JP7212069B2 - Resin composition and method for producing resin composition - Google Patents

Description

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

Conventionally, polymers containing oxazoline groups 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 and styrene or further acrylonitrile. It can be used as a compatibilizer or as a primer for improving adhesion to substrates.

JP-A-4-81458 JP-A-10-46010

The inventors of the present invention have investigated the adhesion of the oxazoline group-containing polymers disclosed in Patent Documents 1 and 2 to various substrates. However, it was found that the adhesiveness was not sufficient. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a copolymer (P) exhibiting high adhesion even to substrates with relatively low polarity (resin substrates, etc.), and An object of the present invention is to provide a resin composition (Q) containing

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

[In 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 of the unit represented by 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 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 [ 1] to the copolymer (P) according to any one of [4].
[6] The polymer chain (B) further has an aromatic vinyl monomer-derived unit and/or an unsaturated carboxylic acid ester-derived unit,
In the polymer chain (B), the total content of units derived from the oxazoline group-containing monomer, units derived from the aromatic vinyl monomer and/or units derived from the unsaturated carboxylic acid ester is 80% by mass or more. A copolymer (P) according to any one of [1] to [5].
[7] A resin composition (Q) comprising the copolymer (P) according to any one of [1] to [6].
[8] A resin composition (Q) comprising 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 a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1) is 5 parts by mass or more and 80 parts by mass or less, the resin composition (Q) according to [8].
[10] With respect to a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1), the The resin composition (Q) according to [8] or [9], wherein the unit content is 3 parts by mass or more and 80 parts by mass or less.
[11] With respect to a total of 100 parts by mass 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 [8] to [10], wherein the unit content is 0.5 parts by mass or more and 49 parts by mass or less.
[12] Characterized by containing the copolymer (P) according to any one of [1] to [6] or the resin composition (Q) according to any one 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 one of [7] to [11] is a resin substrate The resin molded body formed on the surface of the.
[14] The resin molding according to [13], wherein the resin base material is a hydrocarbon resin, or a resin having a heteroatom-containing group or a heteroatom-containing bond.
[15] Characterized by containing the copolymer (P) according to any one of [1] to [6] or the resin composition (Q) according to any one of [7] to [11] Compatibilizer.
[16] The following formula (1), characterized by comprising 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 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 comprise a polymer chain (A) having a unit represented by formula (1) and a polymer chain having a unit derived from an oxazoline group-containing monomer ( B), the adhesiveness to various substrates including polyolefin is excellent.

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 formula (1) below, 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 is excellent in adhesion to various substrates and affinity with various resins.

The unit represented by the above formula (1) contained in the polymer chain (A) (hereinafter referred to as "the unit of formula (1)") has adhesion to substrates with low polarity and compatibility with resins with low polarity. It acts to increase affinity. Since the unit of formula (1) is the same as or similar to the polymer constitutional unit of the low polar base material or the low polar resin, the intermolecular force between the low polar base material and the low polar resin is Such interaction is thought to occur, and adhesion and affinity are enhanced.

Alkyl groups represented by R ¹ to R ⁴ in formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and isopentyl. linear or branched alkyl groups such as groups, n-hexyl groups, isohexyl groups, n-heptyl groups, isoheptyl groups, n-octyl groups, and 2-ethylhexyl groups, cyclopropyl groups, cyclobutyl groups, Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cyclononyl group, cyclodecyl group, dicyclopentanyl group, and adamantyl group are included. Among these, linear or branched alkyl groups are preferred as the alkyl groups for R ¹ to R ⁴ . The number of carbon atoms in the alkyl groups of R ¹ to R ⁴ is preferably 1-12, more preferably 1-8, even more preferably 1-6.

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

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

The polymer chain (A) has an olefin (co)polymer chain such as polyethylene, polypropylene, polybutylene, polyisobutylene, ethylene-propylene copolymer, ethylene-1-butene copolymer partially or It is preferably included in its entirety. More preferred olefin (co)polymers are polyethylene, polypropylene, polybutylene and ethylene-1-butene copolymers.

The polymer chain (A) may further have units represented by the following formula (2-1) and/or units 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 "the unit of 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 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. It represents an alkenyl group of 2-20. 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 R ⁹ and R ¹⁰ may be in a cis-position relationship with each other. They may often be in a trans relationship. 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 units of the base material with low polarity and the resin with low polarity, these groups It is thought that an interaction occurs between the material and the resin, increasing adhesion and affinity. Therefore, the copolymer (P) having the polymer chain (A) containing the unit of formula (1) and the unit of formula (2) is also excellent in adhesion to various substrates and affinity with various resins. Become.

For the alkyl groups having 1 to 20 carbon atoms for R ⁶ to R ¹⁰ in formulas (2-1) and (2-2), the above description of alkyl groups for R ¹ to R ⁴ is referred to. The alkenyl group having 2 to 20 carbon atoms represented by R ⁵ to R ⁸ of formula (2-1) is a group in which one C—C bond contained in the alkyl group represented by R ¹ to R ⁴ is replaced with a C=C bond. and a linear or branched alkenyl group is preferred. The alkenyl groups of R ⁵ to R ⁸ preferably have 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 2 to 6 carbon atoms. A vinyl group is particularly preferred as the alkenyl group for R ⁵ to R ⁸ .

Since it is easy to form the unit represented by formula (2-1), R ⁵ in formula (2-1) is preferably a linear or branched alkenyl group having 2 to 6 carbon atoms. Preferably, R ⁶ is 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 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. is more preferred. Such units of formula (2) can be introduced into the polymer chain (A) by copolymerizing a diene with an olefin or by homopolymerizing or copolymerizing a conjugated diene. Examples of the diene forming the unit of formula (2) include 1,3-butadiene (alias: butadiene), 2-methyl-1,3-butadiene (alias: isoprene), 1,3-pentadiene, and 1,4-pentadiene. , 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene (also known as diisobutene) are preferred, and among them 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3- Conjugated dienes such as pentadiene are more preferred. The number of carbon atoms in the diene is preferably 4 or more, more preferably 5 or more, preferably 20 or less, more preferably 10 or less, and even more preferably 8 or less.

The polymer chain (A) having units of formula (1) and units of formula (2) is, for example, an olefin-diene copolymer such as an ethylene-isoprene copolymer, a butene-butadiene copolymer, an isobutene-isoprene copolymer. It is preferred to include the copolymer chain partially or wholly 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. Other unsaturated monomers are not particularly limited as long as they are compounds having a polymerizable double bond. Examples 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, and 2-vinylpyridine; vinyltrimethoxysilane, Examples 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 formula (1) as a main component, and the content of the unit of formula (1) in the polymer chain (A) is preferably 50% by mass or more. % by mass or more is more preferable, and 60% by mass or more is even more preferable. This makes it easier to enhance the adhesion of the copolymer (P) to various substrates and to enhance the affinity with various resins. The upper limit of the content ratio of the units of formula (1) in the polymer chain (A) is not particularly limited, and the polymer chain (A) may consist only of the units of formula (1). The content ratio of the unit of formula (1) in the compound may be 98% by mass or less, 95% by mass or less, or 90% by mass or less.

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

When the polymer chain (A) has units derived from other unsaturated monomers, the polymer chain (A) comprises units of formula (1) (or further units of formula (2)) and other unsaturated monomers It may be a random copolymer containing units derived from a polymer, or a block copolymer. When the polymer chain (A) is a block copolymer, the polymer chain (A) comprises a polymer block (a1) having units of formula (1) and a polymer block (a1) having units derived from other unsaturated monomers. It is preferable to have a united block (a2).

When the polymer chain (A) has the polymer block (a1) and the polymer block (a2), the polymer block (a1) includes the units of the formula (2) and other units in addition to the units of the formula (1). may have a unit derived from an unsaturated monomer of Examples of other unsaturated monomers in this case include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, and the like; unsaturated carboxylic acids and esters thereof; aromatic vinyl compounds such as styrene, vinyltoluene, methoxystyrene, α-methylstyrene, and 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 of the units of the formula (1) in the polymer block (a1) is preferably 70% by mass or more. , more preferably 80% by mass or more, and even more preferably 90% by mass or more. The polymer block (a1) may consist essentially of the units of the formula (1), and may contain, for example, 99% by mass or more of the units of the formula (1). Alternatively, the total content of the units of formula (1) and the units of 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 preferred. The polymer block (a1) may consist essentially of the units of formula (1) and the units of formula (2), for example, the units of formula (1) and the units of formula (2) are 99 mass % or more.

When the polymer chain (A) has a polymer block (a2) having units derived from another unsaturated monomer, the polymer block (a2) is composed of units 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 the copolymer (P) and the resin composition containing the copolymer (P) Elasticity can be imparted to (Q). Aromatic vinyl monomers are not particularly limited as long as they are compounds in which a vinyl group is bonded to an aromatic ring. Examples include styrene, vinyltoluene, methoxystyrene, α-methylstyrene, α-hydroxymethylstyrene, α-hydroxyethyl Styrenic monomers such as styrene; polycyclic aromatic hydrocarbon ring vinyl monomers such as 2-vinylnaphthalene; aromatic heterocyclic vinyl monomers such as N-vinylcarbazole, 2-vinylpyridine, vinylimidazole, and vinylthiophene and the like. Among these, styrenic monomers are preferred. Styrenic monomers include not only styrene, but also styrene derivatives in which arbitrary substituents are bonded to the vinyl group of styrene or the benzene ring, and the substituents include alkyl groups, alkoxy groups, hydroxyl groups, halogen 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, more preferably 1 to 2 carbon atoms. may be substituted with a group. The styrene-based monomer is preferably unsubstituted styrene in which no substituent is bonded to the vinyl group and benzene ring of styrene.

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 other unsaturated monomers in this case include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, and the like; and esters thereof; and vinylsilanes 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 unit derived from the aromatic vinyl monomer in the polymer block (a2) is 70% by mass. It is preferably 80% by mass or more, more preferably 90% by mass or more. The polymer block (a2) may be substantially composed only of units derived from aromatic vinyl monomers, and may contain, for example, 99% by mass or more of units derived from aromatic vinyl monomers.

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

The polymer chain (A) composed of a block copolymer is preferably a polymer block (a1) to which polymer blocks (a2) are bound on both sides, more preferably a triblock copolymer. . Examples of such triblock copolymers include hydrogenated styrene-butadiene-styrene block copolymers and hydrogenated styrene-isoprene-styrene block copolymers. If 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 formed. can reduce the hardness and brittleness of

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

In addition, it is preferable that the polymer chain (A) has the polymer block (a1) and does not have the polymer block (a2). Further, the polymer chain (A) is preferably composed of units of formula (1), or composed of units of formula (1) and units of formula (2), and composed only of units of formula (1). more preferably.

The weight average molecular weight of the polymer chain (A) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, even more preferably 30,000 or more, and preferably 300,000 or less, and 250,000. The following are more preferable, 200,000 or less are more preferable, and 150,000 or less are even more preferable. By setting the weight average molecular weight of the polymer chain (A) in such a range, the handleability of the copolymer (P) can be easily improved.

The polymer chain (B) contained in the copolymer (P) will be explained. The polymer chain (B) has units derived from oxazoline group-containing monomers. The unit derived from the oxazoline group-containing monomer acts to increase adhesion and affinity between the copolymer (P) and a highly polar base material or a 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. Vinyloxazolines such as 4-dimethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline and 4,4-dimethyl-2-isopropenyl-2-oxazoline are preferred. Among these, 2-isopropenyl-2-oxazoline is preferably used from the viewpoint of availability and reactivity.

The polymer chain (B) may further have units derived from other unsaturated monomers. Other unsaturated monomers are not particularly limited as long as they are compounds having a polymerizable double bond. Examples include vinyl esters such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile; Acids, unsaturated carboxylic acids such as maleic anhydride, methyl (meth)acrylate, and ethyl (meth)acrylate and their esters; aromatics such as styrene, vinyltoluene, methoxystyrene, α-methylstyrene, and 2-vinylpyridine Vinyl compounds; Vinyltrimethoxysilane, γ-(meth)acryloyloxypropylmethoxysilane, and other vinylsilanes. 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 more preferably has a unit derived from a monomer and/or a unit derived from an unsaturated carboxylic acid ester, and more preferably has 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 (meth)acrylic acid ester. For the description of the aromatic vinyl monomer and the styrene monomer, refer to the description of the aromatic vinyl monomer and the styrene monomer of the polymer block (a2) above. If the polymer chain (B) has an aromatic vinyl monomer-derived unit, the heat resistance of the copolymer (P) can be improved, and when the polymer chain (B) is polymerized and formed, It can accelerate the reaction of the oxazoline group-containing monomer. It is also advantageous in terms of manufacturing cost.

As the unsaturated carboxylic acid ester (preferably (meth)acrylic acid ester), specifically, a linear, branched or cyclic aliphatic Examples thereof include (meth)acrylic acid esters to which hydrocarbon groups and aromatic hydrocarbon groups are bonded.

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

Examples of (meth)acrylic acid esters having a cyclic aliphatic hydrocarbon group include (meth)acrylates such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate. ) cycloalkyl acrylate; bridged cyclic (meth)acrylates such as isobornyl (meth)acrylate; The number of carbon atoms in the cycloalkyl group of the cycloalkyl (meth)acrylate is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 12 or less, and still more preferably 10 or less. .

Examples of (meth)acrylic acid esters 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; mentioned. The number of carbon atoms in the aryl group of the aryl (meth)acrylate is preferably 6 or more, preferably 20 or less, and more preferably 14 or less. The number of carbon atoms in the aralkyl group of the aralkyl (meth)acrylate is preferably 7 or more, preferably 14 or less, and more preferably 12 or less. The number of carbon atoms in the aryloxyalkyl group of the aryloxyalkyl (meth)acrylate is preferably 7 or more, preferably 14 or less, and more preferably 12 or less.

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 highly polar resins) can be further improved.

When the polymer chain (B) has units derived from other unsaturated monomers, 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 ease of production of the polymer chain (B).

The content of units 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, and 40% by mass or less. is more preferred. This makes it easier to enhance the effect of improving the adhesion and affinity of the copolymer (P), and facilitates the formation of the polymer chain (B).

When the polymer chain (B) has units derived from aromatic vinyl monomers as units derived from other unsaturated monomers, units derived from oxazoline group-containing monomers and units derived from aromatic vinyl monomers The total content of the units is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and 98% by mass or more Especially preferred.

The polymer chain (B) is preferably grafted onto 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 basic terms in polymer science by the International Union of Pure and Applied Chemistry (IUPAC) Committee on Polymer Nomenclature, a graft polymer is defined as "a If there is one or several blocks and these side chains have structural (chemical structure) or configurational features different from the main chain, the polymer is called a graft polymer.” there is The graft copolymer can be obtained by known production methods such as chain transfer reaction method, polymer initiator method, coupling method, macromonomer method and surface graft method, and only one of these methods is adopted. may be used, or a plurality of them may be used in combination. For details of these methods, reference can be made to Kagaku Binran (Applied Chemistry), 6th edition, edited by the Chemical Society of Japan.

The copolymer (P) is conveniently produced by addition-polymerizing the polymer chain (A) with a monomer component forming the polymer chain (B). Therefore, the copolymer (P) is a monomer containing an oxazoline group-containing monomer in the presence of a polymer having units of formula (1) (hereinafter referred to as "raw polymer (P1)") Those obtained by polymerizing the components are preferred. For details of the starting polymer (P1), the description of the polymer chain (A) above is referred to, and the starting polymer (P1) further has units of formula (2) or units of formula (1). and a polymer block (a2) having a unit derived from another unsaturated monomer.

The polymer chain (B) is preferably grafted onto, for example, the units of formula (1) of the polymer chain (A). When polymer chain (A) has units of formula (2), polymer chain (B) may be grafted onto units of formula (2). The polymer chain (B) may be attached to a carbon atom of the main chain of the unit of formula (1) or the unit of formula (2), and the hydrocarbon group attached to the main chain as a substituent (side chain) It may be attached to a carbon atom. Also, the polymer chain (B) may be bonded to the polymer chain (A) via any 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, 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 still more preferable, and 200,000 or less is even more preferable. By setting the weight-average molecular weight of the copolymer (P) to such a range, it becomes easier 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). It is preferably twice or less, more preferably 12 times or less, still more preferably 10 times or less, even more preferably 7 times or less, and particularly preferably 5 times or less. This makes it easier to increase the adhesion 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 starting 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 the polymer chain (A), thereby forming a polymer chain ( A copolymer (P) is obtained in which B) is attached to the polymer chain (A).

In the polymerization step, the polymer chain (B) is bonded to the unit of formula (1) of the starting polymer (P1) (when the unit of formula (2) is also present, the unit of formula (1) or the unit of formula (2)). From the point of view of ensuring that the As a result, a radical is generated at the site, and the monomer component forming the polymer chain (B) can be subjected to addition polymerization.

Polymerization step WHEREIN: Only 1 type may be used for a raw material polymer (P1), and it may use 2 or more types together. In the latter case, it becomes easy to adjust the weight average molecular weight and physical properties of the copolymer (P).

As the monomer component used for forming the polymer chain (B), in addition to the oxazoline group-containing monomer, other unsaturated monomers can also be used. As other unsaturated monomers, vinyl cyanide monomers, aromatic vinyl monomers and/or unsaturated carboxylic acid esters are preferably used. For details of these monomer components, refer to the description of the oxazoline group-containing monomer forming the polymer chain (B) and the other unsaturated monomer forming the polymer chain (B).

Polymerization of the monomer component can be carried out using known polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, but solution polymerization is preferred. As a polymerization method, for example, both a batch polymerization method and a continuous polymerization method can be used.

The amount of the starting polymer (P1) used in the polymerization is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on a total of 100 parts by mass of the starting polymer (P1) and the monomer component. It is more preferably 15 parts by mass or more, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even 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 a total of 100 parts by mass of the starting polymer (P1) and the monomer component. It 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 even more preferably 85 parts by mass or less.

The solvent used in the polymerization can be appropriately selected according to the composition of the monomer components, and organic solvents used in ordinary radical polymerization reactions 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 and ethylene glycol dimethyl ether. , diethylene glycol dimethyl ether, ethers such as 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, alcohols such as n-butanol; nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile; chloroform; These solvents may be used alone or in combination of two or more.

The polymerization reaction between the starting polymer (P1) and the monomer component is preferably carried out in the presence of a polymerization initiator. Examples of polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, dimethyl-2,2'-azobis(2-methylpropane). azo compounds such as 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-amylperoxy 2-ethylhexyl carbonate can be used. These may use only 1 type and may use 2 or more types together. Among these, it is preferable to use an organic peroxide having a strong hydrogen abstraction power, and it is particularly preferable to use a peroxycarbonate-based peroxide. The amount of the polymerization initiator to be used is preferably 0.05 to 3 parts by weight per 100 parts by weight of the monomer component.

The total concentration of the starting polymer (P1) and the monomer component in the reaction solution is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 80% by mass or less. , 70% by mass or less. During the polymerization reaction, it is also possible to appropriately add the starting polymer (P1), monomer components, polymerization catalyst, solvent, and the like.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or under a stream of air. 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 is preferably carried out for 1 to 20 hours, for example.

At the time of polymerization, the monomer components may be charged all at once or may be added in portions. It is preferable to charge the monomer components all at once, since it is easy to graft polymerize the oxazoline group-containing monomer onto the polymer chain (A) to form the polymer chain (B).

The present invention also provides a resin composition (Q) containing a copolymer (P) having polymer chains (A) and polymer chains (B) as described above. The resin composition (Q) of the present invention is excellent in adhesion to various substrates and 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 formula (1), more preferably an oxazoline group-containing polymer. It is preferably used, and by including these other polymers, the homogeneity of the resin composition (Q) is enhanced.

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

The polymer having the unit of formula (1) included as another polymer in the resin composition (Q) may be any polymer having the unit of formula (1) described in the polymer chain (A). The polymer chain (A) may have units derived from the polymer having the unit of formula (2) or other unsaturated monomers. The polymer having the unit of formula (1) has a unit derived from the same monomer as the unit derived from the monomer possessed by the polymer chain (A) from the viewpoint of enhancing compatibility with the copolymer (P). is more preferable.

In the resin composition (Q), the content ratio of the copolymer (P) is It is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, and even more preferably 15 parts by mass or more. The upper limit of the content 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), or The content of the copolymer (P) may be 90 parts by mass or less, or 80 It may be not more than 70 parts by mass, or not more than 60 parts by mass.

In the resin composition (Q), the content ratio of the polymer chain (A) is 5 parts with respect to a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1). It is preferably at least 8 parts by mass, more preferably at least 8 parts by mass, still more preferably at least 12 parts by mass, and preferably at most 80 parts by mass, more preferably at most 70 parts by mass, further preferably at most 60 parts by mass. Part by mass or less is even more preferred. This makes it easier to improve the adhesion of the resin composition (Q) to various substrates. The content of the polymer chain (A) in the resin composition (Q) is the polymer chain (A) contained in the copolymer (P) and the polymer chain contained in the polymer having the unit of formula (1). It means the total content of (A).

In the resin composition (Q), the content ratio of the unit of formula (1) is It is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 60 parts by mass or less, 50 parts by mass or less is even more preferable. This makes it easier to improve the adhesion of the resin composition (Q) to various substrates. Alternatively, in the resin composition (Q), the unit of formula (1) and the formula The total content of 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 less than part. In addition, the content ratio of the unit of formula (1) in the resin composition (Q) is included in the polymer having the unit of formula (1) and the unit of formula (1) included in the copolymer (P). Means the total content of units of formula (1), and the content of units of formula (2) in the resin composition (Q) is the same as the units of formula (2) contained in the copolymer (P). It means the total content of the units of formula (2) contained in the polymer having the units of formula (1). Further, the content ratio of the unit of formula (2) means the total content ratio of the unit represented by formula (2-1) and the unit represented by formula (2-2).

In the resin composition (Q), the unit derived from the oxazoline group-containing monomer is added to a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1). The content is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, still more 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 improve the adhesion of the resin composition (Q) to various substrates. The content ratio of the units derived from the oxazoline group-containing monomer in the resin composition (Q) is the unit derived from the oxazoline group-containing monomer contained in the copolymer (P) and the oxazoline group-containing polymer. means the total content of units derived from oxazoline group-containing monomers.

The resin composition (Q) contains the units of formula (1) and oxazoline groups with respect to a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the units of formula (1). The total content of monomer-derived units is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more. This makes it easier to improve the adhesion of the resin composition (Q) to various substrates. The upper limit of the content ratio of the unit of 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 composed of the formula (1). It may be composed only of units and units derived from oxazoline group-containing monomers, and relative to a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) and the total content of the unit of formula (1) and the unit 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 Alternatively, in the resin composition (Q), the unit of formula (1) and the formula The total content ratio of the unit of (2) and the unit 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. , 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 formula (1) is It is particularly preferable that the amount is 10 parts by mass or more, and the total content of the units of formula (1) and the units derived from the oxazoline group-containing monomer is 20 parts by mass or more. Alternatively, in the resin composition (Q), the unit of formula (1) and the formula The total content of the units of (2) is 10 parts by mass or more, and the total content of the units of formula (1), the units of formula (2), and the units derived from the oxazoline group-containing monomer is 20 parts by mass or more. is particularly preferred.

In the resin composition (Q), the content ratio of the unit of formula (1) is 10 parts by mass or more with respect to the total 100 parts by mass of the unit of formula (1) and the unit derived from the oxazoline group-containing monomer. , more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, preferably 98 parts by mass or less, more preferably 95 parts by mass or less, and even more preferably 93 parts by mass or less. This makes it easier to improve the adhesion of the resin composition (Q) to various substrates. Alternatively, in the resin composition (Q), the unit of formula (1) and the unit of formula (1) and the formula The total content of units (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 too.

The content ratio of the unit of formula (1), the content ratio of the unit of 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 when polymerizing the group-containing polymer and the monomer residual ratio (the ratio of the unreacted and remaining monomer contained in the resulting reaction solution) , the amount of each unit incorporated into the copolymer (P) or the oxazoline group-containing polymer. As described later, when the resin composition (Q) is obtained by polymerizing the monomer component containing the oxazoline group-containing monomer in the presence of the starting polymer (P1), the starting polymer (P1) Considering the amount of units of formula (1) and units of formula (2) contained, the content ratio of units of formula (1) and the content ratio of units of formula (2) in the resin composition (Q) The content ratio of units derived from the oxazoline group-containing monomer is calculated. At this time, the starting polymer (P1) is all reacted with the monomer component, and its residual rate is considered to be 0%. In addition, 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 contains the copolymer (P) and the oxazoline group. It may be composed only of the containing polymer, for example, 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 99 parts by mass or more. may 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 formula (1). Examples of such polymers include vinyl chloride, chlorine halogen-containing polymers such as vinyl chloride resin; acrylic polymers such as polymethyl methacrylate; polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, etc. Styrenic polymers; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamides such as nylon 6, nylon 66, and nylon 610; polyacetals; polycarbonates; sulfone; polyoxypentylene; polyamide-imide;

The resin composition (Q) may contain a solvent. Examples of solvents include 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, n - alcohols such as butanol; nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile; chloroform; These solvents may contain only one type, or may contain two or more types.

The resin composition (Q) may contain various additives. Examples of additives include antioxidants such as hindered phenol, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; Absorbents; near-infrared absorbers; flame retardants such as tris(dibromopropyl) phosphate, triallyl phosphate, antimony oxide; antistatic agents including anionic, cationic, and nonionic surfactants; inorganic pigments, organic pigments, coloring agents such as dyes; organic fillers and inorganic fillers; resin modifiers; organic fillers and inorganic fillers; The content of each additive in the resin composition (Q) is preferably 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 still more preferable, and 200,000 or less is even more preferable. The weight average molecular weight of the resin composition (Q) means a polystyrene-equivalent value of the resin composition (Q) measured by gel permeation chromatography, and the resin composition (Q) is the copolymer (P) and oxazoline. When a group-containing polymer and a polymer having units of formula (1) are contained, the weight average molecular weight of the resin composition (Q) is the total weight average molecular weight of these multiple types 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). 20 times or less is more preferable, 12 times or less is more preferable, 10 times or less is more preferable, 7 times or less is even more preferable, and 5 times or less is particularly preferable. This makes it easier to improve the adhesion of the resin composition (Q) to various substrates.

The method for producing the resin composition (Q) is not particularly limited, but the raw material polymer (P1) and a monomer component containing an oxazoline group-containing monomer are polymerized to form a copolymer (P). When doing so, 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). In this case, the copolymer (P) is obtained by not separating the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) existing as the unreacted raw material polymer (P1). and an oxazoline group-containing polymer and a resin composition (Q) containing a polymer having units of formula (1). In this case, the method for producing the resin composition (Q) is to convert the copolymer (P), the oxazoline group-containing polymer, and the units of formula (1) by the polymerization step described in the method for producing the copolymer (P). A polymer having

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 form the resin composition (Q). Further, in the method for producing the copolymer (P) described above, after completion of the graft copolymerization reaction to the raw material polymer (P1), another monomer is added and the polymerization reaction is performed to obtain the resin composition (Q). may be obtained. Alternatively, a mixture of the copolymer (P) obtained by the above-described method for producing the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) is added with another polymer. A coalescence (for example, another oxazoline group-containing polymer) may be added to form the resin composition (Q). 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) contain a polymer chain (A) having a unit of formula (1) and a polymer chain (B) having a unit derived from an oxazoline group-containing monomer. As a result, it has excellent adhesion to various substrates from high polarity to low polarity (non-polarity) and affinity with various resins. Therefore, it can be suitably used as a primer (also referred to as an undercoating agent, an undercoating agent, or a sealer) for improving adhesion when forming a resin layer on a substrate. For example, when forming a coating layer mainly composed of acrylic polymer, urethane polymer, etc. on a polymethyl methacrylate base material or polycarbonate base material, which is a resin base material with relatively high polarity, or with a resin base material with relatively low polarity. When a coating layer mainly composed of acrylic polymer, urethane polymer or the like is formed on a certain polyolefin substrate, the copolymer (P) or resin composition (Q) is used as a primer to form a bond between the substrate and the coating layer. can increase the adhesion of.

The present invention also provides a resin molded article in which a layer containing the copolymer (P) or the resin composition (Q) described above is formed on the surface of a resin substrate. The layer containing the copolymer (P) or the resin composition (Q) formed on the resin molded article of the present invention has excellent adhesion to various resin substrates, so the layer peels off from the resin substrate. Problems such as this are less likely to occur. In addition, since the layer containing the copolymer (P) or the resin composition (Q) has a high affinity with various resins from high polarity to low polarity (non-polar), another resin layer is further formed on the layer. When the (coating layer) is laminated and formed, the adhesion between the coating layer and the resin molding is high, and problems such as peeling of the coating layer are less likely to occur.

The resin base material constituting the resin molding is preferably a hydrocarbon resin, or a resin having a heteroatom-containing group or a heteroatom-containing bond. 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 polyolefins such as polyethylene and polypropylene Resin is more preferred. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like. Examples of the heteroatom-containing group include a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, and the like. Examples of the heteroatom-containing bond include an ether bond, an ester bond, a carbonate bond, an amide bond, and a thioether. binding and the like. As the resin having a heteroatom-containing group or a heteroatom-containing bond, a resin having at least one selected from a carboxy group, an ester bond and a carbonate ester bond is preferred.

The copolymer (P) and the resin composition (Q) are also useful as a compatibilizer for various resins. can improve the one-component stability of When the copolymer (P) or the resin composition (Q) is used as a compatibilizer for various resins, the blending amount is, for example, 1 part by mass with respect to a total of 100 parts by mass of the resins to be compatibilized. It is preferably at least 10 parts by mass, more preferably at least 10 parts by mass, for example at most 60 parts by mass, preferably at most 55 parts by mass, more preferably at most 50 parts by mass. In addition, additives when melt-kneading resins, dispersants when melt-kneading compositions containing resins and secondary materials (e.g., fibers, fillers, pigments, etc.), resins, hot melts, and asphalt improvement It can also be used as a substance. Furthermore, by adding the copolymer (P) or the resin composition (Q) to the resin, compatibility improvement, fluidity improvement, heat resistance improvement, impact resistance improvement, scratch resistance improvement, Effects such as improved paintability on the surface of molded products and anti-blocking effects can also be expected. For example, the copolymer (P) and the resin composition (Q) can be used as modifiers for polyolefin resins with low polarity and modifiers for various thermoplastic resins containing acidic protons. Specific examples of modifiers for polyolefin resins include properties such as hardness, tensile strength, impact resistance, heat resistance, weather resistance, workability, adhesion, and compatibility. be able to. Further, as a modifier for the acidic proton-containing thermoplastic resin, specifically, while suppressing or preventing deterioration of various properties (heat resistance, hardness, tensile strength, etc.) of the acidic proton-containing thermoplastic resin, Properties such as toughness, tensile strength, impact strength, heat resistance, weather resistance, workability, adhesion and compatibility can be modified. Examples of the acidic proton-containing thermoplastic resin include polycarbonate, polyarylate, and polyamide.

This application claims 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. It is claimed. The entire contents of the specifications of Japanese Patent Application No. 2019-004296 filed on January 15, 2019 and Japanese Patent Application No. 2019-237076 filed on December 26, 2019 are included in this application. Incorporated for reference.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

(1) Preparation of resin composition (1-1) Preparation Example 1
40 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation, styrene unit content: 20% by mass) as SEBS block copolymer and toluene were placed in a 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen inlet pipe. 200 g was charged and heated to 80° C. with stirring to dissolve the SEBS block copolymer. 48 g of isopropenyloxazoline (IPO) 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 (manufactured by Kayaku Akzo Co., Ltd., Kayacarbon (registered trademark) BIC-75) in 1.6 g of toluene was added thereto, and the mixture was stirred for 15 minutes under reflux. reacted with Thereafter, an initiator solution prepared by dissolving 0.96 g of tert-butylperoxyisopropyl carbonate in 20 g of toluene was added dropwise for 5 hours at a constant rate to carry out solution polymerization while maintaining the temperature at 105°C to 120°C. After the end of the initiator feed, the mixture was subsequently aged under reflux for 3 hours. The resulting reaction liquid had a styrene residual rate of 4.2% by mass and an isopropenyloxazoline residual rate of 0.0% by mass. Thereafter, 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 is an SEBS block copolymer chain. A resin composition 1 containing a graft copolymer bonded to an ethylene-butylene block was obtained. 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-like appearance. The weight-average molecular weight and number-average molecular weight were determined by polystyrene conversion using gel permeation chromatography (GPC) (the weight-average molecular weight and 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 styrene-butadiene-styrene block copolymer, and the polymerizable double bond equivalent determined by the iodometric titration method is 2. 0.65 mmol/g. This corresponds to 82% by mass of the unit of formula (1) in the butadiene block, and the styrene unit content in Tuftec (registered trademark) P1083 is 20% by mass. The content of units of formula (1) in the copolymer was 66% by mass.

(1-2) Preparation Example 2
In Preparation Example 1, the same operation as in Preparation Example 1 was performed except that the amount of isopropenyloxazoline (IPO) used was changed from 48 g to 16 g and the amount of styrene (St) was changed from 112 g to 144 g. , a copolymer formed by polymerization of isopropenyloxazoline and styrene, and a graft copolymer in which the copolymer chain was bonded to the ethylene-butylene block of the SEBS block copolymer chain. . The resulting reaction liquid had a styrene residual rate of 6.5% by mass and an isopropenyloxazoline residual rate of 0.0% by mass. Resin composition 2 had a weight average molecular weight of 155,000, a number average molecular weight of 38,000, and an appearance of cloudy latex.

(1-3) Preparation Example 3
80 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation) and 240 g of toluene as SEBS block copolymers were charged into a 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen inlet pipe. C. to dissolve the SEBS block copolymer. 4.8 g of isopropenyloxazoline (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 (manufactured by Kayaku Akzo Co., Ltd., Kayacarbon (registered trademark) BIC-75) in 0.64 g of toluene was added thereto, and the mixture was stirred for 15 minutes under reflux. reacted with Thereafter, an initiator solution prepared by dissolving 0.96 g of tert-butylperoxyisopropyl carbonate in 20 g of toluene was added dropwise for 5 hours at a constant rate to carry out solution polymerization while maintaining the temperature at 105°C to 120°C. After the end of the initiator feed, the mixture was subsequently aged under reflux for 3 hours. The resulting reaction liquid had a styrene residual rate of 10.1% by mass and an isopropenyloxazoline residual rate of 0.0% by mass. Thereafter, 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 is an SEBS block copolymer chain. A resin composition 3 containing a graft copolymer bonded to an ethylene-butylene block was obtained. Resin composition 3 had a weight-average molecular weight of 175,000 and a number-average molecular weight of 63,000, and had a cloudy latex-like appearance.

(1-4) Preparation Example 4
40 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation) as SEBS block copolymer and 120 g of toluene were charged into a 2 L reactor equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen inlet pipe, and stirred for 80 minutes. C. to dissolve the SEBS block copolymer. 2.4 g of isopropenyloxazoline (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 prepared by dissolving 0.32 g of tert-butylperoxyisopropyl carbonate (manufactured by Kayaku Akzo Co., Ltd., Kayacarbon (registered trademark) BIC-75) in 1.6 g of toluene was added thereto, and the mixture was stirred under reflux for 15 minutes. reacted with Thereafter, a solution of monomer components 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 for 3 hours at a constant rate, and tert-butylperoxy was added to 20 g of toluene. An initiator solution in which 1.28 g of isopropyl carbonate was dissolved was added dropwise at a constant rate for 5 hours, and solution polymerization was carried out while maintaining the temperature at 105°C to 120°C. After the end of the initiator feed, the mixture was subsequently aged under reflux for 3 hours. The resulting reaction liquid had a styrene residual rate of 8.3% by mass and an isopropenyloxazoline residual rate of 0.0% by mass. Thereafter, 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 is an SEBS block copolymer chain. A resin composition 4 containing a graft copolymer bonded to an ethylene-butylene block of 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-like appearance.

(1-5) Preparation Example 5
306 g of toluene, 9.45 g of isopropenyloxazoline (IPO), and 305.55 g of styrene (St) were charged in a 2 L reactor equipped with a stirrer, temperature sensor, cooling tube, and nitrogen inlet tube, and the oil bath temperature was adjusted while passing nitrogen. was heated to 120°C. An initiator solution prepared by dissolving 1.37 g of tert-amylperoxy 3,5,5-trimethylhexanoate (manufactured by Kayaku Akzo Co., Ltd., Kayaester (registered trademark) AN) in 9.0 g of toluene was added thereto, The reaction was run under reflux with stirring for 15 minutes. After that, a solution prepared by dissolving 17.55 g of isopropenyloxazoline (IPO) and 567.45 g of styrene (St) in 558 g of toluene was added dropwise for 3 hours at a constant rate, and then tert-amylperoxy 3,5, An initiator solution in which 39.13 g of 5-trimethylhexanoate was dissolved was added dropwise at a constant rate for 5 hours, and solution polymerization was carried out while maintaining the temperature at 105°C to 120°C. After finishing the supply of the initiator, the mixture was aged under reflux for 3 hours. The resulting reaction solution was then cooled and slowly added to 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, thereby obtaining a resin composition 5 containing a copolymer (oxazoline group-containing polymer) polymerized from isopropenyloxazoline and styrene. Obtained. Resin composition 5 had a weight average molecular weight of 200,000, a number average molecular weight of 100,000, and was colorless and transparent in appearance.

(1-6) Preparation Example 6
Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation), which is an SEBS block copolymer, was used as resin composition 6 .

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

(1-8) Preparation Example 8
40 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation, styrene unit content: 20% by mass) as SEBS block copolymer and toluene were placed in a 2 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen inlet pipe. 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 oil bath temperature was raised to 120° C. while passing nitrogen. An initiator solution prepared by dissolving 0.64 g of tert-butylperoxyisopropyl carbonate (manufactured by Kayaku Akzo Co., Ltd., Kayacarbon (registered trademark) BIC-75) in 1.6 g of toluene was added thereto, and the mixture was stirred for 15 minutes under reflux. reacted with Thereafter, an initiator solution prepared by dissolving 3.0 g of tert-butylperoxyisopropyl carbonate in 20 g of toluene was added dropwise for 5 hours at a constant rate to carry out solution polymerization while maintaining the temperature at 105°C to 120°C. After the end of the initiator feed, the mixture was subsequently aged under reflux for 3 hours. The resulting reaction liquid had a styrene residual rate of 2.3% by mass, an acrylonitrile residual rate of 0.2%, and an isopropenyloxazoline residual rate of 0.3% by mass. After that, the resulting 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 obtain a copolymer formed by polymerization of isopropenyloxazoline, acrylonitrile, and styrene, and a SEBS block copolymerization of the copolymer chain. A resin composition 8 containing the graft copolymer bonded to the ethylene-butylene blocks of the coalescing chain was obtained. Resin composition 8 had a weight average molecular weight of 236,000, a number average molecular weight of 32,000, and an appearance of cloudy latex.

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

(2) Solubility Test Resin compositions 1 to 4 and 7 to 9 were each added to tetrahydrofuran (THF) so as to have a concentration of 20% by mass, and mixed for 30 minutes with a paint shaker. When the resin THF solution after mixing was observed, resin compositions 1 to 4 and 8 were milky white translucent uniform liquids, and resin composition 9 was a colorless and transparent uniform liquid, whereas resin composition 7 was a transparent and colorless uniform liquid. separated into two layers. Resin compositions 1 to 4, 8, and 9 containing a copolymer obtained by grafting an oxazoline group-containing polymer chain to an SEBS block copolymer chain are resin compositions obtained by blending an oxazoline group-containing polymer and an SEBS block copolymer. Unlike 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 50 mL capped glass container (manufactured by Maruem Co., Ltd., screw tube bottle), the lid was closed, and the mixture was shaken and stirred with a paint shaker to prepare a resin solution having a concentration of 20% by mass. The test plate was coated with the resin solution using a #60 bar coater and dried at 80° C. for 30 minutes to form a coating film having a thickness of about 20 μm. The blade of a utility knife (A-300, manufactured by NT) is applied perpendicularly to the coating film to make cuts, and 11 cross-cut lines are provided at intervals of 1 mm in columns and rows to form 1 mm ² squares. 100 squares were produced. For the 100 squares of the cut coating film, the number of coating films that did not peel off on the test plate (the number of remaining coating films) was measured, and the remaining rate of the coating film was calculated by the following formula: Remaining coating film Rate (%) = number of remaining coating films/100 x 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 of was evaluated as "C". A PP (polypropylene) plate (manufactured by Nippon Test Panel Co., Ltd., standard test plate PP, 2.0 mm×70 mm×150 mm) was used as the test plate.

Resin compositions 1 to 5, 8 and 9 were examined for adhesion to the PP plate. Table 1 shows the ratio of raw material charging amounts of resin compositions 1 to 5, the composition and average molecular weight of the resin composition, the results of the adhesion test, the ratio of the raw material charging amounts of resin compositions 8 and 9, and the composition of the resin composition. Table 2 shows the results of the average molecular weight and adhesion test. The composition of the resin composition indicates 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 monomer residual ratio. Resin compositions 1 to 4, 8, and 9 contain a copolymer having an SEBS-derived polymer chain (A) and a polymer chain (B) having units 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 formula (1). Resin composition 5 contained a copolymer composed only of polymer chains (B). Regarding adhesion to the PP plate, resin compositions 1 to 3 and 8 were evaluated as A, resin compositions 4 and 9 were evaluated as B, and resin composition 5 was evaluated as C. Resin compositions 1 to 4, 8 and 9 exhibited excellent adhesion to the PP plate.

(3-2) Coating film adhesion test 2
Put 6 g of the resin composition and 24 g of THF (tetrahydrofuran) in a glass container with a lid (manufactured by Maruem Co., Ltd., screw tube bottle) with a capacity of 50 mL, close the lid, shake and stir with a paint shaker to obtain a resin solution with a concentration of 20% by mass. prepared. The test plate was coated with the resin solution using a #60 bar coater and dried at 80° C. for 30 minutes to form a coating film having a thickness of about 20 μm. The blade of a utility knife (A-300, manufactured by NT) is applied perpendicularly to the coating film to make cuts, and 11 cross-cut lines are provided at intervals of 1 mm in columns and rows to form 1 mm ² squares. 100 squares were produced. A cellophane adhesive tape (Cellotape (registered trademark), manufactured by Nichiban Co., Ltd., width 15 mm) was attached to the surface of the cut 100-square coating film so as not to trap air, and the tape was firmly rubbed with a finger. After leaving it for 10 seconds, hold the edge of the tape and hold it perpendicular to the surface of the coating film. The residual rate was determined: residual rate (%) of coating film = number of remaining coating films/100 x 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 of was evaluated as "C". As test plates, PBT (polybutylene terephthalate) plate (manufactured by Engineering Test Service Co., PBT3300, 2.0 mm × 70 mm × 150 mm), PC (polycarbonate) plate (manufactured by Nippon Test Panel Co., standard test plate PC, 2.0 mm × 70 mm × 150 mm), and a PMMA (polymethyl methacrylate) plate (manufactured by Engineering Test Service, PMMA, 2.0 mm × 60 mm × 120 mm) was used.

Resin compositions 2 to 6, 8 and 9 were examined for adhesion to PBT, PC and PMMA plates. Results are shown in Tables 3 and 4. Resin compositions 2 to 4, 8, and 9 were evaluated as A for all test plates, while resin compositions 5 and 6 were inferior in adhesion, and resin composition 6 was evaluated as A. The test plate was also evaluated as C. Resin compositions 2 to 4, 8 and 9 also exhibited excellent adhesion to PBT, PC and PMMA plates. In addition, a resin composition containing a copolymer having a lower SEBS-derived polymer chain (A) content than Resin Composition 4, that is, a resin composition having a SEBS value of less than 20 in the SEBS/(IPO+St) ratio. Thus, resin compositions having a SEBS/(IPO+St) ratio of, for example, 15/85 or 10/90 were more effective than resin composition 6 in improving adhesion to PBT, PC and PMMA plates. In addition, an effect of improving adhesion to the PBT plate was obtained as compared with resin composition 5.

(4) Compatibility test A resin solution X in which a polystyrene resin (Epocross (registered trademark) RPS-1005; manufactured by Nippon Shokubai Co., Ltd.) was added to tetrahydrofuran (THF) so that the concentration was 20% by mass, and an olefin component-containing resin. (Tuftec (registered trademark) P1083; manufactured by Asahi Kasei Corporation) was added to tetrahydrofuran (THF) so that the concentration was 20% by mass, and 5 g each of resin solution Y was added to a 20 mL glass container (screw tube), and the lid was closed. The mixture was sealed and mixed with a shaker machine (shaking machine) for 1 minute to obtain a mixed resin solution (X+Y). The mixed resin solution (X+Y) separated into two layers when it was allowed to stand for 10 minutes after stirring and mixing. Next, 5 g of the resin solution 3 obtained by adding the resin composition 3 to tetrahydrofuran (THF) to a concentration of 20% by mass was added to the resin mixture solution (X + Y), sealed with a lid, and shaker machine (shaker) ) for 1 minute. The mixed resin solution (X+Y) to which the resin composition 3 was added was a uniform solution that did not separate into two layers even after standing for 10 minutes after stirring and mixing. That is, the resin composition 3 containing a copolymer obtained by grafting an oxazoline group-containing polymer chain to an SEBS block copolymer chain improves the miscibility between the polystyrene resin and the polystyrene 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 and adhesives that enhance the adhesion between various substrates such as metals and plastics and resin coating layers, compatibilizers for various resins, and additives. , can be used as a modifier. Specifically, optical films, printed wiring boards, rubber reinforcing resins such as tire cords, various engineering plastics such as bumpers, instrument panels, and interior and exterior parts related to automobiles and transportation equipment such as electrical parts, and daily necessities such as home appliances, furniture, and miscellaneous goods. It is used for industrial materials such as related products, construction/civil engineering, stationery/office supplies.

Claims (11)

It 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, and the polymer chain (B) is the polymer a copolymer (P) grafted onto the chain (A); and

[In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
Containing an oxazoline group-containing polymer and a polymer having a polymer chain (Aa) having a unit represented by the following formula (1a) (provided that the polymer does not have an oxazoline group) ,

[In formula (1a), R ^1a to R ^4a each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
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,
Total content of the polymer chain (A) and the polymer chain (Aa) with respect to a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the polymer chain (Aa) A resin composition (Q) having a ratio of 5 parts by mass or more and 80 parts by mass or less. The resin composition (Q) according to claim 1, wherein the content of the unit represented by formula (1) in the polymer chain (A) is 50% by mass or more. The resin composition (Q) according to claim 1 or 2, wherein the content of 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 (B) further has an aromatic vinyl monomer-derived unit and/or an unsaturated carboxylic acid ester-derived unit,
In the polymer chain (B), the total content of units derived from the oxazoline group-containing monomer, units derived from the aromatic vinyl monomer and/or units derived from the unsaturated carboxylic acid ester is 80% by mass or more. The resin composition (Q) according to any one of claims 1 to 3 . The unit represented by the formula (1) and the unit represented by the formula (1a) are The resin composition (Q) according to any one of claims 1 to 4 , wherein the total content of units represented by is 3 parts by mass or more and 80 parts by mass or less. The content ratio of units derived from the oxazoline group-containing monomer is 0.00 parts per 100 parts by mass in total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the polymer chain (Aa). The resin composition (Q) according to any one of claims 1 to 5 , which is 5 parts by mass or more and 49 parts by mass or less. A primer comprising the resin composition (Q) according to any one of claims 1 to 6 . A resin molded article comprising a layer containing the resin composition (Q) according to any one of claims 1 to 6 formed on the surface of a resin substrate. 9. The resin molding according to claim 8 , wherein the resin base material is a hydrocarbon resin or a resin having a heteroatom-containing group or a heteroatom-containing bond. A compatibilizer comprising the resin composition (Q) according to any one of claims 1 to 6 . A monomer component containing an oxazoline group-containing monomer is polymerized in the presence of a polymer having a polymer chain (Aa) having a unit represented by the following formula (1a) to obtain a polymer represented by the following formula (1). obtaining 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 formula (1a), R ^1a to R ^4a each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]

[In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
A method for producing a resin composition (Q) containing the copolymer (P), the oxazoline group-containing polymer, and the polymer having the polymer chain (Aa),
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,
Total content of the polymer chain (A) and the polymer chain (Aa) with respect to a total of 100 parts by mass of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the polymer chain (Aa) A method for producing a resin composition (Q) in which the proportion is 5 parts by mass or more and 80 parts by mass or less.