TW202037625A - 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 them.

In the past, oxazoline group-containing polymers have been known (for example, Patent Documents 1 and 2). The oxazoline group-containing polymer disclosed in Patent Documents 1 and 2 is a copolymer of 2-isopropenyl-2-oxazoline and styrene or further copolymerized with acrylonitrile. According to the characteristic of oxazoline group Polar effect, when used as a compatibilizer for various resins, it can be used in a primer for improving adhesion to a substrate. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 4-81458 Patent Document 2: Japanese Patent Application Publication No. 10-46010

[The problem to be solved by the invention]

When the inventors of the present invention studied the adhesion between the oxazoline group-containing polymer disclosed in Patent Documents 1 and 2 and various types of substrates, they found that polyolefins, etc., have relatively low polarity. The formed substrate did not show sufficient adhesion. The present invention was completed in view of the above-mentioned facts, and its object is to provide a copolymer (P) that can exhibit high adhesion even to substrates with relatively low polarity (resin substrates, etc.) and a combination of resins containing them物(Q). [Means to solve the problem]

[式(1)中，R¹ ~R⁴ 分別獨立表示氫原子或碳數1~20的烷基] [2]如[1]所記載之共聚合物(P)，其中，聚合物鏈(B)為在聚合物鏈(A)中進行接枝。 [3]如[1]或[2]所記載之共聚合物(P)，其中，上述聚合物鏈(A)中，上述式(1)表示的單元的含有比例為50質量%以上。 [4]如[1]~[3]中任一項所記載之共聚合物(P)，其中，上述聚合物鏈(B)中，來自含噁唑啉基的單體的單元的含有比例為1質量%以上50質量%以下。 [5]如[1]~[4]中任一項所記載之共聚合物(P)，其中，上述聚合物鏈(A)為具有： 具有上述式(1)表示的單元的聚合物嵌段(a1)與具有來自芳香族乙烯單體的單元的聚合物嵌段(a2)。 [6]如[1]~[5]中任一項所記載之共聚合物(P)，其中，上述聚合物鏈(B)進一步具有來自芳香族乙烯單體的單元及/或來自不飽和羧酸酯的單元，上述聚合物鏈(B)中，來自含噁唑啉基的單體的單元與來自芳香族乙烯單體的單元及/或來自不飽和羧酸酯的單元的合計含有比例為80質量%以上。 [7]一種樹脂組合物(Q)，為含有[1]~[6]中任一項所記載之共聚合物(P)。 [8]一種樹脂組合物(Q)，為含有[1]~[6]中任一項所記載之共聚合物(P)與含噁唑啉基的聚合物。 [9]如[8]所記載之樹脂組合物(Q)，其中，相對於上述共聚合物(P)與上述含噁唑啉基的聚合物與具有上述式(1)表示的單元的聚合物的合計為100質量份，上述聚合物鏈(A)的含有比例為5質量份以上80質量份以下。 [10]如[8]或[9]所記載之樹脂組合物(Q)，其中，相對於上述共聚合物(P)與上述含噁唑啉基的聚合物與具有上述式(1)表示的單元的聚合物的合計為100質量份，上述式(1)表示的單元的含有比例為3質量份以上80質量份以下。 [11]如[8]~[10]中任一項所記載之樹脂組合物(Q)，其中，相對於上述共聚合物(P)與上述含噁唑啉基的聚合物與具有上述式(1)表示的單元的聚合物的合計為100質量份，上述來自含噁唑啉基的單體的單元的含有比例為0.5質量份以上49質量份以下。 [12]一種底漆，為含有[1]~[6]中任一項所記載之共聚合物(P)或[7]~[11]中任一項所記載之樹脂組合物(Q)。 [13]一種樹脂成形體，為將含有[1]~[6]中任一項所記載之共聚合物(P)或[7]~[11]中任一項所記載之樹脂組合物(Q)的層形成在樹脂基材的表面。 [14]如[13]所記載之樹脂成形體，其中，上述樹脂基材為烴系樹脂，或是具有含雜原子的基或含雜原子的鍵結的樹脂。 [15]一種相溶化劑(compatibilizer)，為含有[1]~[6]中任一項所記載之共聚合物(P)或[7]~[11]中任一項所記載之樹脂組合物(Q)。 [16]一種共聚合物(P)的製造方法，共聚合物(P)具有：具有下述式(1)表示的單元的聚合物鏈(A)與具有來自含噁唑啉基的單體的單元的聚合物鏈(B)，其製造方法具有：在具有下述式(1)表示的單元的聚合物的存在下，與含有含噁唑啉基的單體的單體成份進行聚合的步驟。 [化2]

[式(1)中，R¹ ~R⁴ 分別獨立表示氫原子或碳數1~20的烷基] [發明的效果]The present invention includes the following inventions. [1] 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 . [化1]

[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) described in [1], wherein the polymer chain ( B) is grafting in the polymer chain (A). [3] The copolymer (P) as described in [1] or [2], wherein the content of the unit represented by the formula (1) in the polymer chain (A) is 50% by mass or more. [4] The copolymer (P) as described in any one of [1] to [3], wherein the content ratio of the unit derived from the oxazoline group-containing monomer in the polymer chain (B) It is 1% by mass to 50% by mass. [5] The copolymer (P) as described in any one of [1] to [4], wherein the polymer chain (A) has: a polymer block having a unit represented by the formula (1) The segment (a1) and the polymer block (a2) having a unit derived from an aromatic vinyl monomer. [6] The copolymer (P) according to any one of [1] to [5], wherein the polymer chain (B) further has units derived from aromatic vinyl monomers and/or derived from unsaturated The unit of carboxylic acid ester, the total content ratio of the unit derived from the oxazoline group-containing monomer and the unit derived from the aromatic vinyl monomer and/or the unit derived from the unsaturated carboxylic acid ester in the above-mentioned polymer chain (B) It is 80% by mass or more. [7] A resin composition (Q) containing the copolymer (P) described in any one of [1] to [6]. [8] A resin composition (Q) containing the copolymer (P) described in any one of [1] to [6] and an oxazoline group-containing polymer. [9] The resin composition (Q) according to [8], wherein the copolymer (P) and the oxazoline group-containing polymer are polymerized with the unit represented by the formula (1) The total of the substances is 100 parts by mass, and the content ratio of the polymer chain (A) is 5 parts by mass or more and 80 parts by mass or less. [10] The resin composition (Q) according to [8] or [9], wherein the copolymer (P) and the oxazoline group-containing polymer are represented by the above formula (1) The total of the polymer of the unit is 100 parts by mass, and the content ratio of the unit represented by the above formula (1) is 3 parts by mass or more and 80 parts by mass or less. [11] The resin composition (Q) according to any one of [8] to [10], wherein the copolymer (P) and the oxazoline group-containing polymer have the formula (1) The total of the polymer of the unit shown is 100 parts by mass, and the content ratio of the unit derived from the oxazoline group-containing monomer is 0.5 part by mass or more and 49 parts by mass or less. [12] A primer containing the copolymer (P) described in any one of [1] to [6] or the resin composition (Q) described in any one of [7] to [11] . [13] A resin molded body comprising the copolymer (P) described in any one of [1] to [6] or the resin composition described in any one of [7] to [11] ( The layer of Q) is formed on the surface of the resin substrate. [14] The resin molded body 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] A compatibilizer containing the copolymer (P) described in any one of [1] to [6] or the resin combination described in any one of [7] to [11]物(Q). [16] A method for producing a copolymer (P), the copolymer (P) having: a polymer chain (A) having a unit represented by the following formula (1) and a monomer having an oxazoline group-containing monomer The polymer chain of the unit (B), its production method has: in the presence of a polymer having the unit represented by the following formula (1), and the monomer component containing an oxazoline group-containing monomer polymerized step. [化2]

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

Because the copolymer (P) and the resin composition (Q) of the present invention have: a polymer chain (A) having a unit represented by the formula (1) and a polymer having a unit derived from an oxazoline group-containing monomer The chain (B) has good adhesion to various substrates containing 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 . 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 a polymer chain (A) and a polymer chain (B), it has good adhesion to various substrates and good affinity with various resins.

[化3]

The unit represented by the above formula (1) contained in the polymer chain (A) (hereinafter referred to as "the unit of formula (1)") has low adhesion to a substrate with low polarity and low polarity to improve the adhesion to the resin Interact in a way that is compatible with each other. Presumably, since the unit of formula (1) is the same as or similar to the polymer constituent unit of the low-polarity substrate and low-polarity resin, intermolecular force is generated between the low-polarity substrate and low-polarity resin. Interaction, and become a person who improves adhesion and affinity.

Examples of the alkyl group of R ¹ to R ⁴ in the above formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, Isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl and other linear or branched alkyl, cyclopropyl, cyclobutyl, cyclopentyl Cyclic alkyl groups such as cyclohexyl, cyclohexyl, cyclononyl, cyclodecyl, dicyclopentyl, adamantyl, etc. Among them, the alkyl group of R ¹ to R ⁴ is preferably a linear or branched alkyl group. The carbon number of the alkyl group of R ¹ to R ⁴ is preferably 1-12, more preferably 1-8, and still more preferably 1-6.

The unit of formula (1) can be formed by (co)polymerizing an olefin and a conjugated diene. From the viewpoint of facilitating the formation of (co)polymers in this way, R ¹ and R ² in formula (1) each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms as Preferably, R ³ and R ⁴ are hydrogen atoms. In addition, when the conjugated diene is (co)polymerized, when the group having a double bond is in the main chain or the side chain, it is preferable to hydrogenate the double bond to form a unit of formula (1). In addition, by (co)polymerizing a diene compound other than a conjugated diene, the double bond contained in the obtained (co)polymer may be hydrogenated to form a unit of formula (1).

As the olefin forming the unit of formula (1), for example, ethylene, propylene, 1-butene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 1-decene Tetraene, 1-octadecene, etc. The carbon number of the olefin is preferably 2 or more, more preferably 3 or more, more preferably 20 or less, more preferably 12 or less, and even more preferably 6 or less. As the conjugated diene, 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, etc. may be mentioned. The carbon number of the conjugated diene is preferably 4 or more, more preferably 5 or more, 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 containing polyethylene, polypropylene, polybutene, polyisobutylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, etc. as the main chain structure Part or all of is better. As the olefin (co)polymer, polyethylene, polypropylene, polybutene, 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 the "unit of formula (2)".

In the following formula (2-1), R ⁵ represents an alkenyl group with 2 to 20 carbons, and R ⁶ to R ⁸ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, or an alkenyl group with 2 to 20 carbons. . In the following formula (2-2), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group with 1 to 20 carbon atoms. R ⁹ and R ¹⁰ may be cis or trans. (trans) relationship. It is presumed that the unit represented by the following formula (2-1) and the unit represented by the following formula (2-2) are similar to the polymer constituent units of the low-polarity substrate and the low-polarity resin. , Interaction between resins to improve adhesion and affinity. Therefore, a copolymer (P) having a polymer chain (A) containing a unit of formula (1) and a unit of formula (2) also has excellent adhesion to various substrates and affinity with various resins. .

[化4]

Regarding the C1-C20 alkyl group of R ⁶ to R ¹⁰ in the formula (2-1) and formula (2-2), refer to the description of the above-mentioned R ¹ to R ⁴ alkyl group. As the alkenyl group having 2 to 20 carbon atoms in R ⁵ to R ⁸ of formula (2-1), ^one of the CC bonds contained in the alkyl group of R ¹ to R ⁴ is bonded by C=C. The substituted group is preferably a linear or branched alkenyl group. The carbon number of the alkenyl group of R ⁵ to R ⁸ is preferably 2-12, more preferably 2-8, and still more preferably 2-6. As the alkenyl group of R ⁵ to R ⁸ , a vinyl group is particularly preferred.

From the viewpoint of easy formation of 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, and R ^{6 is} a hydrogen atom Or a linear or branched alkyl group having 1 to 6 carbon atoms is preferred, and R ⁷ and R ⁸ are preferably hydrogen atoms. In addition, 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 Further better. Such a unit of formula (2) can be introduced into the polymer chain (A) by copolymerizing a diene and an olefin, or by polymerizing or copolymerizing a conjugated diene alone. As the dienes forming the unit of formula (2), 1,3-butadiene (alias: butadiene), 2-methyl-1,3-butadiene (alias: isoprene), 1 , 3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene (alias: diisobutene) and other alkanadienes are Among them, conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene are more preferable. The carbon number of the diene is preferably 4 or more, more preferably 5 or more, more preferably 20 or less, more preferably 10 or less, and even more preferably 8 or less.

The polymer chain (A) having the unit of formula (1) and the unit of formula (2), for example, may contain ethylene-isoprene copolymer, butene-butadiene copolymer, isobutylene-isoprene The copolymer chain of an olefin such as an olefin copolymer and a diene is preferably part or all of the main chain structure. The copolymer of olefin and diene is preferably 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 polymerizable double bonds, and examples include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, (methyl) ) Unsaturated carboxylic acids such as methyl acrylate and ethyl (meth)acrylate and their esters; aromatic ethylene such as styrene, vinyl toluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine, etc. Compounds; vinyl silanes such as ethylene trimethoxysilane, γ-(meth)acryloyloxypropylmethoxysilane (γ-(meth)acryloyloxypropylmethoxysilane), etc. 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 the main component. In the polymer chain (A), the content of the unit of formula (1) is preferably 50% by mass or more, and 55% by mass % Or more is more preferable, and 60 mass% or more is still more preferable. In this way, it becomes easy to increase the adhesion of the copolymer (P) to various substrates or to increase the affinity with various resins. The upper limit of the content ratio of the unit of formula (1) in the polymer chain (A) is not particularly limited. The polymer chain (A) may be composed of only the unit of formula (1), and the polymer chain (A) The content ratio of the unit of formula (1) 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 ratio of the unit of formula (1) and the unit of formula (2) may be 50% by mass or more, 55% by mass or more, or 60% by mass or more. In addition, the polymer chain (A) may be composed only of the unit of formula (1) and the unit of formula (2), and the unit of formula (1) and the unit of formula (2) in the polymer chain (A) The total content ratio of the product can 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) may contain units of formula (1) (or further include units of formula (2)) and units derived from other unsaturated monomers. The random copolymer of the unit can also be a block copolymer. When the polymer chain (A) is a block copolymer, the polymer chain (A) is polymerized with a polymer block (a1) having units of formula (1) and units derived from other unsaturated monomers. The block (a2) is preferred.

When the polymer chain (A) has a polymer block (a1) and a polymer block (a2), the polymer block (a1) may have a unit of formula (2) in addition to the unit of formula (1) , It further has units derived from other unsaturated monomers. Examples of other unsaturated monomers at this time include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, methyl (meth)acrylate, (meth) Unsaturated carboxylic acids such as ethyl acrylate and their esters; aromatic vinyl compounds such as styrene, vinyl toluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine, etc.; ethylene trimethoxysilane, γ -(Meth)acryloxypropyl methoxysilane and other vinyl silanes. Moreover, the polymer block (a1) contains more units of formula (1), the better. In the polymer block (a1), the content of the units of formula (1) is preferably 70% by mass or more, and 80% by mass % Or more is more preferable, and 90 mass% or more is still more preferable. The polymer block (a1) may be substantially composed of only the unit of the formula (1), for example, the unit of the formula (1) may be 99% by mass or more. Or, in the polymer block (a1), the total content of the unit of formula (1) and the unit of formula (2) is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass The above is further and better. The polymer block (a1) may also consist essentially of only the unit of formula (1) and the unit of formula (2), for example, the unit of formula (1) and the unit of formula (2) may be 99% by mass or more .

When the polymer chain (A) contains a polymer block (a2) having a unit derived from another unsaturated monomer, the polymer block (a2) is preferably composed of a unit derived from an aromatic vinyl monomer. At this time, the polymer block (a1) can be used as a soft component, and the polymer block (a2) can be used as a hard component, which can be used for copolymers (P) and resins containing copolymers (P). Composition (Q) imparts elasticity. The aromatic vinyl monomer is not particularly limited as long as it is a compound in which a vinyl group is bonded to an aromatic ring. Examples include styrene, vinyl toluene, methoxystyrene, α-methylstyrene, and α-hydroxymethyl Styrenic monomers such as styrene and α-hydroxyethylstyrene; vinyl monomers such as polycyclic aromatic hydrocarbons such as 2-vinylnaphthalene; N-vinylcarbazole, 2-vinylpyridine, vinylimidazole, vinylthiophene And other aromatic heterocyclic vinyl monomers. Among these, styrene-based monomers are preferred. Among the styrene-based monomers, not only styrene, but also styrene derivatives bonded with optional substituents on the vinyl and benzene ring of styrene. Examples of the substituent include alkyl, alkoxy Group, hydroxyl group, halogen group, amine group, nitro group, sulfonic acid group, etc. The alkyl group and alkoxy group bonded to styrene preferably have a carbon number of 1 to 4, and more preferably the carbon number 1-2. The alkyl group and alkoxy group bonded to styrene have at least the hydrogen atom Part of it may be substituted by a hydroxyl group or a halogen group. In addition, the styrene-based monomer is preferably unsubstituted styrene in which a substituent is not bonded to the vinyl group and benzene ring of styrene.

The polymer block (a2) may further contain units derived from other unsaturated monomers in addition to units derived from aromatic vinyl monomers. Examples of other unsaturated monomers at this time include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid, maleic anhydride, methyl (meth)acrylate, (meth) Unsaturated carboxylic acids such as ethyl acrylate and their esters; vinyl silanes such as ethylene trimethoxysilane, γ-(meth)acryloxypropyl methoxysilane, etc. In addition, the polymer block (a2) should contain more units derived from aromatic vinyl monomers, and the content of units derived from aromatic vinyl monomers in the polymer block (a2) should be 70% by mass or more. Preferably, it is more preferably 80% by mass or more, and more preferably 90% by mass or more. The polymer block (a2) may be substantially composed of only units derived from aromatic vinyl monomers. For example, the units derived from aromatic vinyl monomers may be 99% by mass or more.

As a polymer chain (A) containing 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 polymer chain (A) containing a unit of formula (1) ) And the polymer block (a1) of the unit of formula (2) and the polymer chain (A) of the polymer block (a2) having a unit derived from an aromatic vinyl monomer, for example, benzene Hydrogenated ethylene-butadiene-styrene block copolymers (for example, styrene-ethylene/butylene-styrene block copolymers), styrene-isoprene-styrene block copolymers Hydrogenated products (for example, styrene-ethylene/propylene-styrene block copolymer), hydrogenated products of styrene-isoprene block copolymer, etc. These hydrogenated products are those in which part or all of the diene units derived from the so-called butadiene and isoprene are hydrogenated, and all of them are hydrogenated. The polymer block (a1) is a unit of formula (1) If a part is hydrogenated, the polymer block (a1) has a unit of formula (1) and a unit of formula (2). In addition, in the above-mentioned designation, each block is distinguished by "-", and the designation "∕" in each block indicates the monomer unit in the constituent block.

As the polymer chain (A) composed of a block copolymer, a polymer block (a2) is preferably bonded to both sides of the polymer block (a1), and a triblock copolymer For better. Examples of such triblock copolymers include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, etc. . If the copolymer (P) has such a polymer chain (A), for example, when forming a resin coating film containing the copolymer (P), the flexibility of the coating film can be improved and the hardness and brittleness of the coating film can be reduced.

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

In addition, the polymer chain (A) preferably has the polymer block (a1) and does not have the polymer block (a2). In addition, although the polymer chain (A) is composed of the unit of the formula (1), it is preferably composed of the unit of the formula (1) and the unit of the formula (2), and is preferably composed of only the unit of the formula (1) The composition is better.

The weight average molecular weight of the polymer chain (A) is preferably 5,000 or more, more preferably 10,000 or more, more preferably 20,000 or more, more preferably 30,000 or more, and more preferably 300,000 or less More preferably, it is more preferably less than 250,000, more preferably less than 200,000, and more preferably less than 150,000. When the weight average molecular weight of the polymer chain (A) is in this range, the operability of the copolymer (P) can be improved.

The polymer chain (B) contained in the copolymer (P) will be described. 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 improve the adhesion and affinity between the copolymer (P) and the substrate with high polarity and the resin with high polarity. 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. Preferred examples include 2-vinyl-2-oxazoline, 5-methyl 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 2-isopropen-2-oxazoline, 4,4-dimethyl Vinyl oxazoline such as -2-isopropenyl-2-oxazoline. Among these, 2-isopropenyl-2-oxazoline is preferable from the viewpoint of easy availability and reactivity.

The polymer chain (B) may further contain units derived from other unsaturated monomers. Other unsaturated monomers are not particularly limited as long as they are compounds having polymerizable double bonds, and examples include vinyl esters such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile; Base) acrylic acid, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate and other unsaturated carboxylic acids and their esters; styrene, vinyl toluene, methoxystyrene, α-methylbenzene Aromatic vinyl compounds such as ethylene and 2-vinylpyridine; vinyl silanes such as ethylene trimethoxysilane and γ-(meth)acryloxypropyl methoxysilane. 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, and preferably has a unit derived from an aromatic vinyl A monomer unit and/or a unit derived from an unsaturated carboxylic acid ester are more preferable, and a unit derived from an aromatic vinyl monomer is more preferable. 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)acrylate. For the description of the aromatic vinyl monomer and the styrene-based monomer, refer to the description of the aromatic vinyl monomer and the styrene-based monomer of the polymer block (a2). If the polymer chain (B) has units derived from an aromatic vinyl monomer, the heat resistance of the copolymer (P) can be improved, and in addition, the polymer chain (B) can be promoted to contain oxazoline The reaction of the monomer. In addition, it is also more advantageous in terms of manufacturing cost.

As the above-mentioned unsaturated carboxylic acid ester (preferably (meth)acrylate), specifically, the oxygen atom of the ester bond of (meth)acrylic acid is linear, branched, or cyclic. (Meth)acrylates in which aliphatic hydrocarbon groups and aromatic hydrocarbon groups are bonded.

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

Examples of (meth)acrylates having a cyclic aliphatic hydrocarbon group include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and (meth) Cycloalkyl (meth)acrylates such as cyclohexyl acrylate; bridged ring (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, more preferably 5 or more, more preferably 20 or less, more preferably 12 or less Preferably, 10 or less is more preferable.

Examples of (meth)acrylates having aromatic hydrocarbon groups include phenyl (meth)acrylate, toluene (meth)acrylate, stubble (meth)acrylate, naphthyl (meth)acrylate, (meth) (Meth)acrylate such as binaphthyl acrylate and anthracene (meth)acrylate; aralkyl (meth)acrylate such as benzyl (meth)acrylate; benzene (meth)acrylate Aryloxyalkyl (meth)acrylates such as oxyethyl and the like. The number of carbon atoms in the aryl group of the aryl (meth)acrylate is preferably 6 or more, and 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, more preferably 14 or less, and more preferably 12 or less. The carbon number of the aryloxyalkyl group of the aryloxyalkyl (meth)acrylate is preferably 7 or more, more preferably 14 or less, and more preferably 12 or less.

If the polymer chain (B) has units derived from unsaturated carboxylic acid esters, the affinity of the copolymer (P) with various resins (especially resins with high polarity) can be further improved.

When the polymer chain (B) has units derived from other unsaturated monomers, the polymer chain (B) can be a random copolymer of oxazoline group-containing monomers and other unsaturated monomers, or it can be a block Copolymer, but from the viewpoint of easy manufacturability of the polymer chain (B), random copolymers are preferred.

The content ratio 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 more preferably 50% by mass or less, and 40% by mass or less is more preferable. In this way, it is easy to increase the adhesion enhancement effect and the affinity enhancement effect of the copolymer (P), and the formation of the polymer chain (B) also becomes easy.

When the polymer chain (B) has a unit derived from an aromatic vinyl monomer as a unit derived from another unsaturated monomer, the total content ratio of the unit derived from the oxazoline group-containing monomer and the unit derived from the aromatic vinyl monomer , Preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass or more.

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 the graft chain. In addition, according to the glossary of the basic terms of polymer science of the International Union of Pure and Applied Chemistry (IUPAC) Polymer Nomenclature Committee, it is stated that the so-called grafted polymer means "there is a bond in a certain polymer One or several types of blocks on the main chain are used as side chains, and when these side chains have a different structure (chemical structure) or configuration characteristics from the main chain, the polymer is called grafted high molecular". The graft copolymer can be obtained by a chain transfer reaction method, a polymer initiator method, a coupling method, a macromonomer method (macromonomer), a surface grafting method and other known manufacturing methods, and these can be used. There is only one of the methods, and you can use a combination of multiple methods. For details of these methods, please refer to the 6th edition of the Chemistry Outline (Edition of Applied Chemistry) compiled by the Chemical Society of Japan.

The copolymer (P) can be produced simply by addition polymerization of the monomer components forming the polymer chain (B) on the polymer chain (A). Therefore, the copolymer (P) will contain an oxazoline group-containing monomer in the presence of a polymer having a unit of formula (1) (hereinafter referred to as "base polymer (P1)") It is better to obtain the monomer components by polymerization. The details of the base polymer (P1) refer to the above description of the polymer chain (A). The base polymer (P1) is a unit further having the formula (2), and may also be a polymer containing a unit having the formula (1) Block (a1) and polymer block (a2) having units derived from other unsaturated monomers.

The polymer chain (B) is preferably grafted to the unit of formula (1) of the polymer chain (A). When the polymer chain (A) has the unit of formula (2), the polymer chain (B) may also be grafted on the unit of formula (2). The polymer chain (B) may be bonded to the carbon atom of the main chain of the unit of formula (1) or the unit of formula (2), or may be bonded to the main chain as a substituent (side chain) On the carbon atom of the hydrocarbon group. In addition, the polymer chain (B) may be bonded to the polymer chain (A) through an arbitrary bonding group (for example, an ester bond, an amide bond, a urethane bond, etc.).

The weight average molecular weight of the copolymer (P) is preferably 10,000 or more, more preferably 20,000 or more, more preferably 30,000 or more, still more preferably 50,000 or more, and particularly preferably 70,000 or more In addition, it is preferably less than 700,000, more preferably less than 500,000, more preferably less than 300,000, and even more preferably less than 200,000. When the weight average molecular weight of the copolymer (P) is in this range, the operability of the copolymer (P) can be improved.

The weight average molecular weight of the copolymer (P) is preferably 1.1 times or more the weight average molecular weight of the polymer chain (A), more preferably 1.2 times or more, more preferably 1.3 times or more, and more preferably 20 Times or less is preferable, 12 times or less is more preferable, 10 times or less is more preferable, 7 times or less is still more preferable, and 5 times or less is particularly preferable. In this way, it becomes easy to improve 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 base polymer (P1). By polymerizing the monomer components containing the oxazoline group-containing monomer in the polymerization step to form the polymer chain (B), the base polymer (P1) is given to the polymer chain (A), so that The copolymer (P) in which the polymer chain (B) is bonded to the polymer chain (A) is obtained.

From the polymer chain (B) in the polymerization step, when the unit of formula (1) of the base polymer (P1) (unit of formula (2) is present, it can be bonded to the unit of formula (1) or formula (2) From the viewpoint of the mode of the unit of ), the polymerization step preferably removes hydrogen from the hydrocarbon group of the unit. Thereby, free radicals can be generated there, and the monomer components forming the polymer chain (B) can undergo addition polymerization.

In the polymerization step, only one type of base polymer (P1) may be used, or two or more types may be used in combination. 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 that can be used in the formation of the polymer chain (B), in addition to the oxazoline group-containing monomer, other unsaturated monomers may 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, please refer to the description of the oxazoline group-containing monomer forming the above-mentioned polymer chain (B) and other unsaturated monomers forming the polymer chain (B).

The polymerization of the monomer components can be carried out using known polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization, but it is preferable to use a solution polymerization method. As the polymerization form, for example, any of a batch polymerization method and a continuous polymerization method can be used.

The amount of the base polymer (P1) used during polymerization is 100 parts by mass relative to the total of the base polymer (P1) and monomer components, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. 15 parts by mass or more is more preferable, and more preferably 80 parts by mass or less, more preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. The amount of monomer components used is 100 parts by mass relative to the total of the raw polymer (P1) and the monomer components, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and more preferably 40 parts by mass or more Preferably, it is more 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 an organic solvent used in general radical polymerization reactions can be used. Specifically, examples include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane and cyclohexane; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Class; Ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, anisole; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; siloxus such as methyl siloxu, ethyl siloxu, and butyl siloxus; alcohols such as methanol, ethanol, isopropanol, and n-butanol Classes; Nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile; chloroform; dimethyl sulfoxide, etc. Only one type of these solvents may be used, or two or more types may be used in combination.

The polymerization reaction between the raw polymer (P1) and the monomer components is preferably carried out in the presence of a polymerization initiator. As the polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-carboxamidinopropane), dihydrochloride, dimethyl-2, Azo compounds such as 2'-azobis(2-propionic acid methyl ester) and 4,4'-azobis(4-cyanovaleric acid); persulfates such as potassium persulfate; hydroperoxidation Cumene, dicumyl hydroperoxide, di-tertiary butyl peroxide, lauryl peroxide, benzyl peroxide, tertiary butyl peroxyisopropyl carbonate, peroxide-2- Tripentyl ethylhexanoate, tertiary pentyl peroxycaprylate, tertiary amyl peroxide isononanoate, tertiary pentyl peroxide isopropyl carbonate, tertiary pentyl peroxide-2-ethylhexyl carbonate Organic peroxides such as esters, etc. These may use only 1 type, and may use 2 or more types together. Among these, it is preferable to use organic peroxides with strong dehydrogenation power, and it is particularly preferable to use peroxycarbonate-based peroxides. The amount of the polymerization initiator used is, for example, 0.05 to 3 parts by mass relative to 100 parts by mass of the monomer components.

The total concentration of the raw polymer (P1) and monomer components in the reaction solution is preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 80% by mass % Or less is preferable, and 70 mass% or less is more preferable. In the polymerization reaction, the base polymer (P1), monomer components, polymerization catalyst, solvent, etc. may be added as appropriate.

The polymerization reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen or a gas flow. 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. For example, it is preferably carried out for 1 hour to 20 hours.

During the polymerization, the monomer components can be poured in at the same time or added separately. In addition, from the viewpoint of easy graft polymerization of the oxazoline group-containing monomer in the polymer chain (A) to form the polymer chain (B), it is preferable to pour the monomer components at the same time.

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

The resin composition (Q) may contain a copolymer (P) as a resin component, and may contain another polymer as a resin component. When the resin composition (Q) contains other polymers, as the other polymers, oxazoline group-containing polymers and/or polymers having units of formula (1) are preferably used, and oxazole-containing It is more preferable to have a line-based polymer, and by containing such other polymer, the homogeneity of the resin composition (Q) is improved.

The oxazoline group-containing polymer contained as another polymer in the resin composition (Q) may be a unit derived from an oxazoline group-containing monomer described in the above-mentioned polymer chain (B), or It may have a unit derived from another unsaturated monomer as described in the above-mentioned polymer chain (B). The oxazoline group-containing polymer has the same monomer-derived unit as the monomer-derived unit possessed by the polymer chain (B) from the viewpoint of improving the compatibility with the copolymer (P) For better.

The polymer having the unit of formula (1) contained in the resin composition (Q) as another polymer may be the one having the unit of formula (1) described in the above polymer chain (A), or it may be It is a polymer having a unit of formula (2) described in the polymer chain (A), and a unit derived from another unsaturated monomer. The polymer having the unit of formula (1) has the same monomer-derived unit as the monomer-derived unit possessed by the polymer chain (A) from the viewpoint of improving the compatibility with the copolymer (P) The unit is better.

In the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer and the polymer having the unit of formula (1) is 100 parts by mass, and the copolymer (P) is The content ratio is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, and 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 of the copolymer (P) alone, compared to the copolymer (P). ), the total of the polymer containing the oxazoline group and the polymer having the unit of formula (1) is 100 parts by mass, and the content ratio of the copolymer (P) may be 90 parts by mass or less, or 80 parts by mass Below, 70 parts by mass or less or 60 parts by mass or less.

In the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) is 100 parts by mass, and the polymer chain (A) The content ratio is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, more preferably 12 parts by mass or more, in addition, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, It is more preferably 60 parts by mass or less, and more preferably 50 parts by mass or less. In this way, it becomes easy to improve the adhesion of the resin composition (Q) to various substrates. In addition, the content ratio of the polymer chain (A) in the resin composition (Q) refers to the polymer chain (A) contained in the copolymer (P) and the polymer having the unit of formula (1) The total content ratio of the contained polymer chains (A).

In the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of the formula (1) is 100 parts by mass, and the unit of the formula (1) The content ratio is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and 60 Parts by mass or less is more preferable, and 50 parts by mass or less is more preferable. In this way, it becomes easy to improve the adhesion of the resin composition (Q) to various substrates. Or, in the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) is 100 parts by mass, formula (1) The total content ratio of the unit and the unit of formula (2) can be 3 parts by mass or more, 5 parts by mass or more or 10 parts by mass or more, in addition, it can also be 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 addition, the content ratio of the unit of the formula (1) in the resin composition (Q) means the unit of the formula (1) contained in the copolymer (P) and the polymer having the unit of the formula (1) The total content ratio of the unit of formula (1) contained, and the content ratio of the unit of formula (2) in the resin composition (Q) refer to the content of the formula (2) contained in the copolymer (P) The unit and the total content ratio of the unit of the formula (2) contained in the polymer having the unit of the formula (1). In addition, 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).

In the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer of the formula (1) is 100 parts by mass, which is derived from the oxazoline group-containing monomer The content ratio of the body unit is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, and more preferably 49 parts by mass or less, and 40 parts by mass or less More preferably, it is more preferably 30 parts by mass or less. In this way, it becomes easy to improve the adhesion of the resin composition (Q) to various substrates. In addition, the content ratio of the unit derived from the oxazoline group-containing monomer in the resin composition (Q) means the unit derived from the oxazoline group-containing monomer contained in the copolymer (P) and the oxazoline group-containing monomer The total content ratio of the unit derived from the oxazoline group-containing monomer contained in the oxazoline group-containing polymer.

In the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) is 100 parts by mass, and the unit of formula (1) is derived from The total content of oxazoline-based monomer units is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more . In this way, it becomes easy 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) in the resin composition (Q) to the unit derived from the oxazoline group-containing monomer is not particularly limited, and the resin composition (Q) may essentially consist of only the formula ( The unit of 1) is composed of a unit derived from an oxazoline group-containing monomer, and the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) is 100 parts by mass, the total content of the unit of formula (1) and the unit derived from the oxazoline group-containing monomer 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 The following. Or, in the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) is 100 parts by mass, formula (1) The total content ratio of the unit of the formula (2) and the unit derived from the oxazoline group-containing monomer can 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 Above, in addition, 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 total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of the formula (1) is 100 parts by mass, and the unit of the formula (1) The content ratio is 10 parts by mass or more, and the total content ratio of the unit of formula (1) and the unit derived from the oxazoline group-containing monomer is particularly preferably 20 parts by mass or more. Or, in the resin composition (Q), the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) is 100 parts by mass, formula (1) The total content ratio of the unit and the unit of formula (2) is 10 parts by mass or more, and the total content ratio of the unit of formula (1), the unit of formula (2) and the unit derived from the oxazoline group-containing monomer It is particularly preferable to be 20 parts by mass or more.

In the resin composition (Q), the total of the unit of formula (1) and the unit derived from the oxazoline group-containing monomer is 100 parts by mass, and the content of the unit of formula (1) is 10 parts by mass or more Preferably, 20 parts by mass or more is more preferable, more preferably 30 parts by mass or more, in addition, 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 more preferable . In this way, it becomes easy to improve the adhesion of the resin composition (Q) to various substrates. Or, in the resin composition (Q), with respect to the total of the unit of formula (1), the unit of formula (2), and the unit derived from the oxazoline group-containing monomer is 100 parts by mass, the formula (1) The total content ratio of the unit and the unit of formula (2) may be 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, and may be 98 parts by mass or less, 95 parts by mass or less, or 93 parts by mass or less.

The content ratio of the unit of formula (1) in the resin composition (Q), the content ratio of the unit of formula (2), and the content ratio of the unit derived from the oxazoline group-containing monomer can be obtained from the copolymer (P) The amount of each monomer used when the oxazoline group-containing polymer is polymerized and the monomer residual ratio (the ratio of the unreacted monomer remaining in the resulting reaction solution) is calculated The amount of each unit mixed in the copolymer (P) and the oxazoline group-containing polymer is determined. 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 polymer (P1), the raw polymer (P1) The amount of the unit of formula (1) and the unit of formula (2) contained, the content ratio of the unit of formula (1) in the resin composition (Q), the content ratio of the unit of formula (2), derived from The content ratio of the unit of the oxazoline group-containing monomer. At this time, the raw polymer (P1) reacts with all monomer components, and its residual rate is regarded as 0%. In addition, the calculated residual rate of the base polymer (P1) corresponding to the content ratio is only regarded as 0%, and the base polymer (P1) may be contained in the resin composition (Q).

In 100 parts by mass of the solid content of the resin composition (Q), the total content ratio of the copolymer (P) and the oxazoline group-containing polymer is preferably 50 parts by mass or more, more preferably 70 parts by mass or more , More preferably 80 parts by mass or more, more preferably 90 parts by mass or more. 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) may essentially consist of only the copolymer (P ) And an oxazoline group-containing polymer. For example, in 100 parts by mass of the solid content of the resin composition (Q), the total content of the copolymer (P) and the oxazoline group-containing polymer may also be It is 99 parts by mass or more. When the resin composition (Q) contains a solvent, the solid content of the resin composition (Q) means the amount of the resin composition (Q) other than the solvent.

The resin composition (Q) may also contain oxazoline group-containing polymers and polymers other than polymers having units of formula (1). Examples of such polymers include, for example, vinyl chloride and vinyl chloride. Halogen-containing polymers such as resins; acrylic polymers such as polymethyl methacrylate; polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile- Styrenic polymers such as butadiene-styrene copolymers; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; nylon 6, Polyamides such as nylon 66 and nylon 610; polyacetal; polycarbonate; polyphenylene ether; polyphenylene sulfide; polyether ether ketone; polysulfide; polyether sulfide; polyoxybenzylene (ployoxybenzylene) ); Polyamide imine; rubbery polymers such as polybutadiene rubber, (meth)acrylic rubber ABS resin, and ASA resin.

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; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. ; Ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, anisole; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methyl Esters such as oxybutyl acetate; ceroxu such as methyl siloxu, ethyl siloxu, and butyl siloxu; alcohols such as methanol, ethanol, isopropanol, and n-butanol ; Nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile; chloroform; dimethyl sulfide etc. These solvents may contain only one type or two or more types.

The resin composition (Q) may contain various additives. Examples of additives include, for example, hindered phenol-based, phosphorus-based, and sulfur-based antioxidants; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; ultraviolet absorbers ; Near-infrared absorber; ginseng (dibromopropyl) phosphate, triallyl phosphate, antimony oxide and other flame retardants; antistatic agents containing anionic, cationic, and nonionic surfactants; Coloring agents for inorganic pigments, organic pigments, dyes, etc.; organic fillers, inorganic fillers; resin modifiers; organic fillers, inorganic fillers, etc. 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 in the range of 0 to 2 parts by mass based on 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, more preferably 30,000 or more, more preferably 50,000 or more, and more preferably 70,000 or more Preferably, in addition, it is preferably 700,000 or less, more preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. The weight average molecular weight of the resin composition (Q) refers to the polystyrene conversion value measured by subjecting the resin composition (Q) to gel permeation chromatography. The resin composition (Q) contains a copolymer ( In the case of P) and an oxazoline group-containing polymer and a polymer having a unit of formula (1), the weight average molecular weight of the resin composition (Q) is the weight average molecular weight of all the plural types of polymers.

The weight average molecular weight of the resin composition (Q) is preferably 1.1 times or more the weight average molecular weight of the polymer chain (A) of the copolymer (P), more preferably 1.2 times or more, and more preferably 1.3 times or more Preferably, in addition, 20 times or less is preferable, 12 times or less is more preferable, 10 times or less is more preferable, 7 times or less is still more preferable, and 5 times or less is particularly preferable. In this way, it becomes easy 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 by polymerizing the above-mentioned base polymer (P1) and the monomer component containing the oxazoline group-containing monomer, the copolymer (P) In the case of polymerization, it is easy to perform polymerization together with the oxazoline group-containing polymer. In the method for producing the copolymer (P) explained above, along with the copolymer (P), the oxazoline group-containing polymer corresponding to the polymer chain (B) of the copolymer (P) is also produced at the same time, but At this time, by not separating the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) existing as the unreacted base polymer (P1), it is possible to A resin composition (Q) containing a copolymer (P), an oxazoline group-containing polymer, and a polymer having a unit of formula (1) was obtained. In the method for producing the resin composition (Q) at this time, the copolymer (P) and the oxazoline group-containing polymer with the formula can be obtained through the polymerization step described in the method for producing the copolymer (P) (1) A polymer of the unit.

The manufacturing method of the resin composition (Q) is not limited to the above-mentioned method, and the copolymer (P) may be isolated as a resin composition (Q) mixed with another polymer. In addition, in the method for producing the copolymer (P), after the graft copolymerization reaction of the base polymer (P1) is completed, another monomer may be added to perform the polymerization reaction to obtain the resin composition (Q ). Alternatively, a mixture of the copolymer (P) obtained in the above-mentioned method for producing the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit of formula (1) may be used as a further A resin composition (Q) in which another polymer (for example, another oxazoline group-containing polymer) is added. When other polymers are added and mixed, melt-kneading may also be performed. 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) comprise 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 , And become the one with good adhesion to various substrates from high polarity to low polarity (non-polar) and affinity with various resins. Therefore, it can be suitably used as a primer (also referred to as primer, primer, and sealant) for improving the adhesion when forming a resin layer on a substrate. For example, as a case where a coating layer mainly composed of acrylic polymer, urethane polymer, etc. is formed on a polymethyl methacrylate substrate or a polycarbonate substrate of a relatively high polarity resin substrate, As a case where a coating layer mainly composed of acrylic polymer, urethane polymer, etc. is formed on a polyolefin substrate of a resin substrate with a relatively low polarity, the copolymer (P) and the resin are combined The compound (Q) is used as a primer to improve the adhesion between the substrate and the coating layer.

The present invention also provides a resin molded body 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) forming the resin molded body of the present invention has good adhesion with various resin substrates, and it is not easy to peel off from the resin substrate. . In addition, the layer containing the copolymer (P) or the resin composition (Q) has high affinity with various resins ranging from high polarity to low polarity (non-polar), and other resins are further laminated on this layer. In the case of a layer (coating layer), the adhesion between the coating layer and the resin molded body is high, and it is difficult to cause defects such as peeling of the coating layer.

As the resin substrate constituting the resin molded body, a hydrocarbon resin or a resin having a heteroatom-containing group or a heteroatom-containing bond is preferable. As the above-mentioned hydrocarbon resins, any of aliphatic hydrocarbon resins, alicyclic hydrocarbon resins and aromatic hydrocarbon resins may be used, but aliphatic hydrocarbon resins are preferred, and polyolefin resins such as polyethylene and polypropylene are more preferred. good. Examples of the above-mentioned hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like. Examples of the heteroatom-containing group include, for example, a hydroxyl group, a carboxyl group, a sulfonic acid group, a urethane group, and the like. Examples of the heteroatom-containing bond include, for example, an ether bond, an ester bond, and a carbonate bond. , Amide bond, thioether bond, etc. As the resin having a heteroatom-containing group or a heteroatom-containing bond, a resin having at least one selected from a carboxyl group, an ester bond, and a carbonate bond is preferred.

Copolymer (P) and resin composition (Q) are also useful as miscibility agents for various resins. For example, they can improve the miscibility with low-polarity polyolefin resins and polyester resins, and can increase the unity of multiple resin mixtures. Liquid stability. When the copolymer (P) or the resin composition (Q) is used as a compatibilizer for various resins, the blending amount is 100 parts by mass, for example, 1 part by mass, 5 parts by mass relative to the total of the resin to be miscible The above is preferably, more preferably 10 parts by mass or more, for example, 60 parts by mass or less, preferably 55 parts by mass or less, and more preferably 50 parts by mass or less. In addition, it can also be used as an additive when resin is melt-kneaded, a dispersant when a composition containing resin and auxiliary materials (for example, fibers, fillers, pigments, etc.) is melt-kneaded, a modifier of resin or hot melt adhesive or asphalt use. Furthermore, by adding the copolymer (P) and the resin composition (Q) to the resin, it can be expected to improve compatibility, fluidity, heat resistance, impact resistance, and scratch resistance. Improve the paintability of the molded product surface and prevent blocking. For example, the copolymer (P) and the resin composition (Q) can be used as a modifier for polyolefin resins with low polarity and as a modifier for various thermoplastic resins containing acidic protons. And, as a modifier of polyolefin resin, specifically, it can modify the hardness, tensile strength, impact strength, heat resistance, weather resistance, processability, adhesion and compatibility of polyolefin resin. Characteristics. In addition, as a modifier of acidic proton-containing thermoplastic resins, specifically, it suppresses or prevents the degradation of various characteristics (heat resistance, hardness, tensile strength, etc.) of acidic proton-containing thermoplastic resins, and at the same time It can be modified such as hardness, tensile strength, impact resistance, heat resistance, weather resistance, processability, adhesion, and compatibility. Examples of the thermoplastic resin containing acidic protons include, for example, polycarbonate, polyarylate, and polyamide.

This application claims the right 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. The entire contents of the Japanese Patent Application No. 2019-004296 filed on January 15, 2019 and the Japanese Patent Application No. 2019-237076 filed on December 26, 2019 are incorporated as references for this application. [Example]

Hereinafter, the present invention will be specifically explained by examples and comparative examples, but the present invention is not limited to these.

(1) Preparation of resin composition (1-1) Preparation example 1 In a 2L reaction tank equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction tube, pour the SEBS block copolymer Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation, styrene unit content 20 mass) %) 40 g and 200 g of toluene are heated to 80°C while stirring to dissolve the SEBS block copolymer. To this, 48 g of isopropenyl oxazoline (IPO) and 112 g of styrene (St) were added, and the temperature of the oil bath was raised to 120°C while blowing nitrogen. A starter solution prepared by dissolving 0.64 g of tertiary butyl peroxyisopropyl carbonate (manufactured by KAYAKU NOURYON CORPORATION, Kayakarubon (registered trademark) BIC-75) in 1.6 g of toluene was added and stirred for 15 minutes The reaction was carried out under reflux. After that, the starter solution prepared by dissolving 0.96 g of isopropyl tributyl peroxide in 20 g of toluene was dripped and supplied at a constant rate for 5 hours, and the solution was maintained at 105°C to 120°C. polymerization. After the supply of the starter was finished, the maturing was continued for 3 hours under reflux. 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, toluene was added and diluted so that the solid content became 40% by mass, and then added to a large amount of n-hexane while slowly stirring. The precipitated white solid was taken out, and the solvent was removed by drying at 90°C for about 3 days to obtain a copolymer composed of isopropenyl oxazoline and styrene and the copolymer chain was copolymerized in SEBS block Resin composition 1 of a graft copolymer in which the ethylene-butene block of the material chain is bonded. The weight average molecular weight of the resin composition 1 was 162,000, the number average molecular weight was 35,000, and the appearance was white turbid emulsion. The weight average molecular weight and the number average molecular weight are obtained by converting polystyrene using gel permeation chromatography (GPC) (the weight average molecular weight and the number average molecular weight in the following preparation examples are both obtained in the same way).

In addition, Tuftec (registered trademark) P1083 of the SEBS block copolymer used as a raw material is a hydrogenated product of a styrene-butadiene-styrene block copolymer. The polymerizability determined by the iodine titration method The double bond equivalent is 2.65 mmol/g. This corresponds to the ratio of the unit of formula (1) in the butadiene block being 82% by mass. Since the styrene unit content in Tuftec (registered trademark) P1083 is 20% by mass, the raw material SEBS block copolymer The content ratio of the unit of formula (1) is 66% by mass.

(1-2) Modulation example 2 In Preparation Example 1, the use amount of isopropenyloxazoline (IPO) was changed from 48 g to 16 g, and the use amount of styrene (St) was changed from 112 g to 144 g, and the same operation as Preparation Example 1 was performed. Obtained containing a copolymer formed by the polymerization of isopropenyl oxazoline and styrene and a graft copolymer in which the copolymer chain is bonded to the ethylene-butene block of the SEBS block copolymer chain The resin composition 2. 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 weight average molecular weight of the resin composition 2 was 155,000, the number average molecular weight was 38,000, and the appearance was white turbid emulsion.

(1-3) Modulation example 3 In a 2L reaction tank equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction tube, 80 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation) as a SEBS block copolymer and 240 g of toluene were poured into one side While stirring, heat to 80°C to dissolve the SEBS block copolymer. To this, 4.8 g of isopropenyloxazoline (IPO) and 155.2 g of styrene (St) were added, and the temperature of the oil bath was raised to 120°C while blowing nitrogen gas. A starter solution prepared by dissolving 0.64 g of tertiary butyl peroxide (manufactured by KAYAKU NOURYON CORPORATION, Kayakarubon (registered trademark) BIC-75) in 0.64 g of toluene was added, and stirred for 15 minutes The reaction was carried out under reflux. Thereafter, the initiator solution in which 0.96 g of isopropyl tributyl peroxide was dissolved in 20 g of toluene was dropped and supplied at a constant rate for 5 hours, and solution polymerization was performed while maintaining the temperature at 105°C to 120°C. After the supply of the starter was finished, the maturing was continued for 3 hours under reflux. The residual rate of styrene in the obtained reaction liquid was 10.1% by mass, and the residual rate of isopropenyloxazoline was 0.0% by mass. After that, the obtained reaction solution was cooled, toluene was added to dilute it so that the solid content became 40% by mass, and then added to a large amount of n-hexane while slowly stirring. The precipitated white solid was taken out, and the solvent was removed by drying at 90°C for about 3 days to obtain a copolymer composed of isopropenyl oxazoline and styrene and the copolymer chain was copolymerized in SEBS block Resin composition 3 of graft copolymer in which the ethylene-butene block of the material chain is bonded. The weight average molecular weight of the resin composition 3 was 175,000, the number average molecular weight was 63,000, and the appearance was white turbid emulsion.

(1-4) Modulation example 4 In a 2L reaction tank equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction tube, 40 g of Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation) as a SEBS block copolymer and 120 g of toluene are poured into one side While stirring, heat to 80°C to dissolve the SEBS block copolymer. To this, 2.4 g of isopropenyl oxazoline (IPO) and 77.6 g of styrene (St) were added, and the temperature of the oil bath was increased to 120°C while blowing nitrogen. A starter solution prepared by dissolving 0.32 g of isopropyl carbonate tertiary butyl peroxide (manufactured by KAYAKU NOURYON CORPORATION, Kayakarubon (registered trademark) BIC-75) in 1.6 g of toluene was added to it and stirred for 15 minutes The reaction was carried out under reflux. After that, a solution of monomer components in which 2.4 g of isopropenyl oxazoline (IPO) and 77.6 g of styrene (St) were dissolved in 50 g of toluene was dropped and supplied at a constant rate for 3 hours, and the solution was added to 20 g of toluene. The starter solution in which 1.28 g of tertiary butyl peroxide is dissolved is fed dropwise at a constant rate for 5 hours, and solution polymerization is performed while maintaining the temperature at 105°C to 120°C. After the supply of the starter was finished, the maturing was continued for 3 hours under reflux. The residual rate of styrene in the obtained reaction liquid was 8.3% by mass, and the residual rate of isopropenyloxazoline was 0.0% by mass. After that, the obtained reaction solution was cooled, toluene was added so that the solid content became 40% by mass, diluted, and then added while slowly stirring in a large amount of n-hexane. The precipitated white solid was taken out, and the solvent was removed by drying at 90°C for about 3 days to obtain a copolymer composed of isopropenyl oxazoline and styrene and the copolymer chain was copolymerized in SEBS block Resin composition 4 of a graft copolymer in which the ethylene-butene block of the material chain is bonded. The weight average molecular weight of the resin composition 4 was 172,000, the number average molecular weight was 51,000, and the appearance was white turbid emulsion.

(1-5) Preparation example 5 Pour 306 g of toluene, 9.45 g of isopropenyl oxazoline (IPO), and 305.55 g of styrene (St) into a 2L reaction tank equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen inlet pipe. Increase the temperature of the oil bath to 120°C while nitrogen. A starter solution prepared by dissolving 1.37 g of 3,5,5-trimethylhexanoic acid tertiary amyl peroxide (manufactured by KAYAKU NOURYON CORPORATION, Kayaester (registered trademark) AN) in 9.0 g of toluene was added to it, The reaction was carried out under reflux while stirring for 15 minutes. Then, a liquid prepared by dissolving 17.55 g of isopropenyl oxazoline (IPO) and 567.45 g of styrene (St) in 558 g of toluene was dripped and fed at a constant rate for 3 hours, and then peroxidized in 27 g of toluene The starter solution prepared by dissolving 39.13 g of 3,5,5-trimethylhexanoic acid tripentyl ester was dripped and supplied at a constant rate for 5 hours, and solution polymerization was performed while maintaining the temperature at 105°C to 120°C. After the supply of the starter was finished, the maturing was continued for 3 hours under reflux. After that, the obtained reaction solution was cooled, and added while slowly stirring in a large amount of n-hexane. The precipitated white solid was taken out and dried at 90°C for about 3 days to remove the solvent to obtain a resin containing a copolymer (oxazoline group-containing polymer) formed by the polymerization of isopropenyl oxazoline and styrene Composition 5. The weight average molecular weight of the resin composition 5 was 200,000, the number average molecular weight was 100,000, and the appearance was colorless and transparent.

(1-6) Modulation example 6 As the resin composition 6, Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation), which is a SEBS block copolymer, was used.

(1-7) Preparation example 7 4.8 g of resin composition 5 and 1.2 g of resin composition 6 (prepared at a mass ratio of 8:2) were mixed to form a resin composition 7.

(1-8) Preparation example 8 In a 2L reaction tank equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction tube, pour the SEBS block copolymer Tuftec (registered trademark) P1083 (manufactured by Asahi Kasei Corporation, styrene unit content 20 mass) %) 40 g and 350 g of toluene are heated to 80°C while stirring to dissolve the SEBS block copolymer. To this, 16 g of isopropenyl oxazoline (IPO), 32 g of acrylonitrile (AN), and 112 g of styrene (St) were added, and the temperature of the oil bath was raised to 120° C. while blowing nitrogen. A starter solution prepared by dissolving 0.64 g of tertiary butyl peroxide isopropyl carbonate (manufactured by KAYAKU NOURYON CORPORATION, Kayakarubon (registered trademark) BIC-75) in 1.6 g of toluene was added to it, and stirred for 15 minutes. The reaction is carried out under reflux. After that, the starter solution prepared by dissolving 3.0 g of tributyl peroxide isopropyl carbonate in 20 g of toluene was dripped and supplied 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 supply of the starter was finished, the maturing was continued for 3 hours under reflux. The residual rate of styrene in the obtained reaction liquid was 2.3% by mass, the residual rate of acrylonitrile was 0.2%, and the residual rate of isopropenyloxazoline was 0.3% by mass. After that, the obtained reaction solution was cooled, and added to a large amount of n-hexane while slowly stirring. The precipitated white solid was taken out, and the solvent was removed by drying at 90°C for about 3 days to obtain a copolymer formed by polymerization of isopropenyloxazoline, acrylonitrile and styrene, and the copolymer chain is in SEBS Resin composition 8 of graft copolymer in which the ethylene-butene blocks of the block copolymer chain are bonded. The weight average molecular weight of the resin composition 8 was 236,000, the number average molecular weight was 32,000, and the appearance was white turbid emulsion.

(1-9) Modulation example 9 In Preparation Example 8, 16 g of isopropenyl oxazoline (IPO), 32 g of acrylonitrile (AN), and 112 g of styrene (St) as monomer components were changed to 16 g of isopropenyl oxazoline (IPO) and Except for 144 g of methyl methacrylate (MMA), the same operation as in adjustment example 8 was performed to obtain a copolymer containing isopropenyl oxazoline and methyl methacrylate polymerized and the copolymer chain was The resin composition 9 of graft copolymer in which the ethylene-butene block of the SEBS block copolymer chain is bonded. 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 weight average molecular weight of the resin composition 9 was 282,000, the number average molecular weight was 30,000, and the appearance was colorless and transparent.

(2) Solubility test Tetrahydrofuran (THF) was added to the resin compositions 1 to 4 and 7 to 9 so as to have a concentration of 20% by mass, and mixed with a paint shaker for 30 minutes. When observing the mixed resin THF solution, with respect to the resin compositions 1 to 4 and 8, it became a milky white translucent uniform liquid, the resin composition 9 became a colorless and transparent uniform liquid, and the resin composition 7 was separated into two layers. Resin compositions 1 to 4, 8, 9 containing copolymers containing oxazoline group-containing polymer chains grafted onto SEBS block copolymer chains and the oxazoline group-containing polymer and SEBS block The resin composition 7 in which the copolymer is blended is different, and becomes the one with better uniformity.

(3) Coating film adhesion test (3-1) Coating film adhesion test 1 Pour 6 g of the resin composition and 24 g of THF into a 50 mL glass container with a lid (manufactured by Maruemu, screw vial) and close Put the lid on, shake and stir with a paint shaker to prepare a resin solution with a concentration of 20% by mass. The resin solution was applied on the test plate using a #60 rod coater and dried at 80°C for 30 minutes to form a coating film with a thickness of about 20 μm. Scribe the blade of a cutting knife (manufactured by NT Incorporated, A-300) perpendicular to the coating film and cut out the cuts. By making 11 intersecting lines in the vertical and horizontal rows at 1 mm intervals, 100 pieces of 1mm ² square. For the cut 100 pieces of coating film, calculate the number of coating films that did not peel off on the test board (the number of residual coating films), and calculate the residual rate of coating film according to the following formula: residual rate of coating film (%) = coating Remaining number of film/100×100. If the residual rate of the coating film is 80% or more, it is evaluated as "A", the residual rate of the coating film is 20% or more and less than 80% is evaluated as "B", and the remaining rate is less than 20% is evaluated as "C"". As the test plate, a PP (polypropylene) plate (manufactured by Japan Testpanel, standard test plate PP, 2.0 mm×70 mm×150 mm) was used.

The adhesion to PP board was discussed for resin compositions 1 to 5, 8, and 9. The ratio of the feed amount of the raw materials of the resin compositions 1 to 5, the composition and average molecular weight of the resin composition, and the results of the adhesion test are shown in Table 1. The ratio of the feed amount of the raw materials of the resin compositions 8 and 9, and the resin composition Table 2 shows the composition and average molecular weight of the product, and the results of the adhesion test. The composition of the resin composition indicates the content ratio of each unit based on the amount of the polymer, and is calculated from the amount of raw materials fed and the monomer residual ratio. Resin compositions 1 to 4, 8, 9 contain a copolymer having a polymer chain (A) derived from SEBS and a polymer chain (B) having units derived from an oxazoline group-containing monomer, and the polymer chain ( A) As a unit of formula (1), it contains an ethylene unit (-CH ₂ -CH ₂ -) and a butene unit (-CH(-CH ₂ -CH ₃ )-CH ₂ -), and the resin composition 5 contains Copolymers composed only of polymer chains (B). The adhesion of the PP board was evaluated as A with respect to the resin compositions 1 to 3, 8, the resin composition 4, 9 was evaluated as B, and the resin composition 5 was evaluated as C. Resin compositions 1 to 4, 8, and 9 have good adhesion to the PP board.

[Table 1] Resin composition No. 1 2 3 4 5 Feed in IPO/St ratio Mass ratio 30/70 10/90 3/97 3/97 3/97 SEBS/(IPO+St) ratio Mass ratio 20/80 20/80 33/67 20/80 ─ composition Formula (1) unit content ratio quality% 13 14 twenty three 14 0 Formula (2) unit content ratio quality% 3 3 5 3 0 IPO unit content ratio quality% 25 8 2 3 3 Mw ×10 ⁴ 16.2 15.5 17.5 17.2 20.0 Mn ×10 ⁴ 3.5 3.8 6.3 5.1 10.0 Adhesion (PP board) ─ A A A B C

[Table 2] Resin composition No. 8 9 Feed in Monomer component ratio Mass ratio St/AN/IPO/= 70/20/10 MMA/IPO= 90/10 SEBS/monomer component ratio Mass ratio 20/80 20/80 composition Formula (1) unit content ratio quality% 14 14 Formula (2) unit content ratio quality% 3 3 IPO unit content ratio quality% 8 8 Mw ×10 ⁴ 23.6 28.2 Mn ×10 ⁴ 3.2 3.0 Adhesion (PP board) ─ A B

(3-2) Coating film adhesion test 2 Pour 6 g of resin composition and 24 g of THF (tetrahydrofuran) into a glass container with a lid (Maruemu Co., Ltd., screw vial) with a volume of 50 mL, close the lid, and shake with the paint The device was shaken and stirred to prepare a resin solution with a concentration of 20% by mass. A #60 rod coater resin solution was used on the test plate and dried at 80°C for 30 minutes to form a coating film with a film thickness of about 20 μm. Scribe the blade of a cutting knife (manufactured by NT Incorporated, A-300) perpendicular to the coating film and cut out the cuts. By making 11 intersecting lines in the vertical and horizontal rows at 1 mm intervals, 100 pieces of 1mm ² square. A cellophane adhesive tape (manufactured by Nichiban Corporation, Cellotape (registered trademark), width 15 mm) was attached to the surface of the 100 cut coating film without air ingress, and the tape was rubbed quickly with fingers. After standing for 10 seconds, pull the edge of the tape to maintain a right angle with the coating film surface, and instantly tear off the tape, calculate the number of pieces of the coating film that did not peel off, and calculate the residual rate of the coating film by the following formula: residual coating film Rate (%) = remaining number of coating film/100×100. If the residual rate of the coating film is 80% or more, it is evaluated as "A", the residual rate of the coating film is 20% or more and less than 80% is evaluated as "B", and the remaining rate is less than 20% is evaluated as "C"". As the test plate, a PBT (polybutylene terephthalate) plate (manufactured by Engineering Test Service, PBT3300, 2.0 mm × 70 mm × 150 mm), a PC (polycarbonate) plate (manufactured by Japan Testpanel, a standard test plate) was used PC, 2.0 mm × 70 mm × 150 mm), PMMA (polymethyl methacrylate) plate (manufactured by Engineering Test Service, PMMA, 2.0 mm × 60 mm × 120 mm).

The adhesion to PBT boards, PC boards, and PMMA boards was discussed for resin compositions 2-6, 8, and 9. The results are shown in Table 3 and Table 4. Compared with resin compositions 2 to 4, 8, and 9 for each test plate, each test plate is evaluated as A, resin compositions 5 and 6 have poor adhesion, and resin composition 6 is for each test plate. . Resin compositions 2 to 4, 8, and 9 have good adhesion to PBT boards, PC boards, and PMMA boards. Moreover, even if it is a resin composition containing a copolymer having a smaller proportion of the polymer chain (A) derived from SEBS than the resin composition 4, that is, the value of SEBS in the ratio of SEBS/(IPO+St) does not reach The resin composition of 20, the SEBS/(IPO+St) ratio of 15/85, 10/90, etc., can still obtain adhesion to PBT boards, PC boards, and PMMA boards compared to resin composition 6. The lifting effect. In addition, an effect of improving the adhesion of the resin composition 5 to the PBT board can be obtained.

[table 3] Resin composition No. 2 3 4 6 Feed in IPO/St ratio Mass ratio 10/90 3/97 3/97 ─ SEBS/(IPO+St) ratio Mass ratio 20/80 33/67 20/80 100/0 composition Formula (1) unit content ratio quality% 14 twenty three 14 66 Formula (2) unit content ratio quality% 3 5 3 14 IPO unit content ratio quality% 8 2 3 0 Mw ×10 ⁴ 15.5 17.5 17.2 Mn ×10 ⁴ 3.8 6.3 5.1 Adherence PBT board ─ A A A C PC board ─ A A A C PMMA board ─ A A A C

[Table 4] Resin composition No. 8 9 Feed in Monomer component ratio Mass ratio St/AN/IPO/= 70/20/10 MMA/IPO= 90/10 SEBS/(full monomer composition) ratio Mass ratio 20/80 20/80 composition Formula (1) unit content ratio quality% 14 14 Formula (2) unit content ratio quality% 3 3 IPO unit content ratio quality% 8 8 Mw ×10 ⁴ 23.6 28.2 Mn ×10 ⁴ 3.2 3.0 Adherence PBT board ─ A A PC board ─ A A PMMA board ─ A A

(4) Compatibility test A polystyrene resin (Epocros (registered trademark) RPS-1005, manufactured by Nippon Shokubai Co., Ltd.) was added to the resin solution X in tetrahydrofuran (THF) at a concentration of 20% by mass, and the resin containing olefin components ( Tuftec (registered trademark) P1083; manufactured by Asahi Kasei Co., Ltd.) The resin solution Y added to tetrahydrofuran (THF) at a concentration of 20% by mass is poured into a 20 ml glass container (spiral tube) and sealed with a lid. , Mix for 1 minute with a shaker (vibrator) to obtain a resin mixed solution (X+Y). The resin mixed solution (X+Y) was stirred and mixed and left for 10 minutes to separate into two layers. Next, 5 g of the resin solution 3 added to tetrahydrofuran (THF) so that the resin composition 3 has a concentration of 20% by mass was added to the resin mixed solution (X+Y), and sealed with a lid to form a shaker (vibrator) Mix for 1 minute. The resin mixed solution (X+Y) to which the resin composition 3 is added, even if it is left for 10 minutes for 2 layers after stirring and mixing, it is still a uniform solution without separation. In other words, the resin composition 3 containing a copolymer in which the oxazoline group-containing polymer chain is grafted onto the SEBS block copolymer chain improves the mutual solubility between the polystyrene resin and the polystyrene resin. , It has the function of dissolving agent.

The copolymer (P) and the resin composition (Q) of the present invention can be used as primers, adhesives, compatibilizers for various resins to improve the adhesion between various substrates such as metals and plastics and resin coating layers, Use of additives and modifiers. Specifically, it can be used in optical films, printed wiring boards, tire cords, and other rubber reinforcement resins, as various engineering plastics, buffers, control panels, electronic components, and other automotive-conveyor related interiors and exteriors Components, household appliances, furniture, miscellaneous goods and other daily necessities related products, construction-civil engineering, stationery-office supplies and other industrial materials.

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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, [化1]

[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) 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 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 in the polymer chain (B), the content of units derived from an oxazoline group-containing monomer is 1% by mass or more 50% by mass or less. The copolymer (P) according to any one of claims 1 to 4, wherein the polymer chain (A) is 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 claims 1 to 5, wherein 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 above-mentioned polymer chain (B), the total content ratio of the unit derived from the oxazoline group-containing monomer, the unit derived from the aromatic vinyl monomer and/or the unit derived from the unsaturated carboxylic acid ester is 80% by mass or more . A resin composition (Q) containing the copolymer (P) according to any one of claims 1 to 6. A resin composition (Q) containing the copolymer (P) according to any one of claims 1 to 6 and an oxazoline group-containing polymer. The resin composition (Q) according to claim 8, wherein relative to the total of the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1) 100 parts by mass, the content ratio of the polymer chain (A) is 5 parts by mass or more and 80 parts by mass or less. The resin composition (Q) according to claim 8 or 9, wherein the copolymer (P), the oxazoline group-containing polymer, and the polymer having the unit represented by the formula (1) The content of the unit represented by the above formula (1) is 3 parts by mass or more and 80 parts by mass or less in total. The resin composition (Q) according to any one of claims 8 to 10, wherein the copolymer (P), the oxazoline group-containing polymer, and the polymer having the formula (1) The total amount of the polymer of the unit is 100 parts by mass, and the content ratio of the unit derived from the oxazoline group-containing monomer is 0.5 part by mass or more and 49 parts by mass or less. A primer 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. A resin molded body which is 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 Formed on the surface of the resin substrate. The resin molded body according to claim 13, wherein the resin base material is a hydrocarbon resin, or a resin having a heteroatom-containing group or a heteroatom-containing bond. A compatibilizer, which contains 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 method for producing a copolymer (P). The copolymer (P) has: a polymer chain (A) having a unit represented by the following formula (1) and a polymer chain having a unit derived from an oxazoline group-containing monomer The polymer chain (B) has a production method comprising: in the presence of a polymer having a unit represented by the following formula (1), the step of polymerizing with a monomer component containing an oxazoline group-containing monomer, [化2]

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