Polyurethane resin composition, polyurethane (methyl) acrylate resin with carboxylic acid group as well as preparation method and application of polyurethane (methyl) acrylate resin

Abstract

The invention provides a polyurethane resin composition, a polyurethane (methyl) acrylate resin with a carboxylic acid group, a preparation method of the polyurethane (methyl) acrylate resin with the carboxylic acid group, a curable composition and a composite mold material. The polyurethane resin composition contains a polyurethane resin having a plurality of isocyanate groups, a (meth) acrylate having a hydroxyl group, and a monohydric alcohol having a carboxylic acid group. The monohydric alcohol with the carboxylic acid group is selected from hydroxyl ethyl maleate, (2-hydroxyl ethyoxyl) ethyl maleate or 2-hydroxyl propyl maleate; and the monohydric alcohol with the carboxylic acid group is selected from hydroxyl ethyl maleate, (2-hydroxyl ethyoxyl) ethyl maleate or 2-hydroxyl propyl maleate. The polyurethane (methyl) acrylate resin with the carboxylic acid group is formed by carrying out condensation reaction on a polyurethane resin composition, and in the condensation reaction, hydroxyl of monohydric alcohol with the carboxylic acid group and hydroxyl of (methyl) acrylate with the hydroxyl react with isocyanate groups of polyurethane resin with isocyanate groups. The composite mold material comprises polyurethane (methyl) acrylate resin with carboxylic acid groups, a fiber material and a chemical thickening agent.

Description

Technical Field

[0001] The present invention relates to a polyurethane (meth) acrylate resin for composite materials such as sheet moldings or block moldings, and more particularly to a polyurethane (meth) acrylate resin having a carboxylic acid group and a polyurethane resin composition for forming the polyurethane (meth) acrylate resin having a carboxylic acid group. Background 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), such as parts of transportation vehicles (such as automobiles, ships, airplanes, etc.), sports equipment, construction products, or furniture products.

[0003] Unsaturated polyester glass fiber reinforced molding material is a kind of composite material, and comprises unsaturated polyester resin, glass fiber and chemical thickener (such as magnesium oxide or calcium oxide, etc.). Through the action between the chemical thickener and the unsaturated polyester resin, the state of the unsaturated polyester glass fiber reinforced molding material will be changed from low viscosity (high fluidity) to high viscosity (no fluidity), and thickening phenomenon will be presented, and when the unsaturated polyester glass fiber reinforced molding material is subjected to compression molding treatment under high temperature pressing conditions, the action of the chemical thickener and the unsaturated polyester resin will disappear, so that the state of the unsaturated polyester glass fiber reinforced molding material can be changed from no fluidity to high fluidity, and can have operability in the compression molding process, and because of fluidity, the molded product is not easy to have the problem of poor appearance such as sand hole defects. However, the unsaturated polyester glass fiber reinforced molding material has the problem of poor mechanical properties (such as toughness).

[0004] In order to solve the above problems, polyurethane (meth) acrylate resin is used to replace the unsaturated polyester resin, and the polyurethane (meth) acrylate resin is formed by the reaction of polyurethane resin having isocyanate group and (meth) acrylate having hydroxyl group. However, the polyurethane (meth) acrylate resin does not have the property of reacting with the chemical thickener, so that the formed composite material will not have thickening phenomenon. At the same time, when the molding process is carried out under high temperature pressing conditions, due to the lack of fluidity, the molded product is prone to have poor appearance problems such as sand hole defects. Summary of the invention

[0005] A first object of the present invention is to provide a polyurethane resin composition.

[0006] The polyurethane resin composition of the present invention comprises a polyurethane resin having a plurality of isocyanate groups (-N=C=O), a (meth)acrylate having a hydroxyl group (-OH), and a monohydric alcohol having a carboxylic acid group (-COOH). The monohydric alcohol having a carboxylic acid group (-COOH) is selected from hydroxyethyl maleate, (2-hydroxyethoxy)ethyl maleate, 2-hydroxypropyl maleate, or any combination thereof.

[0007] In the polyurethane resin composition of the present invention, the (meth)acrylate having a hydroxyl group is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate or any combination thereof.

[0008] In the polyurethane resin composition of the present invention, the equivalent ratio of the sum of the hydroxyl content of the (meth)acrylate having a hydroxyl group and the hydroxyl content of the monohydric alcohol having a carboxylic acid group to the isocyanate group of the polyurethane resin having multiple isocyanate groups is 1:1 to 1.05:1.

[0009] A second object of the present invention is to provide a urethane (meth)acrylate resin having a carboxylic acid group.

[0010] In the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention, the polyurethane (meth) acrylate resin having a carboxylic acid group is formed by a condensation reaction of the above-mentioned polyurethane resin composition, and in the condensation reaction, the hydroxyl group of the monohydric alcohol having a carboxylic acid group and the hydroxyl group of the (meth) acrylate having a hydroxyl group react with the isocyanate group of the polyurethane resin having multiple isocyanate groups.

[0011] In the polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention, the acid value of the polyurethane (meth)acrylate resin having a carboxylic acid group ranges from 10 mgKOH / g to 40 mgKOH / g.

[0012] The third object of the present invention is to provide a polyurethane (meth) acrylate resin having a carboxylic acid group.

[0013] The polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention is as follows:

[0014]

[0015] R 1 is hydrogen or methyl,

[0016] R 2 , R 3 and R 4 is an organic group,

[0017] R 5 for T 2 is an organic group having an isocyanate group or an organic group not having an isocyanate group, T 21 is an organic group, T 22 is hydrogen or methyl,

[0018] X is -CH2-CH2-, -CH2-CH2-O-CH2-CH2- or

[0019] m and n are 1 or more.

[0020] In the polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention, R 3 for n 1 is 1 or more.

[0021] In the polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention, R 2 It is an alkyl group.

[0022] In the polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention, R 4 and T 21 It is an alkyl group or an alkyl ether.

[0023] In the polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention, the acid value of the polyurethane (meth)acrylate resin having a carboxylic acid group ranges from 10 mgKOH / g to 40 mgKOH / g.

[0024] The fourth object of the present invention is to provide a method for preparing a polyurethane (meth) acrylate resin having a carboxylic acid group.

[0025] The preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention comprises the following steps: condensing the hydroxyl group of a monohydric alcohol having a carboxylic acid group and the hydroxyl group of a (meth) acrylate having a hydroxyl group with the isocyanate group of a polyurethane resin having a plurality of isocyanate groups, 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.

[0026] In the preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention, the monohydric alcohol having a carboxylic acid group and the (meth) acrylate having a hydroxyl group are mixed to obtain a mixture, and then the mixture is subjected to the condensation reaction with the polyurethane resin having multiple isocyanate groups.

[0027] In the method for preparing the polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention, the (meth)acrylate having a hydroxyl group is reacted with the polyurethane resin having a plurality of isocyanate groups to obtain a reaction mixture, and then the monohydric alcohol having a carboxylic acid group is reacted with the reaction mixture.

[0028] In the preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention, the preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group further comprises subjecting the reaction components of a polyol material and a polyisocyanate material to a condensation reaction to obtain the polyurethane resin having multiple isocyanate groups.

[0029] In the preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention, the preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group further comprises reacting a diol with maleic anhydride to obtain the monool having a carboxylic acid group, wherein the diol is selected from ethylene glycol, diethylene glycol or propylene glycol.

[0030] In the preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention, the (meth) acrylate having a hydroxyl group is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate or any combination thereof.

[0031] The fifth object of the present invention is to provide a curable composition.

[0032] The curable composition of the present invention comprises the polyurethane (meth) acrylate resin having a carboxylic acid group and at least one polymerizable diluent monomer.

[0033] In the curable composition of the present invention, the polymerizable diluent 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, methyl styrene, vinyl toluene or any combination thereof.

[0034] The sixth purpose of the present invention is to provide a composite molding material.

[0035] The composite molding material of the present invention comprises a resin component, at least one fiber material, and at least one chemical thickener. The resin component is selected from the above-mentioned polyurethane (meth) acrylate resin having a carboxylic acid group or the above-mentioned curable composition.

[0036] In the composite molding material of the present invention, the chemical thickener is selected from alkaline earth metal oxides, alkaline earth metal hydroxides or any combination thereof.

[0037] The beneficial effects of the present invention are as follows: the carboxylic acid group of the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention can react with a chemical thickener, so that the state of the polyurethane (meth) acrylate resin having a carboxylic acid group can be changed from low viscosity (high fluidity) to high viscosity (no fluidity), thereby showing a thickening phenomenon, and when a composite mold material containing the polyurethane (meth) acrylate resin having a carboxylic acid group is subjected to compression molding under high-temperature pressing conditions, the state can be changed from no fluidity to high fluidity, thereby being operable during the compression molding process, and because of the fluidity, the molded product is less likely to have problems of poor appearance such as sand holes. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a flow chart for explaining the preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention. DETAILED DESCRIPTION

[0039] The present invention will be described in detail below.

[0040] <Polyurethane resin composition>

[0041] The polyurethane resin composition 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 carboxylic acid group (-COOH). The monohydric alcohol having a carboxylic acid group (-COOH) is selected from hydroxyethyl maleate. (2-Hydroxyethoxy)ethyl maleate 2-Hydroxypropyl Maleate Or any combination of the above.

[0042] The polyurethane resin having multiple isocyanate groups is, for example but not limited to X 1 is an organic group, X 2 for T 1 is an aromatic group, T 11 is hydrogen or -NCO, m, n 1 and t is greater than 1. m, n 1 and t can be adjusted according to the desired ratio of the isocyanate groups of the polyurethane resin having multiple isocyanate groups (-N=C=O) to the (meth)acrylate having a hydroxyl group and the hydroxyl group of the monohydric alcohol having a carboxylic acid group (-COOH). The aromatic group is for example, but not limited to, phenyl, n 1 is 1 or more, Etc. In the present invention, (meth)acrylate refers to acrylate or methacrylate. The (meth)acrylate having a hydroxyl group can be used alone or in combination, and the (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 invention, the (meth)acrylate having a hydroxyl group is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate, or any combination thereof.

[0043] In some embodiments of the present invention, the equivalent ratio of the sum of the hydroxyl content of the (meth)acrylate having a hydroxyl group and the hydroxyl content of the monohydric alcohol having a carboxylic acid group to the isocyanate group of the polyurethane resin having multiple isocyanate groups is 1:1 to 1.05:1.

[0044] <Polyurethane (meth) acrylate resin having a carboxylic acid group and preparation method thereof>

[0045] See also Figure 1 The method for preparing the polyurethane (meth) acrylate resin having a carboxylic acid group comprises step S. In step S, the hydroxyl group of the monohydric alcohol having a carboxylic acid group of the polyurethane resin composition and the hydroxyl group of the (meth) acrylate having a hydroxyl group are condensed with the isocyanate group of the polyurethane resin having a plurality of isocyanate groups to form the polyurethane (meth) acrylate resin.

[0046] In one embodiment, in step S, the monohydric alcohol having a carboxylic acid group and the (meth)acrylate having a hydroxyl group are mixed to obtain a mixture, and then the mixture is subjected to the condensation reaction with the polyurethane resin having multiple isocyanate groups. In another embodiment, in step S, the (meth)acrylate having a hydroxyl group is reacted with the polyurethane resin having multiple isocyanate groups to obtain a reaction mixture, and then the monohydric alcohol having a carboxylic acid group is reacted with the reaction mixture.

[0047] See also Figure 1 In some embodiments of the present invention, the method for preparing the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention further comprises step Q.

[0048] In step Q, a reaction component comprising at least one polyol material and at least one polyisocyanate material is subjected to a polycondensation reaction to obtain the polyurethane resin having multiple isocyanate groups. The polyisocyanate material is an isocyanate compound having two or more isocyanate groups, and the polyol material is a polyol compound having two or more hydroxyl groups.

[0049] In some embodiments of the present invention, in order to make the polyurethane resin with multiple isocyanate groups have appropriate rigidity, the equivalent ratio of the content of isocyanate groups of the polyisocyanate material to the content of hydroxyl groups of the polyol material is 1.5:1 to 10:1. In some embodiments of the present invention, in order to make the polyurethane resin with multiple isocyanate groups have appropriate rigidity, the polyol material is a polyol with a number-average molecular weight less than 2000. The polyol with a number-average molecular weight less than 2000 is, for example, but not limited to, polypropylene glycol, polyoxyethylene ether, polyoxypropylene ether or polytetrahydrofuran. The polyisocyanate material is, for example, but not limited to, aromatic ring polyisocyanates. The aromatic ring polyisocyanates are, for example, but not limited to, tolyl diisocyanate, polyisocyanate or diphenylmethane diisocyanate. In some embodiments of the present invention, the polyisocyanate material is selected from tolyl diisocyanate, polyisocyanate or diphenylmethane diisocyanate. The polyisocyanate material is, for example, but not limited to, a product purchased from TOSOH with a model number of MR200, a product purchased from Wanhua Chemical with a model number of PM200, a product purchased from BASF with a model number of M20S, a product purchased from Covestro with a model number of 44V20, a product purchased from HUNTSMAN with a model number of 5005, a product purchased from TOSOH with a model number of NM, or a product purchased from Wanhua Chemical with a model number of MDI-50.

[0050] In some embodiments of the present invention, the reaction component further comprises a catalyst. The catalyst is, for example, but not limited to, an organotin catalyst, an organobismuth catalyst, or an organozinc catalyst. The organotin catalyst is, for example, but not limited to, dibutyltin dilaurate. In some embodiments of the present invention, the amount of the catalyst is 50 mg to 200 mg based on 1 kg of the total amount of the polyurethane (meth) acrylate resin having a carboxylic acid group.

[0051] In some embodiments of the present invention, the reaction component further comprises an inhibitor. The inhibitor can be an inhibitor currently used in free radical curing system resin, such as 2,5-dihydroxytoluene, so it is not described in detail.

[0052] In some embodiments of the present invention, the reaction components further include diluent monomers, such as, but not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofuranyl acrylate, tetrahydrofuranyl methacrylate, styrene, methyl styrene, or vinyl toluene.

[0053] Specifically, the polyisocyanate material, the catalyst, the inhibitor and the diluent monomer are mixed to obtain a mixture, and then the mixture is mixed with the polyol material to obtain the reaction component.

[0054] See also Figure 1 In some embodiments of the present invention, the method for preparing the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention further comprises step R. In step R, a diol is reacted with maleic anhydride to obtain the monool having a carboxylic acid group. The diol is selected from ethylene glycol, diethylene glycol or glycerol. In the reaction of step R, the temperature is raised in stages.

[0055] In detail, the diol and the maleic anhydride are reacted at a first temperature for a first stage, then the temperature is raised from the first temperature to a second temperature, and a second stage reaction is carried out at the second temperature. In some embodiments of the present invention, the first temperature is 50°C to 70°C. In some embodiments of the present invention, the first temperature is 55°C to 65°C. In some embodiments of the present invention, the second temperature is 70°C to 90°C. In some embodiments of the present invention, the second temperature is 75°C to 85°C.

[0056] In some embodiments of the present invention, the polyurethane (meth) acrylate resin having a carboxylic acid group is R 1 is hydrogen or methyl, R 2 is an organic group, R 3 is an organic group, R 4 is an organic group, R 5 for X is -CH2-CH2-, -CH2-CH2-O-CH2-CH2- or T 2 is an organic group having an isocyanate group or an organic group not having an isocyanate group, T 21 is an organic group, T 22 is hydrogen or methyl, and m and n are 1 or more.

[0057] In order to make the polyurethane (meth) acrylate resin having a carboxylic acid group have an appropriate acid value, so as to have a better thickening effect and make the composite molding formed by the polyurethane (meth) acrylate resin having a carboxylic acid group have lower water absorption, preferably, m / n is 1.8 to 3. 2 The organic group is, for example, an alkyl group. The alkyl group is, for example, ethyl or propyl.

[0058] R 3The organic group is an organic group containing an aromatic group. The organic group containing an aromatic group is, for example, phenyl, n 1 is 1 or more.

[0059] The organic group having an isocyanate group is, for example, a phenyl group having an isocyanate group, n 1 is 1 or more. The organic group without an isocyanate group, such as phenyl, n 1 is 1 or more.

[0060] R 4 and T 21 The organic group is, for example, an alkyl group, an alkenyl group or an alkyl ether. The alkyl group is, for example, an ethyl group or a propyl group. The alkenyl group is, for example, an allyl group. The alkyl ether is, for example, but not limited to, -C2H4-O-C2H4-, -C3H6-O-C3H6- or -C4H8-O-C4H8-, etc.

[0061] In some embodiments of the present invention, for R 1 is methyl, R 2 is an alkyl group, R 4 is an alkyl ether, R 5 for T 21 is an alkyl ether, T 22 Methyl, m and n 1 is 1 or more.

[0062] In some embodiments of the present invention, in order to accelerate the reaction between the polyurethane (meth) acrylate resin having a carboxylic acid group and the chemical thickener and reduce the water absorption of the composite molding material, the acid value of the polyurethane (meth) acrylate resin having a carboxylic acid group ranges from 10 mgKOH / g to 40 mgKOH / g. In some embodiments of the present invention, the acid value of the polyurethane (meth) acrylate resin having a carboxylic acid group ranges from 15 mgKOH / g to 30 mgKOH / g.

[0063] <Curable Composition>

[0064] The curable composition comprises the polyurethane (meth) acrylate resin having a carboxylic acid group and a polymerizable diluent monomer.

[0065] In the present invention, the polymerizable diluent monomer is used as a viscosity adjuster to make the curable composition have an appropriate viscosity, so as to give the curable composition an appropriate fluidity so as to be able to cope with the conditions required for subsequent operations. The polymerizable diluent monomer is, for example, but not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofuranyl acrylate, tetrahydrofuranyl methacrylate, styrene, methyl styrene, or vinyl toluene. In some embodiments of the present invention, the polymerizable diluent 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, tetrahydrofuranyl acrylate, tetrahydrofuranyl methacrylate, styrene, methylstyrene, vinyltoluene or any combination thereof.

[0066] <Compound mold material>

[0067] The composite mold material comprises a resin component, at least one fiber material, and at least one chemical thickener. The resin component is selected from the polyurethane (meth) acrylate resin having a carboxylic acid group or the curable composition.

[0068] In some embodiments of the present invention, the total amount of the fiber material is 67 to 135 parts by weight, based on 100 parts by weight of the total amount of the resin component. The fiber material is, for example, but not limited to, glass fiber, carbon fiber, or polyamide fiber. In some embodiments of the present invention, the fiber material is selected from glass fiber, carbon fiber, or polyamide fiber.

[0069] In some embodiments of the present invention, the total amount of the chemical thickener is 1 to 1.5 parts by weight based on the total amount of the resin component as 100 parts by weight. The chemical thickener is, for example, but not limited to, alkaline earth metal oxides or alkaline earth metal hydroxides. In some embodiments of the present invention, the chemical thickener is selected from alkaline earth metal oxides, alkaline earth metal hydroxides, or any combination thereof. The alkaline earth metal oxides are, for example, but not limited to, magnesium oxide or calcium oxide. The alkaline earth metal hydroxides are, for example, but not limited to, magnesium hydroxide or calcium hydroxide.

[0070] In some embodiments of the present invention, the composite mold material further comprises at least one inorganic filler. The inorganic filler is, for example, but not limited to, titanium dioxide, silicon dioxide, calcium carbonate, aluminum oxide, aluminum hydroxide, or silicon carbide. In some embodiments of the present invention, the inorganic filler is selected from titanium dioxide, silicon dioxide, calcium carbonate, aluminum oxide, aluminum hydroxide, or silicon carbide.

[0071] In some embodiments of the present invention, the composite mold material further comprises at least one additive. The additive is, for example, but not limited to, a flame retardant, an inhibitor, a mold release agent, a hardener, a viscosity modifier, a wetting dispersant, or a low shrinkage agent. In some embodiments of the present invention, the total amount of the flame retardant is 220 to 300 parts by weight based on the total amount of the resin component as 100 parts by weight. The flame retardant is, for example, but not limited to, aluminum hydroxide. In some embodiments of the present invention, the total amount of the inhibitor is 0.01 to 0.03 parts by weight based on the total amount of the resin component as 100 parts by weight. The inhibitor is, for example, but not limited to, 2,6-di-tert-butyl-p-cresol. In some embodiments of the present invention, the total amount of the mold release agent is 3 to 5 parts by weight based on the total amount of the resin component as 100 parts by weight. The mold release agent is, for example, but not limited to, zinc stearate. In some embodiments of the present invention, the total amount of the hardener is 3 to 4 parts by weight based on the total amount of the resin component as 100 parts by weight. The hardener is, for example, but not limited to, tert-butyl peroxybenzoate. In some embodiments of the present invention, the total amount of the viscosity modifier is 30 to 40 parts by weight based on 100 parts by weight of the total amount of the resin component. The viscosity modifier is, for example, but not limited to, a diluent monomer. The diluent monomer is, for example, but not limited to, styrene. In some embodiments of the present invention, the total amount of the wetting dispersant is 2 to 3 parts by weight based on 100 parts by weight of the total amount of the resin component. The wetting dispersant is, for example, but not limited to, a commercial product with a brand of BYK Additives & Instruments of Germany and a model of BYK-W 996. In some embodiments of the present invention, the total amount of the low shrinkage agent is 13 to 28 parts by weight based on 100 parts by weight of the total amount of the resin component. The low shrinkage agent is, for example, but not limited to, vinyl acetate.

[0072] The composite molding material can be used for parts of transportation vehicles (such as automobiles, ships, airplanes, etc.), sports goods, construction goods, furniture goods, etc.

[0073] The present invention will be further described with reference to the following examples, but it should be understood that the examples are only for illustration and should not be construed as limitations on the implementation of the present invention.

[0074] Synthesis Example 1 Hydroxyethyl Maleate

[0075] 391.3 g of ethylene glycol and 562.0 g of maleic anhydride were placed in a reaction kettle, and the molar ratio of the ethylene glycol to the maleic anhydride was 1.10. Then, the reaction was heated to 55° C. and carried out at 55° C. for 60 minutes in the first stage, and then the reaction was heated to 70° C. and carried out at 70° C. for 300 minutes in the second stage to obtain hydroxyethyl maleate.

[0076] Synthesis Example 2 (2-Hydroxyethoxy)ethyl maleate

[0077] 116.7 g of diethylene glycol and 98.1 g of maleic anhydride were placed in a reaction kettle, and the molar ratio of the diethylene glycol to the maleic anhydride was 1.10. Then, the reaction was heated to 55° C. and carried out at 55° C. for 60 minutes in the first stage, and then the reaction was heated to 80° C. and carried out at 80° C. for 300 minutes in the second stage to obtain (2-hydroxyethoxy)ethyl maleate.

[0078] Synthesis Example 3 2-Hydroxypropyl Maleate

[0079] 443.9 g of propylene glycol and 520.0 g of maleic anhydride were placed in a reaction kettle, and the molar ratio of the propylene glycol to the maleic anhydride was 1.10. Then, the reaction was heated to 55° C. and carried out at 55° C. for 60 minutes in the first stage, and then the reaction was heated to 80° C. and carried out at 80° C. for 300 minutes in the second stage to obtain 2-hydroxypropyl maleate.

[0080] Example 1 Polyurethane methacrylate resin having carboxylic acid groups and curable composition

[0081] 640.0 g of polyisocyanate [brand: TOSOH; model: MR200; isocyanate content of 31.25±0.75%; isocyanate content of 4.76 equivalents], 0.82 g of 2,5-dihydroxytoluene (as an inhibitor) and 0.308 g of dibutyltin dilaurate (as a catalyst) are dispersed in 412 g of methyl methacrylate (as a diluent monomer), mixed evenly, and then heated to 50±2° C. to obtain a first mixture.

[0082] 317.5 g of polypropylene glycol (brand: Oriental Union Chemical Corp.; model: PPG400; average molecular weight: 400; in 317.5 g of polypropylene glycol, the hydroxyl content is 1.59 equivalents) was slowly added to the first mixture, and the addition time was 50±10 minutes. During the addition, the temperature was controlled at 54±6°C, and the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polypropylene glycol was 3:1. Then, the temperature 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.

[0083] A third mixture is slowly dripped into the second mixture, and the dripping time is 50±10 minutes, and during the dripping process, the temperature is controlled at 50±5°C, and the third mixture contains 340.8 grams of hydroxyethyl methacrylate and 127.1 grams of hydroxyethyl maleate of Synthesis Example 1, and the equivalent ratio of the content of hydroxyl groups in the third mixture to the content of isocyanate groups in the polyurethane resin having multiple isocyanate groups is 1.05. Then, the temperature is maintained at 50±2°C for 2.5±0.5 hours, and the isocyanate content is measured during the process. When the isocyanate content is 0.67%, 206 grams of methyl methacrylate (a polymerizable diluent monomer) is added to obtain a curable composition. The curable composition contains a polyurethane methacrylate resin having a carboxylic acid group and methyl methacrylate, and the viscosity of the curable composition is 1600cps, and the acid value is 21mgKOH / g.

[0084] Example 2 Polyurethane methacrylate resin having carboxylic acid group and curable composition

[0085] 150.0 g of poly(methyl phenyl isocyanate) (brand: Wanhua Chemical; model: PM200; isocyanate content of 31.25±0.75%; in 150.0 g of poly(methyl phenyl isocyanate), the isocyanate 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) are dispersed in 90.0 g of methyl methacrylate (as a diluent monomer), mixed evenly, and then heated to 50±2° C. to obtain a first mixture.

[0086] 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 equivalents) was slowly added to the first mixture, and the addition time was 50±10 minutes, and during the addition process, the temperature was controlled at 54±6°C, and the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polypropylene glycol was 3:1. Then, the temperature 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.

[0087] A third mixture is slowly dripped into the second mixture, and the dripping time is 50±10 minutes, and during the dripping process, the temperature is controlled below 50±5°C, and the third mixture contains 72.6 grams of hydroxyethyl methacrylate and 38.0 grams of (2-hydroxyethoxy)ethyl maleate of Synthesis Example 2, and the equivalent ratio of the hydroxyl content of the third mixture to the isocyanate content of the polyurethane resin having multiple isocyanate groups is 1.03. Then, the temperature is maintained at 50±2°C for 2.5±0.5 hours, and the isocyanate content is measured during the process. When the isocyanate content is 0.48%, 90.0 grams of methyl methacrylate (a polymerizable diluent monomer) is added to obtain a curable composition. The curable composition contains a polyurethane methacrylate resin having a carboxylic acid group and methyl methacrylate, and the viscosity of the curable composition is 2600cps, and the acid value is 20mgKOH / g.

[0088] Example 3 Polyurethane methacrylate resin having carboxylic acid groups and curable composition

[0089] 640.0 g of poly(methyl phenyl isocyanate) (brand: Wanhua Chemical; model: PM200; isocyanate content of 31.25±0.75%; in 640.0 g of poly(methyl phenyl isocyanate), the isocyanate 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) are dispersed in 412.0 g of methyl methacrylate (as a diluent monomer), mixed evenly, and then heated to 50±2° C. to obtain a first mixture.

[0090] 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 to the first mixture, and the addition time was 50±10 minutes, and during the addition process, the temperature was controlled at 54±6°C, and the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polypropylene glycol was 3:1. Then, the temperature 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.

[0091] A third mixture is slowly dripped into the second mixture, and the dripping time is 50±10 minutes, and during the dripping process, the temperature is controlled at 50±5°C, and the third mixture contains 340.8 grams of hydroxyethyl methacrylate and 138.2 grams of 2-hydroxypropyl maleate of Synthesis Example 3, and the equivalent ratio of the content of hydroxyl groups in the third mixture to the content of isocyanate groups in the polyurethane resin having multiple isocyanate groups is 1.02. Then, the temperature is maintained at 50±2°C for 2.5±0.5 hours, and the content of isocyanate groups is measured during the process. When the content of isocyanate groups is 0.23%, 206.0 grams of methyl methacrylate (a polymerizable diluent monomer) is added to obtain a curable composition. The curable composition contains a polyurethane methacrylate resin having a carboxylic acid group and methyl methacrylate, and the viscosity of the curable composition is 1900cps, and the acid value is 22mgKOH / g.

[0092] Evaluation Project

[0093] Viscosity (unit: cps) measurement: The curable compositions of Examples 1 to 3 were placed in a viscosity meter (brand: BROOKFIELD; model: DV-IPrime; including a viscometer, a constant temperature water bath circulation tank, and an S14 rotor), and the temperature was controlled at 25° C. with a constant temperature water bath circulation tank, and the test was performed at 100 rpm.

[0094] Acid value (unit: mgKOH / g) measurement: 0.6±0.1 g of the polyurethane methacrylate resin having a carboxylic acid group and the curable composition of Examples 1 to 3 were dissolved in 10 mL of a solvent component (comprising toluene and isopropanol, and the weight ratio of toluene to isopropanol was 1:1), then, a phenolphthalein indicator was dropped, and titration was performed with a 0.1 N potassium hydroxide ethanol solution.

[0095] Measurement of the content of isocyanate group (-N=C=O) (unit: %): 0.25±0.05 g of the polyurethane resin having multiple isocyanate groups and the polyurethane methacrylate resin having carboxylic acid groups of Examples 1 to 3 were dissolved in 15 mL of a component (comprising di-n-butylamine and toluene, and in the component, the concentration of the di-n-butylamine was 0.1 N), then the reaction was stirred continuously for 10 min, and then bromophenol blue indicator was dropped, and titrated to the endpoint with 0.1 N aqueous hydrochloric acid solution.

[0096] Thickening property measurement: 100 parts by weight of the curable composition of 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 speed of 1000 rpm for 10 minutes. Then, the composition was placed in an environment of 23±1°C for 0 days, 3 days, 6 days and 13 days, and the viscosity was measured using a viscosity meter (brand: BROOKFIELD; model: DV-IPrime), and the measurement results are shown in Table 1.

[0097] Table 1

[0098]

[0099]

[0100] Referring to Table 1, the viscosity of the curable compositions of Examples 1 to 3 increases with the storage days, which indicates that the polyurethane methacrylate resin having a carboxylic acid group of the present invention can indeed react with the chemical thickener to increase the viscosity and have a thickening effect.

[0101] Charpy impact test: The curable compositions of Examples 1 to 3 were uniformly mixed with 0.015±0.005wt% of cobalt isooctanoate and 1.5±0.5wt% of methyl ethyl ketone peroxide (1-2%), and then degassed to obtain a mixture. The mixture was poured into a glass mold with a thickness of 4 mm, and subjected to a curing reaction at room temperature for 24 hours, followed by a baking treatment at 105°C for 2 hours to obtain a cured cast plate. The cured cast plate was cut into test pieces of 80 mm×10 mm×4 mm, and tested with an impact tester (brand: Cometech; model: QC-639) according to ISO 179 plastic unnotched impact strength test specification. The test results are shown in Table 2. Unsaturated polyester resin (brand: REICHHOLD; model: POLYLITE 413-000) was uniformly mixed with 0.015±0.005wt% of cobalt isooctanoate and 1.5±0.5wt% of methyl ethyl ketone peroxide, and the above process was repeated, and the impact tester was used for testing.

[0102] Table 2

[0103]

[0104] Referring to Table 2, the impact strength of the test pieces formed from the curable compositions obtained from Examples 1 to 3 is significantly better than that of the test pieces formed from the unsaturated polyester resin, which indicates that the polyurethane methacrylate resin having a carboxylic acid group of the present invention can indeed perform better in terms of toughness improvement.

[0105] Application Example 1 Composite mold material

[0106] 100 parts by weight of the curable composition of Example 1, 38 parts by weight of styrene (as a viscosity adjuster), 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 an acidic group (as a wetting dispersant; brand: German BYK; model: BYK-W 996), 3 parts by weight of tert-butyl peroxybenzoate (as a hardener) and 1.5 parts by weight of magnesium oxide (as a chemical thickener) are placed in a high shear disperser and stirred for 5 minutes. Then, 300 parts by weight of aluminum hydroxide (as a flame retardant) are divided into several equal parts and added in batches, and then stirred at a speed of 1000 rpm for 10 minutes to obtain a mixture. Then, the mixture, 3 parts by weight of zinc stearate (as a release agent) and 108 parts by weight of carbon fiber (size 1 cm) are introduced into a biaxial kneader to obtain a halogen-free flame-retardant agglomerated composite molding material. The halogen-free flame-retardant bulk composite molding material is introduced into a mold of a compression molding machine, and a 50 kg / cm2 heat treatment is applied to the halogen-free flame-retardant bulk composite molding material at 150°C. 2 The pressure is used for compression molding to obtain a molded product.

[0107] Application Examples 2 to 3

[0108] The preparation methods of Application Examples 2 to 3 are substantially the same as those of Application Example 1, with the main difference being that the types or amounts of components are changed, see Table 3.

[0109] Table 3

[0110]

[0111] Evaluation Project

[0112] Average flexural strength (unit: MPa) measurement: According to the specification of ISO 14125, the molded product of the application example is cut into 5 samples to be tested with a size of 100 mm×15 mm×3 mm. Then, a universal tensile strength tester (brand: Instron; model: 5892) is used to measure the flexural strength of the samples to be tested, and the average flexural strength is calculated.

[0113] Flame retardancy measurement: The molded product of the application example is cut into 5 test pieces with a size of 127 mm × 12.7 mm × 3 mm. Then, the test pieces are tested by the vertical combustion method, and each test piece is in contact with the flame for 10 seconds, then leaves the flame, and the first self-extinguishing time is measured. Then, it is in contact with the flame for 10 seconds, then leaves the flame, and the second self-extinguishing time is measured. Then, the first self-extinguishing time and the second self-extinguishing time are added together to obtain the total time. When the total time is less than 10 seconds, it is judged to meet the V0 level.

[0114] Table 4

[0115]

[0116] Referring to Table 4, the molded products of Application Examples 1 to 3 have good bending strength that meets the requirements of the industry, which means that the components in the composite mold material can indeed be mixed evenly, resulting in the molded products having good properties.

[0117] In summary, the polyurethane (meth) acrylate resin having a carboxylic acid group of the present invention can react with a chemical thickener, so that the state can be changed from low viscosity (high fluidity) to high viscosity (no fluidity), and a thickening phenomenon is exhibited. When the composite mold material containing the polyurethane (meth) acrylate resin having a carboxylic acid group is subjected to compression molding under high-temperature pressing conditions, the state can be changed from no fluidity to high fluidity, and can be operable during the compression molding process. Moreover, due to the fluidity, the various components in the composite mold material can be mixed evenly, so that the molded product has good quality, so the purpose of the present invention can be achieved.

Claims

1. A polyurethane resin composition, characterized in that Include: A polyurethane resin having multiple isocyanate groups; a (meth)acrylate having a hydroxyl group; and a monohydric alcohol having a carboxylic acid group, 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.

2. The polyurethane resin composition according to claim 1, characterized in that: The (meth)acrylate having a hydroxyl group is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate or any combination thereof.

3. The polyurethane resin composition according to claim 1, characterized in that: The equivalent ratio of the sum of the hydroxyl content of the (meth)acrylate having a hydroxyl group and the hydroxyl content of the monohydric alcohol having a carboxylic acid group to the isocyanate group of the polyurethane resin having a plurality of isocyanate groups is 1:1 to 1.05:

1.

4. A polyurethane (meth) acrylate resin having a carboxylic acid group, characterized in that: The polyurethane (meth) acrylate resin having a carboxylic acid group is formed by a condensation reaction of the polyurethane resin composition as described in any one of claims 1 to 3, and in the condensation reaction, the hydroxyl group of the monohydric alcohol having a carboxylic acid group and the hydroxyl group of the (meth) acrylate having a hydroxyl group are subjected to the condensation reaction with the isocyanate group of the polyurethane resin having multiple isocyanate groups.

5. The polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 4, characterized in that: The acid value of the urethane (meth) acrylate resin having a carboxylic acid group ranges from 10 mgKOH / g to 40 mgKOH / g.

6. A polyurethane (meth) acrylate resin having a carboxylic acid group, characterized in that: The polyurethane (meth) acrylate resin having a carboxylic acid group is shown below. R 1 is hydrogen or methyl, R 2 , R 3 and R 4 is an organic group, R 5 for T 2 is an organic group having an isocyanate group or an organic group not having an isocyanate group, T 21 is an organic group, T 22 is hydrogen or methyl, X is -CH2-CH2-, -CH2-CH2-O-CH2-CH2- or m and n are 1 or more.

7. The polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 6, characterized in that: R 3 for n 1 is 1 or more.

8. The polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 7, characterized in that: R 2 It is an alkyl group.

9. The polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 7, characterized in that: R 4 and T 21 It is an alkyl group or an alkyl ether.

10. The polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 7, characterized in that: The acid value of the urethane (meth) acrylate resin having a carboxylic acid group ranges from 10 mgKOH / g to 40 mgKOH / g.

11. A method for preparing a polyurethane (meth) acrylate resin having a carboxylic acid group, characterized in that The method comprises the following steps: condensing the hydroxyl group of a monohydric alcohol having a carboxylic acid group and the hydroxyl group of a (meth)acrylate having a hydroxyl group with the isocyanate group of a polyurethane resin having multiple isocyanate groups, 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.

12. The method for preparing a polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 11, characterized in that: The monohydric alcohol having a carboxylic acid group and the (meth)acrylate having a hydroxyl group are mixed to obtain a mixture, and then the mixture is subjected to the condensation reaction with the polyurethane resin having a plurality of isocyanate groups.

13. The method for preparing a polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 11, characterized in that: The (meth)acrylate having a hydroxyl group is reacted with the polyurethane resin having a plurality of isocyanate groups to obtain a reaction mixture, and then the monohydric alcohol having a carboxylic acid group is reacted with the reaction mixture.

14. The method for preparing a polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 11, characterized in that: The method for preparing the polyurethane (meth) acrylate resin having a carboxylic acid group further comprises subjecting the reaction components of a polyol material and a polyisocyanate material to a polycondensation reaction to obtain the polyurethane resin having a plurality of isocyanate groups.

15. The method for preparing a polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 11, characterized in that: The preparation method of the polyurethane (meth) acrylate resin having a carboxylic acid group further comprises reacting a diol with maleic anhydride to obtain the monool having a carboxylic acid group, wherein the diol is selected from ethylene glycol, diethylene glycol or propylene glycol.

16. The method for preparing a polyurethane (meth) acrylate resin having a carboxylic acid group according to claim 11, characterized in that: The (meth)acrylate having a hydroxyl group is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate or any combination thereof.

17. A curable composition, characterized in that The invention comprises: the polyurethane (meth) acrylate resin having a carboxylic acid group as claimed in any one of claims 4 to 10, and a polymerizable diluent monomer.

18. The curable composition according to claim 17, wherein: The polymerizable diluent 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, methyl styrene, vinyl toluene or any combination thereof.

19. A composite mold material, characterized in that The invention comprises: a resin component, a fiber material, and a chemical thickener; the resin component is selected from the polyurethane (meth) acrylate resin having a carboxylic acid group as described in any one of claims 4 to 10 or the curable composition as described in any one of claims 17 to 18.

20. The composite mold material according to claim 19, characterized in that: The chemical thickener is selected from alkaline earth metal oxides, alkaline earth metal hydroxides or any combination thereof.

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