JP2019026825A - Copolymer, coating composition, and article - Google Patents

Abstract

To provide a copolymer, a coating composition, and an article that has an improved coating performance of a plastic base material, and achieves both of low adsorbing or anti-fogging properties and the coating performance of the plastic base material.SOLUTION: A copolymer contains a hydrophilic constitutional unit, the hydrophilic constitutional unit containing at least one constitutional unit selected from the group consisting of constitutional units represented by the formula (1), formula (2) and formula (3), where, the (1), (2) and (3) constitutional units in total being 40 mol% or more.SELECTED DRAWING: None

Description

  The present invention relates to copolymers, coating compositions, and articles.

  Conventionally, it has been proposed to use 2-methacryloyloxyethyl phosphorylcholine (MPC) as a means for imparting biocompatibility to materials used in environments in contact with biological substances, for example, containers used for bioassays or cell culture. Has been. The phosphorylcholine group has an extremely weak interaction with biological materials such as proteins, and has a property of suppressing adsorption and denaturation of biological materials.

  For example, Patent Literature 1 and Patent Literature 2 use a copolymer having a formylcholine group for imparting biocompatibility and an alkoxysilyl group for binding to a base material for a long time. Techniques for imparting stable surface hydrophilicity are described.

JP 2009-184300 A Japanese Patent Laying-Open No. 2015-63577

  However, copolymers having properties different from conventional copolymers may be useful. Then, an object of this invention is to provide the copolymer which has a hydrophilic group which is not restricted to a phosphorylcholine group.

（式（１）において、Ｒ_１１は、水素原子、またはメチル基であり、Ｒ_１２は、ＮＨ、または酸素原子であり、ｍは、０〜４の整数であり、Ｒ_１３は、水素原子、水酸基、またはメトキシ基であり、＊は結合を表す。）

（式（２）において、Ｒ_２１は、水素原子、またはメチル基であり、＊は結合を表す。）

（式（３）において、Ｒ_３１は、水素、またはメチル基であり、Ｒ_３２は、水素原子、またはメチル基であり、＊は結合を表し、ｎは、２〜１００の整数である。）。
［２］前記親水性構成単位が、前記式（１）で表される構成単位を含み、前記式（１）中、Ｒ_１１が水素原子、またはメチル基であり、Ｒ_１２がＮＨまたは酸素原子であり、ｍが２であり、Ｒ_１３が水酸基である、［１］に記載の共重合体。
［３］疎水性構成単位を更に含み、前記疎水性構成単位が、下記式（４）および下記式（５）からなる群より選択される少なくとも一つの構成単位である、［１］または［２］に記載の共重合体。

（式（４）において、Ｒ_４１は、水素原子、またはメチル基であり、Ｒ_４２は、炭素数１〜１０の直鎖または分枝鎖のアルキル、あるいは炭素数３〜８の脂環式アルキル、あるいはこれらの組み合わせであり、＊は、結合を表す。）

（式（５）において、Ｒ_５１は、水素原子、またはメチル基であり、＊は、結合を表す。）
［４］前記疎水性構成単位が、式（４）で表される構成単位であり、前記式（４）中、Ｒ_４２が、ブチル基、シクロヘキシル基、イソプロピル基およびイソブチル基からなる群より選択される少なくとも一つである、［１］〜［３］のいずれか一つに記載の共重合体。
［５］前記共重合体中の前記疎水性構成単位の含有量が、１０ｍｏｌ％以上４０ｍｏｌ％以下である、［１］〜［４］のいずれか一つに記載の共重合体。
［６］架橋性構成単位を更に含み、前記架橋性構成単位が、下記式（６）または下記式（７）で表される構成単位である、［１］〜［５］のいずれか一つに記載の共重合体。

（式（６）において、Ｒ_６１は、水素原子、またはメチル基であり、ｓは、４であり、Ｒ_６２は、独立して、水素原子、またはメチル基であり、＊は、結合を表す。）。

（式（７）において、Ｒ_７１は、水素原子、またはメチル基であり、Ｒ_７２、Ｒ_７３およびＲ_７４は、独立して、メトキシ基、エトキシ基、水素原子またはメチル基であり、ただし、Ｒ_７２、Ｒ_７３およびＲ_７４のうち１つ、２つまたは３つは、独立して、メトキシ基、またはエトキシ基であり、＊は、結合を表し、ｐは、２〜１０の整数である）。
［７］前記共重合体中の前記架橋性構成単位の含有量が、１ｍｏｌ％以上１０ｍｏｌ％以下である、［１］〜［６］のいずれか一つに記載の共重合体。
［８］環状ポリオレフィン基板に、前記共重合体の０．３重量％水またはアルコール溶液を塗布し、乾燥したとき、前記共重合体が塗布された前記ポリスチレン基板の、純水に対する接触角が、３０°以上である、［６］または［７］に記載の共重合体。
［９］［１］〜［８］のいずれか一つに記載の共重合体および溶剤を含む、コーティング組成物。
［１０］低吸着性コート用である、［９］に記載のコーティング組成物。
［１１］防曇コート用である、［９］に記載のコーティング組成物。
［１２］基材と、前記基材上に形成された［１］〜［８］のいずれか一つに記載の共重合体を含むポリマー層とを備える物品。
［１３］前記ポリマー層の、純水に対する接触角が、５°以上９０°以下である、［１２］に記載の物品。
［１４］前記ポリマー層が、１ｎｍ以上１００ｎｍ以下の厚みを有する、［１２］または［１３］に記載の物品。 The present invention includes the following aspects.
[1] including at least one hydrophilic structural unit, wherein the hydrophilic structural unit is selected from the group consisting of structural units represented by the following formula (1), the following formula (2), and the following formula (3). A copolymer containing structural units, wherein the total of the structural units represented by the formulas (1), (2) and (3) is 40 mol% or more:

(In the formula (1), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is NH or an oxygen atom, m is an integer of 0 to 4, R ₁₃ is a hydrogen atom, (It is a hydroxyl group or a methoxy group, and * represents a bond.)

(In Formula (2), R ₂₁ represents a hydrogen atom or a methyl group, and * represents a bond.)

(In Formula (3), R ₃₁ is hydrogen or a methyl group, R ₃₂ is a hydrogen atom or a methyl group, * represents a bond, and n is an integer of 2 to 100.) .
[2] The hydrophilic structural unit includes the structural unit represented by the formula (1), and in the formula (1), R ₁₁ is a hydrogen atom or a methyl group, and R ₁₂ is NH or an oxygen atom. The copolymer according to [1], wherein m is 2, and R ₁₃ is a hydroxyl group.
[3] Further comprising a hydrophobic structural unit, wherein the hydrophobic structural unit is at least one structural unit selected from the group consisting of the following formula (4) and the following formula (5): [1] or [2 ] The copolymer as described in.

(In Formula (4), R ₄₁ is a hydrogen atom or a methyl group, and R ₄₂ is a linear or branched alkyl having 1 to 10 carbon atoms, or an alicyclic alkyl having 3 to 8 carbon atoms. Or a combination thereof, and * represents a bond.)

(In Formula (5), R ₅₁ represents a hydrogen atom or a methyl group, and * represents a bond.)
[4] the hydrophobic structural unit is a structural unit represented by the formula (4), the formula (4), R ₄₂ is selected from the group consisting of butyl group, a cyclohexyl group, an isopropyl group and an isobutyl group The copolymer according to any one of [1] to [3], which is at least one of the above.
[5] The copolymer according to any one of [1] to [4], wherein the content of the hydrophobic structural unit in the copolymer is 10 mol% or more and 40 mol% or less.
[6] Any one of [1] to [5], further including a crosslinkable structural unit, wherein the crosslinkable structural unit is a structural unit represented by the following formula (6) or the following formula (7): The copolymer described in 1.

(In Formula (6), R ₆₁ is a hydrogen atom or a methyl group, s is 4, R ₆₂ is independently a hydrogen atom or a methyl group, and * represents a bond. .)

(In the formula (7), R ₇₁ is a hydrogen atom or a methyl group, and R ₇₂ , R ₇₃ and R ₇₄ are independently a methoxy group, an ethoxy group, a hydrogen atom or a methyl group, provided that One, two or three of R ₇₂ , R ₇₃ and R ₇₄ are independently a methoxy group or an ethoxy group, * represents a bond, and p is an integer of 2 to 10 ).
[7] The copolymer according to any one of [1] to [6], wherein the content of the crosslinkable structural unit in the copolymer is 1 mol% or more and 10 mol% or less.
[8] When a 0.3 wt% water or alcohol solution of the copolymer is applied to a cyclic polyolefin substrate and dried, the contact angle of the polystyrene substrate on which the copolymer is applied to pure water is The copolymer according to [6] or [7], which is 30 ° or more.
[9] A coating composition comprising the copolymer according to any one of [1] to [8] and a solvent.
[10] The coating composition according to [9], which is for a low adsorptive coat.
[11] The coating composition according to [9], which is for an antifogging coat.
[12] An article comprising a base material and a polymer layer containing the copolymer according to any one of [1] to [8] formed on the base material.
[13] The article according to [12], wherein a contact angle of the polymer layer with respect to pure water is 5 ° or more and 90 ° or less.
[14] The article according to [12] or [13], wherein the polymer layer has a thickness of 1 nm to 100 nm.

  According to the present invention, a copolymer having a hydrophilic group not limited to a phosphorylcholine group can be provided.

  Embodiments of the present invention will be described below.

（式（１）において、Ｒ_１１は、水素原子、またはメチル基であり、Ｒ_１２は、ＮＨ、または酸素原子であり、ｍは、０〜４の整数であり、Ｒ_１３は、水素原子、水酸基、またはメトキシ基であり、＊は結合を表す。）

（式（２）において、Ｒ_２１は、水素原子、またはメチル基であり、＊は結合を表す。）

（式（３）において、Ｒ_３１は、水素、またはメチル基であり、Ｒ_３２は、水素原子、またはメチル基であり、＊は結合を表し、ｎは、２〜１００の整数である。）。 The polymer P which is a copolymer according to this embodiment includes a hydrophilic structural unit, and the hydrophilic structural unit is a structural unit represented by the following formula (1), the following formula (2), and the following formula (3). The total of the structural units represented by the formula (1), the formula (2) and the formula (3) is 40 mol% or more and 45 mol% or more. It is preferable. By containing in the said range, the polymer P obtained has the outstanding low adsorptivity.

(In the formula (1), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is NH or an oxygen atom, m is an integer of 0 to 4, R ₁₃ is a hydrogen atom, (It is a hydroxyl group or a methoxy group, and * represents a bond.)

(In Formula (2), R ₂₁ represents a hydrogen atom or a methyl group, and * represents a bond.)

(In Formula (3), R ₃₁ is hydrogen or a methyl group, R ₃₂ is a hydrogen atom or a methyl group, * represents a bond, and n is an integer of 2 to 100.) .

  The polymer P may contain any one of the structural units represented by formula (1), formula (2), and formula (3) alone, or may contain two or more types in combination. However, it is preferable that at least the structural unit represented by the formula (1) is included from the viewpoint of enhancing the low adsorptivity. Since the base material surface-treated with such a polymer P can reduce cytotoxicity and has excellent biocompatibility and low adsorptivity, for example, when used as a cell culture container, Cell aggregates can be produced satisfactorily.

  As a monomer that is a raw material of the structural unit represented by the formula (1), (meth) acrylates corresponding to the structure of the formula (1) can be used, and these are used alone or in combination of two or more. be able to. Examples of such monomers include N- (2-hydroxyethyl) acrylamide (HEAA), 2-hydroxyethyl methacrylate (HEMA), and the like.

(Meth) acrylate corresponding to the structure of Formula (2) or Formula (3) can be used as a monomer that is a raw material for the structural unit represented by Formula (2) or the structural unit represented by Formula (3). These can be used singly or in combination of two or more. Examples of the (meth) acrylate monomer corresponding to the structure of the formula (2) include 2-methacryloyloxyethyl phosphorylcholine (MPC). Examples of the (meth) acrylate monomer corresponding to the structure of the formula (3) include methoxypolyethylene glycol methacrylate (PEGMA) and methacrylic acid diethylene glycol monomethyl ether (DEGM).
In the formula (3), n is preferably 4 to 50 from the viewpoint of suppressing nonspecific adsorption of the protein to the obtained polymer P.

In one embodiment, in the polymer P, the hydrophilic structural unit includes a structural unit represented by the formula (1), and in the formula (1), R ₁₁ is a hydrogen atom or a methyl group, and R ₁₂ may be NH or an oxygen atom, m may be 2, and R ₁₃ may be a hydroxyl group. Examples of the monomer that is a raw material for the hydrophilic structural unit in the case where R ₁₁ is a hydrogen atom include N- (2-hydroxyethyl) acrylamide (HEAA). Further, examples of the monomer wherein R ₁₁ is as a raw material for the hydrophilic constituent unit in the case where a methyl group, for example, 2-hydroxyethyl methacrylate (HEMA) is.

（式（４）において、Ｒ_４１は、水素原子、またはメチル基であり、Ｒ_４２は、炭素数１〜１０の直鎖または分枝鎖のアルキル、あるいは炭素数３〜８の脂環式アルキル、あるいはこれらの組み合わせであり、＊は、結合を表す。炭素数１〜１０の直鎖または分枝鎖のアルキルとしては、メチル、エチル、プロピル、メチルエチル、ブチル、１，２−ジメチルエチル、ペンチル、１−メチルブチル、２−メチルブチル、およびヘキシル等が挙げられる。炭素数３〜８の脂環式アルキルとしては、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル等が挙げられる。）

（式（５）において、Ｒ_５１は、水素原子、またはメチル基であり、＊は、結合を表す。） In one embodiment, the polymer P further includes a hydrophobic structural unit, and the hydrophobic structural unit is at least one structural unit selected from the group consisting of the following formula (4) and the following formula (5): Also good.

(In Formula (4), R ₄₁ is a hydrogen atom or a methyl group, and R ₄₂ is a linear or branched alkyl having 1 to 10 carbon atoms, or an alicyclic alkyl having 3 to 8 carbon atoms. Or a combination thereof, and * represents a bond, and examples of the linear or branched alkyl having 1 to 10 carbon atoms include methyl, ethyl, propyl, methylethyl, butyl, 1,2-dimethylethyl, Pentyl, 1-methylbutyl, 2-methylbutyl, hexyl, etc. Examples of the alicyclic alkyl having 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.)

(In Formula (5), R ₅₁ represents a hydrogen atom or a methyl group, and * represents a bond.)

  By including the structural unit represented by the formula (4) or the formula (5), the polymer P has improved coatability on a plastic substrate such as polypropylene, and has low adsorption and coatability on the plastic substrate. Can be made compatible.

In one embodiment, in the polymer P, the hydrophobic structural unit is a structural unit represented by the formula (4), and in the formula (4), R ₄₂ represents a butyl group, a cyclohexyl group, an isopropyl group, and an isobutyl group. It may be at least one selected from the group consisting of groups, and is preferably a butyl group or a cyclohexyl group. That is, as a monomer used as a raw material for the structural unit of formula (4), (meth) acrylate corresponding to the structure of formula (4) can be used, and this can be used alone or in combination of two or more. Can do. Examples of such a monomer include n-butyl methacrylate, cyclohexyl methacrylate, isopropyl methacrylate, and isobutyl methacrylate. Among these, n-butyl methacrylate and cyclohexyl methacrylate are preferable as the monomer that is a raw material of the structural unit of the formula (4). Moreover, styrene etc. are mentioned as a monomer used as the raw material of the structural unit of Formula (5).

  In one embodiment, the polymer P may have a content of the hydrophobic structural unit in the copolymer of 10 to 40 mol%, and preferably 20 to 35%. The polymer P containing the hydrophobic structural unit within the above range tends to be able to achieve both a low adsorptivity and a coating property to a plastic substrate even better.

（式（６）において、Ｒ_６１は、水素原子、またはメチル基であり、ｓは、４であり、Ｒ_６２は、独立して、水素原子、またはメチル基であり、＊は、結合を表す。式（６）において、好ましくは、Ｒ_６２はすべて水素原子であり、−Ｎ_３は、パラ位に置換されている。）。

（式（７）において、Ｒ_７１は、水素原子、またはメチル基であり、Ｒ_７２、Ｒ_７３およびＲ_７４は、独立して、メトキシ基、エトキシ基、水素原子またはメチル基であり、ただし、Ｒ_７２、Ｒ_７３およびＲ_７４のうち１つ、２つまたは３つは、独立して、メトキシ基、またはエトキシ基であり、＊は、結合を表し、ｐは、２〜１０の整数である好ましい実施形態において、式（７）におけるｐは、２〜６であり、より好ましくは、２〜４である。）。 In one embodiment, the polymer P may further include a crosslinkable structural unit, and the crosslinkable structural unit may be a structural unit represented by the following formula (6) or the following formula (7).

(In Formula (6), R ₆₁ is a hydrogen atom or a methyl group, s is 4, R ₆₂ is independently a hydrogen atom or a methyl group, and * represents a bond. In formula (6), preferably, all of R ₆₂ are hydrogen atoms, and —N ₃ is substituted at the para position.

(In the formula (7), R ₇₁ is a hydrogen atom or a methyl group, and R ₇₂ , R ₇₃ and R ₇₄ are independently a methoxy group, an ethoxy group, a hydrogen atom or a methyl group, provided that One, two or three of R ₇₂ , R ₇₃ and R ₇₄ are independently a methoxy group or an ethoxy group, * represents a bond, and p is an integer of 2 to 10 In preferable embodiment, p in Formula (7) is 2-6, More preferably, it is 2-4.)

By including the structural unit represented by Formula (6), when the polymer P is applied to a base material, the polymer P can further improve the bonding property between the polymer P and the base material. Therefore, when the base material to which the polymer P is applied is subjected to a heat treatment, a washing process, or the like, the polymer P remains on the surface without being detached from the base material. For this reason, such a base material can have a sustained low adsorptivity, with a decrease in function associated with the desorption of the polymer P being reduced.
As a monomer that is a raw material of the structural unit of the formula (6), (meth) acrylate corresponding to the structure of the formula (6) can be used, and these can be used alone or in combination of two or more. . Examples of such monomers include methacryloyloxyethyl 4-azido cinnamate (MECAz).

By including the structural unit represented by Formula (7), when the polymer P is applied to a base material, the polymer P can further improve the bonding property between the polymer P and the base material. Therefore, when the base material to which the polymer P is applied is subjected to a heat treatment, a washing process, or the like, the polymer P remains on the surface without being detached from the base material. For this reason, such a base material can have a sustained low adsorptivity, with a decrease in function associated with the desorption of the polymer P being reduced.
As a monomer that is a raw material of the structural unit of the formula (7), a (meth) acrylate corresponding to the structure of the formula (7) can be used, which can be used alone or in combination of two or more. . Examples of such monomers include 3- (methacryloxy) propyldimethylmethoxysilane, 3- (methacryloxy) propyldimethylethoxysilane, 3- (methacryloxy) propylmethyldiethoxysilane, and 3- (methacryloxy) propylmethyldimethoxysilane. , 3- (methacryloxy) propyltrimethoxysilane, 3- (methacryloxy) propyltriethoxysilane and the like.

  In one embodiment, in the polymer P, the content of the crosslinkable structural unit in the copolymer may be 1 mol% or more and 10 mol% or less, and is preferably 2% or more and 7% or less. The polymer P containing the crosslinkable structural unit within the above range has good binding properties to a substrate.

  In one embodiment, the polymer P containing the crosslinkable structural unit is coated with a 0.3% by weight water or alcohol solution of the copolymer on a cyclic polyolefin substrate and dried. Further, the contact angle of the polystyrene substrate with respect to pure water may be 30 ° or more, preferably 50 ° or more, and more preferably 60 ° or more. This makes it possible to improve the hydrophobicity of the coated substrate (to suppress wettability) while achieving low adsorptivity. A copolymer exhibiting such physical properties has not been known so far.

  The polymer P can be a random copolymer or a block copolymer. The random copolymer is preferable because uniform cell non-adhesiveness can be obtained on the surface of the base material coated with the random copolymer.

  The content and composition of each structural unit in the polymer P can be controlled by adjusting the amount of the raw material monomer used for the polymerization reaction in the production of the polymer P described below.

  Moreover, the weight average molecular weight Mw of the polymer P is 10,000-1 million, Preferably, it is 20000-500000. In one embodiment, the number average molecular weight Mn of the polymer P is 5000 to 100,000, preferably 10,000 to 80,000. When the weight average molecular weight and the number average molecular weight are within the above ranges, the polymer P has good handleability at the time of synthesis and excellent low adsorptivity.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) are converted values obtained from a standard polyoxyethylene calibration curve obtained by GPC measurement. In the present embodiment, the measurement conditions are as follows.
Apparatus: Gel permeation chromatography apparatus (manufactured by JASCO Corporation, LC-2000Plus series)
Column: manufactured by Tosoh Corporation, TSK-GELPHA-M, ALPHA-2500
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: methanol / water = 7/3 (vol / vol) mixed solvent sample concentration: 0.05 wt%

[Method for producing polymer P]
The synthesis of the polymer P of the present embodiment can be performed using methods known in the art, including preparation of monomer compounds and polymerization thereof. As the monomer compound, a commercially available compound can be used. Examples of the polymerization method include a radical polymerization method. Moreover, when using radical polymerization method, the method of superposing | polymerizing using a radical polymerization initiator is suitable. In this case, methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be employed. Among these, solution polymerization is preferable. In the solution polymerization, each monomer may be charged all at once, or a part of the monomers may be charged into a reaction vessel and the rest may be dropped. Further, as will be described later, a polymerizable functional group, a chain transfer group or the like may be introduced on the base material to synthesize the polymer P on the base material.

As the radical polymerization initiator that can be used in the radical polymerization method, any one or more of an azo compound and an organic peroxide can be used.
Examples of the azo compound include 2,2′-azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis (2-methylpropionate), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN). Etc.), and any one or more of these can be used.
Examples of the organic peroxide include ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). 1 or more types can be used.
The amount (number of moles) of the radical polymerization initiator is preferably 0.05% to 3% of the total number of moles of monomers used as raw materials. The weight average molecular weight (Mw) of the obtained polymer can be adjusted to 10,000 to 1,000,000 by appropriately setting the amount of the polymerization initiator within the above range and appropriately setting the reaction temperature and reaction time.

The polymerization solvent used for the production of the polymer P is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the polymer. For example, water, methanol, ethanol, propanol, t-butanol, benzene And ketone solvents such as toluene, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, chloroform, methyl ethyl ketone, and mixed solvents thereof. These solvents can be used alone or in combination of two or more.
The polymerization solvent may contain other additives as necessary.

[Use of polymer P]
(Application of polymer P to coating composition)
The coating composition according to this embodiment includes a polymer P and a solvent.

  The amount of polymer P contained in the coating composition can be adjusted depending on the type of substrate to be applied, the thickness of the resulting film, and the coating method. The concentration of the polymer P in the coating composition can be, for example, from 0.01% by weight to 3.0% by weight, and preferably from 0.1% by weight to 2.5% by weight.

  In addition to the polymer P, the coating composition may contain a solvent and optionally additives such as a surfactant. Solvents include water, ethanol, methanol, isopropanol, n-butanol, t-butyl alcohol, n-pentanol, cyclohexanol and other alcohols, benzene, toluene, tetrahydrofuran, dioxane, dichloromethane, chloroform, acetone, methyl acetate, acetic acid. Examples include ethyl, butyl acetate, methyl ethyl ketone, methyl butyl ketone, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and cyclohexanone. These solvents can be used alone or in combination of two or more. Among these, alcohol is preferable because it does not denature the plastic substrate and is easy to dry.

(Application of polymer P to substrate)
The article according to the present embodiment includes a base material and a polymer layer containing the polymer P formed on the base material. That is, the polymer P of the present invention is applied to the surface of the substrate by applying a coating composition containing the polymer P to the substrate and removing the solvent. As the substrate, a substrate made of an inorganic or organic material can be used.

  As the substrate, a slide-shaped substrate, a microwell plate, a culture dish, a petri dish, a container, a microfluidic substrate, a test tube, a tube, a particle, a membrane, and the like can be used, but are not limited thereto. The optimal shape can be selected in a timely manner. Examples of the base material include inorganic substances and organic polymer substances. Examples of the inorganic substance include silica, alumina, glass, metal and the like. Examples of the organic polymer material include thermoplastic resins, and examples of the thermoplastic resin include linear polyolefin resins such as polyethylene and polypropylene; polystyrene resins; cyclic polyolefin resins; fluorine-containing resins; polycarbonate resins and the like. It is done. Among them, it is preferable to use a saturated cyclic polyolefin resin that is particularly excellent in heat resistance, chemical resistance, low fluorescence, and moldability. In this specification, the saturated cyclic polyolefin resin refers to a homopolymer having a cyclic olefin structure or a saturated polymer obtained by hydrogenating a copolymer of a cyclic olefin and an α-olefin.

  Examples of the method for modifying the surface of the substrate using the coating composition containing the polymer P include a method of immersing the substrate in the coating composition, or a method of applying the coating composition to the substrate by, for example, spray coating. Although it is mentioned, it is not limited to these, Surface modification can be performed by the other method well-known in the said field | area. The surface modification is not limited to being all or continuous, but also includes partial or discontinuous.

  In order to enhance the adhesion between the substrate surface and the coating composition containing the polymer P that coats the substrate surface, it is preferable to activate the substrate surface. As a means for activation, there are a method of plasma treatment under an oxygen atmosphere, an argon atmosphere, a nitrogen atmosphere, an air atmosphere and the like, and a method of treatment with an excimer laser such as argon fluoride and krypton fluoride. A method of plasma treatment in an oxygen atmosphere is preferred.

  When the polymer P contains the structural unit represented by the formula (7), it is preferable to heat-treat the substrate at 50 to 120 ° C. for 5 minutes to 100 hours after surface modification with the coating composition containing the polymer P. . The silanol group produced from the structural unit represented by the formula (7) undergoes dehydration condensation with the functional group of the base material or the silanol group of the polymer P, whereby the binding property between the coating composition containing the polymer P and the base material is increased. Can be improved. Thereby, as mentioned above, when the base material to which the coating composition containing the polymer P is applied is subjected to heat treatment, washing treatment, or the like, the polymer P tends to stay on the surface without being detached from the base material. Such a base material can have a reduced function due to the desorption of the polymer P, and can have a continuous ability to immobilize a physiologically active substance and a low adsorptivity.

When the polymer P contains the structural unit represented by the formula (6), it is preferable that the substrate is surface-modified with a coating composition containing the polymer P and then irradiated with light. It The conditions of light irradiation, include 10 mJ / cm ² or more 1000 mJ / cm ² or less, it is preferably, 100 mJ / cm ² or more 700 mJ / cm ² or less at 50 mJ / cm ² or more 800 mJ / cm ² or less Is more preferable. By light irradiation, nitrene is generated from the structural unit represented by the formula (6), and reacts with the base material or the polymer P. Thereby, the bondability between the coating composition containing the polymer P and the substrate can be improved. As a result, when the substrate to which the coating composition containing the polymer P is applied is subjected to a heat treatment, a washing treatment, or the like, the polymer P tends to stay on the surface without being detached from the substrate. Such a base material can have a reduced function due to the desorption of the polymer P, and can have a continuous ability to immobilize a physiologically active substance and a low adsorptivity.

The coating amount of the coating composition on the substrate can be 0.01 to 10 g / m ² in terms of the amount of polymer P from the viewpoint of low adsorptive expression and coating film uniformity, It is preferable to set it as 0.1-5 g / m < ² >.
In the article, the polymer layer may have a thickness of 1 nm or more and 100 nm or less from the viewpoint of low adsorptivity and coating uniformity. The thickness of the coating film made of the polymer P can be appropriately changed based on the use of the substrate.

  The article may have a contact angle of the polymer layer with respect to pure water of 5 ° or more and 90 ° or less. The contact angle of the coating film made of the polymer P can be changed based on the use of the substrate. For example, the thickness of the coating film, the type and composition of the monomer constituting the polymer P, the coating film forming method, etc. are selected. Can be adjusted.

  Since the coating composition of this embodiment has excellent low adsorptivity and is useful as a biocompatible material, it can be used for a low adsorptive coating. Therefore, the base material to which the polymer P is applied can be used as an article such as a cell culture container, a cell storage container, a medical device, an artificial organ, a biochip, a biosensor, or a bioassay device.

  Alternatively, the coating composition of this embodiment can also be used for an antifogging coat.

  Anti-fogging is a technology and function that prevents fogging, and is used for glass used in building materials, vehicles, bathrooms, transparent materials such as lenses and glasses, and materials such as mirrors, where visibility is important. ing. “Condensation” occurs on the surface (inside) of these solids, and “cloudiness” occurs due to light scattering by the delicate water droplets. An example of the anti-fogging technique is hydrophilic treatment of the material surface. By making the surface of the material hydrophilic, it is possible to form a water film before water droplets are generated, thereby reducing light scattering and preventing fogging.

  However, it may be difficult to uniformly apply a conventional antifogging coating polymer to the surface of a plastic substrate such as polypropylene.

  On the other hand, as will be described later in Examples, the polymer P of the present embodiment has improved coating properties on plastic substrates such as polypropylene and can be easily anti-fogged. That is, the polymer P can achieve both an antifogging property and a coating property on a plastic substrate.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  Hereinafter, although the effect of the present invention is explained in detail using an example and a comparative example, the present invention is not limited to the following example.

(Synthesis Example 1)
(HEAA / BMA polymer synthesis 1)
0.645 g (5.6 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.341 g (2.4 mmol) of n-butyl methacrylate (BMA, manufactured by Kanto Chemical Co., Inc.) And 0.0263 g (0.16 mmol) of 2,2′-azobis (isobutyronitrile) were dissolved in 5 mL of ethanol, and the obtained mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution (coating composition) was prepared.

(Synthesis Example 2)
(Synthesis of HEAA / CHMA polymer)
0.645 g (5.6 mmol) N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.404 g (2.4 mmol) cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry), and 0 0.0263 g (0.16 mmol) of 2,2′-azobis (isobutyronitrile) was dissolved in 5 mL of ethanol, and the resulting mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 3)
(Synthesis of HEAA / iPMA polymer)
0.645 g (5.6 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.308 g (2.4 mmol) of isopropyl methacrylate (iPMA, manufactured by Tokyo Chemical Industry), and 0 0.0263 g (0.16 mmol) of 2,2′-azobis (isobutyronitrile) was dissolved in 5 mL of ethanol, and the resulting mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 4)
(Synthesis of HEAA / iBMA polymer)
0.645 g (5.6 mmol) N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.341 g (2.4 mmol) isobutyl methacrylate (iBMA, manufactured by Tokyo Chemical Industry), and 0 0.0263 g (0.16 mmol) of 2,2′-azobis (isobutyronitrile) was dissolved in 5 mL of ethanol, and the resulting mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 5)
(Synthesis of HEAA / styrene polymer)
0.645 g (5.6 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.25 g (2.4 mmol) of styrene (manufactured by Wako Pure Chemical Industries), and 0.0263 g ( 0.12 mmol) of 2,2′-azobis (isobutyronitrile) was dissolved in 5 mL of ethanol, and the resulting mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 6)
(Synthesis of HEAA / MPC / BMA polymer)
0.374 g (3.25 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.385 g (1.3 mmol) of 2-methacryloyloxyethyl phosphorylcholine (MPC, manufactured by NOF), 0.277 g (1.95 mmol) of n-butyl methacrylate (BMA, manufactured by Kanto Chemical Co., Inc.) and 0.0213 g (0.13 mmol) of 2,2′-azobis (isobutyronitrile) in 5 mL of ethanol After dissolving, the obtained mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 7)
(Synthesis of HEAA / PEGMA / BMA polymer)
0.394 g (3.4 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.37 g (0.79 mmol) of polyethylene glycol methacrylate (PEGMA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.256 g (1.8 mmol) of n-butyl methacrylate (BMA, manufactured by Kanto Chemical Co., Ltd.) and 0.0197 g (0.12 mmol) of 2,2′-azobis (isobutyronitrile) in 5 mL of ethanol Then, the resulting mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 8)
(Synthesis of HEAA / BMA / silane coupling agent polymer)
0.617 g (5.36 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.341 g (2.4 mmol) of n-butyl methacrylate (BMA, manufactured by Kanto Chemical Co., Inc.) 0.055 g (0.24 mmol) of 3- (methacryloxy) propyldimethylmethoxysilane (silane coupling agent, Gelest), and 0.026 g (0.16 mmol) of 2,2′-azobis (isobutyro) (Nitrile) was dissolved in 5 mL of ethanol, and the obtained mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 9)
(Synthesis of HEAA / BMA / MECAz polymer)
0.617 g (5.36 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.341 g (2.4 mmol) of n-butyl methacrylate (BMA, manufactured by Kanto Chemical Co., Inc.) , 0.072 g (0.24 mmol) methacryloyloxyethyl 4-azido cinnamate (MECAz, manufactured by Nard Laboratories), and 0.026 g (0.16 mmol) 2,2′-azobis (isobutyronitrile) Was dissolved in 5 mL of ethanol, and the obtained mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 10)
(HEAA / BMA polymer synthesis 2)
0.461 g (4 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.569 g (4 mmol) of n-butyl methacrylate (BMA, manufactured by Kanto Chemical Co., Ltd.) After 026 g (0.16 mmol) of 2,2′-azobis (isobutyronitrile) was dissolved in 5 mL of ethanol, the obtained mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 11)
(Synthesis of HEAA / BMA polymer 3)
0.276 g (2.4 mmol) of N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.796 g (5.6 mmol) of n-butyl methacrylate (BMA, manufactured by Kanto Chemical Co., Inc.) , And 0.026 g (0.16 mmol) of 2,2′-azobis (isobutyronitrile) were dissolved in 5 mL of ethanol, and the resulting mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

(Synthesis Example 12)
(Synthesis of HEAA / MPC / silane coupling agent polymer)
0.866 g (7.52 mmol) N- (2-hydroxyethyl) acrylamide (HEAA, manufactured by Tokyo Chemical Industry), 0.07 g (0.237 mmol) 2-methacryloyloxyethyl phosphorylcholine (MPC, manufactured by NOF), And 0.055 g (0.24 mmol) of 3- (methacryloxy) propyldimethylmethoxysilane (silane coupling agent, Gelest), and 0.0263 g (0.16 mmol) of 2,2′-azobis (isobutyro) (Nitrile) was dissolved in 4 mL of ethanol, and the resulting mixed solution was introduced into the reaction vessel. Next, after blowing argon gas for 10 minutes, it sealed, and made it react at 60 degreeC for 20 hours, and obtained the ethanol solution containing the target polymer. A portion of the obtained polymer solution was transferred to a sample bottle and vacuum-dried for 48 hours to measure the weight, and the concentration of this polymer solution was calculated. Based on this value, 0.3 wt% for coating was used. An ethanol solution was prepared.

[Low adsorption]
The low adsorptivity of the plastic substrates of Examples and Comparative Examples was evaluated according to the following production and evaluation methods.

(Production of plastic substrate)
In a 96-well plate made of polystyrene, 0.3% by weight ethanol solutions of Synthesis Examples 1 to 7 and 10 were dispensed into separate wells and allowed to stand at room temperature for 30 minutes. Thereafter, the solution was recovered from the plate, and then the surface of the substrate was dried at room temperature to obtain a plastic substrate whose surface was coated with a polymer. These were used as plastic substrates of Examples 1a to 7a and 10a, respectively.

  Separately, 0.3 wt% ethanol solutions of Synthesis Examples 8, 9, and 12 were dispensed into separate wells in a plasma-treated polystyrene 96-well plate and allowed to stand at room temperature for 10 minutes. Thereafter, the solution was recovered from the plate, and then the surface of the substrate was dried at room temperature. The plate into which the solutions of Synthesis Examples 8 and 12 were dispensed was heated in a vacuum at 60 ° C. for 3 days to obtain a plastic substrate whose surface was coated with a polymer. Moreover, about the plate which dispensed the solution of the synthesis example 9, after irradiating UV, it washed with water and dried, and the plastic substrate by which the surface was coated with the polymer was obtained. These were used as the plastic substrates of Examples 8a, 9a, and 11a, respectively.

To a 96-well plate made of polystyrene, the 0.3 wt% ethanol solution of Synthesis Example 11 was dispensed and allowed to stand at room temperature for 30 minutes. Thereafter, the solution was recovered from the plate, and then the surface of the substrate was dried at room temperature to obtain a plastic substrate whose surface was coated with a polymer. This was used as the plastic substrate of Comparative Example 1a.
A 96-well plate made of polystyrene that was not plasma-treated was used as Comparative Example 2a, and a 96-well plate made of polystyrene that was plasma-treated was used as Comparative Example 3a.

To the prepared 96-well plates of Examples 1a to 11a and Comparative Examples 1a, 2a, and 3a, a peroxidase-labeled avidin solution prepared to 0.4 μg / mL with PBS was dispensed and allowed to stand at room temperature for 1 hour. Avidin was adsorbed on the well surface. After washing the wells with PBS containing 0.1% Tween 20, each well was developed with a commercially available HRP coloring solution (manufactured by Sumitomo Bakelite Co., Ltd.), and the absorbance at 450 nm was measured with a commercially available plate reader. The adsorption amount of was measured. Absorbance represents the amount of peroxidase-labeled avidin adsorbed.
Table 1 below shows the evaluation results of low adsorptivity.

ＨＥＡＡ＝Ｎ−（２−ヒドロキシエチル）アクリルアミド
ＢＭＡ＝メタクリル酸ｎ−ブチル
ＣＨＭＡ＝メタクリル酸シクロヘキシル
ｉＰＭＡ＝メタクリル酸イソプロピル
ｉＢＭＡ＝メタクリル酸イソブチル
ＭＰＣ＝２−メタクリロイルオキシエチルホスホリルコリン
ＰＥＧＭＡ＝メトキシポリエチレングリコールメタクリレート
シランカップリング剤＝３−（メタクリロキシ）プロピルジメチルメトキシシラン
ＭＥＣＡｚ＝メタクリロイルオキシエチル４−アジド桂皮酸エステル

HEAA = N- (2-hydroxyethyl) acrylamide BMA = n-butyl methacrylate CHMA = cyclohexyl methacrylate iPMA = isopropyl methacrylate iBMA = isobutyl methacrylate MPC = 2-methacryloyloxyethyl phosphorylcholine PEGMA = methoxy polyethylene glycol methacrylate silane coupling Agent = 3- (methacryloxy) propyldimethylmethoxysilane MECAz = methacryloyloxyethyl 4-azido cinnamic acid ester

  From the evaluation results of low adsorptivity, in all the plastic substrates of Examples 1a to 11a, the amount of protein adsorbed significantly decreased as compared with the plastic substrates without polymer coating of Comparative Examples 2a and 3a. It was shown that the polymer coating of the embodiment imparted low adsorptivity to the surface of the plastic substrate. In Comparative Example 1a, protein adsorption to the polymer-coated surface is suggested, and it is shown that the content of the hydrophilic group represented by HEAA is important for exhibiting low adsorption. ing.

[Contact angle]
According to the following production and evaluation methods, the contact angles of the plastic substrates of the examples and comparative examples were evaluated.

(Production of plastic substrate)
Cyclic polyolefin plastic substrates were immersed in 0.3 wt% ethanol solutions of Synthesis Examples 1 to 7 and 10, respectively, and allowed to stand at room temperature for 30 minutes. Thereafter, the substrate was taken out of the solution, and then the surface of the substrate was dried at room temperature to obtain a plastic substrate whose surface was coated with a polymer. These were used as the plastic substrates of Examples 1b to 7b and 10b, respectively.

  Separately, the cyclic polyolefin plastic substrate was immersed in a 0.3 wt% ethanol solution of Synthesis Examples 8, 9, and 12, and allowed to stand at room temperature for 10 minutes. Thereafter, the substrate was removed from the solution, and then the surface of the substrate was dried at room temperature. The substrate into which the solutions of Synthesis Examples 8 and 12 were dispensed was heated at 80 ° C. in a vacuum for 3 days to obtain a plastic substrate whose surface was coated with a polymer. Moreover, about the plate which dispensed the solution of the synthesis example 9, after irradiating UV, it washed with water and dried, and the plastic substrate by which the surface was coated with the polymer was obtained. These were used as the plastic substrates of Examples 8b, 9b, and 11b, respectively.

The plastic substrate made of cyclic polyolefin was immersed in the 0.3 wt% ethanol solution of Synthesis Example 11 and allowed to stand at room temperature for 30 minutes. Thereafter, the substrate was taken out of the solution, and then the surface of the substrate was dried at room temperature to obtain a plastic substrate whose surface was coated with a polymer. This was used as the plastic substrate of Comparative Example 1b.
As Comparative Example 2b, a plastic substrate made of cyclic polyolefin that was not plasma-treated was used. As Comparative Example 3b, a plastic substrate made of cyclic polyolefin that was plasma-treated was used.

Using a CA-V contact angle meter manufactured by Kyowa Interface Chemical Co., Ltd., the contact angle of the prepared plastic substrate with respect to pure water was measured. The value of the contact angle was measured at 85 seconds after 2.0 μL of ultrapure water was dropped on the surface of the object to be measured.
Table 2 below shows the evaluation results of the contact angle.

  From the evaluation results of the contact angles, the contact angles of the plastic substrates of Examples 1b to 7b and 10b were all 30 ° or less, whereas the contact angles of the plastic substrates of Comparative Examples 1b and 2b were 50 ° or more. From this, it can be seen that the plastic substrates of Examples 1b to 7b and 10b have a lower contact angle and higher hydrophilicity than the plastic substrates of Comparative Examples 1b and 2b. In addition, the plastic substrates of Examples 8b, 9b, and 11b showed a high contact angle, and the examples coated with a polymer containing a crosslinkable component generally showed a high contact angle. From this, it can be seen that the plastic substrates of Examples 8b, 9b, and 11b have a high contact angle and a low adsorptivity even though the hydrophilicity of the substrate surface is low.

[Coating properties]
According to the following production and evaluation methods, the coatability of the plastic substrates of Examples and Comparative Examples was evaluated.

The 2.0 wt% ethanol solutions of Synthesis Examples 8 and 12 were dispensed into separate tubes in plasma-treated polypropylene microtubes, and allowed to stand at room temperature for 10 minutes. Thereafter, the solution was recovered from the tube, and then the surface of the tube was dried at room temperature, and then heated in a vacuum at 80 ° C. for 3 days to obtain a microtube whose surface was coated with a polymer. These were used as plastic substrates of Examples 12 and 13, respectively.
At this time, the surface state of the tube was visually observed to confirm the state of the coating composition.
As Comparative Example 4, a plasma-treated microtube was used.

Into the prepared microtubes of Examples 12 and 13 and Comparative Example 4, the peroxidase-labeled avidin solution prepared with PBS to 0.4 μg / mL was dispensed and allowed to stand at room temperature for 1 hour, and avidin was added to the tube surface. Adsorbed. After washing the tubes with PBS containing 0.1% Tween20, color each tube using a commercially available HRP coloring solution (manufactured by Sumitomo Bakelite), transfer the solution to a 96-well plate, and then use a commercially available plate reader. The absorbance of avidin was measured by measuring the absorbance at 450 nm. Absorbance represents the amount of peroxidase-labeled avidin adsorbed.
Moreover, the surface states of the microtubes of Examples 12 and 13 and Comparative Example 4 were visually confirmed.
Table 3 below shows the evaluation results of the coating properties.

  From the evaluation results of the coating properties, both Examples 12 and 13 showed low protein adsorption in comparison with Comparative Example 4. However, in Example 13, peeling of the coating composition was observed, and the low adsorptivity was lower than Example 12. On the other hand, since Example 12 having a hydrophobic component had good coatability and low adsorptivity, introduction of a hydrophobic component into the polymer according to the material of the plastic substrate to be coated, It became clear that it becomes an effective means for exhibiting low adsorptivity.

[Crosslinking]
According to the following production and evaluation methods, the crosslinkability of the plastic substrates of the examples was evaluated. Crosslinkability was judged by whether or not low adsorptivity was maintained after the plastic substrate was immersed in a solvent.

  A 2.0 wt% ethanol solution of Synthesis Example 8 was dispensed into a plasma-treated polypropylene microtube and allowed to stand at room temperature for 10 minutes. The solution was then collected from the tube and the surface of the tube was then dried at room temperature. This was used as the plastic substrate of Example 14. The plastic substrate of Example 14 differed from the plastic substrate of Example 12 in that it was not heated at 80 ° C. in a vacuum for 3 days, ie, not crosslinked.

A part of the produced microtube of Example 14 and Example 12 produced above was immersed in ethanol at room temperature for 30 minutes, taken out from ethanol, and dried at room temperature. A peroxidase-labeled avidin solution prepared to 0.4 μg / mL with PBS is dispensed into a tube immersed in ethanol and a tube not immersed in the tube, and left at room temperature for 1 hour to adsorb avidin on the tube surface. I let you. After washing the tubes with PBS containing 0.1% Tween20, color each tube using a commercially available HRP coloring solution (manufactured by Sumitomo Bakelite), transfer the solution to a 96-well plate, and then use a commercially available plate reader. The absorbance of avidin was measured by measuring the absorbance at 450 nm. Absorbance represents the amount of peroxidase-labeled avidin adsorbed.
Table 4 below shows the evaluation results of crosslinkability.

  From the results of the evaluation of the crosslinkability, in Example 14 which had a crosslinkable component but was not crosslinked under appropriate conditions, although low adsorbability was exhibited immediately after coating, low adsorbability may be reduced by washing with ethanol. Indicated. On the other hand, in Example 12, which had the same structure and was crosslinked under appropriate conditions, good low adsorptivity was maintained even after washing with ethanol. From this, it became clear that the cross-linking of the plastic substrate and the polymer chains is effective for stabilizing the coated polymer on the surface and stably exhibiting the function of the polymer material for a long period of time.

[Anti-fogging property]
Using the 96-well plate of Examples 1a to 8a and 10a and Comparative Example 1a prepared in the same manner as the plastic substrate prepared in the evaluation of low adsorptivity, the antifogging property was evaluated according to the following evaluation method.

Exhaled air was applied to the 96-well plates of Examples 1a to 8a and 10a and Comparative Example 1a, and the presence or absence of cloudiness was visually confirmed.
Table 5 below shows the evaluation results of antifogging properties. In addition, regarding the item of “antifogging” in Table 5, “◯” indicates that no fogging occurred, and “x” indicates that fogging occurred.

  From the evaluation results of anti-fogging properties, the amount of monomer as a raw material for hydrophobic structural units is small (<50%), whereas the anti-fogging properties of the plastic substrates of Examples 1a to 8a are “◯”, whereas hydrophobic structural units The plastic substrate of Example 10a and Comparative Example 1a with a large amount of monomer as a raw material (≧ 50%) was “x”. From this, it was considered that it is important to reduce the amount of monomer (<50%) as a raw material of the hydrophobic constituent unit in order to exhibit the antifogging property.

  Similarly to Example 8b, the plastic substrate of Example 8a coated with a polymer containing a crosslinkable component is considered to have a high contact angle and low hydrophilicity on the substrate surface. It was revealed that the 8a plastic substrate was able to achieve antifogging properties.

  The present invention provides a copolymer, a coating composition, and an article that have improved coatability on a plastic substrate and have both low adsorptivity or anti-fogging property and coatability on a plastic substrate. Can do.

Claims (14)

Containing hydrophilic building blocks,
The hydrophilic structural unit includes at least one structural unit selected from the group consisting of structural units represented by the following formula (1), the following formula (2), and the following formula (3), and the formula (1) A copolymer having a total of 40 mol% or more of the structural units represented by formula (2) and formula (3):

(In the formula (1), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is NH or an oxygen atom, m is an integer of 0 to 4, R ₁₃ is a hydrogen atom, (It is a hydroxyl group or a methoxy group, and * represents a bond.)

(In Formula (2), R ₂₁ represents a hydrogen atom or a methyl group, and * represents a bond.)

(In Formula (3), R ₃₁ is hydrogen or a methyl group, R ₃₂ is a hydrogen atom or a methyl group, * represents a bond, and n is an integer of 2 to 100.) . The hydrophilic structural unit includes a structural unit represented by the formula (1), and in the formula (1), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is NH or an oxygen atom, The copolymer according to claim 1, wherein m is 2 and R ₁₃ is a hydroxyl group. Further comprising a hydrophobic building block,
The copolymer according to claim 1 or 2, wherein the hydrophobic structural unit is at least one structural unit selected from the group consisting of the following formula (4) and the following formula (5).

(In Formula (4), R ₄₁ is a hydrogen atom or a methyl group, and R ₄₂ is a linear or branched alkyl having 1 to 10 carbon atoms, or an alicyclic alkyl having 3 to 8 carbon atoms. Or a combination thereof, and * represents a bond.)

(In Formula (5), R ₅₁ represents a hydrogen atom or a methyl group, and * represents a bond.) At least the hydrophobic structural unit is a structural unit represented by the formula (4), the formula (4), R ₄₂ is butyl group, a cyclohexyl group, is selected from the group consisting of isopropyl and isobutyl groups The copolymer as described in any one of Claims 1-3 which is one.   The copolymer as described in any one of Claims 1-4 whose content of the said hydrophobic structural unit in the said copolymer is 10 mol% or more and 40 mol% or less. Further comprising a crosslinkable structural unit,
The copolymer as described in any one of Claims 1-5 whose said crosslinkable structural unit is a structural unit represented by following formula (6) or following formula (7).

(In Formula (6), R ₆₁ is a hydrogen atom or a methyl group, s is 4, R ₆₂ is independently a hydrogen atom or a methyl group, and * represents a bond. .)

(In the formula (7), R ₇₁ is a hydrogen atom or a methyl group, and R ₇₂ , R ₇₃ and R ₇₄ are independently a methoxy group, an ethoxy group, a hydrogen atom or a methyl group, provided that One, two or three of R ₇₂ , R ₇₃ and R ₇₄ are independently a methoxy group or an ethoxy group, * represents a bond, and p is an integer of 2 to 10 ).   The copolymer as described in any one of Claims 1-6 whose content of the said crosslinkable structural unit in the said copolymer is 1 mol% or more and 10 mol% or less.   When a 0.3% by weight water or alcohol solution of the copolymer is applied to a cyclic polyolefin substrate and dried, the polystyrene substrate on which the copolymer is applied has a contact angle of 30 ° or more with respect to pure water. The copolymer according to claim 6 or 7, wherein   The coating composition containing the copolymer and solvent as described in any one of Claims 1-8.   The coating composition according to claim 9, which is used for a low-adsorption coating.   The coating composition according to claim 9, which is used for an antifogging coat.   An article provided with a base material and a polymer layer containing the copolymer according to any one of claims 1 to 8 formed on the base material.   The article according to claim 12, wherein a contact angle of the polymer layer with respect to pure water is 5 ° or more and 90 ° or less.   The article according to claim 12 or 13, wherein the polymer layer has a thickness of 1 nm to 100 nm.