TW574306B - Unsaturated resin composition - Google Patents

Description

It is called 306. Description of the invention (1) The technical field to which the invention belongs ... The present invention relates to an unsaturated polyester resin composition and a molded article made from the composition. In more detail, it relates to a non-D polyester resin composition and a molded article made from the resin composition, 1 = fiber reinforced plastic (FRP), lining, Tao prayer, bright coating bucket, temple Various fields are quite useful. Stomach know-how consists of color-fast coatings and linings, and inventions that are quite laminates and corrugated sheets in terms of unsaturation. 'If this is a major obstacle, the aforementioned insufficiency has less single-shot vinyl. In addition, if compared with polyester trees, the problem to be solved is based on removal: The polyester resin composition is excellent in transparency, weather resistance, and color, so it is widely used in residential parts. Plastic), bright light for outdoor parts ^, flat panel, etc. " The unsaturated polyester resin composition used cannot fully exhibit its characteristics because it is hardened by anaerobic air and hardened. It has good miscibility with the dicyclopentenepentenyl unsaturated polyester resin that can be included in the polyester resin composition and the included stupid ethylene as the bulk. That is, it is conventionally used to include allyl double bonds; as unsaturated polyvinegar, although it can improve the air, the conventional unsaturated polyester resin containing allyl ether groups is more allyl lice atoms Stop reaction and chain transfer reaction 2066-4593-PF (N); Ahddub.ptd Page 5 574306 5. Description of the invention (2) The reaction speed of the hardening reaction becomes slower. If it is used in laminates, it is a problem. In addition, the above-mentioned dicyclopentadienyl-containing compounds (yellow) have high storage stability and poor fastness. In order to improve the color fastness of hardened products, usually the properties such as fastness are quite excellent. The double bond included in the unsaturated vinyl resin used as a vinyl monomer for cross-linking and even unsaturated polyester resins is difficult to make up with the (fluorenyl) propylene-containing overall resin composition. Decrease in hardenability and weather resistance of materials. As mentioned above, the effective methods for dicyclopentane-containing color, storage stability, and hardening reaction are the status quo. In view of this situation, the polyester resin composition of the present invention, and its molded products, weather resistance, and color fastness ensure the necessary molding workability and forming properties of the unsaturated polyester resin composition article 0 ', which is difficult to complete. It is a major deficiency that produces a dilute base unsaturated polyester resin that is difficult to release from the mold force σ. The unsaturated polyester resin is colored and hardened (molded). If the dicyclopentenyl unsaturated polyester resin is transparent, If weather-resistant, color (meth) acrylfluorene-based compounds are used instead of styrene, the α, / 5-unsaturated compounds of the fumaric acid will be copolymerized, so that the The color of the hardened product is strong. The improvement of the properties and weatherability of the ethylenically unsaturated polyester resin has not been identified. The purpose is to provide an unsaturated 'wherein' has good transparency 'and even with an open mold. The method can also be 'typed' and has sufficient air hardening and means for solving the problem using the molding of the resin composition: The present invention relates to a molded article, which is:

2066-4593-PF (N); Ahddub.ptd Page 6 574306 V. Description of the invention (3) (1) The (A) system includes the reaction product of dicyclopentadiene and maleic acid Saturated polyester. The rearrangement ratio of the maleic acid-derived group (cis-based group) to the maleic acid-derived group (trans-based group) included in the unsaturated polyester is 60%. 100% by weight of 95% unsaturated polyester (hereinafter referred to as minutes); (B) 0.5 to 80 points of polymer containing (fluorenyl) acrylic group; and (C) polymerizable monomer 10 to Unsaturated polyester resin composition composed of 180 points (Invention 1); (2 ^ The resin composition according to item (1) (Invention 2), wherein the aforementioned dibadene and maleic acid The reaction product between the acids includes an ionic chain-linking agent; "Stomach (3 I The resin composition as described in (1) (Invention 3), wherein (B) component includes a modified vinyl ester resin, and this resin is 5 to 40% of the hydroxyl groups included in the vinyl ester resin and / or ethylene resin, which are obtained by the acid addition reaction; (4), the resin composition as described in (2) (invention *) Where (B) component includes Vinyl resin, this resin is 5 to 40% of the bases included in the ethylene and / or ethyl alcohol brewing resin, and the acidity is obtained by the addition reaction; D (5) is as described in (1) Resin composition (Invention 5), φ ⑷ 1 minute: (meth) acrylic urethane; "(B) (Di = 7A :): Diester composition (Invention 6), where , Fluorenyl) acrylic urethane; 7 The resin composition (invention 7) according to item (1), wherein 2066-4593-PF (N); Ahddub.ptd page 7 574306 5. Description of the invention (4 ) ----—- (B) The component includes poly (meth) acrylate; (8) The resin composition according to item (2) (Invention 8), wherein (B) component includes poly (methyl) ) Acrylate; and, (9) using unsaturated polyS as described in (1), (2), (3), (4), (5), (6), (7) or (8) The resin composition is a molded article (Invention 9). Example of the invention: The composition of the present invention 1 is a reaction product between dicyclopentane and maleic acid including the component (A) Unsaturated polyester, The rearrangement ratio of the maleic acid-derived group (cis group) to the fumaric acid-derived group (trans group) included in the unsaturated polyester is 60 to 95% unsaturated Unsaturated polyester resin composition composed of polyester (A); (B) component (fluorenyl group) acrylfluorene group-containing polymer (B) and (C) component polymerizable monomer (C). To harden the composition of the present invention 1, a group derived from fumaric acid (trans group) (trans alpha from fumaric acid, stone-unsaturated group-containing group) and polymerization The reaction between unsaturated groups included in the monomer (c) results in the allyl double bond of the dicyclopentenyl group included in the component (A) and the (methyl) group included in the (B) component. The reaction between the acrylofluorenyl group and the unsaturated group included in the polymerizable monomer (C); and the residual maleic acid-derived group (cis group) (cis-α derived from maleic acid, / 5-group containing unsaturated bond) and (meth) acrylfluorene group included in component (B) and unsaturated group included in polymerizable monomer (c)

574306 Fifth, the reaction of invention description (5), so that it can exert rapid hardening and sufficient space? Sex. In addition, the heat resistance and durability of the cured product = unsaturated polyacetic acid (A) system, including unsaturated polybasic acids produced by the reaction between dicyclopentadiene butadiene, and A phase-saturated polyester containing a dicyclopentenyl group included in the unsaturated polyester, which is obtained by polymerization of an acid component and polycondensation of a polyhydric alcohol and / or an epoxidized m bis (hereinafter referred to as an alcohol component). The total weight is 5 ~ 36% by weight, and even 5 ~ 30.

When the content of the dicyclopentenyl group is less than 5% by weight, air hardenability is obtained. : On the other hand, if it exceeds 36% by weight, the resin composition becomes hard, and when FRP is blended to form FRP, molding cracks are liable to occur. & J If the content of dicyclopentyl is within the above-mentioned suitable range, it has excellent chemical properties. Even if it is made into FRP, it can be turned over-☆, and "hardness characteristics of workmanship." It also shows a poor mechanically strong substitution of the-part of the aforementioned acid 2 (a part of the unsaturated polybasic acid other than the reaction product of dicyclopentadiene and maleic acid), and further includes aromatic saturation in two steps. Saturated polyπ acids such as polyacids or aliphatic saturated polyazoles. The content of unsaturated gallic acid is 0.001% of the acid component. If the unsaturated polybasic acid is less than 20 mol%, the curing reactivity is insufficient, and it is not good. And 'substituting a part of a saturated polybasic acid, a monobasic acid may be used as needed. Moreover, instead of a part of the xiyuan alcohol component, monoethanol can also be used as needed. The acid value of unsaturated polyacetic acid (A) is not particularly limited. Generally speaking, the ancient acid value is 55 or less, preferably 40 or less, and more preferably 30 or less. This series is resistant to 2066-4593-PF ( N); Ahddub.ptd Page 9 574306 V. Description of the invention (6) --- The viewpoint of pharmaceutical properties seems to be ideal. At the same time, 'the molecular weight of the unsaturated polyester (A) is not particularly limited', but the number-average molecular weight is from 600 to 300, and preferably from 65 to 2000, and from 70 to 150. The range is more preferable, and this is preferable from the viewpoint of miscibility with the polymerizable monomer. The unsaturated polybasic acid system used as the aforementioned acid component is a substituent in the molecule that reacts with a hydroxyl group or an epoxy group included in an alcohol component to form an ^ ester bond. It has two substituents and a polymerizable group. Unsaturated compounds are preferred. As specific examples of the aforementioned unsaturated polybasic acid, for example, U, 0-unsaturated polybasic acid such as maleic acid, fumaric acid, aconitic acid, itaconic acid, and the like; dihydromuconic acid Etc., 7-unsaturated polybasic acids; anhydrides of these acids, dentates of these acids, and alkyl esters of these acids. These acids may be used alone or in combination of two or more. As a substitute for a part of the aforementioned acid component, examples of the saturated polybasic acid to be used include, for example, malonic acid, succinic acid, methylsuccinic acid, 2, 2-monomethylsuccinic acid, 2, 3-Dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-di Aliphatic saturated polybasic acids such as fluorenylglutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; phthalic acid, Aromatic saturated polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc .; Heteric acid, 丨, hexahydrophthalic acid, cyclobutane-1,1 ~ Dicarboxylic acids, cyclohexane-trans-i, 4-dicarboxylic acids, alicyclic saturated polybasic acids, anhydrides of these acids, halides of these acids,

574306 V. Description of the invention (7)

And the I-j-yl ester derivatives on it. These acids can be used alone or in combination of two or more. Specific examples of the polyhydric alcohol which is one of the alcohol components mentioned above include, for example, 2-methyl-1,3 T diol, dimethyl-1,3-propane 1,7-heptane Alcohol, I 4-Cyclohexanediol, Ethylene Glycol, Isodiol Diethylene Glycol, 1,3-Propanediol-A ...-Propanediol, 14-Butyl j-alcohol, 1,3- Butanediol, 2, 3-propanediol, 1,5-Λ- ^, ^, fluorenyl alcohol, 1,6-hexanediol, 2,2-diol (neopentyl glycol), 9 ^ u, A ^, 0 ^ ^, 2-ethyl-1,4-butanediol, 1,8-octanediol, 1 q ^ ^ η A, I nonanediol, 1,10-decanediol, L 4-arum ， 1,4-Dijinga |: Ban 1 ^ Jiafu] Tochihakiro, 2,2-diethyl-1,3 ~ propylene glycol, 3 -methyl ~ 1,4-pentanediol, 2, 2-Diethyl-butadiene, Γ ,,,, and alcohol, polyhydroxyethyl-fluorene and yamiko with molecular weights from 200 to 200 0: Sampling for 300 to 3000 " 仏 G — and knife ... Hydroxypropanediol, glycerol, trimethylmethoxide, p-xylylene glycol, glutamate, d-methylpropane, Α, gasified two-year-old alcohol, hydrogenated bivalent oxide, adduct Wait. These alcohols may be used in combination of two or more kinds. Combined with the earlier use alone, Shan v 丨, one of the mounting compounds with one of the knives, I # each do 丨 ^ ^ For example: Ethylene oxide, P ^, and grains, for example, p, m Yuan clothing Oxypropane, butylene oxide, stupid yakiniku, bi-year-old A's, 4, and & These epoxy compounds can be used as I # or in combination of two or more kinds. In the early days, when the person who knows the reaction product between the bicyclic olefinic difluorene included in the component (A), the case of using acenaphthene and cis butadiene (invention 2), \ belongs to the ion seal The chain agent's ene-acid dicyclopentane was preserved for the purpose of blocking the effect of prosthesene on the conversion of the p-type cis-butanedioic acid bicyclic fluorene anisotropin S, ^ J 岈For the past 574306 V. Description of the invention (8) t, 690 1 How can the Hassen number not be reduced to a tree below 20 ^, and the color of things can be reduced to Hassen number 10 ~ 2〇 And even 10 ~ 100% of the human response and storage stability have been significantly improved. It is suitable for a large amount of polymerization of the conventionally used unsaturated polyester resin composition having a dibasic weight of ^%, which can be used within a range of ==. In the past, although all the hardening was completed, it was too costly. In addition, in order to promote hardening, due to the large amount of hardening dose used, it will be more than 1% of the weight of the tongue and premature body that was stored in a state of poor hardening. 'And these results can reduce the amount of this residual monomer to less than 1%, or even 0.8% by weight or less, especially 0.5% by weight or less. In February, it has enough transparency and weather resistance. Hardened products with chemical resistance and color fastness (such as molded products). As the metal ion chain-sealing agent used in the present invention 2, if it is a conventional compound = a compound having metal ion chain-sealing ability, it is not particularly limited and is used in a sentence. Examples include (1) amino acids and salts thereof. ; (2) 3 group phosphate, monoalkenyl esters and salts of these vinegars; (3) n-vinyl glutenyl esters, N-fluorenyl aspartic acid esters and salts of these esters; (4) ketone derivatives; (5) phenol derivatives; etc. These compounds can be used, and can also be used in combination of two or more. (1) As an amino acid and its salt system, an acid and its salt having three or more carboxyl groups, but It is preferable from the viewpoint of metal ion blocking energy. Presentations include: triacetamine, ethylenediaminetetraacetic acid, -octade-^^ monoethylenetriamine, pentaethylsulfonium, diethylenetetraethylene Hexaacetic acid, cyclohexane], ^ diamine tetraacetic acid, N-hydroxyethyl ethylene monoamine diacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid, ethylene diamine tetra

574306 Propyl group ~ N′-Carbohydratino aspartic acid, N-alkenyl-N, -carboxymethyl group; ammonia ^ and alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts of these compounds Wait. (2) Examples of scaly acid monobasic esters, monobasic acid dilute esters, and salts of these esters' include lauryl phosphate, stearyl phosphate, and the like. (3) As the salt of N-glycyl glutamate, n-fluorenyl aspartic acid ester, and some esters, it can be made ^ ψ μ L f ^ φ. For example, yakunomoto (share) Sold

AmisoftHS-11, gs ~ i1, etc. (4) Examples of the mesenedione derivatives include acetoacetone, phenylacetone, and the like. (5) Examples of the chrysophenol derivative include chrysol ketone, stilbene, peptin, and r-stilbene. For the metal ion chain-linking agent described above, lactic acid and salts thereof having three carboxyl groups or more are preferred from the viewpoint of color resistance, especially ethylenediaminetetraacetic acid and diethylenetriamine. Pentaacetic acid, triethylenetetraaminehexaacetic acid, cyclohexane1,2-monoaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid and its salts compared to dicyclopentadiene and maleic acid In total, the use amount of the aforementioned gold ion chain-linking agent is 5 to 5000 ppm, or even 10 to 100 mouth, especially 15 to 50 Ppm. If the amount of the metal ion chain-linking agent exceeds 500 ppm, after the unsaturated polyester resin composition is prepared, a metal compound having a reducing effect is mixed in the resin composition, and == peroxide, etc. In the case of free radical hardening, the metal compound is captured by the residual metal ion chain-linking agent.

574306

5. Description of the invention (ίο) Hardening is impeded, so it is not good. In addition, if it is less than 5 PPm, the effect of reducing coloration cannot be sufficiently obtained. Furthermore, in the present invention, the dicyclopentenyl group refers to the formula (1): [化 1]

Substituted group and / or formula (2) [Chemical Formula 2]

(2) the substituents represented. (A) The reaction product between dicyclopentadiene and maleic acid included in the component is in the absence or presence of a metal ion chain-linking agent, for example, it can be used in dicyclopentadiene and maleic anhydride It was obtained by adding water dropwise to the reaction. That is, a maleic acid addition reaction product having a substituent described in the above formulae (1) and (2) can be obtained including the reaction product. At this time, the amounts of water and dicyclopentadiene are preferably 0.8 to 1.1 moles per mole relative to 1 mole of maleic anhydride. Addition of unsaturated polybasic acids, including saturated polybasic acids, etc. as required

2066-4593-PF (N); Ahddub.ptd Page 14 574306 V. Description of the invention (11) An acid is obtained in the reaction product obtained, and an unsaturated polyester is prepared by the condensation reaction between the compound and an alcohol component. (A). The method for increasing the hardening reactivity of unsaturated polyester resin compositions, and increasing the number of groups derived from fumaric acid (trans alpha, human unsaturated bond) included in unsaturated polyacetate are conventionally known. (For example, 3 "Poly Resin Handbook" (June 3 (1, 988, Nikkan Kogyo Kogyo, by Takayama Eiichiro), page 67, lines 10-13, which states that "the conversion of maleic acid is It is considered to be an important reason, because the copolymerizable 'maleic acid diester and the maleic acid diester are very different from each other. The anti-m is far more than the cis τ dicarboxylic acid. It is more likely to be more complete with the structure of the benzene hill tree. "The same book, 7 °, pages 10 ~ 12, 的 resins with a large amount of acid harden fast and have high heat generation, excellent resistance, and excellent properties." Plastic, 2, (6), 1 (1 9 5 6) "(Akita, Okazawa Hirahei), measured the conversion ratio between unsaturated polyester and styrene with different fish conversion ratios: :::咼 (the content of fumarate is relatively high; fat ") June 15, 1961, Shimada Shimbun republished by Yoshida Shimbada. Works by Masahiro Yang and Inoki 28 pages 20 ~ In line 22, "Research on the complex m: was published, but for commercially available polyester resins, dibutene butadiene 1 it [or even a trace amount even if detected", also in the case of polyacetate. According to the conventional technique: the units of the di-dicarboxylic acid are rearranged to the trans trans-Ding degree ^ set ^ at 210 rhyme. C, and take a longer trans-Δ interval to use the dish

574306 V. Description of the invention (12) --- For example, morpholine rearrangement catalyst will improve the rearrangement efficiency of rearrangement to succinic acid units. In general, the rearrangement rate of the rearranged to fumaric acid units is more than 98%, which makes the case of particularly low radon exceeding. Once these techniques are used, the hardening reactivity of the resin composition obtained by each technique is still low, and obviously, only the colorer is obtained. The inventor discovered that, contrary to the conventional knowledge, in order to improve the hardening reactivity of an unsaturated polyg-containing resin composition containing a dipentene group, coexistence with a polymer containing (fluorenyl) acrylfluorene, It is most effective to add a group derived from maleic acid (cis α, stone-unsaturated group) from unsaturated polyacetic acid ^. That is, when the curing reactivity of the resin composition of the present invention is improved and the heat resistance of the cured product is improved, the group derived from the maleic acid included in the component (A) is also increased in contrast to the conventionally known technology. (Cis α, / 3-unsaturated bond-containing group) is the most effective. The increase in the group derived from the maleic acid included in the component (A) (cis α, / 3-unsaturated bond-containing group) is based on the addition of the group derived from the maleic acid included in the component (A). Unit reduction was achieved by rearrangement to fumaric acid units. For the reduction of rearrangement of maleic acid-derived units to fumaric acid units, the reaction is better at a lower temperature, but because the condensation reaction takes too long at low temperature, from an economic point of view , In 17〇 ~ 205. (:, It is best to carry out the reaction at 180 ~ 200 ° C, and the rearrangement rate of the unit rearrangement from maleic acid to the early position of fumaric acid is made 60% to 5%, or even 60% 90% is better, and 60 ~ 85% is the best. If the aforementioned rearrangement rate is less than 60%, the reaction temperature must be set below about 160 ° C, and the condensation reaction cannot be carried out without the assistance of an esterification catalyst. When it is colored, on the other hand, if

574306 V. Description of the invention (13)-When the rearrangement rate exceeds 95%, the reaction between the (A) component and the (B) component is low # The hardenability of the resin composition of the present invention is reduced, and the molded product 3 is obtained The color fastness is also reduced. The polymer (B) containing (fluorenyl) acrylic fluorenyl group is divided into + "T package (fluorenyl) acrylic fluorenyl group with more than one, even 2 to 3) σ Ί 〃 '本 & quot Come here> Zhuo Duo expresses anaerobic hardenability, but when used in combination with the (A) component, the original properties of the Japanese ingredients /, τ, be ι C Β) completely improve the air hardening / 'Wang, 1¾ ϋ The present invention The air hardenability of the resin composition is improved. As the life of the polymer (B) containing a (meth) acrylfluorene group, for example, 5 to 40% of a vinyl ester resin and / or a vinyl ester resin-containing group is subjected to an addition reaction of an acid anhydride. The resulting modified ethylene, (B1), and a polymer including this (βΐ); a polymer including (methyl · tree month carbamic acid ester (B2); including a poly (fluorenyl) diacrylic acid ( Β3) polymer and so on. "Natural acid" and "the so-called inclusion of the aforementioned (B1) ~ (B3) components refers to the inclusion of various components." Moreover, as a reactive diluent in the production of these polymer compounds The polymerizable monomers used can stand within the range of 50% by weight or less. Moreover, (bi) ~ can be used alone or in combination with more than two types. Knife, ^ ^ ^ 口 Z 禋 or more. In the case where the polymerizable monomer (G ^ hv star · fr) used as the reactive diluent is included, the included polymerizable early moon bean [gamma] C) is used as the polymerizable monomer (c). The acid value of the aforementioned vinyl vinegar resin is 2 to 5; the acid value of the fat is preferably 10 to 55. !! 〇, and said modified vinyl vinegar tree The aforementioned vinyl vinegar resin is usually completed by epoxy resin and unsaturated one yuan

574306 V. Description of the invention (14)-The polymer obtained between S and Y. η The purpose of closing the moon is a compound capable of using at least one saprolite in one molecule. As this specific example, "multi-variety and multi-variation", water-sweetener>, epoxide, epoxy varnish, epoxidized diene, resin epoxide of dry oil, and the like. These resins may be used alone or in combination of two or more kinds. As the foregoing: [gamma] propionate, meat: ί :: enduric acid 'can be exemplified by (acryloyl) -containing propylene di-earths, such as acrylic acid, methyl methacrylate, phoenix, and derivatives of cinnamic acid. . These carboxylic acids may be used alone or in combination of two or more kinds. Even if it's needed, it can be modified by reacting the anhydride with 5 ~ 40% of the vinyl ester resin. Examples of the other g anhydride include phthalic anhydride, maleic acid, hydrazone, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid: safranin tetrahydrogenated Binary compounds such as phthalic anhydride, 3,6-m-tetrahydrophthalate-sense-fluorenylmethyl bridge tetra-ratified phthalic acid if, tetramophthalic anhydride, and phthalic anhydride Acid anhydride. These acid anhydrides may be used alone or in combination of two or more kinds. The reaction can be performed, for example, between the aforementioned epoxy resin and an unsaturated monocarboxylic acid at 60 to 130 ° C for 3 to 15 hours. Hes said (fluorenyl) acrylic aminocarbamate is obtained through the reaction between an acidic alkyl ester and a polyisocyanate. At this time, the amount of the isocyanate group relative to the hydroxyl group is 1 mole. ~ 0.98 mol. (Meth) acrylic polymer. ’Relative to hydroxyl

574306 V. Description of the invention (15) As specific examples of the aforementioned (meth) acrylic monohydroxyalkyl ester, for example, 2 ~ ethyl (meth) acrylate, (1-hydroxypropyl (methyl) ) Acrylic esters, low ethylene glycol mono (fluorenyl) acrylic acid propylene glycol mono (fluorenyl) acrylic acid, etc. This monoester can be used alone or in combination of two or more kinds. Also, as the aforementioned polyisocyanate, Specific Example 5 Examples include: diethylene diisocyanate hydrogenated fluorene phenylene diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate isophorone diisocyanate, and phenyl methane diisocyanate hydrogenated diphenyl. Some isocyanates, such as sintered diisocyanate, may be used alone or in combination of two or more types. ≪ > The aforementioned poly (fluorenyl) acrylic acid ester system may make the unsaturated monobasic acid or its derivative, or Gather different A polymer obtained by reacting a cyanate ester with a polyester polyol, and then reacting a hydroxyalkyl (meth) acrylate with an isocyanate residue, or a polymer obtained by reacting a (hydroxy) monohydroxyalkyl (meth) acrylate or glycidol The polymer obtained by reacting (meth) acrylic acid ester with polyester polycarboxylic acid. As the aforementioned polyester polycarboxylic acid and polyester polyol, the aforementioned unsaturated polyester can be used as the aforementioned unsaturated monocarboxylic acid or Its derivatives and (fluorenyl) acrylic acid are used for the purpose, and the aforementioned unsaturated polyester vinyl resin and (fluorenyl) acrylic urethane raw materials can still be used. As the blending amount of component (B) Compared with 100 points of the (A) component, 0.5 to 80 points, or even 3 to 70 points is better. If the blending amount of the (B) 1 component is less than 0.5 point, it cannot be fully achieved. The g of the present invention which improves the hardenability and air hardenability will be produced when it exceeds 80 minutes. Discoloration, etc.

Page 19 574306 V. Description of Invention (16) His problem. (c) a polymerizable monomer of the component (in the case of c and ^, the polymer is a component for viscosity adjustment and hardening with (A) component and (B) in an eight-series system. A copolymerizable component of the component is used as a polymerizable monomer ( C) series, can be used as A…, and can also be used as a high viscosity polymer to describe the melting of each component σ. The solvent of the product is used to adjust the viscosity of the (meth) acrylic The molecular weight of the monomer is preferably 350 or less, and if it exceeds 3 50, the water resistance and heat resistance of the resin composition are reduced, which is not good. As the polymerizable monomer (C), ethylene, vinylbenzene, Styrene monomers such as tertiary olefin, p-chlorostyrene, p-fluorenylbenzylbenzene, fluorenyl acrylate, (fluorenyl) propylene, (fluorenyl) butyl acrylate, ester, (fluorenyl) Lauryl acrylate (fluorenyl) acrylic acid-2-hydroxyethyl glycidyl (meth) acrylate di (fluorenyl) acrylate, diethylene glycol di (fluorenyl) acrylate, etc.] Specific examples include, for example, ·· Bt-butyl-benzyl ethylene, α-fluorenyl styrene, p-chloromethylstyrene, diethyloxy (methyl) acrylic , (Fluorenyl) ethyl acetate, (meth) acrylic acid di (fluorenyl) -2-ethylhexyl, (meth) acrylic acid cyclohexyl (meth) acrylic acid 2-hydroxypropyl acrylate,, ( Zinc (meth) acrylate: ethylene glycol glycol (meth) acrylate, neopentyl (fluorenyl) acrylic monomer, etc. In addition, the function of adjusting viscosity is also reduced, so it is not good. In particular, if methyl is used Methyl acrylate is preferred from the viewpoint of producing a high-performance molded product. These polymerizable monomers can be used alone or in combination of two or more types. Depending on the type and formulation of the polymerizable monomer , Can also adjust the surface hard sound

2066-4593-PF (N); Ahddub.p t d p. 20 574306 5. Description of the invention (17) and reactivity. As the amount of (C) component, relative, it is 10 to 180 points, or even 30 to 100 points, for A) 100 points, which is better from a point of view. The shrinkage of the earth in the paternal association is based on the production of the aforementioned (A) component, (b) component, and conventional polymerization inhibitors. As for the above-mentioned polymerization inhibitor, each of the specific diphenols, methylhydroquinones, and methoxyparabens can be used as needed, and examples include para-phenol, 2,5-di- Tributylhydroquinone, benzene first-butylhydroquinone, catechol, naphthol, nitrobenzol, 2 4th = butylcatechol, 4-hydroxy-2, 2, 6, 6-Tetramethylpiperidine, Hydrocarbyloxy I——Third-Butylphenylphenyllithium, Hydrocarbyloxy-2,2,6,6_tetramethylmonoxide, 2 6-Tetramethyl Test-4-yl-acetic acid, buconyl-2, 2, "milk =, piperidin-4-yl-2-ethylhexanoate, [monohydroxy-2, methyl-4-yl-stearin Sour vinegar and the like are not limited to these four inhibitors, which 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 or two can be formulated. More than one of the aforementioned polymerization inhibitors can be used. In addition, the resin composition of the present invention can be appropriately added with various additives according to the purpose or predetermined physical properties. U When used in molding materials, calcium carbonate, hydrogen can be added as needed. ,, aluminum, sticky Fillers such as talc, etc .; Thickeners such as oxides or hydroxides of alkaline earth metals; Internal release agents such as stearic acid, calcium stearate, and stearic acid; glass fibers, carbon fibers, Amine or polyester

2066-4593 · PF (N); Ahddub.ptd Page 21 574306 V. Description of the invention (18) Reinforcing agents made of organic fibers, etc .; benzene peroxide, dodecane peroxide, methyl ethyl peroxide Testosterone, third butyl-2-ethylhexanoate S, third butyl octanoate, third butyl benzoate, cumene hydroperoxide, cyclic peroxide Organic peroxides such as hexanone, diisopropylperoxide, etc .; or 2,2, -azobisisobutyronitrile, 2-phenylazo-2,4-difluorenyl-4-fluorenyloxy Polymerization initiators such as azo compounds such as valeronitrile, pigments, and others. When used as a coating material for lamination and gloss coating, the pigment composition may be included in the resin composition of the present invention in an amount of 0 to 70 minutes, if necessary. It may also include thixotropic agents such as fine powder anhydrous silicon dioxide, asbestos, and the like; and polymerization accelerators formed from metal soaps such as cobalt octenate, manganese naphthenate, and copper naphthenate. Even if necessary, the same fillers and thickeners as those used for molding materials can be used. When forming a resin composition for lamination and gloss coating, one or two or more of the aforementioned organic peroxides are added at the time of molding, and at a normal temperature or a medium temperature of 40 to 150C, or even a medium temperature of 40 to 100 ° C, It can be hardened by reduced pressure, normal pressure or pressure. It is even possible to apply photo-hardening with a photosensitizer such as phenyl alkyl ether. The added amount of the hardener is 0.2 to 5 minutes with respect to the resin composition. 'The aforementioned photosensitizers may also be referred to as photohardeners. In the present specification, these photohardeners are collectively used as photosensitizers. However, as a photosensitizer with a sensitivity in the visible " light range, hexaarylbiphenyl Blends between imidazole compounds and nitrogen-donating compounds, or, for example,

574306 V. Description of the invention (19): --- "surface" 27 (7) 548 (1 989), Sato et al. Highlights of the 3rd Polymer Materials Symposium 1B, P · 1 8 (1 994) In addition to the camphorquinones, tris (benzyl) benzyl dibenzylphosphine oxides, fluorenylthiaxanthone, biscyclopentadienyl titanium-bis (pentafluorobenzyl) f, it can even be used from the ultraviolet A wide range of photosensitizers with sensitivity in the visible range. Examples of such a photosensitizer include bis (2,6-dioxophenylphenylhydrazone) -2,4,4-trifluorenylpentylphosphine oxide, and bis (2,4,6-trifluorenyl) Phenylphosphonium oxide) phosphonium oxides such as phosphonium oxide, 2,4,6-trimethylphenylphosphonium-diphenylphosphine oxide, 2,6-dioxophenylphenylphosphonium-diphenylphosphine oxide, etc. Compound specifically. These compounds are commercially available and can be used, for example:

Darocurl 1 73 (trade name, manufactured by Chiba · Specialty · Chemicals, 2-hydroxy-2-methyl-1-phenylpropane-j-one) and bis (2,6-dioxophenhydrazone) -2 , 4,4-trifluorenylpentylphosphine oxide (Chiba ·

Special ty · Chemicals) Irugakyual 700 (trade name, Chiba ·) mixed at a ratio of 75/25 (weight ratio)

Specialty. Chemicals); Irugakyual84 (trade name, Chiba. Specialty. Chemicals, 1-hydroxy-cyclohexyl-phenyl ketone) and bis (2, 6-dioxophenylide) —2,4 , 4-tris (trimethylpentylphosphine oxide) (made by Chiba · Specialty. Chemicals) at a ratio of 75/25 (weight ratio) Irugakyual 80 0 (trade name, manufactured by Chiba · Specialty • Chemicals) or 50 / 50 (weight ratio) Irugakyual 85 0 (trade name, manufactured by Chiba · Specialty-Chemicals); Irugakyua 819 (trade name, manufactured by Chiba · Specialty • Chemicals, double (2,4,6-San 曱base

2066-4593-PF (N); Ahddub.ptd Page 23 574306 V. Description of the invention (20) The present Si &) -benzene scale oxide) · T 11 r * 1 · * m, 2 4 R Λ Λ ln TP0 (trade name, BASF clothing 2,4,6_: dimethylbenzidine-dibenzylphosphine oxide) and the like. _8 is two = the ratio of the photosensitizer, for example, the photohardenability of the resin composition is deteriorated: if it is divided, the resin composition performance may be deteriorated. On the other hand, 0.05 ~ 8: = 1〇00 minutes /, 丄 ☆ Dao Wenjia ○ · 1 ~ 5 minutes are particularly eliminated. According to the resin composition of the present invention, the right, left, and left, such as w, ^ π + wind, are related to obtaining a hardened material that has a fast hardening speed and a high residual strength, because it is air-hardenable and fast. Properties, color, solid block molding compound ⑽c), wash cast material as large molding compound (SMC) or *, spray molding to make the application = resin hand molding is a bright coating agent, can be obtained and lining Long material base or group of people ::: Molded products are used in signboards, cubicle elevated sinks, bathtubs, stone; r platform is m; wall components, face wash vanity, cabinet Dali loading sandalwood, window with handle Frame: Swimming: water yachts, nautical materials, the steel pipe or reinforced concrete pipe inner lining paving materials, etc. *. As transparent: =: material, bed material, impregnated with this composition, it can also be used as a strong material, making wood ΛΙ 4 / tl TF reinforced wood and flooring materials. Example:

574306 V. Description of the invention (21) Hereinafter, the present invention will be further described in detail through examples and comparative examples. In the present invention, the molecular weight is calculated by GPC (gel permeation chromatography) 'using a polystyrene calibration curve' to obtain a number average molecular weight (μ n) and a weight average molecular weight (M w). In addition, the acid value measurement method is implemented in accordance with j s K-6 9 0 1, 5 · 3.5 · 2 indicator titration method, and J I S K-〇 〇 7 0, 7 · 1 neutralization titration method. Production Example 1 (Production of Unsaturated Polyester (A1)) Into a 4-necked flask, maleic anhydride 98 points, dicyclopentadiene 1 32 points, and ethylenediamine tetrachloride as a metal ion chain-linking agent were placed. After the acetic acid was heated to 80 ° C under a nitrogen flow, 18 minutes of water was added dropwise to maintain the temperature of the content at 1000 ° C. After the dropping was completed, the reaction was carried out at 120 ° C for 1 hour, and then the temperature was raised and maintained at 160 ° C for 1 hour to obtain a dicycloglutaric maleic acid adduct. Next, add 196 minutes of maleic acid needles, 296 minutes of phthalic anhydride, and 359 minutes of propylene glycol and mix them. Dehydration was performed at 2000C over 15 hours according to the traditional method under nitrogen flow. The condensation reaction yields dicyclopentenyl-containing residues and polyg (A1) having an acid value of 30. The obtained unsaturated polyester (A1) had a number-average molecular weight (Mη) based on GPC of 1150, a weight-average molecular weight (Mw) of 6000, and a fumaric acid rearrangement rate based on 1 MNR of 80%. Production Example 2 (Production of Unsaturated Polyester (a 2)) Except that ethylenediaminetetraacetic acid was not used, the same procedure as in Production Example 1 was performed to obtain a dicyclopentenyl-containing unsaturated polyester having an acid value of 32. (A2). The obtained unsaturated polyester (A2) is based on the GPC number average score

2066-4593-PF (N); Ahddub.ptd Page 25 574306 Five 'invention description (22) The sub-quantity (Μη) is 1100, the weight average molecular weight (Mw) is 6600, the weight of fumaric acid based on 4 MNR The displacement is 78 ° / 〇. Production Example 3 (Production of Unsaturated Polyester U3)) The same preparation as in Production Example 2 was carried out in the same manner as in Production Example 2 except that the dehydration condensation reaction was performed at 220 ° C over 18 hours to obtain an acid. Dicyclopentenyl-containing unsaturated polyacetate (A3) with a value of 22. The obtained unsaturated poly (A3) had a number-average molecular weight (Mη) based on GPC of 1180, a weight-average molecular weight (Mw) of 9800, and an MNR-based fumaric acid rearrangement rate of 96 ° / °. Production Example 4 (Production of Unsaturated Polymerization (A4)) In a 4-necked flask were placed 98 points of maleic anhydride, dicyclopentadiene (95%) 1 11 points, and ethylenediamine tetraacetic acid 0 · 0 One minute 'under a nitrogen flow, it was performed in the same manner as in Production Example 1' to obtain dicyclopentadiene maleate adduct. Next, add maleic anhydride 44 points, diethylene glycol 1 17 points, and carry out dehydration condensation reaction at 180 ° C over 17 hours to obtain a dicyclopentenyl-containing unsaturated acid value of 20. Poly vinegar (A4). The obtained unsaturated polyacetate (A4) had a number average molecular weight (Mη) based on GPC of 850, a weight average molecular weight (Mw) of 4960, and a fumaric acid rearrangement rate based on 1 H MNR of 63 ° / °. . Production Example 5 (Production of Unsaturated Polyacetic Acid (Α5)) In a 4-necked flask, 4 98 minutes of isophthalic acid, 686 points of maleic anhydride, 403 points of propylene glycol, and 670 points of dipropylene glycol were placed in a 4-necked flask. In the flow, dehydration condensation reaction was performed at 21 0 ° C for 24 hours to obtain an acid value of 20,

2066-4593-PF (N); Ahddub.ptd Page 26 574306 V. Description of the invention (23) Number average molecular weight (Mη) based on GPC is 2600, weight average molecular weight (Mw) is 6 0 0 0, based on iH MNR's unsaturated polyacetic acid (A 5) has a fumaric acid rearrangement rate of 98%. Production Example 6 (Production of Vinyl Ester Resin (b 1)) In a reactor equipped with a thermometer, a cooler, a gas introduction tube, and a stirrer, the product obtained by the reaction between bisphenol A and epoxy propane was placed. Epoxy resin with an epoxy equivalent of 182.3 (trade name: Epotot YD-127, manufactured by Toto Kasei Co., Ltd.) 474 points, 230% methacrylic acid, 0.07 points for methyl-p-phenylene-S, and triethylfluorene Base gasified ammonium was 2.1 minutes, and the reaction was performed at 11 5 ° C for 6 hours under an air stream to obtain a vinyl ester resin (B1) having an acid value of 4.0. Production Example 7 (Production of modified vinyl ester resin (B2)) The same procedure as in the case of vinyl ester resin (B1) was carried out. To the obtained vinyl ester resin, maleic anhydride 38 points and succinic anhydride were further added. The reaction was carried out for 1 minute at 1 05 ° C. for 1 hour to add 8% of the total hydroxyl groups to obtain a modified vinyl ester resin (B2) having an acid value of 20 · 0. Production Example 8 (Production of methacrylic acid urethane (B3)) In a 4-necked flask were placed 30% of 2-hydroxypropyl (meth) acrylate, 0.16 points of parabenzoquinone, and dibutyl Tin dilaurate 0.82 minutes, followed by the liquid diphenylphosphorane diisocyanate oligomer (isocyanate equivalent weight 135) 270 minutes under a stream of air at 60 ° C for 2 hours into the mixture of this flask After completion of the dripping, the mixture was stirred at the same temperature for 3 hours. The temperature was further increased to 90 ° C and the locust was stirred for 1 hour to obtain methyl urethane aminophosphonate (β 3). Production Example 9 (production of polyfluorenyl acrylate (B4))

2066-4593-PF (N); Ahddub. Ptd page 2? 574306 V. Description of the invention (24) In a 4-necked flask, 173 minutes of neopentyl glycol and bisphenol A-ethylene oxide 2 molga The product was 347 minutes and isophthalic acid 261 minutes, and reacted at 2 15 ° C for 10 hours under a nitrogen flow. When the acid value became 2, it was cooled to 12 ° C, and then fumaric acid 183 was added. The temperature was raised to 200 ° C for 4 hours, and when the acid value reached 65, it was cooled to 130 ° C. Glycidyl propylene propylene was further added, and the reaction was carried out at 130 ° C for 3 hours to obtain unsaturated polyfluorenyl acrylate (B4) having an acid value of 10. Example 8 and Comparative Example 7

The resin etc. obtained in Production Example 9 were blended at the ratios shown in Tables 1 and 2 to obtain an unsaturated polyester resin composition. The blending ratios of the 2-fluorenyl hydroquinone and the third butylcatechol shown in Tables 1 and 2 are expressed by the content ratio (Ppm) with respect to all the obtained resin compositions. — In addition, the cobalt octenate-based cobalt octenate mineral oil essence bath (Co content 8% by weight), the copper naphthenate-based copper naphthenate mist generating solvent solution (Cu Content 5 wt%). The obtained resin composition was evaluated by the following method. The results are shown in Tables 1 and 2. (Chroma of composition)

It represents the Hasson number of the formulated composition. (Air-hardenability) Add 5% by weight of titanium white to the resin composition and knead it completely, and add 1% by weight of Parkyua 0 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) as a hardening catalyst. The coating roller applies a thickness of 0.5 mm to the glass plate.

2066-4593.PF (N); Ahddub.ptd Page 28 574306 V. Description of Invention (25) '1 ~ ---. Immediately put the coated glass plate into the 80 X: oven, set 1

After taking it out, when the finger touches the coating surface, if there is no sticky J shape, § works well (0); if there is a sticky situation, roll (X). 2. Tianxie bad (acetone solubility) Drop one drop of acetone on the coated surface, wipe it with absorbent cotton after 30 seconds, and wipe the surface with fingers, the coating film did not fall off, and there was no stickiness. Τ, good (0) ; If the coating film is not peeled off but sticky, it is regarded as: good (△); if the coating film is peeled off, it is regarded as bad (χ). (Glass transition temperature (Tg)) A guide plate with a thickness of 2 mm composed of two glass plates of 100 mm X 100 mm. The resin composition added with the titanium dioxide and the catalyst is flowed into the guide plate at 80 ° C for 2 hours. Take out the / hardened product made of the resin composition from the glass plate. 'This wash cast hardened product is made into a test piece of 5min X 5mm'. The thermal analysis device Tα-50WS manufactured by Shimadzu Corporation is used. (Thermo-mechanical analysis) method to measure Tg. (Hue of hardened product) The hue e j of the wash cast hardened product was measured in accordance with J I S K 540. (Weather resistance) A 50 mm X 50 mm test piece was prepared from the above-mentioned wash-hardened product, and an e-value (&) after 10,000 hours of irradiation with an aging tester was measured according to j is K 5 4 0 0. Obtain the color difference Z \ E (E2 — Ei). Here, the E value is a value indicating the degree of discoloration, and the smaller the value of △ £

2066-4593-PF (N); Ahddub.ptd Page 29 574306 V. Description of the invention (26) means the better the weather resistance. (Residual monomer) A 5 g powdery sample was cut from the cast hardened material, the soluble component was extracted with ethyl acetate, washed with a large amount of ethyl acetate, and dried under reduced pressure at 70 ° C. The weight change of the sample was measured, and the weight loss portion was expressed as a fraction of 1000 as a monomer component remaining in the wash-hardened product. (Water resistance) A 50 mm x 20 mm test piece was prepared from the cast hardened product, and was immersed in pure water of ㈣C to determine the time during which the test piece cracked, and this time was regarded as the water resistance retention time. Small altar (storage stability) The resin composition was stored at 40 ° C, and the time to initial energy was measured. ~ Staying the same

2066-4593-PF (N); Ahddub.ptd

574306 V. Description of the invention (27) [Table 1] Example No. 1 2 3 4 5 6 7 8 (A1) component 100 100 100 100 100 (A2) component 100 (A3) component unsaturated polyester resin (A4) component 100 100 (A5) component (B1) component 12 43 points (B2) component 25 67 points (B3) component 43 67 (B4) component 57 21 styrene 30 40 30 40 60 40 21 30 methyl methacrylate Esters 30 21 24 21 11 31 50 27 Methacrylic acid 2-hydroxyl 1 propyl 1 U Other 2-methylhydroquinone 50 50 50 50 50 50 50 50 (ppm) Tertiary butylcatechol 30 30 30 30 50 30 30 50 Chroma (Hassen) 40 50 50 100 100 300 50 50 Intrinsic viscosity (25t) (Pa · s) 0.3 0.32 0.35 0.3 0.38 0.3 0.32 0.33 Caprylic acid (ppm) — 1000 500 500 1 — 500 500 Additive copper cyanate (ppm) 100 100 100 100 One 100 100 — Titanium white (%) 5 5 5 5 5 5 5 5 Air-hardenability 0.00000 acetone solubility Δ 〇Δ 〇〇〇〇Δ Evaluation of chestnuts Glass transition temperature Tg (° C) 110 122 130 130 120 120 148 120 Residual monomer (%) 0.8 0.6 0.5 0.3 0.5 0.5 0.5 0.8 Hue E · 4 4 4 6 6 10 4 4 Weatherability ΔΕ 3 3 3 5 3 5 3 3 Water resistance (hours) 100 300 300 300 300 200 200 100 6 weeks 6 weeks 6 weeks 4 weeks 4 weeks 4 weeks 4 weeks 4 weeks Storage stability is very different. \ \ \ \ \ \ \ 〆, wiy \ trophy 〆, 、, ^ X trophy different groups of different bottles, 、, 一, 一 ', ✓, 一, J, J \ Often often often often ΙϋΙΗ 2066-4593-PF (N); Ahddub.ptd page 31 Page 574306 V. Description of the invention (28) [Table 2] Comparative Example No. 1 2 3 4 5 6 7 Unsaturated polyester resin composition Main component (minutes) (A1) component (A2) component (A3) component 100 ( A4) component 100 (A5) component 100 100 100 100 100 (B1) component 25 (B2) component 25 (B3) component 43 (B4) component 100 acetophenone 50 43 67 40 40 40 80 methyl methacrylate 40 40 21 20 2-hydroxypropyl methacrylate other (ppm) 2-methyl terephthalate 50 50 50 50 50 50 50 Second butylcatechol 50 50 50 30 30 30 50 Properties Color (Hamiao) 400 50 200 250 250 300 250 250 Viscosity (25 ° C) (Pa-s) 0.35 0.31 0.4 0.3 0.33 0.35 0.31 Additive cinnamate (ppm) One 1000 1000 — 1000 One — Copper Ring Acid (ppm) — 100 One 100 100 100 100 Titanium White (%) 5 5 5 5 5 5 5 Evaluate chestnut air hardening Δ Δ △ XXX Δ C_ Solubility XXXXXXX Glass transition temperature Tg (t :) 70 60 96 90 90 85 90 Residual monomer (%) 2.5 3.0 1.5 1.5 1.5 2.0 2.0 Hue É 12 4 8 10 10 10 10 Weather resistance ΔΕ 10 10 12 5 5 10 5 Water resistance (hours) 50 20 300 300 300 200 200 Storage stability The second week produces a gel 4 weeks without abnormality 6 weeks , \ Often 4 weeks New Zealand abnormal 4 weeks New Zealand abnormal 4 weeks are not the same / ,,,;? It is often known from Tables 1 and 2 that, compared to Comparative Example 1, although the constituent components of the unsaturated polyester are the same, Examples 1 to 6 of the present invention have good air hardenability and high Tg. The body is also very few, the water-resistant know-how

2066-4593-PF (N); Ahddub.ptd Page 32 ^ 74306 V. Description of the Invention (29) (Comparative Example 1) Although it is 50 hours, it is famous for its coloration after hardening (tone E1 = width increased to 1QG ~ Gang hours. Even the door and weather resistance of Comparative Example 2 and Examples 7 and 8 are quite excellent. If Examples 4, 5 and 6 are compared; the same can be said. The color of the ionic chain-linking agent is reduced. The effect 乂 M based on the metal Huanhe of the present invention is quite remarkable. For storage stability, for example, Bi Zhiyi, which satisfies the requirements of the present invention, has a double content; 1: It is widely known that the storage stability is insufficient after use. Also, thin Unsaturated polymer particles based on radicals, as shown in Comparative Examples 4 to 7, are generally different series of unsaturated polyacetate resins. M Unsaturated polyacetate containing dicyclopentenyl groups cannot obtain the effect of the present invention, and Tg also As in Example 9—Cobalt octenate mineral oil solution (Co content 8% by weight) 0.4% was mixed with 100% of the resin composition obtained in Example 6 and stirred for 77 minutes. / Install the RTM (resin transfer molding) casting machine (standard model made by Vinusgasmer), and adjust the RTM washing machine, 俾Perkyua A (manufactured by Nippon Oil & Fats Co., Ltd.) capable of mixing 1-minute acetamidine-peroxide is used as a hardener. Next, a mineral oil essence solution of cobalt octenate of the above-mentioned type is used for 0.4 minutes as anhydrous silicon dioxide. Aerozil # 300 (manufactured by Japan Aerozil Co., Ltd.) 2.5 points and titanium white 5 points were added to the resin composition 100 points obtained in Example 2, and they were kneaded completely and adjusted to make a gloss coating. The resin for the layer was added with 1% by weight of Permek N (manufactured by Japan Oils and Fats Co., Ltd.) with fluorenyl ethyl ketone peroxide as a main agent, and the mixture was completely mixed. This mixed resin was coated by a spray method to a thickness of 0.3 mm. Convex mold for FRP bathtubs.

2066-4593-PF (N); Ahddub.p t d p.33 574306

After hardening at 40 ° C for 30 minutes, after confirming the non-pointiness of the bright coating surface, the pre-foamed glass fiber made by pre-setting the glass content to 25% by weight was poured, and the convex mold was combined with After the mold is closed, the resin composition is injected into the closed mold using an RTM casting machine at an injection pressure of about 0.3 Mpa '(3Kg / cm2). After leaving it to stand at room temperature for i hours, the mold was opened, and as a result, a beautiful FRP bathtub capable of being easily demolded was obtained. Sweat is followed by filling the demolded FRP bathtub with hot water at 90 ° C, and measuring the continuous time from the inner surface of the bath rainbow (glossy coating surface) to the foaming time, which is satisfactory from 250 to 250 hours. result. # Comparative Example 8 A FRP bathtub was produced in the same manner as in Example 9, using the resin composition obtained in Comparative Example 1 as the resin composition for washing and casting, and using the resin composition of Comparative Example 3 as the party coating. . There is a protrusion at the corners of the product. "And" Yao said that with the incompletely hardened part of the resin composition, the concave mold cannot be completely demolded, and a part of the surface of the concave mold is peeled off, and the product becomes defective and the shape is damaged. Comparative Example 9 The thickness of the Dangguang coating was set to 0.5 mm. A FRp bathtub was produced in the same manner as in Comparative Example 8 except that Comparative Example 6 was used for the resin composition for casting. When the same test as in Example 9 was performed, 90 hours foaming. Example 1 0 Further, the wash-hardened products of Examples 3, 4, 5, β, and 7 were applied at 120. 〇 After 1 hour of heat treatment, residual monomers cannot be detected by this method.

574306 V. Description of the invention (31) Comparative Example 1 After further curing the cast hardened products of Comparative Examples 1, 2, 3, 4, 5, 6, and 7 at 1 2 0 C for 1 hour, the residual monomers were measured. Each item is 1.2%. Effects of the Invention: The resin composition of the present invention has sufficient storage stability, and can obtain excellent air-hardening property and high hardening degree when hardened. In addition, the cured product has a good degree of hardening, and the cured product has good heat resistance, chemical resistance, and weather resistance. Therefore, it is used as a bright coating for various castings and various molded products and as a laminated composition of products. Molding materials such as smc, MC, etc. ^ Some molding materials are applied to thermoformed moldings, which can give excellent performance.

2066-4593-PF (N); Ahddub.ptd p. 35 574306 Schematic description of 2066-4593-PF (N); Ahddub.ptd p. 36 Amendment i Application date Λ Standard 1 1 Case No. J 90133446, 1 Category: < i \ ZIf 丁-Supplement Λ t (filled by the Bureau) Invention Patent Specification 574306

The name of the invention Chinese Unsaturated Resin Composition English Unsaturated Resin Composition Name of the inventor (Chinese) 1. Name of Nakagawa Masaru (English) 1. Nationality 1. Japanese residence and residence 1. Takemidai, Suita City, Osaka Prefecture, Japan 4- 7-2-901 Applicant's name (name) (Chinese) 1. Name of Albi Dongpla Co., Ltd. (English) 1. Nationality 1. Japanese residence, residence (office) 1. Osaka, Japan Representative name (Chinese) of No.7, 27, Ichome, Ibaraki, Ibaraki 1. Name of the representative of Takejiku No. 2 (English) 1.

2066-4593-PFl (N) .ptc Page 1

Claims (1)

574306 Article L iiSh · "Species #saturated polyester resin composition, including: (A) unsaturated polyester comprising a reaction product between dicyclopentadiene and maleic acid, and the unsaturated polyester 100 parts by weight of unsaturated polyester in which the rearrangement ratio of the maleic acid-derived group (cis-based group) to the maleic acid-derived group (trans-based group) is 60 to 95%; (B) a polymer containing (fluorenyl) acrylfluorenyl group 0.5 to 80 parts by weight; and (C) at least one selected from the group consisting of a stupid vinyl monomer and a (meth) acrylic monomer It is composed of 10 to 18 parts by weight. 2. The unsaturated polyester resin composition according to item 1 of the scope of patent application, wherein the reaction product between dicyclopentadiene and maleic acid includes Metal ion-bonding agent 3. The unsaturated polyester resin composition according to item 1 of the scope of the patent application, wherein (β) component includes modified vinyl ester resin, and this resin is a vinyl sl resin and / or 5 to 40% of the hydroxyl groups included in the vinyl ester resin are obtained by adding an acid Sf to an addition reaction. 4 The unsaturated polyester resin composition according to item 2 of the scope of the patent application, wherein (B) component includes modified vinyl ester resin, and this resin is a kind of hydroxyl group included in vinyl resin and / or vinyl ester resin. 5 to 40%, obtained by adding an acid anhydride to the reaction. 5 · The unsaturated polyester resin composition described in item 1 of the scope of the patent application, wherein the (B) component includes amino (meth) acrylic acid 6. The resin composition according to item 2 of the scope of the patent application, wherein the (β) component includes aminomethacrylate (meth) acrylate. 2066-4593-PFl (N) .ptc Page 37 574306 Case No. 90133446 Amendment VI. Patent Application Scope 7. The resin composition according to item 1 of the patent application scope, wherein (B) component includes polymer (Meth) acrylate. 8. The unsaturated polyester resin composition according to item 2 of the scope of patent application, wherein the component (B) includes poly (meth) acrylate. 2066-4593-PFl (N) .ptc Page 38