Polyurethane resin composition, and polyurethane (METH)acrylate resin having carboxylic acid group and preparation method therefor and use thereof

Abstract

Provided in the present invention are a polyurethane resin composition, a polyurethane (meth)acrylate resin having a carboxylic acid group, a method for preparing the polyurethane (meth)acrylate resin having a carboxylic acid group, a curable composition, and a composite molding material. The polyurethane resin composition comprises 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 having a carboxylic acid group is selected from hydroxyethyl maleate, (2-hydroxyethoxy)ethyl maleate or 2-hydroxypropyl maleate. The polyurethane (meth)acrylate resin having a carboxylic acid group is formed by means of a condensation reaction of the polyurethane resin composition, wherein during the condensation reaction, a hydroxyl group in the monohydric alcohol having a carboxylic acid group and a hydroxyl group in the (meth)acrylate having a hydroxyl group react with an isocyanate group in the polyurethane resin having isocyanate groups. The composite molding material comprises the polyurethane (meth)acrylate resin having a carboxylic acid group, a fiber material, and a chemical thickener.

Description

Polyurethane resin composition, polyurethane (meth)acrylate resin with carboxylic acid group, and preparation method and application thereof 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 forming the polyurethane (meth)acrylate resin having a carboxylic acid group. Background Art

[0002] Composite materials such as sheet molding compound (SMC) and bulk molding compound (BMC) are widely used in various fields due to their excellent properties (such as heat resistance and chemical resistance). These include parts for vehicles (such as automobiles, ships, and airplanes), sporting goods, construction products, and furniture.

[0003] Unsaturated polyester glass fiber reinforced molding material is a kind of of this composite material, and comprises unsaturated polyester resin, glass fiber and chemical thickener (such as magnesium oxide or calcium oxide etc.).By the effect between this chemical thickener and this unsaturated polyester resin, the state of this unsaturated polyester glass fiber reinforced molding material can be changed into high viscosity (no fluidity) by low viscosity (high fluidity), and present thickening phenomenon, and when this unsaturated polyester glass fiber reinforced molding material carries out compression molding process under high temperature pressing condition, the effect of this chemical thickener and this unsaturated polyester resin can disappear, cause the state of this unsaturated polyester glass fiber reinforced molding material to be changed into high fluidity by no fluidity, and can have operability in compression molding process, and owing to having fluidity, cause formed product to be difficult for the problem of bad appearance such as sand hole defect.But this unsaturated polyester glass fiber reinforced molding material has the problem that mechanical characteristic (such as toughness) is not good.

[0004] To address these issues, polyurethane (meth)acrylate resins have been used to replace unsaturated polyester resins. These polyurethane (meth)acrylate resins are formed by reacting a polyurethane resin containing isocyanate groups with a (meth)acrylate containing hydroxyl groups. However, these polyurethane (meth)acrylate resins lack the ability to react with chemical thickeners, resulting in a lack of thickening in the resulting composite material. Furthermore, due to their lack of fluidity during compression molding under high-temperature lamination conditions, the resulting molded product is susceptible to poor appearance, such as sand holes.

[0005] Summary of the Invention

[0006] A first object of the present invention is to provide a polyurethane resin composition.

[0007] The polyurethane resin composition of the present invention comprises a polyurethane resin having multiple 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.

[0008] 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.

[0009] 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.

[0010] A second object of the present invention is to provide a polyurethane (meth)acrylate resin having a carboxylic acid group.

[0011] 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. 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.

[0012] 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 is in the range of 10 mgKOH / g to 40 mgKOH / g.

[0013] The third object of the present invention is to provide a polyurethane (meth)acrylate resin having a carboxylic acid group.

[0014] The polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention is shown below.

[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 is in the range of 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 method for preparing a polyurethane (meth)acrylate resin having a carboxylic acid group of the present invention comprises the following steps: condensing the hydroxyl groups of a monohydric alcohol having a carboxylic acid group and the hydroxyl groups of a (meth)acrylate having a hydroxyl group with the isocyanate groups 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.

[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 multiple 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 glycerol.

[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, tetrahydrofuranyl acrylate, tetrahydrofuranyl methacrylate, styrene, methylstyrene, vinyltoluene, 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 groups of the polyurethane (meth)acrylate resin having carboxylic acid groups of the present invention can react with a chemical thickener, causing the state of the polyurethane (meth)acrylate resin having carboxylic acid groups to change from low viscosity (high fluidity) to high viscosity (no fluidity), thereby exhibiting a thickening phenomenon. Moreover, when a composite molding material containing the polyurethane (meth)acrylate resin having carboxylic acid groups is subjected to a compression molding process under high-temperature pressing conditions, the state can be further changed from no fluidity to high fluidity, thereby enabling operability during the compression molding process. Moreover, due to the fluidity, the molded product is less likely to have poor appearance problems such as sand holes. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] FIG1 is a flow chart for explaining a method for preparing a polyurethane (meth)acrylate resin having a carboxylic acid group according to 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 hydroxyl groups and the hydroxyl groups of the monohydric alcohol having carboxylic acid groups (-COOH). The aromatic groups are, for example, but not limited to, phenyl, n 1 is 1 or more, 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] 1 , the method for preparing the polyurethane (meth)acrylate resin having a carboxylic acid group includes step S. In step S, the hydroxyl groups of the monohydric alcohol having a carboxylic acid group in the polyurethane resin composition and the hydroxyl groups of the (meth)acrylate having a hydroxyl group are condensed with the isocyanate groups of the polyurethane resin having multiple isocyanate groups to form the polyurethane (meth)acrylate resin.

[0046] In one embodiment, in step S, the monoalcohol 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 monoalcohol having a carboxylic acid group is reacted with the reaction mixture.

[0047] Referring to FIG. 1 , in some embodiments of the present invention, the method for preparing the polyurethane (meth)acrylate resin having a carboxylic acid group further comprises step Q.

[0048] In step Q, a polyurethane resin having multiple isocyanate groups is obtained by subjecting reaction components comprising at least one polyol material and at least one polyisocyanate material to a condensation polymerization reaction. The polyisocyanate material is an isocyanate compound having two or more isocyanate groups, while the polyol material is a polyol compound having two or more hydroxyl groups.

[0049] In some embodiments of the present invention, to ensure that the polyurethane resin having multiple isocyanate groups has appropriate rigidity, the equivalent ratio of the isocyanate group content of the polyisocyanate material to the hydroxyl group content of the polyol material is 1.5:1 to 10:1. In some embodiments of the present invention, to ensure that the polyurethane resin having multiple isocyanate groups has appropriate rigidity, the polyol material is a polyol with a number-average molecular weight of less than 2000. Examples of polyols with a number-average molecular weight of less than 2000 include, but are not limited to, polypropylene glycol, polyoxyethylene ether, polyoxypropylene ether, or polytetrahydrofuran. Examples of polyisocyanate materials include, but are not limited to, aromatic polyisocyanates. Examples of aromatic polyisocyanates include, but are 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 components further include a catalyst. Examples of such catalysts include, but are not limited to, organotin catalysts, organobismuth catalysts, or organozinc catalysts. Examples of such organotin catalysts include, but are not limited to, dibutyltin dilaurate. In some embodiments of the present invention, the catalyst is used in an amount of 50 mg to 200 mg per kilogram of the total amount of the polyurethane (meth)acrylate resin having carboxylic acid groups.

[0051] In some embodiments of the present invention, the reaction components further include an inhibitor. The inhibitor can be an inhibitor currently used in free radical curing system resins, such as 2,5-dihydroxytoluene, and will not be described in detail.

[0052] In some embodiments of the present invention, the reaction components further comprise a diluent monomer, 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, methylstyrene, or vinyltoluene.

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

[0055] Specifically, the diol and 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, thereby having a better thickening effect and making 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 3 The 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 is, for example, a phenyl group, n 1 is 1 or more.

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

[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 is methyl, m and n 1 is 1 or more.

[0062] In some embodiments of the present invention, to accelerate the interaction between the polyurethane (meth)acrylate resin having carboxylic acid groups and the chemical thickener and reduce the water absorption of the composite molding material, the polyurethane (meth)acrylate resin having carboxylic acid groups has an acid value ranging from 10 mgKOH / g to 40 mgKOH / g. In some embodiments of the present invention, the polyurethane (meth)acrylate resin having carboxylic acid groups has an acid value ranging 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 serves as a viscosity modifier, imparting an appropriate viscosity to the curable composition and providing the curable composition with appropriate fluidity to enable it to adapt to the conditions required for subsequent operations. Examples of the polymerizable diluent monomer include, but are 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, methylstyrene, or vinyltoluene. 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 molding 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 may be, 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 100 parts by weight of the total amount of the resin component. The chemical thickener may be, for example, but not limited to, an alkaline earth metal oxide or an alkaline earth metal hydroxide. 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 oxide may be, for example, but not limited to, magnesium oxide or calcium oxide. The alkaline earth metal hydroxide may be, for example, but not limited to, magnesium hydroxide or calcium hydroxide.

[0070] In some embodiments of the present invention, the composite molding material further comprises at least one inorganic filler. Examples of such inorganic fillers include, but are 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 molding material further includes at least one additive. Such additives include, but are not limited to, flame retardants, inhibitors, release agents, hardeners, viscosity modifiers, wetting and dispersing agents, or shrinkage modifiers. In some embodiments of the present invention, the total amount of the flame retardant is 220 to 300 parts by weight based on 100 parts by weight of the total resin component. Such flame retardants include, but are 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 100 parts by weight of the total resin component. Such inhibitors include, but are not limited to, 2,6-di-tert-butyl-p-cresol. In some embodiments of the present invention, the total amount of the release agent is 3 to 5 parts by weight based on 100 parts by weight of the total resin component. Such release agents include, but are 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 100 parts by weight of the total resin component. The hardener may be, for example, but not limited to, tert-butyl perbenzoate. 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 may be, for example, but not limited to, a diluent monomer. The diluent monomer may be, for example, but not limited to, styrene. In some embodiments of the present invention, the total amount of the wetting dispersant may be 2 to 3 parts by weight based on 100 parts by weight of the total amount of the resin component. The wetting dispersant may be, for example, but not limited to, a commercially available product of BYK Additives & Instruments (Germany) and model number BYK-W 996. In some embodiments of the present invention, the total amount of the low shrinkage agent may be 13 to 28 parts by weight based on 100 parts by weight of the total amount of the resin component. The low shrinkage agent may be, for example, but not limited to, vinyl acetate.

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

[0073] The present invention will be further described with reference to the following examples. However, it should be understood that these examples are for illustration only and should not be construed as limiting 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 at a molar ratio of 1.10. The mixture was then heated to 55° C. and subjected to a first-stage reaction at 55° C. for 60 minutes. Subsequently, the mixture was heated to 70° C. and subjected to a second-stage reaction at 70° C. for 300 minutes 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 at a molar ratio of 1.10. The mixture was then heated to 55° C. and subjected to a first-stage reaction at 55° C. for 60 minutes. Subsequently, the mixture was heated to 80° C. and subjected to a second-stage reaction at 80° C. for 300 minutes 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 at a molar ratio of 1.10. The mixture was then heated to 55°C and subjected to a first-stage reaction at 55°C for 60 minutes. The mixture was then heated to 80°C and subjected to a second-stage reaction at 80°C for 300 minutes 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: 31.25±0.75%; isocyanate 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), mixed thoroughly, and then heated to 50±2° C. to obtain a first mixture.

[0082] 317.5 grams of polypropylene glycol (brand: Oriental Union Chemical Corp.; model: PPG400; average molecular weight: 400; hydroxyl content of 1.59 equivalents per 317.5 grams of polypropylene glycol) was slowly added dropwise to the first mixture over 50 ± 10 minutes. During the addition, the temperature was controlled at 54 ± 6°C, and the equivalent ratio of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the polypropylene glycol was 3:1. The temperature was then maintained at 50 ± 2°C for 2.5 ± 0.5 hours to obtain a second mixture comprising a polyurethane resin having multiple isocyanate groups.

[0083] A third mixture was slowly added dropwise to the second mixture over a period of 50±10 minutes. During the addition, the temperature was controlled at 50±5°C. The third mixture contained 340.8 g of hydroxyethyl methacrylate and 127.1 g of hydroxyethyl maleate from Synthesis Example 1. The equivalent ratio of the hydroxyl group content of the third mixture to the isocyanate group content of the polyurethane resin having multiple isocyanate groups was 1.05. The temperature was then 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 curable composition contained a polyurethane methacrylate resin having carboxylic acid groups and methyl methacrylate, and had a viscosity of 1600 cps and an acid value of 21 mgKOH / g.

[0084] Example 2 Polyurethane Methacrylate Resin Having Carboxylic Acid Groups and Curable Composition

[0085] 150.0 g of poly(methylphenyl)isocyanate) (brand: Wanhua Chemical; model: PM200; isocyanate content of 31.25±0.75%; the isocyanate content in 150.0 g of poly(methylphenyl)isocyanate) 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 thoroughly, and then heated to 50±2° C. to obtain a first mixture.

[0086] 74.4 grams of polypropylene glycol (brand: Donglian Chemical; model: PPG400; average molecular weight: 400; hydroxyl group content in 74.4 grams of polypropylene glycol is 0.37 equivalents) was slowly added dropwise to the first mixture over a period of 50±10 minutes. During the addition, the temperature was controlled at 54±6°C, and the equivalent ratio of the isocyanate groups of the polyphenylene isocyanate to the hydroxyl groups of the polypropylene glycol was 3:1. The temperature was then maintained at 50±2°C for 2.5±0.5 hours to obtain a second mixture comprising a polyurethane resin having multiple isocyanate groups.

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

[0088] Example 3 Polyurethane Methacrylate Resin Having Carboxylic Acid Groups and Curable Composition

[0089] 640.0 g of poly(methylene phenyl isocyanate) (brand: Wanhua Chemical; model: PM200; isocyanate content of 31.25±0.75%; in 640.0 g of poly(methylene 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 thoroughly, and then heated to 50±2° C. to obtain a first mixture.

[0090] 317.5 grams of polypropylene glycol (brand: Donglian Chemical; model: PPG400; average molecular weight: 400; hydroxyl group content in 317.5 grams of polypropylene glycol is 1.59 equivalents) was slowly added dropwise to the first mixture over a period of 50±10 minutes. During the addition, the temperature was controlled at 54±6°C, and the equivalent ratio of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the polypropylene glycol was 3:1. The temperature was then maintained at 50±2°C for 2.5±0.5 hours to obtain a second mixture comprising a polyurethane resin having multiple isocyanate groups.

[0091] A third mixture was slowly added dropwise to the second mixture over a period of 50±10 minutes. The temperature was maintained at 50±5°C during the addition process. The third mixture contained 340.8g of hydroxyethyl methacrylate and 138.2g of 2-hydroxypropyl maleate from Synthesis Example 3. The equivalent ratio of the hydroxyl group content of the third mixture to the isocyanate group content of the polyurethane resin having multiple isocyanate groups was 1.02. The temperature was then maintained at 50±2°C for 2.5±0.5 hours, and the isocyanate group content was measured during the process. When the isocyanate group content reached 0.23%, 206.0g of methyl methacrylate (a polymerizable diluent monomer) was added to obtain a curable composition. The curable composition contained a polyurethane methacrylate resin having carboxylic acid groups and methyl methacrylate, and had a viscosity of 1900cps and an acid value of 22mgKOH / g.

[0092] Evaluation Project

[0093] 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 thermostatic water bath, and an S14 rotor). The viscosities were measured using a thermostatic water bath controlled at 25°C and 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, with the weight ratio of toluene to isopropanol being 1:1). Then, phenolphthalein indicator was added dropwise, and titration was performed with a 0.1 N potassium hydroxide ethanol solution.

[0095] Measurement of the isocyanate group (-N=C=O) content (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, wherein the concentration of di-n-butylamine in the component was 0.1 N). The reaction was stirred continuously for 10 minutes. Subsequently, bromophenol blue indicator was added dropwise, and the mixture was titrated to the endpoint with 0.1 N aqueous hydrochloric acid.

[0096] Thickening property measurement: 100 parts by weight of the curable compositions of Examples 1 to 3 and 1 part by weight of magnesium oxide were introduced into a high-shear disperser and sheared and dispersed at 1000 rpm for 10 minutes. The compositions were then allowed to stand at 23±1°C for 0, 3, 6, and 13 days. Viscosity was measured using a viscometer (Brand: Brookfield; Model: DV-I Prime). The results are shown in Table 1.

[0097] Table 1

[0098] Referring to Table 1, the viscosity of the curable compositions of Examples 1 to 3 increases with storage days, indicating 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 thus have a thickening effect.

[0099] Charpy impact test: The curable compositions of Examples 1 to 3 were uniformly mixed with 0.015±0.005 wt% of cobalt isooctanoate and 1.5±0.5 wt% of methyl ethyl ketone peroxide (1-2%), and then degassed to obtain a mixture. The mixture was poured into a 4 mm thick glass mold and subjected to a curing reaction at room temperature for 24 hours. Subsequently, the mixture was baked 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 using an impact tester (Brand: Cometech; Model: QC-639) in accordance with ISO 179, a standard for testing the unnotched impact strength of plastics. The test results are shown in Table 2. Unsaturated polyester resin (brand: REICHHOLD; model: POLYLITE 413-000) was uniformly mixed with 0.015±0.005 wt % of cobalt isooctanoate and 1.5±0.5 wt % of methyl ethyl ketone peroxide. The above process was repeated and the mixture was tested using an impact tester.

[0100] Table 2

[0101] Referring to Table 2, the impact strength of the test pieces formed from the curable compositions obtained in Examples 1 to 3 is significantly better than that of the test pieces formed from the unsaturated polyester resin. This indicates that the polyurethane methacrylate resin having carboxylic acid groups of the present invention can indeed perform better in terms of toughness improvement.

[0102] Application Example 1 Composite Moulding Material

[0103] 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, Germany; model: BYK-W 996), 3 parts by weight of tert-butyl perbenzoate (as a hardener), and 1.5 parts by weight of magnesium oxide (as a chemical thickener) were placed in a high-shear disperser and stirred for 5 minutes. Then, 300 parts by weight of aluminum hydroxide (as a flame retardant) were added in equal portions. The mixture was then stirred at 1000 rpm for 10 minutes to obtain a mixture. This mixture, 3 parts by weight of zinc stearate (as a release agent), and 108 parts by weight of carbon fibers (1 cm in size) were then introduced into a biaxial kneader to obtain a halogen-free flame-retardant, pelletized composite molding material. The halogen-free flame-retardant bulk composite molding material is introduced into the mold of the compression molding machine, and the halogen-free flame-retardant bulk composite molding material is subjected to 50 kg / cm 2 The pressure is pressed to obtain a molded product.

[0104] Application Examples 2 to 3

[0105] 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 ingredients are changed, see Table 3.

[0106] Table 3

[0107] Evaluation Project

[0108] Average Flexural Strength (MPa) Measurement: Based on ISO 14125, the molded article of the application example was cut into five test specimens measuring 100 mm × 15 mm × 3 mm. The flexural strength of each specimen was measured using a universal tensile tester (Instron, Model 5892). The average flexural strength was calculated.

[0109] Flame retardancy measurement: The molded article of the application example was cut into five test pieces measuring 127 mm x 12.7 mm x 3 mm. The test pieces were then tested using the vertical combustion method. Each test piece was exposed to the flame for 10 seconds, then removed from the flame, and the first self-extinguishing time was measured. The test piece was then exposed to the flame for 10 seconds, then removed from the flame, and the second self-extinguishing time was measured. The first and second self-extinguishing times were then summed to obtain the total time. A total time of less than 10 seconds was considered to meet the V0 level.

[0110] Table 4

[0111] Referring to Table 4, the molded products of Application Examples 1 to 3 have good flexural strength that meets industry requirements, which indicates that the components in the composite mold material can indeed be mixed evenly, resulting in the molded products having good properties.

[0112] In summary, the polyurethane (meth)acrylate resin having carboxylic acid groups of the present invention can react with a chemical thickener, causing its state to change from low viscosity (high fluidity) to high viscosity (no fluidity), thereby exhibiting a thickening phenomenon. Furthermore, when a composite mold material containing the polyurethane (meth)acrylate resin having carboxylic acid groups is subjected to compression molding under high-temperature pressing conditions, its state can be transformed from no fluidity to high fluidity, thereby enabling operability during the compression molding process. Moreover, due to its fluidity, the various components in the composite mold material can be evenly mixed, resulting in a molded product of good quality, thereby effectively achieving the objectives of the present invention.

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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