JPH0216923B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a curable resin composition that has excellent adhesion, water resistance, chemical resistance, and mechanical strength. In recent years, as the uses of radical curable resins such as unsaturated polyester resins and vinyl ester resins have expanded, the performance required of these radical curable resins has become increasingly sophisticated. For example, hot water storage tanks are now required to have water resistance and chemical resistance that exceed the water resistance and chemical resistance of existing radical curable resins. Water resistance and chemical resistance naturally depend on the structure of the polymer, and unsaturated polyester resin,
Existing radical curable resins such as vinyl ester resins all have ester bonds in the constituent molecules of the main chain polymer or main chain oligomer, and the concentration of these ester bonds is a factor that influences performance. It has been known. Therefore, even if we try to further improve the physical properties of these existing radical-curing resins, as long as there are factors such as ester bonds that impair the physical properties, it is virtually impossible to improve the physical properties beyond a certain level. It turns out that it is impossible. As a result of various studies on curable resins that eliminate the drawbacks of existing radical curable resins and can be used in a wider range of applications, the present inventors discovered that the main chain contains factors that impair physical properties such as ester bonds. The main chain polymer is a polymer obtained by polymerization of vinyl monomers that do not have a urethane bond, and the side chain has an acryloyl group or a methacryloyl group as a crosslinking point by radical curing via a urethane bond in the side chain. I discovered something,
Already suggested. However, when this side chain unsaturated bond type resin is used alone, it has the disadvantage that curing is slow and complete curing takes a relatively long time. From this point of view, the present inventors further investigated and found that a curable resin composition comprising a side chain unsaturated bond type resin, an unsaturated alkyd, and, if necessary, a polymerizable monomer, overcomes the above drawbacks. They discovered what they could do and completed the present invention. That is, the present invention provides (A) a side chain obtained by copolymerizing at least one vinyl monomer selected from styrene, vinyltoluene, acrylonitrile, and (meth)acrylic acid ester with a hydroxyalkyl (meth)acrylate; An adduct of vinyl copolymer a having hydroxyl groups, diisocyanate and hydroxyalkyl (meth)acrylate, with free isocyanate groups and (meth)acrylate in the molecule.
The main chain is obtained by reacting with unsaturated isocyanate b that shares an acryloyl group, and the main chain is composed of a polymer obtained by polymerization of vinyl monomer, and the side chain has a (meth)
95 to 5% by weight of a side chain unsaturated bond type resin having a molecular weight of 10,000 or more and having an acryloyl group, and (B) an α,β-unsaturated polybasic acid or its acid anhydride, or this and a saturated polybasic acid or its acid. A curable resin composition containing 5 to 95% by weight of an unsaturated alkyd obtained by esterifying a mixture with an anhydride and a polyhydric alcohol, and (C) optionally containing unsaturated side chains. The present invention relates to a curable resin composition characterized in that 10 to 60 parts by weight of a polymerizable monomer is further blended with 100 parts by weight of a mixture of a bonded resin and an unsaturated alkyd. In the present invention, the effect of blending the side chain unsaturated bond type resin and the unsaturated alkyd is extremely remarkable.
In other words, side chain unsaturated bond type resins have the disadvantage of slow curing and require a relatively long time for complete curing, while unsaturated alkyds have poor water resistance,
Although it has the disadvantage of insufficient chemical resistance and adhesion, these defects in both components can be resolved by mixing a high molecular weight (molecular weight of approximately 10,000 or more) side chain unsaturated bond type resin and unsaturated alkyd. It has excellent hardening properties and adhesion.
A curable resin composition with extremely excellent water resistance and mechanical strength is provided. The side chain unsaturated bond type resin used in the present invention is a resin whose main chain is made of a polymer obtained by polymerization of vinyl monomers, and which has an acryloyl group or a methacryloyl group in the side chain via two urethane bonds. It is a radical curing resin. The side chain unsaturated bond type resin is schematically shown below (in the formula, ~ represents a main chain polymer synthesized by polymerization of vinyl monomers). Specific methods for producing the side chain unsaturated bond type resin include, for example, the following method. (a) A vinyl copolymer having a hydroxyl group in its side chain, obtained by copolymerizing at least one vinyl monomer selected from styrene, vinyltoluene, acrylonitrile, and (meth)acrylic acid ester with a hydroxyalkyl (meth)acrylate. Synthesizing a, (b) Reacting diisocyanate and hydroxyalkyl (meth)acrylate at a ratio of hydroxyl group to isocyanate group of 1:1 (mole ratio),
Synthesize an unsaturated isocyanate b that shares a free isocyanate group and a (meth)acryloyl group in one molecule of the reaction product, and (c) add a hydroxyl group to the side chain in step (a) dissolved in a solvent or monomer. Vinyl copolymer a having
and the unsaturated isocyanate b of step (b) are reacted in a monomer or solvent solution. Examples of the hydroxyalkyl (meth)acrylate used in the reaction of step (a) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. As the vinyl monomer for copolymerizing with hydroxyalkyl (meth)acrylate to form vinyl copolymer a, at least one vinyl monomer selected from styrene, vinyltoluene, acrylonitrile, and (meth)acrylic acid ester is used. used. (Meth)acrylic acid esters include esters of acrylic acid such as methyl, ethyl, butyl, 2-ethylhexyl, octyl, and methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl,
Examples include esters of methacrylic acid such as lauryl, benzyl, cyclohexyl, and tetrahydrofurfuryl. Other vinyl monomers such as vinyl acetate, acrylic acid, and methacrylic acid can also be used for modification. The content of hydroxyl groups in the vinyl copolymer a cannot be determined unconditionally since it varies depending on the purpose, but it is generally preferably within the range of 1 to 50 mol%. Solution polymerization is preferable for the polymerization in step (a) since it can proceed directly to the next step, but a method in which the polymer obtained by pearl polymerization or bulk polymerization is dissolved in a monomer and subjected to the next reaction is also used. It's okay. In order to introduce a (meth)acryloyl group into the side chain via two urethane bonds by reacting with the hydroxyl group of the vinyl copolymer a obtained in step (a), use the method of step (b). An unsaturated isocyanate b obtained by reacting a diisocyanate and a hydroxyalkyl (meth)acrylate such that the molar ratio of hydroxyl groups to isocyanate groups is substantially 1:1 is used. . As the hydroxyalkyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-
Examples include hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. Examples of the diisocyanate include 2,4-tolylene diisocyanate, mixed isocyanate of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexocyanate. Examples include methylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. In step (b), the reaction between hydroxyalkyl (meth)acrylate and diisocyanate is performed by dissolving the diisocyanate in a solvent or monomer,
This is done by dropping the hydroxyalkyl (meth)acrylate. The next step [step (c)] for obtaining a side chain unsaturated bond type resin having an unsaturated bond in the side chain is a reaction between the hydroxyl group of the main chain polymer side chain and an unsaturated isocyanate. The reaction between the hydroxyl group of the main chain polymer having a hydroxyl group in the side chain obtained in step (a) and the isocyanate group of the unsaturated isocyanate obtained in step (b) is carried out in a solvent or a monomer. When the reaction is carried out using a solvent, it is preferable to remove the solvent and prepare a monomer solution depending on the purpose. In order to replace the solvent and monomer, it is preferable to add a solvent with a lower boiling point than the monomer and distill off the solvent using the difference in boiling point. If the reaction is carried out in monomer solution, the product can be used as is. Examples of the solvent used in step (b) and step (c) include esters such as ethyl acetate, ketones such as methyl ethyl ketone, ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene, etc. Examples of monomers include styrene, vinyltoluene, methyl methacrylate, acrylonitrile, and ethyl acrylate. The unsaturated alkyd used in the present invention is obtained by esterifying an α/β-unsaturated polybasic acid or its acid anhydride, or a mixture of this with a saturated polybasic acid or its acid anhydride, and a polyhydric alcohol. That's what you get. Examples of the α/β-unsaturated polybasic acid or its acid anhydride include maleic anhydride, maleic acid, fumaric acid, and itaconic acid. As a saturated polybasic acid or its acid anhydride,
Examples include phthalic anhydride, isophthalic acid, terephthalic anhydride, hexahydrophthalic anhydride, succinic acid, adipic acid, sebacic acid, and tetrachlorophthalic anhydride. Although it has unsaturated bonds, it is not an unsaturated acid in the sense of α/β-unsaturated polybasic acids, but is a polybasic acid that is conventionally treated like a saturated acid. Examples include phthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and Hett's acid. As the polyhydric alcohol, divalent to trivalent alcohols are used, and divalent glycol is usually preferably used. Typical examples include propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, bisphenol A-ethylene oxide adduct, and bisphenol A-ethylene oxide adduct. Phenol A-propylene oxide adduct, 1,4-
Examples include cyclohexanedimethanol, trimethylolpropane, and glycerin. Esterification is carried out according to conventional methods. The type of unsaturated alkyd cannot be determined simply because it depends on the physical properties required for the product.
Copolymerizable monomers can be used in combination with unsaturated alkyds if necessary, and for most applications it is preferable to use monomers in combination, but for applications such as molding materials and decorative laminates, Monomers may not be used together. Examples of copolymerizable monomers include styrene, vinyltoluene, methyl methacrylate, diallyl phthalate, and the like. The mixing ratio of the side chain unsaturated bond type resin and the unsaturated alkyd cannot be determined unconditionally as it varies depending on the performance required of the product, but generally it is 5 to 95% by weight of the side chain unsaturated bond type resin, It preferably consists of 20-80% by weight and 95-5% by weight of unsaturated alkyds, preferably 80-20% by weight. Outside this range, the remarkable effects of the present invention cannot be obtained. In the present invention, a polymerizable monomer may be further added to the composition comprising the side chain unsaturated bond type resin and the unsaturated alkyd, if necessary. Polymerizable monomers include styrene, methyl methacrylate, ethyl methacrylate, and acrylic acid 2.
Ethylhexyl, ethylene glycol diacrylate, polyethylene glycol diacrylate,
Ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate,
Examples include trimethylolpropane trimethacrylate, pentaerythrit triacrylate, pentaerythrittetraacrylate, pentaerythritute trimethacrylate, pentaerythritutetramethacrylate, etc., and these may be used in combination. The amount of polymerizable monomer is
The amount is preferably 10 to 60 parts by weight based on 100 parts by weight of the mixture of side chain unsaturated bond type resin and unsaturated alkyd. The curable resin composition of the present invention can be cured by a conventionally known method. That is, in order to cure the curable resin composition of the present invention, an organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide, kyumene hydroperoxide, etc. may be added and the composition may be heated and cured. Alternatively, UV curing may be carried out by adding a photosensitizer such as benzoin, benzyl, benzophenone, 2-hydroxy-3-benzoylpropane, benzoin methyl ether, etc. Further, the organic peroxide and an accelerator such as an organic acid salt of cobalt (for example, cobalt naphthenate), an aromatic tertiary amine (for example, dimethylaniline), etc. may be used in combination to cure at room temperature. A reinforcing material, a filler, a coloring agent, a mold release agent, etc. can be added to the curable resin composition as necessary. The curable resin composition of the present invention is not only useful for producing fiber-reinforced plastics and cast products, but can also be used as a paint or adhesive. Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, "parts" and "%" in the examples mean "parts by weight" and "% by weight", respectively, unless otherwise specified. Example 1 (1) Synthesis of side chain unsaturated bond type resin (A) In a separable flask (1) equipped with a stirrer, a thermometer with a gas inlet tube, a dropping funnel, and a reflux condenser, 300 g of benzene and azobisisobutylene were added. Contains 1g of lonitrile and 0.3g of lauryl mercaptan.
After purging with nitrogen gas, a monomer mixture of 250 g of styrene, 16 g of acrylonitrile, and 43 g of 2-hydroxypropyl methacrylate was added dropwise under reflux of benzene. After the dropwise addition was completed, benzene was continued to be refluxed for 16 hours to complete the polymerization. After lowering the temperature to 60°C, 0.1 g of hydroquinone was added to stop the reaction, and a main chain polymer a containing styrene-acrylonitrile-2-hydroxypropyl methacrylate having a hydroxyl group in the side chain as a copolymerization component was obtained. . As a result of analyzing the obtained main chain polymer a by GPC, the number average molecular weight was estimated to be about 30,000. Furthermore, in a separate separable flask of the same type, 174 g of 2,4-tolylene diisocyanate,
Prepare 182g of benzene, 0.01g of hydroquinone, and 0.2g of dibutyltin dilaurate, and add 2-hydroxypropyl methacrylate while maintaining the temperature at 60℃.
144g was dropped. After the dropwise addition was completed, the solution was kept at 60° C. for 5 hours, and as a result of infrared analysis, a benzene solution of unsaturated isocyanate b in which the hydroxyl groups had completely disappeared was obtained. Next, 150 g of a benzene solution of unsaturated isocyanate b was added to the entire amount of main chain polymer a having hydroxyl groups in the side chains mentioned above, and the reaction was continued at 60°C for 6 hours. As a result of infrared analysis, free isocyanate groups were detected. has almost completely disappeared. Next, about 180 g of benzene was distilled off under a reduced pressure of about 200 mmHg, 410 g of styrene was added, and about 300 g of the remaining benzene was further distilled off under a reduced pressure of about 200 mmHg. A styrene solution of a side chain unsaturated bond type resin (A) having a methacryloyl group via two urethane bonds in the side chain was obtained, having a pale yellow color and a viscosity of 18.2 poise. (2) Synthesis of unsaturated polyester resin (B) A bisphenol A-propylene oxide adduct (with propylene oxide at both ends) was placed in a four-necked flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube. Add 350g of fumaric acid (1 mole each) and 116g of fumaric acid, and add 210~220 g
Esterification was carried out at °C. When the acid value reached 35.4, 0.05 g of hydroquinone was added, poured into a metal vat, and cooled to obtain an unsaturated alkyd with a yellowish brown color and a melting point of about 80°C. 300 parts of ground unsaturated alkyd and 300 parts of styrene
1 part in a three-necked flask while stirring.
The mixture was heated to 60°C and dissolved to obtain a yellowish brown unsaturated polyester resin (B) with a viscosity of 4.7 poise. 2 parts of methyl ethyl ketone peroxide for each 100 parts of the side chain unsaturated bond type resin (A), the unsaturated polyester resin (B), or a mixture thereof;
1 part cobalt naphthenate and dimethylaniline
The composition obtained by adding 0.1 part of
The physical properties of the cast product obtained from the composition of the present invention are as shown in Table 1, and the physical properties of the cast product obtained from the composition of the present invention are as follows:
The physical properties were well-balanced and superior to those of cast products made using either the unsaturated polyester resin (B) alone or the unsaturated polyester resin (B) alone. The coating film hardness is the value obtained by coating the composition on a glass plate with a bar coater to a thickness of 0.2 mm and curing it.

[Table] Example 2 (1) Synthesis of side chain unsaturated bond type resin (C) Stirrer, thermometer with gas introduction tube, dropping funnel,
Charge benzene 260, 1 g of azobisisobutyronitrile, and 1 g of lauryl mercaptan to a separable flask equipped with a reflux condenser.
After purging with nitrogen gas, a mixed monomer mixture of 104 g of styrene, 100 g of methyl methacrylate, and 35 g of 2-hydroxyethyl acrylate was added dropwise under reflux of benzene. After the dropwise addition was completed, reflux was continued for 16 hours at the boiling point of benzene to complete the polymerization. After lowering the temperature to 60℃, hydroquinone 0.1
The reaction was stopped by adding g to obtain main chain polymer c having a hydroxyl group in the side chain. As a result of analyzing the obtained main chain polymer c by GPC, the number average molecular weight was estimated to be about 35,000. Furthermore, 222 g of isophorone diisocyanate, 180 g of benzene, 0.3 g of dibutyltin dilaurate, and 0.01 g of hydroquinone were placed in another separable flask of the same type, and 116 g of 2-hydroxyethyl acrylate was added dropwise while maintaining the temperature at 60°C. did. After the dropwise addition was completed, the solution was kept at 60° C. for 5 hours, and as a result of infrared analysis, it was determined that the hydroxyl groups completely disappeared and unsaturated isocyanate d (benzene solution) was produced. Next, 160 g of unsaturated isocyanate d (benzene solution) was added to the entire amount of the main chain polymer c having hydroxyl groups in the side chain, and the reaction was continued at 60°C for 5 hours. As a result of infrared analysis, free isocyanate was detected. It was determined that the nato group had completely disappeared. Then add about 100% of benzene under reduced pressure of about 250mmHg.
After distilling off 260 g of trimethylolpropane triacrylate, about 200 g of benzene was added.
was distilled away. The obtained resin was in the form of a pale yellow syrup.
Further, 185 g of methyl methacrylate was added to this to obtain a side chain unsaturated bond type resin (C) having a viscosity of 39.9 poise. (2) Synthesis of unsaturated polyester resin (D) 230 g of neopentyl glycol and 232 g of isophthalic acid were charged into a four-necked flask (1) equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube, and the mixture was heated with a stream of nitrogen gas. Esterification was carried out at 200-210°C. When the acid value reached 21.7, 78 g of itaconic acid was added, and esterification was continued until the acid value reached 39.7. After lowering the temperature to 150°C, 0.08 g of hydroquinone and 200 g of trimethylolpropane triacrylate were added. Next, 132 g of methyl methacrylate was added and uniformly dissolved to form an unsaturated polyester resin (D) with a Gardner color number of 2 and a viscosity of 24.9 poise.
was synthesized. 1 part of a photoinitiator (Irgakiure #651 manufactured by Ciba Corporation) was added to 100 parts of a resin obtained by mixing a side chain unsaturated bond type resin (C) and an unsaturated polyester resin (D) in the proportions shown in Table 2. After painting the added composition by applying masking tape to both ends of a bonderite-treated steel plate, a polyethylene terephthalate film with a thickness of 100 μm was adhered and defoamed using a roll. The thickness of the coating film is determined by the thickness of the masking tape, in this case approximately 70μ.
It was hot. This was cured by passing 20 cm under the lamp at a speed of 15 m/min using an ultraviolet irradiation device with an output of 30 kW. The physical properties of the obtained coating film are as shown in Table 2, and the physical properties of the resin composition of the present invention are those of the side chain unsaturated bond type resin (C) alone or the unsaturated polyester resin.
(D) It was observed that the physical properties were better than those of the single material.

[Table] Example 3 (1) Synthesis of side chain unsaturated bond type resin (E) Stirrer, thermometer with gas introduction tube, dropping funnel,
300 g of benzene, 1 g of azobisisobutyronitrile, and 0.5 g of lauryl mercaptan were placed in a separable flask (No. 1) equipped with a reflux condenser, and after purging with nitrogen gas, 280 g of styrene and 2-hydroxypropyl methacrylate were added under reflux of benzene. 43 g of mixed monomers were added dropwise. After the dropwise addition was completed, benzene was continued to be refluxed for 16 hours to complete the polymerization. The temperature was lowered to 60° C., and 0.1 g of hydroquinone was added to terminate the reaction, yielding a main chain polymer e having a hydroxyl group in the side chain. Next, 150 g of the unsaturated isocyanate b (benzene solution) used in Example 1 was added to the entire amount of the main chain polymer e having hydroxyl groups in the side chains, and the reaction was continued at 60°C for 6 hours. As a result of the analysis, it was found that the free isocyanate groups had completely disappeared, and a pale yellow side chain unsaturated bond type resin (E) was obtained. (2) Synthesis of unsaturated polyester resin (F) In a four-necked flask equipped with a stirrer, a fractionating condenser, a gas inlet tube, and a thermometer, add 250 g of propylene glycol and 291 g of dimethyl terephthalate.
g and 2.5 g of zinc acetate were charged, and the transesterification reaction was carried out at 180 to 200° C. while distilling methanol. At the stage when about 90 c.c. of methanol has been distilled off,
147 g of maleic anhydride was added, and esterification was continued at 190 to 200°C in a nitrogen gas stream, and the reaction was stopped when the acid value reached 34.4. After lowering the temperature to 150°C, 0.06 g of hydroquinone was added, poured into a stainless steel vat, and cooled. The obtained unsaturated alkyd was light yellowish brown in color and had a softening point of about 75°C. 100 parts of unsaturated alkyd and 100 parts of ethyl acetate were mixed at room temperature to obtain an unsaturated polyester resin solution (F). 3 parts of titanium white, 0.5 parts of tertiary butyl hydroperoxide, and naphthene are added to 100 parts of a resin prepared by mixing a side chain unsaturated bond type resin (E) and an unsaturated polyester resin solution (F) in the proportions shown in Table 3. 0.05 part of cobalt acid and silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd.)
A composition containing 5 pm of KF-96 (10 centistokes) was applied to a bonderite-treated steel plate to a thickness of 0.2 mm, and then baked at 80°C for 30 minutes and at 120°C for 30 minutes to form a coating film. The physical properties of the obtained coating film are as shown in Table 3, and the physical properties of the resin composition of the present invention are those of the side chain unsaturated bond type resin (E) alone or the unsaturated polyester resin solution. (F) The physical properties were superior to those used alone.

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Claims (1)

[Scope of Claims] 1 (A) Side obtained by copolymerization of at least one vinyl monomer selected from styrene, vinyltoluene, acrylonitrile, and (meth)acrylic acid ester and hydroxyalkyl (meth)acrylate. Vinyl copolymer a having a hydroxyl group in the chain and unsaturated isocyanate b which is an adduct of diisocyanate and hydroxyalkyl (meth)acrylate and shares free isocyanate groups and (meth)acryloyl groups in the molecule. A side chain unsaturated bond type resin whose main chain is made of a polymer obtained by polymerization of a vinyl monomer and which has a (meth)acryloyl group in the side chain via a urethane bond and has a molecular weight of 10,000 or more. obtained by esterifying 95 to 5% by weight of (B) an α,β-unsaturated polybasic acid or its acid anhydride, or a mixture of this and a saturated polybasic acid or its acid anhydride, and a polyhydric alcohol. A curable resin composition containing 5 to 95% by weight of an unsaturated alkyd. 2 Add a polymerizable monomer to 100 parts by weight of the mixture of side chain unsaturated bond type resin and unsaturated alkyd.
The curable resin composition according to claim 1, characterized in that 10 to 60 parts by weight is blended.