epoxy resin composition

Abstract

The objective is to provide an epoxy resin composition that offers excellent impact resistance. [Solution] An epoxy resin composition in which particles of an impact-improving material are dispersed in an epoxy resin, wherein the impact-improving material comprises a glycidyl group-containing copolymer having α-olefin and α,β-unsaturated glycidyl ester as copolymer components, the weight ratio of the epoxy resin to the impact-improving material is 20:80 to 90:10, and the particle size of the particles of the impact-improving material is 5 μm or less.

Description

Technical Field

[0001] The present invention relates to a resin composition containing an epoxy resin.

Background Art

[0002] The cured product of an epoxy resin is excellent in many aspects such as dimensional stability, mechanical strength, electrical insulation properties, heat resistance, water resistance, chemical resistance, etc. However, the cured product of an epoxy resin has low fracture toughness and may exhibit very brittle properties, and such properties often become a problem in a wide range of applications.

[0003] [[ID=CH16]]As one of the methods for solving these problems, blending a rubber component into an epoxy resin has been conventionally performed. Among them, a method of blending rubber-like polymer particles prepared in advance in a particulate form using a polymerization method in an aqueous medium typified by emulsion polymerization, dispersion polymerization, and suspension polymerization is, for example, a non-crosslinked rubber component with respect to an epoxy resin. Compared with a method of generating a dispersed phase of a rubber component in a continuous phase of a cured epoxy resin by causing phase separation in the curing process after dissolution and mixing, in principle, it is difficult to cause fluctuations in the dispersed state due to blending and curing conditions. Since various advantages such as less mixing of the rubber component into the continuous phase of the cured epoxy resin and less decrease in heat resistance and rigidity by crosslinking the rubber component in advance are considered, various manufacturing methods as shown below have been proposed. [[ID=CH17]] [[ID=CH18]]

[0004] [[ID=CH19]] Patent Document 1 (Japanese Patent Laid-Open No. 5-295237) discloses a method of pulverizing a coagulum of a rubber-like polymer latex and then mixing it with an epoxy resin. In this method, the rubber-like polymer is separated from water by once taking it out as a coagulum, but the handling of this and the process of mixing with an epoxy resin are complicated and not industrially preferable. Furthermore, when the rubber-like polymer is once taken out as a coagulum and then mixed with an epoxy resin and redispersed, it is difficult to redisperse the rubber-like polymer particles in the state of primary particles in the epoxy resin even by using a pulverization or dispersion operation by a considerable mechanical shearing force.

[0005] Patent document 2 (Japanese Patent Publication No. 6-107910) discloses a method for obtaining a mixture by mixing a rubbery polymer latex and an epoxy resin, and then removing the water by distillation. In this method, since the epoxy resin and water do not mix well, dried material is generated in the areas that do not mix, forming lumps that will negatively affect the quality unless removed. Furthermore, a large amount of water must be removed in the presence of the epoxy resin, which makes the operation difficult.

[0006] Patent document 3 (U.S. Patent No. 4,778,851) discloses a method for obtaining a mixture by mixing a rubbery polymer latex with an epoxy resin in the presence of an organic solvent. In this method, when mixing the rubbery polymer latex and the epoxy resin, it is necessary to separate or distill off a large amount of water (more water than the amount of water that the organic solvent can dissolve) that is present in the system (mixture) along with the organic solvent. However, separating the organic solvent layer from the water layer requires a considerable amount of time, such as 24 hours, or the organic solvent layer and the water layer form a stable emulsified suspension state, making separation practically difficult. Furthermore, if water is distilled off, a large amount of energy is required, and water-soluble impurities such as emulsifiers and auxiliary materials usually used in the production of rubbery polymer latex remain in the composition, resulting in inferior quality. For this reason, the removal of water by either separation or distillation is complicated and industrially undesirable.

[0007] Patent document 4 (WO2018 / 131570) discloses a method for mixing 13 μm fine particles of ethylene-glycidyl methacrylate copolymer, which have been pre-ground, into epoxy resin using a batch mixer, without melting the copolymer, thus maintaining the original particle size. However, there are challenges, such as the need for pre-ground particles and the difficulty in further reducing the dispersion particle size while maintaining productivity. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 5-295237 [Patent Document 2] Japanese Patent Application Publication No. 6-107910 [Patent Document 3] U.S. Patent No. 4,778,851 [Patent Document 4] WO2018 / 131570 publication [Overview of the project] [Problems that the invention aims to solve]

[0009] The object of the present invention is to provide an epoxy resin composition that provides excellent impact resistance. [Means for solving the problem]

[0010] The present invention relates to a resin composition in which a polyethylene copolymer having a glycidyl methacrylate group is dispersed in a liquid epoxy resin.

[0011] The embodiments of the present invention are as follows: [1] An epoxy resin composition which is a dispersion in which particles of an impact-improving material are dispersed in an epoxy resin, The impact-improving material comprises a glycidyl group-containing copolymer having α-olefin and α,β-unsaturated glycidyl ester as copolymer components. The weight ratio of epoxy resin to impact-improving material is 20:80 to 99:1. An epoxy resin composition in which the particle size of the impact-improving material particles is 12 μm or less. [2] The epoxy resin composition according to [1], wherein in the glycidyl group-containing copolymer, the α-olefin is ethylene and the α,β-unsaturated glycidyl ester is glycidyl (meth)acrylate. [3] The epoxy resin composition according to [1] to [2], wherein the glycidyl group-containing copolymer comprises an α-olefin and an α,β-unsaturated glycidyl ester, plus another monomer, the other monomer being at least one monomer selected from vinyl acetate (VA) and alkyl (meth)acrylate. [4] The epoxy resin composition according to [1] to [3], wherein the amount of the α,β-unsaturated glycidyl ester is 3 to 20% by weight based on the glycidyl group-containing copolymer. [5] The composition according to [1] to [4], wherein in the glycidyl group-containing copolymer, the α,β-unsaturated glycidyl ester is 3 to 20% by weight and vinyl acetate (VA) is 1 to 10% by weight. [6] The composition according to [1] to [5], wherein in the glycidyl group-containing copolymer, the α,β-unsaturated glycidyl ester is 3 to 20% by weight and the alkyl acrylate is 二十 to 30% by weight. [7] The composition according to [1] to [6], wherein the MFR measured under the conditions of 190° C. and 21.2 N for the impact modifier is 3 to 400 g / 10 min. [8][[ID=十六]] The epoxy equivalent of the epoxy resin is 50 to 10,000 g / eq as measured by JIS K7236, and the viscosity of the epoxy resin is 1000 mPa·s to 50000 mPa·s as measured using a Brookfield viscometer under the conditions of 25° C. and 10 rpm. The composition according to [1] to [7]. [Advantages of the Invention]

[0012] Since the epoxy resin composition of the present invention has a small dispersion average particle diameter, it gives a cured product of an epoxy resin having excellent impact resistance. [Brief Description of the Drawings]

[0013] [Figure 1] It is a schematic diagram for explaining one aspect of the production method of the present invention including the schematic of a continuous kneader.

[0014] The epoxy resin composition is obtained by the production method shown below.

[0015] Steps (1) to (4) are carried out in a kneader, particularly a continuous kneader. The kneader may be single - shaft or multi - shaft (particularly, two - shaft). The kneader has a cylinder and a screw accommodated in the cylinder. The screw has flights. The kneaded material (epoxy resin and impact modifier) passes through the clearance between the flights and the cylinder.

[0016] <Step (1)> After supplying the impact modifier, a step of heating to melt or soften it. Melting or softening of the impact modifier is possible by various methods, but it is preferable to arrange kneading segments such as a forward disk on the upstream side of segments having an effect of blocking molten resin such as a neutral disk, a reverse disk, a reverse flight, a seal ring, etc.

[0017] <Step (2)> A step of supplying an epoxy resin (liquid epoxy resin) to the kneader. To supply the epoxy resin to the kneader, it can be quantitatively supplied through a liquid addition nozzle or the like by a gear pump, a deforming pump, a rotary lobe pump, etc.

[0018] <Step (3)> A step of dispersing and mixing the impact modifier melted in the first step and the liquid epoxy resin supplied to the kneader in the second step. In step (3), a mixture of the impact modifier and the epoxy resin (impact modifier / epoxy resin mixture) is obtained. The impact modifier / epoxy resin mixture is a dispersion in which the impact modifier is dispersed in the epoxy resin. The impact modifier / epoxy resin mixture has a sea - island structure in which the continuous phase is the epoxy resin and the dispersed phase is the impact modifier.

[0019] The third step is preferably carried out in the kneading zone of the kneader. The kneading zone of the kneader is composed of a blocking part and a kneading part. The kneading zone has a kneading part upstream and a blocking part downstream. The kneading part disperses and mixes the impact modifier and the epoxy resin.

[0020] <Process (4)> Step (4) is an optional step that may be omitted. In step (4) (the fourth step), epoxy resin is again supplied to the kneader in the same manner as in the second step, and the impact modifier that was already dispersed in the epoxy resin in the third step is diluted (dilution zone). Since epoxy resin has a lower viscosity than impact modifier, it is difficult to reduce the particle size of the impact modifier if the amount of epoxy resin is large. Therefore, it is preferable to supply the epoxy resin in two separate steps, the second and the fourth step. Furthermore, by adding unheated epoxy resin to the molten impact modifier, the temperature of the impact modifier / epoxy resin mixture can be rapidly reduced.

[0021] <Additional steps> Furthermore, additional steps can be used as needed.

[0022] In step (5) (the fifth step), degassing by suction using a vacuum vent is preferable. Step (5) is preferably carried out in a kneading machine.

[0023] In step (6) (the sixth step), it is preferable to quickly lower the temperature of the epoxy resin containing the impact-improving material obtained from the kneader by passing it through a heat exchanger or the like.

[0024] The resulting epoxy resin composition may be stored in a tank.

[0025] Figure 1 is a schematic diagram illustrating one embodiment of the manufacturing method of the present invention, including an outline of a continuous kneading machine. The continuous kneader has a first region 11, a second region 12, a third region 13, a fourth region 14, and a fifth region 15. In the first step (first region 11), after supplying the thermoplastic impact-improving material, the thermoplastic impact-improving material is heated in order to melt it. In the second step (second region 12), liquid epoxy resin is supplied to the kneader. In the third step (third region 13), the molten impact-improving material and epoxy resin are mixed to obtain a dispersion in which particles of the impact-improving material are dispersed in the epoxy resin. In the fourth step (fourth region 14), epoxy resin is further supplied to the kneader. By adding epoxy resin, which is the dispersion medium, the impact modifier dispersed in the epoxy resin is diluted. In this way, a resin composition in the form of a dispersion is obtained. In the fifth step (fifth region 15), degassing is performed by suction using a vacuum vent. Furthermore, the temperature of the resin composition is lowered by passing the dispersion through a heat exchanger. The resin composition is then sent to a tank (storage tank).

[0026] The materials used in this invention are described below. <Epoxy resin>

[0027] The epoxy resin is preferably a prepolymer having epoxy groups. The epoxy resin may also be an epoxy resin known as a polyepoxide. The epoxy resin is preferably having two or more epoxy groups in one molecule.

[0028] Examples of epoxy resins include glycyrol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, phenol novolac-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cyclic aliphatic glycidyl ethers, epoxy resins having a butadiene structure, dicyclopentadiene-type epoxy resins, alkylene oxy-skeleton-containing epoxy resins, and fluorene-containing epoxy resins.

[0029] The epoxy resin is preferably a homopolymer or copolymer obtained by polymerizing, for example, diglycidyl ether of bisphenol A, novolac-type epoxy resin, trifunctional or tetrafunctional epoxy resin, or a high molecular weight epoxy resin (for example, diglycidyl ether of bisphenol A with high molecular weight), or an unsaturated monoepoxide (for example, glycidyl (meth)acrylate, allyl glycidyl ether).

[0030] Examples of polyepoxides used in the present invention include glycidyl ethers of polyhydric alcohols and polyhydric phenols, polyglycidylamines, polyglycidylamides, polyglycidylimides, polyglycidyl hydantoins, polyglycidyl thioethers, epoxidized fatty acids or epoxidized drying oils, epoxidized polyolefins, epoxidized unsaturated polyesters, and mixtures thereof. Polyepoxides are synthesized from monohydric, dihydric, and trihydric phenols, and novolac resins are also included. In addition to epoxidized cycloolefins, polyepoxides also include polymers and copolymers of glycidyl (meth)acrylate and allyl glycidyl ether.

[0031] Polyepoxides are generally preferred to have an epoxy equivalent weight of 80-2000 or 200-1000. Polyepoxides can be obtained by well-known methods, but a commonly used method is to react an excess amount of epihalohydrin with a polyhydric alcohol or polyhydric phenol in the presence of a base.

[0032] The epoxy equivalent of the epoxy resin is preferably 50-10,000 g / eq, 100-5,000 g / eq, or 150-3,000 g / eq, as measured according to JIS K7236.

[0033] The polyepoxide used in the present invention may contain a monoepoxide as a reactive diluent, such as butyl glycidyl ether, or an aliphatic glycidyl ether such as phenyl glycidyl ether or cresyl glycidyl ether. As is generally known, the monoepoxide affects the stoichiometry of the polyepoxide formulation, which can be adjusted by the amount of curing agent or by other well-known methods.

[0034] The epoxy resin is liquid at 25°C. The viscosity of the epoxy resin may be between 1,000 mPa·s and 50,000 mPa·s, 1,500 mPa·s and 20,000 mPa·s, or 2,000 mPa·s and 10,000 mPa·s. Viscosity can be measured using a Brookfield viscometer at 25°C and 10 rpm.

[0035] <Impact-absorbing material> The impact-improving material used in the present invention is an epoxy group-containing olefin resin, and the olefin is ethylene, propylene, butene-1, etc. Specific examples of epoxy group-containing unsaturated monomers include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconic acid, etc. Furthermore, glycidyl ethers and glycidyl esters obtained by copolymerizing vinyl ethers, vinyl acetate, vinyl propionate and other vinyl esters, acrylic acids such as methyl, ethyl, propyl, and butyl, and methacrylic acid esters, etc., can be mentioned. Specific examples of epoxy group-containing olefin resins include ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl methacrylate-glycidyl methacrylate copolymer, ethylene-glycidyl acrylate copolymer, ethylene-vinyl acetate-glycidyl acrylate copolymer, ethylene-glycidyl ether copolymer, etc.

[0036] The impact-improving material is preferably a glycidyl group-containing copolymer having α-olefin and α,β-unsaturated glycidyl ester as copolymer components. The impact-improving material may also be a mixture containing a glycidyl group-containing copolymer and an ethylene-α-olefin copolymer having ethylene and α-olefin with 3 to 20 carbon atoms as copolymer components.

[0037] Glycidyl group-containing copolymers are copolymers obtained by copolymerizing α-olefins, glycidyl esters of α,β-unsaturated acids, and, if necessary, unsaturated monomers copolymerizable with these. It is preferable that the total copolymerized components of the glycidyl group-containing copolymer contain α-olefins and glycidyl esters of α,β-unsaturated acids in an amount of 60% or more by weight, 70% or more by weight, 90% or more by weight, 95% or more by weight, or 100% by weight. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, and 1-octene. Two or more of these may be used. Examples of glycidyl esters of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconic acid. Two or more of these may be used. Glycidyl methacrylate is preferably used. Furthermore, examples of unsaturated monomers copolymerizable with the above components include vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acids and methacrylic acid esters such as methyl, ethyl, propyl, and butyl, acrylonitrile, and styrene.

[0038] In a glycidyl group-containing copolymer, it is preferable that the α-olefin is ethylene and the α,β-unsaturated glycidyl ester is glycidyl (meth)acrylate. The glycidyl group-containing copolymer preferably comprises an α-olefin and an α,β-unsaturated glycidyl ester, plus another monomer, wherein the other monomer is preferably at least one monomer selected from vinyl acetate (VA) and alkyl (meth)acrylate (preferably with alkyl groups having 1 to 4 carbon atoms).

[0039] Preferred examples of glycidyl group-containing copolymers include ethylene / glycidyl methacrylate (GMA) copolymer, ethylene / glycidyl methacrylate (GMA) / vinyl acetate (VA) copolymer, ethylene / glycidyl methacrylate (GMA) / (meth)acrylic acid ester copolymer, ethylene / glycidyl acrylate (GA) / vinyl acetate (VA) copolymer, ethylene / glycidyl methacrylate (GMA) / methyl acrylate copolymer, ethylene / glycidyl methacrylate (GMA) / ethyl acrylate copolymer, and ethylene / glycidyl methacrylate (GMA) / butyl acrylate copolymer. Two or more of these may be used.

[0040] With respect to the amount of glycidyl group-containing copolymer, The amount of glycidyl ester of α,β-unsaturated acid (especially glycidyl methacrylate (GMA) or glycidyl acrylate (GA)) is 1-30% by weight, 2-25% by weight, 3-20% by weight, or 5-15% by weight. The amount of vinyl acetate (VA) is 0-25% by weight, 1-15% by weight, 2-10% by weight, or 3-8% by weight. The amount of (meth)acrylic acid ester (especially methyl methacrylate (MMA) or methyl acrylate (MA)) is 0-25% by weight, 1-15% by weight, 2-10% by weight, or 3-8% by weight. α-olefins (especially ethylene) make up the remainder. That's fine.

[0041] Ethylene-α-olefin copolymers are obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms. In addition to the above-mentioned ethylene and α-olefin having 3 to 20 carbon atoms, other components may be added within a range that does not adversely affect the effects of the present invention. In this case, if the other component has a glycidyl ester of an α,β-unsaturated acid as a copolymer component, it shall be a glycidyl group-containing copolymer. That is, ethylene-α-olefin copolymers do not contain glycidyl groups.

[0042] Examples of α-olefins with 3 to 20 carbon atoms in the ethylene-α-olefin copolymer include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, and 1-decene, with 1-butene and 1-octene being particularly preferred.

[0043] In a mixture of a glycidyl group-containing copolymer and an ethylene-α-olefin copolymer, the amount of ethylene-α-olefin copolymer may be 1 to 200 parts by weight, 5 to 100 parts by weight, or 10 to 50 parts by weight per 100 parts by weight of the glycidyl group-containing copolymer.

[0044] A particularly preferred example of an impact-improving material is an ethylene / glycidyl (meth)acrylate copolymer (for example, Bondfast® manufactured by Sumitomo Chemical).

[0045] The resin composition is a dispersion in which impact-improving particles are dispersed in epoxy resin (liquid epoxy resin).

[0046] In the resin composition, the weight ratio of epoxy resin to impact modifier may be 20:80~99.5:0.5, 30:70~99:1, 40:60~98:2, 60:40~95:5, or 80:20~90:10.

[0047] The average particle size of the impact-improving material particles in the resin composition may be 15 μm or less, 12 μm or less, 10 μm or less, 5 μm or less, 4 μm or less, or 3 μm or less, and may be 0.3 μm or more, 0.5 μm or more, or 1 μm or more. The average particle size is preferably 1 to 4 μm or 2 to 3 μm. The average particle size can be measured by dynamic light scattering (DLS) (or static light scattering).

[0048] <Other ingredients> The resin composition may contain other components. Other components include, for example, additives. Examples of additives include antioxidants, lubricants, UV absorbers, heat stabilizers, antistatic agents, polymerization inhibitors, defoamers, solvents, anti-aging agents, radical inhibitors, adhesion modifiers, flame retardants, surfactants, storage stability modifiers, ozone aging inhibitors, thickeners, plasticizers, radiation shielding agents, coupling agents, conductivity modifiers, phosphorus-based peroxide decomposers, pigments, metal deactivators, and property modifiers. These additives may be used individually or in combination of two or more. The amount of additive may be 30% by weight or less, 0.1 to 20% by weight, or 1 to 10% by weight relative to the resin composition.

[0049] In this specification, the symbol "~" indicating a numerical range generally includes the lower and upper numerical limits indicated before and after the symbol "~", but may not include one or both of the lower and upper numerical limits. That is, "1~10" generally means "1 or more and 10 or less", but may also mean "greater than 1 and 10 or less", "1 or more and less than 10", or "greater than 1 and less than 10". [Examples]

[0050] Next, the present invention will be specifically described with reference to examples, comparative examples, and test examples. However, these descriptions are not intended to limit the present invention. In the following, parts, percentages, or ratios refer to parts by weight, weight percentage, or weight ratio unless otherwise specified.

[0051] The equipment, materials, and test methods used in the following are as follows:

[0052] Continuous mixing machine: Co-rotating twin-screw extruder TEM-26SX (manufactured by Shibaura Machine Co., Ltd.), cylinder bore: 26.6 mm

[0053] Epoxy resin: Mitsubishi Chemical JER828 (Bisphenol A type epoxy resin, epoxy equivalent 184-194 g / eq, viscosity 12,000-15,000 mPa·s)

[0054] Impact-absorbing material: BondFirst® CG5001 (GMA concentration 19%, MFR 380g / 10min) manufactured by Sumitomo Chemical Co., Ltd.

[0055] [Measurement of dispersed particle size] Using a HORIBA Partica LA-950v2 (laser diffraction / scattering type), the particle size distribution of the diluent is measured, and the values ​​of D50 and Dmax are read.

[0056] Example 1 A resin composition was manufactured using a continuous kneader schematicly shown in Figure 1. The kneader was set to rotate at 400 rpm, the first step was set to 200°C, and the impact modifier was supplied at 5 kg / h and melted. In the second step, epoxy resin was supplied at 5 kg / h, and in the third step, one reverse flight with a clearance between the flight and cylinder of 0.66% of the cylinder diameter D and a lead length of 0.25D was used in the damming section, and one flight was used in the kneading section, generating a pressure of 0.6 MPa 1D upstream of the boundary to obtain resin composition 1.

[0057] Example 2 A resin composition was produced using a continuous kneader schematicly shown in Figure 1. The kneader was set to rotate at 400 rpm, the first step was set to 200°C, and the impact modifier was supplied at 5 kg / h and melted. In the second step, epoxy resin was supplied at 10 kg / h, and in the third step, one reverse flight with a clearance between the flight and cylinder of 0.66% of the cylinder diameter D and a lead length of 0.25D was used in the damming section, and one flight was used in the kneading section, generating a pressure of 0.2 MPa 1D upstream of the boundary to obtain resin composition 2.

[0058] Example 3 A resin composition was manufactured using a continuous kneader schematicly shown in Figure 1. The kneader was set to rotate at 600 rpm, the first step was set to 200°C, and the impact modifier was supplied at 5 kg / h and melted. In the second step, epoxy resin was supplied at 10 kg / h. In the third step, one reverse flight with a clearance between the flight and cylinder of 0.66% of the cylinder diameter D and a lead length of 0.25D was used in the damming section, and one flight was used in the kneading section to generate a pressure of 0.8 MPa 1D upstream of the boundary. In the fourth step, epoxy resin was supplied at 5 kg / h to obtain resin composition 3.

[0059] Example 4 A resin composition was manufactured using a continuous kneader schematicly shown in Figure 1. The kneader was set to rotate at 1200 rpm, the first step was set to 200°C, and an impact modifier was supplied at 5 kg / h and melted. In the second step, epoxy resin was supplied at 5 kg / h. In the third step, one reverse flight with a clearance between the flight and cylinder of 0.66% of the cylinder diameter D and a lead length of 0.25D was used in the damming section, and one flight was used in the kneading section to generate a pressure of 0.7 MPa 1D upstream of the boundary. In the fourth step, epoxy resin was supplied at 10 kg / h to obtain resin composition 4.

[0060] Example 5 A resin composition was manufactured using a continuous kneader schematicly shown in Figure 1. The kneader was set to rotate at 800 rpm, the first step was set to 200°C, and the impact-improving material was supplied at 5 kg / h and melted. In the second step, epoxy resin was supplied at 5 kg / h. In the third step, one reverse flight with a clearance between the flight and cylinder of 0.66% of the cylinder diameter D and a lead length of 0.25D was used in the damming section, and one flight was used in the kneading section to generate a pressure of 1.4 MPa upstream of the boundary 1D. In the fourth step, epoxy resin was supplied at 115 kg / h to obtain resin composition 5. [Industrial applicability]

[0061] The resin composition of the present invention can be used as an adhesive and structural material, among other components, in various fields such as sporting goods, automobiles, pressure tanks, aircraft, and tensioning materials. [Explanation of symbols]

[0062] 10 Continuous Mixing Machines 11 First area 12 Second area 13 Third area 14 Fourth area 15 Fifth area 20 Heat exchanger 30 tanks

Claims

1. An epoxy resin composition which is a dispersion in which particles of an impact-improving material are dispersed in an epoxy resin, The impact-improving material comprises a glycidyl group-containing copolymer having α-olefin and α,β-unsaturated glycidyl ester as copolymer components. The weight ratio of epoxy resin to impact-improving material is 20:80 to 99:

1. An epoxy resin composition in which the particle size of the impact-improving material particles is 12 μm or less.

2. The epoxy resin composition according to claim 1, wherein in the glycidyl group-containing copolymer, the α-olefin is ethylene and the α,β-unsaturated glycidyl ester is glycidyl (meth)acrylate.

3. The epoxy resin composition according to claim 1, wherein the glycidyl group-containing copolymer comprises an α-olefin and an α,β-unsaturated glycidyl ester, plus another monomer, the other monomer being at least one monomer selected from vinyl acetate (VA) and alkyl (meth)acrylate.

4. The epoxy resin composition according to claim 1, wherein the amount of α,β-unsaturated glycidyl ester is 3 to 20% by weight relative to the glycidyl group-containing copolymer.

5. The composition according to claim 1, wherein the glycidyl group-containing copolymer contains 3 to 20% by weight of α,β-unsaturated glycidyl ester and 1 to 10% by weight of vinyl acetate (VA).

6. The composition according to claim 1, wherein the glycidyl group-containing copolymer contains 3 to 20% by weight of an α,β-unsaturated glycidyl ester and 20 to 30% by weight of an alkyl acrylate.

7. The composition according to claim 1, wherein the MFR of the impact-improving material, measured under the conditions of 190°C and 21.2N, is 3 to 400 g / 10 min.

8. The composition according to claim 1, wherein the epoxy equivalent of the epoxy resin is 50 to 10,000 g / eq as measured according to JIS K7236, and the viscosity of the epoxy resin is 1,000 mPa·s to 50,000 mPa·s as measured using a Brookfield viscometer at 25°C and 10 rpm.

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