned carboxyl-containing monomer is a compound of octacarboxylate and carboxyl, and there is no particular limitation on the δ polymerizable double bond in the knife system. ^ ^ Butyric acid, ethylene benzoic acid and other acrylic acids, methyl acrylic acid, and unsaturated monocarbonic acid of the temple; maleic acid, Fumar Page 282066-4592-PF (N) .ptd 548285

Unsaturated dicarbonic acids such as acids, itaconic acid, citraconic acid, etc .; monoesters of gallic acid; monomers containing long-chain carboxyl groups, and the like. Specific examples of the aforementioned ^ unsaturated dicarbon monoacetate, such as monomethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl fumarate, base, fumarate maleate Monobutyl acid, monooctyl fumarate &, crotonic acid mono: dj, can be used alone or in combination of two or more kinds. Such local school. : Molded product on special compound) For discoloration resistance, methylpropenoic acid is preferred. For hard θ, the mixing ratio of the carboxyl group-containing monomer to other monomers is preferred, and the ratio is preferably 1/99 / ~. The range of 5 0/50 is more preferably in the range of 3/97 to 30/7 (). The unsaturated epoxy propyl compound is exemplified as having the ability to react with a carboxyl group. Heavy bonded compounds. Specific examples of the aforementioned unsaturated ring to oxypropyl compounds are allyl glycidylester, glycidyl (meth) acrylate, methylglycidyl (acrylate), Mono (meth) acrylate of epoxy resin, etc. These can be used alone or in combination of two or more of them as appropriate. The unsaturated glycidyl compound is used in a ratio of 0. 8 to 0. 98 mole to 1 mole of carboxyglycid. However, it is preferable to perform the reaction under known conditions from the viewpoint of reaction efficiency. When a carboxyl group is reacted with an epoxy group, a conventional esterification catalyst may be a tertiary amine such as diethylamine, N, N′-dimethylbenzylamine; benzyldimethyl Halides of organic oniums such as ammonium chloride and phosphonium gaseous compounds; trivalent phosphine compounds such as triphenylphosphine. 548285 V. Description of the invention (27) Furthermore, the average molecular weight of the polymer contained in the "(f group) @ 归 系 浆液 组合 物 (E)" is adjusted so that the weight-average molecular weight (Mw) is about 3 0 0 0 ~ loooooo The number average molecular weight (-) is about 10,000 to 20000 '. However, from the viewpoint of molding workability, it may be 0. The block polymerization is preferably based on nitrogen mist. Under the fence. "When the reaction is completed, the ratio of the polymer of the reaction mixture to the early body component or monomer composition that is the reaction is the total of the two.

The weight of the polymer is preferably 7 to 80% by weight, and the unreacted monomer component or monomer composition is preferably "to" by weight. The (meth) acrylic-based slurry composition (EJ), (ε2), (E3) can also be appropriately mixed with the molded product, and the two types are preferably mixed at 25t, and have an early polymerization rate of 0.02 and "diluted" And # .G Pa.R viscosity. Viscosity: The monomers used in the dilution are, for example, (meth) acrylic acid, (meth) acrylic acid methyl, (meth) acrylic acid propyl, (meth), butadiene, IT soil内 内 芙, (Di: L (meth) acrylic acid 2-ethyl "odor, 2-acid lauryl, cyclohexyl (meth) acrylate, (meth) acrylic acid, (meth) acrylic acid Acid 2, hydroxyethyl, methacrylic acid) 2-hydroxypropyl acrylate, cyclopropene ^ propylene oxide I (meth) propylene = propyl propyl acetic acid vinegar; ethacrylic acid vinegar, double I epoxy Allyl \ :; Mody% oxypropyl (methyl) lactone propyl propylene propylene epoxy propyl (fluorenyl)】 diluted, neofluorenyl epoxy propyl (methyl) acrylic acid vinegar, etc. Di (meth) acrylates' trihydroxymethylpropane tri (meth) acrylate, tris

2066-4592-PF (N) .ptd Page 30 548285

: Three or more (meth) acrylic acid esters such as stilbane t (meth) acrylate, triglyceride (US), tetraol tetra (meth) acrylate, dipentaerythritol hexyl (methacrylate), etc. ^) Acrylic monomer. Among them, giving high-performance molded products " brother-family is methyl methacrylate. The monomer used for the dilution is usually a diluent used for (fluorenyl) propylene-based pulp, but it can also be used for the (G) component and / or (G1) component to be described later. It can be reused for the (G) component and / or (μ dilution). It is preferable that the chain transfer agent combined with the "(fluorenyl) propylene-based slurry composition (E2) and (E3) is inactivated by a conventional method. In the case of inertization treatment, for example, maleic anhydride and a basic compound disclosed in Japanese Patent Publication No. 53-2 2 89 can be used in combination to inactivate it. The reaction product (F) of dicyclopentadiene and maleic acid used in the production of (G) component and / or (A) component can be obtained by placing water droplets in dicyclopentadiene and maleic acid. Make it react. Furthermore, the reaction ratio of dicyclopentadiene to maleic acid is preferably 0.8-i 2 moles to 1 mole of dicyclopentadiene, and more preferably 1.0 to 1.1 moles. When the reaction ratio to 1 mol dicyclopentane dimaleic acid exceeds 1.2 mol, in the next step m the epoxy compound stage, the viscosity of the entire system sharply increases and is easily hardened. In the case of less than 0.8 mol, dicyclopentadiene generates more diacetate components and reduces the production of the 3-membered copolymer component used in the present invention. It is because the reaction product (F) generally has characteristics such as an acid value of 200 to 29. , 548285

As the epoxy compound (B) 'for reacting the reaction product (F), the same one as in the case of the invention 1 can be used. Specifically, epoxy resins having two or more, preferably two to three or more epoxy groups in one molecule, for example, bisphenol A type epoxy resin, bisphenol f type epoxy resin, and phenolic ring Oxygen resin, 2 or more shells, preferably 2 to 3 valent polyhydric alcohols, such as neopentyl glycerol diglycidyl ether, polyethylene glycerol diglycidyl ether, polypropylene 1 hexamethylene oxide scale, trishydroxypropylpropane triglycidyl ether, etc .; polyvalent carbonic acid propylene oxide esters of 2 to 3 valences compared with 2 or more valences, such as terephthalate dipropylene oxide S Said, dipropylene oxide adipic acid and the like. These can be used alone or in combination of two or more. The reaction of the% oxygen compound (B) with the aforementioned reaction product (F) of dicyclopentadiene and maleic acid is a reaction of epoxy group and carbonic acid. A known esterification catalyst can be used. Known reaction conditions make it react. At this time, the number average molecular weight of the product (3% copolymer) is 80 () to 250,000, preferably 850 to 1,500, and the weight average molecular weight is 2000 to 2000 (), It is preferably from 300 to 1,000, the acid value of the solid content is from 3 to 20, more preferably from 3 to 15, and particularly preferred is 5:15 to react the mounting oxygen compound (B) to obtain the use of the present invention = Copolymer (G) is preferred. In the field a where the number average molecular weight is less than 800, the hot water resistance of the resin composition of the present invention is insufficient, and the viscosity of the product (three-member copolymer) increases, the reaction time increases, and gelation occurs during the reaction. And obvious coloring is not preferred. Repeatedly, when producing a 3 ′ copolymer (G), the product u) reacted with 1 mole of dicyclopentene at a ratio of G · 8 to 1.2 moles of maleic acid, and 2 The above epoxy-based epoxy compounds ⑴

548285 V. Description of the invention (30) In the product (A), the epoxidation of carboxyl group 1 mole and the epoxy group (β) 's epoxy group ratio of 0.8 to 1.2 mole are reacted to produce a ternary copolymer, usually 'A ternary copolymer (G) having the aforementioned number average molecular weight, weight average molecular weight, and acid value of the solid content can be produced. Further, when produced by the production method of the present invention 5, a ternary copolymer having better characteristics can also be produced. In order to improve the heat resistance and the hardening reactivity of the resin composition of the present invention 11, it is most effective to increase the cis α, / 9 -unsaturated bond of maleic acid derived from the polymer component. When introducing cis-type 0 ;, in the case of cold-unsaturated bonding, cis-type introduction α can be obtained by reacting maleic anhydride addition to the aforementioned ternary copolymer ((;) containing the hydroxyl group '). Unsaturated modified 3-membered copolymer (Gi). At this time, it is not possible to react with maleic anhydride by addition of 5 to 40% of the hydroxyl groups contained in the 3-membered copolymer (G). It can be colored, and it can cause the transposition to trans α, / 3 -unsaturated bond (α, ^ _ unsaturated double bond of fumaric acid) at a relatively low temperature of 20 ~ 丨 2 (). The reaction results in a modified ternary copolymer (Gi). Furthermore, by the addition reaction of maleic anhydride, Xiao b reduces the trans-α produced by the reaction part of monocyclopentadiene and maleic acid. Proportion of saturated bonds. When the ratio of trans-α, unsaturated-unsaturated bonds increases, the discoloration resistance of the molded product using the resin composition of the present invention decreases, so trans α, no-unsaturated bonds, that is The translocation rate for the fumaric acid unit is preferably 70% or less, more preferably 30% or less, and particularly preferably 10% or less ...

The modified ternary copolymer (Gi) has a number average molecular weight of 8,000 or more, more preferably 850 or more ', and particularly preferably 860 or more and 3,000 or less, more preferably? Below, especially good is 2 or less, especially good is 1 500 or less, for example ~ 0U

2066-4592-PF (N), ptd Page 33 548285 V. Description of the invention (31) 3000, more preferably 800 to 2500, particularly preferably 850 to 2000, and even more preferably 850 to 1,500. The weight average molecular weight is 2000 ~ 2000 () The acid value of the solid content is 10 to 55, more preferably 15 to 55, particularly 15 to 50, and even more preferably 20 to 50. The compounding amount of the ternary copolymer (G) and / or the modified ternary copolymer (g) is 5 to 150 for 100 parts of the (E) component, preferably! Bu 〇04, and more It is preferably 30 to 50 parts. (G) When the blending amount of the ingredients is less than 5, the air hardenability is insufficient. When it exceeds 150 parts, the obtained molded product is too rigid and becomes In order to adjust the diluting of the plutonium component and / or the (Gi) component of the usable net, it is also possible to use a monomer for the aforementioned (E) component dilution: a monomer and a polymerizable monomer described later ((H) Component) to be diluted. When using the diluted monomer of the component (E), the component (e) is used, and when the diluted monomer of the (H) component is used, the (h) component is used. The resin of the present invention 15 The composition is based on the group 5 of the present invention, a vinyl acetate resin, and / or a 5 to 40% addition reaction of maleic anhydride and (modified ethylene S) The composition of the resin (L). 3) The component (I) is used for imparting the properties and properties of the present invention, and Digestion (Ε = incompatibility in the case of containing methacrylic acid ester as a monomer. Jiamei: ^ 2 in the case of di3,3 acrylic acid ester, because the boiling point of the fluorinated acrylic acid ester is as low as 10 lt. The field composition of the resin composition of the present invention 11 is volatile. °% of the opening blade is combined with a small depression, which is sprayed.

2066-4592-PF (N) .ptd Page 34 548285 V. Description of the invention (32) KI field ΐ "Excessive volatility to reduce yield (yield), etc. The aforementioned purpose of reducing the volatility of volatility is to use mil. * 300 ^ 3000 ^ Resin (丨) / 辻 ® Resin (1) and / or acid modified vinyl ester acid modified ^ diadiene ester resin CD 价 acid value is 2 ~ 10, the aforementioned modified ^ vinyl acetate resin The acid value of (Ιι) is preferably from 10 to 55. Acidic: (I) • It is usually an epoxy resin and an unsaturated monocarbon group: a compound. Specific examples include, for example, polypropylated lactate, Epoxy novolac (ηονο1 (where, = epoxide of fatty acid, ring of dry oil =-broad cinnamon: monocarbonic acid, for example, acrylic acid, methyl acrylic acid, ..w, and, if necessary, It is also possible to mix 5 to 40% of the groups contained in the vinyl ester resin with maleic acid liver and / or fumaric acid wild reaction to form a knife and / or (L) component. ) It is 100 parts, preferably 5 to 50 parts, and more preferably 7 to 12. When the blending amount is less than 5, it cannot be used for other purposes. If it exceeds 50 parts, discoloration and the like occur. He asked-^ ^ Ming 11 or 15 resin composition 'has the characteristics of excellent transparency and few color, acid value is 2 ~ 40, viscosity is 25 ~ 02 ~ 2〇 ^ .s, can be just like this Use, in order to adjust the viscosity, monomers 548285 can also be added V. Description of the invention (33) (Η). Polymerizable monomer (H) can also be used as a solvent, can also be used for the synthesis of high viscosity poly-eight polymers The viscosity of the polymerizable monomer (H) and the solvent of the carcass are adjusted. (Styrene), vinyl toluene (toluene α-methylstyrene, p-gasified styrene-butylstyrene, methyl) Styrene based ethylene such as styrene, divinylbenzene, P-gasified phthalate, dipropylpropylbenzene, mono- and diallyl cyanurate triallyl vinegar, Here, cyanuric acid = 1, cyanuric acid and cyanuric acid, and allylmethacrylamide, such as lysine, etc. It is particularly preferred to have ethylene. Base: Base and bonded compounds, such as hydroxymethyl dimer, unsaturated red τ 丞 敬 敬 (feUethy 010 melanune), dilute propyl, glycerol diallyl Cidene adipate: acetal, allyl esters of hydroxymethyl glycoluril, etc., and this imparts air hardening properties to the resin composition. These polymerizable properties can be used in combination of two types The above is used. The type of polymerizable monomer is also adjusted by its combination of surface hardness and reactivity. The amount of the (Η) component is preferably from the viewpoint of less crosslinking shrinkage. (E) The 100 part of the component is at 200. It is more preferably 50 parts or less. In order to obtain a clear viscosity adjustment effect of the ⑴ component, it is preferable to use 5 parts to produce the aforementioned (F) component, (G) component, and / or ) Component and / or (L) component, a conventional polymerization inhibitor may be used if necessary. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, methoxyl-lean, t-butyl

548285 V. Description of the invention (34) Hydroquinone, 2,5-di-t-butylhydroquinone, benzoquinone, t-butylcatechol, catechol, α- Caiolol, nitrophenol, 2,4-di-1-butyl phenol (Phenol), 4-hydroxyl-2, 2, 6, 6-tetrafluorenyl (Piperidine) -1-meridian , Di-1-butyl nitroxyl (ni troxy 1), 1-hydroxy-2,2,6,6-tetramethylpiperidine, hydroxy-2, 2, 6, 6-tetramethylpiperidine— 4-yl-acetate, 丨-via 1-2, 2, 6, 6-tetrafluorenyl-4-ene-2-ethylhexanoate, 1- via-yl 2, 2, 6, 6-tetramethylnumidin-4-yl-stearate, but " is not limited to the above. These can be used alone or in combination of two or more. In order to improve the storage stability of the resin composition of the present invention, one type of polymerization inhibitor or two or more types in combination are used separately. In addition, various additives can be appropriately added to the resin composition of the present invention depending on the use and desired physical properties. For example, if you use it as a molding material, you can see f-fillers such as oxides, hydroxides, and other oxides or hydroxides of acid-earth metals such as clay, oxychloride, clay (⑽y), and talc; etc. Internal release agents such as stearic acid; glass: fiber: organic fiber composed of fatty acid, hard fiber, aramide and polyester ^ carbon fiber, carbon fiber J compound, lauryl peroxide, methyl ethyl methyl Supplement: agent; benzyl y-peroxy-2-ethylhexyl ester, t-butylperoxyoctyl, ° lice, benzoic acid, cumene hydroperoxide, cyclohexane peroxide, 1, 1 ~ butylperoxy: bisU decabutylcyclohexyl) peroxydicarbonate, s-pinenyl peroxide, 2, 2 '~ azobisisobutyronitrile, 2-phenylazo— Polymerization initiation of azo compounds such as organic peroxy valeronitrile, etc. ~~ methyl-4-, pigments and their

2066-4592-PF (N) .ptd p. 37 m 548285

In the case where a coating for a laminate and a gel coat is used, if necessary, 100 parts of the resin composition of the present invention may contain pigments of 0.1 to 700 parts. Further, it may contain thixotropy imparting agents such as fine powder anhydrous silica, asbestos, and the like, and polymerization accelerators for metal stone such as cobalt octylate and manganese naphthenate. The resin composition of the present invention has a fast hardening speed, and a small amount of residual monomers can be used to obtain a hardened material with a high degree of hardening. In addition, the air-hardening unsaturated bond ^ is related to cross-linking, and therefore has heat resistance, chemical resistance, Excellent discoloration ^ Good. Therefore, it can be used as a molding material suitable for sheet molding compounds (SMC), bulk molding compounds (BMC), injection molding materials, and various gel coats. Molding, pull-out molding, resin molding, spray-up molding, and matrix molding. The molded products obtained by the company can be used for various purposes such as bathtubs, washstands, marbles, earthen yachts, swimming pools, etc. ~ ιΐΐΐ 'For convenience of explanation, the present invention 1 ~ ® L i 纟 明 11 ~ 18 will be explained separately. These inventions can be made within the scope of each of the two inventions: the limitation is the invention. The description is based on Gong Ming from the nth month to the eighteenth, and the present invention can be described from n to 182 1 0. The present invention 1 ~ In addition, the molecular weight m㈣ chromatography of the present invention (Gel

548285 V. Description of Invention (36)

Permeation Chromatogarphy; GPC), the molecular weights of the number average molecular weight (Mη) and the weight average molecular weight (Mw) were determined using a polystyrene calibration curve. The acid value is determined by the JIS K-6 90 0, 1, 5, 3, 5 and 2 titration method, and the hydroxyl value is based on the JIS K-0 0 70, 7.1 neutralization titration method. Examples Hereinafter, the present invention will be described in more detail through examples and comparative examples, but the present invention is not limited thereto. First, Examples and Comparative Examples of the present invention 1 to 10 will be described.

Example 1 (Production of radically curable resin composition (EM-1)) Dicyclopentadiene 1 3 2 parts were placed in a reactor equipped with a thermometer, a cooler, a gas introduction tube, a dropping funnel, and a stirrer. 1, maleic anhydride 1, 103, metal ion blocking agent ethylene diamine tetraacetic acid (trade name TEKRON (transliteration) DO, manufactured by Imperial Chemical Co., Ltd.) 〇 02, after heating to 80 ° C, 19 parts of water were dripped while keeping the temperature of the content at 100 ° C. After the completion of the dropping, it was allowed to react at 120 ° C for 1 hour, and the temperature was maintained at 160 ° C for 1 hour. The acid value dropped to 115 ° C at the time when the acid value became 220, and the epoxy equivalent was 182 ·

3 bisphenol epoxy resin (brand name epi tote yd-127, manufactured by Todo Chemical Co., Ltd.) 1, 7 parts, esterification catalyst triethylene pentylamine chloride compound 1, 3 parts, polymerization inhibitor fluorene group The hydroquinone is 0.05, and the reaction is performed for 2 hours to obtain an acid value of 9. After that, it was slowly cooled to below 40 ° C, and dissolved in 43 parts of 2-hydroxypropyl methacrylate, 171 parts of methacrylate and 171 part of styrene to obtain a ternary copolymer ( Epoxy maleimide resin) 60% by weight, (D) component 6% 6% by weight of methacrylic acid 2-hydroxypropyl group, 24% by weight of methyl methacrylate, and 10% by weight of styrene

548285 V. Description of the invention (37) The radical-curable resin composition of the present invention. The obtained radically curable resin composition had a viscosity of 3.1 Pa · s (25 ° C), a color number of 30 (Hazen value), and a number average molecular weight (Mn) of the ternary copolymer measured by GPC was 870 The weight average molecular weight (Mw) was 5700. The translocation from maleic acid unit to fumaric acid by ih-NMR was 20%. Example 2 (Production of radically curable resin composition (EM_2)) Maleic anhydride was added to a ternary copolymer (epoxy maleimide resin) having an acid value of 8 obtained in the case of Example 1 丨5 parts, 5 parts of succinic acid, and 11 7 · 5 parts of styrene monomer are used as diluents, and they are reacted in an air stream at 110 ° C for 2 hours to make the hydroxyl groups contained in the ternary copolymer 21% of maleic anhydride and succinic acid were added to obtain a ternary copolymer having an acid value of 28. After that, it was immediately cooled to below 40 ° C, and dissolved in 180. 5 parts of methyl methacrylate, and 60% by weight of a modified terpolymer was obtained. (D) 24% by weight of methmethacrylate and benzene. A modified radical curable resin composition composed of 16% by weight of ethylene. The obtained radical curable resin composition had a viscosity of 4.0 Pa · s (25 ° C), a color number of 30 (Hazen value), and a number average molecular weight (Mη) of the ternary copolymer measured by Gpc was 910, The weight average molecular weight (mw) was 6000. In addition, the translocation ratio from maleic acid unit to fumaric acid by 1 η-NMR was 13%. Example 3 A bisphenol-type epoxy resin (trade name: Epitote YD-901, Toto Chemical Co., Ltd.) 442

548285 V. Description of the invention (38) Epoxy equivalent 1 82 · 3 bisphenol epoxy resin (commercially known as epi tote YD-127, manufactured by Dongdu Chemical Co., Ltd.) used in Example 1 and Erkou

Part 2.0 of the phenol phosphorus bromide compound is an esterification catalyst, a polymerization inhibitor 曱 -based gas oxygen para @benzene diphenol 0 · 0 7 part, a thinner styrene part 1 4 0, it reacts for 4 hours at 100 The obtained 3-membered copolymer with an acid value of 6 · 7 (epoxy maleimide tree ^ / 24 additional maleic anhydride as a diluent, plus divinylbenzenediol dimethacrylic acid ^ 14 0, in the air stream In the reaction, it was reacted for 2 hours at 10 hours to make a 3-membered copolymer, ie, 11% of the hydroxyl group contained in the a-body was added with maleic anhydride to obtain a modified 3-membered copolymer having an acid value of 17. After that, it was slowly cooled to 40 or less , Dissolved in 440 parts of methyl methacrylate, to obtain a modified ternary copolymer 50% by weight, (D) component methacrylate 30.6% by weight, diethylene propylene glycol Q dimethyl Modified free radical curable resin composition consisting of acrylate 9.7 wt% and styrene 9.9.7 wt%. The obtained free radical curable resin composition has a viscosity of 4 · 5 pa · s (25 ° C) , Color number 40 (Hazen value), the number average molecular weight (Mn) of the ternary copolymer measured by GPC was 150,000, and the weight average molecular weight (Mw) was 990 0. Moreover, the translocation rate from maleic acid unit to fumaric acid by 1 η-NMR was 15%. Example 4 Put the phenyl phosphorus bromide compound 丨 · 〇 part in place of the third used in Example 1 Ethylpentylamine chloride compound, 143 parts of 2-hydroxypropyl methacrylate, reacted at 110 for 5 hours to reach an acid value of 5. After that, it was slowly cooled to 40 or less, and dissolved in methyl methacrylate 7丨 part and styrene 7 丨 part, 60% by weight of modified ternary copolymer was obtained, (D) 20% by weight of methyl methacrylate

548285 V. Description of the invention Modified radical curable resin composition consisting of (39)%, 10% by weight of methmethacrylate and 10% by weight of styrene. The obtained radical curable resin composition had a viscosity of 3.9 Pa · s (25 ° C), a color number of 20 (Hazen value), and a number average molecular weight (Mη) of the ternary copolymer measured by GPC was 880, The weight average molecular weight (Mw) was 6,500. In addition, the conversion rate from maleic acid unit to fumaric acid by 1 H-NMR was 18%. Production Example 1 (Production of Vinyl Ester Resin (VE-1)) In the same reactor as in Example 1, a double-equivalent epoxy resin (brand name epi cote YD-901, Toto (Manufactured by Kasei Chemical Co., Ltd.) 500 parts, 96 parts of methacrylic acid, 1, 8 parts of tetraphenylphosphorobromide compound, and 12 parts of hydroquinone hydroquinone. After 7 hours, S became an acid value of 5, and then 3,20 parts of unsaturated monomer phenethylhydrazone was added to obtain a vinyl ester resin having an acid value of 3.2. The obtained radical-curable resin composition had a viscosity of 4.1 · s (25 ° C) and a color number of 80 (Hazen value). Production Example 2 (Production of Vinyl Ester Resin (VE-2)) A bisphenol epoxy resin (trade name epi cote YD-127) with an epoxy equivalent of 1 8 2 · 3 was placed in the same reactor as in Example 1. (Manufactured by Dongdu Chemical Co., Ltd.) 4, 7 parts, 2, 3 0 fluorenyl acrylic acid, 2 · 1 part of the tetraphenyl compound, and 0 · 1 4 parts of methyl hydroxide hydroquinone, in the air stream After the reaction was performed at II 5 ° C for 6 hours, S was converted to an acid value of 4.0, and then 302 ethylenic unsaturated monomers were added to give an ethylene resin with an acid value of 2.8. The obtained radical-curable resin composition had a viscosity of 1 · 5 Pa · s (25. (3) and a color number of 40

2066-4592-PF (N) .ptd Page 42 548285 V. Explanation of the invention (40) --- (Hazen value) 〇 Application Examples 1 to 9 and Comparative Application Examples 1 to 2 Add separately to the obtained composition Copper naphthenate, cobalt octanoate, 4-a =; 2, 2, 6,6, —tetramethyleguidine decabutylphthalate “… old) and 2-methylhydroquinone and The evaluation of the composition shown in Table 1 was prepared. The results are shown in Table 1. ^ The compounding ratio of the additives shown in Table 1 represents the content ratio (ppm) to the entire resin composition obtained. The 2-methylhydroquinone is the amount used in the reaction. Also, the octanoic acid described in Table 1 is a mineral spirit (Co content 8% by weight) as the octanoic acid. Copper alkanoate is a fog solvent solution of copper sintered acid copper (Cu content 5 wt%

2066-4592-PF (N) .ptd Page 43 548285 V. Description of the invention (41) Suitable group pfltm ^ # zlzlzlzlzl -1 -1 lining! I sleep α) ssi_sc > lE) il—8-

Ha Xin 豳 觊 豳 觊; & 铧 Ι ^ ®Ι1! ≫ _α) 11 ^ PP κι Ban Emirates a § 4-_foot-2,2,6,6-4 VE-2 VE 丨 EM-4 EM -3 EM 丨 2 EM-1 0.4 115 〇 一一 500 500 30 吕 一 吕 0-4 3 125 〇〇100 58 30 一一 一 0_4 120 〇〇100 5 吕 30 100 00 0 · 3 ~ T " 115 〇〇5 00 5 Lu 30 100 § ml 0.2 120 〇100 100 5 Lu 30 18 20 80 ο · 6 115 Δ 〇 Yi Lu 58 50 Yi Lu 50 50 0-2 130 〇18 500 30 00 20 80 ο_2 0_6 1_8MM 1 · 2ΜΜ di Painting_ 2066-4592-PF (N) .ptd 130 115 90 110 〇05 Yilu 500 30 00 20 80 Δ 100 500 50 18 50 50 〇Lu 08 50 100 150 Yilu 5 Yilu 000 50 Yilu Yilu spu a ^ 2 Page 44 548285 V. Explanation of the invention (42) From the results in Table 1, among the application examples, air hardenability, residual monomers, and weather resistance should be excellent. It must be emphasized that the application example of ethylene-resin (VE-1, VE-2) having a large susceptibility to gas and mixing 20 parts with a lower Tg than the resin composition (EM-1, 2, 3, 4) of the present invention has a lower Tg The Tg of 5, 7, and 8 all increased, and the residual monomer also decreased, which significantly improved the hardenability. (Air-hardening-touch dryness)

5% by weight of titanium white was added to the resin composition, and Bacol (transliteration) 0 (trade name, manufactured by Japan Oils & Fats Co., Ltd.) 2.0% by weight was added as a hardening catalyst, and the applicator was added. (Applicator) was applied to a glass plate with a thickness of 0.5 mm. Place the coated glass plate in an 80 ° C oven for 1 hour and take it out. When touching the coating surface with your fingertips, it is good if it is not sticky (〇), slightly sticky (△), sticky The case is defective (X). (Air-hardening-methanone solubility) One drop of acetone was dropped on the coating surface, and after 30 seconds, it was wiped with absorbent cotton. The coating film did not peel off when it touched the surface with fingertips, and it was good when there was no stickiness (〇) When the coating film is slightly peeled and sticky, it is (△), and when the coating is peeled off, it is bad (X). , (Glass transition temperature (Tg))

A resin composition containing the aforementioned titanium white and a catalyst was poured into a 2 mm-thick introduction plate (gu. 1 de) composed of two glass plates of 100 m × 100 m and hardened at 80 ° C for 2 hours. The cast-hardened product composed of the resin composition was taken out from a glass plate, and a test piece of 5111111 x 5 mm was made from the cast-hardened product. A thermal analysis device manufactured by Shimadzu Corporation was used for ^^ and TMA (thermal Mechanical points

548285 V. Description of the invention (43) analysis) method for measuring Tg. (Hue) The hue (Ei) of the said cast hardened | cured material was measured based on J IS K 5400. (Weather resistance) A 50 mm X 50 mm test piece was made from the above-mentioned cast hardened material, and the E value (E2) after exposure to the weather meter for 100 hours was measured according to jis K 5400. Find the difference ΔΕ (E2-Ei). Here, the E value is a value indicating the degree of discoloration, and a small value of ΔE indicates excellent weather resistance. (Residual monomer) A 5 g powdery sample was cut from the injection-hardened product, and the soluble component was extracted with ethyl acetate, washed with a large amount of ethyl acetate, and dried under reduced pressure at 70 to measure the weight change of the sample. , Residual monomer component in the injection-hardened material is expressed as a weight loss fraction. (Storage stability) The period during which the resin composition containing various additives was kept in the same state as that in the first period was measured during the storage. The following is a description of Examples 11 to 19 and Comparative Examples of the present invention. 1 each case 3 (manufacturing of (meth) acrylic-based slurry composition (E_i)) equipped with a thermometer, cooler, and nitrogen gas: " Γΐίϊ releases thermoplastic methacrylic polymer (Sumitomo Chemical Industries) ): Part G UM: fX ME, MW 80,000, granular polymer i) 150 parts of polymer and gas, and replace the mixing tank with nitrogen, and then the content is dropped and the temperature is raised to ㈣ to dissolve the methyl propylene Sparse

548285 V. Description of the invention (44) Combined in fluorenyl methyl acrylate. The time required for dissolution is 2 hours. The viscosity of the obtained (fluorenyl) acrylonitrile slurry composition (E -1) was 0.85 pa * s (25 ° C). Production Example 4 (Production of (meth) propane-fluorene-based slurry composition (E-2)) Into a mixing tank provided with a thermometer, a cooler, a nitrogen gas introduction tube, and a stirrer, methacrylate 2 was placed. The inside of the mixing tank was replaced with nitrogen gas. Next, the polymerization initiator was added by adding 2, 2, -azoisobutyronitrile 0.1 part and chain transfer agent n_dodecyl mercaptan 0.1 part, and the polymerization reaction was started. 7 hours after the start of the polymerization reaction, the viscosity of the reaction solution became 3 · 3 P a · s. Therefore, at this time point, 35 parts of methyl methacrylate were added to the reaction solution and quenched to 40 ° C to complete. reaction. The viscosity of the obtained (meth) acrylic-based slurry composition (E-2) was 0.62 Pa · s (25 ° C), and the solid content concentration was 22.2% by weight. The number average molecular weight (Mη) of the solid content measured by (GPC) was 2 1 000, and the weight average molecular weight (Mw) was 62,000. Production Example 5 (Production of (meth) propylene-based slurry composition (E-3)) In the same reactor as in the case of (meth) propylene-based slurry composition (E-2), methyl methacrylate was placed. There were 190 parts of ester and 10 parts of methacrylic acid, and the inside of the mixing tank was replaced with nitrogen gas. Next, the temperature was raised to 80 ° C while introducing nitrogen, and then polymerization initiators 2, 2'-azoisobutyronitrile 0.03 and chain transfer agent η-dodecyl mercaptan 1.2 were added. And the polymerization reaction started. The reaction solution had a viscosity of 2.8 Pa · s 5 hours after the start of the polymerization reaction, and was added with Anteji W-400 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd., oxidation inhibitor). Reaction stopped while

548285 V. Description of the invention (45) A (meth) acrylic-based slurry composition containing a carboxyl group is obtained. To the obtained (meth) acrylic-based slurry composition containing a carboxyl group, an unsaturated epoxy propyl compound, glycidyl propionate methyl S, 15 parts, and a g-catalyst benzyltrimethylammonium chloride compound were added. · After 02 heating, the temperature was raised to 95 ° C, and the esterification reaction was performed for 11 hours under the air mist. After the completion of the esterification reaction, 100 parts of methyl methacrylate was added to obtain a radical-curable (fluorenyl) acrylic-based slurry composition (E-3) having a solid content concentration of 30.2% by weight. The obtained (meth) propylene-based slurry composition (E-3) had an acid value of 1.8 and a viscosity of 1.0pa · s (25 ° C), and the number of the solid content was measured using (GPC) The average molecular weight (Mη) was 22000, the weight average molecular weight (Mw) was 61,000, and the acid value was 4.9. Production Example 6 (Production of ternary copolymer (G-1)) In a reactor equipped with a thermometer, a cooler, a gas introduction tube, a dropping funnel, and a stirrer, 1,32 parts of dicyclopentadiene, and Malay were placed. Acid anhydride 1 〇3, metal ion blocking agent ethylene diamine tetraacetic acid (trade name TAKRON (transliteration) DO, manufactured by Imperial Chemical Co., Ltd.) 〇12, after heating to 80 ° C, 'the contents of the The temperature is 丨 〇〇 begging and dripping water 丨 9 parts. After the dropping was completed, it was allowed to react at 120 ° C for 1 hour, and the temperature was maintained at M16 (rci hours). At the time when the acid value became 220, the temperature dropped to 100 ° C, and the epoxy equivalent of 182.3 bisphenol ring Oxygen resin (trade name Epitote YD-127, manufactured by Toto Chemical Co., Ltd.) 1, 3, esterification catalyst triethylenepentylamine chloride compound 1, 3, polymerization inhibitor methyl hydroquinone 〇 · 〇 Five and 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine 0.02 and diluent methacrylic acid 2 monohydroxyl 43 were formed, and the reaction was performed for 2 hours to obtain an acid value of 8. After that, slowly cool to 4〇

2066-4592-PF (N) .ptd Page 48 548285 V. Description of the invention (46) Below ° C, it is dissolved in 1 7 1 parts of methyl methyl acrylate and 71 parts of styrene. Elementary copolymer (epoxy maleimide resin) 60% by weight ('E' component fluorenyl acrylic acid 2-hydroxopropyl 6% by weight and methacrylate methacrylate 24% by weight and (H) component benzene A composition consisting of 10% by weight of ethylene. The obtained ternary copolymer (G-1) had a viscosity of 3.1 Pa .s (25 ° C), a color number of 20 (Hazen value), and a number average molecular weight (Μη) of the ternary copolymer measured by GPC was 870, The weight average molecular weight (^^) was 5,700. The translocation ratio from maleic acid unit to fumaric acid by iH-NMR was 8%. Production Example 7 (Production of Modified Terpolymer (Gi-1)) Except the use of 43 parts of styrene instead of the diluent fluorenyl acrylic acid 2-hydrogen used in the production of a composition containing terpolymer (G-1) Except for oxypropyl group, a ternary copolymer having an acid value of 8 was obtained in the same manner as in the case of a composition containing a ternary copolymer (G-1), and 20 maleic anhydride was added, and the diluent styrene monomer 74 was added. · 5 parts and react at ho ° c for 2 hours in an air stream to add 21% of the hydroxyl groups contained in the ternary copolymer to maleic anhydride to obtain a modified ternary copolymer having an acid value of 2 8 Fit ((Gi-1)). After that, it was cooled to below 40 ° C, and dissolved in 180.5 parts of methyl methacrylate to become a modified ternary copolymer ^ -1) 60% by weight, (E) component plus 24.2% by weight of methyl acrylate And (Η) a composition consisting of styrene and 5.8% by weight. The ternary copolymer (h-1) paid has a viscosity of 4.0 Pa * s (25 ° C), a color number of 30 (Hazen value), and the number average of the ternary copolymer (Gi-1) measured by GPC. Molecular weight (Μη) is 910, weight average molecular weight

2066-4592-PF (N) .ptd Page 49 548285 (Mw) is 60 00. The conversion ratio from maleic acid unit to fumaric acid in 1 η-NMR was 10%. Example 8 (manufacturing of vinegar vinegar (I — 1))

In a reactor equipped with a thermometer, a cooler, a gas introduction pipe, and a stirrer, an epoxy resin having an epoxy equivalent of 182.3 (trade name epi t〇te YD) was obtained by reacting bisphenol A with epichlorohydrin. —127, manufactured by Toto Kasei (Yueyou)) 474 parts, 230 methacrylic acid parts, methyl terephthalate 0.07 parts, diethylbenzyl ammonium chloride 2 parts, 115 parts under air current . (: 6 hours of reaction to obtain a vinyl ester resin (I — j) having an acid value of 4.0. Production Example 9 (Production of Modified Vinyl Ester Resin (1- —)) 1) In the same manner as in the case of vinyl ester resin, 38 maleic anhydrides and 13 fumaric anhydrides were continuously added, and reacted at 105 ° C. for 1 hour, and an 8% addition reaction of peroxy group was obtained to obtain an acid value 2 〇 · 〇 Modified vinyl ester resin (L-1). Production Example 10 (Production of unsaturated polyester resin composition (j —!))

498 parts of isophthalic acid, 686 parts of maleic anhydride, 403 parts of propylene glycol, and 67 parts of dipropylene glycol were placed in a 4-neck flask, and finally reacted at 21 0 ° C in a nitrogen gas flow 1 Dehydration condensation was performed in 6 hours to obtain an unsaturated polyester resin having an acid value of 20 and a number average molecular weight (MΓ0 2600 weight average molecular weight of 6,000. The mixing ratio of the unsaturated polyester resin and the styrene monomer was At 60/40, unsaturated polyester resin was mixed with stupid ethylene, and polymerization inhibitor t-butylhydroquinone was added at 50 ppm to obtain unsaturated polyester resin composition (J-1). J -1) viscosity is 0.

Pa · s, color number 200 (Hazen value

2066-4592-PF (N) .ptd Page 50 548285 V. Description of the invention (48)) The acid value is 12. Production Example 11 (Production of Unsaturated Polyester Resin Composition (J-2)) Into a 4-necked flask (flask), 98 parts of maleic acid, 1, 32 parts of dicyclopentadiene, and 18 parts of pure water were placed. And finally the nitrogen flow. C 1 30 was reacted for 3 hours to obtain a maleic acid adduct of dicyclopentadiene. Next, 196 parts of maleic anhydride, 296 parts of fumaric anhydride, and 359 parts of propylene glycol were added and mixed, and the dehydration condensation reaction was performed under a nitrogen gas flow at 200 ° C for 10 hours in a general manner to obtain an acid value of 2 0 is a dicyclopentadienyl-containing unsaturated polyester resin. The unsaturated polyester resin was mixed with styrene at a mixing ratio of the unsaturated polyester resin and the styrene monomer of 6 5/3 5 and the polymerization inhibitor methyl hydroquinone was added at 50 ppm to obtain Dicyclopentadienyl unsaturated polyester resin composition (J-2). This composition (J-2) had a viscosity of 0.3 Pa .s and a color number of 70 0 (Hazen value) and an acid value of 1 3 · 0. Examples 5 to 10 and Comparative Examples 1 to 6 Compositions of resins and the like obtained in the production examples described in Table 2 were produced, and evaluations described in Table 2 were performed. The results are shown in Table 2. The evaluation method was the same as the method described above, and the added amount of Bacol (tone #) 0 (trade name: Made in Japan Oils and Fats Co., Ltd.) used as the hardening catalyst was 1% by weight. 'Furthermore, for reference, the (g) component, ((^) component, (j) component (L) in the case where the (E) component is 100 parts in Examples 5 to 丨 〇 in Table 3 are shown. ) And (H) components in each amount. The neopentylglycol monomethylpropionate S purpose and the methyl methacrylate formaldehyde purpose in Table 2 are (e)

2066-4592-PF (N) .ptd Page 51 548285 V. Description of the invention (49) Contained in ingredients. Yi mg mg porphyrin 漤 a Xue 铕 ban application example number weather resistance ΔE hue Ei residues a) 漭 eggplant warm air hardening injection nl Φ WS methyl methacrylate neopentyl ethylene dimethyl methacrylate δα a 1 CO composition (Jl) (Ii-l) component (1-1) component? Ii (E-3) component (E-2) component (El) component 溶解 acetone solubility refers to dryness ΓΟ 1— * O l—fc g C > 〇Kn 1— 〇1— * Lu Ln ΓΟ I— * o 1— ^ Μ ΐ > 〇Kn H- ^ Lu 1— »· 〇C ^ k to H-- · o o- * Dad 〇〇Ln H- * 3 I— * · 〇 ^ 3 ΓΟ o CO Η- · 谷 〇〇 \ J} 1— o H- * 〇OD to oi \ D 1 — *-s 〇〇Ln 1— k 〇I— * 1— * 〇kO CO o CO · — 〇〇Kn g »— * 1— 〇1—fc 1— bg X 〇Kn f— * 〇-i L =.» — * H- ^ < wO 〇CO Ln X 〇Kn 1— * Lu foot! 1 2 »— * 1— CO Ln» — * o XX Ln H- o pin 丨 J 3 »— CD 1— ^ Ln g X 1 > Kn H-fc ο L = c; ί3 CO Ln Ln 〇〇Ln >-* Ο ^ plane L = L · — * 〇Ln I-— 〇〇Ln · —fc 吕 1— * g Vr DIL =.

HHI Page 52 2066-4592-PF (N) .ptd 548285 V. Description of the invention (50) Table 3 Example Example No. 5 6 7 8 9 10 Tree II Composition Complex (澉 (E) Ingredient 100 100 100 100 100 100 (G), (Gi) component 46.1S 46.15 46.15 34-44 38.0S 34-43 (Π, (Ιι) component-_ _ 8.46 9.56 (H) component 7.69 7.69 7.69 9.07 25.39 22.96 In the case of the examples, the hardenability and practicality of any of the coating films are quite good. In addition, the Tg is increased, the residual monomer is reduced, the hardenability of the resin composition is good, and the original hot water resistance can be fully exerted. Furthermore, hardening The subsequent coloring (hue E!) And weather resistance are also excellent. On the other hand, in the cases of Comparative Examples 1 to 4, even if a part of the resin component used in the present invention should satisfy the constituent components of the present invention, the hardenability is poor. There are many residual monomers, and the cured product also has a monomer odor. Comparative Example 5 is an example of a dicyclopentadiene unsaturated polyester resin. Although the degree of unsaturation is also the proportion of each polymer component The molecular chain length of the maleic unsaturated bond is not visible in comparison with that of Comparative Example 4. Acetate is very different, 'but Tg 6 5 is lower than 25' and there are more residual monomers, so the weather resistance is also significantly deteriorated. In Comparative Example 6, by combining with the (E ~ 3) component, dicyclopentadiene The unsaturated bond of maleic acid, a polymer containing a (meth) acryloacryl group, and a combination of a (meth) acryloacryl monomer have good hardening properties, but have a large disadvantage of poor color of the hardened product.

2066-4592-PF (N) .ptd Page 53 548285

Example 11 In 100 parts of the resin composition obtained in Example 7 = _ liquid (containing 8% by weight of co content) 0.4 parts, add = stone / into the machine (made by VENUS glass company, standard type); : Mixing 1 part of acetophenone peroxide (Japanese grease, k = Mr. A) as a hardener and adjusting RTM injection. Next, the resin composition obtained in Example 9 Cobalt acrylate petroleum solvent solution 0.4, AER0SIL # 3 00 manufactured by anhydrous osmium dioxide / two-strand osmium) is mixed and adjusted to become a resin composition for a transparent gel coating (gel coat), and then added After 5 knives were kneaded and adjusted, a resin composition for primer gei coat was prepared. PERMEK N (manufactured by Nippon Oil & Fats Co., Ltd.) (i.e., manufactured by Nippon Oil & Fats Co., Ltd.) is added to the resin composition for the transparent adhesive coating, and the mixture is mixed by weight%. Grab w — 873 (manufactured by ANEST Iwata (stock)) spray coating thickness 〇8min. It was allowed to harden at 50 C for 60 minutes, and then the same weight of pERMEK N1 as the resin composition for primer gel coat was added and mixed. The W-87 3 was sprayed repeatedly with the same high viscosity as above. The transparent adhesive coating has a thickness of 0.2mm. It is allowed to harden at 50 ° C for 60 minutes. After confirming that the coating surface of the primer rubber coating is tack free, cover it with a preform glass fiber made with a glass content of 25% by weight in advance. After the convex type and the concave type are combined and closed, the injection pressure of the RTM injection machine is about 0.3MPa (3kg / cm2) and the resin is injected.

2066-4592-PF (N) .ptd Page 54 548285 V. Description of the invention (52) In a closed model, leave it at room temperature for 1 hour, and then cure it after 1 hour and then open the model. The FRP bath was obtained. The obtained FRP bath can be easily released and has a beautiful appearance. The obtained FRP bath was placed in 90 ×: hot water, and the continuous time until the inner surface of the bath was expanded was measured, and a result satisfying 5000 hours was obtained. Comparative Example 7 In the same manner as in Example 11, the resin composition obtained in Comparative Example 4 was used as a resin composition for injection, and the resin composition obtained in Comparative Example 1 was made into a resin composition for a transparent adhesive coating and a primer coating. A resin composition for a layer. After spraying the resin composition for a transparent adhesive coating in the same manner as in Example 丨, the resin composition for a transparent adhesive coating discharged from the spray gun became a sticky spider web, and a coating film could not be formed on the FRp type. Therefore, the glue coating is carried out by bristle coating, but the transparent glue coating and the primer glue coating fall down in a vertical flow of 9 to prevent the coating from being applied only with a thickness of 0.2 mm. ^ The FRP bath was made under the same hardening conditions as in Example 11. After the mold was released, the method and the convex mold were released, and the shape was broken, and the product could not be obtained. For the convenience of explanation, the inventions of the foregoing embodiments, comparative examples, and the like are described as examples of the present invention 1 to 10 and examples of the present invention u to 19, but those who write the examples of the invention 1 to 10 conform to the present invention Those who also pay a book of 1 to 10 can also be used as examples of 1 to 10 of the present invention. Λ According to the present invention, a resin composition having a dicyclopentadienyl group can be produced, which can fully exhibit the original air-hardening property, and has a fast hardening with little coloring after hardening. 548285 V. Description of the invention (53) The resin composition of the present invention exhibits excellent air hardenability, and has a good hardening color and high hardening degree. In addition, the hardened material has good weather resistance, and can be used as a laminated structure of various molded articles and outdoor products to provide excellent performance.

2066-4592-PF (N) .ptd page 56 548285 Illustration of simple diagrams 2066-4592-PF (N) .ptd page 57

Claims (1)

548 Na sixty r Jue Li Li 1 · A radically curable resin composition, which is a product produced by the reaction of dicyclopentadiene i · 〇mol and maleic acid 0.8 · 1 ~ 2 mol (A), and the epoxy compound (B) having two or more epoxy groups is 1 mole to the carboxyl group contained in the reaction product (A) and the epoxy group (b) has an epoxy group of 0.8 to 0.98 The ternary copolymer (C) obtained by the molar reaction is dissolved in the polymerizable monomer (D) which can be copolymerized with the ternary copolymer (C) to obtain 2 · As described in the first item of the scope of patent application The radically curable resin composition in which the polymerizable monomer (D) contains an aliphatic polymerizable monomer as an essential component. 3. A type of radically curable resin composition, which is a product (a) reacted by a ratio of dicyclopentadiene i · 〇mol and maleic acid 0 · 8 ~ 1 · 2 mole, More than one epoxy-based epoxy compound (b) is 1 mole to the carboxyl group contained in the reaction product (A) and the epoxy compound (b) has an epoxy group of 0.8 to 0.998 mole. After the ternary copolymer (c) obtained by the proportion reaction, the modified ternary copolymer (dagger) obtained by adding the hydroxyl group contained in the obtained ternary copolymer and the polybasic acid anhydride is dissolved in A polymerized monomer (d) copolymerized with the modified 3-membered copolymer (q). 4. The radically curable resin composition according to item 3 of the scope of the patent application, wherein the polymerizable monomer (D) contains an aliphatic polymerizable monomer as an essential component. 5 · A method for producing a radically curable resin composition, comprising: (1) in the presence of a metal ion blocking agent, at 170 ° C with dicyclodipentane 1.0 mol and maleic acid 0.8 ~ 1.2 Molar reaction product 2066-4592-PF (N) .ptd Page 58 548285 VI. Application for patent scope (A); (2) Epoxy compound (b) with 2 or more epoxy groups for the reaction product (A) A ternary copolymer (c) obtained by reacting 1 mol of the carboxyl group and an epoxy group of the epoxy compound (b) at a ratio of 0.8 to 098 mol; and (3) the obtained ternary copolymer ( c) It is soluble in the polymerizable monomer (D) which can react with the ternary copolymer. 6. The method for producing a radically curable resin composition according to item 5 of the scope of the patent application, wherein a part or all of the polymerizable monomer (D) used for dissolving the ternary copolymer (C) is The reaction product (a) is reacted in the presence of the epoxy compound (B) in the presence of the epoxy compound (B) to obtain a ternary copolymerized human body.口 7. The method for producing a radically curable resin composition as described in item 5 of the scope of the patent application, wherein the polymerizable monomer (D) is a polymer containing a fat-based polymerizable monomer as an essential component. 8. A method for producing a radically curable resin composition, comprising: 1.0 mole of valerene and maleic acid (A), and (1) in the presence of a metal ion blocking agent, which Secondary product one • 8 ~ 1 · 2 mole ratio reaction product (3) The obtained ternary copolymer (c) The hydroxyl group contained in the after-synthetic methoxy group J and the Page 59 548285 VI. Scope of patent application Modified ternary copolymer obtained by addition reaction of polybasic acid anhydride, (4) Dissolving distant modified ternary copolymer in a polymer that can react with the modified ternary polymer Sex monomer (D). 9. The method for producing a radically curable resin composition according to item 8 in the scope of the patent application, wherein a part or all of the polymerizable monomer (D) used for dissolving the ternary copolymer (C) is When the reaction product (a) reacts with the epoxy compound (B), it is reacted to obtain a ternary copolymer. I 0 · The method for producing a radically curable resin composition according to item 8 of the scope of the patent application, wherein the polymerizable monomer (D) contains an aliphatic polymerizable monomer as an essential component. II · A radically curable resin composition consisting of (fluorenyl) acrylic slurry composition (E) 100 parts by weight, plus a reaction product (F) of dicyclopentadiene and maleic acid, A ternary copolymer (G) having a number average molecular weight of 800 to 2500 obtained by reacting with an epoxy compound (B) having two or more epoxy groups and / or a hydroxyl group and a horse contained in the ternary copolymer A modified ternary copolymer (Gi) obtained by addition reaction of maleic anhydride or polybasic anhydride containing maleic anhydride is composed of 5 to 150 parts by weight. 1 2. The radically curable resin composition as described in item 1 of the scope of the patent application, further comprising 5 to 200 parts by weight of the polymerizable monomer (H). 1 3 · The radically curable resin composition according to item π of the patent application scope, wherein the component (E) contains a carboxyl group contained in a copolymer of methacrylic acid and an alkyl methacrylate, which is unsaturated. Composition of a glycidyl reactant. 2066-4592-PF (N) .ptd Page 60 548285 VI. Scope of Patent Application 1 4 · The radically hardenable tree month composition as described in item 11 of the scope of patent application, which is derived from the (G) component and ( Or) The translocation rate of maleic acid unit to fumaric acid unit contained in (G!) Component is below 70%. 1 ··· A type of radical curable resin composition composed of (meth) acrylic acid-based slurry composition (E) 100 weight part, plus the reaction product of dicyclopentadiene and maleic acid (F) a ternary copolymer (G) having a number average molecular weight of 800 to 2500 obtained by reacting with an epoxy compound (B) having two or more epoxy groups and / or the ternary copolymer Modified ternary copolymer (Gi) obtained by addition reaction of hydroxyl group with maleic anhydride or maleic anhydride-containing polybasic anhydride (Gi) 5 to 150 weight parts, and vinyl ester resin (I) and (Or) modified vinyl ester resin (L) obtained by addition reaction of 5 to 40% of the hydroxyl groups contained in the vinyl ester resin (I) with maleic anhydride and / or succinic anhydride (L) 5 to 50 parts by weight Composed of. 16. The radically curable resin composition according to item 15 of the scope of the patent application, further comprising 5 to 200 parts by weight of a polymerizable monomer (H). 1 7 · The radically curable resin composition described in item 15 of the scope of the patent application, wherein the component (E) is a carboxyl group and an unsaturated ring contained in a copolymer of methacrylic acid and fluorenyl acrylic alkyl vinegar. Composition of oxypropyl compounds. 1 8 · The radically curable resin composition as described in Item 5 of the declared patent scope, where the maleic acid contained in the component (G) and / or (Gi) is in the early position to the fumaric unit. The indexing rate is below 70%. 19 · A molded product, which is the radical hardening property described in the scope of patent application Nos. 1, 2, 3, 4, 11, 1, 2, 1, 3, 1, 4, 16, 16, 7 or 18 2066-4592-PF (N) .ptd Page 61 548285 6. Scope of patent application Manufactured from resin composition. _Circle Page 62 2066-4592-PF (N) .ptd