TWI750201B - Cluster copolymers, compositions and films - Google Patents

Abstract

The object of the present invention is to provide a group-linked copolymer that does not use chlorine-containing compounds and has strong adhesion (adhesion) not only to high-polarity materials but also to low-polarity materials. The group-linked copolymer, comprising: an A-group link having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group; and a B-group link having a structural unit derived from a vinyl monomer, the A-group linking The average glass transition temperature of the group is above 25°C, the average glass transition temperature of the B group is lower than the average glass transition temperature of the A group, and the average glass transition temperature of the A group is the same as the average glass transition temperature of the B group. The difference between them is 50°C or more.

Description

Linked copolymers, compositions and films

The present invention relates to a grouped copolymer, a composition containing the grouped copolymer, and a film containing a layer composed of the composition.

Polypropylene resin (hereinafter also referred to as PP) and polyethylene resin (hereinafter also referred to as PE) are general-purpose resins which are inexpensive and excellent in moldability, chemical resistance, water resistance, and electrical properties. This PP and PE are widely used in automobiles, home appliances, agriculture and printing. In addition, cycloolefin resin (hereinafter also referred to as COP) has excellent characteristics such as high transparency, low hygroscopicity, and low specific gravity. This COP is used for optical components such as displays and touch panels as a substitute for glass and a substitute for transparent plastic. However, polyolefin-based resins such as PP, PE, and COP have small polarities and have few functional groups present on the surface of the member, making it difficult to coat, bond, and the like.

As a method for solving the above-mentioned problems, it is known to apply physical treatments such as corona treatment, plasma treatment, and ultraviolet treatment, and chemical treatments by organic solvents to the surface of the adherend (polyolefin-based resin). Methods to improve adhesion. For example, in Patent Document 1, chemical treatment with an organic solvent is proposed (see Patent Document 1 (paragraphs 0019 and 0023)). However, a special device is required for the physical treatment, and there is a risk that the performance of the film may be lowered due to physical stimulation. In chemical treatment, since the surface is dissolved and swollen by an organic solvent, there is a risk of lowering the film performance, and there is a problem that quality control such as solvent ratio and treatment time is complicated.

In addition, as a method of improving adhesiveness without performing surface treatment, Patent Document 2 proposes to use a chlorinated polyolefin-based resin having strong adhesion to polyolefin-based resin as a primer or an adhesive (see Patent Document 2 (see Patent Document 2). Paragraphs 0008, 0012)). However, chlorinated polyolefin-based resins tend to avoid the use of chlorinated polyolefin resins due to the recent increase in environmental awareness due to the presence of chlorine.

In addition, (meth)acrylic resins are widely used as adhesives for optical members such as displays and touch panels, adhesives, primers, and compositions for hard coats of optical members. This (meth)acrylic resin does not contain chlorine, and has a wide variety of monomers used as its raw materials, and can arbitrarily control physical and chemical properties such as hardness, transparency, weather resistance, and chemical resistance. However, since the (meth)acrylic resin is a highly polar material, it is not suitable for a member formed of a polyolefin-based resin.

Here, a technique for improving the adhesion of a (meth)acrylic resin to a polyolefin-based resin has been proposed. For example, Patent Document 3 describes a primer composition comprising a primer composition containing an acryloxy group or a methacryloyloxy group bonded to a secondary carbon atom or a tertiary carbon atom. A polymer of a (meth)acrylate monomer unit (refer to Patent Document 3 (claim 1)). Patent Document 4 describes a polymer having a (meth)acrylate monomer having an alicyclic hydrocarbon group bonded to an acryloxy group or a methacryloyloxy group, and a composition of an adhesion-imparting resin (see Patent Document 4). (paragraphs 0008, 0009)). Patent Document 5 describes a composition comprising an acrylic polymer and a (meth)acrylic polymer containing a (meth)acrylic monomer having an alicyclic structure of three or more rings as a monomer unit (see Patent Document 5 (paragraphs 0039 to 0043)). [Prior Art Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2015-114456 Patent Document 2: Japanese Patent Laid-Open No. 6-306227 Patent Document 3: International Publication No. 2004/018575 Patent Document 4: Japanese Patent Laid-Open No. 2008-239768 5: Japanese Patent Laid-Open No. 2014-74179

As described above, a technique for improving the adhesion of (meth)acrylate-based resin to polyolefin-based resin has been proposed. However, even with the methods of Patent Documents 3 to 5, there is a problem that the adhesive force to the polyolefin-based resin and the adhesive force are low.

The purpose of the present invention is to provide a grouped copolymer that does not use chlorine-containing compounds, and is suitable for not only metals, polyethylene terephthalate resins, polyamide resins, and polycarbonate resins. , Polyacrylic acid methyl resin, polyvinyl alcohol resin, triacetyl cellulose and other high-polar materials, and also have strong adhesion (adhesion) to low-polar materials such as polyolefin resins.

A group-linked copolymer of the present invention capable of solving the above-mentioned problems comprises: an A-group link having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group; and a B-group link having a structure derived from a vinyl monomer The structural unit, the average glass transition temperature of the A group is above 25 ℃, the average glass transition temperature of the B group is lower than the average glass transition temperature of the A group, and the average glass transition temperature of the A group is the same as the average glass transition temperature of the A group. The difference between the average glass transition temperatures of the B clusters is 50°C or more.

By localizing the polycyclic aliphatic hydrocarbon groups due to the A-group linkage, it is conceivable that the adhesion (adhesion) of the group-linked copolymer to low polarity materials (eg, COP films) can be improved. In addition, it is conceivable that the B group with a low average glass transition temperature can function as a soft segment, and the coating properties and flexibility thereof can be improved. Furthermore, by properly selecting the vinyl monomer linked by the B group, the adhesion to highly polar materials (eg, acrylic films) can also be improved. Therefore, by using the aforementioned group-linked copolymer, the adhesion to the low-polarity material and the high-polarity material can be improved.

The group-linked copolymer is preferably an A-B-A-type group-linked copolymer. The vinyl monomer having a polycyclic aliphatic hydrocarbon group is preferably a (meth)acrylic acid polycyclic aliphatic hydrocarbon ester. It is preferable that the content rate of this B group link is 5 to 60 mass % in the whole 100 mass % of this group link copolymer. The molecular weight distribution (PDI) of the group-linked copolymer is preferably 2.5 or less. The group-linked copolymer is preferably polymerized by living radical polymerization.

In the present invention, a composition characterized by containing the group-linked copolymer is also included. As such a composition, a primer composition, a surface modification composition, an adhesive composition, and an adhesive composition are mentioned. In addition, the present invention includes a film comprising: a base material and a layer formed of the composition containing the grouped copolymer on at least a part of at least one side of the base material. The base material is preferably a polyolefin resin.

According to the present invention, it is possible to provide a group-linked copolymer that does not use a chlorine-containing compound and has strong adhesion (adhesion) not only to high-polarity materials but also to low-polarity materials.

Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are merely examples. The present invention is not limited to any of the following embodiments.

<1. Group-linked copolymer> The group-linked copolymer has an A-group link and a B-group link, the A-group link has a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group, and the B-group link has a vinyl-based monomer. A single structural unit. In addition, in the group-linked copolymer of the present invention, the average glass transition temperature of the A group is 25°C or higher, the average glass transition temperature of the B group is lower than the average glass transition temperature of the A group, and the A group has a lower average glass transition temperature than the A group. The difference between the average glass transition temperature and the average glass transition temperature of the B group is 50°C or more.

The A group can also be called "A segment", and the B group can also be called "B segment". The "vinyl monomer" is a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule, and a monomer having a vinyl group in the molecule is preferable.

In this specification, a "structural unit derived from a vinyl monomer" is a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer becomes a carbon-carbon single bond. In addition, in this specification, "(meth)acrylic acid" represents "at least one of acrylic acid and methacrylic acid", and "(meth)acrylate" represents "at least one of acrylic acid ester and methacrylic acid ester".

The glass transition temperature (Tg) of the coalescence is a value calculated by the following FOX formula (Equation (1)). In the mathematical formula (1), Tg is the representative glass transition temperature (°C). Tgi is the glass transition temperature (°C) at which the vinyl monomer i forms a homopolymer. Wi is the mass ratio of vinyl monomer i in the all-vinyl monomers forming the group, ΣWi = 1. i is a natural number from 1 to n.

[Mathematical formula 1]

The glass transition temperatures of representative homopolymers are shown in Table 1.

【Table 1】

Various constituent components and the like of the group-linked copolymer of the present invention will be described below.

(A group link) The A group link has a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group. The polycyclic aliphatic hydrocarbon group is an alicyclic hydrocarbon group having a polycyclic structure, and means a hydrocarbon group having two or more aliphatic rings (alicyclic). As for the polycyclic structure, a bridged ring structure, a spiro ring structure and a condensed ring structure can be mentioned, but the bridged ring structure is preferable. The bridged ring structure is a structure in which two non-adjacent carbon atoms constituting a ring are connected by a carbon chain composed of one or more carbon atoms. The bridged alicyclic hydrocarbon group can include a condensed ring structure and a spiro ring structure in addition to the structure linked by a carbon chain. The number of carbon atoms constituting the polycyclic aliphatic hydrocarbon group is preferably 7 or more, preferably 9 or more, more preferably 20 or less, more preferably 15 or less. The adhesion (adhesion) of the group-linked copolymer to low polar materials is improved by localization of the A-group-linked polycyclic aliphatic hydrocarbon group.

Specific examples of the polycyclic aliphatic hydrocarbon group include adamantyl, 2-methyladamantyl, 2-ethyladamantyl, norbornyl, 1-methylnorbornyl, 5,6- Dimethylnorbornyl, isobornyl, tetracyclo[4.4.0.12,5.17,10]dodecyl, 9-methyltetracyclo[4.4.0.12,5.17,10]dodecyl, bornyl, Dicyclopentyl, dicyclopentenyl, etc. Among these, an adamantyl group, a norbornyl group, an isobornyl group, and a dicyclopentyl group are preferable from the viewpoints of easy availability, solubility, and excellent adhesion to low-polarity materials.

As the vinyl monomer having a polycyclic aliphatic hydrocarbon group, (meth)acrylic acid polycyclic aliphatic hydrocarbon ester is preferable. Specific examples of (meth)acrylic acid polycyclic aliphatic hydrocarbon esters include 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantane (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl ( Meth)acrylate, dicyclopentenyl (meth)acrylate, etc. As the vinyl monomer having a polycyclic aliphatic hydrocarbon group, it can be used alone or in combination of two or more.

The average glass transition temperature (TgAave) of the group A is 25°C or higher, preferably 30°C or higher, more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 80°C or higher, and 250°C or lower. Preferably, it is preferably 230°C or lower, more preferably 200°C or lower, and particularly preferably 150°C or lower. By having a bulky polycyclic structure as described above, and having an average glass transition temperature of 25° C. or higher, it is conceivable that high density can be expressed even for low-polarity materials. The average glass transition temperature of the A-linked is a value calculated from all the A-linked monomers.

When the group-linked copolymer has a plurality of A groups, the glass transition temperature (TgA) of each A group is preferably 25°C or higher, preferably 40°C or higher, more preferably 50°C or higher, and 80°C or higher. Particularly preferred, it is preferably 250°C or lower, more preferably 230°C or lower, more preferably 200°C or lower, and particularly preferably 150°C or lower. When the glass temperature of each A group is within the above range, the adhesion to low-polarity materials will be further improved.

When the group-linked copolymer is used in a primer composition or a surface modification composition, the average glass transition temperature (TgAave) of the A-group linkage is preferably above 60°C, preferably above 80°C, and preferably above 250°C The temperature is preferably below, preferably below 200°C, more preferably below 150°C. When the average glass transition temperature of the A group is within the above range, the adhesion to the substrate will be further improved when it is used in a primer composition or a surface modification composition.

When the group-linked copolymer used in the primer composition or surface modifier has a plurality of A groups, the glass transition temperature (TgA) of each A group is preferably 60°C or higher, preferably 80°C or higher , preferably below 250°C, preferably below 200°C, more preferably below 150°C. When the average glass transition temperature of each A group is within the above range, the adhesion to the substrate will be further improved when used in a primer composition or a surface modification composition.

When the group-linked copolymer is used in a primer composition or a surface modification composition, the average glass transition temperature (TgAave) of the A group-linked is 25°C or higher, preferably 30°C or higher, preferably 35°C or higher , preferably below 60°C, preferably below 58°C, more preferably below 55°C. When the average glass transition temperature of the A group is within the above range, the adhesion between the substrate and the adherend will be further improved when used in an adhesive composition or an adhesive composition.

When the group-linked copolymer used in the adhesive composition or adhesive composition has a plurality of A groups, the glass transition temperature (TgA) of each A group is preferably less than 60°C, preferably 58°C or lower , preferably below 55°C. When the glass transition temperature (TgA) of all A groups is less than 60°C, the adhesion between the substrate and the adherend will be further improved when used in an adhesive composition or an adhesive composition.

When the group-linked copolymer has a plurality of A groups, the difference between the glass transition temperature (TgAmax) of the A group with the highest glass transition temperature and the glass transition temperature (TgAmin) of the A group with the lowest glass transition temperature is 0°C or higher, preferably less than 50°C, more preferably 20°C or lower, more preferably 10°C or lower.

The A-group linkage is preferably composed of only a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group. The A group can also contain a group derived from a polycyclic aliphatic hydrocarbon group that does not have a polycyclic aliphatic hydrocarbon group within the range that the glass transition temperature of the A group can be maintained and the adhesion of the obtained group copolymer to the low-polarity material can be maintained. The structural unit of vinyl monomers (other structural units).

In this case, the content of the structural unit derived from the vinyl monomer having a polycyclic aliphatic hydrocarbon group is preferably 40% by mass or more, more preferably 60% by mass or more, and 80% by mass in 100% by mass of the A group. More than mass % is better. In addition, the content of other structural units that may be included in the A group is preferably 60 mass % or less, more preferably 40 mass % or less, and more preferably 20 mass % or less in 100 mass % of the A group.

Other structural units that can be included in the A group linkage are not particularly limited as long as they are formed from vinyl monomers that can be polymerized with vinyl monomers having polycyclic aliphatic hydrocarbons and all vinyl monomers that form B group linkages limit. Examples of vinyl monomers capable of forming other structural units of A group linkage include aromatic vinyl monomers, vinyl monomers having hydroxyl groups, vinyl monomers having carboxyl groups, and vinyl monomers having sulfonic acid groups. , vinyl monomers with phosphoric acid groups, vinyl monomers containing tertiary amines, vinyl monomers containing quaternary ammonium salt groups, vinyl monomers containing heterocycles, vinyl amides, vinyl containing epoxy groups base monomers, vinyl carboxylates, alpha-olefins, dienes, (meth)acrylic monomers, etc. Vinyl monomers capable of forming other structural units linked to A can be used alone, or two or more of them can be used in combination.

As the aromatic vinyl monomer, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2 -Hydroxymethylstyrene, 1-vinylnaphthalene, etc. As a vinyl monomer which has a hydrocarbon group, a hydroxyalkyl (meth)acrylate etc. are mentioned. Examples of the carboxyl group-containing vinyl monomer include monomers in which acid anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride are reacted with vinyl monomers having the hydrocarbon group, crotonic acid, maleic acid, and itaconic acid. ,(Methacrylate. Examples of vinyl monomers having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, ethyl disulfonic acid (meth)acrylic acid, methylpropylsulfonic acid (meth)acrylamide, and sulfonic acid. Ethyl ester (meth) acrylamide, etc. Examples of the vinyl monomer having a phosphoric acid group include methacryloyloxyethyl phosphate and the like. Examples of the tertiary amine-containing vinyl monomer include N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, 2- (Dimethylamino)(meth)acrylate, N,N-dimethylamino(meth)acrylate, etc. Examples of vinyl monomers containing a quaternary ammonium salt group include N-2-hydroxy-3-acryloyloxypropyl-N,N,N-trimethylammonium chloride, N-methacryloylamino Ethyl-N,N,N-dimethylbenzylammonium chloride, etc. Examples of the heterocyclic-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, and the like . Examples of vinyl amides include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-mercaptolactam, and the like. Glycidyl (meth)acrylate etc. are mentioned as an epoxy group containing vinyl monomer. As vinyl carboxylate, vinyl acetate, vinyl pivalate, vinyl benzoate, etc. are mentioned. As alpha-olefin, 1-hexene, 1-octene, 1-decene, etc. are mentioned. Examples of the diene include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

As the (meth)acrylic monomer, (meth)acrylic acid, (meth)acrylic acid aliphatic alkyl (straight-chain alkyl, branched-chain alkyl) ester, (meth)acrylic acid cycloaliphatic alkyl (mono) ring structure) ester, (meth)acrylate having hydrocarbon group, (meth)acrylate having alkoxy group, (meth)acrylate having sulfonic acid group, (meth)acrylate having tertiary acid group , (meth)acrylate with epoxy group, (meth)acrylate with polyethylene glycol structural unit, (meth)acrylate with aromatic ring group, (meth)acrylamide, etc.

Examples of aliphatic alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate base) isobutyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like. As alicyclic alkyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, etc. are mentioned. Examples of (meth)acrylates having a hydrocarbon group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate Hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl acrylate. As (meth)acrylate which has an alkoxy group, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, etc. are mentioned. As (meth)acrylate which has a sulfonic acid group, ethyl disulfonate (meth)acrylate etc. are mentioned. As an unsaturated monomer which has a tertiary amine, 2-(dimethylamino)ethyl (meth)acrylate, N,N- dimethylaminopropyl (meth)acrylate, etc. are mentioned. As (meth)acrylate which has an epoxy group, glycidyl (meth)acrylate etc. are mentioned. As the (meth)acrylate having a polyethylene glycol structural unit, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tetraethylene glycol mono(meth)acrylate may be mentioned. ) acrylate, polyethylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and the like. As (meth)acrylate which has an aromatic ring group, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. are mentioned. Examples of (meth)acrylamide include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylamide. (meth)acrylamide, etc.

Among these, as vinyl monomers that can form other structural units of A-group linkages, there are (meth)acrylates having aliphatic alkyl groups, (meth)acrylates having alicyclic alkyl groups having a monocyclic structure (methyl) ) acrylates, aromatic vinyl monomers, vinyl monomers having hydroxyl groups, and vinyl monomers having carboxyl groups are preferred.

When the grouped copolymer is used in a primer composition or a surface modification composition, the content of the structural unit derived from the (meth)acrylate having a polycyclic aliphatic alkyl group is 100% by mass of the A group Among them, it is preferably less than 15 mass %, more preferably 10 mass % or less, and more preferably 5 mass % or less. In the group A, if the content of the structural unit derived from the (meth)acrylate having an aliphatic alkyl group is within the above-mentioned range, when it is used in a primer composition or a surface modification composition, the adhesion with the substrate will be reduced. The stickiness is further improved.

When the tethered copolymer is used in a bonding composition or an adhesive composition, the content of the structural unit derived from the (meth)acrylate having an aliphatic alkyl group is 15 mass % in 100 mass % of the A tethered % or more is preferable, 20 mass % or more is more preferable, and 25 mass % or more is more preferable. In the group A, if the content of the structural unit derived from the (meth)acrylate having an aliphatic alkyl group is within the above range, when used in an adhesive composition or an adhesive composition, the adhesion between the substrate and the adherend will be reduced. The stickiness is further improved.

Furthermore, when the group-linked copolymer is used in a bonding composition or an adhesive composition, it is preferable that the group A has a reactive functional group. As this reactive functional group, a hydroxyl group, a carboxyl group, an epoxy group, etc. are mentioned. When the aforementioned reactive functional group is introduced, the content of the structural unit derived from the vinyl group in the reactive functional group is preferably 0.1 mass % or more, preferably 0.5 mass % or more, and 1.0 mass % in 100 mass % of the A group linkage. It is more preferably at least 5.0 mass %, more preferably at most 4.0 mass %, and more preferably at most 3.0 mass %. In the group A, if the content of the structural unit derived from the vinyl monomer having a reactive functional group is within the above range, when used in an adhesive composition or an adhesive composition, the adhesion between the substrate and the adherend will be improved. further improvement.

When two or more structural units are contained in the A group, the various structural units contained in the A group can be contained in the A group in any form such as random polymerization, group polymerization, etc., from the viewpoint of homogeneity. It is better to be included in the form of random aggregation. The group-linked copolymer of the present invention can have a plurality of A groups. When there are a plurality of A-group linkages, the monomer composition of each A-group linkage can be homogeneous or heterogeneous.

(B group linkage) The B group linkage has a structural unit derived from a vinyl monomer, and does not substantially have a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group. "Substantially not having" means that its content is 20 mass % or less, preferably 10 mass % or less, more preferably 5 mass % or less, and more preferably 2 mass % or less, in 100 mass % of B groups. In addition, the average glass transition temperature (TgBave) of the B group is lower than the average glass transition temperature (TgAave) of the A group, and the average glass transition temperature (TgAave) of the A group is lower than the average glass transition temperature (TgAave) of the B group. The glass transition temperature (TgBave) difference (TgAave-TgBave) is 50 degreeC or more. The difference (TgAave-TgBave) is preferably 70°C or higher, more preferably 90°C or higher, preferably 250°C or lower, more preferably 200°C or lower, and more preferably 150°C or lower. The B group with a low average glass transition temperature functions as a soft segment to improve the coatability and softness of the group copolymer. In addition, the average glass transition temperature of the B group is calculated by this mathematical formula (1). The average glass transition temperature of the B-group linkage is a value calculated from all the B-group-linked monomers.

The average glass transition temperature (TgBave) of the B group is preferably above -100 °C, preferably above -70 °C, more preferably above -50 °C, preferably below 60 °C, preferably below 30 °C , preferably below 10°C. When the average glass transition temperature (TgBave) of the B group is -100°C or more, the coatability to low-polarity materials becomes good, and when it is 60°C or less, the coatability to high-polarity materials becomes good, and the flexibility improves .

When the group-linked copolymer has a plurality of B groups, the glass transition temperature (TgB) of each B group is preferably above -100°C, preferably above -70°C, more preferably above -50°C, and The temperature is preferably 60°C or lower, more preferably 30°C or lower, and more preferably 10°C or lower. When the average glass transition temperature (TgBave) of each B group is -100°C or more, the coatability to low-polarity materials becomes good, and when the average glass transition temperature (TgBave) of each B group is below 60°C, the coatability to high-polarity materials becomes good, and the flexibility promote.

When the group-linked copolymer has a plurality of B groups, the difference between the glass transition temperature (TgBmax) of the B group with the highest glass transition temperature and the glass transition temperature (TgBmin) of the B group with the lowest glass transition temperature is 0°C or higher, preferably less than 50°C, more preferably 20°C or lower, more preferably 10°C or lower.

When the group-linked copolymer has a plurality of A-group linkages and/or B-group linkages, the difference between the minimum value (TgAmin) of the glass transition temperature of the A-group linkage and the maximum glass transition temperature (TgBmax) of the B-group linkage ( TgAmin-TgBmax) is preferably 50°C or higher, preferably 70°C or higher, more preferably 90°C or higher. In addition, the difference (TgAmax-TgBmin) between the maximum value (TgAmax) of the glass transition temperature of the group A and the minimum value (TgBmin) of the glass transition temperature of the group B is preferably 250°C or lower, preferably 200°C or lower. , preferably below 150°C.

The vinyl monomer used for the B group linkage can be appropriately selected within the range satisfying the conditions of the glass transition temperature. In addition, when the grouped copolymer is used as an adhesive composition or an adhesive composition, it is preferable to select the vinyl monomer used for the B grouping according to the polarity of the adherend (high polarity material).

Specific examples of the vinyl monomer used for the B group linkage include aromatic vinyl monomers, vinyl monomers having hydroxyl groups, vinyl monomers having carboxyl groups, vinyl monomers having sulfonic acid groups, Phosphate group-containing vinyl monomers, tertiary amine-containing vinyl monomers, quaternary ammonium salt group-containing vinyl monomers, heterocycle-containing vinyl monomers, vinyl amides, epoxy group-containing vinyl monomers Monomers, vinyl carboxylates, alpha-olefins, dienes, (meth)acrylic monomers, etc. The vinyl monomers that can be used in combination with the B group can be used alone, or two or more of them can be used in combination.

As the aromatic vinyl monomer, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2 -Hydroxymethylstyrene, 1-vinylnaphthalene, etc. Hydroxyalkyl (meth)acrylate etc. are mentioned as a vinyl monomer which has a hydrocarbon group. Examples of the carboxyl group-containing vinyl monomer include monomers in which acid anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride are reacted with a vinyl monomer having the carboxyl group, crotonic acid, maleic acid, and itaconic acid. ,(Methacrylate. Examples of vinyl monomers having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, ethyl disulfonic acid (meth)acrylic acid, methylpropylsulfonic acid (meth)acrylamide, and sulfonic acid. Ethyl ester (meth) acrylamide, etc. Examples of the vinyl monomer having a phosphoric acid group include methacryloyloxyethyl phosphate and the like. Examples of the tertiary amine-containing vinyl monomer include N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, 2- (Dimethylamino)(meth)acrylate, N,N-dimethylamino(meth)acrylate, etc. Examples of vinyl monomers containing a quaternary ammonium salt group include N-2-hydroxy-3-acryloyloxypropyl-N,N,N-trimethylammonium chloride, N-methacryloylamino Ethyl-N,N,N-dimethylbenzylammonium chloride, etc. Examples of the heterocyclic-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, and the like . Examples of vinyl amides include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-mercaptolactam, and the like. As an epoxy group-containing vinyl monomer, glycidyl (meth)acrylate etc. are mentioned. As vinyl carboxylate, vinyl acetate, vinyl pivalate, vinyl benzoate, etc. are mentioned. As alpha-olefin, 1-hexene, 1-octene, 1-decene, etc. are mentioned. Examples of the diene include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

As the (meth)acrylic monomer, (meth)acrylic acid, (meth)acrylic acid aliphatic alkyl (straight-chain alkyl, branched-chain alkyl) ester, (meth)acrylic acid cycloaliphatic alkyl (mono) ring structure) ester, (meth)acrylate having hydrocarbon group, (meth)acrylate having alkoxy group, (meth)acrylate having sulfonic acid group, (meth)acrylate having tertiary acid group , (meth)acrylate with epoxy group, (meth)acrylate with polyethylene glycol structural unit, (meth)acrylate with aromatic ring group, (meth)acrylamide, etc.

Examples of aliphatic alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate base) isobutyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-dodecyl (meth)acrylate, ( Meth) n-octadecyl acrylate, etc. As alicyclic alkyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, etc. are mentioned. Examples of the (meth)acrylate having a hydrocarbon group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxypropyl (meth)acrylate, and 4-hydroxypropyl (meth)acrylate. - Hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate. As (meth)acrylate which has an alkoxy group, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, etc. are mentioned. As (meth)acrylate which has a sulfonic acid group, ethyl disulfonic acid (meth)acrylate etc. are mentioned. As an unsaturated monomer which has a tertiary amine, 2-(dimethylamino)ethyl ester (meth)acrylate, N,N- dimethylaminopropyl (meth)acrylate, etc. are mentioned. Glycidyl (meth)acrylate etc. are mentioned as (meth)acrylate which has an epoxy group. Examples of (meth)acrylates having a polyethylene glycol structural unit include diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tetraethylene glycol mono(meth)acrylate. ) acrylate, polyethylene glycol mono(meth)acrylate, methylglycol(meth)acrylate, methoxytriethyleneglycol(meth)acrylate, methoxytetraethyleneglycol( meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and the like. As (meth)acrylate which has an aromatic ring group, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. are mentioned. Examples of (meth)acrylamide include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylamide. (meth)acrylamide, etc.

As the vinyl monomer used for the B group linkage, vinyl monomers containing a heterocycle and (meth)acrylic monomers are preferred, and vinyl monomers containing a heterocycle and aliphatic (meth)acrylic acid alkyl groups are preferred. (straight-chain alkyl, branched-chain alkyl) esters, hydroxyl-containing (meth)acrylates, alkoxy-containing (meth)acrylates are preferably heterocyclic-containing vinyl monomers, aliphatic The (meth)acrylate group of an alkyl group (preferably with 1 to 18 carbon atoms, preferably with 1 to 10 carbon atoms) is more preferable.

When two or more structural units are contained in the B group, the various structural units contained in the B group can be contained in the B group in any form such as random polymerization, group polymerization, etc., self-homogeneous. Opinions are preferably included in the form of random aggregation. The group-linked copolymer of the present invention can have a plurality of B groups. When there are a plurality of B group linkages, the monomer composition of each B group linkage can be homogeneous or can be heterogeneous.

(Group-Linked Copolymer) The group-linked copolymer has A-linkage and B-linkage. It is also preferable that the group-linked copolymer is composed only of the A-group-link and the B-group-link. Since the group-linked copolymer has a plurality of polymer groups with different properties such as glass transition temperature and polarity, it is conceivable that the group-linked copolymer will undergo phase separation on the surface of the coated substrate. The phase separation is that when the group-linked copolymer has groups with different properties such as glass transition temperature and polarity, there is a strong interaction between the groups of the same species, and the phenomenon of self-aggregation. For example, in the aforementioned group-linked copolymers, it is found that there is a phase structure in which the A-groups and the B-groups are adjacent to each other, respectively. The phase separation structure will form a layered structure, a gyroscopic structure, a cylinder structure or a sea-island structure according to the mass ratio, volume ratio and degree of polymerization of each group in the group-linked copolymer. In addition, the phase separation structure is not particularly limited.

By localization of polycyclic aliphatic hydrocarbons based on A-group linkages, group-linked copolymers have high adhesion (adhesion) to low polarity materials. It is also conceivable that due to the phase separation of this substance, the A groups form physical pseudo-crosslinks with each other, and thus a more excellent cohesive force is exhibited. In addition, the B group with a low glass transition temperature functions as a soft segment, and the coatability and softness of the group copolymer are improved. Further, it is conceivable that the type of the vinyl monomer linked by the B group can be appropriately selected to control the surface properties of the low-polarity material and improve the adhesion to the high-polarity material.

The structure of the block copolymer of the present invention can be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of such a grouped copolymer can be appropriately selected according to the desired physical properties of the copolymer, but a linear grouped copolymer is preferable from the viewpoints of cost and ease of polymerization. In addition, the linear group-linked copolymer can be in any structure (arrangement), but from the viewpoint of the physical properties of the linear group-linked copolymer or the physical properties of the composition, the A group is represented by A. , and when the B group is represented by B, it has the form (A-B)n-type, (A-B)n-A-type, (B-A)n-B-type (n is an integer greater than 1, such as 1 A copolymer having at least one structure selected from the group consisting of an integer to 3) is preferable. In these structures, the A-group linkage and the B-group-link can be directly combined, or other group-links other than the A-group-link and the B-group-link exist between the A-group-link and the B-group-link.

As a linear link copolymer, with a first A link, a B link directly or via other link to this first A link, a B link directly or via other link to this B link The structure of the second A-linkage; the A-linkage with the first B-linkage, the A-linkage directly or via other linkages combined with this first B-linkage, the A-linkage directly or via other linkages The structure of the second group B; preferably. In the structure having the first A-group linkage and the second A-group linkage, the first A-group linkage and the second A-group linkage are preferably present at the ends of the group-linked copolymer, respectively. In the structure having the first B group linkage and the second B group linkage, it is preferable that the first B group linkage and the second B group linkage are present at the ends of the grouped copolymer, respectively.

Among these, from the viewpoints of easiness in handling during processing and physical properties of the composition, there are also bipolymers represented by AB and terpolymers represented by AB-A. And the terpolymer represented by B-A-B is preferable, and the terpolymer represented by A-BB-A is more preferable. If the three-group linkage structure represented by A-B-A is constituted, the cross-linked structure between the group-linked copolymers is higher due to the pseudo-cross-linking between the A-group linkages. Therefore, it is conceivable that the cohesive force of the polymer layer is improved, and higher adhesiveness (adhesion force) can be found. In addition, in the case of a three-group link copolymer represented by A-BB-A, the two A-group links located at both ends may be the same or different from each other. When it is a three-group linkage copolymer represented by B-A-B, the two B-group linkages located at both ends may be the same or different from each other.

The average molecular weight of the group-linked copolymer was determined by colloidal permeation chromatography (Gel permeation chromatography, GPC). The weight average molecular weight (Mw) of the group-linked copolymer is preferably 3,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, preferably 1,000,000 or less, preferably 800,000 or less, and more preferably 500,000 or less. When the weight average molecular weight is 3,000 or more, the adhesion (adhesion) becomes favorable, and when the weight average molecular weight is 1,000,000 or less, the viscosity does not become too high, and the applicability becomes favorable.

When the grouped copolymer is used in a primer composition or a surface modification composition, the weight average molecular weight (Mw) of the grouped copolymer is preferably above 3000, preferably above 5000, more preferably above 10000, and below 200000 Excellent, preferably below 150,000, more preferably below 100,000, and particularly preferably below 80,000. When the weight average molecular weight is in the above-mentioned range, when used in a primer composition or a surface modification composition, the adhesion to the substrate is further improved.

When the group-linked copolymer is used in an adhesive composition or an adhesive composition, the weight-average molecular weight (Mw) of the group-linked copolymer is preferably above 3,000, preferably above 50,000, more preferably above 80,000, preferably below 800,000, Preferably below 500000, more preferably below 300000, particularly preferably below 100000. When the weight average molecular weight is in the above-mentioned range, when used in an adhesive composition or an adhesive composition, the adhesion between the substrate and the adherend is further improved.

The molecular weight distribution (PDI) of the group-linked copolymer is preferably 2.5 or less, more preferably 2.2 or less, and more preferably 2.0 or less. In addition, in this invention, molecular weight distribution (PDI) is calculated|required by (weight average molecular weight (Mw) of a grouped copolymer) / (number average molecular weight (Mn) of a grouped copolymer). The smaller the PDI is, the narrower the molecular weight distribution is and the more uniform the molecular weight is. When the value is 1.0, the molecular weight distribution is the narrowest. When PDI is 2.5 or less, compared with the molecular weight of the designed copolymer, the content of the thing with a small molecular weight and the thing with a large molecular weight is low, and the adhesiveness (adhesion) improves.

The content of the A group in the group-linked copolymer is preferably 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, based on 100% by mass of the entire group-linked copolymer. 95 mass % or less is preferable, 85 mass % or less is more preferable, and 75 mass % or less is more preferable. The content rate of each group link is obtained from the preliminary ratio of the monomer constituting the group link copolymer and the copolymerization ratio of each monomer.

The content rate of B groups in the group-linked copolymer is preferably 5% by mass or more, more preferably 15% by mass or more, more preferably 25% by mass or more, based on 100% by mass of the entire group-linked copolymer. 60 mass % or less is preferable, 50 mass % or less is more preferable, and 40 mass % or less is more preferable.

By adjusting the content of the A group and the B group within this range, the group copolymer having the intended effect can be adjusted. When the group-linked copolymer has A1 grouping and A2 grouping as A grouping, the mass ratio (A1/A2) of these is preferably 0.4 or more, preferably 0.7 or more, more preferably 0.8 or more, and 2.3 or more. The following is preferable, preferably 1.5 or less, more preferably 1.2 or less.

When the group-linked copolymer has B1 grouping and B2 grouping as B grouping, the mass ratio (B1/B2) of these is preferably 0.4 or more, preferably 0.7 or more, more preferably 0.8 or more, and 2.3 or more. The following is preferable, preferably 1.5 or less, more preferably 1.2 or less.

The group-linked copolymer of the present invention has strong adhesion (adhesion) not only to high-polarity materials but also to low-polarity materials such as polyolefin-based resins. Therefore, the group-linked copolymer of the present invention can be used as a primer composition, an adhesive composition, and an adhesive composition for fixing a low-polarity material and a high-polarity material. Furthermore, the grouped copolymer of the present invention can be used as a tackifier of an acrylic adhesive.

(Manufacturing method of group-linked copolymer) As a method for producing the group-linked copolymer of the present invention, it is possible to first produce an A-group linkage by a polymerization reaction of a vinyl monomer, and then polymerize the B-group-linked monomer to the A-group It is also possible to first produce the B group, and then polymerize the monomer of the A group in the B group; it is also possible to make the AB group first, and then further polymerize the A group of the monomer in the AB group to produce the ABA group It is also possible to make BA groups first, and then further polymerize the monomers of B groups in BA groups to produce BAB groups.

Although the polymerization method is not particularly limited, living radical polymerization is preferable. That is, as the group-linked copolymer, one polymerized by living radical polymerization is preferable. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the inactivation of the growth end is caused by the stop reaction and the chain reaction, and there is a tendency to form a mixture of polymers having various molecular weights and non-uniform compositions. In contrast, the living radical polymerization method can maintain the simplicity and versatility of the conventional radical polymerization method, and at the same time, it is difficult to cause a stop reaction and a chain reaction, and it can grow without inactivating the growth end, so that it is easy to be precise. It is preferable to control the molecular weight distribution to produce a polymer of uniform composition.

Living radical polymerization methods include a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chemical bond transfer agent (RAFT method); method method (TERP method) and other methods. In the ATRP method, since an amine complex is used, the acidic group of the vinyl monomer having an acidic group may not be used without protection. In the RAFT method, when a variety of monomers are used, it is difficult to form a low molecular weight distribution, and there are situations in which defects such as sulfur odor and dyeing occur. Among these methods, it is preferable to use the TERP method from the viewpoint of diversity of usable monomers, molecular weight control in the polymer range, uniform composition, or coloration.

In addition, the living radical polymerization method, especially the TERP method, because the polymer chain is uniformly reacted with the monomer and polymerized at the same time, the structure of all polymers having a structural unit such as a polycyclic aliphatic hydrocarbon group forming a pseudo-crosslinked structure is close to uniform, and many It is preferable that the probability of the cycloaliphatic hydrocarbon group participating in the pseudo-crosslinking is increased.

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator. The methods described in No. 2004/072126 and International Publication No. 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d). (a) A vinyl monomer is polymerized using the organic tellurium compound represented by the general formula (1). (b) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (1) and an azo-type polymerization initiator. (c) A vinyl monomer is polymerized using a mixture of the organic tellurium compound represented by the general formula (1) and the organic ditellurium compound represented by the general formula (2). (d) The vinyl monomer is polymerized using a mixture of the organic tellurium compound represented by the general formula (1), the azo-type polymerization initiator, and the organic ditellurium compound represented by the general formula (2).

[於通式(1)中，R¹ 為表示碳數1至8的烷基、芳香基或芳香族雜環基。R² 及R³ 各自為表示氫原子或碳數1至8的烷基。R⁴ 為表示碳數1至8的烷基、芳香基、取代芳香基、芳香族雜環基、烷氧基、醯基、醯胺基、氧羰基、氰基、烯丙基或炔丙基。 於通式(2)中，R⁵ 為表示碳數1至8的烷基、芳香基或芳香族雜環基。][Chemical formula 1]

[In the general formula (1), R ¹ is an alkyl group, an aromatic group or an aromatic heterocyclic group representing a carbon number of 1 to 8. R ² and R ³ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group having a carbon number of 1 to 8 . In the general formula (2), R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

The group represented by R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and is specifically shown below. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, Linear or branched alkyl groups such as octyl, and cycloalkyl groups such as cyclohexyl. A straight or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. As an aromatic group, a phenyl group, a naphthyl group, etc. are mentioned. As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, etc. are mentioned.

The groups represented by R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically shown below. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, Linear or branched alkyl groups such as octyl, and cycloalkyl groups such as cyclohexyl. A straight or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

The group represented by R ⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an alkene group A propyl group or a propargyl group is specifically shown below. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, Linear or branched alkyl groups such as octyl, and cycloalkyl groups such as cyclohexyl. A straight or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. As an aromatic group, a phenyl group, a naphthyl group, etc. are mentioned. Phenyl is preferred. As a substituted aryl group, a substituted phenyl group, a substituted naphthyl group, etc. are mentioned. Examples of the substituent in the substituted aryl group include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl group represented ^{by -COR 41 (R 41} has 1 to 8 carbon atoms). such as alkyl, aryl, alkoxy or aryloxy with 1 to 8 carbon atoms), sulfonyl and trifluoromethyl. Again these substituents can be substituted for one or both. As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, etc. are mentioned. The alkoxy group is preferably an alkyl group having 1 to 8 carbon atoms bonded to an oxygen atom, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like. As an acyl group, an acetyl group, a propionyl group, a benzyl group, etc. are mentioned. Examples of the amide group include -CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group). The oxycarbonyl group is preferably a group represented by -COOR ⁴³ (R ⁴³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group), and examples thereof include carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, Propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, phenoxycarbonyl and the like. As a preferable oxycarbonyl group, a methoxycarbonyl group and an ethoxycarbonyl group are mentioned. Examples of the allyl group include -CR ⁴⁴¹ R ⁴⁴² -CR ⁴⁴³ =CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are each a hydrogen atom and an alkyl group having 1 to 8 carbon atoms, and each of R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ is A hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and the respective substituents can also be linked in a cyclic structure). Examples of the propargyl group include -CR ⁴⁵¹ R ⁴⁵² -C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are hydrogen atoms or alkyl groups having ^{1 to 8 carbon atoms, and R 453} are hydrogen atoms and alkyl groups having 1 to 8 carbon atoms. , aryl or silyl) etc.

Specific examples of the organic tellurium compound represented by the general formula (1) include (methyltelluriummethyl)benzene, (methyltelluriummethyl)naphthalene, and ethyl-2-methyl-2-methyl. yl telluryl-propionate, ethyl-2-methyl-2-n-butyl telluryl-propionate, (2-trimethylsilyloxyethyl)-2-methyl-2- Butyl telluryl-propionate, (2-hydroxyethyl)-2-methyl-2-methyltellurium-propionate or (3-trimethylsilylpropargyl)-2-methyl All organic tellurium described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870 compound.

The group represented by R ⁵ is an alkyl group having 1 to 8 carbon atoms, an aryl group, and an aromatic heterocyclic group, and is specifically shown below. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, Linear or branched alkyl groups such as octyl, and cycloalkyl groups such as cyclohexyl. A straight or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. As an aromatic group, a phenyl group, a naphthyl group, etc. are mentioned. As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, etc. are mentioned.

Specific examples of the organic ditelluride compound represented by the general formula (2) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, Dicyclopropylditelluride, di-n-butylditelluride, di-sec-butylditelluride, di-tert-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis(para Methoxyphenyl)ditelluride, bis-(p-aminophenyl)ditelluride, bis(p-nitrophenyl)ditelluride, bis(p-cyanophenyl)ditelluride, bis-( p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride or dipyridyl ditelluride and the like.

The azo-type polymerization catalyst can be used without particular limitation as long as it is an azo-type polymerization catalyst used for ordinary radical polymerization. For example, 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2 ,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanenitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate ( MAIB), 4,4'-azobis(4-cyanovaleric acid) (ACVA), 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2 '-Azobis(2-methylbutanamide), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), 2,2' -Azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis [2-Methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2,4,4-trimethylpentane), 2-cyano-2-propane azocarbamide, 2,2'-azobis(N-butyl-2-methylpropionamide), or 2,2'-azobis(N-cyclohexyl-2-methylpropane) amide), etc.

In the polymerization step, in a container substituted with an inert gas, the vinyl monomer and the organotellurium compound of the general formula (1) are used for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc. according to the type of the vinyl monomer, The azo-type polymerization catalyst and/or the organic ditellurium compound of the general formula (2) are further mixed. At this time, nitrogen, argon, helium, etc. are mentioned as an inert gas. Argon and nitrogen are preferred.

The amount of the vinyl monomer used in (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the intended copolymer. The vinyl monomer is preferably 5 mol to 10000 mol relative to 1 mol of the organic tellurium compound of the general formula (1).

When using the organic tellurium compound of the general formula (1) of the (b) and the azo-type polymerization catalyst together, the azo-type polymerization catalyst is preferably 0.01 mol to 10 mol per 1 mol of the organic tellurium compound of the general formula (1).

When the organic tellurium compound of the general formula (1) of the (c) and the organic ditellurium compound of the general formula (2) are used together, the organic ditellurium compound of the general formula (2) is used in 1 mol of the organic tellurium compound of the general formula (1). The tellurium compound is preferably 0.01 mol to 100 mol.

When the organic tellurium compound of the general formula (1) of the (d), the organic ditellurium compound of the general formula (2), and the azo-type polymerization catalyst are used in combination, with respect to the organic tellurium compound of the general formula (1) and the general formula ( 2) The total amount of the organic ditellurium compound is 1 mol, and the azo type polymerization catalyst is preferably 0.01 ml to 100 mol.

Although the polymerization reaction can be carried out without a solvent, it can also be carried out by stirring the mixture using an aprotic solvent or a protic solvent commonly used in radical polymerization. Examples of aprotic solvents that can be used include anisole, benzene, toluene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl methacrylate). ethyl ketone), dioxane, hexafluoroisopropanol, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate or trifluorotoluene Wait. Further, examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

The amount of solvent to be used can be adjusted appropriately. For example, relative to 1 g of vinyl monomer, it is preferably 0.01 ml or more, preferably 0.05 ml or more, more preferably 0.1 ml or more, preferably 50 ml or less, and 10 ml or less. Preferably, it is 1 ml or less.

The polymerization reaction can be performed by mixing and stirring the vinyl monomer and the organotellurium compound of the general formula (1). The reaction temperature and reaction time can be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained copolymer, but they are usually stirred at 0 to 150° C. for 1 minute to 100 hours. TERP method can obtain high recovery rate and precise molecular weight distribution even at low polymerization temperature and short polymerization time. At this time, the pressure is generally carried out at normal pressure, but it does not matter if it is pressurized or reduced.

After the termination of the polymerization reaction, the desired copolymer can be isolated from the obtained reaction mixture by using a solvent and removal of residual vinyl monomers by general separation and purification means.

The group-linked copolymer of the present invention can be obtained, for example, by a living radical polymerization method by sequentially polymerizing the vinyl monomers constituting the group-linking. Specifically, a polymerization method having a step of polymerizing one A group linkage, a step of polymerizing a B group linkage, and a step of polymerizing the other A group linkage can be cited. , polymerize the vinyl monomer that forms one of the two A groups, after polymerizing one A group, polymerize the vinyl monomer that forms the B group, after polymerizing the B group, will form Another group of vinyl monomers linked by two A groups are polymerized.

The growth end of the polymer obtained by the polymerization reaction is in the form of -TeR ^{1 (R 1} in the formula is the same as above) derived from a tellurium compound, and although it is gradually deactivated due to the operation in the air after the termination of the polymerization reaction, there are some Tellurium atoms will remain. Since the copolymer with the tellurium atom remaining at the end will be dyed and has poor thermal stability, it is better to remove the tellurium atom.

As a method for removing the tellurium atom, the following methods can be used or a combination of these methods can be used: radical reduction method using tributyltin or thiol compound, etc.; adsorption using activated carbon, silica gel, activated alumina, activated clay, molecular sieve and polymer The method of adsorbing the agent, etc.; the method of adsorbing the metal with ion exchange resin, etc.; adding a hydrogen peroxide solution or a peroxide such as benzyl peroxide, and blowing air or oxygen into the system to oxidize the tellurium atom at the end of the copolymer Decomposition, liquid-liquid extraction method and solid-liquid phase extraction method to remove residual tellurium compounds by washing with water or an appropriate combination of solvents; purification methods in solution state such as ultrafiltration to extract only those with a specific molecular weight or less.

<2. Composition> The grouped copolymer can be used as a composition containing the grouped copolymer. In addition to the aggregated copolymer, the composition can also contain organic solvents, plasticizers, colorants (pigments, dyes, etc.), coupling agents, preservatives, antistatic agents, antioxidants, ultraviolet absorbers, and surfactants , flame retardants, fillers, cross-linking agents, fillers and other additives. This composition can be used as a primer composition, a surface modification composition, an adhesive composition, and an adhesive composition by appropriately adjusting the additives according to the application.

This composition does not use chlorine-containing compounds, and has strong adhesion (adhesion) not only to high-polarity materials but also to low-polarity materials. Therefore, by coating and processing the composition on the surface of a film or a molded article made of a low-polarity material, it becomes possible to coat and subsequently coat a high-grade material with low adhesion to the low-polarity material. In particular, the composition of the present invention can be suitably used for polyolefin resins among low-polarity materials.

(Primer composition) When this composition is used as a primer composition, it is preferable that the primer composition contains the group-linked copolymer and a solvent. The primer composition can, for example, be coated on the surface of the low-polarity material to improve the adhesion of the high-polarity material to the surface of the low-polarity material. Specifically, with regard to the surface of the low-polarity material, it becomes possible to apply the hard-coat composition widely used for optical members, and to bond the thin film made of the high-polarity material.

As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. In particular, in order to improve the coatability of the primer composition, it is preferable to combine the block copolymer and other additive components with a soluble organic solvent. Also, from the viewpoint of the ease of handling of the primer composition, the total concentration of the group-linked copolymer and other solid components is preferably 50% by mass or less. In addition, it is preferable that the solvent does not impair the properties of the substrate (film, etc.) coated with the primer composition.

Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as diethyl ether and tetrahydrofuran; acetates such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; N,N-dimethyl ether Carboxamide and N-methylpyrrolidone and other amides; aromatic hydrocarbon compounds such as benzene, toluene and xylene; aliphatic hydrocarbon compounds such as n-hexane; alicyclic hydrocarbon compounds such as cyclohexane. These organic solvents may each be used alone, or two or more of them may be used in combination.

(Surface-modifying composition) The primer composition can be used as a surface-modifying composition in combination with various additives. As the surface-modifying composition, for example, a composition for hard coats containing the aggregated copolymer, a solvent, and a hard coat agent can be mentioned. Using the composition for a hard coat layer, a hard coat layer containing a highly polar material can be directly formed on the surface of a low polar material.

As this solvent, the same thing as a primer composition can be used. As this hard coating agent, an acrylic material is mentioned, for example. The acrylic material is not particularly limited, but monomeric radical polymerizable monofunctional acrylates, difunctional acrylates, trifunctional acrylates, and 4- to 6-functional acrylates; oligomers Free-radical polymerized epoxy acrylate, urethane acrylate, polyester acrylate, copolymer acrylate, polybutadiene acrylate, siloxane acrylate, amino resin acrylate, etc. The acrylic material can be used alone or in combination of two or more.

Although it does not specifically limit as a hardening type of a hard coating agent, Ultraviolet (UV) hardening type by photochemical reaction; room temperature hardening type and two-component reaction hardening type thermosetting type are mentioned. That is, although it does not specifically limit as a hard coating agent, Generally known UV curable resin, a urethane resin, and a condensation resin are mentioned.

(Adhesive composition) When this composition is used as an adhesive composition, it is preferable that an epoxy resin and a curing agent are combined in the adhesive composition in addition to the group-linked copolymer. Furthermore, the adhesive composition may contain a hardening accelerator. The adhesive composition is excellent in adhesion to low-polarity materials and high-polarity materials.

The epoxy resin is not particularly limited, and examples thereof include epoxy resins having more than bifunctional groups, such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; phenol novolak type epoxy resin and cresol novolak type epoxy resin Epoxy resins with trifunctional or higher groups such as resins. The term "difunctional or more" refers to epoxy resins containing two or more epoxy groups in one molecule. The term "trifunctional or more" refers to epoxy resins containing three or more epoxy groups in one molecule.

The curing agent for the epoxy resin is not particularly limited, and examples thereof include bisphenol A, a compound containing two or more amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, and phenolic hydroxyl groups in one molecule. Bisphenol F, Bisphenol S and phenolic resins.

In addition, the adhesive composition is preferably composed of a soluble organic solvent in combination with the group-linked copolymer and other additive components in order to improve coatability. In this case, from the viewpoint of the ease of handling of the adhesive composition, the total concentration of the block copolymer and other solid components is preferably 50 mass % or less.

Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as diethyl ether and tetrahydrofuran; acetates such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; N,N-dimethyl ether Carboxamide and N-methylpyrrolidone and other amides; aromatic hydrocarbon compounds such as benzene, toluene and xylene; aliphatic hydrocarbon compounds such as n-hexane; alicyclic hydrocarbon compounds such as cyclohexane; these organic solvents can be used independently It is also possible to use two or more kinds in combination.

(Adhesive composition) When the composition is used as an adhesive composition, the adhesive composition preferably contains the grouped copolymer and a cross-linking agent. By mixing and crosslinking a crosslinking agent capable of reacting with the reactive functional group possessed by the group-linked copolymer, the cohesion force and the adhesiveness can be further improved. The cross-linking agent is not particularly limited, and examples include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, amine-based cross-linking agents, and vinyl-containing urethane acrylates Cross-linking agent, resin cross-linking agent with oxazoline group, metal chelate type cross-linking agent, metal salt, metal alkoxide, metal chelate, ammonium salt, hydrazine compound and acrylic polymer resin paste, etc.

In the adhesive composition, the content of the crosslinking agent is preferably 0.01 mass part or more, preferably 0.1 mass part or more, more preferably 1 mass part or more, relative to 100 mass parts of the grouped copolymer. 20 parts by mass or less is preferable, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. When the content of the crosslinking agent is within the above range, the adhesive force becomes good.

The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups temporarily protected by blocking agents or quantification) in one molecule. The isocyanate-based crosslinking agent may be used alone or in combination of two or more.

Examples of the isocyanate-based crosslinking agent include aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. Aromatic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and polymethylene polyphenyl isocyanate; isotrimethylol Cyanate addition products such as trimethylolpropane/toluene diisocyanate trimer adduct, trimethylolpropane/hexamethylene diisocyanate trimer adduct and isocyanurate body of hexamethylene diisocyanate Products; trimethylolpropane adducts of xylylene diisocyanate; trimethylolpropane adducts of hexamethylene diisocyanate; polyether polyisocyanates, polyester polyisocyanates and these and various Adducts of polyols, polyisocyanates with polyfunctional groups such as isocyanurate bonds, biuret bonds, and allophanate bonds.

When an isocyanate-based cross-linking agent is used as the cross-linking agent, the content of the isocyanate-based cross-linking agent is preferably 0.01 mass part or more, more preferably 0.1 mass part or more, relative to 100 mass parts of the grouped copolymer. It is preferably 1 mass part or more, preferably 20 mass parts or less, more preferably 15 mass parts or less, more preferably 10 mass parts or less. When the content of the crosslinking agent is within the above range, the adhesive force becomes good.

The epoxy-based crosslinking agent is a polyfunctional epoxy compound having two or more epoxy groups in one molecule. The epoxy-based crosslinking agent may be used alone or in combination of two or more. Examples of the epoxy-based crosslinking agent include bisphenol A, epichlorohydrin-type epoxy resins, vinyl glycidyl ether, N,N,N',N'-tetraglycidyl-m-xylenediamine, Diglycidylaniline, diamineglycidylamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol Diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitan polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipate diglycidyl ether, Diglycidyl phthalate, triglycidyl tris(2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and the like.

When an epoxy-based cross-linking agent is used as the cross-linking agent, the content of the epoxy-based cross-linking agent is preferably 0.01 mass part or more, more preferably 0.05 mass part or more with respect to 100 mass parts of the aggregated copolymer. , more preferably 0.1 mass parts or more, preferably 5 mass parts or less, preferably 4 mass parts or less, more preferably 3 mass parts or less. When the content of the crosslinking agent is within the above range, the adhesive force becomes good.

The adhesive composition can also be mixed with a cross-linking accelerator and an adhesion-imparting agent as required. The crosslinking accelerator is not particularly limited, and examples include conventional catalysts such as organotin, tertiary amines, p-toluenesulfonic acid, and benzenesulfonic acid, and, in the case of epoxy-based compounds, phosphoric acid catalysts such as triphenylphosphine and the like. . The adhesion imparting agent is not particularly limited, and examples include polymerized rosin, rosin ester, C5-based petroleum resin, dicyclopentadiene-based petroleum resin, and terpene-based petroleum resin, or hydrogenated resins of these, low-molecular-weight styrene resin, low molecular weight α-methylstyrene resin, etc.

The adhesive composition preferably contains an organic solvent in combination with the grouped copolymer and other additive components in order to improve coatability. In this case, from the viewpoint of the ease of handling of the adhesive composition, the total concentration of the aggregated copolymer and other solid content is preferably 50 mass % or less.

Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as diethyl ether and tetrahydrofuran; acetates such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; N,N-dimethyl ether Carboxamide and N-methylpyrrolidone and other amides; aromatic hydrocarbon compounds such as benzene, toluene and xylene; aliphatic hydrocarbon compounds such as n-hexane; alicyclic hydrocarbon compounds such as cyclohexane; these organic solvents can be used independently It is also possible to use two or more kinds in combination.

<3. Film> The film of the present invention includes a substrate and a layer, and at least a part of the layer on at least one side of the substrate is composed of the above-mentioned composition.

Examples of the base material include low-polarity materials such as polyolefin resins such as polypropylene (PP), polyethylene (PE), and cycloolefin resin (COP); and metals, glass, and polyethylene terephthalate resins. , Polyamide resin, polycarbonate resin, polyacrylic methyl resin, polyvinyl alcohol resin, triacetate cellulose and other highly polar materials. As a shape of a base material, a film (belt shape and a sheet shape are included) are mentioned.

As a layer formed from this composition, a primer layer, a surface modification layer (for example, a hard coat layer), an adhesive layer, and an adhesive layer are mentioned.

The primer layer can be formed by applying the primer composition to a substrate and drying it. The coating method is not particularly limited, but includes a reverse coating method, a gravure coating method, a spray coating method, a coincidence coating method, a wire bar coating method, a curtain coating method, and a dip coating method. method and rod coating method. The heating and drying temperature after coating varies depending on the material and application of the substrate, but is preferably 200°C or lower in order to suppress deformation of the substrate, and 25°C from the viewpoint of phase separation of the self-aggregated copolymer. The above is better. The thickness of the primer layer (thickness after drying) is not particularly limited, but is preferably 10 nm to 10 μm.

This surface modification layer (for example, a hard coat layer) can be formed by hardening a heterogeneous coating agent by apply|coating this composition for hard coat layers to a base material, and drying it. Although the coating method of the composition for hard coats is not particularly limited, the same method as the above-mentioned primer composition can be employed. The method of hardening the hard coating agent may be appropriately selected according to the hard coating agent.

This adhesive agent layer can be formed by apply|coating this adhesive agent composition to a base material, and drying it. The coating method of the adhesive composition is not particularly limited, and examples include reverse coating, gravure coating, spray coating, coincidence coating, wire bar coating, and curtain coating. Cloth method, dip coating method, bar coating method. The drying conditions are not particularly limited as long as the used solvent is sufficiently volatilized, but generally, heating at 50°C to 200°C for 0.1 to 60 minutes is preferable.

When the base material and the adherend are bonded through the adhesive layer, the bonding layer can be heated and hardened by pressing the base material and the adherend to be bonded. For pressing, for example, a roll laminator, a flat plate press, a wafer laminator, a vacuum laminator, an elastomer press, and an autoclave can be used. As a heating condition, it is preferable to carry out 0.1 minute to 5 minutes under the pressure of 0.01MPa to 5.0MPa. The heat-hardening conditions are not particularly limited as long as the adhesive composition is hardened, but generally, heating at 50 to 200° C. for 0.1 to 180 minutes is preferable.

The adhesive layer can be formed by applying the adhesive composition to the base material and then appropriately applying curing treatment. Coating of the adhesive composition can be carried out by using a gravure coater, a reverse coater, a coincidence coater, a dip coater, a bar coater, a knife coater, a jet coater, etc. commonly used coater to implement. In addition, although the adhesive composition may be directly coated on the substrate to form the adhesive layer, the adhesive layer formed on the release liner may also be transferred to the substrate. The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm to 200 μm.

When two or more curing treatments (drying, crosslinking, polymerization, etc.) are performed on the adhesive layer, these can be performed simultaneously or in multiple stages. In the adhesive composition using a partial polymer (acrylic polymer resin syrup), as a curing treatment, a copolymerization reaction (partial polymerization followed by a further polymerization reaction to form a complete polymer) is finally performed. In the case of a photocurable adhesive composition, light irradiation is performed. Cross-linking, drying and other hardening treatments can also be performed according to requirements. For example, when drying with a photocurable adhesive composition is required, photocuring may be performed after drying. In an adhesive composition using a complete polymer, drying (heat drying), cross-linking, etc., as required, is typically performed as the curing treatment described above.

[Examples] Hereinafter, the present invention is not limited to these examples, although specific descriptions will be given based on the examples of the present invention. In addition, various physical property measurements were performed by the following machines. In addition, the meanings of abbreviations are as follows. BTEE: Ethyl 2-methyl-2-n-butyldodecyl propionate AIBN: 2,2'-azobis(isobutyronitrile) IBXA: isobornyl acrylate DCPTAA: dicyclopentyl acrylate CHA: Cyclohexyl Acrylate BA: Butyl Acrylate MA: Methacrylate MEA: Methoxyethyl Acrylate DMAAm: N,N-Dimethacrylamide HEA: Hydroxyethyl Acrylate AA: Acrylic Acid VP : Vinylpyrrolidone Ani: Anisole MP: 1-Methoxy-2-propanol MeOH: Methanol

^{(Polymerization rate) 1} H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) was measured using a nuclear magnetic resonance (NMR) measuring apparatus (manufactured by Bruker, model: AVANCE 500 (frequency: 500 MHz)). About the obtained NMR spectrum, the integral ratio of the vinyl group derived from a monomer, and the peak derived from a polymer was calculated|required, and the polymerization rate of each monomer was calculated.

(Weight Average Molecular Weight (Mw) and Molecular Weight Distribution (PDI)) It was determined by gel permeation chromatography (GPC) using a high-speed liquid chromatography (manufactured by Tosoh Corporation, model HLC-8320GPC). Two pieces of TSKgel SuperMultopore HZ-H (Φ4.6 mm×150 mm) (manufactured by Tosoh Corporation) were used as the column, tetrahydrofuran was used as the mobile phase, and a differential refractive index detector was used as the detector. The measurement conditions were as follows: the column temperature was 40° C., the sample concentration was 1 mg/mL, the sample injection volume was 10 μL, and the flow rate was 0.35 mL/min. A calibration curve was prepared using polystyrene (manufactured by Tosoh Corporation, TSK standard) as a standard substance, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured, and the molecular weight distribution (PDI) was calculated from these measured values.

<Production of Copolymer> (Agglomerated Copolymer No. 1) In a flask equipped with an argon gas introduction tube and a stirring blade, 42.7 mg of BTEE, 3.70 g of IBXA, 4.7 mg of AIBN, and 3.50 g of anisole were prepared so as to be Reaction at 60°C for 24 hours to polymerize A1 groups. The polymerization rate of IBXA was 99%. The Mw of the obtained A1 conglomerate was 19920 and the PDI was 1.33.

A mixed solution of 1.14 g of BA, 4.7 mg of AIBN, and 1.20 g of anisole previously substituted with argon was further added to the reaction liquid, and the mixture was reacted at 60° C. for 24 hours to polymerize the B group linkage. The polymerization rate of BA was 98%. The Mw of the obtained A1-B group-linked copolymer was 30910, and the PDI was 1.34.

A mixed solution of 3.70 g of IBXA, 4.7 mg of AIBN, and 3.60 g of anisole previously substituted with argon was further added to the reaction liquid, and the mixture was reacted at 60° C. for 58 hours to polymerize the A2 linkage. The polymerization rate of IBXA was 99%. The Mw of the obtained A1-B-A2 group interpolymer was 46810, and the PDI was 1.84. After the completion of the reaction, an organic solvent (anisole or the like) is added to the reaction solution for dilution. The diluted reaction solution was poured into acetonitrile under stirring to precipitate a polymer. The precipitated polymer was filtered and dried by suction to obtain the aggregated copolymer No.1.

(Bag copolymer No. 2 to 15) In the same manner as the production method of the gang copolymer No. 1, the gang copolymer No. 2 to 15 was produced. Tables 2 and 3 show used raw material monomers, organic tellurium compounds, azo-type polymerization initiators, solvents, polymerization conditions, and polymerization rates. In addition, in Tables 4 and 5, the Mw and PDI of each group-linked copolymer are shown.

【Table 2】

【table 3】

【Table 4】

【table 5】

(Random Copolymer No. 1) In a flask equipped with an argon gas introduction tube and a stirring blade, BTEE 41.5 mg, IBXA 5.40 g, BA 2.90 g, AIBN 4.5 mg, and anisole 7.50 g were prepared and reacted at 60°C. 87 hours to polymerize. The polymerization rate of IBXA and BA was 100%. Furthermore, the Mw of the obtained random copolymer No. 1 was 62190, and the PDI was 1.26. After the completion of the reaction, an organic solvent (anisole or the like) is added to the reaction solution for dilution. The diluted reaction solution was poured into acetonitrile under stirring to precipitate a polymer. The precipitated polymer was filtered by suction and dried to obtain random copolymer No.1.

(Random Copolymer Nos. 2 to 4) In the same manner as the production method of the random copolymer No. 1, the aggregated copolymers No. 2 to 4 were produced. Table 6 shows the used raw material monomers, organic tellurium compounds, azo-type polymerization initiators, solvents, polymerization conditions, and polymerization rates, and also shows the Mw and PDI of each random copolymer.

【Table 6】

With respect to the above-obtained grouped copolymer and random copolymer, the solubility and substrate adhesion were evaluated.

(Solubility) About the grouped copolymer Nos. 2 and 3 and the random copolymer No. 1 and 2, the solubility to the solvent was evaluated. Specifically, a solvent (methyl ethyl ketone (MEK) or 1-methoxy-2-propanol (MP)) was added to the copolymer so that the solid content was 30 mass %, and the mixture was stirred at 23° C. for 60 minutes. After stirring, the solubility was assessed visually. As for the solubility, those that were uniformly dissolved were rated as "○", and those that were not dissolved (precipitation, insolubility, emulsification, etc.) were rated as "x". The results are shown in Table 7.

【Table 7】

(Substrate Adhesion) Regarding the grouped copolymers Nos. 1 to 8 and 13 to 15, and the random copolymers No. 1 to 3, the adhesion to the substrate was evaluated. Specifically, the copolymer was mixed with a solvent (MEK) so that the solid content was 1 mass % to prepare a coating agent. The obtained coating agent was coated on a substrate with a bar coater (wet film thickness; 6.87 μm), and was dried in a hot air dryer (130° C.) for 10 minutes to obtain a coated substrate . In addition, aliphatic cyclic polyolefin (COP) or polypropylene (PP) was used as the material of the base material, and the thickness of the base material was 100 μm.

Regarding the resulting coated substrate, the appearance was evaluated by visual observation of the coating. As for the appearance, those with no whitening or peeling were rated as "○", and those with whitening or peeling were rated as "X". The surface adhesion of the coatings was also evaluated. The surface adhesion was obtained by pressing the coating surface with a finger, and those with no change were rated as "○", and those with fingerprints left or the coating adhered to the fingers were rated as "x". The adhesion of the coating to the substrate was evaluated by a hundred grid adhesion test (the old JIS K5400 (1990) specification, the interval of the incisions is 1 mm). The results are shown in Table 8.

【Table 8】

Adhesive compositions and primer compositions were prepared using the above-obtained grouped copolymers and random copolymers, and the adhesion and the like were evaluated.

(Adhesive composition) The aggregated copolymer Nos. 9 to 14 were mixed in a solvent (MEK) so that the solid content was 10% by mass to prepare an adhesive composition. The obtained adhesive composition was applied on a COP film (thickness: 100 μm) as a base material by a bar coater (wet film thickness; 50 μm), and was dried in a hot air dryer (130° C.) for 10 minutes. minutes to form an adhesive layer (thickness after drying; 2.5 μm). Then, the laminated body which carried the polyethylene terephthalate (PET) film used as the to-be-adhered body on the adhesive layer was obtained. This laminated body was thermally pressed under the conditions of 100° C. and 1 MPa for 3 minutes using a press machine (MP-WCH, manufactured by Toyo Seiki Co., Ltd.) to produce a dissimilar membrane composite.

The obtained dissimilar film composite was cut into a width of 30 mm and a length of 100 mm, and the surface on the side of the COP film was fixed to a rigid adherend (SUS plate, length 125 mm) to prepare a test piece. In addition, in this dissimilar film composite, an adhesive layer was formed over the entire width from one end in the longitudinal direction to a position of 90 mm. For this test piece, a 180-degree peeling test was performed using a tensile compression tester (SV-52NA, manufactured by Imada Seisakusho). The unbonded end of the flexible adhesive material (PET film) of the test piece was folded back, the rigid adhesive material and the COP film were sandwiched by a clamp, and the flexible adhesive material was attached to the other clamp. The clip was moved at a speed of 50 mm/min until the next length was peeled off by 25 mm, and the peeling force (resistance) (unit: N/30 mm) at that time was measured. The results are shown in Table 9. In addition, the same experiment was performed about the grouped copolymer Nos. 11 to 13, and about changing the base material to a PET film (thickness 100 μm) and changing the adherend to a PP film (thickness 50 μm).

【Table 9】

(Primer composition) The grouped copolymers No. 2 to 4, 13 and 14, and the random copolymers No. 2 and 4 were mixed in a solvent (MEK) so that the solid content was 1 mass % to prepare a primer composition thing. The obtained primer composition was coated on a corona-treated COP film (thickness: 100 μm) with a bar coater (wet film thickness; 6.87 μm), and was placed in a hot air dryer (130° C.). Dry for 10 minutes to form a primer layer. Next, on the primer layer, a hard coat composition containing urethane acrylate was applied with a bar coater (wet film thickness; 11.45 μm) and dried in a hot air dryer (80° C.) for 1 minute. , forming a hard coating. Then, using a UV curing device (electrodeless UV lamp system (LICHT HAMMER ^® 6) manufactured by Heraeus), under the conditions of a peak illuminance of 900 (mW/cm ² ) and a cumulative light intensity of 350 (mJ/cm ² ) The coating composition layer is hardened to obtain a material coated with a hard coat layer on the COP film.

Regarding the obtained material, the adhesion of the hard coat layer to the substrate was evaluated by a 100 grid adhesion test (the old JIS K5400 (1990) specification, the interval of the incisions is 1 mm), and the results are shown in Table 10. The hardness of the hard coat surface layer was also evaluated by the iron wool resistance test. For iron velvet resistance, in order to hold the iron velvet number #0000 into a ball, rub it repeatedly by hand for several times. The results are shown in Table 10.

【Table 10】

(Adhesive composition) An adhesive composition was prepared by mixing a crosslinking agent with a cross-linking agent using 1 part by mass of the block copolymer No. 11 or 12 and 9 parts by mass of the solvent (tetrahydrofuran). In addition, the crosslinking agent used was Crosslinking Agent 1 (manufactured by Mitsubishi Petrochemical Chemicals, TETRAD-X) or Crosslinking Agent 2 (Duranate ^® TPA-100, manufactured by Asahi Kasei Corporation). In addition, the combined amount of the crosslinking agent was 0.021 parts by mass when the crosslinking agent 1 (TETRAD-X) was used, and 0.0066 parts by mass when the crosslinking agent 2 (D-TPA) was used.

The obtained adhesive composition was coated on a substrate (thickness: 100 μm) with a bar coater (wet film thickness; 50 μm), and was dried in a hot air dryer (100° C.) for 1 minute to form a Adhesive layer (thickness after drying; 2.5 μm). After that, an adherend (thickness 50 μm) was placed on the adhesive layer, and pressed with a load of 100 kgf (980 N) using a press roll (manufactured by Tester Sangyo Co., Ltd., SA-1100) to obtain a base body. This layered product was crosslinked under the conditions of 23° C. and 50% relative humidity to produce a dissimilar membrane composite.

The obtained dissimilar film composite was cut into a width of 30 mm and a length of 100 mm, and the side surface of the base material was fixed to a rigid adherend (SUS plate, length 125 mm) to prepare a test piece. In addition, in this dissimilar film composite, an adhesive layer was formed over the entire width from one end in the longitudinal direction to a position of 90 mm. About this test piece, the peeling test of 180 degree|times was performed similarly to this adhesive agent composition. The results are shown in Table 11

【Table 11】

The present invention includes the following aspects.

Type 1 A group-linked copolymer comprising: A group-link having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group; and a B-link having a structural unit derived from a vinyl monomer, the The average glass transition temperature of the A group is above 25°C, the average glass transition temperature of the B group is lower than the average glass transition temperature of the A group, and the average glass transition temperature of the A group is equal to the average glass transition temperature of the B group. The difference between the glass transition temperatures is 50°C or more.

Form 2 The gang-linked copolymer according to Form 1, wherein the gang-linked copolymer is an AB-A type gang-linked copolymer.

Form 3 The grouped copolymer according to Form 1 or 2, wherein the vinyl monomer having a polycyclic aliphatic hydrocarbon group is (meth)acrylic acid polycyclic aliphatic hydrocarbon ester.

Form 4 The grouped copolymer according to any one of Forms 1 to 3, wherein the content of the B group is 5 to 60 mass % in 100 mass % of the entire grouped copolymer.

Form 5 The group-linked copolymer of any one of Forms 1 to 4, wherein the molecular weight distribution (PDI) of the group-linked copolymer is 2.5 or less.

Form 6 The grouped copolymer of any one of Forms 1 to 5, wherein the grouped copolymer is polymerized by living radical polymerization.

Form 7 A composition comprising the grouped copolymer of any one of Forms 1-6.

Form 8 A film comprising a substrate and a layer formed of the composition of Form 7 on at least a portion of at least one side of the substrate.

Form 9 The film of Form 8, wherein the substrate is a polyolefin resin.

Form 10 The composition of Form 7, wherein the composition is a primer composition.

Form 11 The composition of Form 7, wherein the composition is a surface modification composition.

Form 12 The composition of Form 7, wherein the composition is an adhesive composition.

Form 13 The composition of Form 7, wherein the composition is an adhesive composition.

The group-linked copolymer of the present invention has strong adhesion (adhesion) not only to high-polarity materials but also to low-polarity materials such as polyolefin-based resins. Therefore, the grouped copolymer of the present invention can be used as a primer composition, an adhesive composition, and an adhesive composition when a low-polarity material and a high-polarity material are fixed. In addition, the grouped copolymer of the present invention can be used as an adhesiveness imparting agent of an acrylic adhesive.

Claims (20)

A group-linked copolymer comprising: A group-linked, having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group and a structural unit derived from a vinyl monomer having a reactive functional group, the reactive functional The group is a hydroxyl group, a carboxyl group or an epoxy group; and the group B has a structural unit derived from a vinyl monomer, and the average glass transition temperature of the group A is above 25°C and below 150°C. The content of the structural unit derived from the vinyl monomer having a polycyclic aliphatic hydrocarbon group is 40% by mass or more in 100% by mass of the A group, the vinyl monomer having a polycyclic aliphatic hydrocarbon group , is acrylic polycyclic aliphatic hydrocarbon ester, the content of the structural unit derived from the vinyl monomer having the reactive functional group in the A group is 0.1 mass % in the A group in 100% by mass % to 5.0 mass %, the average glass transition temperature of the B group is lower than the average glass transition temperature of the A group, the difference between the average glass transition temperature of the A group and the average glass transition temperature of the B group It is 50 degreeC or more, and the content rate of this B group link is 5-60 mass % in the whole 100 mass % of this group link copolymer. The grouped copolymer according to claim 1, wherein the grouped copolymer is an A-B-A type grouped copolymer. The group-linked copolymer according to claim 1, wherein the vinyl monomer having a polycyclic aliphatic hydrocarbon group is selected from the group consisting of 1-adamantyl acrylate, 2-adamantyl acrylate, 2-methyl-2 - the group consisting of adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, norbornyl acrylate, isobornyl acrylate, dicyclopentyl acrylate and dicyclopentenyl acrylate at least one of them. The grouped copolymer according to claim 1, wherein the weight average molecular weight of the grouped copolymer is 3,000 to 1,000,000. The grouped copolymer according to claim 1, wherein the molecular weight distribution (PDI) of the grouped copolymer is 2.5 or less. The grouped copolymer according to claim 1, wherein the grouped copolymer is polymerized by living radical polymerization. A composition comprising the group-linked copolymer according to any one of claims 1 to 6. The composition according to claim 7, which does not contain an acid catalyst or an acid generator. A composition comprising a gang-linked copolymer and no acid catalyst or acid generator, wherein the gang-linked copolymer comprises: A gang-linked having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group; and The B group has a structural unit derived from vinyl monomers, the average glass transition temperature of the A group is 25°C or higher and 150°C or lower, and the A group is derived from the polycyclic aliphatic hydrocarbon group. The content of the structural unit of the vinyl monomer is 40% by mass or more in 100% by mass of the A group, and the vinyl monomer having a polycyclic aliphatic hydrocarbon group is an acrylic acid polycyclic aliphatic hydrocarbon ester, and the The average glass transition temperature of the B group is lower than the average glass transition temperature of the A group, and the difference between the average glass transition temperature of the A group and the B group is more than 50 ℃, the B group The content rate of agglomerate is 5 to 60 mass % in 100 mass % of the whole block-linked copolymer. The composition according to claim 9, wherein the group-linked copolymer is an A-B-A type group-linked copolymer. The composition according to claim 9, wherein the vinyl monomer having a polycyclic aliphatic hydrocarbon group is selected from the group consisting of 1-adamantyl acrylate, 2-adamantyl acrylate, 2-methyl-2-adamantyl Of the group consisting of alkyl acrylates, 2-ethyl-2-adamantyl acrylates, norbornyl acrylates, isobornyl acrylates, dicyclopentyl acrylates and dicyclopentenyl acrylates at least one. The composition according to claim 9, wherein the weight-average molecular weight of the group-linked copolymer is 3,000 to 1,000,000. The composition according to claim 9, wherein the molecular weight distribution (PDI) of the group-linked copolymer is 2.5 or less. The composition of claim 9, wherein the group-linked copolymer is polymerized by living radical polymerization. A film, comprising: a substrate and a layer, the layer is located on at least a part of at least one side of the substrate, and is composed of the composition according to any one of claims 7 to 14. The film of claim 15, wherein the substrate is a polyolefin resin. The composition according to any one of claims 7 to 14, wherein the composition is a primer composition. The composition according to any one of claims 7 to 14, wherein the composition is a surface modification composition. The composition according to any one of claims 7 to 14, wherein the composition is an adhesive composition. The composition according to any one of claims 7 to 14, wherein the composition is an adhesive composition.