KR102112439B1 - Block copolymers, compositions and films - Google Patents

Abstract

A block copolymer having strong adhesion (adhesiveness) to not only high-polarity materials but also low-polarity materials without using a chlorine-containing compound is provided. The block copolymer has an A block having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group, and a B block having a structural unit derived from a vinyl monomer, wherein the average glass transition temperature of the A block is 25 ° C or higher. It is characterized in that the average glass transition temperature of the B block is lower than the average glass transition temperature of the A block, and the difference between the average glass transition temperature of the A block and the average glass transition temperature of the B block is 50 ° C or higher.

Description

Block copolymers, compositions and films

The present invention relates to a block copolymer, a composition containing the block copolymer, and a film having a layer formed from the composition.

Polypropylene resins (hereinafter referred to as "PP") and polyethylene resins (hereinafter referred to as "PE") are inexpensive, general-purpose resins excellent in moldability, chemical resistance, water resistance, and electrical properties. The PP and PE are widely used in applications such as automobiles, home appliances, agriculture, and printing. Moreover, the cycloolefin resin (hereinafter referred to as "COP") has excellent characteristics such as high transparency, low hygroscopicity, and low specific gravity. This COP is used as a glass replacement material and a transparent plastic replacement material for optical members such as displays and touch panels. However, polyolefin-based resins such as PP, PE, and COP have a small polarity and have few functional groups present on the surface of the member, making it difficult to coat or adhere.

As a method for solving the above problems, a method of improving adhesion by subjecting the surface of an adherend (polyolefin resin) to physical treatment such as corona treatment, plasma treatment, ultraviolet treatment, or chemical treatment with an organic solvent is known. . For example, in Patent Document 1, chemical treatment with an organic solvent has been proposed (see Patent Document 1 (paragraphs 0019, 0023)). However, the physical treatment requires a special device, and there is a problem that there is a fear that the film performance may be deteriorated by physical stimulation. Since chemical treatment dissolves and swells the surface with an organic solvent, there is a concern that film performance may deteriorate, and there is also a problem that quality control such as solvent ratio and treatment time is complicated.

Moreover, as a method of improving the adhesion without surface treatment, Patent Document 2 proposes to use a chlorinated polyolefin resin having a strong adhesion to a polyolefin-based resin as a primer or adhesive (Patent Document 2 (paragraphs 0008 and 0012). ) Reference). However, since the chlorinated polyolefin resin contains chlorine, its use tends to be avoided due to the growing interest in environmental issues.

By the way, (meth) acrylic resin is widely used as a hard coat composition for adhesives, adhesives, primers, and optical members for optical members such as displays and touch panels. This (meth) acrylic resin does not contain chlorine, and is rich in kinds of monomers as raw materials, and can physically control physical properties and chemical properties such as hardness, transparency, weather resistance, and chemical resistance. However, since the (meth) acrylic resin is a material having a high polarity, it is not suitable for a member made of a polyolefin resin.

Therefore, a technique for improving the adhesion of the (meth) acrylic resin to the polyolefin resin has been proposed. For example, in Patent Document 3, a primer composition containing a polymer containing a (meth) acrylic acid ester monomer unit in which an acryloyloxy group or a methacryloxy group is bonded to a secondary carbon atom or a tertiary carbon atom is described ( See Patent Document 3 (Claim 1)). In Patent Document 4, a composition containing a polymer having a (meth) acrylic acid ester monomer in which an alicyclic hydrocarbon group is bonded to an acryloyloxy group or a methacryloxy group, and a tackifying resin is described (Patent Document 4 (paragraphs 0008 and 0009). ) Reference). In Patent Document 5, a composition containing an acrylic polymer and a (meth) acrylic polymer containing a (meth) acrylic monomer having a tricyclic or higher alicyclic structure as a monomer unit is described (Patent Document 5 (paragraph 0039-0043)) Reference).

Japanese Patent Publication No. 2015-114456 Japanese Patent Publication No. Hei 6-306227 International Publication No. 2004/018575 Japanese Patent Publication 2008-239768 Japanese Patent Publication 2014-74179

As described above, a technique for improving adhesion of a (meth) acrylic resin to a polyolefin resin has been proposed. However, even in the methods of Patent Documents 3 to 5, there was a problem that the adhesive strength and the adhesive strength to the polyolefin-based resin were low.

The object of the present invention is to use only high polarity materials such as metal, polyethylene terephthalate resin, polyamide resin, polycarbonate resin, polyacrylic acid methyl resin, polyvinyl alcohol resin, and triacetyl cellulose without using a compound containing chlorine. In addition, it is to provide a block copolymer having strong adhesion (adhesiveness) to low-polarity materials such as polyolefin-based resins.

The block copolymer of the present invention capable of solving the above problems has an A block having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group, and a B block having a structural unit derived from a vinyl monomer, and the A block. The average glass transition temperature of is 25 ° C or higher, the average glass transition temperature of the B block is lower than the average glass transition temperature of the A block, and the difference between the average glass transition temperature of the A block and the average glass transition temperature of the B block It is characterized by being 50 ° C or higher.

It is thought that the adhesion (adhesion) of the block copolymer to the low-polar material (for example, COP film) improves because the polycyclic aliphatic hydrocarbon group is localized in the A block. In addition, it is considered that the B block having a low average glass transition temperature functions as a soft segment, thereby improving coatability and flexibility. In addition, by appropriately selecting the type of the vinyl monomer of the B block, adhesion to a high-polarity material (for example, an acrylic film) can also be enhanced. Therefore, the adhesiveness of a low polarity material and a high polarity material can be improved by using the said block copolymer.

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

In the present invention, a composition characterized by containing the block copolymer is also included. Examples of such a composition include a primer composition, a surface modification composition, an adhesive composition, and an adhesive composition. In addition, the present invention also includes a film characterized by having a base and a layer formed of a composition containing the block copolymer on at least a portion of at least one side of the base. The base material is preferably a polyolefin-based resin.

ADVANTAGE OF THE INVENTION According to this invention, the block copolymer which has strong adhesion (adhesiveness) to not only a high polarity material but also a low polarity material can be provided without using a compound containing chlorine.

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

<1. Block copolymer>

The block copolymer has an A block having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group, and a B block having a structural unit derived from a vinyl monomer. And, in the block copolymer of the present invention, the average glass transition temperature of the A block is 25 ° C or higher, the average glass transition temperature of the B block is lower than the average glass transition temperature of the A block, and the average glass of the A block The difference between the transition temperature and the average glass transition temperature of the B block is 50 ° C or higher.

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

In the present specification, "a structural unit derived from a vinyl monomer" refers to a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is a carbon-carbon single bond. Moreover, in this specification, "(meth) acrylic" represents "at least one of acrylic and methacryl", and "(meth) acrylate" represents "at least one of acrylate and methacrylate."

The glass transition temperature (Tg) of the block is a value calculated by the following FOX formula (Formula (1)). In the formula (1), Tg represents the glass transition temperature (° C) of the block. Tgi represents the glass transition temperature (° C) when the vinyl monomer i formed a homopolymer. Wi represents the mass ratio of vinyl monomer i in all the vinyl monomers forming the block, and is ΣWi = 1. i is a natural number from 1 to n.

Table 1 shows the glass transition temperatures of representative homopolymers.

The various components and the like of the block copolymer of the present invention will be described below.

(A block)

The A block 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 rings). Examples of the polycyclic structure include a temporary exchange structure, a spiro ring structure, and a condensed ring structure, but a temporary exchange structure is preferable. The temporary exchange 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. In addition to the structure connected by a carbon chain, a temporary exchange type aliphatic hydrocarbon group may have a condensed ring structure and a spiro ring structure. The number of carbon atoms constituting the polycyclic aliphatic hydrocarbon group is preferably 7 or more, more preferably 9 or more, 20 or less is preferable, and more preferably 15 or less. When the polycyclic aliphatic hydrocarbon group is localized in the A block, the adhesion (adhesive strength) of the block copolymer to the low polarity material is improved.

Specific examples of the polycyclic aliphatic hydrocarbon group include adamantyl group, 2-methyladamantyl group, 2-ethyladamantyl group, norbornyl group, 1-methyl-norbornyl group, and 5,6-dimethyl-norbo Neil group, isobornyl group, tetracyclo [4.4.0.12,5.17,10] dodecyl group, 9-methyl-tetracyclo [4.4.0.12,5.17,10] dodecyl group, bornyl group, dicyclopentanyl group, dicyclopentenyl group And the like. Among these, an adamantyl group, a norbornyl group, an isobornyl group, and a dicyclopentanyl group are preferable from the viewpoint of availability, solubility, and excellent adhesion to a low-polar material.

The vinyl monomer having a polycyclic aliphatic hydrocarbon group is preferably a (meth) acrylic acid polycyclic aliphatic hydrocarbon ester. As a specific example of (meth) acrylic acid polycyclic aliphatic hydrocarbon ester, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylic Rate, 2-ethyl-2-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) And acrylates. The vinyl monomer having a polycyclic aliphatic hydrocarbon group may be used alone or in combination of two or more.

The average glass transition temperature (TgAave) of the A block 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, 250 degreeC or less is preferable, More preferably, it is 230 degrees C or less, More preferably, it is 200 degrees C or less, Especially preferably, it is 150 degrees C or less. It is considered that it has a bulky polycyclic structure as described above and an average glass transition temperature of 25 ° C or higher, whereby high adhesion to a low-polar material can be exhibited. The average glass transition temperature of the A block is a value calculated from monomers of all A blocks.

When the block copolymer has a plurality of A blocks, the glass transition temperature (TgA) of each A block is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, particularly preferably It is preferably 80 ° C or higher, preferably 250 ° C or lower, more preferably 230 ° C or lower, further preferably 200 ° C or lower, particularly preferably 150 ° C or lower. When the glass transition temperature of each A block is within the above range, adhesion to a low-polarity material is further improved.

When the block copolymer is used in a primer composition or a surface modification composition, the average glass transition temperature (TgAave) of the A block is preferably 60 ° C or higher, more preferably 80 ° C or higher, and preferably 250 ° C or lower And more preferably 200 ° C or less, and more preferably 150 ° C or less. When the average glass transition temperature of the A block is within the above range, when used in a primer composition or a surface modification composition, adhesion to the substrate is further improved.

When the block copolymer used for the primer composition or the surface modification composition has a plurality of A blocks, the glass transition temperature (TgA) of each A block is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, 250 degrees C or less is preferable, More preferably, it is 200 degrees C or less, More preferably, it is 150 degrees C or less. When the glass transition temperature of each A block is within the above range, when used in a primer composition or a surface modification composition, adhesion to the substrate is further improved.

When the block copolymer is used in an adhesive composition or an adhesive composition, the average glass transition temperature (TgAave) of the A block is 25 ° C or higher, preferably 30 ° C or higher, more preferably 35 ° C or higher, and 60 ° C Less than is preferable, More preferably, it is 58 degrees C or less, More preferably, it is 55 degrees C or less. When the average glass transition temperature of the A block is within the above range, when used in an adhesive composition or an adhesive composition, adhesion between the substrate and the adherend is further improved.

When the block copolymer used for the adhesive composition or the adhesive composition has a plurality of A blocks, the glass transition temperature (TgA) of each A block is preferably less than 60 ° C, more preferably 58 ° C or less, and more preferably It is 55 degrees C or less. When the glass transition temperature (TgA) of all the A blocks is less than 60 ° C, when used in an adhesive composition or an adhesive composition, the adhesion between the substrate and the adherend is further improved.

When the block copolymer has a plurality of A blocks, the difference between the glass transition temperature (TgAmax) of the A block having the highest glass transition temperature and the glass transition temperature (TgAmin) of the A block having the lowest glass transition temperature is: 0 ° C or more and less than 50 ° C are preferable, more preferably 20 ° C or less, and even more preferably 10 ° C or less.

It is also preferable that the A block is composed of only structural units derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group. The A block is a structural unit (another structural unit) derived from a vinyl monomer having no polycyclic aliphatic hydrocarbon group in a range capable of maintaining the glass transition temperature of the A block and the adhesion of the obtained block copolymer to the low-polar material. ).

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 more preferably 80% by mass in A block 100% by mass. It is more than mass%. Further, the content of other structural units that can be included in the A block is preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less in 100% by mass of the A block.

The other structural units that may be included in the A block are not particularly limited as long as they are formed of a vinyl monomer having a polycyclic aliphatic hydrocarbon group and a vinyl monomer copolymerizable with all of the vinyl monomers forming the B block. Specific examples of the vinyl monomer that can form other structural units of the A block include aromatic vinyl monomers, vinyl monomers having hydroxyl groups, vinyl monomers having carboxyl groups, vinyl monomers having sulfonic acid groups, vinyl monomers having phosphoric acid groups, Vinyl monomers containing tertiary amines, vinyl monomers containing quaternary ammonium bases, vinyl monomers containing heterocycles, vinylamides, vinyl monomers containing epoxy groups, vinyl carboxylates, α-olefins, dienes, (meta ) Acrylic monomers and the like. The vinyl monomers capable of forming other structural units of the A block may be used alone or in combination of two or more.

Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 1-vinylnaphthalene. . As a vinyl monomer which has a hydroxyl group, hydroxyalkyl (meth) acrylate etc. are mentioned. Examples of the vinyl monomer having a carboxyl group include a monomer in which an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride is reacted with the vinyl monomer having a hydroxyl group, crotonic acid, maleic acid, itaconic acid, and (meth) acrylic acid. Can be. Examples of the vinyl monomer having a sulfonic acid group include vinyl sulfonic acid, styrenesulfonic acid, ethyl disulfonate (meth) acrylate, methylpropylsulfonic acid (meth) acrylamide, and ethyl sulfonate (meth) acrylamide. A methacryloyloxyethyl phosphate ester etc. are mentioned as a vinyl monomer which has a phosphoric acid group. Vinyl monomers containing tertiary amines include N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, 2- (dimethylamino) ethyl (meth) acrylate, And N, N-dimethylaminopropyl (meth) acrylate. As a vinyl monomer containing a quaternary ammonium base, N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride, N-methacryloylaminoethyl-N, N, N -Dimethylbenzylammonium chloride, and the like. 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, etc. are mentioned as a vinyl monomer containing a heterocycle. Examples of vinyl amides include N-vinyl formamide, N-vinyl acetamide, and N-vinyl-ε-caprolactam. Glycidyl (meth) acrylate etc. are mentioned as a vinyl monomer containing an epoxy group. Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate. Examples of α-olefins include 1-hexene, 1-octene, and 1-decene. Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.

Examples of the (meth) acrylic monomer include (meth) acrylic acid, (meth) acrylic acid aliphatic alkyl (straight chain alkyl, branched chain alkyl) ester, (meth) acrylic alicyclic alkyl (monocyclic structure) ester, and hydroxyl group (meth) Acrylate, (meth) acrylate having an alkoxy group, (meth) acrylate having a sulfonic acid group, (meth) acrylate containing a tertiary amine, (meth) acrylate containing an epoxy group, having a polyethylene glycol structural unit (Meth) acrylate, (meth) acrylate having an aromatic ring group, (meth) acrylamide, and the like.

Examples of the (meth) acrylic acid aliphatic alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate, and sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of the (meth) acrylic acid alicyclic alkyl ester include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxy And hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate. As a (meth) acrylate which has an alkoxy group, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. are mentioned. Examples of the (meth) acrylate having a sulfonic acid group include disulfonic acid ethyl (meth) acrylate. As a tertiary amine containing unsaturated monomer, 2- (dimethylamino) ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc. are mentioned. As a (meth) acrylate containing an epoxy group, glycidyl (meth) acrylate etc. are mentioned. Examples of the (meth) acrylate having a polyethylene glycol structural unit include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) And acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. Examples of the (meth) acrylate having an aromatic ring group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Examples of the (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide.

Among these, as the vinyl monomer that can form other structural units of the A block, (meth) acrylate having an aliphatic alkyl group, (meth) acrylate having an alicyclic alkyl group having a monocyclic structure, aromatic vinyl monomer, hydroxyl group Vinyl monomers having, and vinyl monomers having a carboxyl group are preferred.

When the block copolymer is used in a primer composition or a surface modification composition, the content of the structural unit derived from the (meth) acrylate having an aliphatic alkyl group is preferably less than 15% by mass in 100% by mass of the A block, It is more preferably 10% by mass or less, and still more preferably 5% by mass or less. When the content of the structural unit derived from the (meth) acrylate having an aliphatic alkyl group in the A block is within the above range, when used in a primer composition or a surface modification composition, adhesion to the substrate is further improved.

When the block copolymer is used in an adhesive composition or an adhesive composition, the content of the structural unit derived from the (meth) acrylate having an aliphatic alkyl group is preferably 15% by mass or more in 100% by mass of the A block, and more Preferably it is 20 mass% or more, More preferably, it is 25 mass% or more. When the content of the structural unit derived from (meth) acrylate having an aliphatic alkyl group in the A block is within the above range, when used in an adhesive composition or an adhesive composition, the adhesion between the substrate and the adherend is further improved.

Moreover, when the said block copolymer is used for an adhesive composition or an adhesive composition, it is preferable that A block has a reactive functional group. A hydroxyl group, a carboxyl group, an epoxy group, etc. are mentioned as said reactive functional group. When the reactive functional group is introduced, the content of the structural unit derived from the vinyl monomer having the reactive functional group is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably in 100% by mass of the A block. Preferably it is 1.0 mass% or more, 5.0 mass% or less is preferable, More preferably, it is 4.0 mass% or less, More preferably, it is 3.0 mass% or less. When the content of the structural unit derived from the vinyl monomer having a reactive functional group in the A block is within the above range, when used in an adhesive composition or an adhesive composition, the adhesion between the substrate and the adherend is further improved.

When two or more types of structural units are contained in the A block, the various structural units contained in the A block may be contained in any block, such as random copolymerization or block copolymerization, in the A block, and random copolymerization from the viewpoint of uniformity. It is preferably contained in the aspect of. The block copolymer of the present invention may have a plurality of A blocks. When having multiple A blocks, the monomer composition of each A block may be the same or different.

(B block)

The B block has a structural unit derived from a vinyl monomer, and substantially no structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group. The "substantially does not have" content is 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less in 100% by mass of the B block. In addition, the average glass transition temperature (TgBave) of the B block is lower than the average glass transition temperature (TgAave) of the A block, and the average glass transition temperature (TgAave) of the A block and the average glass transition temperature of the B block ( The difference of TgBave (TgAave-TgBave) is 50 ° C or higher. 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 even more preferably 150 ° C or lower. The B block having a low average glass transition temperature functions as a soft segment, thereby improving the coatability and flexibility of the block copolymer. In addition, the average glass transition temperature of B block is calculated by said Formula (1). The average glass transition temperature of the B block is a value calculated from monomers of all B blocks.

The average glass transition temperature (TgBave) of the B block is preferably -100 ° C or higher, more preferably -70 ° C or higher, more preferably -50 ° C or higher, and preferably 60 ° C or lower, more preferably Is 30 ° C or less, more preferably 10 ° C or less. When the average glass transition temperature (TgBave) of the B block is -100 ° C or higher, the coatability to a low-polarity material is improved, and if it is 60 ° C or less, the coatability to a high-polarity material is improved, and flexibility is improved.

When the block copolymer has a plurality of B blocks, the glass transition temperature (TgB) of each B block is preferably -100 ° C or higher, more preferably -70 ° C or higher, and even more preferably -50 ° C or higher Is, preferably 60 ° C or less, more preferably 30 ° C or less, and even more preferably 10 ° C or less. When the glass transition temperature (TgB) of each B block is -100 ° C or higher, the coatability to a low-polarity material is improved, and if it is 60 ° C or less, the coatability to a high-polarity material is improved, and flexibility is improved.

When the block copolymer has a plurality of B blocks, the difference between the glass transition temperature (TgBmax) of the B block having the highest glass transition temperature and the glass transition temperature (TgBmin) of the B block having the lowest glass transition temperature is: 0 ° C or more and less than 50 ° C are preferable, more preferably 20 ° C or less, and further preferably 10 ° C or less.

When the block copolymer has a plurality of A blocks and / or B blocks, the difference (TgAmin-TgBmax) between the minimum value (TgAmin) of the glass transition temperature of the A block and the maximum value (TgBmax) of the glass transition temperature of the B block is , 50 ° C or higher is preferred, more preferably 70 ° C or higher, and even more preferably 90 ° C or higher. Moreover, the difference (TgAmax-TgBmin) between the maximum value (TgAmax) of the glass transition temperature of the A block and the minimum value (TgBmin) of the glass transition temperature of the B block is preferably 250 ° C or less, more preferably 200 ° C or less, More preferably, it is 150 ° C or lower.

The vinyl monomer used for the B-block can be appropriately selected in a range that satisfies the requirements of the glass transition temperature. Moreover, when using the said block copolymer as an adhesive composition and an adhesive composition, it is preferable to select the vinyl monomer used for a B block according to the polarity of the to-be-adhered object (high polar material) to select.

Specific examples of the vinyl monomer used in the B block include an aromatic vinyl monomer, a vinyl monomer having a hydroxyl group, a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, a vinyl monomer having a phosphoric acid group, and a tertiary amine Vinyl monomers, vinyl monomers containing quaternary ammonium bases, vinyl monomers containing heterocycles, vinylamides, vinyl monomers containing epoxy groups, vinyl carboxylates, α-olefins, dienes, and (meth) acrylic monomers. Can be. The vinyl monomers used for the B block may be used alone or in combination of two or more.

Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 1-vinylnaphthalene. . As a vinyl monomer which has a hydroxyl group, hydroxyalkyl (meth) acrylate etc. are mentioned. Examples of the vinyl monomer having a carboxyl group include a monomer in which an acid anhydride such as maleic anhydride, succinic anhydride and phthalic anhydride is reacted with the vinyl monomer having a hydroxyl group, crotonic acid, maleic acid, itaconic acid, and (meth) acrylic acid. Can be. Examples of the vinyl monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, ethyl (meth) acrylate disulfonic acid, methylpropylsulfonic acid (meth) acrylamide, and ethyl (meth) acrylamide sulfonate. A methacryloyloxyethyl phosphate ester etc. are mentioned as a vinyl monomer which has a phosphoric acid group. Vinyl monomers containing tertiary amines include N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, 2- (dimethylamino) ethyl (meth) acrylate, And N, N-dimethylaminopropyl (meth) acrylate. As a vinyl monomer containing a quaternary ammonium base, N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride, N-methacryloylaminoethyl-N, N, N -Dimethylbenzylammonium chloride, and the like. 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, etc. are mentioned as a vinyl monomer containing a heterocycle. Examples of vinyl amides include N-vinyl formamide, N-vinyl acetamide, and N-vinyl-ε-caprolactam. Glycidyl (meth) acrylate etc. are mentioned as a vinyl monomer containing an epoxy group. Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate. Examples of α-olefins include 1-hexene, 1-octene, and 1-decene. Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.

Examples of the (meth) acrylic monomer include (meth) acrylic acid, (meth) acrylic acid aliphatic alkyl (straight chain alkyl, branched chain alkyl) ester, (meth) acrylic alicyclic alkyl (monocyclic structure) ester, and hydroxyl group (meth) Acrylate, (meth) acrylate having an alkoxy group, (meth) acrylate having a sulfonic acid group, (meth) acrylate containing a tertiary amine, (meth) acrylate containing an epoxy group, having a polyethylene glycol structural unit (Meth) acrylate, (meth) acrylate having an aromatic ring group, (meth) acrylamide, and the like.

Examples of the (meth) acrylic acid aliphatic alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-dodecyl (meth) acrylate, n-stearyl (meth) acrylate, etc. Can be. Examples of the (meth) acrylic acid alicyclic alkyl ester include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxy And hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate. As a (meth) acrylate which has an alkoxy group, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. are mentioned. Examples of the (meth) acrylate having a sulfonic acid group include disulfonic acid ethyl (meth) acrylate. As a tertiary amine containing unsaturated monomer, 2- (dimethylamino) ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc. are mentioned. As a (meth) acrylate containing an epoxy group, glycidyl (meth) acrylate etc. are mentioned. Examples of the (meth) acrylate having a polyethylene glycol structural unit include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) And acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. Examples of the (meth) acrylate having an aromatic ring group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Examples of the (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide.

The vinyl monomer used in the B block is preferably a vinyl monomer containing a hetero ring, a (meth) acrylic monomer, more preferably a vinyl monomer containing a hetero ring, an aliphatic alkyl (meth) acrylic acid (straight chain alkyl, branched) Chain alkyl) esters, (meth) acrylates having hydroxyl groups, (meth) acrylates having alkoxy groups, more preferably vinyl monomers containing heterocycles, aliphatic alkyl (preferably 1 to 18 carbon atoms, more preferred) It is a (meth) acrylate having 1 to 10 carbon atoms.

When two or more types of structural units are contained in the B block, the various structural units contained in the B block may be contained in any of the B block, such as random copolymerization and block copolymerization, and random copolymerization from the viewpoint of uniformity. It is preferably contained in the aspect of. The block copolymer of the present invention may have a plurality of B blocks. When having a plurality of B blocks, the monomer composition of each B block may be the same or different.

(Block copolymer)

The block copolymer has an A block and a B block. It is also preferable that the block copolymer comprises only A blocks and B blocks. Since the block copolymer has a plurality of polymer blocks having different properties such as glass transition temperature and polarity, it is considered that the block copolymer causes phase separation on the surface of the coated substrate. Phase separation is a phenomenon in which a block copolymer self-assembles by strong interaction of homogeneous blocks when it has blocks having different properties such as glass transition temperature and polarity. For example, in the case of the block copolymer, A blocks and B blocks each express an adjacent phase structure. The phase-separated structure forms a lamella structure, a gyro structure, a cylinder structure, or a sea-island structure according to the mass ratio, volume ratio, polymerization degree, etc. of each block in the block copolymer. In addition, the phase separation structure is not particularly limited.

Since the polycyclic aliphatic hydrocarbon group is localized in the A block, the block copolymer has high adhesion (adhesion) to the low-polar material. In addition, it is believed that the A-blocks physically form pseudo-crosslinks by the phase separation, thereby exhibiting better cohesion. In addition, the B block having a low glass transition temperature functions as a soft segment, thereby improving the coatability and flexibility of the block copolymer. In addition, it is considered that by appropriately selecting the type of the vinyl monomer of the B block, the surface properties of the low-polarity material can be controlled, and adhesion with the high-polarity material can be improved.

The structure of the block copolymer of the present invention may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of such a block copolymer may be appropriately selected depending on the properties of the required copolymer, but is preferably a linear block copolymer from the viewpoint of cost and ease of polymerization. In addition, the linear block copolymer may have any structure (array), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, when the A block is represented by A and the B block is B, (AB) n type , (AB) nA type, (BA) nB type (n is an integer of 1 or more, for example, an integer of 1 to 3) is preferably a copolymer having at least one structure selected from the group consisting of. In these structures, the A block and the B block may be directly coupled, and other blocks other than the A block and the B block may exist between the A block and the B block.

As the linear block copolymer, a structure having a first A block, a B block directly or through another block to the first A block, and a second A block directly or through another block to the B block; A structure having a first B block, an A block directly coupled to the first B block or through another block, and a second B block directly coupled to the A block or through another block; is preferable. In the structure having the first A block and the second A block, the first A block and the second A block are preferably present at the ends of the block copolymer, respectively. In the structure having the first B block and the second B block, it is preferable that the first B block and the second B block are present at the ends of the block copolymer, respectively.

Among these, from the viewpoint of handling properties during processing and physical properties of the composition, diblock copolymers represented by AB, triblock copolymers represented by ABA, and triblock copolymers represented by BAB are preferred, more preferably It is a triblock copolymer represented by ABA. By constructing the triblock structure represented by A-B-A, the crosslinking structure of the copolymers becomes more advanced by the pseudo crosslinking of the A blocks. Therefore, it is considered that the cohesive force of the polymer layer is improved, and higher adhesion (adhesive force) can be expressed. In the case of a triblock copolymer represented by A-B-A, the two A blocks located at both ends may be the same or different from each other. Moreover, in the case of the triblock copolymer represented by B-A-B, two B blocks located at both ends may be the same or different from each other.

The average molecular weight of the block copolymer is measured by gel permeation chromatography (GPC). The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, more preferably 800,000 or less, and more preferably Less than 500,000. When the weight average molecular weight is 3,000 or more, the adhesion (adhesive strength) becomes good, and when the weight average molecular weight is 1,000,000 or less, the viscosity is not too high, and the coatability becomes good.

When the block copolymer is used in a primer composition or a surface modification composition, the weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and 200,000 The following is preferable, more preferably 150,000 or less, more preferably 100,000 or less, particularly preferably less than 80,000. When the weight average molecular weight is within the above range, when used in a primer composition or a surface modification composition, adhesion to the substrate is further improved.

When the block copolymer is used in an adhesive composition or an adhesive composition, the weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 50,000 or more, more preferably 80,000 or more, and 800,000 or less Is preferred, more preferably 500,000 or less, more preferably 300,000 or less, particularly preferably 100,000 or less. When the weight average molecular weight is within the above 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 block copolymer is preferably 2.5 or less, more preferably 2.2 or less, and even 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 block copolymer) / (number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the molecular weight distribution, the more uniform the molecular weight is, and when the value is 1.0, the narrowest molecular weight distribution. When the PDI is 2.5 or less, compared with the molecular weight of the designed copolymer, the content of the one with a small molecular weight or the one with a large molecular weight is low, and adhesion (adhesion) is improved.

The content of the A block in the block copolymer is preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass or more, and 95% by mass, among 100% by mass of the entire block copolymer. The following is preferable, More preferably, it is 85 mass% or less, More preferably, it is 75 mass% or less. The content rate of each block is determined from the injection ratio of the monomers constituting the block copolymer and the polymerization rate of each monomer.

The content of the B block in the block copolymer is preferably 5% by mass or more, more preferably 15% by mass or more, more preferably 25% by mass or more, and 60% by mass or more in 100% by mass of the entire block copolymer. The following is preferred, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

By adjusting the content of the A block and the B block within the above range, a block copolymer having a desired function can be adjusted. When the block copolymers have A1 blocks and A2 blocks as A blocks, the mass ratio (A1 / A2) of these is preferably 0.4 or more, more preferably 0.7 or more, more preferably 0.8 or more, and 2.3 or less It is preferable, More preferably, it is 1.5 or less, More preferably, it is 1.2 or less.

When the block copolymers have B1 blocks and B2 blocks as B blocks, the mass ratio (B1 / B2) of these is preferably 0.4 or more, more preferably 0.7 or more, more preferably 0.8 or more, and 2.3 or less It is preferable, More preferably, it is 1.5 or less, More preferably, it is 1.2 or less.

The block copolymer of the present invention has strong adhesion (adhesiveness) to not only high-polarity materials but also low-polarity materials such as polyolefin-based resins. Therefore, the block 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. Moreover, the block copolymer of this invention can be used as a tackifier of an acrylic adhesive.

(Method for producing block copolymer)

As a method for producing the block copolymer of the present invention, by the polymerization reaction of a vinyl monomer, an A block may be prepared first, and a monomer of a B block may be polymerized to the A block; a B block is prepared first, and an A of the B block. The monomers of the block may be polymerized; an AB block may be prepared, and the A block may be polymerized by further polymerizing the A block monomer to the AB block; or, a BA block may be prepared, and the B block monomer may be further added to the BA block. You may polymerize to produce a BAB block.

The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, it is preferable that it is superposed | polymerized by living radical polymerization as said block copolymer. In the conventional radical polymerization method, not only an initiation reaction and a growth reaction, but also a stop reaction and a chain transfer reaction, a loss of activity at the growth end occurs, and tends to be a mixture of polymers of various molecular weights and heterogeneous compositions. On the other hand, the living radical polymerization method, while maintaining the simplicity and versatility of the conventional radical polymerization method, does not easily undergo a stop reaction or chain transfer, and the growth end grows without loss of activity, thereby precisely controlling the molecular weight distribution and uniformity. It is preferred from the viewpoint of easy production of the polymer of the composition.

In the living radical polymerization method, a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); a method using an organic tellurium compound due to a difference in the method of stabilizing the polymerization growth terminal. (TERP method). Since the ATRP method uses an amine complex, there may be cases where the acidic group of a vinyl monomer having an acidic group cannot be used without protecting it. The RAFT method is difficult to achieve a low molecular weight distribution when a plurality of monomers are used, and may have problems such as sulfur odor and coloration. Among these methods, it is preferable to use the TERP method from the viewpoint of diversity of monomers that can be used, molecular weight control in the polymer region, uniform composition, or coloring.

Further, in the living radical polymerization method, especially the TERP method, the composition of all polymers such as structural units having a polycyclic aliphatic hydrocarbon group that polymerizes while polymer chains are uniformly reacted with monomers to form a pseudo-crosslinked structure is approached to be uniform, Polycyclic aliphatic hydrocarbon groups are preferred because of the increased probability of their involvement in pseudo-crosslinking.

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator, for example, International Publication Nos. 2004/14848, International Publication 2004/14962, International It is the method described in publication 2004/072126, and international publication 2004/096870.

The following (a)-(d) is mentioned as a specific polymerization method of TERP method.

(a) The vinyl monomer is polymerized using the organic tellurium compound represented by the general formula (1).

(b) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (1) and an azo-based polymerization initiator.

(c) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (1) and an organic ditellurium compound represented by the general formula (2).

(d) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (1), an azo-based polymerization initiator, and an organic ditellurium compound represented by the general formula (2).

[In General Formula (1), R ¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents 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 amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.

In 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 specifically, as follows.

As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, And straight-chain or branched-chain alkyl groups such as octyl groups, and cyclic alkyl groups such as cyclohexyl groups. It is preferably a straight or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

A phenyl group, a naphthyl group, etc. are mentioned as an aryl group. A pyridyl group, furyl group, thienyl group, etc. are mentioned as an aromatic heterocyclic group.

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 as follows.

As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, And straight-chain or branched-chain alkyl groups such as octyl groups, and cyclic alkyl groups such as cyclohexyl groups. It is preferably a straight or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

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 amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group, specifically Is as follows.

As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, And straight or branched chain alkyl groups such as octyl group and cyclic alkyl groups such as cyclohexyl group. It is preferably a straight or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

A phenyl group, a naphthyl group, etc. are mentioned as an aryl group. It is preferably a phenyl group.

As a substituted aryl group, the phenyl group which has a substituent, the naphthyl group which has a substituent, etc. are mentioned. As a substituent of the aryl group having the above substituent, for example, a halogen atom, hydroxyl group, alkoxy group, amino group, nitro group, cyano group, carbonyl-containing group represented by -COR ⁴¹ (R ⁴¹ is carbon number 1 -8 alkyl group, aryl group, C1-C8 alkoxy group or aryloxy group), sulfanyl group, trifluoromethyl group, etc. are mentioned. Moreover, it is preferable that these substituents are 1 or 2 substituted.

A pyridyl group, furyl group, thienyl group, etc. are mentioned as an aromatic heterocyclic group.

As the alkoxy group, a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom is preferable, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- And a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

As an acyl group, an acetyl group, a propionyl group, a benzoyl group, etc. are mentioned.

As an amide group, -CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, a C1-C8 alkyl group, or an aryl group) is mentioned.

As the oxycarbonyl group, 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) is preferable, for example, a carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n -Butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, and the like. Preferred oxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups.

As the allyl group, -CR ⁴⁴¹ R ⁴⁴² -CR ⁴⁴³ = CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ are each independently As a hydrogen atom, a C1-C8 alkyl group, or an aryl group, each substituent may be connected in a cyclic structure).

As the propargyl group, -CR ⁴⁵¹ R ⁴⁵² -C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, R ⁴⁵³ is hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, and aryl groups Or a silyl group).

The organic tellurium compound represented by the general formula (1) specifically, (methyltelanylmethyl) benzene, (methyltelanylmethyl) naphthalene, ethyl-2-methyl-2-methyltelanyl-propionate, ethyl -2-methyl-2-n-butyltelanyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methyltelanyl-propionate, (2-hydroxyethyl) -2- Methyl-2-methyltelanyl-propionate or (3-trimethylsilylproparyl) -2-methyl-2-methyltelanyl-propionate, etc., International Publication No. 2004/14848, International Publication No. 2004 / All of the organic tellurium compounds described in 14962, International Publication 2004/072126, and International Publication 2004/096870 can be exemplified.

The group represented by R ⁵ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, and specifically, as follows.

As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, And straight-chain or branched-chain alkyl groups such as octyl groups, and cyclic alkyl groups such as cyclohexyl groups. It is preferably a straight or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

A phenyl group, a naphthyl group, etc. are mentioned as an aryl group.

A pyridyl group, furyl group, thienyl group, etc. are mentioned as an aromatic heterocyclic group.

Specific examples of the organic ditellurium compound represented by the general formula (2) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, and dicyclopropylditelu Ride, di-n-butylditelluride, di-s-butylditelluride, di-t-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis- (p-methoxyphenyl Ditelluride, bis- (p-aminophenyl) ditelluride, bis- (p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ) Ditelluride, dinaphthylditelluride or dipyridylditelluride, and the like.

The azo-based polymerization initiator can be used without particular limitation as long as it is an azo-based polymerization initiator used in 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-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'- Azobis (4-cyanovaleric acid) (ACVA), 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobis (2-methylbutylamide), 2, 2'-Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70), 2,2'-Azobis (2-methylamidinopropane) dihydrochloride, 2,2'-Azo Bis [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-propyl azoformamide, 2,2'-azobis (N-butyl-2-methylpropionamide), or 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) and the like.

In the polymerization process, in a container substituted with an inert gas, the vinyl monomer and the organic tellurium compound of formula (1) are further azo-based for the purpose of promoting reaction depending on the type of the vinyl monomer and controlling molecular weight and molecular weight distribution. The polymerization initiator and / or the organic ditellurium compound of formula (2) are mixed. At this time, examples of the inert gas include nitrogen, argon, and helium. Preferably, argon and nitrogen are good.

The amount of the vinyl monomer used in the above (a), (b), (c) and (d) may be appropriately adjusted depending on the properties of the target copolymer. It is preferable that the vinyl monomer is 5 mol to 10000 mol with respect to 1 mol of the organic tellurium compound of the general formula (1).

When the organic tellurium compound of the general formula (1) of the above (b) is used in combination with an azo-based polymerization initiator, the azo-based polymerization initiator is 0.01 mol to 10 mol with respect to 1 mol of the organic tellurium compound of the general formula (1). desirable.

When the organic tellurium compound of the general formula (1) of the above (c) and the organic ditellurium compound of the general formula (2) are used together, 1 mol of the organic tellurium compound of the general formula (1) of the general formula (2) It is preferable that the organic ditellurium compound is 0.01 mol to 100 mol.

When the organic tellurium compound of the general formula (1) of the above (d) and the organic ditellurium compound of the general formula (2) and an azo-based polymerization initiator are used together, the organic tellurium compound of the general formula (1) and the general formula ( It is preferable to set the azo-based polymerization initiator to 0.01 mol to 100 mol with respect to 1 mol in total of the organic ditellurium compound of 2).

The polymerization reaction may be performed even in a solventless manner, but the aprotic solvent or a protic solvent generally used in radical polymerization may be used, and the mixture may be stirred. Non-protonic solvents that can be used include, for example, anisole, benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methylethylketone), Dioxane, hexafluoroisopropanol, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate or trifluoromethylbenzene. Moreover, as a protonic solvent, water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol or diacetone alcohol etc. are illustrated, for example. Can be.

The amount of the solvent to be used may be appropriately adjusted, for example, for 1 g of the vinyl monomer, 0.01 ml or more is preferable, more preferably 0.05 ml or more, further preferably 0.1 ml or more, and 50 ml or less is preferable. , More preferably 10 ml or less, and more preferably 1 ml or less.

The polymerization reaction can be carried out by mixing a vinyl monomer with the organic tellurium compound of the general formula (1), and stirring the mixture. The reaction temperature and reaction time may be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained copolymer, but is usually stirred at 0 to 150 ° C for 1 minute to 100 hours. With the TERP method, high yield and precise molecular weight distribution can be obtained even at a low polymerization temperature and a short polymerization time. At this time, the pressure is usually performed at normal pressure, but it may be pressurized or reduced.

After completion of the polymerization reaction, the intended copolymer can be separated from the obtained reaction mixture by using a conventional separation and purification means to remove the solvent used, residual vinyl monomer, and the like.

The block copolymer of the present invention can be obtained, for example, by sequentially polymerizing a vinyl monomer constituting a block by a living radical polymerization method. Specifically, in the case of an ABA block, a living radical polymerization method is used to polymerize the vinyl monomer constituting one of the two A blocks, polymerize one A block, and polymerize one A block. , Polymerizing the vinyl monomer constituting the B block, polymerizing the B block, and polymerizing the B block, polymerizing the vinyl monomer constituting the other block of the two A blocks, and the other A block The polymerization method provided with the process of superposing | polymerizing is mentioned.

The growth end of the copolymer obtained by the polymerization reaction is in the form of -TeR ¹ (where R ¹ is the same as the above) derived from the tellurium compound, and the active terminal is lost due to the operation in the air after the completion of the polymerization reaction, The tellurium atom may remain. It is preferable to remove the tellurium atom because the copolymer where the tellurium atom remains at the terminal is colored or has poor thermal stability.

As a method for removing the tellurium atom, a radical reduction method using a tributylstannan or thiol compound or the like; a method for adsorbing with activated carbon, silica gel, activated alumina, activated clay, a molecular sieve, or a polymer adsorbent; ion exchange resin, etc. A method for adsorbing metals; by adding a peroxide such as hydrogen peroxide or benzoyl peroxide, or blowing air or oxygen into the system to oxidatively decompose the tellurium atom at the end of the copolymer, and combining the residual tellurium by washing with water or a suitable solvent. A liquid-liquid extraction method or a solid-liquid extraction method for removing a compound; a purification method in a solution state such as limit filtration for extracting and removing only those having a specific molecular weight or less; can be used, or a combination of these methods can also be used.

<2. Composition>

The said block copolymer can be used as a composition containing a block copolymer. The composition, in addition to the block copolymer, organic solvents, plasticizers, colorants (pigments, dyes, etc.), coupling agents, preservatives, antistatic agents, antioxidants, ultraviolet absorbers, surfactants, flame retardants, fillers, crosslinking agents, fillers, etc. You may contain the additive of the. The composition can be used as a primer composition, a surface modification composition, an adhesive composition, an adhesive composition, etc. by appropriately adjusting the additives according to the use.

The composition does not use a compound containing chlorine, and has strong adhesion (adhesiveness) to not only high-polarity materials but also low-polarity materials. Therefore, by coating the composition on the surface of a film or a molded article made of a low-polar material, it becomes possible to coat, adhere, or the like, a high-polar material lacking adhesion to the low-polar material. In particular, the composition of the present invention can be suitably used for a polyolefin-based resin among low-polar materials.

(Primer composition)

When using the said composition as a primer composition, it is preferable that a primer composition contains the said block copolymer and a solvent. By coating the primer composition on the surface of the low-polar material, for example, adhesion of the high-polar material to the surface of the low-polar material can be improved. Specifically, coating of a hard coat composition that is widely used for an optical member or a film composed of a high-polar material can be performed on a low-polar material surface.

As the solvent, water, an organic solvent or a mixed solvent thereof is used. In particular, in order to improve the coatability of the primer composition, it is preferable to blend a block copolymer and an organic solvent in which other additive components are soluble. Moreover, from the viewpoint of handleability of the primer composition, it is preferable that the total concentration of the block copolymer and other solid components is 50% by mass or less. Moreover, it is preferable that the said solvent does not impair the performance of the base material (film, etc.) to which the primer composition is applied.

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; acetone and methyl ethyl Ketones such as ketone and methyl isobutyl ketone; ethers such as diethyl ether and tetrahydrofuran; acetic acid esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; N, N-dimethylformamide, N-methylpi And amides such as lollydon; aromatic hydrocarbon compounds such as benzene, toluene and xylene; aliphatic hydrocarbon compounds such as n-hexane; alicyclic hydrocarbon compounds such as cyclohexane; and the like. These organic solvents may be used alone or in combination of two or more.

(Surface modification composition)

It can also be used as a surface modification composition by blending various additives in the primer composition. As said surface-modifying composition, the hard coat composition containing the said block copolymer, a solvent, and a hard coating agent is mentioned, for example. When the composition for a hard coat is used, a hard coating layer containing a high polarity material can be directly formed on the surface of the low polarity material.

As the solvent, the same one as the primer composition can be used. As said hard coating agent, an acrylic material is mentioned, for example. The acrylic material is not particularly limited, but, for example, monomeric radical polymerization type monofunctional acrylate, bifunctional acrylate, trifunctional acrylate, and 4-6 functional acrylate; oligomer radical polymerization type epoxy And acrylates, urethane acrylates, polyester acrylates, copolymer acrylates, polybutadiene acrylates, silicone acrylates, and amino resin acrylates. The acrylic materials may be used alone or in combination of two or more.

The curing type of the hard coating agent is not particularly limited, and examples thereof include ultraviolet (UV) curing type by photochemical reaction; thermosetting type of room temperature curing type and two-component reaction curing type, and the like. That is, the hard coating agent is not particularly limited, and examples thereof include generally known UV curable resins, urethane resins, and condensation resins.

(Adhesive composition)

When the said composition is used as an adhesive composition, it is preferable to mix | blend an epoxy resin and a hardening agent in addition to the said block copolymer. Moreover, the adhesive composition may contain a curing accelerator or the like. The said adhesive composition is excellent in the adhesiveness of a low polarity material and a high polarity material.

The epoxy resin is not particularly limited, and bifunctional or more bifunctional epoxy resins such as bisphenol F-type epoxy resins; phenol novolac-type epoxy resins, and cresol novolac-type epoxy resins and more trifunctional epoxy resins. Can be. Bifunctional abnormality is an epoxy resin containing two or more epoxy groups in one molecule. A trifunctional abnormality is an epoxy resin containing three or more epoxy groups in one molecule.

The curing agent for the epoxy resin is not particularly limited, and bisphenol A, bisphenol F, which is a compound containing two or more amine, polyamide, acid anhydride, polysulfide, boron trifluoride, and phenolic hydroxyl groups in one molecule. , Bisphenol S and phenol resins.

Moreover, in order to make coatability favorable, it is preferable to mix | blend the block copolymer and the organic solvent in which other additive components are soluble. In this case, from the viewpoint of handleability of the adhesive composition, the total concentration of the block copolymer and other solid components is preferably 50% by 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; acetone and methyl ethyl Ketones such as ketone and methyl isobutyl ketone; ethers such as diethyl ether and tetrahydrofuran; acetic acid esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; N, N-dimethylformamide, N-methylpi And amides such as lollidon; aromatic hydrocarbon compounds such as benzene, toluene and xylene, aliphatic hydrocarbon compounds such as n-hexane, and alicyclic hydrocarbon compounds such as cyclohexane. These organic solvents may be used alone or in combination of two or more.

(Adhesive composition)

When using the said composition as an adhesive composition, it is preferable that an adhesive composition contains the said block copolymer and a crosslinking agent. By mixing and crosslinking a crosslinking agent capable of reacting with a reactive functional group possessed by the block copolymer, cohesion and adhesion can be further improved. The crosslinking agent is not particularly limited, and isocyanate-based crosslinking agents, aziridine-based crosslinking agents, epoxy-based crosslinking agents, amine-based crosslinking agents, urethane acrylate-based crosslinking agents having vinyl groups, resin crosslinking agents having oxazoline groups, metal chelating type crosslinking agents, metal salts, metal alkoxy And metal chelating compounds, ammonium salts, hydrazine compounds, and acrylic polymer syrups.

In the pressure-sensitive adhesive composition, the content of the crosslinking agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, and 20 parts by mass or more with respect to 100 parts by mass of the block copolymer. The following is preferable, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less. When the content of the crosslinking agent is within the above range, the adhesive strength becomes good.

The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups temporarily protected by a blocking agent or water-quantizing agent) in one molecule. The isocyanate-based crosslinking agents 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 isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; 2, Aromatic diisocyanates such as 4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct, trimethylolpropane / Isocyanate adducts such as hexamethylene diisocyanate trimer adduct and isocyanurate of hexamethylene diisocyanate; trimethylolpropane adduct of xylylene diisocyanate; trimethylolpropane part of hexamethylene diisocyanate Water; and the like; polyether polyisocyanate, polyester polyisocyanate, and mixtures thereof and adducts, isocyanurate bond of various polyols, biuret bond, an allophanate bond, etc. The multi-neunghwa the polyisocyanate.

When an isocyanate-based crosslinking agent is used as the crosslinking agent, the content of the isocyanate-based crosslinking agent is preferably 0.01 parts by mass or more relative to 100 parts by mass of the block copolymer, more preferably 0.1 parts by mass or more, and even more preferably 1 mass It is a part or more, 20 mass parts or less is preferable, More preferably, it is 15 mass parts or less, More preferably, it is 10 mass parts or less. When the content of the crosslinking agent is within the above range, the adhesive strength becomes good.

The epoxy crosslinking agent refers to a polyfunctional epoxy compound having two or more epoxy groups in one molecule. The epoxy crosslinking agents may be used alone or in combination of two or more. Examples of the epoxy crosslinking agent include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, Diglycidylaniline, diamineglycidylamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentylglycoldiglycol Diether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, Pentaerythritol polyglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid di Glycidyl ester, and o-phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, and the like.

When an epoxy-based crosslinking agent is used as the crosslinking agent, the content of the epoxy-based crosslinking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and more preferably 0.1 mass by mass with respect to 100 parts by mass of the block copolymer. It is a part or more, and 5 mass parts or less is preferable, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less. When the content of the crosslinking agent is within the above range, the adhesive strength becomes good.

The pressure-sensitive adhesive composition may, if necessary, mix a crosslinking accelerator, a tackifier, and the like. The crosslinking accelerator is not particularly limited, and known catalysts such as organic tin, tertiary amine, paratoluenesulfonic acid, and benzenesulfonic acid, and phosphoric acid catalysts such as triphenylphosphine in the case of epoxy compounds Can be. The tackifier is not particularly limited, and polymerization rosin, rosin esters, C5 petroleum resin, dicyclopentadiene petroleum resin, terpene petroleum resin, or hydrogenated resins thereof, low molecular weight styrene resin, low And molecular weight α-methylstyrene resin.

It is preferable that the above-mentioned pressure-sensitive adhesive composition is formulated with a block copolymer and an organic solvent in which other additive components are soluble in order to improve coating properties. In this case, from the viewpoint of handleability of the pressure-sensitive adhesive composition, the total concentration of the block copolymer and other solid components is preferably 50% by 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; acetone and methyl ethyl Ketones such as ketone and methyl isobutyl ketone; ethers such as diethyl ether and tetrahydrofuran; acetic acid esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; N, N-dimethylformamide, N-methylpi And amides such as lollidon; aromatic hydrocarbon compounds such as benzene, toluene and xylene, aliphatic hydrocarbon compounds such as n-hexane, and alicyclic hydrocarbon compounds such as cyclohexane. These organic solvents may be used alone or in combination of two or more.

<3. Film ＞

The film of the present invention is characterized by having a base and a layer formed of the composition on at least a part of at least one side of the base.

Examples of the substrate include low-polar materials such as polyolefin-based resins such as polypropylene (PP), polyethylene (PE), and cycloolefin resin (COP); metal, glass, polyethylene terephthalate resin, polyamide resin, and polycarbonate resin, And high-polarity materials such as polyacrylic acid methyl resin, polyvinyl alcohol resin, and triacetyl cellulose; and the like. A film (including a tape and a sheet) is mentioned as a described shape.

Examples of the layer formed of the composition include a primer layer, a surface modification layer (for example, a hard coating layer), an adhesive layer, and an adhesive layer.

The primer layer can be formed by coating the primer composition on a substrate and drying it. The coating method is not particularly limited, and examples thereof include reverse coat method, gravure coat method, spray coat method, kiss coat method, wire bar coat method, curtain coat method, dip coat method, and bar coat method. have. The heating and drying temperature after coating varies depending on the material and use of the substrate, but is preferably 200 ° C or less to suppress deformation of the substrate, and preferably 25 ° C or more from the viewpoint of phase separation of the block copolymer. The thickness of the primer layer (thickness after drying) is not particularly limited, but is preferably 10 nm to 10 μm.

The surface modification layer (for example, a hard coating layer) may be formed by coating the hard coat composition on a substrate, drying it, and curing the hard coating agent. Although the coating method of the said hard coat composition is not specifically limited, The same method as the said primer composition can be employ | adopted. The method of curing the hard coating agent may be appropriately selected depending on the hard coating agent.

The said adhesive layer can be formed by apply | coating the said adhesive composition to a base material, and drying it. Although the coating method of the said adhesive composition is not specifically limited, For example, reverse coat method, gravure coat method, spray coat method, kiss coat method, wire bar coat method, curtain coat method, dip coat method, bar coat There is a law. The drying conditions are not particularly limited as long as the solvent used is sufficiently volatilized, but it is generally preferable to heat at 50 ° C to 200 ° C for 0.1 minute to 60 minutes.

When the substrate and the adherend are adhered through the adhesive layer, the substrate and the adherend may be compressed to heat and cure the adhesive layer. For the pressing, for example, a roll laminator, a flat plate press, a wafer laminator, a vacuum laminator, an elastic body press, and an autoclave can be used. As pressurized conditions, it is preferable to carry out at a pressure of 0.01 MPa to 5.0 MPa for 0.1 minute to 5 minutes. The heat curing condition is not particularly limited as long as the adhesive composition is cured, but it is generally preferable to heat at 50 ° C to 200 ° C for 0.1 minute to 180 minutes.

The said adhesive layer can be formed by apply | coating the said adhesive composition to a base material, and suitably performing hardening process. The coating of the pressure-sensitive adhesive composition can be carried out using conventional coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, and the like. Further, the pressure-sensitive adhesive layer may be coated with the pressure-sensitive adhesive composition directly on the substrate to form the pressure-sensitive adhesive layer, or the pressure-sensitive adhesive layer formed on the release liner may be transferred to the substrate. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 μm to 200 μm.

In the case where two or more kinds of curing treatments (drying, crosslinking, polymerization, etc.) are performed on the pressure-sensitive adhesive composition, these can be performed simultaneously or in multiple steps. In the pressure-sensitive adhesive composition using a partially polymerized product (acrylic polymer syrup), as a curing treatment, a copolymerization reaction is finally performed (a partial polymerization is provided to a better copolymerization reaction to form a complete polymerization product). If it is a photocurable adhesive composition, light irradiation is performed. If necessary, curing treatment such as crosslinking and drying may be performed. For example, when it is necessary to dry in a photocurable adhesive composition, you may perform photocuring after drying. In the pressure-sensitive adhesive composition using a fully polymerized product, typically, as the curing treatment, treatments such as drying (heat drying) and crosslinking are performed as necessary.

Example

Hereinafter, the present invention will be specifically described based on Examples, but nothing is limited thereto. In addition, various physical property measurements were performed with the following equipment. In addition, the meaning of the abbreviation is as follows.

BTEE: Ethyl-2-methyl-2-n-butyltelanyl-propionate

AIBN: 2,2'-azobis (isobutyronitrile)

IBXA: Isobornyl acrylate

DCPTAA: dicyclopentanyl acrylate

CHA: Cyclohexyl acrylate

BA: Butyl acrylate

MA: Methyl acrylate

MEA: Methoxyethyl acrylate

DMAAm: N, N-dimethylacrylamide

HEA: Hydroxyethyl acrylate

AA: Acrylic acid

VP: Vinyl pyrrolidone

Ani: anisole

MP: 1-methoxy-2-propanol

MeOH: methanol

(Polymerization rate)

¹ H-NMR was measured (solvent: deuterated chloroform, internal standard: tetramethylsilane) using a nuclear magnetic resonance (NMR) measuring device (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 computed.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))

It was determined by gel permeation chromatography (GPC) using a high-speed liquid chromatograph (manufactured by Tosoh Corporation, model HLC-8320GPC). As a column, two TSKgel Super Multipore HZ-H (Φ4.6 mm × 150 mm) (manufactured by Tosoh Corporation), tetrahydrofuran as the mobile phase, and a differential refractive index detector as the detector were used. For the measurement conditions, the column temperature was 40 ° C, the sample concentration was 1 mg / mL, the sample injection amount was 10 μL, and the flow rate was 0.35 mL / min. As a standard substance, a calibration curve (calibration curve) was prepared using polystyrene (manufactured by Tosoh Corporation, TSK Standard), and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured, and molecular weight distribution (PDI) from these measured values. Calculated.

<Production of copolymer>

(Block copolymer No. 1)

To a flask equipped with an argon gas introduction tube and a stirring blade, BTEE 42.7 mg, IBXA 3.70 g, AIBN 4.7 mg, and anisole 3.50 g were added and reacted at 60 ° C. for 24 hours to polymerize the A1 block. The polymerization rate of IBXA was 99%. The Mw of the obtained A1 block was 19,920 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 was further added to the reaction solution, and the B block was polymerized by reacting at 60 ° C. for 24 hours. The polymerization rate of BA was 98%. Mw of the obtained A1-B block copolymer was 30,910 and PDI was 1.34.

To the reaction solution, a mixed solution of 3.70 g of argon-substituted IBXA, 4.7 mg of AIBN, and 3.60 g of anisole was further added, and reacted at 60 ° C for 58 hours to polymerize the A2 block. The polymerization rate of IBXA was 99%. Mw of the obtained A1-B-A2 block copolymer was 46,810 and PDI was 1.84. After completion of the reaction, an organic solvent (anisole, etc.) was added to the reaction solution and diluted. The diluted reaction solution was poured into acetonitrile under stirring to precipitate a polymer. Block copolymer No. 1 was obtained by suction filtration and drying of the precipitated polymer.

(Block copolymer No. 2 ~ 15)

Block copolymers No. 2 to 15 were produced in the same manner as in the method for producing block copolymer No. 1. In Tables 2 and 3, raw material monomers used, organic tellurium compounds, azo-based polymerization initiators, solvents, polymerization conditions, and polymerization rates are described. In addition, in Tables 4 and 5, Mw and PDI of each block copolymer are described.

(Random copolymer No. 1)

BTEE 41.5 mg, IBXA 5.40 g, BA 2.90 g, AIBN 4.5 mg, and anisole 7.50 g were added to a flask equipped with an argon gas introduction tube and a stirring blade, and were polymerized by reacting at 60 ° C. for 87 hours. The polymerization rate of IBXA and BA was 100%. Moreover, Mw of the obtained random copolymer No. 1 was 62,190, and PDI was 1.26. After completion of the reaction, an organic solvent (anisol, etc.) was added to the reaction solution and diluted. The diluted reaction solution was poured into acetonitrile under stirring to precipitate a polymer. The precipitated polymer was suction filtered and dried to obtain random copolymer No.1.

(Random copolymer No.2 ~ 4)

Random copolymers No. 2 to 4 were produced in the same manner as in the production method of random copolymer No. 1. Table 6 lists the raw material monomers used, organic tellurium compound, azo-based polymerization initiator, solvent, polymerization conditions, polymerization rate, and Mw and PDI of each random copolymer.

For the block copolymer and random copolymer obtained above, solubility and substrate adhesion were evaluated.

(Solubility)

For block copolymers No. 2 and 3 and random copolymers No. 1 and 2, solubility in solvents was evaluated. Specifically, the copolymer was added to a solvent (methylethylketone (MEK) or 1-methoxy-2-propanol (MP)) so that the solid content was 30% by mass, and stirred at 23 ° C for 60 minutes. After stirring, the solubility was evaluated visually. The solubility was evaluated as "x" for those that were uniformly dissolved and "x" and those that were not dissolved (precipitation, insoluble, emulsified, etc.). Table 7 shows the results.

(Base adhesion)

Block copolymers No. 1 to 8 and 13 to 15 and random copolymers No. 1 to 3 were evaluated for adhesion to the substrate. Specifically, the copolymer was mixed with a solvent (MEK) so that the solid content was 1% by mass, to prepare a coating agent. The obtained coating agent was applied on a substrate with a bar coater (wet film thickness; 6.67 μm) and dried in a hot air dryer (130 ° C.) for 10 minutes to obtain a coated substrate. Further, as the material of the substrate, an aliphatic cyclic polyolefin (COP) or polypropylene (PP) was used, and the thickness of the substrate was 100 μm.

About the obtained coating base material, the coating layer was visually observed to evaluate the appearance. The appearance was evaluated as "○" for the absence of whitening or bunching and "X" for the whitening or bunching. Moreover, the surface stickiness of the coating layer was evaluated. The stickiness of the surface was evaluated by pressing the coated surface with a finger to evaluate that there was no change to "○", to leave fingerprints or to attach a coating layer to "X". The adhesiveness of the base material of the coating layer was evaluated by a cross-cut tape method (former JIS K5400 (1990) standard, 1 mm spacing of incision lines). Table 8 shows the results.

Using the block copolymer and random copolymer obtained above, an adhesive composition and a primer composition were prepared, and adhesiveness and the like were evaluated.

(Adhesive composition)

Block copolymers Nos. 9 to 14 were mixed in a solvent (MEK) so as to have a solid content of 10% by mass, thereby producing an adhesive composition. The obtained adhesive composition was applied onto a COP film (100 μm thick) as a substrate with a bar coater (wet film thickness; 50 μm), dried in a hot air dryer (130 ° C.) for 10 minutes, and adhered layer (thickness after drying; 2.5 μm). Formed. Then, a polyethylene terephthalate (PET) film serving as an adherend was placed on the adhesive layer to obtain a laminate. This laminated body was thermocompressed for 3 minutes under conditions of 100 ° C and 1 MPa using a press machine (MP-WCH, manufactured by Toyo Seiki Works) to prepare a heterogeneous film composite.

The obtained heterogeneous film composite was cut into a width of 30 mm and a length of 100 mm, and the side of the COP film was fixed to a rigid adherend (SUS plate, length of 125 mm) to prepare a test piece. In addition, in the heterogeneous film composite, an adhesive layer is formed on the entire width from one end in the longitudinal direction to a position of 90 mm. The test piece was subjected to a 180-degree peel test using a tensile compression tester (SV-52NA, manufactured by Imada Manufacturing Co., Ltd.). The end to which the flexible adherend (PET film) of the test piece was not folded was folded, the rigid adherend and the COP film were pinned with fixed tongs, and the flexible adherend was mounted on the other tong. The tongs were moved at a rate of 50 mm / min until the adhesive length peeled 25 mm, and the peeling force (resistance) (unit: N / 30 mm) at that time was measured. Table 9 shows the results. In addition, about the block copolymers No. 11-13, the test was performed similarly also about having changed the base material into a PET film (100 micrometers in thickness) and an adherend into a PP film (50 micrometers in thickness).

(Primer composition)

Block copolymer No. 2-4, 13 and 14, random copolymer No. 2 and 4 were mixed in a solvent (MEK) so that the solid content was 1% by mass, thereby preparing a primer composition. The obtained primer composition was applied on a corona-treated COP film (100 μm thick) with a bar coater (wet film thickness; 6.67 μm) and dried in a hot air dryer (130 ° C.) for 10 minutes to form a primer layer. Subsequently, a hard coat composition containing urethane acrylate was applied onto the primer layer with a bar coater (wet film thickness; 11.45 μm) and dried in a hot air dryer (80 ° C.) for 1 minute to form a hard coat composition layer. Then, using a UV curing device (electrodeless UV lamp system (LIGHT HAMMER (registered trademark) 6), manufactured by Heraeus), peak illuminance 900 (mW / cm ² ), accumulated light amount 350 (mJ / cm ² ) Under the conditions of, the hard coat composition layer was cured to obtain a material coated with a hard coating layer on a COP film.

About the obtained material, the adhesiveness of the hard coating layer with respect to the base material was evaluated by the cross-cut tape method (former JIS K5400 (1990) standard, 1 mm spacing of incision lines), and the results are shown in Table 10. Moreover, the hardness of the hard coat surface layer was evaluated by the steel wool resistance test. The steel wool resistance was evaluated by rounding the steel wool count ＃ 0000, manually reciprocating it several times, and rubbing it to evaluate that "○" and "X" were those with no flaws. Table 10 shows the results.

(Adhesive composition)

The adhesive composition was prepared by mixing 1 part by mass of the block copolymer No. 11 or 12, 9 parts by mass of a solvent (tetrahydrofuran), and a crosslinking agent. Moreover, crosslinking agent 1 (made by Mitsubishi Gas Chemical, TETRAD-X) or crosslinking agent 2 (made by Asahi Kasei, Duranate (trademark) TPA-100) was used. Moreover, the compounding quantity of a crosslinking agent was made into 0.021 mass parts in the case of crosslinking agent 1 (TETRAD-X), and 0.0066 mass parts in the case of crosslinking agent 2 (D-TPA).

The obtained pressure-sensitive adhesive composition was applied onto a substrate (100 μm thick) with a bar coater (wet film thickness; 50 μm) and dried in a hot air dryer (100 ° C.) for 1 minute to form an adhesive layer (thickness after drying; 2.5 μm). did. Thereafter, an adherend (50 μm thick) was placed on the adhesive layer, and then compressed using a nip roll (Tester Industry Co., SA-1100) at a load of 100 kgf (980 N) to obtain a laminate. The laminated body was crosslinked under conditions of 23 ° C and 50% relative humidity to prepare a heterogeneous film composite.

The obtained heterogeneous film composite was cut into a width of 30 mm and a length of 100 mm, and the side of the substrate was fixed to a rigid adherend (SUS plate, length of 125 mm) to prepare a test piece. In addition, in the heterogeneous film composite, an adhesive layer is formed on the entire width from one end in the longitudinal direction to a position of 90 mm. About this test piece, similarly to the said adhesive composition, the 180 degree peeling test was done. Table 11 shows the results.

The present invention includes the following aspects.

Aspect 1

A block having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group, and a B block having a structural unit derived from a vinyl monomer, wherein the average glass transition temperature of the A block is 25 ° C or higher, and the B block Block copolymer, characterized in that the average glass transition temperature of the lower than the average glass transition temperature of the A block, the difference between the average glass transition temperature of the A block and the average glass transition temperature of the B block is 50 ° C or more.

Aspect 2

The block copolymer according to aspect 1, which is an A-B-A type block copolymer.

Aspect 3

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

Aspect 4

The block copolymer according to any one of embodiments 1 to 3, wherein the content of the B block is 5% by mass to 60% by mass in 100% by mass of the entire block copolymer.

Aspect 5

The block copolymer according to any one of aspects 1 to 4, wherein the block copolymer has a molecular weight distribution (PDI) of 2.5 or less.

Aspect 6

The block copolymer according to any one of embodiments 1 to 5, wherein the block copolymer is polymerized by living radical polymerization.

Aspect 7

A composition comprising the block copolymer according to embodiments 1 to 6.

Aspect 8

A film comprising a base and a layer formed of the composition according to aspect 7 on at least a portion of at least one side of the base.

Aspect 9

The film according to embodiment 8, wherein the base material is a polyolefin-based resin.

Aspect 10

The composition of aspect 7 which is a primer composition.

Aspect 11

The composition of aspect 7 which is a surface modification composition.

Aspect 12

The composition of aspect 7 which is an adhesive composition.

Aspect 13

The composition according to aspect 7 which is an adhesive composition.

Industrial availability

The block copolymer of the present invention has strong adhesion (adhesiveness) to not only high-polarity materials but also low-polarity materials such as polyolefin-based resins. Therefore, the block 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. Moreover, the block copolymer of this invention can be used as a tackifier of an acrylic adhesive.

Claims (14)

A block having a structural unit derived from a vinyl monomer having a polycyclic aliphatic hydrocarbon group, and a B block having a structural unit derived from a vinyl monomer,
The average glass transition temperature of the A block is 25 ° C or higher and 150 ° C or lower,
The content of the structural unit derived from the vinyl monomer having the polycyclic aliphatic hydrocarbon group in the A block is 40% by mass or more in 100% by mass of the A block,
The vinyl monomer having the polycyclic aliphatic hydrocarbon group is an acrylic acid polycyclic aliphatic hydrocarbon ester,
The average glass transition temperature of the B block is lower than the average glass transition temperature of the A block, and the difference between the average glass transition temperature of the A block and the average glass transition temperature of the B block is 50 ° C. or higher,
The block copolymer, characterized in that the content of the B block is 5 mass% to 60 mass% in 100 mass% of the entire block copolymer. The method according to claim 1,
A block copolymer, which is an ABA type block copolymer. The method according to claim 1,
The vinyl monomer having the polycyclic aliphatic hydrocarbon group is 1-adamantyl acrylate, 2-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate , A block copolymer of at least one member selected from the group consisting of norbornyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate and dicyclopentenyl acrylate. The method according to claim 1,
The block copolymer having a weight average molecular weight of 3,000 to 1,000,000 of the block copolymer. The method according to claim 1,
The block copolymer having a molecular weight distribution (PDI) of 2.5 or less. The method according to claim 1,
The A block has a structural unit derived from a vinyl monomer having a reactive functional group,
The reactive functional group is a hydroxyl group, a carboxyl group or an epoxy group,
The block copolymer in which the content rate of the structural unit derived from the vinyl monomer having the reactive functional group in the A block is 0.1 mass% to 5.0 mass% in 100 mass% of the A block. The method according to claim 1,
The block copolymer is a polymer that is polymerized by living radical polymerization. A composition comprising the block copolymer according to any one of claims 1 to 7. A film comprising a substrate and a layer formed of the composition according to claim 8 on at least a portion of at least one side of the substrate. The method according to claim 9,
The film, wherein the substrate is a polyolefin-based resin. The method according to claim 8,
A composition that is a primer composition. The method according to claim 8,
A composition that is a surface modification composition. The method according to claim 8,
A composition that is an adhesive composition. The method according to claim 8,
A composition that is an adhesive composition.