Copolymer, adhesive, molded article, laminate, engineering plastic modifier, engineering plastic composition, and method for producing copolymer

Abstract

Provided is a copolymer comprising: a monomer unit a derived from a monomer that has a glycidyl group; at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid ester and monomer units derived from vinyl ester; and a monomer unit c derived from a C2-8 olefin monomer, wherein the proportion of the total of the monomer unit a and the monomer unit b with respect to the total number of moles of all monomer units constituting the copolymer is not less than 10 mol%.

Description

Copolymers, adhesives, molded articles, laminates, modifiers for engineering plastics, engineering plastic compositions, and methods for producing copolymers.

[0001] The present invention relates to copolymers, adhesives, molded articles, laminates, modifiers for engineering plastics, engineering plastic compositions, and methods for producing copolymers.

[0002] Olefin resins are used in a variety of applications due to their excellent mechanical strength, chemical resistance, corrosion resistance, etc. Olefin resins are molded into films, laminates, etc., for example by injection molding, extrusion molding, blow molding, etc. As an example of an olefin resin, an olefin resin composition (C) is known that comprises an olefin resin (B) and an olefin resin, wherein the amount of olefin resin (B) is 1 to 99,900 parts by weight per 100 parts by weight of polar group-containing olefin copolymer (A), obtained by copolymerizing ethylene and / or α-olefin having 3 to 20 carbon atoms with a polar group-containing monomer containing an epoxy group in the presence of a transition metal catalyst, and the olefin resin composition (C) is characterized in that the amount of olefin resin (B) is 1 to 99,900 parts by weight per 100 parts by weight of polar group-containing olefin copolymer (A). (See Patent Document 1).

[0003] Japanese Patent Publication No. 2014-208811

[0004] However, olefin resins like those described in Patent Document 1 are insoluble in solvents at room temperature (for example, toluene at 25°C), making them difficult to handle. Furthermore, while Patent Document 1 explores improving the adhesive strength to polyamides as a highly polar material, there is still room for further improvement in adhesive strength.

[0005] One aspect of the present invention aims to provide a copolymer that exhibits high solubility in a solvent at room temperature (e.g., toluene at 25°C) and excellent adhesive strength to highly polar materials (e.g., polyamides). Another aspect of the present invention aims to provide an adhesive, a molded article, a modifier for engineering plastics, an engineering plastic composition, a molded article obtained using the engineering plastic composition, and a method for producing the copolymer.

[0006] The present invention includes, for example, the following: [1] A copolymer comprising monomer unit a derived from a monomer having a glycidyl group, at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid esters and monomer units derived from vinyl esters, and monomer unit c derived from an olefin monomer having 2 to 8 carbon atoms, wherein the total proportion of monomer unit a and monomer unit b is 10 mol% or more with respect to the total number of moles of all monomer units constituting the copolymer. [2] The copolymer according to [1], wherein monomer unit a is a monomer unit derived from glycidyl methacrylate. [3] The copolymer according to [1] or [2], wherein monomer unit b is at least one monomer unit selected from the group consisting of monomer units derived from methyl acrylate and monomer units derived from vinyl acetate. [4] The copolymer according to any one of [1] to [3], wherein monomer unit c is a monomer unit derived from ethylene. [5] The copolymer according to any one of [1] to [4], wherein the total proportion of monomer unit a and monomer unit b is 30 mol% or less with respect to the total number of moles of all monomer units constituting the copolymer. [6] The copolymer according to any one of [1] to [5], wherein the proportion of monomer unit b is 15 mol% or less with respect to the total number of moles of all monomer units constituting the copolymer. [7] The copolymer according to any one of [1] to [6], wherein the melt flow rate at a temperature of 190°C and a load of 2.16 kgf is 1 to 400 g / 10 min. [8] An adhesive comprising the copolymer according to any one of [1] to [7]. [9] A molded article comprising the copolymer according to any one of [1] to [7].

[10] A laminate comprising a molded article and an adhesive layer formed on the surface of the molded article, wherein the adhesive layer comprises the copolymer according to any one of [1] to [7].

[11] A modifier for engineering plastics comprising the copolymer according to any one of [1] to [7].

[12] An engineering plastic composition comprising a copolymer according to any one of [1] to [7] and an engineering plastic.

[13] A molded article comprising the engineering plastic composition described in

[12] .

[14] A method for producing a copolymer, comprising copolymerizing a monomer having a glycidyl group, at least one monomer selected from the group consisting of (meth)acrylic acid ester monomers and vinyl ester monomers, and an olefin monomer having 2 to 8 carbon atoms by high-pressure radical polymerization, wherein the total proportion of monomer units a derived from the monomer having a glycidyl group in the copolymer and at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid esters and monomer units derived from vinyl esters in the copolymer is 10 mol% or more with respect to the total number of moles of all monomer units constituting the copolymer.

[0007] According to the present invention, it is possible to provide a copolymer that has high solubility in a solvent at room temperature (e.g., toluene at 25°C) and excellent adhesive strength to highly polar materials (e.g., polyamides). Furthermore, according to the present invention, it is possible to provide an adhesive obtained using the copolymer, a molded article, a modifier for engineering plastics, an engineering plastic composition, a molded article obtained using the engineering plastic composition, and a method for producing the copolymer.

[0008] The following describes in detail some examples of the present invention. However, the present invention is not limited to the following examples.

[0009] A copolymer according to one embodiment of the present invention comprises monomer unit a derived from a monomer having a glycidyl group, at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid esters and monomer units derived from vinyl esters, and monomer unit c derived from an olefin monomer having 2 to 8 carbon atoms, wherein the total proportion of monomer units a and monomer units b is 10 mol% or more of the total number of moles of all monomer units constituting the copolymer. Such a copolymer has high solubility in a solvent at room temperature (e.g., toluene at 25°C) and excellent adhesion strength to highly polar materials (e.g., polyamides). The inventors speculate that this is because the total proportion of monomer units a and monomer units b is relatively high, which increases the polarity of the copolymer, moderately reduces the crystallinity due to monomer units c, makes the polymer chains more likely to spread in a solvent at room temperature, and improves solubility. Furthermore, it is believed that the glycidyl group of monomer unit a reacts with the terminal groups (amino groups, carboxyl groups, etc.) of highly polar materials such as polyamides to form strong covalent bonds, or that the glycidyl group of monomer unit a has a high affinity for the terminal groups (amino groups, carboxyl groups, etc.) of highly polar materials such as polyamides, resulting in excellent adhesive strength. In addition, it is believed that monomer unit b, which is a polar group, and monomer unit c, whose crystallinity has decreased and mobility has increased, enhance physical interaction with the adherend surface (hydrogen bonding, van der Waals forces) and wettability, resulting in excellent adhesive strength to highly polar materials. However, the mechanism of the present invention is not limited to the reasons stated above.

[0010] <Copolymer> The copolymer is a copolymer comprising monomer unit a derived from a monomer having a glycidyl group, at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid esters and monomer units derived from vinyl esters, and monomer unit c derived from an olefin monomer having 2 to 8 carbon atoms, wherein the total proportion of monomer units a and monomer units b is 10 mol% or more of the total number of moles of all monomer units constituting the copolymer. Hereinafter, such a copolymer will also be referred to as "Copolymer A".

[0011] Monomer unit a may be a monomer unit derived from an unsaturated carboxylic acid glycidyl ester, a monomer unit derived from a glycidyl ether having an unsaturated group, or a combination thereof. From the viewpoint of having higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials, monomer unit a may be a monomer unit derived from an unsaturated carboxylic acid glycidyl ester.

[0012] The unsaturated carboxylic acid glycidyl ester that derives monomer unit a may be a compound represented by the following formula (1), from the viewpoint of having higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials. In formula (1), R １ This represents an alkenyl group having 2 to 18 carbon atoms, and the alkenyl group may have one or more substituents. Examples of compounds represented by formula (1) include glycidyl acrylate, glycidyl methacrylate, and glycidyl itaconic acid ester. The compound represented by formula (1) may be glycidyl methacrylate from the viewpoint of having higher solubility in solvents at room temperature and better adhesion strength to highly polar materials. That is, monomer unit a may be a monomer unit derived from glycidyl methacrylate from the viewpoint of having higher solubility in solvents at room temperature and better adhesion strength to highly polar materials.

[0013]

[0014] A glycidyl ether having an unsaturated group that derives monomer unit a may be a compound represented by the following formula (2), from the viewpoint of having higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials. In formula (2), R ２ X represents an alkenyl group having 2 to 18 carbon atoms, and the alkenyl group may have one or more substituents. X is CH ２ -O(CH ２ R ２It represents a (bonded) or oxygen atom. Examples of compounds represented by formula (2) include allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

[0015]

[0016] The proportion of monomer unit a in copolymer A may be 0.1 mol% or more, 0.5 mol% or more, 0.8 mol% or more, 1 mol% or more, 1.2 mol% or more, 1.5 mol% or more, 1.8 mol% or more, 2 mol% or more, 2.2 mol% or more, 2.5 mol% or more, 2.7 mol% or more, or 2.9 mol% or more, relative to the total number of moles of all monomer units constituting copolymer A, from the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesion strength to highly polar materials. The proportion of monomer unit a in copolymer A may also be 5 mol% or less, 4 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.6 mol% or less, 1.2 mol% or less, 1 mol% or less, or 0.8 mol% or less, relative to the total number of moles of all monomer units constituting copolymer A, from the viewpoint of achieving superior storage stability of the copolymer. From these perspectives, the proportion of monomer units a in copolymer A may be 0.1 to 5 mol%, 1 to 4 mol%, or 1.5 to 3 mol%.

[0017] Monomer unit b may be a monomer unit derived from (meth)acrylic acid ester, a monomer unit derived from vinyl ester, or a combination thereof. In this specification, "(meth)acrylate" means acrylate or methacrylate, and this is also true for similar compounds.

[0018] Examples of (meth)acrylic acid esters that derive monomer units from (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. The (meth)acrylic acid ester may be methyl acrylate from the viewpoint of higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials. That is, monomer unit b may be a monomer unit derived from methyl acrylate from the viewpoint of higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials.

[0019] Examples of vinyl esters that derive monomer units from vinyl esters include vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, and vinyl pivalate. The vinyl ester may be vinyl acetate from the viewpoint of higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials. That is, monomer unit b may be a monomer unit derived from vinyl acetate from the viewpoint of higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials.

[0020] The proportion of monomer unit b in copolymer A may be 8 mol% or more, 10 mol% or more, 10.5 mol% or more, 11 mol% or more, 11.2 mol% or more, 11.4 mol% or more, or 11.5 mol% or more, relative to the total number of moles of all monomer units constituting copolymer A, from the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesion strength to highly polar materials. The proportion of monomer unit b in copolymer A may be 20 mol% or less, 18 mol% or less, 16 mol% or less, 15 mol% or less, 14.9 mol% or less, 14.8 mol% or less, 14.6 mol% or less, 14.5 mol% or less, or 14.4 mol% or less, relative to the total number of moles of all monomer units constituting copolymer A, from the viewpoint of maintaining pellet shape and facilitating handling, and superior adhesion strength to highly polar materials. The monomer unit b may be 14.2 mol% or less, 14 mol% or less, 13.8 mol% or less, 13.6 mol% or less, 13.5 mol% or less, 13.4 mol% or less, 13.2 mol% or less, 13 mol% or less, 12.8 mol% or less, 12.6 mol% or less, 12.5 mol% or less, 12.4 mol% or less, 12.2 mol% or less, 12 mol% or less, 11.8 mol% or less, 11.6 mol% or less, or 11.5 mol% or less. From these viewpoints, the proportion of monomer unit b in copolymer A may be 8 to 20 mol%, 10 to 16 mol%, or 11 to 16 mol%.

[0021] Monomer unit c may be a monomer unit derived from ethylene, a monomer unit derived from an α-olefin, or a combination thereof, or it may be a monomer unit derived from ethylene. Examples of α-olefins include linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; cyclic olefins such as norbornene, 5-methylnorbornene, and 1-methylnorbornene; and aromatic olefins such as styrene, methylstyrene, and divinylbenzene.

[0022] The proportion of monomer units c in copolymer A may be 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 82 mol% or more, 84 mol% or more, or 86 mol% or more, relative to the total number of moles of all monomer units constituting copolymer A. The proportion of monomer units c in copolymer A may be 90 mol% or less, relative to the total number of moles of all monomer units constituting copolymer A. From the viewpoint of higher solubility in solvents at room temperature and superior adhesion strength to highly polar materials, the proportion of monomer units c in copolymer A may be 88 mol% or less, or 86 mol% or less, relative to the total number of moles of all monomer units constituting copolymer A. The proportion of monomer units derived from ethylene may be within the same range as the proportion of monomer units c. From these viewpoints, the proportion of monomer units c in copolymer A may be 50 to 90 mol%, 70 to 90 mol%, or 80 to 88 mol%.

[0023] The total ratio of monomer units a and b in copolymer A is 10 mol% or more relative to the total number of moles of all monomer units constituting the copolymer. From the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesion strength to highly polar materials, the total ratio of monomer units a and b in copolymer A may be 11 mol% or more, 12 mol% or more, 12.5 mol% or more, 12.8 mol% or more, 12.9 mol% or more, 13 mol% or more, 13.5 mol% or more, 14 mol% or more, 14.2 mol% or more, or 14.4 mol% or more relative to the total number of moles of all monomer units constituting copolymer A. The total ratio of monomer units a and b in copolymer A may be 30 mol% or less, 25 mol% or less, 20 mol% or less, 18 mol% or less, 16 mol% or less, 15.5 mol% or less, 15 mol% or less, 14.9 mol% or less, 14.7 mol% or less, 14.5 mol% or less, 14.4 mol% or less, 14.2 mol% or less, 14 mol% or less, 13.5 mol% or less, or 13 mol% or less, from the viewpoint of facilitating handling by maintaining the pellet shape and from the viewpoint of achieving superior adhesion strength to highly polar materials. From these viewpoints, the total ratio of monomer units a and b in copolymer A may be 10 to 30 mol%, 12 to 20 mol%, or 12.5 to 16 mol%.

[0024] The total proportion of monomer units a and monomer units b in copolymer A may be 10 mol% or more, 11 mol% or more, 12 mol% or more, 12.5 mol% or more, 12.8 mol% or more, 12.9 mol% or more, 13 mol% or more, 13.5 mol% or more, 14 mol% or more, 14.2 mol% or more, or 14.4 mol% or more, relative to the total number of moles of monomer units a, monomer units b, and monomer units c constituting copolymer A, from the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesion strength to highly polar materials. The total ratio of monomer units a and b in copolymer A may be 30 mol% or less, 25 mol% or less, 20 mol% or less, 18 mol% or less, 16 mol% or less, 15.5 mol% or less, 15 mol% or less, 14.7 mol% or less, 14.5 mol% or less, 14.4 mol% or less, 14.2 mol% or less, 14 mol% or less, 13.5 mol% or less, or 13 mol% or less, from the viewpoint of facilitating handling by maintaining the pellet shape and from the viewpoint of achieving superior adhesion strength to highly polar materials. From these viewpoints, the total ratio of monomer units a and b in copolymer A may be 10 to 30 mol%, 12 to 20 mol%, or 12.5 to 16 mol%.

[0025] The molar ratio of monomer unit a to monomer unit b (ratio of monomer unit a / ratio of monomer unit b) may be 0.01 or higher, 0.05 or higher, 0.1 or higher, 0.13 or higher, 0.15 or higher, 0.18 or higher, 0.2 or higher, 0.22 or higher, or 0.24 or higher, from the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials. The molar ratio of monomer unit a to monomer unit b (ratio of monomer unit a / ratio of monomer unit b) may be 0.5 or lower, 0.4 or lower, 0.3 or lower, 0.28 or lower, 0.26 or lower, 0.25 or lower, 0.23 or lower, 0.2 or lower, 0.18 or lower, 0.16 or lower, 0.14 or lower, 0.12 or lower, 0.1 or lower, or 0.08 or lower. From these perspectives, the molar ratio of monomer unit a to monomer unit b (ratio of monomer unit a / ratio of monomer unit b) may be 0.01 to 0.5, 0.1 to 0.3, or 0.13 to 0.26.

[0026] The molar ratio of monomer unit a to monomer unit c (ratio of monomer unit a / ratio of monomer unit c) may be 0.001 or higher, 0.005 or higher, 0.01 or higher, 0.012 or higher, 0.014 or higher, 0.016 or higher, 0.018 or higher, 0.02 or higher, 0.025 or higher, 0.03 or higher, or 0.032 or higher, from the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials. The molar ratio of monomer unit a to monomer unit c (ratio of monomer unit a / ratio of monomer unit c) may be 0.1 or lower, 0.05 or lower, 0.04 or lower, 0.035 or lower, 0.03 or lower, 0.025 or lower, or 0.02 or lower. From these perspectives, the molar ratio of monomer unit a to monomer unit c (ratio of monomer unit a / ratio of monomer unit c) may be 0.001 to 0.1, 0.01 to 0.04, or 0.014 to 0.035.

[0027] The molar ratio of monomer unit c to monomer unit b (ratio of monomer unit c / ratio of monomer unit b) may be 0.01 or higher, 0.05 or higher, 0.1 or higher, 0.11 or higher, 0.12 or higher, or 0.13 or higher, from the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials. The molar ratio of monomer unit c to monomer unit b (ratio of monomer unit c / ratio of monomer unit b) may be 0.6 or lower, 0.5 or lower, 0.4 or lower, 0.3 or lower, 0.2 or lower, 0.18 or lower, 0.16 or lower, 0.15 or lower, or 0.14 or lower, from the viewpoint of facilitating handling by maintaining the pellet shape. From these viewpoints, the molar ratio of monomer unit c to monomer unit b (ratio of monomer unit c / ratio of monomer unit b) may be 0.01 to 0.6, 0.05 to 0.4, or 0.1 to 0.2.

[0028] Copolymer A may further contain monomer units other than monomer units a, b, and c. For example, copolymer A may further contain monomer units derived from vinyl ether. Examples of vinyl ethers that can be used to derive monomer units from vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, and phenyl vinyl ether.

[0029] Examples of copolymer A include ethylene-glycidyl (meth)acrylate-methyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-ethyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-n-propyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-isopropyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-n-butyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-isobutyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-vinyl acetate copolymer, and ethylene-glycidyl (meth)acrylate-vinyl ether copolymer. Copolymer A may be at least one selected from the group consisting of ethylene-glycidyl (meth)acrylate-methyl (meth)acrylate copolymer and ethylene-glycidyl (meth)acrylate-vinyl acetate copolymer, from the viewpoint of having higher solubility in solvents at room temperature and superior adhesive strength to highly polar materials.

[0030] The melt flow rate (MFR) of copolymer A may be 1 g / 10 min or more, 5 g / 10 min or more, 7 g / 10 min or more, 10 g / 10 min or more, 15 g / 10 min or more, 20 g / 10 min or more, 30 g / 10 min or more, 40 g / 10 min or more, 50 g / 10 min or more, 60 g / 10 min or more, 70 g / 10 min or more, or 80 g / 10 min or more, from the viewpoint of achieving higher solubility in solvents at room temperature and superior adhesion strength to highly polar materials. The MFR of copolymer A may be 400 g / 10 min or less, 300 g / 10 min or less, 200 g / 10 min or less, 150 g / 10 min or less, 100 g / 10 min or less, 90 g / 10 min or less, 85 g / 10 min or less, 70 g / 10 min or less, 60 g / 10 min or less, 50 g / 10 min or less, 40 g / 10 min or less, 30 g / 10 min or less, 20 g / 10 min or less, or 10 g / 10 min or less. The MFR of copolymer A may be 1 to 400 g / 10 min, 5 to 200 g / 10 min, or 7 to 100 g / 10 min. The MFR of copolymer A can be measured in accordance with JIS K7210 under conditions of a temperature of 190°C and a load of 2.16 kgf. The MFR of copolymer A can be adjusted by changing the polymerization conditions (temperature, pressure, etc.) and the ratio of monomer units used to obtain copolymer A.

[0031] Copolymer A can be synthesized by various methods. For example, copolymer A can be produced by high-pressure radical polymerization. Specifically, the method for producing copolymer A involves copolymerizing a monomer having a glycidyl group, at least one monomer selected from the group consisting of (meth)acrylic acid ester monomers and vinyl ester monomers, and an olefin monomer having 2 to 8 carbon atoms by high-pressure radical polymerization, wherein the total ratio of monomer unit a derived from the monomer having a glycidyl group in the copolymer and at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid esters and vinyl esters in the copolymer is 10 mol% or more of the total number of moles of all monomer units constituting copolymer A. An example of a typical polymerization method for synthesizing copolymer A is a polymerization pressure of 500 kg / cm² in the presence of a polymerization initiator that generates free radicals. ２ The above describes a copolymerization method for at least one monomer selected from the group consisting of monomers having a glycidyl group, (meth)acrylic acid ester monomers, and vinyl ester monomers, and an olefin monomer having 2 to 8 carbon atoms, under polymerization temperature conditions of 40 to 300°C. The polymerization pressure is 1000 kg / cm². ２ It may be greater than or equal to 2000 kg / cm². ２ The following is also possible: The polymerization temperature may be 100 to 250°C, or 150 to 200°C. Since at least one monomer selected from the group consisting of monomers having a glycidyl group, (meth)acrylic acid ester monomers, and vinyl ester monomers, and an olefin monomer having 2 to 8 carbon atoms are randomly copolymerized, at least one monomer selected from the group consisting of monomers having a glycidyl group, (meth)acrylic acid ester monomers, and vinyl ester monomers, and an olefin monomer having 2 to 8 carbon atoms are present in the main chain.

[0032] Copolymer A has excellent adhesive strength to highly polar materials and can therefore be used as an adhesive, for example. That is, another embodiment of the present invention is an adhesive comprising copolymer A.

[0033] When the copolymer A is used as an adhesive, the copolymer A may be dissolved in a solvent and used. Examples of the solvent include methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, xylene, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, and cyclohexanone.

[0034] The copolymer A may be made into resin pellets by melt-kneading with an arbitrary additive. Examples of the additive include a compatibilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, an anti-coloring agent, a plasticizer, a flame retardant, a mold release agent, an antistatic agent, and a coloring agent.

[0035] The content of the copolymer A may be 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more based on the total mass of the resin pellets. The content of the copolymer A may be 100% by mass based on the total mass of the resin pellets.

[0036] The resin pellets can be obtained, for example, by a method including melt-kneading a mixture containing the copolymer A and an arbitrary additive.

[0037] The melt-kneading can be carried out, for example, using a twin-screw kneader or a lab plastomill. Examples of the twin-screw kneader include a co-rotating twin-screw extrusion machine.

[0038] The maximum temperature of the mixture to be melt-kneaded may be 50 to 350°C, 80 to 320°C, 100 to 300°C, 120 to 280°C, or 150 to 250°C.

[0039] The kneading time of the melt-kneading may be 1 second to 1800 seconds, 10 seconds to 1200 seconds, or 30 seconds to 600 seconds.

[0040] Resin pellets can be used, for example, as a molded article or as a modifier for engineering plastics to improve various properties (e.g., impact resistance) of engineering plastics. That is, another embodiment of the present invention is a molded article containing copolymer A, and another embodiment of the present invention is a modifier for engineering plastics containing copolymer A.

[0041] The molded products can be used, for example, as automotive parts, home appliance materials, office automation equipment materials, building materials, drainage equipment, toiletry materials, various tanks, containers, sheets, and the like.

[0042] Copolymer A (or modifier for engineering plastics) may be melt-kneaded with an engineering plastic to form an engineering plastic composition. That is, another embodiment of the present invention is an engineering plastic composition comprising copolymer A and an engineering plastic.

[0043] Engineering plastics refer to plastics that have a temperature deflection under load of 100°C or higher as measured by the ASTM D648 standard, a tensile strength of 50 MPa as measured by the ASTM D638 standard, and a flexural modulus of 2.4 GPa or higher as measured by the ASTM D790 standard. Plastics with a heat resistance of 150°C or higher are called special engineering plastics or super engineering plastics, but in this specification, special engineering plastics and super engineering plastics are also included in engineering plastics.

[0044] Examples of engineering plastics include polybutylene terephthalate, polyphenylene sulfide, polycarbonate, polyethylene terephthalate, liquid crystalline polymers, polyethersulfone, polyamide, polyphthalamide, polyketone, polyetherketone, polyetheretherketone, polyacetal, and polysulfone.

[0045] The engineering plastic composition may further contain other components added separately from copolymer A, such as resin components (excluding those corresponding to copolymer A), fillers, antioxidants, heat stabilizers, ultraviolet absorbers, color inhibitors, plasticizers, flame retardants, mold release agents, antistatic agents, and colorants.

[0046] The resin component may be a copolymer that does not have epoxy groups. This copolymer may be, for example, a copolymer having monomer units derived from ethylene and monomer units derived from α-olefin (i.e., an ethylene-α-olefin copolymer). The copolymer may be a copolymer having monomer units derived from ethylene and monomer units derived from an acrylic compound having (meth)acrylic groups (i.e., an ethylene-(meth)acrylate copolymer). The copolymer may be a copolymer having monomer units derived from ethylene and monomer units derived from a vinyl compound. Examples of copolymers that do not have epoxy groups include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, ethylene-(3-methyl-1-butene) copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, ethylene-norbornene copolymer, ethylene-vinyl acetate copolymer, ethylene-styrene copolymer, ethylene-acrylonitrile copolymer, ethylene-butadiene copolymer, and acrylonitrile-butadiene-styrene copolymer.

[0047] The content of copolymer A may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total mass of the engineering plastic composition. The content of copolymer A may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less, based on the total mass of the engineering plastic composition. The content of copolymer A may be 1 to 50% by mass, based on the total mass of the engineering plastic composition.

[0048] The content of the engineering plastic may be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on the total mass of the engineering plastic composition. The content of the engineering plastic may be 95% by mass or less or 90% by mass or less, based on the total mass of the engineering plastic composition. The content of the engineering plastic may be 50 to 95% by mass, based on the total mass of the engineering plastic composition.

[0049] The engineering plastic composition containing the engineering plastic and the copolymer A can be obtained, for example, by a method including melt-kneading a mixture containing the copolymer A and the engineering plastic. The engineering plastic composition may include a continuous phase containing the engineering plastic and particles containing the copolymer A dispersed in the continuous phase.

[0050] The engineering plastic composition can be molded by any molding method such as an injection molding method, an extrusion molding method, a vacuum molding method, and a hollow molding method to obtain a molded body of the engineering plastic composition. The obtained molded body may be, for example, a member of an automotive part or a member of an electric / electronic part.

[0051] The Izod impact strength of the engineering plastic composition at 23°C is 5 kJ / m ２ or more, 8 kJ / m ２ or more, 10 kJ / m ２ or more, 12 kJ / m ２ or more, 14 kJ / m ２ or more, or 15 kJ / m ２ or more. The Izod impact strength of the engineering plastic composition at 23°C is 40 kJ / m ２ or less, 30 kJ / m ２ or less, or 20 kJ / m ２ or less. From these viewpoints, the Izod impact strength of the engineering plastic composition at 23°C is 5 to 40 kJ / m ２This may also be the case. The Izod impact strength of the engineering plastic composition at 23°C can be measured by the method described in the examples below.

[0052] The copolymer A described above can be bonded to a molded body (for example, a resin molded body) to form a laminate having the molded body and an adhesive layer formed on the surface of the molded body that contains copolymer A. That is, another embodiment of the present invention is a laminate comprising a molded body and an adhesive layer formed on the surface of the molded body, wherein the adhesive layer contains copolymer A.

[0053] When the molded body is a resin molded body, examples of resins used in the resin molded body include polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer, polyethylene polymer, polypropylene polymer, polyvinyl chloride resin, polycarbonate resin, polyurethane resin, and polymethyl methacrylate resin.

[0054] The content of copolymer A in the adhesive layer may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more (i.e., the adhesive layer is substantially composed of copolymer A) based on the total mass of the adhesive layer, from the viewpoint that the adhesive layer has excellent adhesive strength to the molded article.

[0055] The adhesive layer may further contain components other than copolymer A. Examples of components other than copolymer A include resins other than copolymer A, fillers, conductive materials, compatibilizers, antioxidants, heat stabilizers, ultraviolet absorbers, color inhibitors, plasticizers, flame retardants, mold release agents, antistatic agents, colorants, etc. The adhesive layer may contain any of the above-mentioned components other than copolymer A, may not contain any of them, or may not contain any of them (i.e., the adhesive layer may be substantially composed of copolymer A).

[0056] The laminate may have layers other than the molded body and the adhesive layer. The laminate may have, for example, a release layer, a surface protection layer, a gas barrier layer, etc., on the surface of the adhesive layer opposite to the molded body, and the molded body and the adhesive layer may be laminated alternately.

[0057] The laminate may be a film having at least a molded body and an adhesive layer, or it may be a multilayer sheet. Furthermore, because the adhesive layer has excellent adhesion to the molded body, even if the laminate is curved, the molded body and the adhesive layer can maintain a tight bond. For this reason, the laminate is not limited to a two-dimensional shape such as a film, but may also be tubular (multilayer tube) or have a shape that conforms to the shape of a component. Note that "film" refers to a laminate with a thickness of less than 250 μm, and "sheet" refers to a laminate with a thickness of 250 μm or more.

[0058] The thickness of the molded body in the laminate may be, for example, 5 to 5000 μm, 5 to 4000 μm, or 5 to 3000 μm.

[0059] The thickness of the adhesive layer in the laminate may be, for example, 1 to 3000 μm, 1 to 2000 μm, or 1 to 1000 μm.

[0060] The invention will be specifically described below based on examples. However, the present invention is not limited to the following examples. 1. Raw Materials The following polymers were prepared as raw materials. Note that MFR is the melt flow rate at a temperature of 190°C and a load of 2.16 kgf. ・PE (ethylene homopolymer, MFR = 7 g / 10 min) ・EGMA-1 (polymer of 2.6 mol% glycidyl methacrylate (GMA) and 97.4 mol% ethylene, MFR = 3 g / 10 min) ・EGMA-2 (polymer of 2.7 mol% glycidyl methacrylate (GMA), 1.9 mol% vinyl acetate and 95.4 mol% ethylene, MFR = 7 g / 10 min) ・EGMA-3 (polymer of 1.5 mol% glycidyl methacrylate (GMA), 11.4 mol% methyl acrylate and 87.1 mol% ethylene, MFR = 7 g / 10 min) EGMA-4 (a copolymer of 2.9 mol% glycidyl methacrylate (GMA), 11.5 mol% methyl acrylate, and 85.6 mol% ethylene; MFR = 15 g / 10 min) EGMA-5 (a copolymer of 2.9 mol% glycidyl methacrylate (GMA), 11.5 mol% methyl acrylate, and 85.6 mol% ethylene; MFR = 82 g / 10 min) EGMA-6 (a copolymer of 2.2 mol% glycidyl methacrylate (GMA), 12.8 mol% methyl acrylate, and 85.0 mol% ethylene; MFR = 15 g / 10 min) EGMA-7 (a copolymer of 1.5 mol% glycidyl methacrylate (GMA), 14.1 mol% methyl acrylate, and 84.4 mol% ethylene; MFR = 16 g / 10 min) EGMA-8 (a copolymer of 1.1 mol% glycidyl methacrylate (GMA), 15.4 mol% methyl acrylate, and 83.5 mol% ethylene; MFR = 13 g / 10 min)

[0061] 2. Evaluation 2-1. Solubility Evaluation The solubility of 1 g of polymer in each solvent was evaluated by adding it to 10 mL of tetrahydrofuran at 25°C and 10 mL of toluene at 25°C and stirring. Complete dissolution was evaluated as "A", partial dissolution as "B", and no dissolution at all as "C".

[0062] 2-2. Evaluation of Adhesion Strength A sheet-like molded body with a thickness of 0.1 mm was prepared by heating polymer resin pellets at 150°C for 10 minutes using a vacuum press (Imoto Seisakusho Co., Ltd., IMC-19E6 model) and then cooling at 30°C for 5 minutes. A 0.1 mm thick aluminum plate, the prepared molded body, and a 1 mm thick polyamide plate were stacked in this order, and a heat sealer (Tester Sangyo Co., Ltd.) was used to heat seal the laminate with the temperature of the seal bar on the aluminum plate side (heat seal temperature) set to 280°C, the temperature of the silicone sheet on the polyamide plate side to 60°C, the seal surface pressure set to 0.3 MPa, the seal time set to 3 seconds, and the seal width set to 10 mm. A test piece with a width of 10 mm was cut perpendicular to the heat-sealed surface of the prepared laminate, and a 180-degree peel test was performed at a speed of 100 mm / min using a 5564 type tensile testing machine (Instron Co., Ltd.) to measure the peel strength. The average peel strength within a stable range was defined as the adhesive strength.

[0063] 2-3. Evaluation of Impact Strength 90% by mass of polyphenylene sulfide (PPS) was fed from the main feeder into the hopper opening of barrel C1 of a twin-screw compounding extruder (KZW20TW, manufactured by Technovel Co., Ltd.), and 10% by mass of polymer was fed from the secondary feeder. The nozzle head temperature was set to 300°C and the screw rotation speed to 300 rpm, and the PPS and polymer were melt-mixed. The melt-mixed material was discharged from the twin-screw extruder at a discharge rate of 5 kg / hour, and the melt-mixed material was cut with a pelletizer to obtain resin pellets of an engineering plastic composition containing PPS. These resin pellets were injection-molded using an injection molding machine (Sumitomo Heavy Industries, SE100EV) under the conditions of a mold temperature of 135°C, a cylinder temperature of 300°C, and an injection speed of 15 mm / second to produce a sheet-like molded body with a thickness of 3.2 mm. A notched test specimen measuring 63.5 mm in length, 12.7 mm in width, and 3.2 mm in thickness was prepared from the fabricated molded body. Using this test specimen, an Izod impact test was performed in accordance with ASTM D-256, and the Izod impact strength (kJ / m) was measured in an atmosphere of 23°C. ２ ) was measured.

[0064]

Claims

1. A copolymer comprising monomer unit a derived from a monomer having a glycidyl group, at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid esters and monomer units derived from vinyl esters, and monomer unit c derived from an olefin monomer having 2 to 8 carbon atoms, wherein the total proportion of monomer unit a and monomer unit b is 10 mol% or more of the total number of moles of all monomer units constituting the copolymer.

2. The copolymer according to claim 1, wherein the monomer unit a is a monomer unit derived from glycidyl methacrylate.

3. The copolymer according to claim 1, wherein the monomer unit b is at least one monomer unit selected from the group consisting of monomer units derived from methyl acrylate and monomer units derived from vinyl acetate.

4. The copolymer according to claim 1, wherein the monomer unit c is a monomer unit derived from ethylene.

5. The copolymer according to claim 1, wherein the total proportion of monomer unit a and monomer unit b is 30 mol% or less with respect to the total number of moles of all monomer units constituting the copolymer.

6. The copolymer according to claim 1, wherein the proportion of monomer unit b is 15 mol% or less with respect to the total number of moles of all monomer units constituting the copolymer.

7. The copolymer according to claim 1, wherein the melt flow rate at a temperature of 190°C and a load of 2.16 kgf is 1 to 400 g / 10 min.

8. An adhesive comprising the copolymer according to any one of claims 1 to 7.

9. A molded article comprising the copolymer according to any one of claims 1 to 7.

10. A laminate comprising a molded body and an adhesive layer formed on the surface of the molded body, wherein the adhesive layer contains the copolymer described in any one of claims 1 to 7.

11. A modifier for engineering plastics comprising the copolymer according to any one of claims 1 to 7.

12. An engineering plastic composition comprising a copolymer according to any one of claims 1 to 7 and an engineering plastic.

13. A molded article comprising the engineering plastic composition described in claim 12.

14. A method for producing a copolymer, comprising copolymerizing a monomer having a glycidyl group, at least one monomer selected from the group consisting of (meth)acrylic acid ester monomers and vinyl ester monomers, and an olefin monomer having 2 to 8 carbon atoms by high-pressure radical polymerization, wherein the total proportion of monomer units a derived from the monomer having a glycidyl group in the copolymer and at least one monomer unit b selected from the group consisting of monomer units derived from (meth)acrylic acid esters and monomer units derived from vinyl esters in the copolymer is 10 mol% or more with respect to the total number of moles of all monomer units constituting the copolymer.

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