Polyurethane resin composition, polyurethane (meth)acrylate resin with carboxylic acid groups, curable composition and composite molding compound

Abstract

A polyurethane resin composition comprises a polyurethane resin having isocyanate groups, a (meth)acrylate having hydroxyl groups, and an alcohol having carboxylic acid groups. This disclosure also provides a polyurethane (meth)acrylate resin having carboxylic acid groups formed by a condensation reaction of the polyurethane resin composition. In the condensation reaction, the hydroxyl groups of the alcohol having carboxylic acid groups and the hydroxyl groups of the (meth)acrylate having hydroxyl groups react with the isocyanate groups of the polyurethane resin having isocyanate groups. This disclosure further provides a composite molding compound comprising a polyurethane (meth)acrylate resin having carboxylic acid groups, a fibrous material, and a chemical thickener.

Description

Technical Field

[0001] The present disclosure relates to a polyurethane (meth) acrylate resin for composite materials, particularly a polyurethane (meth) acrylate resin having a carboxyl group and a polyurethane resin composition for forming a polyurethane (meth) acrylate resin having a carboxyl group. Prior Art

[0002] Composite materials such as sheet molding compound (SMC) or bulk molding compound (BMC) are widely used in various fields due to their good properties (such as heat resistance and chemical corrosion resistance, etc.), such as parts of transportation vehicles (such as cars, ships, airplanes, etc.), sports goods, building supplies or furniture supplies, etc.

[0003] Unsaturated polyester glass fiber reinforced molding compound is a kind of the composite material, and includes an unsaturated polyester resin, glass fiber and a chemical thickener (such as magnesium oxide or calcium oxide, etc.). Through the interaction between the chemical thickener and the unsaturated polyester resin, the state of the unsaturated polyester glass fiber reinforced molding compound will change from low viscosity (high fluidity) to high viscosity (no fluidity), presenting a thickening phenomenon. And when the unsaturated polyester glass fiber reinforced molding compound is subjected to a compression molding process under high temperature pressing conditions, the interaction between the chemical thickener and the unsaturated polyester resin will disappear, causing the state of the unsaturated polyester glass fiber reinforced molding compound to change from no fluidity to high fluidity, and thus having operability during the compression molding process. And due to having fluidity, the molded product is not likely to have appearance defects such as sand holes. However, the unsaturated polyester glass fiber reinforced molding compound has problems with poor mechanical properties (such as toughness).

[0004] To solve the above problems, a polyurethane (meth) acrylate resin is used to replace the unsaturated polyester resin, and the polyurethane (meth) acrylate resin is formed by reacting a polyurethane resin having an isocyanate group with a (meth) acrylate having a hydroxyl group. However, the polyurethane (meth) acrylate resin does not have the property of interacting with the chemical thickener, resulting in no thickening phenomenon in the formed composite material. At the same time, when performing a compression molding process under high temperature pressing conditions, due to no fluidity, the molded product is likely to have appearance defects such as sand holes. Summary of the Invention

[0005] Therefore, an object of the present disclosure is to provide a polyurethane resin composition.

[0006] Thus, the polyurethane resin composition provided by the present disclosure includes a polyurethane resin having a plurality of isocyanate groups (-N=C=O), a (meth)acrylate having a hydroxyl group (-OH), and an alcohol having a carboxyl group (-COOH).

[0007] Another object of the present disclosure is to provide a polyurethane (meth)acrylate resin having a carboxyl group.

[0008] Thus, the present disclosure further provides a polyurethane (meth)acrylate resin having a carboxyl group, which is formed by a condensation reaction of the above polyurethane resin composition. In this condensation reaction, the hydroxyl group of the alcohol having a carboxyl group and the hydroxyl group of the (meth)acrylate having a hydroxyl group react with the isocyanate group of the polyurethane resin having a plurality of isocyanate groups.

[0009] Another object of the present disclosure is to provide a polyurethane (meth)acrylate resin having a carboxyl group.

[0010] Thus, the present disclosure further provides a polyurethane (meth)acrylate resin having a carboxyl group as shown below, Wherein, R1 is hydrogen or methyl, R2, R3, and R4 are organic groups, R5 is , T2 is an organic group having an isocyanate group or an organic group not having an isocyanate group, T21 is an organic group, T22 is hydrogen or methyl, X is -CH2-CH2-, -CH2-CH2-O-CH2-CH2-, or , m and n are 1 or more.

[0011] Another object of the present disclosure is to provide a method for preparing a polyurethane (meth)acrylate resin having a carboxyl group.

[0012] Thus, the present disclosure further provides a method for preparing a polyurethane (meth)acrylate resin having a carboxyl group, including the following steps: subjecting the hydroxyl group of the alcohol having a carboxyl group and the hydroxyl group of the (meth)acrylate having a hydroxyl group to a condensation reaction with the isocyanate group of the polyurethane resin having a plurality of isocyanate groups.

[0013] Another object of the present disclosure is to provide a curable composition.

[0014] Therefore, the present disclosure further provides a curable composition, comprising the above-mentioned polyurethane (meth)acrylate resin having a carboxyl group and at least one polymerizable diluent monomer.

[0015] Another object of the present disclosure is to provide a composite molding material.

[0016] Therefore, the present disclosure further provides a composite molding material, comprising a resin component, at least one fiber material, and at least one chemical thickener, wherein the resin component is selected from the above-mentioned polyurethane (meth)acrylate resin having a carboxyl group or the above-mentioned curable composition.

[0017] In the present disclosure, the carboxyl group of the polyurethane (meth)acrylate resin having a carboxyl group can act with the chemical thickener, so that the state of the above-mentioned polyurethane (meth)acrylate resin having a carboxyl group can be changed from low viscosity (high fluidity) to high viscosity (no fluidity), showing a thickening phenomenon. And when the composite molding material containing the polyurethane (meth)acrylate resin having a carboxyl group is subjected to a molding process under high-temperature pressing conditions, the state can be changed from no fluidity to high fluidity, and it can have operability during the molding process. And due to the fluidity, the molded product is not likely to have problems such as appearance defects like sand holes. Brief Description of the Drawings

[0018] Other features and effects of the present disclosure will be clearly presented in the embodiments with reference to the drawings, wherein: FIG. 1 is a flowchart for explaining a preparation method of the polyurethane (meth)acrylate resin having a carboxyl group according to the present disclosure. Embodiments

[0019] The following will describe the present disclosure in detail.

[0020] <Polyurethane Resin Composition>

[0021] The polyurethane resin composition of the present disclosure comprises a polyurethane resin having a plurality of isocyanate groups (-N=C=O), a (meth)acrylate having a hydroxyl group, and a monohydric alcohol having a carboxyl group (-COOH), wherein the monohydric alcohol having a carboxyl group (-COOH) is selected from hydroxyethyl maleate ( ), (2-hydroxyethoxy)ethyl maleate ( ), 2-hydroxypropyl maleate ( ) or any combination thereof.

[0022] The above polyurethane resin having a plurality of isocyanate groups is, for example, but not limited to , wherein, X1 is an organic group, X2 is , T1 is an aromatic group, T11 is hydrogen or -NCO, and m, n1 and t are 1 or more. m, n1 and t can be adjusted according to the required ratio of the isocyanate groups of the polyurethane resin having a plurality of isocyanate groups (-N=C=O) to the hydroxyl groups of the above-mentioned (meth)acrylate having a hydroxyl group and the above-mentioned monohydric alcohol having a carboxyl group (-COOH). The above aromatic group is, for example, but not limited to phenyl, , , n1 is 1 or more, or etc.

[0023] In the present disclosure, (meth)acrylate refers to acrylate or methacrylate. The above-mentioned (meth)acrylate having a hydroxyl group can be used alone or in combination of multiple kinds, and the above-mentioned (meth)acrylate having a hydroxyl group is, for example, but not limited to hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate. In some embodiments of the present disclosure, the above-mentioned (meth)acrylate having a hydroxyl group is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate.

[0024] In some embodiments of the present disclosure, the sum of the content of the hydroxyl group of the above-mentioned (meth)acrylate having a hydroxyl group and the content of the hydroxyl group of the above-mentioned monohydric alcohol having a carboxyl group and the equivalent ratio of the isocyanate group of the above-mentioned polyurethane resin having a plurality of isocyanate groups is 1:1 to 1.05:1.

[0025] <Carboxyl group-containing polyurethane (meth)acrylate resin and its preparation method>

[0026] Referring to FIG. 1, the preparation method of the carboxyl group-containing polyurethane (meth)acrylate resin of the present disclosure includes step S. In step S, it is formed by subjecting the hydroxyl group of the monohydric alcohol having a carboxyl group and the hydroxyl group of the above-mentioned (meth)acrylate having a hydroxyl group in the above-mentioned polyurethane resin composition to a condensation reaction with the isocyanate group of the above-mentioned polyurethane resin having a plurality of isocyanate groups.

[0027] Specifically, in step S, the above-mentioned monohydric alcohol having a carboxyl group and the above-mentioned (meth)acrylate having a hydroxyl group are mixed to obtain a mixture, and then this mixture is subjected to the above-mentioned condensation reaction with the above-mentioned polyurethane resin having multiple isocyanate groups. In step S, the above-mentioned (meth)acrylate having a hydroxyl group is reacted with the above-mentioned polyurethane resin having multiple isocyanate groups to obtain a reaction mixture, and then the above-mentioned monohydric alcohol having a carboxyl group is reacted with this reaction mixture.

[0028] Referring to FIG. 1, in some embodiments of the present disclosure, the method for preparing a polyurethane (meth)acrylate resin having a carboxyl group of the present disclosure further includes step Q.

[0029] In step Q, a polycondensation reaction is carried out on a reaction component containing at least one polyol material and at least one polyisocyanate material to obtain the above-mentioned polyurethane resin having multiple isocyanate groups. Among them, the above-mentioned polyisocyanate material is an isocyanate compound having two or more isocyanate groups, and the above-mentioned polyol material is a polyol compound having two or more hydroxyl groups.

[0030] In some embodiments of the present disclosure, in order to make the above-mentioned polyurethane resin having multiple isocyanate groups have appropriate rigidity, the equivalent ratio of the content of the isocyanate groups of the above-mentioned polyisocyanate material to the content of the hydroxyl groups of the above-mentioned polyol material is 1.5:1 to 10:1. In some embodiments of the present disclosure, in order to make the above-mentioned polyurethane resin having multiple isocyanate groups have appropriate rigidity, the above-mentioned polyol material is a polyol having a number average molecular weight of less than 2000. Such a polyol having a number average molecular weight of less than 2000 is, for example but not limited to, polyoxyethylene ether, polyoxypropylene ether, or polytetrahydrofuran, etc. The above-mentioned polyisocyanate material is, for example but not limited to, aromatic ring polyisocyanates, etc. The above-mentioned aromatic ring polyisocyanates are, for example but not limited to, tolylene diisocyanate, polymethylene polyphenyl isocyanate, or diphenylmethane diisocyanate, etc. In some embodiments of the present disclosure, the above-mentioned polyisocyanate material is selected from tolylene diisocyanate, polymethylene polyphenyl isocyanate, or diphenylmethane diisocyanate. The above-mentioned polyisocyanate material is, for example but not limited to, a product purchased from Tosoh with the model MR200, a product purchased from Wanhua with the model PM200, a product purchased from BASF with the model M20S, a product purchased from Covestro with the model 44V20, a product purchased from Huntsman with the model 5005, a product purchased from Tosoh with the model NM, or a product purchased from Wanhua with the model MDI-50.

[0031] In some embodiments of the present disclosure, the above reaction components further include a catalyst. Such catalysts include, for example but not limited to, organotin catalysts, organobismuth catalysts, or organozinc catalysts, etc. The above organotin catalysts include, for example but not limited to, dibutyltin dilaurate. In some embodiments of the present disclosure, based on 1 kg of the total amount of the above polyurethane acrylate resin having a carboxyl group, the dosage of the above catalyst is 50 mg to 200 mg.

[0032] In some embodiments of the present disclosure, the above reaction components further include an inhibitor. This inhibitor can be the inhibitor previously used in the resin of the free radical curing system, such as 2,5-dihydroxytoluene, so it will not be elaborated here.

[0033] In some embodiments of the present disclosure, the above reaction components further include a diluent monomer. Such diluent monomers include, for example but not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, styrene, methylstyrene, or vinyltoluene, etc.

[0034] Specifically, the above polyisocyanate material, the above catalyst, the above inhibitor, and the above diluent monomer are mixed to obtain a mixture, and then this mixture is mixed with the above polyol material to obtain the above reaction components.

[0035] Referring to FIG. 1, in some embodiments of the present disclosure, the method for preparing the polyurethane (meth) acrylate resin having a carboxyl group of the present disclosure further includes step R. In step R, a diol is reacted with maleic anhydride to obtain the above monohydric alcohol having a carboxyl group, wherein this diol is selected from ethylene glycol, diethylene glycol, or glycerol. In this reaction, the temperature is increased in a stepwise manner.

[0036] Specifically, the above diol and the above maleic anhydride are subjected to a first-stage reaction under the condition of a first temperature, and then the temperature is raised from the above first temperature to a second temperature, and a second-stage reaction is carried out under the condition of the above second temperature. In some embodiments of the present disclosure, the above first temperature is 50 °C to 70 °C. In some embodiments of the present disclosure, the above first temperature is 55 °C to 65 °C. In some embodiments of the present disclosure, the above second temperature is 70 °C to 90 °C. In some embodiments of the present disclosure, the above second temperature is 75 °C to 85 °C.

[0037] In some embodiments of the present disclosure, the above-mentioned polyurethane (meth) acrylate resin having a carboxylic acid group is , where R1 is hydrogen or methyl, R2 is an organic group, R3 is an organic group, R4 is an organic group, and R5 is , X is -CH2-CH2-, -CH2-CH2-O-CH2-CH2-, or , T2 is an organic group having an isocyanate group or an organic group not having an isocyanate group, T21 is an organic group, T22 is hydrogen or methyl, and m and n are 1 or more.

[0038] To enable the polyurethane (meth) acrylate resin having a carboxylic acid group to have an appropriate acid value, and thus have a better thickening effect and enable the composite molding material formed from the above-mentioned polyurethane (meth) acrylate resin having a carboxylic acid group to have a lower water absorption, preferably, m / n is 1.8 to 3. The organic group of R2 is, for example, an alkyl group. This alkyl group is, for example, an ethyl group or a propyl group.

[0039] The organic group of R3 is an organic group containing an aromatic group. The above-mentioned organic group containing an aromatic group is, for example, a phenyl group, , , or , and n1 is 1 or more.

[0040] The above-mentioned organic group having an isocyanate group is, for example, a phenyl group having an isocyanate group, , , or , and n1 is 1 or more. The above-mentioned organic group not having an isocyanate group is, for example, a phenyl group, , or , and n1 is 1 or more.

[0041] The organic groups of R4 and T21 are, for example, an alkyl group, an alkenyl group, or an alkyl ether. The above-mentioned alkyl group is, for example, an ethyl group or a propyl group. The above-mentioned alkenyl group is, for example, an allyl group. The above-mentioned alkyl ether is, for example, but not limited to -C2H4-O-C2H4-, -C3H6-O-C3H6-, or -C4H8-O-C4H8-, etc.

[0042] In some embodiments of the present disclosure, is , R1 is methyl, R2 is alkyl, R4 is alkyl ether, R5 is , T21 is alkyl ether, T22 is methyl, m and n1 are 1 or more.

[0043] In some embodiments of the present disclosure, to accelerate the interaction between the above-mentioned polyurethane (meth)acrylate resin having a carboxyl group and the chemical thickener and reduce the water absorption of the above-mentioned composite molding material, the acid value range of the above-mentioned polyurethane (meth)acrylate resin having a carboxyl group is 10 mgKOH / g to 40 mgKOH / g. In some embodiments of the present disclosure, the acid value range of the above-mentioned polyurethane (meth)acrylate resin having a carboxyl group is 15 mgKOH / g to 30 mgKOH / g.

[0044] <Curable composition>

[0045] The curable composition of the present disclosure includes the above-mentioned polyurethane (meth)acrylate resin having a carboxyl group and a polymerizable diluent monomer.

[0046] In the present disclosure, the above-mentioned polymerizable diluent monomer is used as a viscosity modifier to make the above-mentioned curable composition have an appropriate viscosity, so as to endow the above-mentioned curable composition with appropriate fluidity, so as to meet the conditions required for subsequent operations. The above-mentioned polymerizable diluent monomer is, for example but not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, styrene, methylstyrene, or vinyltoluene, etc. In some embodiments of the present disclosure, the above-mentioned polymerizable diluent monomer is selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, styrene, methylstyrene, vinyltoluene or any combination thereof.

[0047] <Composite molding material>

[0048] The disclosed composite molding material includes a resin component, at least one fiber material, and at least one chemical thickener. Among them, the above resin component is selected from the above polyurethane (meth) acrylate resin having a carboxyl group or the above curable composition.

[0049] In some embodiments of the present disclosure, based on the total amount of the above resin component being 100 parts by weight, the total amount of the above fiber material is 67 parts by weight to 135 parts by weight. The above fiber material is, for example but not limited to, glass fiber, carbon fiber, or polyamide fiber, etc. In some embodiments of the present disclosure, the above fiber material is selected from glass fiber, carbon fiber, or polyamide fiber.

[0050] In some embodiments of the present disclosure, based on the total amount of the above resin component being 100 parts by weight, the total amount of the above chemical thickener is 1 part by weight to 1.5 parts by weight. The above chemical thickener is, for example but not limited to, alkaline earth metal oxide or alkaline earth metal hydroxide, etc. In some embodiments of the present disclosure, the above chemical thickener is selected from alkaline earth metal oxide or alkaline earth metal hydroxide. The above alkaline earth metal oxide is, for example but not limited to, magnesium oxide or calcium oxide, etc. The above alkaline earth metal hydroxide is, for example but not limited to, magnesium hydroxide or calcium hydroxide, etc.

[0051] In some embodiments of the present disclosure, the above composite molding material further includes at least one inorganic filler. The above inorganic filler is, for example but not limited to, titanium dioxide, silica, calcium carbonate, alumina, aluminum hydroxide, or silicon carbide, etc. In some embodiments of the present disclosure, the above inorganic filler is selected from titanium dioxide, silica, calcium carbonate, alumina, aluminum hydroxide, or silicon carbide.

[0052] In some embodiments of the present disclosure, the above-mentioned composite molding material further includes at least one additive. The above-mentioned additives include, for example but not limited to, flame retardants, inhibitors, mold release agents, hardeners, viscosity modifiers, wetting and dispersing agents, or low shrinkage agents, etc. In some embodiments of the present disclosure, based on the total amount of the above resin components being 100 parts by weight, the total amount of the above flame retardant is 220 parts by weight to 300 parts by weight. The above flame retardant includes, for example but not limited to, aluminum hydroxide. In some embodiments of the present disclosure, based on the total amount of the above resin components being 100 parts by weight, the total amount of the above inhibitor is 0.01 parts by weight to 0.03 parts by weight. The above inhibitor includes, for example but not limited to, 2,6-di-tert-butyl-p-cresol. In some embodiments of the present disclosure, based on the total amount of the above resin components being 100 parts by weight, the total amount of the above mold release agent is 3 parts by weight to 5 parts by weight. The above mold release agent includes, for example but not limited to, zinc stearate. In some embodiments of the present disclosure, based on the total amount of the above resin components being 100 parts by weight, the total amount of the above hardener is 3 parts by weight to 4 parts by weight. The above hardener includes, for example but not limited to, tert-butyl peroxybenzoate. In some embodiments of the present disclosure, based on the total amount of the above resin components being 100 parts by weight, the total amount of the above viscosity modifier is 30 parts by weight to 40 parts by weight. The above viscosity modifier includes, for example but not limited to, diluent monomers. The above diluent monomers include, for example but not limited to, styrene. In some embodiments of the present disclosure, based on the total amount of the above resin components being 100 parts by weight, the total amount of the above wetting and dispersing agent is 2 parts by weight to 3 parts by weight. The above wetting and dispersing agent includes, for example but not limited to, a commercially available product with the brand of BYK and the model of BYK-W 996. In some embodiments of the present disclosure, based on the total amount of the above resin components being 100 parts by weight, the total amount of the above low shrinkage agent is 13 parts by weight to 28 parts by weight. The above low shrinkage agent includes, for example but not limited to, vinyl acetate.

[0053] The above-mentioned composite molding material can be used for parts of transportation vehicles (such as automobiles, ships, airplanes, etc.), sports goods, building supplies, or furniture supplies, etc.

[0054] The present disclosure will be further described with the following examples. However, it should be understood that the examples are only for illustrative purposes and should not be construed as limitations on the implementation of the present disclosure.

[0055] Synthesis Example 1 Hydroxyethyl maleate

[0056] 391.3 g of ethylene glycol and 562.0 g of maleic anhydride were placed in a reaction kettle, wherein the molar ratio of the above ethylene glycol to the above maleic anhydride was 1.10. Then, it was heated to 55 °C and subjected to a first-stage reaction at 55 °C for 60 minutes. Then, the temperature was raised to 70 °C and a second-stage reaction was carried out at 70 °C for 300 minutes to obtain hydroxyethyl maleate.

[0057] Synthesis Example 2 (2-Hydroxyethoxy)ethyl maleate

[0058] 116.7 g of diethylene glycol and 98.1 g of maleic anhydride were placed in a reaction kettle, wherein the molar ratio of the above diethylene glycol to the above maleic anhydride was 1.10. Then, it was heated to 55 °C and subjected to a first-stage reaction at 55 °C for 60 minutes. Then, the temperature was raised to 80 °C and a second-stage reaction was carried out at 80 °C for 300 minutes to obtain (2-hydroxyethoxy)ethyl maleate.

[0059] Synthesis Example 3 2-Hydroxypropyl maleate

[0060] 443.9 g of propylene glycol and 520.0 g of maleic anhydride were placed in a reaction kettle, wherein the molar ratio of the above propylene glycol to the above maleic anhydride was 1.10. Then, it was heated to 55 °C and subjected to a first-stage reaction at 55 °C for 60 minutes. Then, the temperature was raised to 80 °C and a second-stage reaction was carried out at 80 °C for 300 minutes to obtain 2-hydroxypropyl maleate.

[0061] Example 1 Polyurethane methacrylate resin having a carboxyl group and a curable composition

[0062] 640.0 g of poly(methylene phenyl isocyanate) [brand: TOSOH; model: MR200; isocyanate group content: 31.25 ± 0.75%; isocyanate group content: 4.76 equivalents], 0.82 g of 2,5-dihydroxytoluene (as an inhibitor), and 0.308 g of dibutyltin dilaurate (as a catalyst) were dispersed in 412 g of methyl methacrylate (as a diluent monomer) and mixed evenly. Then, it was heated to 50 ± 2 °C to obtain a first mixture.

[0063] 317.5 g of polypropylene glycol (brand: Donglian Chemical; model: PPG400; average molecular weight: 400; in 317.5 g of polypropylene glycol, the hydroxyl content is 1.59 equivalents) was slowly added dropwise to the above first mixture, and the dropping time was 50 ± 10 minutes. During the dropping time, the temperature was controlled at 54 ± 6 °C. Among them, the equivalent ratio of the isocyanate groups of the above poly(methylene phenyl isocyanate) to the hydroxyl groups of the above polypropylene glycol is 3:1. Then, it was maintained at 50 ± 2 °C for 2.5 ± 0.5 hours to obtain a second mixture containing a polyurethane resin having a plurality of isocyanate groups.

[0064] A third mixture was slowly added dropwise to the above second mixture, and the dropping time was 50 ± 10 minutes. During the dropping process, the temperature was controlled at 50 ± 5 °C. Among them, the above third mixture contains 340.8 g of hydroxyethyl methacrylate and 127.1 g of hydroxyethyl maleate of Synthesis Example 1, and the equivalent ratio of the hydroxyl content of the above third mixture to the isocyanate group content of the above polyurethane resin having a plurality of isocyanate groups is 1.05. Then, it was maintained at 50 ± 2 °C for 2.5 ± 0.5 hours, and the isocyanate content was measured during the process. When the isocyanate content was 0.67%, 206 g of methyl methacrylate (a polymerizable diluent monomer) was added to obtain a curable composition. The above curable composition contains a polyurethane methacrylate resin having a carboxyl group and methyl methacrylate, and the viscosity of the above curable composition is 1600 cps, and the acid value is 21 mgKOH / g.

[0065] Example 2 Polyurethane Methacrylate Resin with Carboxyl Group and Curable Composition

[0066] 150.0 g of poly(methylene phenyl isocyanate) (brand: Wanhua; model: PM200; isocyanate group content: 31.25 ± 0.75%; in 150.0 g of poly(methylene phenyl isocyanate), the isocyanate group content is 1.12 equivalents), 0.21 g of 2,5-dihydroxytoluene (as an inhibitor), and 0.08 g of dibutyltin dilaurate (as a catalyst) were dispersed in 90.0 g of methyl methacrylate (as a diluent monomer) and mixed evenly. Then, it was heated to 50 ± 2 °C to obtain a first mixture.

[0067] 74.4 g of polypropylene glycol (brand: Donglian Chemical; model: PPG400; average molecular weight: 400; in 74.4 g of polypropylene glycol, the hydroxyl content is 0.37 equivalent) was slowly added dropwise to the above first mixture, and the dropping time was 50 ± 10 minutes. During the above dropping process, the temperature was controlled at 54 ± 6 °C. Among them, the equivalent ratio of the isocyanate group of the above poly(methylene phenyl isocyanate) to the hydroxyl group of the above polypropylene glycol is 3:1. Then, it was maintained at 50 ± 2 °C for 2.5 ± 0.5 hours to obtain a second mixture containing a polyurethane resin having multiple isocyanate groups.

[0068] A third mixture was slowly added dropwise to the above second mixture, and the dropping time was 50 ± 10 minutes. During the dropping process, the temperature was controlled below 50 ± 5 °C. Among them, the above third mixture contains 72.6 g of 2-hydroxyethyl methacrylate and 38.0 g of (2-hydroxyethoxy)ethyl maleate of Synthesis Example 2, and the equivalent ratio of the hydroxyl content of the above third mixture to the isocyanate group content of the above polyurethane resin having multiple isocyanate groups is 1.03. Then, it was maintained at 50 ± 2 °C for 2.5 ± 0.5 hours, and the isocyanate content was measured during the process. When the isocyanate content was 0.48%, 90.0 g of methyl methacrylate (a polymerizable diluent monomer) was added to obtain a curable composition. The above curable composition contains a polyurethane methacrylate resin having a carboxyl group and methyl methacrylate, and the viscosity of the above curable composition is 2600 cps, and the acid value is 20 mgKOH / g.

[0069] Example 3 Polyurethane Methacrylate Resin with Carboxyl Group and Curable Composition

[0070] 640.0 g of poly(methylene phenyl isocyanate) (brand: Wanhua; model: PM200; isocyanate group content: 31.25 ± 0.75%; in 640.0 g of poly(methylene phenyl isocyanate), the isocyanate group content is 4.76 equivalents), 0.83 g of 2,5-dihydroxytoluene (as an inhibitor), and 0.308 g of dibutyltin dilaurate (as a catalyst) were dispersed in 412.0 g of methyl methacrylate (as a diluent monomer), and mixed evenly. Then, it was heated to 50 ± 2 °C to obtain a first mixture.

[0071] 317.5 g of polypropylene glycol (brand: Donglian Chemical; model: PPG400; average molecular weight: 400; in 317.5 g of polypropylene glycol, the hydroxyl content is 1.59 equivalents) was slowly added dropwise to the above first mixture, and the dropping time was 50 ± 10 minutes. During the above dropping process, the temperature was controlled at 54 ± 6 °C. Among them, the equivalent ratio of the isocyanate groups of the above poly(methylene phenyl isocyanate) to the hydroxyl groups of the above polypropylene glycol was 3:1. Then, it was maintained at 50 ± 2 °C for 2.5 ± 0.5 hours to obtain a second mixture containing a polyurethane resin having multiple isocyanate groups.

[0072] A third mixture was slowly added dropwise to the above second mixture, and the dropping time was 50 ± 10 minutes. During the dropping process, the temperature was controlled at 50 ± 5 °C. Among them, the above third mixture contained 340.8 g of 2-hydroxyethyl methacrylate and 138.2 g of 2-hydroxypropyl maleate of Synthesis Example 3, and the equivalent ratio of the hydroxyl content of the above third mixture to the isocyanate group content of the above polyurethane resin having multiple isocyanate groups was 1.02. Then, it was maintained at 50 ± 2 °C for 2.5 ± 0.5 hours, and the content of the isocyanate groups was measured during the process. When the content of the isocyanate groups was 0.23%, 206.0 g of methyl methacrylate (a polymerizable diluent monomer) was added to obtain a curable composition. The above curable composition contained a polyurethane methacrylate resin having a carboxyl group and methyl methacrylate, and the viscosity of the above curable composition was 1900 cps, and the acid value was 22 mgKOH / g.

[0073] Evaluation Items

[0074] Viscosity (unit: cps) measurement: The curable compositions of Examples 1 to 3 were placed in a viscometer (brand: BROOKFIELD; model: DV-I Prime; including a viscometer, a constant temperature water bath circulation tank, and an S14 rotor), and the temperature was controlled at 25 °C by the constant temperature water bath circulation, and the detection was carried out under the condition of 100 rpm.

[0075] Acid value (unit: mgKOH / g) measurement: 0.6 ± 0.1 g of the polyurethane methacrylate resin having a carboxyl group and the curable composition of Examples 1 to 3 were dissolved in 10 mL of a solvent component (including toluene and isopropanol, and the weight ratio of this toluene to isopropanol was 1:1), then, phenolphthalein indicator was dropped in, and titration was carried out with 0.1 N potassium hydroxide ethanol solution.

[0076] Measurement of the content (unit: %) of isocyanate groups (-N=C=O): 0.25 ± 0.05 g of the polyurethane resin and polyurethane methacrylate resin having a plurality of isocyanate groups in Examples 1 to 3 were dissolved in 15 mL of a component (including dibutylamine and toluene, and in this component, the concentration of this dibutylamine was 0.1 N), then, the reaction was continuously stirred for 10 min, and then, bromophenol blue indicator was added dropwise, and titrated with 0.1 N hydrochloric acid aqueous solution to the end point.

[0077] Measurement of thickening property: 100 parts by weight of the curable compositions in Examples 1 to 3 and 1 part by weight of magnesium oxide were introduced into a high-shear type disperser, and subjected to shear dispersion treatment at a rotation speed of 1000 rpm for 10 minutes. Then, it was left standing in an environment of 23 ± 1 °C for 0 days, 3 days, 6 days and 13 days, and the viscosity was measured using a viscometer (brand: BROOKFIELD; model: DV-I Prime), and the measurement results are shown in Table 1.

[0078] Table 1 Curable composition (parts by weight) Example 1 100 0 0 Example 2 0 100 0 Example 3 0 0 100 Chemical thickener (parts by weight) Magnesium oxide 1 1 1 Viscosity (cps) at 23 ± 1 °C 0 days 1825 2900 2225 3 days 6900 10250 8100 6 days 15700 22500 19813 13 days 58750 70750 68750

[0079] Referring to Table 1, the viscosities of the curable compositions of Examples 1 to 3 increased with the increase in the number of storage days, indicating that the polyurethane methacrylate resin having a carboxyl group in this disclosure can indeed interact with the chemical thickener to increase the viscosity and have a thickening effect.

[0080] Charpy impact test: The curable compositions of Examples 1 to 3 were uniformly mixed with 0.015 ± 0.005 wt% cobalt octoate and 1.5 ± 0.5 wt% methyl ethyl ketone peroxide (1 - 2%), and then degassed to obtain a mixture. This mixture was poured into a glass mold with a thickness of 4 mm and cured at room temperature for 24 hours, and then baked at 105 °C for 2 hours to obtain a cured casting plate. This cured casting plate was cut into test pieces of 80 mm × 10 mm × 4 mm and detected by an impact tester (brand: Cometech; model: QC - 639) according to the ISO 179 plastic non - notched impact strength test specification. The test results are shown in Table 2. The unsaturated polyester resin (brand: REICHHOLD; model: POLYLITE 413 - 000) was uniformly mixed with 0.015 ± 0.005 wt% cobalt octoate and 1.5 ± 0.5 wt% methyl ethyl ketone peroxide, and the above process was repeated and detected by an impact tester.

[0081] Table 2 Unsaturated polyester resin Example 1 Example 2 Example 3 Charpy impact strength (kJ / m 2) 7.5 ± 2.5 24 22 25

[0082] Referring to Table 2, the impact strength of the specimens formed from the curable compositions of Examples 1 to 3 is significantly better than that of the specimens formed from unsaturated polyester resin, indicating that the polyurethane methacrylate resin with carboxylic groups in this disclosure can indeed perform better in terms of toughness improvement.

[0083] Application Example 1 Composite Molding Material

[0084] 100 parts by weight of the curable composition of Example 1, 38 parts by weight of styrene (as a viscosity modifier), 28 parts by weight of vinyl acetate (as a low shrinkage agent), 0.03 parts by weight of 2,6-di-tert-butyl-p-cresol (as an inhibitor), 3 parts by weight of a copolymer solution containing acidic groups (as a wetting and dispersing agent; brand: BYK of Germany; model: BYK-W 996), 3 parts by weight of tert-butyl perbenzoate (as a hardening agent), and 1.5 parts by weight of magnesium oxide (as a chemical thickening agent) were placed in a high-shear type disperser and stirred for 5 minutes. Then, 300 parts by weight of aluminum hydroxide (as a flame retardant) were divided into several equal portions and added in batches. Next, stirring was carried out at a speed of 1000 rpm for 10 minutes to obtain a mixture. Then, this mixture, 3 parts by weight of zinc stearate (as a mold release agent), and 108 parts by weight of carbon fibers (with a size of 1 cm) were introduced into a twin-screw kneader to obtain a halogen-free flame-retardant bulk composite molding material. This halogen-free flame-retardant bulk composite molding material was introduced into the mold of a compression molding machine, and under the condition of 150 °C, a pressure of 50 kg / cm² was applied to this halogen-free flame-retardant bulk composite molding material for compression molding treatment to obtain a molded product.

[0085] Application Examples 2 to 3

[0086] The preparation methods of Application Examples 2 to 3 are substantially the same as that of Application Example 1, and the main difference lies in: changing the types or dosages of the components. Refer to Table 3.

[0087] Table 3 Halogen-Free Flame-Retardant Bulk Composite Molding Material Application Example 1 2 3 Curable Composition Example 1 100 0 0 Example 2 0 100 0 Example 3 0 0 100 Styrene 38 30 35 Vinyl acetate 28 25 13 BYK-W 996 3 2.8 2.7 Tert-butyl peroxybenzoate 3 3 3 2,6-Di-tert-butyl-p-cresol 0.03 0.02 0.01 Magnesium oxide 1.5 1 1.3 Aluminum hydroxide 300 240 220 Zinc stearate 3 3 3 Carbon fiber 108 135 67

[0088] Evaluation item

[0089] Measurement of average flexural strength (unit: MPa): According to the specification of ISO 14125, the molded product of the application example was cut into 5 test samples with dimensions of 100 mm × 15 mm × 3 mm, and then, using a universal tensile tester (brand: Instron; model: 5892), the flexural strength of the above test samples was measured, and the average value of the flexural strength was calculated.

[0090] Flame retardancy measurement: Cut the molded product of the application example into 5 specimens with dimensions of 127 mm × 12.7 mm × 3 mm. Then, use the vertical burning method to detect the above specimens, with each specimen in contact with the flame for 10 seconds. Next, remove it from the flame and measure the first self-extinguishing time. Then, contact the flame for 10 seconds, then remove it from the flame and measure the second self-extinguishing time. Then, add the first self-extinguishing time and the second self-extinguishing time to obtain the total time. When the total time is less than 10 seconds, it is determined to meet the V0 level.

[0091] Table 4 Molded product Application example 1 2 3 Average flexural strength (MPa) 92 102 98 Flame retardancy V0 V0 V0

[0092] Referring to Table 4, the molded products of Application Examples 1 to 3 have good flexural strength that meets industry requirements, indicating that the components in the composite molding material of this disclosure can indeed be uniformly mixed, enabling the obtained molded products to have good properties.

[0093] In summary, the polyurethane (meth) acrylate resin with a carboxylic acid group in this disclosure can interact with a chemical thickener, causing the state to change from low viscosity (high fluidity) to high viscosity (no fluidity), presenting a thickening phenomenon. And when the composite molding material containing the polyurethane (meth) acrylate resin with a carboxylic acid group is subjected to a compression molding process under high-temperature pressing conditions, the state can change from no fluidity to high fluidity, enabling it to have operability during the compression molding process. And due to the fluidity, the components in the composite molding material of this disclosure can be uniformly mixed, making the molded products have good quality. Therefore, the purpose of this disclosure can indeed be achieved.

[0094] However, what is described above is only an embodiment of this disclosure, and the scope of implementation of this disclosure cannot be limited thereby. All simple equivalent changes and modifications made according to the scope of the patent application of this disclosure and the content of the patent specification still fall within the scope covered by the patent of this disclosure.

[0095] Q: Steps S: Step R: Step

Claims

1. A polyurethane resin composition comprising: a polyurethane resin having a plurality of isocyanate groups; a (meth)acrylate having hydroxyl groups; and an alcohol having a carboxylic acid group.

2. The polyurethane resin composition as claimed in claim 1, wherein, The alcohol containing a carboxylic acid group is a monohydric alcohol containing a carboxylic acid group.

3. The polyurethane resin composition as claimed in claim 2, wherein, The monohydric alcohol having a carboxylic acid group is selected from hydroxyethyl maleate, (2-hydroxyethoxy)ethyl maleate, 2-hydroxypropyl maleate, or any combination thereof.

4. The polyurethane resin composition as claimed in claim 1, wherein, The hydroxyl-containing (meth)acrylate is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or any combination thereof.

5. The polyurethane resin composition as claimed in claim 1, wherein, The sum of the hydroxyl content of the (meth)acrylate with hydroxyl groups and the hydroxyl content of the alcohol with carboxylic acid groups is in an equivalent ratio of 1:1 to 1.05:1 to the isocyanate groups of the polyurethane resin with multiple isocyanate groups.

6. The polyurethane resin composition as claimed in claim 1, wherein, The polyurethane resin having multiple isocyanate groups is, wherein X1 is an organic group, X2 is, T1 is an aromatic group, T11 is hydrogen or -NCO, and m, n1 and t are 1 or more.

7. The polyurethane resin composition as claimed in claim 6, wherein, The aromatic group is selected from phenyl, , and n1 is 1 or more, or .

8. The polyurethane resin composition as claimed in claim 6, wherein, X1 can be ethyl, propyl, allyl, -C2H4-O-C2H4-, -C3H6-O-C3H6-, or -C4H8-O-C4H8-.

9. A polyurethane (meth)acrylate resin having a carboxylic acid group, formed by a condensation reaction of a polyurethane resin composition as described in any one of claims 1 to 8, wherein, The acid value of the polyurethane (meth)acrylate resin with carboxylic acid groups ranges from 10 mg KOH / g to 40 mg KOH / g.

10. A curable composition comprising: a polyurethane (meth)acrylate resin having a carboxylic acid group as described in claim 9, and a polymerizable dilutable monomer.

11. The curable composition as claimed in claim 10, wherein, The curable composition has an initial viscosity of 1500 cps to 3000 cps.

12. The curable composition as claimed in claim 10, wherein, The polymerizable dilutable monomer is selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, styrene, methylstyrene, vinyltoluene, or any combination thereof.

13. The curable composition as claimed in claim 10, wherein, The polyurethane (meth)acrylate resin with a carboxylic acid group is as follows: wherein R1 is hydrogen or methyl, R2 is alkyl, R3 is, n1 is 1 or more, R4 is alkyl or alkyl ether, R5 is, T2 is an organic group with an isocyanate group or an organic group without an isocyanate group, T21 is an organic group, T22 is hydrogen or methyl, X is -CH2-CH2-, -CH2-CH2-O-CH2-CH2- or, m and n are 1 or more.

14. A composite molding compound, comprising: a resin component and a fiber material, wherein, The resin component is a curable composition as described in any one of claims 10 to 13.

15. The composite molding compound as claimed in claim 14, wherein, The composite molding compound also contains a chemical thickener.

16. The composite molding compound as claimed in claim 15, wherein, The chemical thickener is selected from alkaline earth metal oxides, alkaline earth metal hydroxides, or any combination thereof.

17. The composite molding compound as claimed in claim 15, wherein, Based on a total resin component of 100 parts by weight, the total amount of the chemical thickener is 1 to 1.5 parts by weight.

18. The composite molding compound as claimed in claim 14, wherein, Based on a total amount of 100 parts by weight of the resin component, the total amount of the fiber material is 67 to 135 parts by weight.

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