JP7365135B2 - Surface modifier composition - Google Patents

Description

The present invention relates to a surface modifier composition containing an N-alkenyl lactam block copolymer.

Polymers with a lactam structure have hydrophilic properties and are highly safe for the human body and the environment, so they can be used as dispersion compositions in which solid particles such as colorants are dispersed in a dispersion medium; surface modifiers; adhesives It is widely used in fields such as agents; electronic parts; pharmaceuticals; and cosmetics.

Surface modifiers are widely used for plastics, glass, metals, etc. because they can impart desired properties to the surface of substrates. In particular, when these base materials are used in applications where they come into contact with water or moisture, surface modifiers are used to impart hydrophilicity to the base material surface, but polymers with a lactam structure Used as a surface modifier. For example, it is known that an AB block copolymer having a block containing a structural unit derived from N-vinylpyrrolidone is used as a coating agent (see Patent Document 1 (paragraph 0006)).

It is known that a living polymerization method is used to produce an AB block copolymer (see, for example, Patent Document 2 (Claim 1, page 20, lines 18 to 23)). Living polymerization methods include living anionic polymerization methods, living cationic polymerization methods, living radical polymerization methods, and the like. The living anionic polymerization method and the living cationic polymerization method require strict polymerization conditions, and furthermore, the functional groups that can coexist are limited. In contrast, the living radical polymerization method maintains the versatility of coexisting with polar functional groups, and the simplicity of not being affected by the purity of monomers or solvents, while allowing precise control of molecular weight distribution and production of polymers with uniform composition. . Therefore, a living radical polymerization method is used to produce a block copolymer having a polar group and a narrow molecular weight distribution with a controlled molecular weight and a uniform composition.

Note that when producing a block copolymer, it inevitably contains polymer impurities that are produced as by-products during polymerization. Therefore, methods have been proposed to reduce the content of such polymer impurities. For example, Patent Document 3 describes a purification method in which polymer impurities are selectively removed by liquid-liquid extraction of a block copolymer after polymerization using a specific solvent (Patent Document 3 ( (See paragraphs 0017-0024). However, in Patent Document 3, purification and removal of a styrene homopolymer is studied, but a method for removing a polymer having a lactam structure is not studied.

Japanese Patent Application Publication No. 2015-168764 International Publication No. 2004/096870 Japanese Patent Application Publication No. 2015-113444

Conventional coating agents using N-vinyl lactam block copolymers have had the problem that when the coating layer is exposed to water for a long period of time, the coating layer gradually peels off from the substrate surface. .
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a surface modifier composition that can form a surface modified layer with excellent durability.

The surface modifier composition of the present invention that can solve the above problems is a surface modifier composition containing a polymerization product, wherein the polymerization product is obtained by polymerizing a monomer composition. A block copolymer having an A block having a structural unit derived from an N-alkenyl lactam monomer and a B block having a structural unit derived from a vinyl monomer other than the N-alkenyl lactam monomer. and the molecular weight distribution (PDI) of the polymerization product is 2.0 or less, and the content of the block copolymer is 80% by mass or more in 100% by mass of the polymerization product. It is characterized by

The surface modifier composition of the present invention comprises, as surface modifier components, an A block having a structural unit derived from an N-alkenyl lactam monomer and a structural unit derived from a vinyl monomer other than the N-alkenyl lactam monomer. It contains a polymerization product containing an N-alkenyl lactam block copolymer having a B block having This block copolymer can form a surface-modified layer with excellent hydrophilicity on the base material by having the A block and the B block. Further, in the surface modifier composition of the present invention, the content of the block copolymer is 80% by mass or more. In other words, the content of polymer impurities such as a polymer consisting only of A blocks and a polymer consisting only of B blocks is 20% by mass or less. Therefore, in the surface modifier composition of the present invention, the resulting surface modified layer exhibits excellent durability against water.

The surface modifier composition of the present invention can form a surface modified layer with excellent durability against water.

The surface modifier composition of the present invention is a surface modifier composition containing a polymerization product, wherein the polymerization product is obtained by polymerizing a monomer composition, and is an N-alkenyl A block copolymer having an A block having a structural unit derived from a lactam monomer and a B block having a structural unit derived from a vinyl monomer other than an N-alkenyllactam monomer, and the molecular weight of the polymerization product is Distribution (PDI) is 2.0 or less, and the content of the block copolymer is 80% by mass or more in 100% by mass of the polymerization product.

The surface modifier composition of the present invention comprises, as surface modifier components, an A block having a structural unit derived from an N-alkenyl lactam monomer and a structural unit derived from a vinyl monomer other than the N-alkenyl lactam monomer. It contains a polymerization product containing an N-alkenyl lactam block copolymer having a B block having This block copolymer can form a surface-modified layer with excellent hydrophilicity on the base material by having the A block and the B block. Further, in the surface modifier composition of the present invention, the content of the block copolymer is 80% by mass or more. In other words, the content of polymer impurities such as a polymer consisting only of A blocks and a polymer consisting only of B blocks is 20% by mass or less. Therefore, in the surface modifier composition of the present invention, the resulting surface modified layer exhibits excellent durability against water.

In the present invention, the term "polymerization product" refers to a product obtained when a polymerization operation is performed to obtain the block copolymer. The "polymerization product" includes a desired block copolymer and polymer impurities that are by-produced during the synthesis of this block copolymer.

In the present invention, "polymer impurities" are other polymers that are inevitably produced as by-products when synthesizing a desired block copolymer. For example, polymer impurities produced as by-products when synthesizing AB type diblock copolymers include random polymers having the same composition as the A block and random polymers having the same composition as the B block. Polymer impurities that are produced as by-products when synthesizing the A-B-A type triblock copolymer or the B-A-B type triblock copolymer include random polymers having the same composition as the A block, and the B block. A random polymer having a composition similar to that of Note that "polymer impurities" are polymers that are produced as by-products when synthesizing a desired block copolymer, and do not include polymers that are added separately.

In the present invention, "A block" can be translated as "A segment", and "B block" can be translated as "B segment". In the present invention, "vinyl monomer" refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule. The term "structural unit derived from a vinyl monomer" refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to become a carbon-carbon single bond. "(Meth)acrylic" refers to "at least one of acrylic and methacrylic." "(Meth)acrylate" refers to "at least one of acrylate and methacrylate." "(Meth)acryloyl" refers to "at least one of acryloyl and methacryloyl."

An example of a preferred embodiment of the present invention will be described below. However, the following embodiments are merely illustrative. The present invention is not limited to the following embodiments.

<Polymerization product>
The polymerization product contains a block copolymer having an A block and a B block, and polymer impurities.

The content of the block copolymer in the polymerization product is 80% by mass or more, preferably 85% by mass or more, and more preferably 90% by mass or more based on 100% by mass of the polymerization product.

When the polymerization product is obtained for the purpose of synthesizing an AB type diblock copolymer, the content of AB type diblock copolymer in the polymerization product is It is 80% by mass or more, preferably 85% by mass or more, and more preferably 90% by mass or more in 100% by mass of the product.

When the polymerization product is obtained for the purpose of synthesizing an ABA triblock copolymer or a BAB triblock copolymer, A in the polymerization product -The total content of the B-A type triblock copolymer and the AB type diblock copolymer is 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass, based on 100% by mass of the polymerization product. % by mass or more.

The weight average molecular weight (Mw) of the polymerization product is preferably 5,000 or more, more preferably 6,000 or more, even more preferably 7,000 or more, and preferably 500,000 or less, more preferably 400,000. It is preferably 300,000 or less. If the weight average molecular weight is within the above range, the durability of the modified layer to be formed will be better. The molecular weight of the polymerization product is measured by gel permeation chromatography (hereinafter referred to as "GPC").

The molecular weight distribution (PDI) of the polymerization product is 2.0 or less, preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. . In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of polymerization product)/(number average molecular weight (Mn) of polymerization product). The smaller the PDI, the narrower the width of the molecular weight distribution, resulting in a polymerization product with uniform molecular weight, and when the value is 1.0, the width of the molecular weight distribution is the narrowest. If the molecular weight distribution (PDI) of the polymerization product exceeds 2.0, it will include those with small molecular weights and those with large molecular weights.

(Block copolymer)
Various constituent components of the block copolymer will be explained below.

(A block)
The A block is a polymer block containing a structural unit derived from an N-alkenyl lactam monomer.

The structural unit derived from the N-alkenyl lactam monomer is not particularly limited as long as it is a structural unit derived from a vinyl monomer having a cyclic N-alkenyl lactam structure, but may be a structural unit represented by the following general formula (1). It is preferable that there be.

〔式（１）において、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は、同一又は異なって、水素原子又は置換基を有していてもよい炭素数１～１０のアルキル基を示す。ｍ１は０～４の整数を示す。ｎ１は１～３の整数を示す。〕

[In formula (1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. m1 represents an integer from 0 to 4. n1 represents an integer from 1 to 3. ]

The number of carbon atoms in the alkyl group in R ¹¹ to R ¹⁴ is preferably 1 to 6, more preferably 1 to 4. The alkyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Substituents for R ¹¹ to R ¹⁴ are not particularly limited, but include carboxy groups, sulfonic acid groups, and esters and salts thereof; amino groups; hydroxy groups, and the like.

R ¹¹ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
The above R ¹² to R ¹⁴ are preferably hydrogen atoms.
m1 is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and even more preferably 0.
n1 is preferably 1 or 2, more preferably 1.

Examples of the vinyl monomer forming the structural unit represented by the general formula (1) include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-5-ethylpyrrolidone, N-vinyl-5- Vinyl monomers having a 5-membered ring lactam structure such as propylpyrrolidone, N-vinyl-5-butylpyrrolidone, and 1-(2-propenyl)-2-pyrrolidone; Vinyl monomers having a 6-membered ring lactam structure such as N-vinylpiperidone; Examples include vinyl monomers having a 7-membered lactam structure such as N-vinylcaprolactam. One or more types of vinyl monomers forming the structural unit represented by the general formula (1) can be used. Among these, vinyl monomers having a 5-membered lactam structure are preferred, and N-vinylpyrrolidone is more preferred.

The A block may be composed only of structural units derived from N-alkenyl lactam monomers, or may contain other structural units. From the viewpoint of making the A block hydrophilic, the content of structural units derived from the N-alkenyl lactam monomer in the A block is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass. % or more, particularly preferably 98% by mass or more. The higher the content of structural units derived from the N-alkenyl lactam monomer in the A block, the more hydrophilicity of the substrate surface can be improved.

Specific examples of monomers that can form other structural units of the A block include (meth)acrylates having a chain alkyl group (straight chain alkyl group or branched chain alkyl group), (meth)acrylates having a cyclic alkyl group, (meth)acrylate having a polycyclic structure, (meth)acrylate having an aromatic group, (meth)acrylate having a polyalkylene glycol structural unit, (meth)acrylate having a cyclic ether group, N-dialkylaminoalkyl (meth) ) acrylate, (meth)acrylate with a hydroxy group, (meth)acrylate with a lactone-modified hydroxy group, (meth)acrylate with an alkoxy group, (meth)acrylate with an oxygen-containing heterocyclic group, (meth)acrylate with an amino group ) Acrylates, (meth)acrylates having acidic groups, (meth)acrylic vinyl monomers such as (meth)acrylic acid; α-olefins; aromatic vinyl monomers; heterocycle-containing unsaturated monomers; vinylamides; vinyl carboxylates; dienes There are many examples of this.

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 form such as random copolymerization or block copolymerization in the A block. , is preferably contained in a random copolymerized form from the viewpoint of uniformity. For example, the A block may be formed of a copolymer of a structural unit consisting of an a1 block and a structural unit consisting of an a2 block.

(B block)
The B block is a polymer block containing a structural unit derived from a vinyl monomer other than the N-alkenyl lactam monomer. The number of the structural units in the B block may be one type or two or more types.

Specific examples of vinyl monomers other than N-alkenyl lactam monomers that can form other structural units of block B include (meth)acrylic vinyl monomers, α-olefins, aromatic vinyl monomers, and heterocycle-containing monomers. Saturated monomers, vinylamide, vinyl carboxylates, dienes, etc. can be mentioned.

Examples of the (meth)acrylic vinyl monomer include (meth)acrylates having a chain alkyl group (straight chain alkyl group or branched chain alkyl group), (meth)acrylates having a cyclic alkyl group, and polycyclic structures. (meth)acrylates having an aromatic group, (meth)acrylates having an aromatic group, (meth)acrylates having a cyclic ether group, N-dialkylaminoalkyl (meth)acrylates, (meth)acrylates having a hydroxy group, (meth)acrylates having an acidic group ( Examples include meth)acrylate and (meth)acrylic acid.

The (meth)acrylate having a straight chain alkyl group is preferably a (meth)acrylate having a straight chain alkyl group in which the straight chain alkyl group has 1 to 20 carbon atoms; (meth)acrylates having a linear alkyl group of 10 are more preferred. As the (meth)acrylate having a linear alkyl group, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, Examples include n-octyl (meth)acrylate, n-nonyl (meth)acrylate, decyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

The (meth)acrylate having a branched-chain alkyl group is preferably a (meth)acrylate having a branched-chain alkyl group in which the branched-chain alkyl group has 1 to 20 carbon atoms; Preferred are (meth)acrylates with a branched alkyl group of 10. Examples of the (meth)acrylate having a branched chain alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2- Examples include ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and the like.

The (meth)acrylate having a cyclic alkyl group is preferably a (meth)acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Examples of the cyclic alkyl group include a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group). Specific examples of (meth)acrylates having a cyclic alkyl group with a monocyclic structure include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate.

The (meth)acrylate having a polycyclic structure is preferably a (meth)acrylate having a polycyclic structure having 6 to 12 carbon atoms. Examples of the polycyclic structure include cyclic alkyl groups having a bridged ring structure (eg, adamantyl group, norbornyl group, and isobornyl group). Specific examples of (meth)acrylates having a polycyclic structure include isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and 2-methyl-2-adamantyl. (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like.

The (meth)acrylate having an aromatic group is preferably a (meth)acrylate having an aromatic group having 6 to 12 carbon atoms. Examples of the aromatic group include an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group, an aralkyloxy group, and in particular a phenyl group, a benzyl group, a tolyl group, and a phenoxyethyl group. Groups are preferred. Specific examples of (meth)acrylates having an aromatic group include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.

Examples of (meth)acrylates having a cyclic ether group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, 2-(4-morpholinyl)ethyl (meth)acrylate, (3- Ethyloxetan-3-yl) methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 2- Examples include [(2-tetrahydropyranyl)oxy]ethyl (meth)acrylate and 1,3-dioxane-(meth)acrylate.

The N-dialkylaminoalkyl (meth)acrylates include N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N, N-diethylaminopropyl (meth)acrylate, N,N-diethylaminobutyl (meth)acrylate, N,N-dipropylaminoethyl (meth)acrylate, N,N-dibutylaminoethyl (meth)acrylate, N,N-dibutyl Examples include aminopropyl (meth)acrylate, N,N-dibutylaminobutyl (meth)acrylate, N,N-dihexylaminoethyl (meth)acrylate, N,N-dioctylaminoethyl (meth)acrylate, and the like.

Examples of the (meth)acrylate having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxypropyl (meth)acrylate. Examples include hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate.

Examples of the acidic group include a carboxy group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphinic acid group (- PO ₂ H ₂ ). The (meth)acrylate having an acidic group is a (meth)acrylate having a carboxy group such as a monomer obtained by reacting a hydroxyalkyl (meth)acrylate with an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride. ; (meth)acrylates having a sulfonic acid group such as ethyl sulfonate (meth)acrylate; (meth)acrylates having a phosphoric acid group such as 2-(phosphonooxy)ethyl (meth)acrylate; and preferably It is a (meth)acrylate having a carboxy group.

Examples of the α-olefin include 1-hexene, 1-octene, 1-decene, and the like.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene, and the like.
Examples of the heterocycle-containing unsaturated monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, and 4-vinylpyridine.
Examples of the vinylamide include N-vinylformamide and N-vinylacetamide.
Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate, and the like.
Examples of the dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

The B block is preferably more hydrophobic than the A block. Since the B block is hydrophobic, hydrophilicity can be imparted to the surface of the hydrophobic base material. Hydrophobicity means a property that has a weak interaction with water and a weak affinity for water. Therefore, the rate of miscibility with water, that is, the solubility, is an index of hydrophobicity.

In order to obtain a polymer block that is more hydrophobic than the A block, the content of structural units derived from the hydrophobic vinyl monomer is preferably 80% by mass or more, more preferably 90% by mass in 100% by mass of the B block. The content is more preferably 98% by mass or more. Moreover, the B block may be composed only of hydrophobic vinyl monomers.

The hydrophobic vinyl monomer has a solubility in water at 20°C of less than 50% by weight, preferably less than 40% by weight, more preferably less than 30% by weight. Specifically, the hydrophobic vinyl monomers include (meth)acrylates having a chain alkyl group (straight chain alkyl group or branched chain alkyl group), (meth)acrylates having a cyclic alkyl group, and (meth)acrylates having a polycyclic structure. Examples include meth)acrylate, (meth)acrylate having an aromatic group, (meth)acrylate having a cyclic ether group, N-dialkylaminoalkyl (meth)acrylate, aromatic vinyl monomer, and heterocycle-containing unsaturated monomer. One kind or a combination of two or more kinds thereof can be used.

The B block may have a reactive functional group. If such a reactive functional group is present, a crosslinked structure can be introduced into the surface modified layer to be formed by adding a crosslinking agent to the surface modifier composition. Examples of the reactive functional group include an epoxy group, a hydroxy group, and a carboxy group. Examples of the vinyl monomer having a reactive functional group include (meth)acrylate having a cyclic ether group, (meth)acrylate having a hydroxy group, (meth)acrylate having a carboxyl group, (meth)acrylic acid, and the like.

When introducing a reactive functional group into the B block, the content of structural units derived from a vinyl monomer having a reactive functional group is preferably 1% by mass or more, and 20% by mass based on 100% by mass of the entire block copolymer. % or less is preferable.

When introducing a reactive functional group into the B block, the content of the reactive group is preferably 0.01 mmol/g or more, and preferably 1.5 mmol/g or less in the entire block copolymer.

The vinyl monomer forming the B block can be appropriately selected depending on the material of the base material to which the surface modifier composition is applied. For example, if the base material is a low polar material such as a polyolefin resin such as polypropylene resin, polyethylene resin, cyclic polyolefin resin, or cyclic olefin copolymer resin, (meth)acrylate having a straight chain alkyl group or a (meth)acrylate having a branched chain alkyl group It is preferable that it is at least one selected from the group consisting of (meth)acrylate, (meth)acrylate having a cyclic alkyl group, and (meth)acrylate having a polycyclic structure. In addition, when the base material is polystyrene resin, polyester resin, polyphenylene sulfide resin, or polyether sulfone resin, (meth)acrylate having a straight chain alkyl group, (meth)acrylate having a branched chain alkyl group, aromatic It is preferable that the monomer is at least one selected from the group consisting of (meth)acrylates having groups and aromatic vinyl monomers.

The B block has a content of structural units derived from the N-alkenyl lactam monomer of less than 5% by mass, preferably less than 3% by mass, more preferably less than 1% by mass, and has a content of structural units derived from the N-alkenyllactam monomer. It is preferable not to contain any derived structural units. In other words, the content of structural units derived from vinyl monomers other than the N-alkenyl lactam monomer in the B block is 95% by mass or more, preferably 97% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass or more. Mass%. The lower the content of structural units derived from the N-alkenyl lactam monomer in the B block, the better the adhesion to the base material.

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 mode such as random copolymerization or block copolymerization in the B block. , is preferably contained in a random copolymerized form from the viewpoint of uniformity. For example, the B block may be formed of a copolymer of a structural unit consisting of a b1 block and a structural unit consisting of a b2 block.

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. In addition, the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B. When expressed as, (A-B) _m type, (A-B) _m -A type, and (B-A) _m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3). A copolymer having at least one structure selected from the group is preferred. Among these, from the viewpoint of handling properties during processing and physical properties of the composition, AB type diblock copolymers, ABA type triblock copolymers, and BAB type triblock copolymers are preferred. Preferably, it is a combination. By constructing an A-B type diblock copolymer, an A-B-A type triblock copolymer, or a B-A-B type triblock copolymer, the N-alkenyl lactam monomer contained in the A block It is thought that the derived structural units and the structural units derived from other vinyl monomers included in the B block are localized and can impart hydrophilicity to the surface of the hydrophobic base material. The block copolymer may have blocks other than the A block and B block.

The content of the A block is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, based on 100% by mass of the entire block copolymer. It is more preferably 85% by mass or less, and still more preferably 80% by mass or less. The content of the B block is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 70% by mass or less, based on 100% by mass of the entire block copolymer. It is more preferably 65% by mass or less, and still more preferably 60% by mass or less. By adjusting the content of A block and B block within the above range, the hydrophilicity and durability of the resulting surface modified layer are further improved.

The mass ratio of A block to B block (A block/B block) in the block copolymer is preferably 30/70 or more, more preferably 35/65 or more, still more preferably 40/60 or more, and 90 /10 or less is preferable, more preferably 85/15 or less, still more preferably 80/20 or less. If the mass ratio of the A block and the B block is within the above range, the hydrophilicity and durability of the resulting surface modified layer will be further improved.

The content of structural units derived from the N-alkenyl lactam monomer in the block copolymer is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and 90% by mass. % or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

It is preferable that the block copolymer does not have a substituent containing a sulfur atom at the end. Examples of the sulfur atom-containing substituent include a dithiocarbamate group and a xanthate group. If it does not have a substituent containing a sulfur atom at the end, coloration and odor can be suppressed.

<Method for producing polymerization product>
The polymerization product used in the present invention can be produced by sequentially polymerizing the vinyl monomers constituting the blocks, whereby the A block is first produced and the monomers of the B block are polymerized onto the A block; , a method of polymerizing monomers of the A block into the B block, and the like.

Examples of methods for producing polymer products by polymerization reactions of vinyl monomers include living polymerization methods such as living anionic polymerization, living cationic polymerization, and living radical polymerization. It is preferable to manufacture products. Living anionic polymerization and living cationic polymerization require strict polymerization conditions, and the functional groups that can coexist are limited, whereas living radical polymerization has the versatility to coexist with polar functional groups, as well as the purity of monomers and solvents. This method is preferable because it allows precise control of molecular weight distribution and the production of a polymer with a uniform composition while maintaining simplicity and unaffected by. That is, the block copolymer is preferably one polymerized by living radical polymerization.

In addition, in conventional radical polymerization methods, the growth terminal is deactivated not only by initiation reactions and propagation reactions but also by termination reactions and chain transfer reactions, which tends to result in a mixture of polymers with various molecular weights and non-uniform compositions. . Living radical polymerization, on the other hand, maintains the simplicity and versatility of conventional radical polymerization, but is less likely to cause termination reactions or chain transfer, and grows without deactivating growing terminals, resulting in a change in molecular weight distribution. This is preferable because precise control and production of a polymer with a uniform composition is easy.

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

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. For example, WO 2004/14848, WO 2004/14962, WO This is the method described in No. 2004/072126 and International Publication No. 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(a) A vinyl monomer is polymerized using an organic tellurium compound represented by general formula (3).
(b) A vinyl monomer is polymerized using a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator.
(c) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (3) and an organic ditelluride compound represented by general formula (4).
(d) A vinyl monomer is polymerized using a second mixture of an organic tellurium compound represented by general formula (3), an azo polymerization initiator, and an organic ditelluride compound represented by general formula (4).

〔一般式（３）中、Ｒ³¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を表す。Ｒ³²およびＲ³³は、それぞれ、水素原子または炭素数１～８のアルキル基を表す。Ｒ³⁴は、炭素数１～８のアルキル基、アリール基、芳香族へテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を表す。
一般式（４）中、Ｒ³¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を表す。〕

[In the general formula (3), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. R ³² and R ³³ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an 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 the general formula (4), R ³¹ represents an alkyl group, an aryl group, or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ³¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, and specifically as follows.
Examples of alkyl groups having 1 to 8 carbon atoms include 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. , straight chain or branched alkyl groups such as octyl groups, and cyclic alkyl groups such as cyclohexyl groups. Preferably it is a straight or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

The groups represented by R ³² and R ³³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
Examples of alkyl groups having 1 to 8 carbon atoms include 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. , straight chain or branched alkyl groups such as octyl groups, and cyclic alkyl groups such as cyclohexyl groups. Preferably it is a straight or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

The group represented by R ³⁴ 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 It is a propargyl group, and specifically as follows.
Examples of alkyl groups having 1 to 8 carbon atoms include 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. Examples include straight-chain or branched alkyl groups such as octyl groups, cyclic alkyl groups such as cyclohexyl groups, and the like. Preferably it is a straight or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. Preferably it is a phenyl group.
Examples of the substituted aryl group include a phenyl group having a substituent, a naphthyl group having a substituent, and the like. Examples of the substituent for the aryl group having the above substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by -COR ³¹¹ (R ³¹¹ is a carbon Examples include an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group or aryloxy group having 1 to 8 carbon atoms), a sulfonyl group, a trifluoromethyl group, and the like. Further, it is preferable that one or two of these substituents are substituted.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- Examples include butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the amide group include -CONR ³²¹ R ³²² (R ³²¹ and R ³²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
The oxycarbonyl group is preferably a group represented by -COOR ³³¹ (R ³³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group), such as a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group. Examples include n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, and phenoxycarbonyl group. Preferred oxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl groups.
As an allyl group, -CR ³⁴¹ R ³⁴² -CR ³⁴³ =CR ³⁴⁴ R ³⁴⁵ (R ³⁴¹ and R ³⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³⁴³ , R ³⁴⁴ and R ³⁴⁵ are , each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and each substituent may be connected in a cyclic structure).
As a propargyl group, -CR ³⁵¹ R ³⁵² -C≡CR ³⁵³ (R ³⁵¹ and R ³⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³⁵³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) , aryl group or silyl group).

Specifically, the organic tellurium compound represented by the general formula (3) is (methyltellanylmethyl)benzene, (methyltellanylmethyl)naphthalene, ethyl-2-methyl-2-methyltellanyl-propionate, ethyl-2- Methyl-2-n-butyltellanyl-propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methyltellanyl-proopionate, (2-hydroxyethyl)-2-methyl-2-methyltellanyl-propionate or (3- trimethylsilylpropargyl)-2-methyl-2-methyltellanyl-propionate, etc., as described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870. All of the organic tellurium compounds mentioned above can be exemplified.

Specific examples of the organic ditelluride compound represented by the general formula (4) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, and ditelluride. -n-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis-(p-methoxyphenyl) ditelluride, bis-(p-aminophenyl) ditelluride, bis Examples include -(p-nitrophenyl) ditelluride, bis-(p-cyanophenyl) ditelluride, bis-(p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, and dipyridyl ditelluride.

The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization. For example, 2,2'-azobis(isobutyronitrile) (AIBN) (65°C, toluene), 2,2'-azobis(2-methylbutyronitrile) (AMBN) (67°C, toluene), 2, 2'-azobis(2,4-dimethylvaleronitrile) (ADVN) (52°C, toluene), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN) (88°C, toluene), dimethyl-2, 2'-azobisisobutyrate (MAIB) (66°C, toluene), 4,4'-azobis(4-cyanovaleric acid) (ACVA) (69°C, water (as Na salt)), 1,1' -Azobis(1-acetoxy-1-phenylethane) (61°C, toluene), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70) (30°C, toluene), 2,2'-azobis(2-methylamidinopropane) dihydrochloride (56°C, water), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (61°C, methanol), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (86°C, water), 2,2'-azobis(N-butyl-2-methylpropionamide) (110°C, ethylbenzene) or dimethyl 1,1'-azobis(1-cyclohexanecarboxylate) (73°C, toluene). Among these, as the azo polymerization initiator, oil-soluble azo polymerization initiators are preferred, and AIBN, AMBN, ADVN, ACHN, and V-70 are more preferred. The numerical value written in parentheses after the compound name of the azo polymerization initiator is the solvent used to measure the 10-hour half-life temperature and the 10-hour half-life temperature. The 10-hour half-life temperature of the azo polymerization initiator refers to the temperature at which the concentration of azo groups in the solvent is halved in 10 hours. Examples of the solvent used for measuring the half-life temperature include toluene, ethylbenzene, etc. for oil-soluble azo polymerization initiators, and water, methanol, etc. for water-soluble azo polymerization initiators.

In the polymerization step, in a container purged with an inert gas, the vinyl monomer and the organic tellurium compound of general formula (3) are added, depending on the type of vinyl monomer, for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc. An azo polymerization initiator and/or an organic ditelluride compound of general formula (4) are mixed. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Preferably, argon or nitrogen is used.

The amount of the vinyl monomer used in (a), (b), (c) and (d) may be adjusted as appropriate depending on the physical properties of the desired copolymer. It is preferable that the vinyl monomer be used in an amount of 5 mol to 10,000 mol per mol of the organic tellurium compound of general formula (3).

When the organic tellurium compound of general formula (3) in the above (b) and an azo polymerization initiator are used together, the amount of the azo compound should be 0.01 mol to 10 mol per 1 mol of the organic tellurium compound of general formula (3). is preferred.

When the organic tellurium compound of the general formula (3) in the above (c) and the organic ditelluride compound of the general formula (4) are used together, the organic tellurium compound of the general formula (4) per 1 mol of the organic tellurium compound of the general formula (3) The amount of the ditelluride compound is preferably 0.01 mol to 100 mol.

When the organic tellurium compound of the general formula (3) in the above (d), the organic ditelluride compound of the general formula (4), and the azo polymerization initiator are used together, the general The amount of the organic ditelluride compound of formula (4) is preferably 0.01 mol to 100 mol, and the amount of the azo polymerization initiator is preferably 0.01 mol to 10 mol per mol of the organic tellurium compound of formula (3).

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

The amount of the solvent to be used may be adjusted as appropriate; for example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml per 1 g of the vinyl monomer composition. The amount is preferably below, more preferably 10 ml or less, still more preferably 1 ml or less.

Although the reaction temperature and reaction time may be adjusted as appropriate depending on the molecular weight or molecular weight distribution of the resulting copolymer, stirring is usually carried out at 0° C. to 150° C. for 1 minute to 100 hours. The TERP method can obtain high yield and precise molecular weight distribution even at low polymerization temperature and short polymerization time. At this time, the pressure is usually normal pressure, but the pressure may be increased or reduced.

After the polymerization reaction is completed, the desired copolymer can be separated from the resulting reaction mixture by removing the solvent used, residual vinyl monomer, etc., by ordinary separation and purification means.

The growing terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR ³¹ (in the formula, R ³¹ is the same as R 31 in the general formula (3)) derived from the tellurium compound, and the growth end is in the form of -TeR 31 (in the formula, R 31 is the same as R ³¹ in the general formula (3)). Although it is deactivated by subsequent operations in air, tellurium atoms may remain. Since a copolymer with tellurium atoms remaining at the terminals is colored and has poor thermal stability, it is preferable to remove the tellurium atoms.

Methods for removing tellurium atoms include a radical reduction method using tributylstannane or a thiol compound; adsorption methods using activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbents, etc.; methods using ion exchange resins, etc. Method of adsorbing metals; adding peroxide such as hydrogen peroxide or benzoyl peroxide, or blowing air or oxygen into the system to oxidize and decompose the tellurium atoms at the end of the copolymer, followed by washing with water or appropriate treatment. Liquid-liquid extraction and solid-liquid extraction methods that remove residual tellurium compounds by combining solvents; purification methods in a solution state such as ultrafiltration that extract and remove only those with a specific molecular weight or less can be used. , these methods can also be used in combination.

The other end of the copolymer obtained by the polymerization reaction (the end opposite to the growing end) is -CR ³² R ³³ R ³⁴ derived from a tellurium compound (wherein R ³² , R ³³ and R ³⁴ are general The form is the same as R ³² , R ³³ and R ³⁴ in formula (3). Therefore, the copolymer obtained by the TERP method does not have a substituent containing a sulfur atom at the end.

(Preferred embodiment of method for producing polymerization product)
Hereinafter, one embodiment of the method for producing the polymerization product will be described.
The production method includes a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator, or a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator. A block polymerization step of polymerizing a first monomer composition containing an N-alkenyl lactam monomer using a second mixture with an organic ditelluride compound represented by general formula (4); and a B block polymerization step of polymerizing a second monomer composition containing a vinyl monomer other than the N-alkenyl lactam monomer using the second mixture, and in all polymerization steps, the azo polymerization initiator is The difference (T _1/2 - Tr) between the 10-hour half-life temperature (T _1/2 ) and the reaction temperature (Tr) is preferably 10°C to 60°C, more preferably 10°C to 50°C, and more preferably The temperature is preferably 10°C to 40°C, particularly preferably 10°C to 30°C.

Generally, in the TERP method, if the vinyl monomer has a lactam structure or acidic group, these lactam structures or acidic groups tend to deactivate the polymerization terminal radical. For example, in a lactam structure, a hydrogen radical may be provided to the polymerization terminal radical to deactivate it. Furthermore, in the case of acidic groups, proton coordination occurs to organic tellurium that forms dormant species, which may inhibit dormant species formation and deactivate polymerization terminals. Therefore, when the vinyl monomer has a lactam structure or an acidic group, the content of polymers ("unlinked components") in which block components are not bonded in the polymerization product tends to increase. However, by setting the polymerization temperature to a temperature that is 10° C. or more lower than the 10-hour half-life temperature of the azo polymerization initiator to be added, the generation of unlinked components can be suppressed.

In the preferred embodiment, the first mixture or the second mixture is used during polymerization. The same first mixture or second mixture is used in the A block polymerization step and the B block polymerization step. That is, for example, when producing an AB type diblock copolymer, after performing the first stage polymerization step, this reaction solution (the first stage polymer and the first mixture or the second mixture A second stage monomer composition is added to the mixture (containing the following) to carry out the second stage polymerization step.

In the first mixture, the amount of the azo polymerization initiator used is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.01 mol or more, per 1 mol of the organic tellurium compound of general formula (3). The amount is 1 mol or more, preferably 10 mol or less, more preferably 2 mol or less, even more preferably 1 mol or less.

In the second mixture, the amount of the azo polymerization initiator used is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.01 mol or more, per 1 mol of the organic tellurium compound of general formula (3). The amount is 1 mol or more, preferably 10 mol or less, more preferably 2 mol or less, even more preferably 1 mol or less.

In the second mixture, the amount of the organic ditelluride compound of general formula (4) to be used is preferably 0.01 mol or more, more preferably 0.1 mol or more, and Preferably it is 0.2 mol or more, preferably 100 mol or less, more preferably 5 mol or less, still more preferably 3 mol or less.

In the A block polymerization step, a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator, or a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator A first monomer composition containing an N-alkenyl lactam monomer is polymerized using a second mixture of the agent and the organic ditelluride compound represented by the general formula (4).

In the A block polymerization step, the amount of vinyl monomer used is preferably 5 mol or more, more preferably 10 mol or more, even more preferably 20 mol or more, and preferably 10,000 mol or less, per 1 mol of the organic tellurium compound of general formula (3). , more preferably 300 mol or less, still more preferably 100 mol or less.

In the B block polymerization step, a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator, or a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator A second monomer composition containing a vinyl monomer other than the N-alkenyl lactam monomer is polymerized using a second mixture of the agent and the organic ditelluride compound represented by the general formula (4).

In the B block polymerization step, the amount of vinyl monomer used is preferably 5 mol or more, more preferably 7 mol or more, even more preferably 10 mol or more, and preferably 10,000 mol or less, per 1 mol of the organic tellurium compound of general formula (3). , more preferably 300 mol or less, still more preferably 100 mol or less.

In the preferred embodiment, the difference (T _1/2 - Tr) between the 10-hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) of all polymerization steps is 10° C. or more. The temperature is 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower, particularly preferably 30°C or lower. In addition, when using multiple azo polymerization initiators, it is preferable that the 10-hour half-life temperature of all the azo polymerization initiators satisfies the above range.

In the preferred embodiment, the reaction temperature is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, particularly preferably 30°C or higher, and preferably 80°C or lower, more preferably 60°C or higher. The temperature is preferably 55°C or lower, more preferably 55°C or lower. Further, the reaction time is preferably 1 hour or more, more preferably 3 hours or more, even more preferably 5 hours or more, and preferably 100 hours or less, more preferably 50 hours or less, and still more preferably 30 hours or less.

In the preferred embodiment, the polymerization rate (monomer conversion rate) of the monomer in the monomer composition serving as a raw material in each polymerization step is preferably 90% by mass or more, more preferably 96% by mass or more, and even more preferably 97% by mass. It is at least 98% by mass, particularly preferably at least 98% by mass.

The preferred embodiment has at least an A block polymerization step and a B block polymerization step. The order of these polymerization steps is not particularly limited, and the A block polymerization step may be performed first and the B block polymerization step later, or the B block polymerization step may be performed first and the A block polymerization step later. Good too. Further, the preferred embodiment may include a step of polymerizing blocks other than the A block and the B block.

<Surface modifier composition>
The surface modifier composition of the present invention contains the polymerization product and may further contain a solvent.

Examples of the solvent include water, organic solvents, and mixed solvents of water and organic solvents. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; diethyl Ethers such as ether and tetrahydrofuran; Acetic esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; Amides such as N,N-dimethylformamide and N-methylpyrrolidone; 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.

In order to improve the coating properties of the surface modifier composition, the solvent preferably contains an organic solvent in which the polymerization product and other additive components are soluble. Furthermore, from the viewpoint of handleability of the surface modifier composition, the total concentration of the polymerization product and other solid components is preferably 50% by mass or less, and preferably 0.1% by mass or more. The solvent is preferably one that does not impair the performance of the substrate (film, etc.) to which the surface modifier composition is applied.

Since the surface modifier composition of the present invention can impart hydrophilicity to the surface of a substrate, it can also be used as a coating agent, a primer composition, etc. Furthermore, in addition to the polymerization product and solvent, the surface modifier composition of the present invention may also contain plasticizers, colorants (pigments, dyes, etc.), coupling agents, preservatives, and antistatic agents, depending on the purpose. , antioxidants, ultraviolet absorbers, surfactants, flame retardants, fillers, crosslinking agents, fillers, and the like.

Examples of the crosslinking agent include compounds having two or more functional groups in one molecule that can react with the reactive functional groups introduced into the block copolymer. The crosslinking agent is not particularly limited, and examples thereof include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, melamine resin crosslinking agents, urea resin crosslinking agents, and the like.

The surface modifier composition can also be made into a hard coat composition that further contains a hard coat agent, and if the hard coat composition is used, a hard coat layer having hydrophilic properties can be formed on the surface of the substrate.

Examples of the hard coating agent include (meth)acrylic materials. Examples of (meth)acrylic materials include, but are not particularly limited to, monomer-based radical polymerization type monofunctional (meth)acrylates, bifunctional (meth)acrylates, trifunctional (meth)acrylates, and 4- to 6-functional (meth)acrylates. ) Acrylate; Oligomer radical polymerization type epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, copolymerization (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, amino resin ( Examples include meth)acrylate. (Meth)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, but includes, for example, an ultraviolet (UV) curing type using a photochemical reaction; a thermosetting type such as a room temperature curing type and a two-component reaction curing type. That is, the hard coating agent is not particularly limited, but includes, for example, commonly known UV curing resin types, urethane resins, and condensation resins.

<Coated material>
The article of the present invention is obtained by applying the surface modifier composition to a base material. The article includes a base material and a modified layer formed on at least a portion of the surface of the base material, and the modified layer is formed from the surface modifier composition.

The base material includes polyolefin resins such as polypropylene resin, polyethylene resin, cyclic polyolefin resin, and cyclic olefin copolymer resin; polystyrene resin; polyester resin; polyphenylene sulfide resin; polyether sulfone resin; metal; glass; polyamide resin ; polycarbonate resin; polymethyl acrylate resin; polyvinyl alcohol resin; triacetyl cellulose and the like. Examples of the shape of the base material include films, fibers, and the like.

In general, a "sheet" is defined by JIS as a flat product that is thin and generally has a small thickness relative to its length and width, and a "film" generally refers to a flat product whose thickness is small relative to its length and width. A thin flat product with an extremely small thickness and an arbitrarily limited maximum thickness, usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900). For example, in terms of thickness, in a narrow sense, a thickness of 100 μm or more is sometimes referred to as a sheet, and a thickness of less than 100 μm is sometimes referred to as a film. However, the boundary between a sheet and a film is not clear, and there is no need to distinguish between the two in terms of the wording in the present invention. Therefore, in the present invention, even when the term ``sheet'' is used, it includes ``film''; However, it also includes "sheets".

An article having a coating of the surface modifier composition of the present invention includes, for example, a base material and a modified layer formed on at least a portion of at least one side of the base material, and the modified layer is formed from the surface modifier composition.

When the shape of the base material is a film, the thickness is not particularly limited and may be selected as appropriate, but is usually preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, and preferably 200 μm or less. , more preferably 100 μm or less, still more preferably 50 μm or less. If the thickness is less than 5 μm, problems such as insufficient base material strength will occur.

The base material may be surface-treated, if desired, on one or both sides by an oxidation method, a roughening method, etc., for the purpose of improving adhesion with a layer provided on the surface. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet type), flame treatment, hot air treatment, and ozone/ultraviolet irradiation treatment. Examples of the roughening method include a sandblasting method and a solvent treatment method. These surface treatment methods are appropriately selected depending on the type of the base film, but corona discharge treatment is generally preferably used in terms of effectiveness and operability. Further, as the base material, one which has been subjected to primer treatment on one or both sides can also be used.

Examples of the modified layer formed from the surface modifier composition include a coating layer, a primer layer, a hard coat layer, and the like.

The coating layer and the primer layer can be formed by applying the coating agent composition to a base material and drying it. Coating methods include, but are not particularly limited to, reverse coating, gravure coating, spray coating, kiss coating, wire barcoding, curtain coating, dip coating, and bar coating. The heating and drying temperature after coating varies depending on the material and purpose of the base material, but is preferably 200°C or lower to suppress deformation of the base material, and 25°C or higher from the viewpoint of phase separation of the block copolymer. It is preferable that there be. The thickness of the layer (thickness after drying) is not particularly limited, but is preferably 10 nm to 10 μm.

The hard coat layer can be formed by applying the hard coat surface modifier composition to a base material, drying it, and curing the hard coat agent. The method for applying the hard coat composition is not particularly limited, but the same method as for the coating layer and primer layer can be adopted. The method for curing the hard coat agent may be appropriately selected depending on the hard coat agent.

Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to these specific examples. In addition, various physical properties were measured using the following equipment. The meanings of the abbreviations are as follows.

VP: N-vinyl-2-pyrrolidone IBXA: Isobornyl acrylate St: Styrene BTEE: Ethyl-2-methyl-2-n-butylterranyl-propionate AIBN: 2,2'-azobis(isobutyronitrile)
ACHN: 1,1'-azobis(1-cyclohexanecarbonitrile)
PMA: Propylene glycol monomethyl ether acetate MP: 1-methoxy-2-propanol

<Evaluation method>
(Polymerization rate)
¹ H-NMR was measured using a nuclear magnetic resonance (NMR) measuring device (manufactured by Bruker, model: AVANCE 500 (frequency 500 MHz)) (solvent: deuterated chloroform, internal standard: tetramethylsilane). Regarding the obtained NMR spectrum, the integral ratio of the peaks of the vinyl group derived from the monomer and the ester side chain derived from the polymer was determined, and the polymerization rate of the monomer was calculated.

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

(Content of block copolymer)
High performance liquid chromatography (product name: HPLC 11Series, manufactured by Agilent Technologies), column (product name: L-Column2 ODS 5 μm, 4.6 x 150 mm, manufactured by CERI), column temperature 40°C, detector (ELSD PL-ELS2100) , manufactured by Polymer Laboratory, evaporator temperature 80°C, nebulizer temperature 70°C, gas flow rate 1.1 SLM), mobile phase A (methanol), mobile phase B (tetrahydrofuran (THF)) at a flow rate of 1 mL/min. The analysis was performed under gradient conditions from 100% mobile phase A to 100% mobile phase B in 7 minutes. For the sample, 10 μL of a 7 mg/mL THF solution was poured. A calibration curve was created using separately synthesized unconnected components of each block, and each was quantified. Further, the content of the block copolymer was determined by removing the amount of unlinked components from the whole.

(Contact angle (underwater bubble method))
The contact angle was measured using a contact angle meter (trade name: DropMaster DM500, manufactured by Kyowa Interface Science Co., Ltd.). The film was fixed on a test stand with the modified layer facing downward, and immersed in a glass cell containing ultrapure water. Using a syringe equipped with an injection needle, air bubbles (1 μL) were attached to the center of the immersed film, and the contact angle between the modified layer and the air bubbles was measured using the θ/2 method. The contact angle was measured by immersing the film immediately after production in ultrapure water. Note that the contact angle of the base material on which no modified layer is formed is 140.2° for ordinary glass and 119.4° for polyethylene terephthalate (PET).

(Durability test against water)
250 mL of pure water was placed in a container, and the liquid temperature was adjusted to 40°C. A film (having a modified layer formed on a base sheet) was immersed in this container and held at 40° C. for 24 hours while stirring. After 24 hours, the film was taken out and the presence or absence of peeling of the modified layer was visually confirmed. The case where there was no peeling of the modified layer was evaluated as "○", and the case where there was peeling was evaluated as "x".

(Dissolution test)
250 mL of pure water was placed in a container, and the liquid temperature was adjusted to 40°C. Two films (base sheets with a modified layer formed thereon) were immersed in this container and held at 40° C. for 24 hours while stirring. After 24 hours, the film was taken out and the amount of poly-VP eluted from the solution was measured. The elution amount was measured by analyzing the absorbance at a wavelength of 220 nm using an ultra-trace UV-visible spectrophotometer (product name: NANODROP 2000c, manufactured by Thermal Fisher. Scientific) and a quartz cell (10 x 10 x 40 mm). A calibration curve was created using a separately synthesized unlinked component of the A block (a homopolymer of N-vinyl-2-pyrrolidone) and quantified.

<Production of polymerization product>
(Manufacturing method No. 1)
In a glove box purged with nitrogen, 6.0 g of VP, 0.180 g of BTEE, 0.020 g of AIBN, and 4.8 g of anisole were charged and reacted at 54° C. for 22 hours. The polymerization rate was 99%.

To this reaction solution, 6.0 g of IBXA, 0.020 g of AIBN, and 4.8 g of anisole, which had been purged with nitrogen in advance, were added, and the mixture was reacted at 54° C. for 27 hours. The polymerization rate was 98%. In addition, the monomers in the first stage of polymerization remaining in the reaction solution were also polymerized, and the polymerization rate of the monomers in the first stage of polymerization remaining in the reaction solution was 100%.

After the reaction was completed, the reaction solution was diluted with tetrahydrofuran (THF) and poured into heptane under stirring. The precipitated polymer was suction filtered and dried to obtain polymerization product No. I got 1. The polymerization product had an Mw of 18,250, a PDI of 1.2, a content of 3% by mass of unlinked components in the first stage of polymerization (polymer having the same composition as the A block), and a content of 3% by mass of unlinked components in the first stage of polymerization, and a content of unlinked components in the second stage of polymerization. The content of the connecting component (a polymer having the same composition as the B block) was 3% by mass, and the content of the block copolymer was 94% by mass. The content of each structural unit in the copolymer was calculated from the charging ratio of monomers used in the polymerization reaction, the polymerization rate, and the content of unlinked components.

(Manufacturing method No. 2)
In a glove box purged with nitrogen, 5.0 g of VP, 0.150 g of BTEE, 0.024 g of ACHN, and 4.0 g of anisole were charged and reacted at 76° C. for 23 hours. The polymerization rate was 100%.

To this reaction solution were added 5.0 g of St, 0.061 g of ACHN, and 4.0 g of anisole, which had been previously purged with nitrogen, and reacted at 76° C. for 70 hours. The polymerization rate was 97%.

After the reaction was completed, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was suction filtered and dried to obtain polymerization product No. I got 2. The polymerization product has an Mw of 29,150, a PDI of 1.3, a content of unlinked components (polymer having the same composition as the A block) in the first stage of polymerization of 8% by mass, and a content of unlinked components in the second stage of polymerization of 8% by mass. The content of the connecting component (polymer having the same composition as the B block) was 5% by mass, and the content of the block copolymer was 87% by mass. The content of each structural unit in the copolymer was calculated from the charging ratio of monomers used in the polymerization reaction, the polymerization rate, and the content of unlinked components.

(Manufacturing method No. 3)
In a glove box that had been purged with nitrogen, 6.0 g of VP, 0.180 g of BTEE, 0.020 g of AIBN, and 4.8 g of anisole were charged and reacted at 62° C. for 27 hours. The polymerization rate was 100%.

To this reaction solution, 6.0 g of IBXA, 0.020 g of AIBN, and 4.8 g of anisole, which had been purged with nitrogen in advance, were added and reacted at 62° C. for 45 hours. The polymerization rate was 100%.

After the reaction was completed, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was suction filtered and dried to obtain polymerization product No. I got 3. The polymerization product has an Mw of 20,040, a PDI of 1.3, a content of unlinked components (polymer having the same composition as the A block) in the first stage of polymerization of 15% by mass, and a content of unlinked components in the second stage of polymerization of 15% by mass. The content of the connecting component (polymer having the same composition as the B block) was 6% by mass, and the content of the block copolymer was 79% by mass. The content of each structural unit in the copolymer was calculated from the charging ratio of monomers used in the polymerization reaction, the polymerization rate, and the content of unlinked components.

(Manufacturing method No. 4)
In a glove box purged with nitrogen, 5.0 g of VP, 0.150 g of BTEE, 0.024 g of ACHN, and 4.0 g of anisole were charged and reacted at 88° C. for 20 hours. The polymerization rate was 100%.

To this reaction solution, 5.0 g of St, 0.061 g of ACHN, and 4.0 g of anisole, which had been purged with nitrogen in advance, were added, and the mixture was reacted at 88° C. for 49 hours. The polymerization rate was 98%.

After the reaction was completed, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was suction filtered and dried to obtain polymerization product No. I got 4. The polymerization product had an Mw of 27,890, a PDI of 1.5, a content of unlinked components (a random polymer having the same composition as the A block) in the first stage of polymerization, and a content of 16% by mass in the second stage of polymerization. The content of unlinked components (random polymer having the same composition as the B block) was 22% by mass, and the content of the block copolymer was 62% by mass. The content of each structural unit in the copolymer was calculated from the charging ratio of monomers used in the polymerization reaction, the polymerization rate, and the content of unlinked components.

Manufacturing method No. 1, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process are both 54 °C, and the difference (T _2/1 -Tr) is 11°C. This manufacturing method No. The polymerization product obtained in Example 1 has a high content of the desired block copolymer of 94% by mass, and has reduced polymer impurities.

Manufacturing method No. 2, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process is both 76 °C, and the difference (T _2/1 -Tr) is 12°C. This manufacturing method No. The polymerization product obtained in Example 2 has a high content of the desired block copolymer of 87% by mass, and has reduced polymer impurities.

Manufacturing method No. 3, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process is both 62 °C, and the difference (T _2/1 - Tr) is 3°C. This manufacturing method No. The polymerization product obtained in step 3 has a low content of the desired block copolymer of 79% by mass, and a high content of polymer impurities.

Manufacturing method No. 4, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process is both 88 °C, and the difference (T _2/1 -Tr) is 0℃. This manufacturing method No. The polymerization product obtained in 4 had a low content of the desired block copolymer of 62% by mass, and a high content of polymer impurities.

<Production of film>
(Film No. 1 to 4) (Base material: ordinary glass (soda lime glass without surface treatment))
(For contact angle measurement)
A surface modifier composition (concentration: 1% by mass) was prepared by dissolving the polymerization product in MP. As a sample used for contact angle measurement, a spin coater (trade name: MS-A100, manufactured by Mikasa) was applied onto a base material (5 cm long, 5 cm wide, 0.7 mm thick) at 200 rpm for 2 seconds. 0.6 ml of the surface modifier composition was applied by spin coating with continuous rotation at 500 rpm for 2 seconds and 2000 rpm for 5 seconds to produce a film having a base material and a modified layer. After spin coating, drying was performed for 30 minutes in a hot air dryer set at 90°C. In the obtained film, a modified layer is formed on the entire surface of one side of the base material.
(for durability test)
A surface modifier composition (concentration: 1% by mass) was prepared by dissolving the polymerization product in MP. As a sample used in the durability test, 0.3 ml of the surface modifier composition was cast onto a base material (5 cm long, 5 cm wide, 0.7 mm thick), and a film having a base material and a modified layer was prepared. was created. After cast coating, drying was performed for 30 minutes in a hot air dryer set at 90°C. In the obtained film, a modified layer is formed on the entire surface of one side of the base material.

(Film No. 5 to 8) (Base material: polyethylene terephthalate (PET))
(For contact angle measurement)
A surface modifier composition (concentration: 1% by mass) was prepared by dissolving the polymerization product in MP. As a sample used for contact angle measurement, a spin coater (product name: MS-A100, manufactured by Mikasa) was applied onto a base material (5 cm long, 5 cm wide, 0.125 mm thick) at 200 rpm for 2 seconds. 0.6 ml of the surface modifier composition was applied by spin coating with continuous rotation at 500 rpm for 2 seconds and 2000 rpm for 5 seconds to produce a film having a base material and a modified layer. After spin coating, drying was performed for 30 minutes in a hot air dryer set at 90°C. In the obtained film, a modified layer is formed on the entire surface of one side of the base material. In the obtained film, a modified layer is formed on the entire surface of one side of the base material.
(for durability test)
A surface modifier composition (concentration: 6% by mass) was prepared by dissolving the polymerization product in MP. As a sample used for the durability test, 0.3 ml of the surface modifier composition was cast onto a base material (5 cm long, 5 cm wide, 0.125 mm thick) to form a film having a base material and a modified layer. was created. After cast coating, drying was performed for 30 minutes in a hot air dryer set at 90°C. In the obtained film, a modified layer is formed on the entire surface of one side of the base material.

The obtained film No. Contact angle measurements and water durability tests were conducted for Nos. 1 to 8, and the results are shown in Table 3.

(Film No. 9 to 12) (Base material: ordinary glass ((soda lime glass without surface treatment)))
A surface modifier composition (concentration: 6% by mass) was prepared by dissolving the polymerization product in MP. A surface modifier composition was applied to the entire surface of both sides of a base material (length: 4 cm, width: 9 cm, thickness: 0.7 mm) to produce a film having a base material and modified layers formed on both sides of the base material. . Note that the surface modifier composition was coated using a bar coater (wet film thickness: 50 μm). For coating, first, one side of the substrate was coated, and then dried for 30 minutes in a hot air dryer set at 90°C. Next, the other side was also coated and dried for 30 minutes in a hot air dryer set at 90°C. Note that two films were produced for each surface modifier composition.

(Film No. 13 to 16) (Base material: polyethylene terephthalate (PET))
A surface modifier composition (concentration: 6% by mass) was prepared by dissolving the polymerization product in MP. A surface modifier composition was applied to the entire surface of both sides of a base material (length: 4 cm, width: 9 cm, thickness: 0.125 mm) to produce a film having a base material and modified layers formed on both sides of the base material. . Note that the surface modifier composition was coated using a bar coater (wet film thickness: 50 μm). For coating, first, one side of the substrate was coated, and then dried for 30 minutes in a hot air dryer set at 90°C. Next, the other side was also coated and dried for 30 minutes in a hot air dryer set at 90°C. Note that two films were produced for each surface modifier composition.

The obtained film No. A dissolution test was conducted for Nos. 9 to 16, and the results are shown in Table 4.

Film no. 1, 2, 5, 6, 9, 10, 13, and 14, the modified layer is the polymerization product No. 1, 2, 5, 6, 9, 10, 13, and 14. This is the case when the surface modifier composition is formed from a surface modifier composition containing 1 or 2. In these films, the modified layer had excellent durability and the amount of poly-VP eluted was small. These results show that the surface modifier composition using a polymerization product with a low content of unlinked components has a modified layer with high adhesion to the substrate and excellent durability.

Film no. In No. 3, 4, 7, 8, 11, 12, 15, and 16, the modified layer is the polymerization product No. 3 or 4. In these films, the durability of the modified layer was poor and the amount of poly-VP eluted was large.

The surface modifier composition of the present invention can impart hydrophilicity to the surface of a hydrophobic substrate by applying it to the surface of the substrate or mixing it with the substrate.

Claims (11)

A surface modifier composition containing a polymerization product, the composition comprising:
The polymerization product is obtained by polymerizing a monomer composition by a living radical polymerization method using an organic tellurium compound,
Containing a block copolymer having an A block having a structural unit derived from an N-alkenyl lactam monomer and a B block having a structural unit derived from a vinyl monomer other than the N-alkenyl lactam monomer,
The content of structural units derived from the N-alkenyl lactam monomer in the block copolymer is 30% by mass or more,
In the 100% by mass of the B block, the content of structural units derived from a hydrophobic vinyl monomer is 98% by mass or more, and the hydrophobic vinyl monomer has a solubility in water at 20 ° C. of less than 50% by mass,
The molecular weight distribution (PDI) of the polymerization product is 2.0 or less, and
A surface modifier composition, wherein the content of the block copolymer is 80% by mass or more based on 100% by mass of the polymerization product. The vinyl monomer other than the N-alkenyl lactam monomer in the B block consists of a (meth)acrylic vinyl monomer, an α-olefin, an aromatic vinyl monomer, a heterocycle-containing unsaturated monomer, vinylamide, vinyl carboxylate, and dienes. The surface modifier composition according to claim 1, which is at least one selected from the group consisting of: A surface modifier composition containing a polymerization product, the composition comprising:
The polymerization product is obtained by polymerizing a monomer composition,
Containing a block copolymer having an A block having a structural unit derived from an N-alkenyl lactam monomer and a B block having a structural unit derived from a vinyl monomer other than the N-alkenyl lactam monomer,
The content of structural units derived from the N-alkenyl lactam monomer in the block copolymer is 30% by mass or more,
The vinyl monomer other than the N-alkenyl lactam monomer in the B block contains a (meth)acrylate having a polycyclic structure,
In the 100% by mass of the B block, the content of structural units derived from a hydrophobic vinyl monomer is 98% by mass or more, and the hydrophobic vinyl monomer has a solubility in water at 20 ° C. of less than 50% by mass,
The molecular weight distribution (PDI) of the polymerization product is 2.0 or less, and
A surface modifier composition, wherein the content of the block copolymer is 80% by mass or more based on 100% by mass of the polymerization product. The surface modifier composition according to any one of claims 1 to 3, wherein the structural unit derived from the N-alkenyl lactam monomer is a structural unit represented by the following general formula (1).

[In formula (1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. m1 represents an integer from 0 to 4. n1 represents an integer from 1 to 3. ] The surface modifier composition according to any one of claims 1 to 4, wherein the B block is more hydrophobic than the A block. The surface modifier composition according to any one of claims 1 to 5, wherein the polymerization product has a weight average molecular weight of 5,000 to 500,000. The surface modification according to any one of claims 1 to 6, wherein the mass ratio of A block to B block (A block/B block) in the block copolymer is 30/70 to 90/10. agent composition. The surface modifier composition according to any one of claims 1 to 7, wherein the block copolymer is an AB type diblock copolymer. The surface modifier composition according to any one of claims 1 to 8, wherein the surface modifier composition further contains a solvent. comprising a base material and a modified layer formed on at least a portion of the surface of the base material,
An article characterized in that the modified layer is formed from the surface modifier composition according to any one of claims 1 to 9. comprising a base material and a modified layer formed on at least a portion of at least one side of the base material,
A film characterized in that the modified layer is formed from the surface modifier composition according to any one of claims 1 to 9.