WO2020149232A1 - Copolymer and resin composition - Google Patents

Abstract

Provided are a copolymer (P) that shows high adhesiveness even to relatively low-polarity substrates and a resin composition (Q) containing the same.　A copolymer (P) having a polymer chain (A) having a unit represented by formula (1) and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer. In formula (1), R¹-R⁴ each independently represent a hydrogen atom or a C1-20 alkyl group.

Description

Copolymer and resin composition

The present invention relates to a copolymer and a resin composition containing the copolymer.

Conventionally, polymers containing an oxazoline group are known (for example, Patent Documents 1 and 2). The oxazoline group-containing polymers disclosed in Patent Documents 1 and 2 are obtained by copolymerizing 2-isopropenyl-2-oxazoline with styrene or further with acrylonitrile. It can be used as a compatibilizing agent or as a primer for improving the adhesion to a substrate.

JP-A-4-81458 Japanese Patent Laid-Open No. 10-46010

The inventors of the present invention examined the adhesion of various polymers to the oxazoline group-containing polymers disclosed in Patent Documents 1 and 2, and found that the polymers composed of polyolefin having a relatively low polarity were used. However, it was revealed that they did not exhibit sufficient adhesion. The present invention has been made in view of the above circumstances, and an object thereof is to provide a copolymer (P) which exhibits high adhesion to a base material (resin base material or the like) having a relatively low polarity, and It is to provide a resin composition (Q) containing the same.

［式（１）中、Ｒ¹～Ｒ⁴はそれぞれ独立して、水素原子または炭素数１～２０のアルキル基を表す。］
［２］ポリマー鎖（Ｂ）がポリマー鎖（Ａ）にグラフトしている［１］に記載の共重合体（Ｐ）。
［３］前記ポリマー鎖（Ａ）中、前記式（１）で表される単位の含有割合が５０質量％以上である［１］または［２］に記載の共重合体（Ｐ）。
［４］前記ポリマー鎖（Ｂ）中、オキサゾリン基含有単量体由来の単位の含有割合が１質量％以上５０質量％以下である［１］～［３］のいずれかに記載の共重合体（Ｐ）。
［５］前記ポリマー鎖（Ａ）が、前記式（１）で表される単位を有する重合体ブロック（ａ１）と芳香族ビニル単量体由来の単位を有する重合体ブロック（ａ２）を有する［１］～［４］のいずれかに記載の共重合体（Ｐ）。
［６］前記ポリマー鎖（Ｂ）がさらに芳香族ビニル単量体由来の単位および／または不飽和カルボン酸エステル由来の単位を有し、
　前記ポリマー鎖（Ｂ）中、オキサゾリン基含有単量体由来の単位と、芳香族ビニル単量体由来の単位および／または不飽和カルボン酸エステル由来の単位との合計含有割合が８０質量％以上である［１］～［５］のいずれかに記載の共重合体（Ｐ）。
［７］［１］～［６］のいずれかに記載の共重合体（Ｐ）を含有することを特徴とする樹脂組成物（Ｑ）。
［８］［１］～［６］のいずれかに記載の共重合体（Ｐ）とオキサゾリン基含有重合体とを含有することを特徴とする樹脂組成物（Ｑ）。
［９］前記共重合体（Ｐ）と前記オキサゾリン基含有重合体と前記式（１）で表される単位を有する重合体の合計１００質量部に対して、前記ポリマー鎖（Ａ）の含有割合が５質量部以上８０質量部以下である［８］に記載の樹脂組成物（Ｑ）。
［１０］前記共重合体（Ｐ）と前記オキサゾリン基含有重合体と前記式（１）で表される単位を有する重合体の合計１００質量部に対して、前記式（１）で表される単位の含有割合が３質量部以上８０質量部以下である［８］または［９］に記載の樹脂組成物（Ｑ）。
［１１］前記共重合体（Ｐ）と前記オキサゾリン基含有重合体と前記式（１）で表される単位を有する重合体の合計１００質量部に対して、前記オキサゾリン基含有単量体由来の単位の含有割合が０．５質量部以上４９質量部以下である［８］～［１０］のいずれかに記載の樹脂組成物（Ｑ）。
［１２］［１］～［６］のいずれかに記載の共重合体（Ｐ）または［７］～［１１］のいずれかに記載の樹脂組成物（Ｑ）を含有することを特徴とするプライマー。
［１３］［１］～［６］のいずれかに記載の共重合体（Ｐ）または［７］～［１１］のいずれかに記載の樹脂組成物（Ｑ）を含有する層が樹脂基材の表面に形成されている樹脂成形体。
［１４］前記樹脂基材が、炭化水素系樹脂、あるいはヘテロ原子含有基またはヘテロ原子含有結合を有する樹脂である［１３］に記載の樹脂成形体。
［１５］［１］～［６］のいずれかに記載の共重合体（Ｐ）または［７］～［１１］のいずれかに記載の樹脂組成物（Ｑ）を含有することを特徴とする相溶化剤。
［１６］下記式（１）で表される単位を有する重合体の存在下、オキサゾリン基含有単量体を含む単量体成分を重合する工程を有することを特徴とする、下記式（１）で表される単位を有するポリマー鎖（Ａ）と、オキサゾリン基含有単量体由来の単位を有するポリマー鎖（Ｂ）とを有する共重合体（Ｐ）の製造方法。

［式（１）中、Ｒ¹～Ｒ⁴はそれぞれ独立して、水素原子または炭素数１～２０のアルキル基を表す。］ The present invention includes the following inventions.
[1] A copolymer having a polymer chain (A) having a unit represented by the following formula (1) and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer ( P).

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
[2] The copolymer (P) according to [1], wherein the polymer chain (B) is grafted to the polymer chain (A).
[3] The copolymer (P) according to [1] or [2], wherein the content ratio of the unit represented by the formula (1) in the polymer chain (A) is 50% by mass or more.
[4] The copolymer according to any one of [1] to [3], wherein the content of the units derived from the oxazoline group-containing monomer in the polymer chain (B) is 1% by mass or more and 50% by mass or less. (P).
[5] The polymer chain (A) has a polymer block (a1) having a unit represented by the formula (1) and a polymer block (a2) having a unit derived from an aromatic vinyl monomer [ The copolymer (P) according to any one of 1] to [4].
[6] The polymer chain (B) further has a unit derived from an aromatic vinyl monomer and/or a unit derived from an unsaturated carboxylic acid ester,
In the polymer chain (B), the total content of the units derived from the oxazoline group-containing monomer, the units derived from the aromatic vinyl monomer and/or the units derived from the unsaturated carboxylic acid ester is 80% by mass or more. The copolymer (P) according to any one of [1] to [5].
[7] A resin composition (Q) containing the copolymer (P) according to any one of [1] to [6].
[8] A resin composition (Q) containing the copolymer (P) according to any one of [1] to [6] and an oxazoline group-containing polymer.
[9] Content ratio of the polymer chain (A) with respect to 100 parts by mass in total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having a unit represented by the formula (1). Is 5 parts by mass or more and 80 parts by mass or less, and the resin composition (Q) according to [8].
[10] Represented by the formula (1) based on 100 parts by mass of the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1). The resin composition (Q) according to [8] or [9], wherein the content ratio of the unit is 3 parts by mass or more and 80 parts by mass or less.
[11] Based on 100 parts by mass of the total amount of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1), the oxazoline group-containing monomer-derived monomer is used. The resin composition (Q) according to any one of [8] to [10], wherein the content ratio of the unit is 0.5 parts by mass or more and 49 parts by mass or less.
[12] The resin composition (Q) according to any one of [1] to [6] or the resin composition (Q) according to any of [7] to [11]. Primer.
[13] A layer containing the copolymer (P) according to any one of [1] to [6] or the resin composition (Q) according to any of [7] to [11] is a resin substrate. The resin molding formed on the surface of the.
[14] The resin molded product according to [13], wherein the resin base material is a hydrocarbon-based resin or a resin having a heteroatom-containing group or a heteroatom-containing bond.
[15] A resin composition (Q) according to any one of [1] to [6] or the resin composition (Q) according to any of [7] to [11]. Compatibilizer.
[16] The following formula (1), which comprises a step of polymerizing a monomer component containing an oxazoline group-containing monomer in the presence of a polymer having a unit represented by the following formula (1). A method for producing a copolymer (P) having a polymer chain (A) having a unit represented by and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer.

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]

The copolymer (P) and the resin composition (Q) of the present invention include a polymer chain (A) having a unit represented by the formula (1) and a polymer chain (A) having a unit derived from an oxazoline group-containing monomer ( Since it has B), it has excellent adhesion to various base materials including polyolefin.

The copolymer (P) of the present invention has a polymer chain (A) having a unit represented by the following formula (1) and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer. Is. In the following formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Since the copolymer (P) of the present invention has the polymer chain (A) and the polymer chain (B), it has excellent adhesiveness to various base materials and affinity with various resins.

The unit represented by the above formula (1) contained in the polymer chain (A) (hereinafter, referred to as “unit of the formula (1)”) is a resin having low adhesion to a substrate having low polarity and resin having low polarity. Acts to increase affinity. Since the unit of the formula (1) is the same as or similar to the polymer constitutional unit of the low-polarity base material or the low-polarity resin, the intermolecular force is exerted between the low-polarity base material and the low-polarity resin. It is considered that the adhesion and the affinity are enhanced by the interaction such as.

Examples of the alkyl group represented by R ¹ to R ^{4 in} the above formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group. Group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, 2-ethylhexyl group and other linear or branched alkyl groups, cyclopropyl group, cyclobutyl group, Examples thereof include cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cyclononyl group, cyclodecyl group, dicyclopentanyl group and adamantyl group. Among these, a linear or branched alkyl group is preferable as the alkyl group represented by R ¹ to R ⁴ . The alkyl group of R ¹ to R ⁴ preferably has 1 to 12 carbon atoms, more preferably has 1 to 8 carbon atoms, and further preferably has 1 to 6 carbon atoms.

The unit of formula (1) can be formed by (co)polymerizing an olefin or a conjugated diene. In view of easy formation of such a (co)polymer, R ¹ and R ^{2 in} the formula (1) are each independently a hydrogen atom or a linear or branched chain having 1 to 6 carbon atoms. It is preferably an alkyl group, and R ³ and R ⁴ are preferably hydrogen atoms. In addition, when the group having a double bond remains in the main chain or the side chain when the conjugated diene is (co)polymerized, the double bond may be hydrogenated to form the unit of the formula (1). preferable. Alternatively, the unit of formula (1) may be formed by (co)polymerizing a diene compound other than the conjugated diene and hydrogenating the double bond contained in the obtained (co)polymer.

Examples of the olefin forming the unit of the formula (1) include ethylene, propylene, 1-butene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 1-tetradecene and 1-octadecene. Can be mentioned. The carbon number of the olefin is preferably 2 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, and further preferably 6 or less. Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene and 1,3-pentadiene. The carbon number of the conjugated diene is preferably 4 or more, more preferably 5 or more, preferably 20 or less, more preferably 10 or less, and further preferably 8 or less.

The polymer chain (A) is an olefin (co)polymer chain such as polyethylene, polypropylene, polybutylene, polyisobutylene, ethylene-propylene copolymer, ethylene-1-butene copolymer partially or in the main chain structure. It is preferable to include it as a whole. As the olefin (co)polymer, polyethylene, polypropylene, polybutylene and ethylene-1-butene copolymer are more preferable.

The polymer chain (A) may further have a unit represented by the following formula (2-1) and/or a unit represented by the following formula (2-2). Hereinafter, the unit represented by the following formula (2-1) and the unit represented by the following formula (2-2) may be collectively referred to as a “unit of the formula (2)”.

In the following formula (2-1), R ⁵ represents an alkenyl group having 2 to 20 carbon atoms, and R ⁶ to R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. It represents 2 to 20 alkenyl groups. In the following formula (2-2), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and even if R ⁹ and R ¹⁰ are in the cis position with each other. It may well be in the trans position. Since the unit represented by the following formula (2-1) and the unit represented by the following formula (2-2) are similar to the polymer constitutional unit of the base material having low polarity or the resin having low polarity, It is considered that an interaction occurs between the material and the resin, and the adhesion and affinity are enhanced. Therefore, the copolymer (P) having the polymer chain (A) containing the unit of the formula (1) and the unit of the formula (2) is also excellent in adhesion to various base materials and affinity with various resins. Become.

For the alkyl groups having 1 to 20 carbon atoms represented by R ⁶ to R ^{10 in} the formulas (2-1) and (2-2), the above description of the alkyl group represented by R ¹ to R ⁴ can be referred to. The alkenyl group of R ⁵ to R ⁸ having 2 to 20 carbon atoms in the formula (2-1) is a group in which one of the C—C bonds contained in the alkyl group of R ¹ to R ⁴ is replaced with a C═C bond. And a linear or branched alkenyl group is preferable. The alkenyl group represented by R ⁵ to R ⁸ preferably has 2 to 12 carbon atoms, more preferably has 2 to 8 carbon atoms, and further preferably has 2 to 6 carbon atoms. A vinyl group is particularly preferable as the alkenyl group for R ⁵ to R ⁸ .

From the viewpoint of easy formation of the unit represented by the formula (2-1), R ^{5 in} the formula (2-1) is preferably a linear or branched alkenyl group having 2 to 6 carbon atoms. R ⁶ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ⁷ and R ⁸ are preferably hydrogen atoms. Further, R ⁹ and R ¹⁰ in the formula (2-2) are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group, and a hydrogen atom. Is more preferable. Such a unit of the formula (2) can be introduced into the polymer chain (A) by copolymerizing a diene with an olefin, or homopolymerizing or copolymerizing a conjugated diene. Examples of the diene forming the unit of the formula (2) include 1,3-butadiene (alias: butadiene), 2-methyl-1,3-butadiene (alias: isoprene), 1,3-pentadiene, 1,4-pentadiene. Alkadienes such as 1,5-hexadiene and 2,5-dimethyl-1,5-hexadiene (also known as diisobutene) are preferable, and among them, 1,3-butadiene, 2-methyl-1,3-butadiene and 1,3- More preferred are conjugated dienes such as pentadiene. The carbon number of the diene is preferably 4 or more, more preferably 5 or more, preferably 20 or less, more preferably 10 or less, and further preferably 8 or less.

The polymer chain (A) having the unit of the formula (1) and the unit of the formula (2) is formed of, for example, an olefin and a diene such as an ethylene-isoprene copolymer, a butene-butadiene copolymer and an isobutene-isoprene copolymer. It is preferable to include the copolymer chain partially or entirely in the structure of the main chain. The copolymer of olefin and diene is preferably a random copolymer.

The polymer chain (A) may further have units derived from other unsaturated monomers. The other unsaturated monomer is not particularly limited as long as it is a compound having a polymerizable double bond, and examples thereof include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, (meth ) Unsaturated carboxylic acids such as methyl acrylate and ethyl (meth)acrylate and their esters; aromatic vinyl compounds such as styrene, vinyltoluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine; vinyltrimethoxysilane, Examples thereof include vinylsilanes such as γ-(meth)acryloyloxypropylmethoxysilane. The polymer chain (A) may be a copolymer of these other unsaturated monomers and olefins, or a copolymer of these other unsaturated monomers, olefins and dienes.

The polymer chain (A) preferably contains the unit of the above formula (1) as a main component, and the content ratio of the unit of the formula (1) in the polymer chain (A) is preferably 50% by mass or more, 55 Mass% or more is more preferable, and 60 mass% or more is further preferable. As a result, the adhesion of the copolymer (P) to various substrates can be easily increased, and the affinity with various resins can be easily increased. The upper limit of the content ratio of the unit of the formula (1) in the polymer chain (A) is not particularly limited, and the polymer chain (A) may be composed of only the unit of the formula (1). The content of the unit of the formula (1) may be 98% by mass or less, 95% by mass or less, or 90% by mass or less.

The polymer chain (A) may have a total content of units of formula (1) and units of formula (2) of 50% by mass or more, 55% by mass or more, or 60% by mass or more. Further, the polymer chain (A) may be composed of only the unit of the formula (1) and the unit of the formula (2), and the unit of the formula (1) and the unit of the formula (2) in the polymer chain (A). May be 98 mass% or less, 95 mass% or less, or 90 mass% or less.

When the polymer chain (A) has a unit derived from another unsaturated monomer, the polymer chain (A) includes a unit of the formula (1) (or a unit of the formula (2)) and another unsaturated monomer. It may be a random copolymer containing a body-derived unit or a block copolymer. When the polymer chain (A) is a block copolymer, the polymer chain (A) is a polymer block (a1) having a unit of the formula (1) and a heavy chain having a unit derived from another unsaturated monomer. It is preferable to have a united block (a2).

When the polymer chain (A) has a polymer block (a1) and a polymer block (a2), the polymer block (a1) includes the unit of the formula (1), the unit of the formula (2) and other units. It may have a unit derived from the unsaturated monomer. Examples of the other unsaturated monomer in this case include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, etc. Unsaturated carboxylic acids and their esters; aromatic vinyl compounds such as styrene, vinyltoluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine; vinyltrimethoxysilane, γ-(meth)acryloyloxypropylmethoxysilane, etc. Vinyl silane etc. are mentioned. The polymer block (a1) preferably contains more units of the formula (1), and the content ratio of the unit of the formula (1) in the polymer block (a1) is preferably 70% by mass or more. , 80% by mass or more is more preferable, and 90% by mass or more is still more preferable. The polymer block (a1) may be substantially composed of only the unit of the formula (1), and for example, the unit of the formula (1) may be 99% by mass or more. Alternatively, the total content of the units of the formula (1) and the unit of the formula (2) in the polymer block (a1) is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. Is more preferable. The polymer block (a1) may be substantially composed only of the unit of the formula (1) and the unit of the formula (2). For example, the unit of the formula (1) and the unit of the formula (2) are 99 mass. % Or more.

When the polymer chain (A) has a polymer block (a2) having a unit derived from another unsaturated monomer, the polymer block (a2) is composed of a unit derived from an aromatic vinyl monomer. Preferably. In this case, the polymer block (a1) can function as a soft component and the polymer block (a2) can function as a hard component, and a copolymer (P) and a resin composition containing the copolymer (P) can be used. Elasticity can be imparted to (Q). The aromatic vinyl monomer is not particularly limited as long as it is a compound having a vinyl group bonded to an aromatic ring, and examples thereof include styrene, vinyltoluene, methoxystyrene, α-methylstyrene, α-hydroxymethylstyrene, α-hydroxyethyl. Styrene type monomers such as styrene; polycyclic aromatic hydrocarbon ring vinyl monomers such as 2-vinylnaphthalene; aromatic heterocyclic vinyl units such as N-vinylcarbazole, 2-vinylpyridine, vinylimidazole, vinylthiophene, etc. Examples thereof include a polymer. Of these, styrene-based monomers are preferable. The styrene-based monomer includes not only styrene but also a styrene vinyl group or a styrene derivative in which an arbitrary substituent is bonded to a benzene ring, and the substituent includes an alkyl group, an alkoxy group, a hydroxyl group, a halogen group. Group, amino group, nitro group, sulfo group and the like. The alkyl group and alkoxy group bonded to styrene preferably have 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. In the alkyl group and alkoxy group bonded to styrene, at least a part of hydrogen atoms is a hydroxyl group or a halogen atom. It may be substituted with a group. The styrene-based monomer is preferably unsubstituted styrene having no substituent bonded to the vinyl group of styrene and the benzene ring.

The polymer block (a2) may have units derived from other unsaturated monomers in addition to the units derived from the aromatic vinyl monomer. Examples of the other unsaturated monomer in this case include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, etc. And unsaturated carboxylic acids and esters thereof; vinyl silanes such as vinyltrimethoxysilane and γ-(meth)acryloyloxypropylmethoxysilane. The polymer block (a2) preferably contains more units derived from the aromatic vinyl monomer, and the content of the units derived from the aromatic vinyl monomer in the polymer block (a2) is 70% by mass. It is preferably at least 80% by mass, more preferably at least 80% by mass, still more preferably at least 90% by mass. The polymer block (a2) may be substantially composed only of units derived from an aromatic vinyl monomer, and for example, the units derived from an aromatic vinyl monomer may be 99% by mass or more.

A polymer chain (A) having a polymer block (a1) having a unit of the formula (1) and a polymer block (a2) having a unit derived from an aromatic vinyl monomer, or a unit of the formula (1) Examples of the polymer chain (A) having a polymer block (a1) having a unit of the formula (2) and a polymer block (a2) having a unit derived from an aromatic vinyl monomer include, for example, styrene-butadiene- Hydrogenated products of styrene block copolymers (eg styrene-ethylene/butylene-styrene block copolymers), hydrogenated products of styrene-isoprene-styrene block copolymers (eg styrene-ethylene/propylene-styrene block copolymers) Polymers), hydrogenated products of styrene-isoprene block copolymers, and the like. In these hydrogenated products, some or all of the units derived from diene such as butadiene and isoprene are hydrogenated, and the hydrogenated products are those in which the polymer block (a1) has a unit of the formula (1). Thus, when partially hydrogenated, the polymer block (a1) has a unit of the formula (1) and a unit of the formula (2). In the above notation, each block is divided by "-", and the notation "/" in each block represents the monomer unit constituting the block.

The polymer chain (A) made of a block copolymer is preferably a polymer block (a1) having polymer blocks (a2) bonded to both sides thereof, and more preferably a triblock copolymer. .. Examples of such triblock copolymers include hydrogenated products of styrene-butadiene-styrene block copolymers and hydrogenated products of styrene-isoprene-styrene block copolymers. When the copolymer (P) has such a polymer chain (A), for example, when a resin coating film containing the copolymer (P) is formed, the flexibility of the coating film is increased and the coating film is The hardness and brittleness of can be reduced.

When the polymer chain (A) has a polymer block (a1) and a polymer block (a2), the content ratio of the polymer block (a1) in the polymer chain (A) is preferably 50% by mass or more, 55 mass% or more is more preferable, 60 mass% or more is still more preferable, 95 mass% or less is preferable, 93 mass% or less is more preferable, and 91 mass% or less is further preferable.

The polymer chain (A) preferably has the polymer block (a1) and does not have the polymer block (a2). The polymer chain (A) is preferably composed of the unit of the formula (1) or the unit of the formula (1) and the unit of the formula (2), and is composed of only the unit of the formula (1). More preferably.

The weight average molecular weight of the polymer chain (A) is preferably 50,000 or more, more preferably 10,000 or more, even more preferably 20,000 or more, even more preferably 30,000 or more, and preferably 300,000 or less, 250,000. The following is more preferable, 200,000 or less is still more preferable, and 150,000 or less is even more preferable. By setting the weight average molecular weight of the polymer chain (A) within such a range, it becomes easy to improve the handleability of the copolymer (P).

Explain the polymer chain (B) contained in the copolymer (P). The polymer chain (B) has a unit derived from an oxazoline group-containing monomer. The unit derived from the oxazoline group-containing monomer acts to enhance the adhesiveness and affinity between the copolymer (P) and the highly polar base material or the highly polar resin. The oxazoline group-containing monomer is not particularly limited as long as it is a compound having an oxazoline group and a polymerizable double bond, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4, Preferred are vinyl oxazolines such as 4-dimethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline and 4,4-dimethyl-2-isopropenyl-2-oxazoline. Among these, 2-isopropenyl-2-oxazoline is preferably used from the viewpoint of easy availability and reactivity.

The polymer chain (B) may further have units derived from other unsaturated monomers. The other unsaturated monomer is not particularly limited as long as it is a compound having a polymerizable double bond, and examples thereof include vinyl esters such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile; and (meth)acryl. Unsaturated carboxylic acids such as acids, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate and their esters; aromatics such as styrene, vinyltoluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine Vinyl compounds; vinyl silanes such as vinyltrimethoxysilane and γ-(meth)acryloyloxypropylmethoxysilane. Among these, the polymer chain (B) preferably has a unit derived from a vinyl cyanide monomer, a unit derived from an aromatic vinyl monomer and/or a unit derived from an unsaturated carboxylic acid ester. It is more preferable to have a unit derived from a monomer and/or a unit derived from an unsaturated carboxylic acid ester, and it is more preferable to have a unit derived from an aromatic vinyl monomer. The unit derived from the aromatic vinyl monomer is preferably a unit derived from a styrene monomer, and the unit derived from the unsaturated carboxylic acid ester is preferably a unit derived from a (meth)acrylic acid ester. For the description of the aromatic vinyl monomer and the styrene-based monomer, the description regarding the aromatic vinyl monomer and the styrene-based monomer of the polymer block (a2) is referred to. When the polymer chain (B) has a unit derived from an aromatic vinyl monomer, the heat resistance of the copolymer (P) can be improved, and when the polymer chain (B) is polymerized and formed. The reaction of the oxazoline group-containing monomer can be promoted. It is also advantageous in terms of manufacturing cost.

Specific examples of the unsaturated carboxylic acid ester (preferably (meth)acrylic acid ester) include linear, branched, or cyclic aliphatic groups at the oxygen atom of the ester bond of (meth)acrylic acid. Examples thereof include (meth)acrylic acid ester having a hydrocarbon group or an aromatic hydrocarbon group bonded thereto.

Examples of the (meth)acrylic acid ester having a linear or branched aliphatic hydrocarbon group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth). Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylic acid Examples thereof include alkyl (meth)acrylates such as n-hexyl and 2-ethylhexyl (meth)acrylate. The alkyl group of the alkyl (meth)acrylate preferably has 1 or more carbon atoms, preferably 18 or less, more preferably 12 or less, and further preferably 6 or less.

Examples of the (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group include (meth)acrylic acid cyclopropyl, (meth)acrylic acid cyclobutyl, (meth)acrylic acid cyclopentyl, (meth)acrylic acid cyclohexyl, and the like (meth ) Cycloalkyl acrylate; and crosslinked cyclic (meth)acrylates such as isobornyl (meth)acrylate. 3 or more are preferable, as for carbon number of the cycloalkyl group of cycloalkyl (meth)acrylate, 4 or more are more preferable, 5 or more are more preferable, 20 or less are more preferable, 12 or less are more preferable, 10 or less are more preferable. ..

Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include phenyl (meth)acrylate, tolyl (meth)acrylate, xylyl (meth)acrylate, naphthyl (meth)acrylate, and binaphthyl (meth)acrylate. Aryl (meth)acrylates such as anthryl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; aryloxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; Can be mentioned. The aryl group of the aryl (meth)acrylate preferably has 6 or more carbon atoms, preferably 20 or less, and more preferably 14 or less. The aralkyl group of the aralkyl (meth)acrylate preferably has 7 or more carbon atoms, preferably 14 or less carbon atoms, and more preferably 12 or less carbon atoms. The aryloxyalkyl group of the aryloxyalkyl (meth)acrylate preferably has 7 or more carbon atoms, preferably 14 or less carbon atoms, and more preferably 12 or less carbon atoms.

If the polymer chain (B) has a unit derived from an unsaturated carboxylic acid ester, the affinity of the copolymer (P) with various resins (particularly resins with high polarity) can be further improved.

When the polymer chain (B) has a unit derived from another unsaturated monomer, the polymer chain (B) is a random copolymer of an oxazoline group-containing monomer and another unsaturated monomer, Although it may be a block copolymer, it is preferably a random copolymer from the viewpoint of easy production of the polymer chain (B).

The content of the unit derived from the oxazoline group-containing monomer in the polymer chain (B) is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 50% by mass or less, 40% by mass or less. Is more preferable. This facilitates enhancing the adhesiveness improving effect and the affinity improving effect of the copolymer (P) and facilitates the formation of the polymer chain (B).

When the polymer chain (B) has a unit derived from an aromatic vinyl monomer as a unit derived from another unsaturated monomer, a unit derived from an oxazoline group-containing monomer and a unit derived from an aromatic vinyl monomer are used. The total content of the units is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, even more preferably 95% by mass or more, and 98% by mass or more. Particularly preferred.

The polymer chain (B) is preferably grafted to the polymer chain (A). Therefore, the copolymer (P) is preferably a graft copolymer having the polymer chain (B) as a graft chain. According to the glossary of the basic terms of polymer science by the International Union of Pure and Applied Chemistry (IUPAC) Nomenclature for Polymers, a grafted polymer is a "bonded to a main chain as a side chain in a polymer. When there are one or several types of blocks, and these side chains have different structural (chemical structure) or arrangement characteristics from the main chain, this polymer is referred to as a graft polymer." There is. The graft copolymer can be obtained by a known production method such as a chain transfer reaction method, a polymer initiator method, a coupling method, a macromonomer method or a surface graft method, and only one of these methods is adopted. Alternatively, a plurality of them may be used in combination. The details of these methods can be referred to the 6th edition of the Chemical Handbook (Applied Chemistry), edited by The Chemical Society of Japan.

The copolymer (P) can be easily produced by addition-polymerizing the monomer component forming the polymer chain (B) to the polymer chain (A). Therefore, the copolymer (P) is a monomer containing an oxazoline group-containing monomer in the presence of a polymer having a unit of the formula (1) (hereinafter referred to as “raw material polymer (P1)”). Those obtained by polymerizing the components are preferred. For details of the raw material polymer (P1), refer to the above description of the polymer chain (A). The raw material polymer (P1) further has a unit of the formula (2) or a unit of the formula (1). It may have the polymer block (a1) having and the polymer block (a2) having a unit derived from another unsaturated monomer.

The polymer chain (B) is preferably grafted, for example, to the unit of the formula (1) of the polymer chain (A). When the polymer chain (A) has the unit of formula (2), the polymer chain (B) may be grafted to the unit of formula (2). The polymer chain (B) may be bonded to a carbon atom of the main chain of the unit of the formula (1) or the unit of the formula (2), and is a hydrocarbon group bonded to the main chain as a substituent (side chain). It may be bonded to a carbon atom. Further, the polymer chain (B) may be bonded to the polymer chain (A) via an arbitrary linking group (eg, ester bond, amide bond, urethane bond, etc.).

The weight average molecular weight of the copolymer (P) is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, even more preferably 50,000 or more, particularly preferably 70,000 or more, and 700,000. The following is preferable, 500,000 or less is more preferable, 300,000 or less is further preferable, 200,000 or less is even more preferable. By setting the weight average molecular weight of the copolymer (P) in such a range, it becomes easy to improve the handleability of the copolymer (P).

The weight average molecular weight of the copolymer (P) is preferably 1.1 times or more, more preferably 1.2 times or more, still more preferably 1.3 times or more the weight average molecular weight of the polymer chain (A), and 20 It is preferably not more than 10 times, more preferably not more than 12 times, even more preferably not more than 10 times, even more preferably not more than 7 times, particularly preferably not more than 5 times. This makes it easy to increase the adhesiveness and affinity of the copolymer (P).

The copolymer (P) can be obtained by a production method including a step (polymerization step) of polymerizing a monomer component containing an oxazoline group-containing monomer in the presence of the raw material polymer (P1). A polymer chain (B) is formed by polymerizing a monomer component containing an oxazoline group-containing monomer in the polymerization step, and the raw material polymer (P1) gives a polymer chain (A), whereby a polymer chain ( A copolymer (P) in which B) is bonded to the polymer chain (A) is obtained.

In the polymerization step, the polymer chain (B) is bonded to the unit of the formula (1) of the starting polymer (P1) (the unit of the formula (1) or the unit of the formula (2) when the unit of the formula (2) is also present). From the viewpoint of doing so, it is preferable that hydrogen is abstracted from the hydrocarbon group of the unit in the polymerization step. As a result, a radical is generated at the location, and the monomer component forming the polymer chain (B) can be addition-polymerized.

In the polymerization step, the raw material polymer (P1) may be used alone or in combination of two or more. In the latter case, it becomes easy to adjust the weight average molecular weight and the physical properties of the copolymer (P).

As the monomer component used for forming the polymer chain (B), other unsaturated monomer can be used in addition to the oxazoline group-containing monomer. As the other unsaturated monomer, it is preferable to use vinyl cyanide monomer, aromatic vinyl monomer and/or unsaturated carboxylic acid ester. For details of these monomer components, the description of the oxazoline group-containing monomer forming the polymer chain (B) and the other unsaturated monomer forming the polymer chain (B) is referred to.

The polymerization of the monomer component can be carried out by using a known polymerization method such as a bulk polymerization method, a solution polymerization method, an emulsion polymerization method or a suspension polymerization method, but it is preferable to use the solution polymerization method. As the polymerization method, for example, either a batch polymerization method or a continuous polymerization method can be used.

The amount of the raw material polymer (P1) used during the polymerization is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the raw material polymer (P1) and the monomer components. The amount is preferably 15 parts by mass or more, more preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less. The amount of the monomer component used is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 40 parts by mass or more with respect to 100 parts by mass of the total amount of the raw material polymer (P1) and the monomer component. The amount is preferably 50 parts by mass or more, more preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and further preferably 85 parts by mass or less.

The solvent used during the polymerization can be appropriately selected according to the composition of the monomer component, and an organic solvent used in a usual radical polymerization reaction can be used. Specifically, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane and cyclohexane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran, dioxane, ethylene glycol dimethyl ether , Ethers such as diethylene glycol dimethyl ether and anisole; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methanol, ethanol, isopropanol, Examples thereof include alcohols such as n-butanol; nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile; chloroform; dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

The polymerization reaction of the raw material polymer (P1) and the monomer component is preferably carried out in the presence of a polymerization initiator. Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, dimethyl-2,2′-azobis(2-methylproton Azo compounds such as pionate) and 4,4′-azobis(4-cyanopentanoic acid); persulfates such as potassium persulfate; cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, Lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-amylperoxyoctoate, t-amylperoxyisononanoate, t-amylper Organic peroxides such as oxyisopropyl carbonate and t-amyl peroxy 2-ethylhexyl carbonate can be used. These may be used alone or in combination of two or more. Among these, it is preferable to use an organic peroxide having a strong hydrogen abstraction force, and it is particularly preferable to use a peroxycarbonate-based peroxide. The amount of the polymerization initiator used is preferably, for example, 0.05 to 3 parts by mass with respect to 100 parts by mass of the monomer component.

The total concentration of the raw material polymer (P1) and the monomer component in the reaction solution is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and preferably 80% by mass or less. , 70% by mass or less is more preferable. It is also possible to appropriately add the raw material polymer (P1), the monomer component, the polymerization catalyst, the solvent and the like during the polymerization reaction.

The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas or under an air stream. The reaction temperature is preferably 50°C to 200°C. The reaction time may be appropriately adjusted while observing the degree of progress of the copolymerization reaction, and for example, 1 hour to 20 hours is preferable.

During polymerization, the monomer components may be charged all at once or added in portions. In addition, it is preferable to charge the monomer components all at once because it is easy to graft polymerize the oxazoline group-containing monomer to the polymer chain (A) to form the polymer chain (B).

The present invention also provides a resin composition (Q) containing the copolymer (P) having the polymer chain (A) and the polymer chain (B) described above. The resin composition (Q) of the present invention has excellent adhesion to various base materials and excellent affinity with various resins.

The resin composition (Q) may contain the copolymer (P) as a resin component, or may contain another polymer as a resin component. When the resin composition (Q) contains another polymer, the other polymer is preferably an oxazoline group-containing polymer and/or a polymer having a unit of the formula (1), more preferably an oxazoline group-containing polymer. It is preferably used, and the homogeneity of the resin composition (Q) is enhanced by containing these other polymers.

The oxazoline group-containing polymer contained as another polymer in the resin composition (Q) may be any polymer having a unit derived from the oxazoline group-containing monomer described in the polymer chain (B), and the polymer described above. It may have units derived from other unsaturated monomers described in the chain (B). From the viewpoint of enhancing the compatibility with the copolymer (P), the oxazoline group-containing polymer more preferably has the same monomer-derived unit as the monomer-derived unit of the polymer chain (B).

The polymer having the unit of the formula (1) contained in the resin composition (Q) as another polymer may be any polymer having the unit of the formula (1) described in the polymer chain (A). It may have a polymer having the unit of the formula (2) described in the polymer chain (A) or a unit derived from another unsaturated monomer. The polymer having the unit of the formula (1) has the same monomer-derived unit as the monomer-derived unit of the polymer chain (A) from the viewpoint of enhancing the compatibility with the copolymer (P). Is more preferable.

The resin composition (Q) contains a copolymer (P), an oxazoline group-containing polymer, and a polymer having a unit of the formula (1) in a total amount of 100 parts by mass. The amount is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, still more preferably 15 parts by mass or more. The upper limit of the content ratio of the copolymer (P) in the resin composition (Q) is not particularly limited, and the resin composition (Q) may be composed only of the copolymer (P). The content ratio of the copolymer (P) may be 90 parts by mass or less based on 100 parts by mass of the total amount of the (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). It may be less than or equal to 70 parts by mass, or less than or equal to 60 parts by mass.

The resin composition (Q) has a content ratio of the polymer chain (A) of 5 with respect to 100 parts by mass in total of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). It is preferably at least 8 parts by mass, more preferably at least 8 parts by mass, further preferably at least 12 parts by mass, preferably at most 80 parts by mass, more preferably at most 70 parts by mass, further preferably at most 60 parts by mass, 50 Even more preferably, it is at most parts by mass. This makes it easier to increase the adhesion of the resin composition (Q) to various base materials. The content ratio of the polymer chain (A) in the resin composition (Q) is determined by the polymer chain (A) contained in the copolymer (P) and the polymer chain contained in the polymer having the unit of the formula (1). It means the total content of (A).

In the resin composition (Q), the content ratio of the unit of the formula (1) is 100 parts by mass of the total amount of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). It is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, Even more preferably 50 parts by mass or less. This makes it easier to increase the adhesion of the resin composition (Q) to various base materials. Alternatively, the resin composition (Q) contains the unit of the formula (1) and the formula (1) based on 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). The total content of the units (2) may be 3 parts by mass or more, 5 parts by mass or more, or 10 parts by mass or more, and 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass. It may be equal to or less than a part. In addition, the content ratio of the unit of the formula (1) in the resin composition (Q) is included in the polymer having the unit of the formula (1) and the unit of the formula (1) contained in the copolymer (P). It means the total content of the units of the formula (1), and the content of the units of the formula (2) in the resin composition (Q) is the same as that of the units of the formula (2) contained in the copolymer (P). It means the total content of the units of the formula (2) contained in the polymer having the units of the formula (1). Further, the content ratio of the unit of the formula (2) means the total content ratio of the unit represented by the formula (2-1) and the unit represented by the formula (2-2).

The resin composition (Q) contains 100 units by weight of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1), and the oxazoline group-containing monomer-derived unit The content ratio is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, further preferably 1.5 parts by mass or more, and preferably 49 parts by mass or less, more preferably 40 parts by mass or less. , 30 parts by mass or less is more preferable. This makes it easier to increase the adhesion of the resin composition (Q) to various base materials. The content ratio of the unit derived from the oxazoline group-containing monomer in the resin composition (Q) is included in the unit derived from the oxazoline group-containing monomer and the oxazoline group-containing polymer contained in the copolymer (P). Means the total content of units derived from the oxazoline group-containing monomer.

The resin composition (Q) contains the unit of the formula (1) and the oxazoline group based on 100 parts by mass of the total amount of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). The total content of the monomer-derived units is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more. This makes it easier to increase the adhesion of the resin composition (Q) to various base materials. The upper limit of the content ratio of the unit of the formula (1) and the unit derived from the oxazoline group-containing monomer in the resin composition (Q) is not particularly limited, and the resin composition (Q) is substantially the same as that of the formula (1). Units and units derived from the oxazoline group-containing monomer may be included, and the total amount of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1) is 100 parts by mass. The total content of the units of the formula (1) and the units derived from the oxazoline group-containing monomer is 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less. May be. Alternatively, the resin composition (Q) contains the unit of the formula (1) and the formula (1) based on 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). The total content of the units of (2) and the units derived from the oxazoline group-containing monomer may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, or 22 parts by mass or more. Further, it may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less.

In the resin composition (Q), the content ratio of the unit of the formula (1) is 100 parts by mass of the total amount of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). It is particularly preferable that the content is 10 parts by mass or more, and the total content ratio of the unit of the formula (1) and the unit derived from the oxazoline group-containing monomer is 20 parts by mass or more. Alternatively, the resin composition (Q) contains the unit of the formula (1) and the formula (1) based on 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). The total content of the units of (2) is 10 parts by mass or more, and the total content of the units of the formula (1), the formula (2), and the units derived from the oxazoline group-containing monomer is 20 parts by mass or more. Is particularly preferable.

In the resin composition (Q), the content ratio of the unit of the formula (1) is 10 parts by mass or more based on 100 parts by mass of the unit of the formula (1) and the unit derived from the oxazoline group-containing monomer. Is more preferable, 20 parts by mass or more is more preferable, 30 parts by mass or more is further preferable, 98 parts by mass or less is preferable, 95 parts by mass or less is more preferable, and 93 parts by mass or less is further preferable. This makes it easier to increase the adhesion of the resin composition (Q) to various base materials. Alternatively, the resin composition (Q) has a unit of the formula (1), a unit of the formula (2), and a unit of the unit derived from the oxazoline group-containing monomer, based on 100 units by mass of the unit of the formula (1). The total content of the units of (2) may be 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, and 98 parts by mass or less, 95 parts by mass or less, or 93 parts by mass or less, Good.

The content ratio of the unit of the formula (1), the content ratio of the unit of the formula (2) and the content ratio of the unit derived from the oxazoline group-containing monomer in the resin composition (Q) are the same as those of the copolymer (P) and the oxazoline. From the amount of each monomer used for polymerizing the group-containing polymer and the monomer residual ratio (the ratio of the monomer remaining without reaction to the obtained reaction liquid) , Can be determined by calculating the amount of each unit incorporated in the copolymer (P) or the oxazoline group-containing polymer. As described below, when the resin composition (Q) is obtained by polymerizing a monomer component containing an oxazoline group-containing monomer in the presence of the raw material polymer (P1), the raw material polymer (P1) is used. In consideration of the amount of the unit of the formula (1) and the unit of the formula (2) included, the content ratio of the unit of the formula (1) or the content ratio of the unit of the formula (2) in the resin composition (Q), The content ratio of the units derived from the oxazoline group-containing monomer is calculated. At this time, all the raw material polymer (P1) reacts with the monomer component, and the residual rate is considered to be 0%. In calculating the content ratio, only the residual rate of the raw material polymer (P1) is regarded as 0%, and the raw material polymer (P1) may be contained in the resin composition (Q).

The total content of the copolymer (P) and the oxazoline group-containing polymer in 100 parts by mass of the solid content of the resin composition (Q) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and 80 parts by mass. The above is more preferable, and 90 parts by mass or more is even more preferable. The upper limit of the content ratio of the copolymer (P) and the oxazoline group-containing polymer in the resin composition (Q) is not particularly limited, and the resin composition (Q) substantially includes the copolymer (P) and the oxazoline group. It may be composed of only the contained polymer. For example, the total content of the copolymer (P) and the oxazoline group-containing polymer is 99 parts by mass or more in 100 parts by mass of the solid content of the resin composition (Q). May be. When the resin composition (Q) contains a solvent, the solid content of the resin composition (Q) means the amount of the resin composition (Q) excluding the solvent.

The resin composition (Q) may contain a polymer other than the oxazoline group-containing polymer and the polymer having the unit of the formula (1). Examples of such a polymer include vinyl chloride and chlorine. Halogen-containing polymers such as vinyl chloride resin; acrylic polymers such as polymethylmethacrylate; polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, etc. Styrene-based polymers; polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetals; polycarbonates; polyphenylene oxides; polyphenylene sulfides; polyether ether ketones; polysulfone; polyethers. Examples include rubber polymers such as ABS resin and ASA resin mixed with sulfone; polyoxypentylene; polyamideimide; polybutadiene rubber and (meth)acrylic rubber.

The resin composition (Q) may contain a solvent. As the solvent, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane and cyclohexane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Ethers such as diethylene glycol dimethyl ether and anisole; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; methanol, ethanol, isopropanol, n -Alcohols such as butanol; nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile; chloroform; dimethyl sulfoxide and the like. These solvents may contain only 1 type and may contain 2 or more types.

The resin composition (Q) may contain various additives. Examples of the additive include antioxidants such as hindered phenol-based, phosphorus-based, and sulfur-based; stabilizers such as light resistance stabilizers, weather resistance stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; ultraviolet rays. Absorbents; near infrared absorbers; flame retardants such as tris(dibromopropyl)phosphate, triallyl phosphate, antimony oxide; antistatic agents containing anionic, cationic, and nonionic surfactants; inorganic pigments, organic pigments, Colorants such as dyes; organic fillers and inorganic fillers; resin modifiers; organic fillers and inorganic fillers; The content ratio of each additive in the resin composition (Q) is preferably in the range of 0 to 5 parts by mass, more preferably 0 to 2 parts by mass in 100 parts by mass of the solid content of the resin composition (Q). ..

The weight average molecular weight of the resin composition (Q) is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, even more preferably 50,000 or more, particularly preferably 70,000 or more, and 700,000. The following is preferable, 500,000 or less is more preferable, 300,000 or less is further preferable, 200,000 or less is even more preferable. The weight average molecular weight of the resin composition (Q) means a value in terms of polystyrene measured by gel permeation chromatography of the resin composition (Q), and the resin composition (Q) is a copolymer (P) and oxazoline. When the group-containing polymer and the polymer having the unit of the formula (1) are contained, the weight average molecular weight of the resin composition (Q) is the total weight average molecular weight of these plural kinds of polymers.

The weight average molecular weight of the resin composition (Q) is preferably 1.1 times or more, more preferably 1.2 times or more, and 1.3 times the weight average molecular weight of the polymer chain (A) of the copolymer (P). The above is more preferable, 20 times or less is preferable, 12 times or less is more preferable, 10 times or less is further preferable, 7 times or less is further more preferable, and 5 times or less is particularly preferable. This makes it easier to increase the adhesion of the resin composition (Q) to various base materials.

The method for producing the resin composition (Q) is not particularly limited, but the copolymer (P) is polymerized by polymerizing the raw material polymer (P1) and a monomer component containing an oxazoline group-containing monomer. At this time, it is convenient to polymerize the oxazoline group-containing polymer together. In the method for producing the copolymer (P) described above, an oxazoline group-containing polymer corresponding to the polymer chain (B) of the copolymer (P) is simultaneously produced together with the copolymer (P). At this time, the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of the formula (1) present as the unreacted raw material polymer (P1) are not separated, so that the copolymer (P) Thus, a resin composition (Q) containing an oxazoline group-containing polymer and a polymer having a unit of the formula (1) can be obtained. In this case, the resin composition (Q) is produced by the steps of the copolymer (P), the oxazoline group-containing polymer and the unit of the formula (1) according to the polymerization step described in the method of producing the copolymer (P). The resulting polymer will be obtained.

The method for producing the resin composition (Q) is not limited to the above method, and the copolymer (P) may be isolated and mixed with another polymer to prepare the resin composition (Q). Further, in the above-mentioned method for producing the copolymer (P), after completion of the graft copolymerization reaction to the raw material polymer (P1), another monomer is further added to carry out the polymerization reaction to carry out the resin composition (Q). You may get Alternatively, another weight may be added to the mixture of the copolymer (P) obtained by the method for producing the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of the formula (1). A resin composition (Q) may be prepared by adding a polymer (for example, another polymer containing an oxazoline group). When another polymer is added and mixed, it may be melt-kneaded, and in this case, a general device such as a kneader or a multi-screw extruder can be used.

The copolymer (P) and the resin composition (Q) include a polymer chain (A) having a unit of the formula (1) and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer. As a result, the adhesiveness to various base materials of high polarity to low polarity (non-polarity) and the affinity with various resins become excellent. Therefore, it can be suitably used as a primer (also referred to as an undercoating agent, an undercoating agent, or a sealer) that improves adhesion when forming a resin layer on a substrate. For example, when forming a coating layer mainly composed of acrylic polymer or urethane polymer on a polymethylmethacrylate substrate or a polycarbonate substrate, which is a resin substrate with a relatively high polarity, or with a resin substrate with a relatively low polarity. When a coating layer containing an acrylic polymer, a urethane polymer or the like as a main component is formed on a polyolefin base material, the base material and the coating layer can be formed by using the copolymer (P) or the resin composition (Q) as a primer. It is possible to improve the adhesion.

The present invention also provides a resin molded product in which a layer containing the above-described copolymer (P) or resin composition (Q) is formed on the surface of a resin base material. The layer containing the copolymer (P) or the resin composition (Q) formed in the resin molded product of the present invention has excellent adhesion to various resin base materials, and therefore the layer peels from the resin base material. It is difficult for problems such as In addition, the layer containing the copolymer (P) or the resin composition (Q) has a high affinity with various resins of high polarity to low polarity (nonpolar), and therefore another resin layer is formed on the layer. When the (coating layer) is laminated, the adhesion between the coating layer and the resin molding is high, and problems such as peeling of the coating layer are unlikely to occur.

The resin base material constituting the resin molded body is preferably a hydrocarbon resin or a resin having a hetero atom-containing group or a bond containing a hetero atom. The hydrocarbon-based resin may be any of an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, and an aromatic hydrocarbon resin, but an aliphatic hydrocarbon resin is preferable, and a polyolefin such as polyethylene or polypropylene is preferable. Resins are more preferred. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the hetero atom-containing group include a hydroxy group, a carboxy group, a sulfo group, and a carbamoyl group. Examples of the hetero atom-containing bond include an ether bond, an ester bond, a carbonic acid ester bond, an amide bond, and a thioether. Examples include binding. The resin having a hetero atom-containing group or a hetero atom-containing bond is preferably a resin having at least one selected from a carboxy group, an ester bond and a carbonic acid ester bond.

The copolymer (P) and the resin composition (Q) are also useful as a compatibilizing agent for various resins, for example, improving miscibility with a polyolefin resin or polyester resin having low polarity, or a mixture of a plurality of resins. It is possible to improve the stability of one liquid. When the copolymer (P) or the resin composition (Q) is used as a compatibilizing agent for various resins, the compounding amount is, for example, 1 part by mass with respect to 100 parts by mass of the total of the resins to be compatibilized. It is preferably not less than 10 parts by mass, more preferably not more than 10 parts by mass, for example not more than 60 parts by mass, preferably not more than 55 parts by mass, more preferably not more than 50 parts by mass. In addition, additives for melt-kneading resins, dispersants for melt-kneading compositions containing resins and auxiliary materials (for example, fibers, fillers, pigments, etc.), resins, hot melts and asphalt modifications It can also be used as a substance. Furthermore, by adding the copolymer (P) or the resin composition (Q) to the resin, compatibility, fluidity, heat resistance, impact resistance, scratch resistance, Effects such as improvement of paintability on the surface of the molded product and prevention of blocking can be expected. For example, the copolymer (P) or the resin composition (Q) can be used as a modifier of a polyolefin resin having low polarity or a modifier of various thermoplastic resins containing an acidic proton. The modifier for the polyolefin resin specifically modifies properties such as hardness, tensile strength, impact strength, heat resistance, weather resistance, workability, adhesion, and compatibility of the polyolefin resin. be able to. Further, as a modifier for an acidic proton-containing thermoplastic resin, specifically, it is possible to suppress or prevent deterioration of various characteristics (heat resistance, hardness, tensile strength, etc.) of the acidic proton-containing thermoplastic resin while It is possible to modify properties such as strength, tensile strength, impact strength, heat resistance, weather resistance, workability, adhesion and compatibility. Examples of the acidic proton-containing thermoplastic resin include polycarbonate, polyarylate, and polyamide.

This application provides the benefit of priority based on Japanese Patent Application No. 2019-004296 filed on January 15, 2019 and Japanese Patent Application No. 2019-237076 filed on December 26, 2019. I argue. The entire contents of the specifications of Japanese Patent Application No. 2019-004296 filed on Jan. 15, 2019 and Japanese Patent Application No. 2019-237076 filed on Dec. 26, 2019 are included in the present application. Incorporated for reference.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(1) Preparation of resin composition (1-1) Preparation example 1
In a 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction pipe, 40 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Co., Ltd., styrene unit content 20% by mass) and toluene as a SEBS block copolymer 200 g was charged and heated to 80° C. with stirring to dissolve the SEBS block copolymer. 48 g of isopropenyl oxazoline (IPO) and 112 g of styrene (St) were added thereto, and the temperature of the oil bath was raised to 120° C. while introducing nitrogen. An initiator solution prepared by dissolving 0.64 g of tert-butylperoxyisopropyl carbonate (Kayakoroku (registered trademark) BIC-75 manufactured by Kayaku Akzo Co., Ltd.) in 1.6 g of toluene was added thereto, and the mixture was refluxed while stirring for 15 minutes. The reaction was carried out. Then, an initiator solution prepared by dissolving 0.96 g of tert-butylperoxyisopropyl carbonate in 20 g of toluene was dropwise added at a constant rate for 5 hours, and solution polymerization was performed while maintaining the temperature at 105°C to 120°C. After the completion of the supply of the initiator, the mixture was aged under reflux for 3 hours. The residual ratio of styrene in the obtained reaction liquid was 4.2% by mass, and the residual ratio of isopropenyloxazoline was 0.0% by mass. After that, the obtained reaction solution was cooled, diluted with toluene so that the solid content was 40% by mass, and then slowly added to a large amount of n-hexane with stirring. The precipitated white solid was taken out, dried at 90° C. for about 3 days, and the solvent was removed to obtain a copolymer formed by polymerization of isopropenyloxazoline and styrene, and the copolymer chain was a SEBS block copolymer chain. To obtain a resin composition 1 containing the ethylene/butylene block-bonded graft copolymer. The resin composition 1 had a weight average molecular weight of 162,000 and a number average molecular weight of 35,000, and had a cloudy latex appearance. The weight average molecular weight and the number average molecular weight were determined by gel permeation chromatography (GPC) in terms of polystyrene (the weight average molecular weight and the number average molecular weight in the following preparation examples were also determined in the same manner).

The SEBS block copolymer Tuftec (registered trademark) P1083 used as a raw material is a hydrogenated product of a styrene-butadiene-styrene block copolymer, and the polymerizable double bond equivalent determined by an iodometric titration method is 2 It was 0.65 mmol/g. This corresponds to that the ratio of the unit of the formula (1) in the butadiene block is 82% by mass, and the content of styrene unit in Tuftec (registered trademark) P1083 is 20% by mass. The content ratio of the unit of formula (1) in the copolymer was 66% by mass.

(1-2) Preparation example 2
By performing the same operation as in Preparation Example 1 except that the amount of isopropenyloxazoline (IPO) used was changed from 48 g to 16 g and the amount of styrene (St) used was changed from 112 g to 144 g in Preparation Example 1. A resin composition 2 containing a copolymer formed by polymerization of isopropenyloxazoline and styrene, and a graft copolymer in which the copolymer chain is bonded to the ethylene/butylene block of the SEBS block copolymer chain was obtained. .. The residual ratio of styrene in the obtained reaction liquid was 6.5% by mass, and the residual ratio of isopropenyloxazoline was 0.0% by mass. The resin composition 2 had a weight average molecular weight of 15,000 and a number average molecular weight of 38,000, and had a cloudy latex appearance.

(1-3) Preparation Example 3
80 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation) and 240 g of toluene were charged as a SEBS block copolymer into a 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction pipe, and stirred while stirring 80 The SEBS block copolymer was dissolved by heating to °C. 4.8 g of isopropenyl oxazoline (IPO) and 155.2 g of styrene (St) were added thereto, and the temperature of the oil bath was raised to 120°C while passing nitrogen. An initiator solution prepared by dissolving 0.64 g of tert-butylperoxyisopropyl carbonate (Kayacarvone (registered trademark) BIC-75, manufactured by Kayaku Akzo Co., Ltd.) in 0.64 g of toluene was added thereto, and the mixture was refluxed with stirring for 15 minutes. The reaction was carried out. Then, an initiator solution prepared by dissolving 0.96 g of tert-butylperoxyisopropyl carbonate in 20 g of toluene was dropwise added at a constant rate for 5 hours, and solution polymerization was performed while maintaining the temperature at 105°C to 120°C. After the completion of the supply of the initiator, the mixture was aged under reflux for 3 hours. The residual ratio of styrene in the obtained reaction liquid was 10.1% by mass, and the residual ratio of isopropenyloxazoline was 0.0% by mass. After that, the obtained reaction solution was cooled, diluted with toluene so that the solid content was 40% by mass, and then slowly added to a large amount of n-hexane with stirring. The precipitated white solid was taken out, dried at 90° C. for about 3 days, and the solvent was removed to obtain a copolymer formed by polymerization of isopropenyloxazoline and styrene, and the copolymer chain was a SEBS block copolymer chain. To obtain a resin composition 3 containing the ethylene/butylene block-bonded graft copolymer. The resin composition 3 had a weight average molecular weight of 175,000 and a number average molecular weight of 63,000, and the appearance was a cloudy latex form.

(1-4) Preparation Example 4
A 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction pipe was charged with 40 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Co., Ltd.) and 120 g of toluene as a SEBS block copolymer, and stirred while stirring 80 The SEBS block copolymer was dissolved by heating to °C. 2.4 g of isopropenyl oxazoline (IPO) and 77.6 g of styrene (St) were added thereto, and the temperature of the oil bath was raised to 120° C. while passing nitrogen. An initiator solution obtained by dissolving 0.32 g of tert-butylperoxyisopropyl carbonate (Kayacarvone (registered trademark) BIC-75 manufactured by Kayaku Akzo Co., Ltd.) in 1.6 g of toluene was added thereto, and the mixture was refluxed while stirring for 15 minutes. The reaction was carried out. Then, a solution of a monomer component in which 2.4 g of isopropenyloxazoline (IPO) and 77.6 g of styrene (St) were dissolved in 50 g of toluene was added dropwise at a constant rate for 3 hours, and 20 g of toluene was charged with tert-butylperoxy. An initiator solution in which 1.28 g of isopropyl carbonate was dissolved was supplied dropwise at a constant rate for 5 hours, and solution polymerization was performed while maintaining the temperature at 105°C to 120°C. After the completion of the supply of the initiator, the mixture was aged under reflux for 3 hours. The residual ratio of styrene in the obtained reaction liquid was 8.3% by mass, and the residual ratio of isopropenyloxazoline was 0.0% by mass. After that, the obtained reaction solution was cooled, diluted with toluene so that the solid content was 40% by mass, and then slowly added to a large amount of n-hexane while stirring. The precipitated white solid was taken out, dried at 90° C. for about 3 days, and the solvent was removed to obtain a copolymer formed by polymerization of isopropenyloxazoline and styrene, and the copolymer chain was a SEBS block copolymer chain. A resin composition 4 containing the ethylene/butylene block-bonded graft copolymer of The resin composition 4 had a weight average molecular weight of 172,000 and a number average molecular weight of 51,000, and had a cloudy latex appearance.

(1-5) Preparation Example 5
A 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing pipe was charged with 306 g of toluene, 9.45 g of isopropenyloxazoline (IPO), and 305.55 g of styrene (St), and the temperature of the oil bath was maintained while nitrogen was passed through. Was heated to 120°C. An initiator solution in which 1.37 g of tert-amylperoxy 3,5,5-trimethylhexanoate (Kayaester (registered trademark) AN, manufactured by Kayaku Akzo Co., Ltd.) was dissolved in 9.0 g of toluene was added thereto. The reaction was carried out under reflux with stirring for 15 minutes. Then, a solution of 17.55 g of isopropenyloxazoline (IPO) and 567.45 g of styrene (St) dissolved in 558 g of toluene was added dropwise at a constant rate for 3 hours, and then 27 g of toluene was charged with tert-amylperoxy 3,5,5. An initiator solution in which 39.13 g of 5-trimethylhexanoate was dissolved was supplied dropwise at a constant rate for 5 hours, and solution polymerization was performed while maintaining the temperature at 105°C to 120°C. After the completion of supplying the initiator, the mixture was aged for 3 hours under reflux. Then, the obtained reaction solution was cooled and slowly added into a large amount of n-hexane with stirring. The precipitated white solid was taken out and dried at 90° C. for about 3 days to remove the solvent, whereby a resin composition 5 containing a copolymer (oxazoline group-containing polymer) formed by polymerization from isopropenyloxazoline and styrene was obtained. Obtained. The resin composition 5 had a weight average molecular weight of 20,000,000 and a number average molecular weight of 10,000,000, and the appearance was colorless and transparent.

(1-6) Preparation Example 6
SEBS block copolymer Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corp.) was used as the resin composition 6.

(1-7) Preparation Example 7
A resin composition 7 was obtained by mixing 4.8 g of the resin composition 5 and 1.2 g of the resin composition 6 (blended at a mass ratio of 8:2).

(1-8) Preparation Example 8
In a 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction pipe, 40 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Co., Ltd., styrene unit content 20% by mass) and toluene as a SEBS block copolymer 350 g was charged and heated to 80° C. with stirring to dissolve the SEBS block copolymer. 16 g of isopropenyl oxazoline (IPO), 32 g of acrylonitrile (AN) and 112 g of styrene (St) were added thereto, and the temperature of the oil bath was raised to 120° C. while passing nitrogen. An initiator solution prepared by dissolving 0.64 g of tert-butylperoxyisopropyl carbonate (Kayacarvone (registered trademark) BIC-75 manufactured by Kayaku Akzo Co., Ltd.) in 1.6 g of toluene was added thereto, and the mixture was refluxed while stirring for 15 minutes. The reaction was carried out. Then, an initiator solution prepared by dissolving 3.0 g of tert-butylperoxyisopropyl carbonate in 20 g of toluene was added dropwise at a constant rate for 5 hours, and solution polymerization was performed while maintaining the temperature at 105°C to 120°C. After the completion of the supply of the initiator, the mixture was aged under reflux for 3 hours. The residual ratio of styrene in the obtained reaction liquid was 2.3% by mass, the residual ratio of acrylonitrile was 0.2%, and the residual ratio of isopropenyloxazoline was 0.3% by mass. Then, the obtained reaction solution was cooled and slowly added to a large amount of n-hexane with stirring. The precipitated white solid was taken out, dried at 90° C. for about 3 days, and the solvent was removed to give a copolymer formed by polymerization of isopropenyloxazoline, acrylonitrile, and styrene, and the copolymer chain of SEBS block copolymer. A resin composition 8 containing a graft copolymer bonded to an ethylene/butylene block of a united chain was obtained. The resin composition 8 had a weight average molecular weight of 236,000 and a number average molecular weight of 32,000, and had a cloudy latex appearance.

(1-9) Preparation Example 9
In Preparation Example 8, except that 16 g of isopropenyloxazoline (IPO), 32 g of acrylonitrile (AN) and 112 g of styrene (St) which are monomer components were changed to 16 g of isopropenyloxazoline (IPO) and 144 g of methyl methacrylate (MMA). Was subjected to the same operation as in Preparation Example 8 to form a copolymer formed from isopropenyloxazoline and methyl methacrylate, and the copolymer chain was bonded to the ethylene/butylene block of the SEBS block copolymer chain. A resin composition 9 containing a graft copolymer was obtained. The residual rate of methyl methacrylate in the obtained reaction liquid was 1.2% by mass, and the residual rate of isopropenyloxazoline was 0.1% by mass. The resin composition 9 had a weight average molecular weight of 282,000 and a number average molecular weight of 30,000, and the appearance was colorless and transparent.

(2) Solubility Experiment Resin compositions 1 to 4 and 7 to 9 were added to tetrahydrofuran (THF) so that the concentration of each was 20% by mass, and they were mixed for 30 minutes with a paint shaker. When the resin THF solution after mixing was observed, the resin compositions 1 to 4 and 8 were milky white translucent uniform liquids, and the resin composition 9 was colorless and transparent uniform liquids, whereas the resin composition 7 Separated into two layers. Resin compositions 1 to 4, 8, and 9 containing a copolymer obtained by grafting an oxazoline group-containing polymer chain onto a SEBS block copolymer chain are resin compositions obtained by blending an oxazoline group-containing polymer and a SEBS block copolymer. Different from 7, the uniformity was excellent.

(3) Coating film adhesion test (3-1) Coating film adhesion test 1
6 g of the resin composition and 24 g of THF were placed in a glass container with a lid (Maru-M Corporation, screw tube bottle) having a volume of 50 mL, the lid was closed, and the mixture was shaken and stirred with a paint shaker to prepare a 20 mass% resin solution. The resin solution was applied to the test plate using a #60 bar coater and dried at 80° C. for 30 minutes to form a coating film having a film thickness of about 20 μm. A cutter knife (NT-A, A-300) blade is applied perpendicularly to the coating film to make a cut, and 11 crosscut lines are provided at 1 mm intervals in each of the vertical and horizontal rows to form a square of 1 mm ² . 100 squares were prepared. The number of coating films on which peeling did not occur on the test plate (the number of remaining coating films) was measured for the cut 100-mass coating film, and the residual ratio of the coating film was calculated by the following formula: Remaining coating film Rate (%)=remaining number of coating film/100×100. When the residual rate of the coating film is 80% or more, it is evaluated as "A", and when the residual rate of the coating film is 20% or more and less than 80%, it is evaluated as "B", and the residual rate of the coating film is less than 20%. The case was evaluated as "C". As the test plate, a PP (polypropylene) plate (standard test plate PP, 2.0 mm×70 mm×150 mm, manufactured by Nippon Test Panel Co., Ltd.) was used.

The resin compositions 1 to 5, 8 and 9 were examined for adhesion to a PP plate. Table 1 shows the ratio of the charged amounts of the raw materials of the resin compositions 1 to 5, the composition of the resin composition and the average molecular weight, and the results of the adhesion test in Table 1. The ratio of the charged amounts of the raw materials of the resin compositions 8 and 9 Table 2 shows the average molecular weight, and the results of the adhesion test. The composition of the resin composition shows the content ratio of each unit based on the amount of the polymer, and was calculated from the charged amount of raw materials and the residual monomer ratio. The resin compositions 1 to 4, 8, and 9 contain a copolymer having a polymer chain (A) derived from SEBS and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer, and a polymer chain ( A) contained ethylene units (—CH ₂ —CH ₂ —) and butylene units (—CH(—CH ₂ —CH ₃ )—CH ₂ —) as units of the formula (1). The resin composition 5 contained a copolymer composed of only the polymer chain (B). Regarding the adhesion to the PP plate, the resin compositions 1 to 3 and 8 were evaluated as A, and the resin compositions 4 and 9 were evaluated as B, while the resin composition 5 was evaluated as C. The resin compositions 1 to 4, 8 and 9 have excellent adhesion to the PP plate.

(3-2) Coating film adhesion test 2
Put a resin composition 6 g and THF (tetrahydrofuran) 24 g in a glass container with a lid (Maru-M Corporation, screw tube bottle) having a capacity of 50 mL, close the lid, shake with a paint shaker and stir to obtain a resin solution having a concentration of 20% by mass. Prepared. The resin solution was applied to the test plate using a #60 bar coater and dried at 80° C. for 30 minutes to form a coating film having a film thickness of about 20 μm. A cutter knife (NT-A, A-300) blade is applied perpendicularly to the coating film to make a cut, and 11 crosscut lines are provided at 1 mm intervals in each of the vertical and horizontal rows to form a square of 1 mm ² . 100 squares were prepared. Cellophane adhesive tape (Cellophane (registered trademark), width 15 mm, manufactured by Nichiban Co., Ltd.) was adhered to the cut surface of the coating film of 100 squares so that air did not enter, and the tape was rubbed firmly with a finger. After leaving for 10 seconds, hold the end of the tape at a right angle to the surface of the coating film, peel off the tape momentarily, measure the number of squares of the coating film that did not peel, and use the following formula The residual rate was determined: residual rate of coating film (%)=remaining number of coating film/100×100. When the residual rate of the coating film is 80% or more, it is evaluated as "A", and when the residual rate of the coating film is 20% or more and less than 80%, it is evaluated as "B", and the residual rate of the coating film is less than 20%. The case was evaluated as "C". As the test plate, a PBT (polybutylene terephthalate) plate (engineering test service company, PBT3300, 2.0 mm x 70 mm x 150 mm), a PC (polycarbonate) plate (japan test panel company, standard test plate PC, 2.0 mm) ×70 mm×150 mm) and a PMMA (polymethylmethacrylate) plate (PMMA, 2.0 mm×60 mm×120 mm, manufactured by Engineering Test Service Co., Ltd.) were used.

The resin compositions 2 to 6, 8 and 9 were examined for adhesion to PBT plate, PC plate and PMMA plate. The results are shown in Tables 3 and 4. While the resin compositions 2 to 4, 8, and 9 were evaluated as A for all the test plates, the resin compositions 5 and 6 were inferior in adhesiveness to those, and the resin composition 6 had The test plate was also rated C. The resin compositions 2 to 4, 8 and 9 also have excellent adhesion to PBT plates, PC plates and PMMA plates. A resin composition containing a copolymer having a smaller content ratio of SEBS-derived polymer chains (A) than the resin composition 4, that is, a resin composition having a SEBS/(IPO+St) ratio of less than 20. Even with a resin composition having a SEBS/(IPO+St) ratio of, for example, 15/85 or 10/90, the effect of improving the adhesion to the PBT plate, the PC plate and the PMMA plate was obtained as compared with the resin composition 6. Further, the effect of improving the adhesiveness to the PBT plate was obtained as compared with the resin composition 5.

(4) Compatibility test Polystyrene resin (Epocros (registered trademark) RPS-1005; manufactured by Nippon Shokubai Co., Ltd.) was added to tetrahydrofuran (THF) at a concentration of 20% by mass, and a resin containing an olefin component. (Tuftec (registered trademark) P1083; manufactured by Asahi Kasei) was added to a 20 mL glass container (screw tube) containing 5 g each of a resin solution Y prepared by adding tetrahydrofuran (THF) to a concentration of 20% by mass and using a lid. The mixture was sealed and mixed with a shaker machine (shaker) for 1 minute to obtain a resin mixed solution (X+Y). The resin mixed solution (X+Y) was stirred and left for 10 minutes and then separated into two layers. Next, 5 g of the resin solution 3 obtained by adding the resin composition 3 to tetrahydrofuran (THF) so that the concentration of the resin composition 3 is 20% by mass is added to the resin mixed solution (X+Y), and the mixture is sealed with a lid and shaker machine (shaker). ) For 1 minute. The resin mixed solution (X+Y) containing the resin composition 3 was a uniform solution without separating into two layers even if left for 10 minutes after stirring and mixing. That is, the resin composition 3 containing the copolymer obtained by grafting the oxazoline group-containing polymer chain onto the SEBS block copolymer chain improves the miscibility between the polystyrene-based resin and the polystyrene-based resin and serves as a compatibilizer. It can be said that it worked.

The copolymer (P) and the resin composition (Q) of the present invention are primers, adhesives, compatibilizers and additives for various resins, which enhance the adhesion between various base materials such as metals and plastics and the resin coating layer. , Can be used as a modifier. Specifically, optical films, printed wiring boards, resins for rubber reinforcement such as tire cords, various engineering plastics such as bumpers, instrument panels, interior/exterior parts for automobile/transport equipment such as electrical components, home appliances, furniture, daily necessities such as miscellaneous goods. Used for industrial products such as related products, construction/civil engineering, stationery/office supplies.

Claims (16)

A copolymer (P) having a polymer chain (A) having a unit represented by the following formula (1) and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer.

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ] The copolymer (P) according to claim 1, wherein the polymer chain (B) is grafted onto the polymer chain (A). The copolymer (P) according to claim 1 or 2, wherein the content ratio of the unit represented by the formula (1) in the polymer chain (A) is 50% by mass or more. The copolymer (P) according to any one of claims 1 to 3, wherein the content of the units derived from the oxazoline group-containing monomer in the polymer chain (B) is 1% by mass or more and 50% by mass or less. The polymer chain (A) has a polymer block (a1) having a unit represented by the formula (1) and a polymer block (a2) having a unit derived from an aromatic vinyl monomer. 4. The copolymer (P) according to any one of 4 above. The polymer chain (B) further has a unit derived from an aromatic vinyl monomer and/or a unit derived from an unsaturated carboxylic acid ester,
In the polymer chain (B), the total content of the units derived from the oxazoline group-containing monomer, the units derived from the aromatic vinyl monomer and/or the units derived from the unsaturated carboxylic acid ester is 80% by mass or more. The copolymer (P) according to any one of claims 1 to 5. A resin composition (Q) comprising the copolymer (P) according to any one of claims 1 to 6. A resin composition (Q) comprising the copolymer (P) according to any one of claims 1 to 6 and an oxazoline group-containing polymer. The content ratio of the polymer chain (A) is 5 parts by mass with respect to 100 parts by mass in total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1). The resin composition (Q) according to claim 8, which is contained in an amount of not less than 80 parts by mass and not more than 80 parts by mass. Containing the unit represented by the formula (1) with respect to 100 parts by mass in total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1). The resin composition (Q) according to claim 8 or 9, wherein the proportion is 3 parts by mass or more and 80 parts by mass or less. Containing units derived from the oxazoline group-containing monomer based on 100 parts by mass in total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1). The resin composition (Q) according to any one of claims 8 to 10, wherein the proportion is 0.5 part by mass or more and 49 parts by mass or less. A primer comprising the copolymer (P) according to any one of claims 1 to 6 or the resin composition (Q) according to any one of claims 7 to 11. A layer containing the copolymer (P) according to any one of claims 1 to 6 or the resin composition (Q) according to any one of claims 7 to 11 is formed on the surface of a resin substrate. Resin molding. The resin molded product according to claim 13, wherein the resin base material is a hydrocarbon resin or a resin having a hetero atom-containing group or a hetero atom-containing bond. A compatibilizing agent comprising the copolymer (P) according to any one of claims 1 to 6 or the resin composition (Q) according to any one of claims 7 to 11. Represented by the following formula (1), characterized by having a step of polymerizing a monomer component containing an oxazoline group-containing monomer in the presence of a polymer having a unit represented by the following formula (1): A method for producing a copolymer (P) having a polymer chain (A) having a unit and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer.

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]