Surface treatment agent, article, and copolymer

Abstract

A surface treatment agent containing a copolymer having a unit (A) based on a polymerizable vinyl monomer having a reactive silyl group and a unit (B) based on a (meth) acrylamide compound having a biocompatible functional group, the ratio of the unit (A) to all the units constituting the copolymer being 0.05-25 mol%, the ratio of the unit (B) to all the units constituting the copolymer is 30-99.95 mol%.

Description

Technical Field

[0001] This invention relates to surface treatment agents, articles, and copolymers.

[0002] This application claims priority based on Japan Patent Application No. 2023-181367, filed on October 20, 2023, the contents of which are incorporated herein by reference. Background Technology

[0003] To prevent biological components such as blood, cells, and proteins from adsorbing onto medical devices and algae from adsorbing onto water tanks, a method using compounds with bio-affinity groups to coat the surfaces of these items has been proposed.

[0004] Patent Document 1 describes a substrate having a surface layer disposed on at least a portion of the surface of a substrate body, said surface layer being composed of a cured product of a compound having biocompatible groups and reactive silyl groups. Examples of compounds having biocompatible groups and reactive silyl groups include copolymers having units based on (meth)acrylates having a polyoxyethylene structure and units based on (meth)acrylates having alkoxysilyl groups.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2019 / 151265 Summary of the Invention

[0008] However, the surface layer described in Patent Document 1 may become insufficient in its ability to inhibit the adsorption of biological components and algae, depending on the usage conditions of the medical device and the rearing conditions in the tank. Therefore, there is a need to further improve its non-adsorption properties.

[0009] The present invention provides surface treatment agents and copolymers capable of forming surface layers with excellent non-adsorption properties for biological components and algae, as well as articles with excellent non-adsorption properties for biological components and algae.

[0010] The present invention provides surface treatment agents, articles and copolymers having the following [1] to

[14] .

[0011] [1] A surface treatment agent comprising a copolymer having: a unit (A) based on a polymerizable vinyl monomer having a reactive silyl group and a unit (B) based on a (meth)acrylamide compound having a biocompatible functional group.

[0012] The proportion of the above-mentioned unit (A) relative to all units constituting the above copolymer is 0.05 to 25 mol%.

[0013] The proportion of the above-mentioned unit (B) relative to all units constituting the above copolymer is 30 to 99.95 mol%.

[0014] [2] According to the surface treatment agent of [1], wherein the proportion of the above-mentioned unit (B) to all units constituting the above-mentioned copolymer is 44 to 99 mol%.

[0015] [3] According to the surface treatment agent of [1] or [2], wherein the proportion of the above unit (A) to all units constituting the above copolymer is 1 to 10 mol%.

[0016] [4] A surface treatment agent according to any one of [1] to [3], wherein the above unit (B) is represented by the following formula (B-1).

[0017]

[0018] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. B It is a single bond or a divalent organic group, n1 is an integer from 1 to 4, n2 is an integer from 0 to 300, R 1 It can be a hydrogen atom or an alkyl group.

[0019] [5] A surface treatment agent according to any one of [1] to [4], wherein the above unit (B) is represented by the following formula (B-1-1).

[0020]

[0021] Where R is a hydrogen atom or a methyl group, n1 is an integer from 1 to 4, R 2 It can be a hydrogen atom, a methyl group, or an ethyl group.

[0022] [6] A surface treatment agent according to any one of [1] to [5], wherein the above unit (A) is represented by the following formula (A-1).

[0023]

[0024] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. A R is a divalent organic group. 3 R is a hydrogen atom or an alkyl group. 4 It is an alkyl group, t is an integer from 1 to 3, and there are multiple R groups. 3 Or R 4 At that time, multiple R 3 Or R 4 They can be the same or different.

[0025] [7] A surface treatment agent according to any one of [1] to [6], wherein it further comprises: a unit (C) having a polyoxyethylene chain constituting the main chain.

[0026] [8] The surface treatment agent according to [7], wherein the above unit (C) is represented by the following formula (C-1) or (C-2).

[0027]

[0028] Where n3 and n4 are each independent integers from 10 to 200, X 1 and Y 1 Each is a divalent group represented independently by formula (1) or (2), R 5 It can be hydroxyl, methoxy, or ethoxy.

[0029]

[0030] Among them, Q 1 Q is a divalent organic group. 2 R is a single bond or an alkylene group having 1 to 5 carbon atoms. 6 It can be cyano or methyl.

[0031] X 1 When Z is the divalent group represented by the above formula (1), in formula (1) 1 For a single bond, the Z of the divalent group represented by equation (1) above... 1 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side,

[0032] X 1 When Z is the divalent group represented by the above formula (2), in formula (2) 2 For a single bond, the Z of the divalent group represented by equation (2) above... 2 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side,

[0033] Y 1 When Z is the divalent group represented by the above formula (1), in formula (1) 1 For oxygen atoms, the Z of the divalent group represented by the above formula (1) is... 1 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side,

[0034] Y 1 When Z is the divalent group represented by the above formula (2), in formula (2) 2 For oxygen atoms, the Z of the divalent group represented by formula (2) above 2The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side.

[0035] [9] An article having a substrate and a surface layer disposed on the substrate,

[0036] The aforementioned surface layer is formed by any one of the surface treatment agents in [1] to [8].

[0037]

[10] According to [9], it is a medical device.

[0038]

[11] According to [9], it is a water tank.

[0039]

[12] A copolymer having: units represented by the following formula (A-1), units represented by the following formula (B-1), and units (C) having polyoxyethylene chains constituting the main chain.

[0040] The proportion of the unit represented by the above formula (A-1) relative to all the units constituting the above copolymer is 0.05 to 25 mol%.

[0041] The unit represented by the above formula (B-1) is in a proportion of 30 to 98 mol% relative to all the units constituting the copolymer.

[0042]

[0043] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. A R is a divalent organic group. 3 R is a hydrogen atom or an alkyl group. 4 It is an alkyl group, t is an integer from 1 to 3, and there are multiple R groups. 3 Or R 4 At that time, multiple R 3 Or R 4 They can be the same or different.

[0044]

[0045] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. B It is a single bond or a divalent organic group, n1 is an integer from 1 to 4, n2 is an integer from 0 to 300, R 1 It can be a hydrogen atom or an alkyl group.

[0046]

[13] According to the copolymer of

[12] , wherein the above unit (B) is represented by the following formula (B-1-1).

[0047]

[0048] Where R is a hydrogen atom or a methyl group, n1 is an integer from 1 to 4, R2 It can be a hydrogen atom, a methyl group, or an ethyl group.

[0049]

[14] According to the copolymer of

[12] or

[13] , wherein the above unit (C) is represented by the following formula (C-1) or (C-2).

[0050]

[0051] Where n3 and n4 are each independent integers from 10 to 200, X 1 and Y 1 Each is a divalent group represented independently by formula (1) or (2), R 5 It can be hydroxyl, methoxy, or ethoxy.

[0052]

[0053] Among them, Q 1 Q is a divalent organic group. 2 R is a single bond or an alkylene group having 1 to 5 carbon atoms. 6 It can be cyano or methyl.

[0054] X 1 When Z is the divalent group represented by the above formula (1), in formula (1) 1 For a single bond, the Z of the divalent group represented by equation (1) above... 1 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side,

[0055] X 1 When Z is the divalent group represented by the above formula (2), in formula (2) 2 For a single bond, the Z of the divalent group represented by equation (2) above... 2 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side,

[0056] Y 1 When Z is the divalent group represented by the above formula (1), in formula (1) 1 For oxygen atoms, the Z of the divalent group represented by the above formula (1) is... 1 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side,

[0057] Y 1When Z is the divalent group represented by the above formula (2), in formula (2) 2 For oxygen atoms, the Z of the divalent group represented by formula (2) above 2 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side.

[0058] The surface treatment agent of the present invention can form a surface layer with excellent non-adsorption properties for biological components and algae.

[0059] The articles of this invention exhibit excellent non-adsorption properties of biological components and algae.

[0060] The copolymers of the present invention can form a surface layer with excellent non-adsorption properties for biological components and algae. Detailed Implementation

[0061] The meanings and definitions of the terms used in this invention are as follows.

[0062] Polymerizable vinyl monomers are compounds that possess polymerizable vinyl properties. Polymerizable vinyl is represented by CH2=CR-, where R is a hydrogen atom or a methyl group.

[0063] (Methacrylamide) compounds are a collective term for acrylamide compounds and methacrylamide compounds.

[0064] (Meth)acrylates are a collective term for acrylates and methacrylates.

[0065] A monomer-based unit refers to a portion derived from a monomer, formed through monomer polymerization.

[0066] In this specification, compounds, groups, structures or units represented by chemical formulas are also designated as compounds, groups, structures or units with the formula number attached. For example, a compound represented by formula (1) is also designated as compound (1), a group represented by formula (1) is also designated as group (1), and a structure represented by formula (1) is also designated as structure (1).

[0067] The "~" sign, which indicates a range of values, means that the values ​​recorded before and after it are included as the lower and upper limits.

[0068] [Surface treatment agent]

[0069] The surface treatment agent of the present invention comprises the following copolymer I.

[0070] Copolymer I: having units (A) based on polymerizable vinyl monomers having reactive silyl groups and units (B) based on (meth)acrylamide compounds having biocompatible functional groups, wherein the proportion of unit (A) to all units constituting the copolymer is 0.05 to 25 mol%, and the proportion of unit (B) to all units constituting the copolymer is 30 to 99.95 mol%.

[0071] Copolymer I may further have units (C) as described later, if needed.

[0072] Copolymer I may further have units (D) as described later, as needed.

[0073] (Unit (A))

[0074] Unit (A) is a unit based on a polymerizable vinyl monomer having a reactive silyl group.

[0075] Reactive silanes are a collective term for hydrolyzable silanes such as alkoxysilanes and silanol groups. Hydrolyzable silanes undergo hydrolysis to form silanol groups (Si-OH). When the reactive silane is hydrolyzable, the silanol groups formed by hydrolysis undergo dehydration condensation to form siloxane bonds (Si-O-Si), resulting in a solidified product. When the reactive silane is a silanol group, the reactive silanes undergo dehydration condensation to form siloxane bonds (Si-O-Si), also resulting in a solidified product.

[0076] As a reactive silyl group, alkoxysilyl groups are preferred, for example, the group (3) can be cited.

[0077] -Si(R) 4 ) 3－t (OR) 3 ) t Equation (3)

[0078] Among them, R 3 R is a hydrogen atom or an alkyl group. 4 It is an alkyl group, and t is an integer from 1 to 3.

[0079] There are multiple R 3 Or R 4 At that time, R 3 Or R 4 They can be the same or different. From a manufacturing point of view, multiple Rs... 3 Or R 4 The same is preferred.

[0080] From the viewpoint of excellent adhesion between the substrate and the surface layer, t is preferably 2 or more, and more preferably 3.

[0081] From the perspective of excellent hydrolysis reaction rate and volatility of byproducts during hydrolysis, R 3 Alkyl groups having 1 to 18 carbon atoms are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and methyl or ethyl groups are particularly preferred.

[0082] From the perspective of minimizing steric hindrance during dehydration condensation reactions, R 4 Alkyl groups having 1 to 18 carbon atoms are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and methyl or ethyl groups are particularly preferred.

[0083] As a unit (A), for example, unit (A-1) can be cited.

[0084]

[0085] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. A R is a divalent organic group. 3 R is a hydrogen atom or an alkyl group. 4 It is an alkyl group, t is an integer from 1 to 3, and there are multiple R groups. 3 Or R 4 At that time, multiple R 3 Or R 4 They can be the same or different.

[0086] Q A Preferred carbon groups are divalent hydrocarbon groups with 2 to 10 carbon atoms. The divalent hydrocarbon group may have an ether-like oxygen atom between carbon atoms, and the hydrogen atom may be replaced by a halogen atom or a hydroxyl group. Examples of halogen atoms include chlorine and fluorine atoms. A Preferred are -C2H4-, -C3H6-, or -C4H8-, more preferably -C3H6- or -C4H8-, and especially preferably -C3H6-.

[0087] R 3 R 4 and t and R in the above equation (3) 3 R 4 Same as t.

[0088] Unit (A) can be a unit based on a (meth)acrylate having a reactive silyl group, and more specifically, it can be a unit based on (meth)acrylate (a-1).

[0089] CH2=CR-C(=O)-O-Q A -Si(R) 4 ) 3－t (OR) 3 ) t Equation (a-1)

[0090] R, Q A R 3 R4 and t in the above equation (A-1) R, Q A R 3 R 4 Same as t.

[0091] Examples of (meth)acrylates (a-1) include CH2=CR-C(=O)-O-(CH2)3-Si(OCH3)3 and CH2=CR-C(=O)-O-(CH2)3-Si(OC2H5)3.

[0092] (Unit (B))

[0093] Unit (B) is a unit based on (meth)acrylamide compounds with biocompatible functional groups.

[0094] Bio-affinity groups are groups that have the property of inhibiting biological components such as blood, cells, and proteins, as well as algae, from adhering to the surface of materials and no longer moving.

[0095] Examples of functional groups that are compatible with organisms include groups (4), (5), and (6).

[0096] - (CH2) n1 - (OCH2CH2) n2 -OR 1 Equation (4)

[0097] -O-P (=O) (-O) － )-O-(CH2) n7 -N ＋ R 7 R 8 R 9 Equation (5) -N ＋ R 10 R 11 - (CH2) n8 -X － Equation (6)

[0098] Where n1 is an integer from 1 to 4, n2 is an integer from 0 to 300, and R 1 It can be a hydrogen atom or an alkyl group.

[0099] R 7 R 8 and R 9 Each is an alkyl group having 1 to 5 carbon atoms, and n7 is an integer from 1 to 5.

[0100] R 10 and R 11 Each is an alkyl group with 1 to 5 carbon atoms, n8 is an integer from 1 to 5, and X－ C (=O) - O － Or S(=O)2-O － .

[0101] From the perspective of ease of acquisition, the preferred group is (4), which is a functional group with affinity to organisms.

[0102] From the perspective of the superior non-adsorption properties of biological components and algae, n1 is preferably 1 or 2.

[0103] From the viewpoint of superior ease of acquisition, n2 is preferably 5 or less, more preferably 3 or less, and especially preferably 0.

[0104] R 1 The alkyl group can be linear or branched, preferably linear. From the viewpoint of superior non-adsorption properties of biological components and algae, the number of carbon atoms in the alkyl group is preferably 1 to 22, more preferably 1 to 5, and particularly preferably 1 or 2.

[0105] As a group (4), n2 is preferably 0, R 1 It can be a hydrogen atom, a methyl group, or an ethyl group.

[0106] (Methacrylamide) compounds that have biocompatible functional groups include, for example, (meth)acrylamide compound (b-1).

[0107] CH2=CR-C(=O)-NH-Q B -X (b-1)

[0108] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. B X is a single bond or a divalent organic group, and X is a biological affinity functional group.

[0109] As unit (B), it is preferred to be a unit of (meth)acrylamide compound in which X in the above formula (b-1) is the above group (4), namely unit (B-1).

[0110]

[0111] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. B It is a single bond or a divalent organic group, n1 is an integer from 1 to 4, n2 is an integer from 0 to 300, R 1 It can be a hydrogen atom or an alkyl group.

[0112] As Q B The divalent organic group in the [organic group] is preferably a divalent hydrocarbon group, more preferably an alkylene group. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 3. As Q B Examples include methylene, ethylene, propylene, and isopropylene.

[0113] As Q B Single bonds are preferred.

[0114] n1, n2, and R 1 With respect to n1, n2 and R in the above equation (4) 1 same.

[0115] Unit (B-1) can be a unit based on (meth)acrylamide compound (b-1).

[0116] CH2=CR-C(=O)-NH-Q B - (CH2) n1 - (OCH2CH2) n2 -OR 1 Equation (b-1)

[0117] R, Q B R 1 n1 and n2 are related to R and Q in the above equation (B-1). B R 1 The same applies to n1 and n2.

[0118] As unit (B), unit (B-1-1) is particularly preferred.

[0119]

[0120] Where R is a hydrogen atom or a methyl group, n1 is an integer from 1 to 4, R 2 It can be a hydrogen atom, a methyl group, or an ethyl group.

[0121] (Unit (C))

[0122] Unit (C) is a unit having a polyoxyethylene chain that constitutes the main chain of copolymer I.

[0123] As a unit (C), for example, unit (C-1) or (C-2) can be cited.

[0124]

[0125] Where n3 and n4 are each independent integers from 10 to 200, X 1 and Y 1 Each is independently a divalent group (1) or (2) as described below, R 5 It can be hydroxyl, methoxy, or ethoxy.

[0126] n3 and n4 are each preferably integers from 40 to 200, and more preferably integers from 40 to 140.

[0127]

[0128] Among them, Q 1 Q is a divalent organic group. 2 R is a single bond or an alkylene group having 1 to 5 carbon atoms. 6 It can be cyano or methyl.

[0129] X 1 When Z is the divalent group represented by the above formula (1), in formula (1) 1 For a single bond, the Z of the divalent group represented by equation (1) above... 1 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side,

[0130] X 1 When Z is the divalent group represented by the above formula (2), in formula (2) 2 For a single bond, the Z of the divalent group represented by equation (2) above... 2 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side,

[0131] Y 1 When Z is the divalent group represented by the above formula (1), in formula (1) 1 For oxygen atoms, the Z of the divalent group represented by the above formula (1) is... 1 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side,

[0132] Y 1 When Z is the divalent group represented by the above formula (2), in formula (2) 2 For oxygen atoms, the Z of the divalent group represented by formula (2) above 2 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side.

[0133] Q 1 The preferred carbon group is a divalent hydrocarbon group with 2 to 10 carbon atoms. The divalent hydrocarbon group may have an ether-like oxygen atom between carbon atoms, and the hydrogen atom may be replaced by a halogen atom, a hydroxyl group, or a cyano group. Examples of halogen atoms include chlorine and fluorine atoms.

[0134] Q 1Preferred are -C(CH3)(COOC2H5)-, -C(CH3)(COOCH3)-, -C(CH3)(CN)-, more preferably -C(CH3)(COOCH3)-, -C(CH3)(CN)-, and especially preferably -C(CH3)(CN)-.

[0135] Q 2 The alkylene groups can be linear or branched, with linear being preferred.

[0136] As unit (C), from the perspective of superior ease of acquisition, X is preferred. 1 and Y 1 Each is an independent unit (C-1-1) of a divalent group (1). In this case, the two Qs in unit (C-1-1) 1 They can be the same or different.

[0137]

[0138] Unit (C) can be, for example, a unit based on a monomer containing a polyoxyethylene chain and having groups with free radical polymerizability at both ends, or a unit based on a polymerization initiator containing a polyoxyethylene chain and free radical generating sites such as azo groups (-N=N-). From the viewpoint of being able to easily introduce a polyoxyethylene chain into the main chain of this copolymer, units based on the above-mentioned polymerization initiator are preferred.

[0139] Examples of polymerization initiators that include polyoxyethylene chains and free radical generation sites include azo-based polymerization initiators having polyoxyethylene chains. Specifically, examples include compounds having a polyoxyethylene (PI) structure. Examples of compounds having a PI structure include VPE-0201 manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.

[0140]

[0141] Where n5 is an integer from 10 to 200, and n6 is an integer from 1 to 100.

[0142] n5 is preferably an integer from 40 to 200, and more preferably an integer from 40 to 140.

[0143] n6 is preferably 2 to 30, and more preferably 3 to 20.

[0144] It should be noted that the above-mentioned unit (C-2) is the structure at the end of the main chain of copolymer I, except for the Y of the above-mentioned unit (C-1). 1 R 5Aside from substitution, it can be the same as unit (C-1) described above. That is, unit (C-2) and unit (C-1) can be structural units from the same individual entity. Specific examples of unit (C-2) also include those equivalent to Y in unit (C-1-1) described above. 1 Part of it was R 5 Replacement units, etc.

[0145] In addition, copolymer I may contain both unit (C-1) and unit (C-2).

[0146] (Unit (D))

[0147] Element (D) is any other element besides element (A), element (B), and element (C).

[0148] Examples of units (D) include units having bio-affinity functional groups (excluding units (B) and (C)), units based on monomers that do not have reactive silyl groups and bio-affinity functional groups, and units based on polymerization initiators that do not have polyoxyethylene chains.

[0149] As a unit having a biocompatible functional group (excluding units (B) and (C)), for example, units represented by formulas (B11), (B2) or (B3) as described in International Publication No. 2019 / 151265 can be cited.

[0150] As a unit based on a monomer that does not have reactive silyl groups and biocompatible functional groups, for example, the unit represented by formula (C) disclosed in International Publication No. 2019 / 151265 can be cited.

[0151] As unit (D), units having biocompatible functional groups are preferred (excluding units (B) and units (C)). From the viewpoint of superior ease of acquisition, unit (D-1) is more preferred.

[0152]

[0153] Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. D It is a single bond or a divalent organic group, n9 is 2 or 3, n10 is an integer from 0 to 300, R 12 It can be a hydrogen atom or an alkyl group.

[0154] As Q D Divalent organic groups, such as -O-Q, can be cited as examples. 3 - . Among them, Q 3 It is a divalent organic group. Q D -O-Q 3 - when, -O-Q 3 The terminal of the -O-side is bonded to Q.D Adjacent carbonyl group.

[0155] As Q 3 Preferably, a divalent hydrocarbon group is used. The divalent hydrocarbon group may have an ether-like oxygen atom between carbon atoms, and the hydrogen atom may be replaced by a halogen atom or a hydroxyl group. Examples of halogen atoms include chlorine and fluorine atoms. The number of carbon atoms in the hydrocarbon group is preferably 2 to 10, more preferably 2 to 6. 3 Preferred are -C2H4-, -C3H6-, or -C4H8-, more preferably -C3H6- or -C4H8-, and especially preferably -C3H6-.

[0156] Q D Single bonds are preferred.

[0157] From the viewpoint of superior water resistance, n10 is preferably 10 or less, more preferably 5 or less, and particularly preferably 0 or 1.

[0158] R 12 The alkyl group can be linear or branched, preferably linear. From the viewpoint of superior non-adsorption properties of biological components and algae, the number of carbon atoms in the alkyl group is preferably 1 to 22, more preferably 1 to 5, and particularly preferably 1 or 2.

[0159] Unit (D-1) can be a unit based on compound (d-1).

[0160] CH2=CR-C(=O)-Q D -O-(CH2) n9 - (OCH2CH2) n10 -OR 12 Equation (d-1)

[0161] R, Q D R 12 n9 and n10 are related to R and Q in the above formula (D-1). D R 12 The same applies to n9 and n10.

[0162] As a compound (d-1), hydroxyethyl methacrylate is preferred, for example.

[0163] (Copolymer I)

[0164] The proportion of unit (A) relative to all units constituting copolymer I is 0.05 to 25 mol%. If the proportion of unit (A) is above the lower limit of the above, the non-adsorption properties of the biological components and algae, their durability, water resistance and abrasion resistance are excellent. If it is below the upper limit of the above, the non-adsorption properties of the biological components and algae are excellent.

[0165] The proportion of the aforementioned unit (A) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and particularly preferably 1 mol% or more. The proportion of the aforementioned unit (A) is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 7 mol% or less. The aforementioned lower and upper limits can be appropriately combined. For example, the proportion of the aforementioned unit (A) is preferably 0.1 mol% to 20 mol%, more preferably 0.5 mol% to 20 mol%, further preferably 0.5 mol% to 10 mol% or 0.5 mol% to 7 mol%, and particularly preferably 1 mol% to 10 mol% or 1% to 7 mol%.

[0166] The proportion of unit (B) relative to all units constituting copolymer I is 30 to 99.95 mol%. If the proportion of unit (B) is above the lower limit of the above, the non-adsorption and acid resistance of the biological components and algae are excellent; if it is below the upper limit of the above, the non-adsorption, durability, water resistance and abrasion resistance of the biological components and algae are excellent.

[0167] The proportion of the above-mentioned unit (B) is preferably 49 mol% or more. When copolymer I does not have unit (C), it is particularly preferably 70 mol% or more. When copolymer I has unit (C), it is particularly preferably 60 mol% or more.

[0168] The proportion of the above-mentioned unit (B) is preferably 99 mol% or less. When copolymer I does not have unit (C), it is particularly preferably 97 mol% or less. When copolymer I has unit (C), it is particularly preferably 98 mol% or less.

[0169] The aforementioned lower and upper limits can be appropriately combined. For example, the proportion of unit (B) is preferably 49 mol% to 99 mol%, particularly preferably 70 mol% to 97 mol% when copolymer I does not have unit (C), and particularly preferably 60 mol% to 98 mol% when copolymer I has unit (C).

[0170] When copolymer I has unit (C), from the viewpoint of better polymerizability, the lower limit of the ratio of unit (B) to the total of unit (B) and unit (C) is preferably 90 mol%, more preferably 94 mol% or 95 mol%.

[0171] From the viewpoint that the non-adsorption properties of biological components and algae are superior, the upper limit of the ratio of unit (B) to the total of units (B) and (C) is preferably 99 mol%, more preferably 98 mol%. The above lower limit and the above upper limit can be appropriately combined.

[0172] When copolymer I has unit (C), the proportion of the total of unit (A), unit (B) and unit (C) relative to all units constituting copolymer I is preferably 50 mol% or more, can be 70 mol% or more, or can be 100 mol% relative to all units constituting copolymer I.

[0173] When copolymer I has units (D-1), the total number of units (D-1) relative to all units constituting copolymer I is preferably 0.1 to 90 mol%, more preferably 20 to 70 mol%, and particularly preferably 20 to 50 mol%.

[0174] From the viewpoint of ease of manufacture, the mass-average molecular weight (hereinafter also referred to as "Mw") of copolymer I is preferably 5,000 to 2,000,000, more preferably 10,000 to 500,000.

[0175] Mw is calculated using size exclusion chromatography.

[0176] Copolymer I can be manufactured by known methods, such as those described in International Publication No. 2019 / 151265. For example, by polymerizing a monomer component containing (meth)acrylate (a-1) and (meth)acrylamide compound (b-1) in the presence of a polymerization initiator, a copolymer having units (A) and (B) can be obtained. In this case, by making the monomer component contain a monomer with groups containing polyoxyethylene chains and having free radical polymerizability at both ends, or by using a polymerization initiator containing polyoxyethylene chains and free radical generation sites as the polymerization initiator, a copolymer having units (A), (B), and (C) can be obtained.

[0177] (Other ingredients)

[0178] The surface treatment agent of the present invention may contain other components besides copolymer I.

[0179] Other components, besides copolymer I, include solid components and liquid media.

[0180] When a surface treatment agent is used to form the surface layer described later, if the surface layer is formed by dry coating, the surface treatment agent may contain only solid components or may contain a liquid medium. If the surface layer is formed by wet coating, a liquid medium is included.

[0181] Other solid components can be components that are cured in the same way as copolymer I, or they can be non-curing components.

[0182] Other solid components include, for example, raw materials used in the manufacture of copolymer I, impurities that are not completely removed in byproducts, catalysts and functional additives; compounds having biocompatible sites but not reactive silyl groups; and compounds having reactive silyl groups but not biocompatible sites.

[0183] As a catalyst, conventionally known catalysts used in the hydrolysis and condensation reactions of reactive silyl groups can be used without particular limitation. Specifically, examples of catalysts include acids such as hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, and sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; bases such as sodium hydroxide, potassium hydroxide, and ammonia; and aluminum-based and titanium-based metal catalysts.

[0184] Examples of functional additives include ultraviolet absorbers, light stabilizers, antioxidants, leveling agents, surfactants, antibacterial agents, dispersants, and inorganic microparticles.

[0185] Examples of compounds having a biocompatible site but not a reactive silyl group include, for example, homopolymers of (meth)acrylamide compounds or (meth)acrylates having a biocompatible functional group, and copolymers of (meth)acrylamide compounds or (meth)acrylates having a biocompatible functional group with monomers that do not have a reactive silyl group.

[0186] The liquid medium can be appropriately selected from known liquid media. Preferably, the liquid medium is capable of uniformly dissolving or dispersing the solid component containing copolymer I.

[0187] Since the liquid medium is eventually removed, its boiling point is preferably 60–160°C, more preferably 60–120°C.

[0188] Alcohols, ethers, ketones, or esters are preferred as liquid media. Examples of liquid media that meet the above boiling point conditions include isopropanol, ethanol, propylene glycol monomethyl ether, 2-butanone, and ethyl acetate. They can be used individually or in combination of two or more.

[0189] The liquid medium may contain water for hydrolyzing the reactive silyl-containing components, such as copolymer I. It should be noted that even in the absence of water in the liquid medium, the reactive silyl-containing components can still undergo hydrolysis due to moisture in the atmosphere.

[0190] From the viewpoint of biological components, the non-adsorbent properties of algae, their durability, water resistance, and abrasion resistance, the content of copolymer I in the surface treatment agent is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, particularly preferably 90% by mass or more, and can be 100% by mass, relative to all solid components.

[0191] When the surface treatment agent contains a catalyst, the catalyst content is preferably 0.01 to 20% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 2% by mass, relative to the content of copolymer I.

[0192] When the surface treatment agent contains a liquid medium, the concentration of the solid component of the surface treatment agent is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.1 to 10% by mass, relative to the total mass of the surface treatment agent. If the concentration of the solid component is within the above range, the film thickness of the surface layer formed by using the surface treatment agent and applying it wet is likely to fall within a suitable range that can fully utilize the non-adsorbent properties and durability of the biological components and algae.

[0193] The solid content concentration of the surface treatment agent can be calculated based on the mass of the surface treatment agent after vacuum drying at 80°C for 3 hours and the mass of the surface treatment agent before heating. Alternatively, the solid content concentration can be calculated based on the total amount of solid components and liquid medium incorporated during the manufacture of the surface treatment agent.

[0194] When the surface treatment agent contains a liquid medium, the content of the liquid medium relative to the total mass of the surface treatment agent is preferably 50 to 99.99% by mass, more preferably 70 to 99.9% by mass, and particularly preferably 90 to 99.9% by mass.

[0195] There are no particular limitations on the manufacturing method of the surface treatment agent. When the solid component containing copolymer I also contains a liquid medium, it is sufficient to simply mix the solid component with the liquid medium.

[0196] A partially hydrolyzed cocondensate can be prepared by partially hydrolyzing and co-condensing copolymer I in the surface treatment agent. A partially hydrolyzed cocondensate can also be prepared by partially hydrolyzing and co-condensing copolymer I with a reactive silane compound that does not have biocompatible sites. In the case of partial hydrolyzing and condensing, the degree of condensation is appropriately adjusted to achieve a viscosity that does not hinder the formation of the surface layer on the substrate as described later.

[0197] From this viscosity point of view, the Mw of the partially hydrolyzed condensate is preferably 2,000 to 2,000,000, more preferably 30,000 to 300,000.

[0198] According to the above surface treatment agent, since it contains copolymer I, it is possible to form a surface layer with excellent non-adsorption properties for biological components and algae.

[0199] The surface layer formed by the surface treatment agent containing copolymer I exhibits non-adsorption properties for biological components and algae due to the presence of bio-affinity functional groups in unit (B). (Methacrylamide) compounds with bio-affinity functional groups exhibit higher hydrophilicity and therefore superior non-adsorption properties compared to (meth)acrylates with the same bio-affinity functional groups.

[0200] Furthermore, the amide bonds in (meth)acrylamide compounds are less susceptible to acid-induced hydrolysis compared to the ester bonds in (meth)acrylates. Therefore, the surface layer formed by the aforementioned surface treatment agents exhibits excellent acid resistance. Since the environment within organisms is typically acidic, the inclusion unit (B) contributes to improved long-term stability within organisms.

[0201] 〔thing〕

[0202] An article according to one embodiment of the present invention has a substrate and a surface layer disposed on the substrate. The surface layer is a layer formed by the surface treatment agent of the present invention.

[0203] The surface layer typically consists of a cured product of the surface treatment agent of the present invention. A surface layer consisting of a cured product of the surface treatment agent means that the surface layer contains at least a cured product containing a reactive silyl group of copolymer I. It should be noted that when the surface treatment agent contains a liquid medium, the cured product becomes a cured product of the substance after the liquid medium has been removed from the surface treatment agent.

[0204] There are no particular limitations on the constituent materials of the substrate. Specifically, examples of constituent materials for the substrate include metals, resins, glass, and composites of two or more of these, which can be appropriately selected depending on the application. From the viewpoint of excellent adhesion to the surface layer, the constituent material of the substrate is preferably a material whose molded body has hydroxyl groups on its surface, with glass being particularly suitable. When the surface of the substrate does not have hydroxyl groups, it is preferable to introduce hydroxyl groups through conventionally known methods, such as physical treatment methods like corona treatment or chemical treatment methods like primer treatment. It should be noted that the substrate does not need to be entirely formed of the above-mentioned materials; it is sufficient that at least a portion or all of the surface on which the surface layer is disposed is formed of the above-mentioned materials.

[0205] As a primer treatment, it is preferable to use a compound containing alkoxysilane or a partially hydrolyzed condensate thereof, or a method using a metal oxide such as silica. The primer treatment method can be either wet coating or dry coating.

[0206] The thickness of the surface layer is preferably 10–100,000 nm, and particularly preferably 10–10,000 nm. If the thickness of the surface layer is above the lower limit of the above values, it is easy to exhibit sufficient non-adsorption properties of biological components and algae, as well as its durability and water resistance. If the thickness of the surface layer is below the upper limit of the above values, the strength is even better.

[0207] The thickness of the surface layer was determined by measuring it using an X-ray reflectivity measuring device, such as the Rigaku ATX-G.

[0208] Articles are obtained by forming a surface layer on the surface of a substrate using a surface treatment agent.

[0209] Methods for forming the surface layer include dry coating methods such as vacuum evaporation, CVD, and sputtering, with wet coating being preferred.

[0210] As a method for forming a surface layer by wet coating, an example is a method that includes the following steps: applying a surface treatment agent containing the liquid medium described above onto a substrate to obtain a coating film (hereinafter also referred to as the "coating step"); and curing the coating film to obtain a surface layer (hereinafter also referred to as the "curing step").

[0211] Coating methods for surface treatment agents in the coating process include, for example, dip coating, spin coating, swiping coating, spray coating, extrusion coating, die coating, inkjet coating, flow coating, roller coating, casting, Langmuir-Broguet process, and gravure coating.

[0212] Heating is preferred as a curing method for the coating film in the curing process. The heating temperature depends on the type of reactive silyl group containing copolymer I, and is preferably 50–150°C, more preferably 100–150°C. It should be noted that the removal of the liquid medium is usually performed simultaneously during the curing process. Therefore, the heating temperature is preferably above the boiling point of the liquid medium. Where heating is difficult due to the material of the substrate, etc., the removal of the liquid medium is avoided. For example, reduced pressure drying can be used as a method.

[0213] When forming a surface layer by wet coating, additional processing steps besides the coating and drying steps may be performed as needed. For example, if the surface treatment agent is water-free, humidification may be performed simultaneously with, before, or after the curing process.

[0214] Furthermore, after the surface layer is formed, excess compound in the surface layer can be removed as needed. Specific methods include, for example, pouring a compound, which serves as a solvent or a liquid medium such as a surface treatment agent, onto the surface layer; or wiping it with a cloth soaked in the compound, which serves as a solvent or a liquid medium such as a surface treatment agent.

[0215] It should be noted that surface treatment agents can also be used as repair agents associated with the deterioration of the surface layer. In this case, wet application methods such as spraying and brushing are preferred. The curing method is preferably heating using a dryer or the like.

[0216] There are no particular limitations on the intended use of the article. However, considering the excellent properties of biological components, the non-absorbent nature of algae, their durability, water resistance, and abrasion resistance, the article is preferably an article with a surface that comes into contact with biological components such as blood, cells, and proteins (hereinafter also referred to as "biological component contact surface") or an article with a surface that comes into contact with water (hereinafter also referred to as "water contact surface").

[0217] Items that come into contact with biological components include, for example, medical devices such as endoscopes, catheters, medical instruments, artificial blood vessels, artificial joints, bags, artificial hearts and lungs, tubes, stents, chips, ampoules, vials, syringes, needles, and 3D-printed instruments for proteins; components of biological analysis instruments such as needles, chips, and vials; and physicochemical instruments such as petri dishes, plates, vials, and chips. Among these, medical devices are particularly suitable due to their frequent contact with biological components.

[0218] Items with water contact surfaces include, for example, water tanks, piping, waterways, swimming pools, boat bottoms, overflow decks, and exterior walls. Among these, water tanks are particularly suitable because they receive sunlight and are easy for algae to attach and grow.

[0219] Example

[0220] The present invention will be described in more detail below through examples and comparative examples, but the present invention is not limited to the following examples as long as it does not depart from its spirit. Examples 1 to 7, 13 and 14 are examples, and Examples 8 to 12 are comparative examples.

[0221] [Evaluation Method]

[0222] (Protein adsorption capacity)

[0223] Add 0.9 g of a mixed solvent obtained by mixing methoxypropanol and diacetone alcohol at a mass ratio of 85:15 and 0.6 g of a 0.1 wt% aqueous nitric acid solution to 0.5 g of a copolymer solution with a solid content concentration of 20% by mass obtained in each example, and stir at 50°C for 16 hours. Then, add 1.33 g of the mixed solvent obtained by mixing methoxypropanol and diacetone alcohol at a mass ratio of 85:15 to obtain a coating solution A with a solid content concentration of 3% by mass.

[0224] 2 mL of coating solution A was added dropwise to a 20 mL glass vial, and the vial was rotated while spreading coating solution A on its inner surface to form a film. Next, the vial was inverted and allowed to stand for 5 minutes, then heat-treated in an oven at 150°C for 30 minutes to cure the film.

[0225] Add 1 mL of human fibrinogen (hFbn) solution adjusted to 1 mg / mL to each of the obtained membrane-coated glass vials, incubate at 4°C for 24 hours or at 37°C for 30 minutes, and then wash the glass vials with phosphate-buffered saline (PBS) containing 0.05% Tween 20 (Sigma Aldrich).

[0226] Next, 1 mL of a 0.1N NaOH aqueous solution containing 5% sodium dodecyl sulfate (SDS) was added to a glass vial, and the vial was kept at 37°C for 2 hours to recover the protein adsorbed on the membrane in the glass vial into the aqueous phase.

[0227] Next, add 1 mL of Micro BCA reagent (made by Thermo Scientific) to the glass vial and incubate at 37°C for 2 hours to confirm that the color development is complete.

[0228] 180 μL of the solution in the glass vial was transferred to a 96-well TCPS plate, and the absorbance at 560 nm was measured using a microplate reader. A standard curve was prepared using absorbance measurements of protein solutions with known concentrations to determine the protein content (mg / mL) in a 0.1N NaOH aqueous solution containing 5% sodium dodecyl sulfate (SDS) and Micro BCA reagent. The determined protein content corresponds to the protein adsorption capacity. The lower the determined protein content, the better the non-adsorption properties of the biological components and algae.

[0229] In the above evaluation, after the measurement, the liquid inside the glass vial was discarded and dried. The bottom surface of the glass vial was scraped with a metal spoon. If no membrane residue was visually detected, it was determined that the membrane had peeled off or dissolved during the measurement, and the result was rated as "unable to measure".

[0230] (Water resistance)

[0231] The glass slide is immersed in the above coating solution A, lifted at 1 mm / second, and heat-treated in an oven at 150°C for 30 minutes to obtain a glass slide with a cured film.

[0232] The obtained glass slides with the cured film were immersed in physiological saline for one week. After drying the removed substrates in an oven at 40°C for 30 minutes, they were visually inspected for film peeling and evaluated according to the following criteria. If no film peeling occurred, the water resistance was excellent.

[0233] <Evaluation Criteria>

[0234] A: No membrane peeling was confirmed.

[0235] B: Partial membrane peeling.

[0236] C: The membrane has been completely peeled off.

[0237] [Explanation of abbreviations]

[0238] KBM503: 3-Methacryloxypropyltrimethoxysilane (CH2=C(CH3)-C(=O)-O-(CH2)3-Si(OCH3)3, molecular weight 248.4, manufactured by Shin-Etsu Silicon Co., Ltd. as "KBM-503").

[0239] HEAA: Hydroxyethylacrylamide (CH2=C(CH3)-C(=O)-NH-(CH2)2-OH, molecular weight 115.13).

[0240] HEMA: Hydroxyethyl methacrylate (CH2=C(CH3)-C(=O)-O-(CH2)2-OH, molecular weight 130.14).

[0241] PEG9A: Polyethylene glycol acrylate with an oxyvinyl repeat number of 9 (CH2=CH-COO-(CH2CH2O)9-CH3, molecular weight 496.6).

[0242] AIBN: An azo polymerization initiator without a polyoxyethylene chain (2,2'-azobisisobutyronitrile, molecular weight 164.21, manufactured by Fujifilm and Kohsen Pure Chemicals Co., Ltd.).

[0243] VPE0201: An azo polymerization initiator with a polyoxyethylene chain (a compound having a structure in the above formula (PI) where n5 is 45-46 and n6 is 6-14, with a molecular weight of 2240, manufactured by Fujifilm and Kohjun Pharmaceutical Co., Ltd. as "VPE-0201").

[0244] [Examples 1~14]

[0245] In a mixed solvent obtained by mixing methoxypropanol and diacetone alcohol at a mass ratio of 85:15, each component was dissolved in the proportions (mol%) shown in Table 1 to achieve a solids concentration of 20% by mass. The resulting solution was then placed into a pressure-resistant glass bottle, sealed, and heated at 80°C for 24 hours to carry out polymerization, thereby obtaining a copolymer solution with a solids concentration of 20% by mass.

[0246] The obtained copolymer solutions were evaluated as described above. The results are shown in Table 1.

[0247]

[0248] The films formed from the copolymer solutions of Examples 1-7, 13 and 14 exhibit excellent protein non-adsorption and water resistance.

[0249] On the other hand, in Example 8, where the proportion of unit (A) in the copolymer is less than 0.05 mol% relative to all units and the proportion of unit (B) exceeds 99.95 mol%, the protein adsorption amount could not be determined, and the water resistance was also C.

[0250] In Example 9, where the proportion of unit (A) in the copolymer to all units exceeds 25 mol%, the protein non-adsorption is poor compared to Examples 1-7, 13 and 14.

[0251] Compared with Examples 1-7, 13 and 14, Examples 10-11, which contain PEG9A or HEMA based on (meth)acrylate with biocompatible functional groups to replace unit (B), exhibit poor protein non-adsorption.

[0252] Compared to Examples 1-7, 13 and 14, Example 12, in which the proportion of unit (B) in the copolymer to all units is less than 30 mol%, exhibits poor protein non-adsorption.

Claims

1. A surface treatment agent comprising a copolymer having: unit A based on a polymerizable vinyl monomer having a reactive silyl group and unit B based on a (meth)acrylamide compound having a biocompatible functional group. The proportion of unit A relative to all units constituting the copolymer is 0.05 to 25 mol%. The proportion of unit B relative to all units constituting the copolymer is 30 to 99.95 mol%.

2. The surface treatment agent according to claim 1, wherein, The proportion of unit B relative to all units constituting the copolymer is 44 to 99 mol%.

3. The surface treatment agent according to claim 1 or 2, wherein, The proportion of unit A relative to all units constituting the copolymer is 1 to 10 moles.

4. The surface treatment agent according to claim 1 or 2, wherein, The unit B is represented by the following formula (B-1), Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. B It is a single bond or a divalent organic group, n1 is an integer from 1 to 4, n2 is an integer from 0 to 300, R 1 It can be a hydrogen atom or an alkyl group.

5. The surface treatment agent according to claim 1 or 2, wherein, The unit B is represented by the following formula (B-1-1), Where R is a hydrogen atom or a methyl group, n1 is an integer from 1 to 4, R 2 It can be a hydrogen atom, a methyl group, or an ethyl group.

6. The surface treatment agent according to claim 1 or 2, wherein, The unit A is represented by the following formula (A-1), Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. A R is a divalent organic group. 3 R is a hydrogen atom or an alkyl group. 4 It is an alkyl group, t is an integer from 1 to 3, and there are multiple R groups. 3 Or R 4 At that time, multiple R 3 Or R 4 They are the same or different.

7. The surface treatment agent according to claim 1 or 2, wherein, It further has: a unit C having a polyoxyethylene chain that constitutes the main chain.

8. The surface treatment agent according to claim 7, wherein, The unit C is represented by the following formula (C-1) or (C-2), Where n3 and n4 are each independent integers from 10 to 200, X 1 and Y 1 Each is a divalent group represented independently by formula (1) or (2), R 5 It is hydroxyl, methoxy, or ethoxy. Among them, Q 1 Q is a divalent organic group. 2 R is a single bond or an alkylene group having 1 to 5 carbon atoms. 6 It is either cyano or methyl. X 1 When Z is the divalent group represented by the formula (1), Z in formula (1) 1 For a single bond, the Z of the divalent group represented by formula (1) is... 1 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side, X 1 When Z is the divalent group represented by equation (2), in equation (2) 2 For a single bond, the Z of the divalent group represented by formula (2) is... 2 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side, Y 1 When Z is the divalent group represented by the formula (1), Z in formula (1) 1 For oxygen atoms, the Z of the divalent group represented by formula (1) 1 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side, Y 1 When Z is the divalent group represented by equation (2), in equation (2) 2 For oxygen atoms, the Z of the divalent group represented by formula (2) 2 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side.

9. An article having a substrate and a surface layer disposed on the substrate, The surface layer is a layer formed by the surface treatment agent according to claim 1 or 2.

10. The article according to claim 9, wherein it is a medical device.

11. The article according to claim 9, wherein it is a water tank.

12. A copolymer comprising: units represented by formula (A-1), units represented by formula (B-1), and unit C having a polyoxyethylene chain constituting the main chain. The proportion of the unit represented by formula (A-1) relative to all units constituting the copolymer is 0.05 to 25 mol%. The unit represented by formula (B-1) is in the proportion of 30 to 98 mol% relative to all units constituting the copolymer. in, R is a hydrogen atom or a methyl group, Q A R is a divalent organic group. 3 R is a hydrogen atom or an alkyl group. 4 It is an alkyl group, t is an integer from 1 to 3, and there are multiple R groups. 3 Or R 4 At that time, multiple R 3 Or R 4 Whether they are the same or different, Where R is a hydrogen atom or a methyl group, and Q is a hydrogen atom or a methyl group. B It is a single bond or a divalent organic group, n1 is an integer from 1 to 4, n2 is an integer from 0 to 300, R 1 It can be a hydrogen atom or an alkyl group.

13. The copolymer according to claim 12, wherein, The unit B is represented by the following formula (B-1-1), Where R is a hydrogen atom or a methyl group, n1 is an integer from 1 to 4, R 2 It can be a hydrogen atom, a methyl group, or an ethyl group.

14. The copolymer according to claim 12 or 13, wherein, The unit C is represented by the following formula (C-1) or (C-2), Where n3 and n4 are each independent integers from 10 to 200, X 1 and Y 1 Each is a divalent group represented independently by formula (1) or (2), R 5 It is hydroxyl, methoxy, or ethoxy. Among them, Q 1 Q is a divalent organic group. 2 R is a single bond or an alkylene group having 1 to 5 carbon atoms. 6 It is either cyano or methyl. X 1 When Z is the divalent group represented by the formula (1), Z in formula (1) 1 For a single bond, the Z of the divalent group represented by formula (1) is... 1 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side, X 1 When Z is the divalent group represented by equation (2), in equation (2) 2 For a single bond, the Z of the divalent group represented by formula (2) is... 2 The end of the side is bonded to X 1 Adjacent (OCH2CH2) n3 Or (OCH2CH2) n4 The end of the oxygen atom side, Y 1 When Z is the divalent group represented by the formula (1), Z in formula (1) 1 For oxygen atoms, the Z of the divalent group represented by formula (1) 1 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side, Y 1 When Z is the divalent group represented by equation (2), in equation (2) 2 For oxygen atoms, the Z of the divalent group represented by formula (2) 2 The end of the side is bonded to Y 1 Adjacent (OCH2CH2) n3 The end of the carbon atom side.

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