JP5549464B2 - Surface treatment agent composition, surface treatment method, surface treatment substrate, copolymer and production method thereof - Google Patents

Description

  The present invention relates to a surface treatment agent composition, a surface treatment method using the surface treatment agent composition, a surface treatment substrate, a copolymer usable for the surface treatment agent composition, and a method for producing the copolymer.

  Conventionally, a wide range of attempts to improve the antifouling property, contamination self-cleaning property, antifogging property, quick drying property of water, antistatic property, etc. Has been made.

As a method for imparting hydrophilicity to a substrate, a composition containing a hydrophilic polymer having a structural unit containing a hydrolyzable silyl group and / or a hydrolyzable silyl group at a polymer terminal and a structural unit containing a hydrophilic group A method for coating an object with a substrate has been proposed.
For example, Patent Documents 1 to 3 describe compositions for hydrophilization treatment of a substrate surface including a hydrophilic polymer having a structural unit containing a hydrolyzable silyl group and a structural unit containing a hydrophilic group. .

JP 2008-222998 A JP 2010-47739 A JP 2010-90373 A

  However, according to the study by the present inventors, by coating the substrate surface with a composition comprising a polymer having a structural unit containing a hydrolyzable silyl group and a structural unit containing a hydrophilic group, and a solvent, Even if the surface of the material is made hydrophilic, the surface of the base material may not be kept hydrophilic for a long time. That is, there was room for improvement in the durability of the substrate surface, especially the water resistance. In particular, even when immersed in water for a long time, it has been difficult to obtain a substrate having excellent water resistance that maintains hydrophilicity on the surface of the substrate.

  In view of this actual situation, the object of the present invention is to provide a substrate with high water resistance that imparts high hydrophilicity to the substrate surface and maintains excellent hydrophilicity even when immersed in water for a long time. It is in providing a surface treating agent composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a copolymer having a structural unit containing a specific amino group as a hydrophilic group and a structural unit containing an epoxy group, an aminosilane compound, It has been found that if a surface treating agent composition containing a solvent is used, a hydrophilic coating layer having excellent water resistance can be imparted to the substrate, and the present invention has been completed.

  Accordingly, the present invention provides a surface treatment agent composition capable of performing a hydrophilic treatment on a substrate surface having excellent water resistance, a surface treatment method using the surface treatment agent composition, a surface treatment substrate, and a surface treatment agent. The present invention provides a copolymer that can be used in the composition and a method for producing the copolymer, and relates to any of the following [1] to [11].

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）で表される構成単位（１）を少なくとも１種、及び、下記一般式（ＩＩ）

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表される構成単位（２）を少なくとも１種、含む共重合体（ｉ）、
加水分解性シリル基と前記共重合体（ｉ）中のエポキシ基と反応しうるアミノ基をそれぞれ１つ以上含むアミノシラン化合物（ｉｉ）、並びに
溶媒（ｉｉｉ）を含む表面処理剤組成物。
［２］．前記アミノシラン化合物（ｉｉ）が下記一般式（ＩＩＩ）

（ただし、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、ＹはＮＨ_２−又はＮＨ_２−Ａ−ＮＨ−を示し、Ｒ^６、及びＲ^７はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）で表されるアミノアルコキシシラン（ｉｉａ）である［１］に記載の表面処理剤組成物。
［３］．前記共重合体（ｉ）中のエポキシ基と前記アミノシラン化合物（ｉｉ）中のアミノ基を反応させて共有結合を形成させた［１］又は［２］に記載の表面処理剤組成物。
［４］．構成単位として下記一般式（Ｉ）

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４は独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）で表される構成単位（１）を少なくとも１種、及び、下記一般式（ＩＶ）

（ただし、ｑは１〜３の整数を示し、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、Ｚは−ＮＨ−、−ＮＨ−Ａ−ＮＨ−又は−ＮＨ（Ａ−ＮＨ_２）−を示し、Ｒ^５は水素原子又はメチル基を示し、Ｒ^６、及びＲ^７は独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）
で表される構成単位（４）を少なくとも１種、含む共重合体。
［５］．構成単位としてさらに下記一般式（ＩＩ）

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表される構成単位（２）を少なくとも１種、含む［４］に記載の共重合体。
［６］．［４］又は［５］に記載の共重合体と溶媒（ｉｉｉ）とを含む表面処理剤組成物。
［７］．前記表面処理が基材表面へ親水性を付与する処理である［３］又は［６］に記載の表面処理剤組成物。
［８］．基材上に［３］、［６］又は［７］に記載の表面処理剤組成物を塗布したのち、乾燥させて基材表面にコーティング層を形成させる基材の表面処理方法。
［９］．［４］又は［５］に記載の共重合体を含むコーティング層が付与された表面処理基材。
［１０］．ラジカル重合開始剤の存在下、溶媒中で、下記一般式（Ｖ）

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）
で表される（メタ）アクリロイルアミノアルキル４級アンモニウム塩（１’）少なくとも１種と、
下記一般式（ＶＩ）

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表されるグリシジル（メタ）アクリレート（２’）少なくとも１種とを共重合反応させる工程（ア）、及び、
前記工程（ア）の重合前、重合中又は重合後の反応液と、下記一般式（ＩＩＩ）

（ただし、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、ＹはＮＨ_２−又はＮＨ_２−Ａ−ＮＨ−を示し、Ｒ^６、及びＲ^７はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）
で表されるアミノアルコキシシラン（ｉｉａ）とを混合し、前記グリシジル（メタ）アクリレート（２’）及び／又は前記工程（ア）で得られた共重合体中のエポキシ基と前記アミノアルコキシシラン（ｉｉａ）中のアミノ基とを反応させて共有結合を形成させる工程（イ）、
を有することを特徴とする［４］又は［５］に記載の共重合体の製造方法。
［１１］．構成単位として下記一般式（Ｉ）

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）
で表される構成単位（１）を少なくとも１種、及び、
下記一般式（ＩＩ）

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表される構成単位（２）を少なくとも１種、含む共重合体（ｉ）、と
下記一般式（ＩＩＩ）

（ただし、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、ＹはＮＨ_２−又はＮＨ_２−Ａ−ＮＨ−を示し、Ｒ^６、及びＲ^７はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）
で表されるアミノアルコキシシラン（ｉｉａ）とを混合し、前記共重合体（ｉ）中のエポキシ基と前記アミノアルコキシシラン（ｉｉａ）中のアミノ基とを反応させて共有結合を形成させる工程（イ’）を有することを特徴とする、［４］又は［５］に記載の共重合体の製造方法。 [1]. As a structural unit, the following general formula (I)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} each independently represents an alkyl group having 1 to 3 carbon atoms, ^{X a -} represents a counter ion, a is at least one kind of structural unit (1) represented by indicating) the valency of the counter ion, and the following general formula (II)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A copolymer (i) containing at least one structural unit (2) represented by:
A surface treating agent composition comprising an aminosilane compound (ii) containing at least one hydrolyzable silyl group and at least one amino group capable of reacting with an epoxy group in the copolymer (i), and a solvent (iii).
[2]. The aminosilane compound (ii) is represented by the following general formula (III)

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ are each independently carbon. The surface treating agent composition according to [1], which is an aminoalkoxysilane (ia) represented by an alkyl group having 1 to 3 carbon atoms, wherein A represents an alkylene group having 2 to 5 carbon atoms.
[3]. The surface treating agent composition according to [1] or [2], wherein an epoxy group in the copolymer (i) and an amino group in the aminosilane compound (ii) are reacted to form a covalent bond.
[4]. As a structural unit, the following general formula (I)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} are independently an alkyl group having 1 to 3 carbon ^{atoms, X a-} Represents a counter ion, a represents a valence of the counter ion) and at least one structural unit (1) represented by the following general formula (IV):

(Where q represents an integer of 1 to 3, r represents an integer of 2 to 5, s represents an integer of 0 to 2, and Z represents —NH—, —NH—A—NH— or —NH ( a-NH ₂₎ - indicates, ^{R 5} represents a hydrogen atom or a methyl group, ^{R 6,} and ^{R 7} independently represent an alkyl group having 1 to 3 carbon atoms, a is an alkylene group having 2 to 5 carbon atoms Indicates)
The copolymer containing at least 1 sort (s) of structural units (4) represented by these.
[5]. As a structural unit, the following general formula (II)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
The copolymer according to [4], which contains at least one structural unit (2) represented by
[6]. A surface treating agent composition comprising the copolymer according to [4] or [5] and a solvent (iii).
[7]. The surface treatment agent composition according to [3] or [6], wherein the surface treatment is a treatment for imparting hydrophilicity to the substrate surface.
[8]. A surface treatment method for a substrate, wherein the surface treatment agent composition according to [3], [6] or [7] is applied on the substrate and then dried to form a coating layer on the substrate surface.
[9]. The surface treatment base material provided with the coating layer containing the copolymer as described in [4] or [5].
[10]. In the presence of a radical polymerization initiator in a solvent, the following general formula (V)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} each independently represents an alkyl group having 1 to 3 carbon atoms, ^{X a -} represents a counter ion, a is shown the valency of the counter ion)
At least one (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) represented by:
The following general formula (VI)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A step (a) of copolymerizing at least one glycidyl (meth) acrylate (2 ′) represented by
The reaction solution before, during or after polymerization in the step (a), and the following general formula (III)

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ are each independently carbon. An alkyl group having 1 to 3 carbon atoms, and A represents an alkylene group having 2 to 5 carbon atoms)
The epoxy group in the copolymer obtained by the said glycidyl (meth) acrylate (2 ') and / or the said process (a) and the said amino alkoxysilane ( a step of reacting with an amino group in ia) to form a covalent bond (a),
The method for producing a copolymer according to [4] or [5], wherein
[11]. As a structural unit, the following general formula (I)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} each independently represents an alkyl group having 1 to 3 carbon atoms, ^{X a -} represents a counter ion, a is shown the valency of the counter ion)
At least one structural unit (1) represented by:
The following general formula (II)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A copolymer (i) containing at least one structural unit (2) represented by the general formula (III):

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ are each independently carbon. An alkyl group having 1 to 3 carbon atoms, and A represents an alkylene group having 2 to 5 carbon atoms)
And a step of reacting an epoxy group in the copolymer (i) with an amino group in the aminoalkoxysilane (ia) to form a covalent bond ( A process for producing a copolymer as described in [4] or [5],

  According to the present invention, a surface treatment agent composition that maintains a high hydrophilicity even when immersed in water for a long time and that can perform a hydrophilic treatment excellent in water resistance on a substrate surface, and a surface treatment agent composition. Copolymers included can be provided. Moreover, the base material which has the hydrophilic coating layer excellent in water resistance can be provided by performing the surface treatment using this surface treating agent composition on the base-material surface.

1 is a diagram showing an IR spectrum of a copolymer of methacryloylaminopropyltrimethylammonium chloride and glycidyl methacrylate obtained in Example 1. FIG. FIG. 3 is a diagram showing an IR spectrum of a reaction product of a copolymer of methacryloylaminopropyltrimethylammonium chloride and glycidyl methacrylate obtained in Example 1 and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. is there. It is the figure which showed IR spectrum of the reaction material of the copolymer of methacryloylaminopropyltrimethylammonium chloride and glycidyl methacrylate obtained in Example 7 and 3-aminopropyltrimethoxysilane.

  In one embodiment, the surface treating agent composition of the present invention has the following general formula (I) as a structural unit.

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４は独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）で表される構成単位（１）を少なくとも１種及び、下記一般式（ＩＩ）

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} are independently an alkyl group having 1 to 3 carbon ^{atoms, X a-} Represents a counter ion, a represents a valence of the counter ion) and at least one structural unit (1) represented by the following general formula (II)

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表される構成単位（２）を少なくとも１種、含む共重合体（ｉ）、及び、加水分解性シリル基と前記共重合体（ｉ）中のエポキシ基と反応しうるアミノ基をそれぞれ１つ以上含むアミノシラン化合物（ｉｉ）、並びに溶媒（ｉｉｉ）を含む表面処理剤組成物である。

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A copolymer (i) containing at least one structural unit (2) represented by the formula (1) and an amino group capable of reacting with a hydrolyzable silyl group and an epoxy group in the copolymer (i), respectively. It is a surface treating agent composition containing the aminosilane compound (ii) containing two or more, and the solvent (iii).

  In another aspect, the surface treating agent composition of the present invention has the following general formula (I) as a structural unit.

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４は独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）で表される構成単位（１）を少なくとも１種、及び、下記一般式（ＩＶ）

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} are independently an alkyl group having 1 to 3 carbon ^{atoms, X a-} Represents a counter ion, a represents a valence of the counter ion) and at least one structural unit (1) represented by the following general formula (IV):

（ただし、ｑは１〜３の整数を示し、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、Ｚは−ＮＨ−、−ＮＨ−Ａ−ＮＨ−又は−ＮＨ（Ａ−ＮＨ_２）−を示し、Ｒ^５は水素原子又はメチル基を示し、Ｒ^６、及びＲ^７は独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）で表される構成単位（４）を少なくとも１種、含む共重合体（ｉｖ）と、溶媒（ｉｉｉ）とを含む表面処理剤組成物である。

(Where q represents an integer of 1 to 3, r represents an integer of 2 to 5, s represents an integer of 0 to 2, and Z represents —NH—, —NH—A—NH— or —NH ( a-NH ₂₎ - indicates, ^{R 5} represents a hydrogen atom or a methyl group, ^{R 6,} and ^{R 7} independently represent an alkyl group having 1 to 3 carbon atoms, a is an alkylene group having 2 to 5 carbon atoms A surface treatment agent composition comprising a copolymer (iv) containing at least one structural unit (4) represented by formula (1) and a solvent (iii).

The structural unit (1) constituting the polymer (i) and the like constituting the surface treating agent composition of the present invention is usually derived from a (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′). In the structural unit (1), R ¹ is a hydrogen atom or a methyl group. In the general formula (I) showing the structure of the structural unit (1), examples of R ² , R ³ , and R ⁴ include a methyl group, an ethyl group, and a propyl group. In the general formula (I), examples of X ^a- include chlorine ion, bromine ion, iodine ion, carboxylate ion, dicarboxylate ion, phosphate ion, alkylsulfonate ion, and sulfamate ion, but imparting hydrophilicity. From this point of view, chlorine ions are preferable. In the said general formula (I), as a value of p, 2-5 are preferable and 3-4 are more preferable.

The structural unit (2) constituting the polymer (i) and the like constituting the surface treating agent composition of the present invention is usually derived from glycidyl (meth) acrylate (2 ′). In the structural unit (2), R ⁵ represents a hydrogen atom or a methyl group. In the general formula (II) showing the structure of the structural unit (2), the value of q is preferably 1 or 2.

In the copolymer (i) constituting the surface treating agent composition of the present invention, the structural unit (1) usually derived from the (meth) acryloylaminoalkyl quaternary ammonium salt monomer (1 ′) and the normal glycidyl (meth) acrylate The molar ratio of the structural unit (2) derived from the monomer (2 ′) can be exemplified by a range of 99/1 to 10/90 as a ratio of (1) / (2). The range is preferably 95/5 to 60/40, more preferably 90/10 to 65/35, particularly preferably 85/15 to 65/35, and 80/20 to 65/35. The range of is most preferable. The molar ratio of the structural units of the copolymer can be directly measured from the copolymer, but it is known that the molar ratio of each monomer charged is almost the same due to the nature of this polymerization reaction. Alternatively, it may be estimated by the molar ratio of each monomer during the polymerization reaction.
Since the ratio of the structural unit (1) is not too low, the surface treating agent composition containing this copolymer (i) has an effect of imparting hydrophilicity. Moreover, since the ratio of a structural unit (2) is not too low, the hydrophilic surface obtained by processing with the surface treating agent composition containing this copolymer has water resistance.

  In the surface treatment agent composition of the present invention, the average degree of polymerization of the copolymer (i) containing the structural unit (1) and the structural unit (2) is in terms of polyethylene glycol by gel permeation chromatography (GPC) method. It can be obtained from the weight average molecular weight of the copolymer (i) and the weighted average molecular weight of the structural unit calculated from the molecular weight and molar ratio of each structural unit, and is preferably in the range of 10 to 10,000, The range of 8000 is more preferable, the range of 50 to 5000 is more preferable, the range of 80 to 3000 is particularly preferable, and the range of 100 to 2000 is most preferable.

The structural unit (4) constituting the copolymer (iv) used in the surface treating agent composition of the present invention may be derived from a (meth) acrylic acid aminoalkoxysilane monomer (IV). In the structural unit (4), R ⁵ represents a hydrogen atom or a methyl group, and examples of R ⁶ and R ⁷ include a methyl group, an ethyl group, and a propyl group. In the general formula (IV) representing the structure of the structural unit (4), the value of q is preferably 1 to 2, the value of r is preferably 3 to 4, and the value of s is preferably 0 to 1. . In the general formula (IV), the alkylene group is a substituted or unsubstituted alkylene group, which may be linear or branched. In the general formula (IV), as Z, —NH—, —NH— (CH ₂ ) ₂ —NH—, —NH— (CH ₂ ) ₃ —NH—, —NH— (CH ₂ ) ₄ —NH _{-, - NH- (CH 2)} 5 -NH -, - NH (CH 2 -CH 2 -NH 2) -, - NH (CH 2 - (CH 2) 2 -NH 2) -, - NH (CH 2 _{- (CH 2) 3 -NH 2} ) -, - NH (CH 2 - (CH 2) 4 -NH 2) - can be exemplified.

The copolymer (iv) containing the structural unit (1) and the structural unit (4) used as the structural unit for the surface treating agent composition of the present invention is an effect of the surface treating agent composition of the present invention, particularly hydrophilic. As long as the effect of imparting is not impaired, the third component may further include a structural unit other than the structural unit (1) and the structural unit (4). Examples of the third component include an unreacted residual monomer at the time of producing the target compound, or a structural unit derived from a monomer obtained by reacting a reagent with a reactive group contained in the residual monomer.
Here, as the structural unit derived from the residual monomer, the following general formula (II)

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表される構成単位（２）が挙げられる。構成単位（２）は、通常、グリシジル（メタ）アクリレートモノマー由来である。ここで、Ｒ^５は水素原子又はメチル基であり、ｑの値としては、１〜２が好ましい。
この構成単位（２）と反応させる試薬としては、加水分解性シリル基又は親水性基を有する求核剤を例示できる。
また、本発明の表面処理剤組成物に用いられる、第３成分を有する共重合体（ｉｖａ）は、構成単位（１）及び構成単位（４）に加えて、さらに構成単位（２）を少なくとも１種、含む共重合体である。

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
The structural unit (2) represented by these is mentioned. The structural unit (2) is usually derived from a glycidyl (meth) acrylate monomer. Wherein, R ⁵ is a hydrogen atom or a methyl group, as the value of q, 1 to 2 is preferred.
Examples of the reagent to be reacted with the structural unit (2) include a nucleophile having a hydrolyzable silyl group or a hydrophilic group.
In addition to the structural unit (1) and the structural unit (4), the copolymer (iva) having the third component used in the surface treating agent composition of the present invention further comprises at least the structural unit (2). It is a copolymer containing one kind.

Each component in the copolymer (iva) further comprising the structural unit (molar ratio of 1 to the structural unit (4) and the structural unit (2) in the copolymer (iv) constituting the surface treating agent composition of the present invention. The molar ratio of (1) / (4) or the ratio of (1) / [(4) + (2)] can be exemplified by a range of 99/1 to 10/90, respectively. -50/50 is preferred, 95 / 5-60 / 40 is more preferred, 90 / 10-65 / 35 is even more preferred, 85 / 15-65 / 35 is particularly preferred, 80 / The range of 20 to 65/35 is most preferred, and the molar ratio of the structural units in the copolymer can be directly measured from the copolymer, but due to the nature of this polymerization reaction, It is known that it is almost the same as the molar ratio. It may be estimated by the molar ratio of the monomers.
In the copolymer (iva), the molar ratio of the structural unit (4) to the structural unit (2) can be exemplified by a range of 99/1 to 10/90 as the ratio of (4) / (2). / 1 to 20/80 is preferred, 99/1 to 30/70 is more preferred, and 99/1 to 40/60 is even more preferred. In addition, (meth) acrylic acid aminoalkoxysilane monomer is produced by reacting the amino group of aminoalkoxysilane with the epoxy group in glycidyl (meth) acrylate monomer (2 ′), and this reaction is quantitative. Therefore, the value of (4) / (2), that is, the introduction rate of aminoalkoxysilane into the epoxy group is almost determined by the molar ratio of glycidyl (meth) acrylate monomer (2 ′) to aminoalkoxysilane at the time of reaction. Is done.
Since the ratio of the structural unit (1) is not too low, the surface treating agent composition containing this copolymer has an effect of imparting hydrophilicity. Moreover, since the ratio of a structural unit (4) is not too low, the hydrophilic surface obtained by processing with the surface treating agent composition containing this copolymer has water resistance.

  In the surface treating agent composition of the present invention, the average degree of polymerization of the copolymer (iv) containing the structural unit (1) and the structural unit (4) or the copolymer (iva) further containing the structural unit (2) is: The weight average molecular weight in terms of polyethylene glycol of the copolymer (i) used as a raw material of these copolymers by the gel permeation chromatography (GPC) method, and the molecular weight and molar ratio of each constituent unit of the copolymer (i) It can be obtained from the weighted average molecular weight of the structural unit calculated from the above, preferably in the range of 10 to 10000, more preferably in the range of 30 to 8000, still more preferably in the range of 50 to 5000, and 80 to 3000. A range is particularly preferred, with a range of 100-2000 being most preferred.

  The aminosilane compound (ii) used in the surface treating agent composition of the present invention contains at least one amino group capable of reacting with a hydrolyzable silyl group and an epoxy group in the copolymer (i) or the like. . Here, as the hydrolyzable silyl group, trimethoxysilyl group, methyldimethoxysilyl group, ethyldimethoxysilyl group, dimethylmethoxysilyl group, diethylmethoxysilyl group, triethoxysilyl group, methyldiethoxysilyl group, dimethylethoxycisyl group Group, alkoxysilyl group such as tripropoxysilyl group, halosilyl group such as trichlorosilyl group, dimethylchlorosilyl group, tribromosilyl group and triiodosilyl group can be exemplified, and the number of hydrolyzable silyl groups is 1-2. Can be exemplified. The number of amino groups contained in the aminosilane compound (ii) used in the present invention may be 1 to 3, and is preferably a diaminosilane compound having two amino groups. The aminosilane compound of the present invention preferably has 5 to 25 carbon atoms.

（ただし、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、ＹはＮＨ_２−又はＮＨ_２−Ａ−ＮＨ−を示し、Ｒ^６、及びＲ^７は独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）に表されるアミノアルコキシシラン（ｉｉａ）である。 The aminosilane compound (ii) used in the present invention is preferably the following general formula (III)

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ independently represent carbon numbers. 1 to 3 alkyl group, and A represents an alkylene group having 2 to 5 carbon atoms).

In the general formula (III), examples of R ⁶ and R ⁷ include a methyl group, an ethyl group, and a propyl group. In the general formula (III), the value of r is preferably 3 to 4, and the value of s is preferably 0 to 1. In the general formula (IV), the alkylene group is a substituted or unsubstituted alkylene group, which may be linear or branched. In the general formula (III), Y represents NH ₂ —, NH ₂ — (CH ₂ ) ₂ —NH—, NH ₂ — (CH ₂ ) ₃ —NH—, NH ₂ — (CH ₂ ) ₄ —NH. _{-, NH 2 - (CH 2} ) 5 -NH- and can be exemplified.

  Examples of the aminoalkoxysilane (ia) represented by the general formula (III) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyldimethylmethoxysilane. 3-aminopropylethyldiethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiethylmethoxysilane, 3-aminopropylethyldimethoxysilane 3-aminopropyltripropoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutyldimethylmethoxy Silane, 4-aminobutylethyldiethoxysilane, 4-aminobutyldiethylethoxysilane, 4-aminobutylmethyldiethoxysilane, 4-aminobutyldimethylethoxysilane, 4-aminobutyldiethylmethoxysilane, 4-aminobutylethyldimethoxy Silane, 4-aminobutyltripropoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-amino Ethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethylmethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, N- (2 -Aminoethyl) -3-aminopropyldi Tylethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) -3- Aminopropyldiethylmethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltripropoxysilane, N- (3-aminopropyl) -3 -Aminopropyltrimethoxysilane, N- (3-aminopropyl) -3-aminopropyltriethoxysilane, N- (3-aminopropyl) -3-aminopropylmethyldimethoxysilane, N- (3-aminopropyl)- 3-aminopropyldimethylmethoxysilane, N- (3-aminopropyl) -3-amino Nopropylethyldiethoxysilane, N- (3-aminopropyl) -3-aminopropyldiethylethoxysilane, N- (3-aminopropyl) -3-aminopropylmethyldiethoxysilane, N- (3-aminopropyl) -3-aminopropyldimethylethoxysilane, N- (3-aminopropyl) -3-aminopropyldiethylmethoxysilane, N- (3-aminopropyl) -3-aminopropylethyldimethoxysilane, N- (3-aminopropyl) ) -3-Aminopropyltripropoxysilane. Among these, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane or 3-aminopropyltrimethoxysilane is preferable, and since the reactivity with the epoxy group is particularly high, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane is more preferred.

  In the surface treating agent composition of the present invention, the aminosilane compound (ii) can be exemplified to be contained in an amount of 10 to 100 mol% with respect to the epoxy group in the structural unit (2). Is more preferable, 30 to 100 mol% is more preferable, and 40 to 100 mol% is particularly preferable.

  Examples of the solvent (iii) used in the surface treating agent composition of the present invention include water and / or an organic solvent. Here, the organic solvent is preferably an organic solvent such as methanol, ethanol or isopropyl alcohol.

  In the surface treating agent composition of the present invention, it can be exemplified that the solvent (iii) is contained in an amount of 1 to 99 wt% of the whole, more preferably 5 to 95 wt%, and the remainder is the aforementioned. In the embodiment containing the copolymer (iv) or the like, or the aminosilane compound, the above-mentioned copolymer (i) or the like and the aminosilane compound (ii).

The surface treatment agent composition of the present invention improves the adhesion to a substrate, and in order to improve the durability of the surface treatment performed using the surface treatment agent composition of the present invention, a silane coupling agent is used. You may further include in the range of 10 wt% or less of the whole. Here, examples of the silane coupling agent include dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane.
In addition, the surface treating agent composition of the present invention may further contain a surfactant in the range of 10 wt% or less of the whole in order to improve the dispersion stability of the composition component and the coating property to the substrate. Here, as the surfactant, a cationic surfactant such as a quaternary ammonium salt, an anionic surfactant such as an alkyl sulfate ester salt, an amphoteric surfactant such as an alkylbetaine, a polyoxyethylene alkyl ether, etc. Nonionic surfactants and fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol can be exemplified.

  In the surface treating agent composition of the aspect containing the aminosilane compound (ii) of the present invention, it is preferable to react the epoxy group in the structural unit (2) with the amino group in the aminosilane compound (ii). As a means for causing the reaction to proceed, heating is preferred. Here, as reaction temperature, 25 degreeC or more can be illustrated, 25-100 degreeC is preferable, 30-80 degreeC is more preferable, and 35-70 degreeC is further more preferable. Moreover, 15-30 hours can be illustrated as reaction time.

  The surface treatment agent containing the surface treatment agent composition of the present invention is a treatment for imparting hydrophilicity, antifouling property, self-cleaning property of contamination, antifogging property, quick drying property such as water, and antistatic property to the substrate surface. Although it can be used, it is particularly suitable for the treatment for imparting hydrophilicity to the substrate surface.

  The substrate that can be surface-treated with the surface treating agent composition of the present invention is not particularly limited as long as it is an inorganic substance that reacts with a hydrolyzable silyl group to form a bond, and the shape thereof is not limited. Examples thereof include a substrate made of a metal such as iron, aluminum, copper, silver, and gold, glass, plastic, or ceramic, a fiber, a cloth, a film, a fine particle, or a coating layer. Among them, a glass substrate, for example, a glass cloth or a slide glass is preferable because the surface treatment effect of the surface treatment agent composition of the present invention is large.

When the substrate is treated with the surface treatment agent composition of the present invention, it is preferable to use the treatment liquid obtained by mixing the surface treatment agent composition of the present invention and an acid and leaving it to stand. The acid is not particularly limited as long as it is an acid capable of hydrolyzing a hydrolyzable silyl group such as an alkoxysilyl group or a halosilyl group, but is preferably an acid having a pKa of 5.0 at most. Hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, trichloroacetic acid, amidosulfuric acid, glycolic acid, acetic acid and the like can be used.
Here, it is preferable that 1-20 wt% of solid content of the surface treating agent composition of this invention is contained in a process liquid, and it is more preferable that 3-10 wt% is contained. Moreover, it is preferable that the pH of a process liquid is 1.0-6.0, it is more preferable that it is 2.0-5.0, and it is further more preferable that it is 2.5-4.0. In addition, pH shall be measured with a pH meter (made by HORIBA) under room temperature conditions (23 ± 5 ° C.).

In the surface treatment method of the present invention, the surface treatment agent composition of the present invention is applied to the substrate and dried.
Examples of the method for applying the surface treating agent composition to the substrate include flow coating (dipping method), spin coating and the like. For example, in the case of flow coating, it can be carried out by immersing the substrate in the treatment liquid for 3 to 60 seconds, preferably 5 to 30 seconds.
After applying the surface treatment agent composition to the substrate, the surface treatment agent composition can be cured by heating and drying. Here, examples of the heating and drying conditions include heating and drying at 60 to 200 ° C., preferably 80 to 160 ° C., for example, for 5 to 120 minutes.
The solvent in the surface treatment agent composition of the present invention is removed by heating and drying, and the hydrolyzable silyl group of the copolymer contained in the surface treatment agent composition of the present invention reacts with the substrate surface. , And a hydrophilic coating layer is formed on the substrate surface.

  The surface treatment substrate of the present invention comprises a copolymer (iv) containing the structural unit (1) and the structural unit (4) contained in the surface treating agent composition of the present invention, or the structural unit (1) and the structural unit (4 ) And a coating layer containing a copolymer (iva) containing the structural unit (2) on the surface. The coating layer is firmly bonded to the surface of the base material by bonding the hydrolyzable silyl group in the copolymer (iv) and the base material, which is presumed to have durability, particularly water resistance. . Further, it is estimated that the coating layer has excellent hydrophilicity due to the quaternary amino group in the copolymer (iv).

  The copolymer (iv) of the present invention has the following general formula (I) as a structural unit.

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４は独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）で表される、通常は（メタ）アクリロイルアミノアルキル４級アンモニウム塩モノマーから導かれる構成単位（１）を少なくとも１種、及び、下記一般式（ＩＶ）

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} are independently an alkyl group having 1 to 3 carbon ^{atoms, X a-} Represents a counter ion, and a represents a valence of the counter ion), and is usually at least one structural unit (1) derived from a (meth) acryloylaminoalkyl quaternary ammonium salt monomer, and The following general formula (IV)

（ただし、ｑは１〜３の整数を示し、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、Ｚは−ＮＨ−、−ＮＨ−Ａ−ＮＨ−又は−ＮＨ（Ａ−ＮＨ_２）−を示し、Ｒ^５は水素原子又はメチル基を示し、Ｒ^６、及びＲ^７は独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）で表される、（メタ）アクリル酸アミノアルコキシシランモノマーから導かれる場合がある構成単位（４）を少なくとも１種、含む共重合体である。

(Where q represents an integer of 1 to 3, r represents an integer of 2 to 5, s represents an integer of 0 to 2, and Z represents —NH—, —NH—A—NH— or —NH ( a-NH ₂₎ - indicates, ^{R 5} represents a hydrogen atom or a methyl group, ^{R 6,} and ^{R 7} independently represent an alkyl group having 1 to 3 carbon atoms, a is an alkylene group having 2 to 5 carbon atoms And a copolymer containing at least one structural unit (4) which may be derived from a (meth) acrylic acid aminoalkoxysilane monomer.

The structural unit (1) which is a structural unit of the copolymer (iv) of the present invention is usually derived from a (meth) acryloylaminoalkyl quaternary ammonium salt monomer (1 ′). In the structural unit (1), R ¹ is a hydrogen atom or a methyl group. In the general formula (I) showing the structure of the structural unit (1), examples of R ² , R ³ , and R ⁴ include a methyl group, an ethyl group, and a propyl group. In the general formula (I), examples of X ^a- include chlorine ion, bromine ion, iodine ion, carboxylate ion, dicarboxylate ion, phosphate ion, alkylsulfonate ion, and sulfamate ion, but imparting hydrophilicity. From this point of view, chlorine ions are preferable. In the said general formula (I), as a value of p, 2-5 are preferable and 3-4 are more preferable.

In the structural unit (4) which is a structural unit of the copolymer (iv) of the present invention, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ and R ⁷ are each a methyl group, an ethyl group, or a propyl group. It can be illustrated. In the general formula (IV) representing the structure of the structural unit (4), the value of q is preferably 1 to 2, the value of r is preferably 3 to 4, and the value of s is preferably 0 to 1. . In the general formula (IV), the alkylene group is a substituted or unsubstituted alkylene group, which may be linear or branched. In the general formula (IV), as Z, —NH—, —NH— (CH ₂ ) ₂ —NH—, —NH— (CH ₂ ) ₃ —NH—, —NH— (CH ₂ ) ₄ —NH _{-, - NH- (CH 2)} 5 -NH -, - NH (CH 2 -CH 2 -NH 2) -, - NH (CH 2 - (CH 2) 2 -NH 2) -, - NH (CH 2 _{- (CH 2) 3 -NH 2} ) -, - NH (CH 2 - (CH 2) 4 -NH 2) - can be exemplified.

As long as the copolymer (iv) of the present invention does not impair the effect of the surface treatment agent composition containing the copolymer of the present invention, particularly the effect of imparting hydrophilicity, (I), (3) Monomers other than IV) may be included. Examples of the third component include a structural unit derived from a monomer obtained by reacting a reagent with an unreacted residual monomer or a reactive group contained in the residual monomer when the target compound is produced.
Here, as the structural unit derived from the residual monomer, the following general formula (II)

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表されるグリシジル（メタ）アクリレートモノマー由来の構成単位（２）が挙げられる。ここで、Ｒ^５は水素原子又はメチル基であり、ｑの値としては、１〜２が好ましい。
この構成単位（２）と反応させる試薬としては、加水分解性シリル基又は親水性基を有する求核剤を例示できる。
また、本発明の第３成分を有する共重合体（ｉｖａ）は、構成単位（１）及び構成単位（４）に加えて、さらに構成単位（２）を少なくとも１種、含む共重合体である。

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
The structural unit (2) derived from the glycidyl (meth) acrylate monomer represented by these is mentioned. Wherein, R ⁵ is a hydrogen atom or a methyl group, as the value of q, 1 to 2 is preferred.
Examples of the reagent to be reacted with the structural unit (2) include a nucleophile having a hydrolyzable silyl group or a hydrophilic group.
The copolymer (iva) having the third component of the present invention is a copolymer further containing at least one structural unit (2) in addition to the structural unit (1) and the structural unit (4). .

The molar ratio of the structural unit (1) and the structural unit (4) in the copolymer (iv) of the present invention, and the molar ratio of each component in the copolymer (iva) further comprising the structural unit (2) are ( As a ratio of 1) / (4) or (1) / [(4) + (2)], a range of 99/1 to 10/90 can be exemplified, and a range of 99/1 to 50/50 is preferable. The range of / 5 to 60/40 is more preferable, the range of 90/10 to 65/35 is more preferable, the range of 85/15 to 65/35 is particularly preferable, and the range of 80/20 to 65/35 is most preferable. . In addition, although the molar ratio of the structural unit in a copolymer can also be measured directly from a polymer, it can be accurately estimated from the molar ratio of each monomer during the polymerization reaction.
In the copolymer (iva), the molar ratio of the structural units (4) and (2) can be exemplified by the range of 99/1 to 10/90 as the ratio of (4) / (2). The range of -20/80 is preferable, 99 / 1-30 / 70 is more preferable, and the range of 99 / 1-40 / 60 is further more preferable. The structural unit (4) is produced by the reaction of the amino group of aminoalkoxysilane with the epoxy group in the structural unit (2). Since this reaction is quantitative, the structural unit (4) / The value of (2), that is, the introduction rate of the aminosilane compound into the epoxy group is determined by the molar ratio of the structural unit (2) and aminoalkoxysilane at the time of reaction.
Since the ratio of the structural unit (1) is not too low, the surface treating agent composition containing this copolymer has an effect of imparting hydrophilicity. Moreover, since the ratio of a structural unit (4) is not too low, the hydrophilic surface obtained by processing with the surface treating agent composition containing this copolymer has water resistance.

  The average degree of polymerization of the copolymer (iv) or copolymer (iva) of the present invention is converted to polyethylene glycol by gel permeation chromatography (GPC) method of the copolymer (i) used as a raw material of these copolymers. And a weighted average molecular weight of the structural unit calculated from the molecular weight and molar ratio of each structural unit of the copolymer (i), and is preferably in the range of 10 to 10,000, The range of -8000 is more preferable, the range of 50-5000 is further more preferable, the range of 80-3000 is especially preferable, and the range of 100-2000 is the most preferable.

  The copolymer of the present invention is represented by the following general formula (V) in a solvent in the presence of a radical polymerization initiator.

（ただし、ｐは１〜６の整数を示し、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２、Ｒ^３、及びＲ^４は独立に炭素数１〜３のアルキル基を示し、Ｘ^ａ−はカウンターイオンを示し、ａは該カウンターイオンの価数を示す）で表される（メタ）アクリロイルアミノアルキル４級アンモニウム塩（１’）と、下記一般式（ＶＩ）

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} are independently an alkyl group having 1 to 3 carbon ^{atoms, X a-} Represents a counter ion, and a represents a valence of the counter ion), and a (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) represented by the following general formula (VI):

（ただし、Ｒ^５は水素原子又はメチル基を示し、ｑは１〜３の整数を示す）
で表されるグリシジル（メタ）アクリレート（２’）とを共重合させる工程（ア）と、前記工程（ア）の重合前、重合中又は重合後の反応液と、下記一般式（ＩＩＩ）

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A step (a) of copolymerizing glycidyl (meth) acrylate (2 ′) represented by formula (1), a reaction solution before, during or after the polymerization of the step (a), and the following general formula (III)

（ただし、ｒは２〜５の整数を示し、ｓは０〜２の整数を示し、ＹはＮＨ_２−又はＮＨ_２−Ａ−ＮＨ−を示し、Ｒ^６、及びＲ^７はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ａは炭素数２〜５のアルキレン基を示す）で表されるアミノアルコキシシラン（ｉｉａ）とを混合し、前記グリシジル（メタ）アクリレート（２’）及び／又は前記工程（ア）で得られた共重合体中のエポキシ基と前記アミノアルコキシシラン（ｉｉａ）中のアミノ基とを反応させて共有結合を形成させることで製造可能である。

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ are each independently carbon. And an aminoalkoxysilane (ia) represented by formula (1-3), wherein A represents an alkylene group having 2 to 5 carbon atoms), and the glycidyl (meth) acrylate (2 ′) and / or Alternatively, it can be produced by reacting the epoxy group in the copolymer obtained in the step (a) with the amino group in the aminoalkoxysilane (ia) to form a covalent bond.

In the (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) which is a raw material used in the production method of the present invention, R ¹ is a hydrogen atom or a methyl group. In the general formula (V), examples of R ² , R ³ , and R ⁴ include a methyl group, an ethyl group, and a propyl group. In the general formula (V), examples of X ^a- include chlorine ion, bromine ion, iodine ion, carboxylate ion, dicarboxylate ion, phosphate ion, alkylsulfonate ion, and sulfamate ion, but imparting hydrophilicity. From this point of view, chlorine ions are preferable. In the said general formula (V), as a value of p, 2-5 are preferable and 3-4 are more preferable.

  The (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) that is a raw material of the production method of the present invention includes (meth) acryloylaminoethyltrimethylammonium chloride, (meth) acryloylaminoethyltrimethylammonium bromide, (meth) acryloyl. Aminoethyltrimethylammonium iodide, (meth) acryloylaminoethyltrimethylammonium methylsulfate, (meth) acryloylaminoethyltrimethylammonium ethylsulfate, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyltriethylammonium bromide, (Meth) acryloylaminoethyl triethylammonium iodide, (meth) acryloylaminoethylto Ethylammonium methylsulfate, (meth) acryloylaminoethyltriethylammonium ethylsulfate, (meth) acryloylaminoethyltripropylammonium chloride, (meth) acryloylaminoethyltripropylammonium bromide, (meth) acryloylaminoethyltripropylammonium iodide, (Meth) acryloylaminoethyltripropylammonium methylsulfate, (meth) acryloylaminoethyltripropylammonium ethylsulfate, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium bromide, (meth) acryloylaminopropyl Trimethylammonium iodide, (medium ) Acryloylaminopropyltrimethylammonium methyl sulfate, (meth) acryloylaminopropyltrimethylammonium ethyl sulfate, (meth) acryloylaminopropyltriethylammonium chloride, (meth) acryloylaminopropyltriethylammonium bromide, (meth) acryloylaminopropyltriethylammonium iodide , (Meth) acryloylaminopropyltriethylammonium methyl sulfate, (meth) acryloylaminopropyltriethylammonium ethyl sulfate, (meth) acryloylaminopropyltripropylammonium chloride, (meth) acryloylaminopropyltripropylammonium bromide, (meth) acryloylamino Propyl Tripropylammonium iodide, (meth) acryloylaminopropyltripropylammonium methyl sulfate, (meth) acryloylaminopropyltripropylammonium ethyl sulfate, (meth) acryloylaminobutyltrimethylammonium chloride, (meth) acryloylaminobutyltrimethylammonium bromide, (Meth) acryloylaminobutyltrimethylammonium iodide, (meth) acryloylaminobutyltrimethylammonium methyl sulfate, (meth) acryloylaminobutyltrimethylammonium ethyl sulfate, (meth) acryloylaminobutyltriethylammonium chloride, (meth) acryloylaminobutyltriethyl Ammonium bromide, (meth) Acryloylaminobutyltriethylammonium iodide, (meth) acryloylaminobutyltriethylammonium methyl sulfate, (meth) acryloylaminobutyltriethylammonium ethyl sulfate, (meth) acryloylaminobutyltripropylammonium chloride, (meth) acryloylaminobutyltripropyl Examples thereof include ammonium bromide, (meth) acryloylaminobutyltripropylammonium iodide, (meth) acryloylaminobutyltripropylammonium methyl sulfate, and (meth) acryloylaminobutyltripropylammonium ethyl sulfate. Among these, methacryloylaminopropyltrimethylammonium chloride is preferable from the viewpoint of availability.

In glycidyl (meth) acrylate (2 ′) which is a raw material used in the production method of the present invention, R ⁵ is a hydrogen atom or a methyl group, and the value of q is preferably 1 or 2.

  Examples of the glycidyl (meth) acrylate (2 ') used as the raw material for the production method of the present invention include glycidyl (meth) acrylate, glycidylmethyl (meth) acrylate, and glycidylethyl (meth) acrylate. Among these, glycidyl methacrylate is preferable from the viewpoint of availability.

In aminoalkoxysilane (ia), which is a raw material used in the production method of the present invention, examples of R ⁶ and R ⁷ include a methyl group, an ethyl group, and a propyl group. In the general formula (III), the value of r is preferably 3 to 4, and the value of s is preferably 0 to 1. In the general formula (IV), the alkylene group is a substituted or unsubstituted alkylene group, which may be linear or branched. In the general formula (III), Y represents NH ₂ —, NH ₂ — (CH ₂ ) ₂ —NH—, NH ₂ — (CH ₂ ) ₃ —NH—, NH ₂ — (CH ₂ ) ₄ —NH. _{-, NH 2 - (CH 2} ) 5 -NH- and can be exemplified.

  As the aminoalkoxysilane (ia) used as the raw material for the production method of the present invention, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane 3-aminopropylethyldiethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiethylmethoxysilane, 3-aminopropylethyldimethoxysilane , 3-aminopropyltripropoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutyldimethyl Toxisilane, 4-aminobutylethyldiethoxysilane, 4-aminobutyldiethylethoxysilane, 4-aminobutylmethyldiethoxysilane, 4-aminobutyldimethylethoxysilane, 4-aminobutyldiethylmethoxysilane, 4-aminobutylethyldimethoxy Silane, 4-aminobutyltripropoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-amino Ethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethylmethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, N- (2 -Aminoethyl) -3-aminopro Rudiethylethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) -3 -Aminopropyldiethylmethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltripropoxysilane, N- (3-aminopropyl)- 3-aminopropyltrimethoxysilane, N- (3-aminopropyl) -3-aminopropyltriethoxysilane, N- (3-aminopropyl) -3-aminopropylmethyldimethoxysilane, N- (3-aminopropyl) -3-aminopropyldimethylmethoxysilane, N- (3-aminopropyl) -3 -Aminopropylethyldiethoxysilane, N- (3-aminopropyl) -3-aminopropyldiethylethoxysilane, N- (3-aminopropyl) -3-aminopropylmethyldiethoxysilane, N- (3-aminopropyl) ) -3-aminopropyldimethylethoxysilane, N- (3-aminopropyl) -3-aminopropyldiethylmethoxysilane, N- (3-aminopropyl) -3-aminopropylethyldimethoxysilane, N- (3-amino) (Propyl) -3-aminopropyltripropoxysilane. Among these, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane or 3-aminopropyltrimethoxysilane is preferable, and N- (2-aminoethyl) -3 is highly reactive with an epoxy group. -Aminopropyltrimethoxysilane is more preferred.

  Examples of the radical polymerization initiator used in the production method of the present invention include organic peroxides such as tert-butyl hydroperoxide and cumene hydroperoxide, 2,2′-azobisisobutyronitrile, dimethyl 2,2 Examples thereof include aliphatic azo compounds such as' -azobis (2-methylpropionate), inorganic peroxides such as ammonium persulfate and potassium persulfate, and nitrates such as ammonium nitrate and potassium nitrate. Moreover, the gas containing oxygen, such as air, a radiation, an ultraviolet-ray, and visible light can be illustrated.

  Examples of the solvent used in the production method of the present invention include organic solvents. Here, as the organic solvent, lower alcohols such as ethanol, methanol and isopropyl alcohol are preferable.

  In the production method of the present invention, (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) and glycidyl (meth) acrylate (2 ′) are 99/1 to 10/90 as a molar ratio of 1 ′ / 2 ′. The range of 99/1 to 50/50 is preferable, the range of 95/5 to 60/40 is more preferable, the range of 90/10 to 65/35 is still more preferable, and 85 The range of / 15 to 65/35 is particularly preferred, and the range of 80/20 to 65/35 is most preferred.

  In the production method of the present invention, the monomer concentration of (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) and glycidyl (meth) acrylate (2 ′) in the reaction solution is exemplified by 10 to 90 wt%. 25 to 75 wt% is more preferable, 35 to 65 wt% is more preferable, and 35 to 55 wt% is particularly preferable. When the monomer concentration is 25 to 75 wt%, the base material can be subjected to a hydrophilic treatment excellent in water resistance by using the obtained copolymer. When the monomer concentration is 35 to 65 wt%, a hydrophilic treatment with particularly excellent water resistance can be applied to the substrate. On the other hand, from the viewpoint of production of the copolymer, the yield may be low when the monomer concentration is lower than 35%. Moreover, when the monomer concentration is higher than 55%, the viscosity of the reaction solution may increase during the polymerization reaction, and it may be necessary to dilute the reaction solution with a solvent during the polymerization reaction.

  In the production method of the present invention, the use amount and use method of the polymerization initiator are not particularly limited, but it is exemplified that 2 to 10 mol% of the polymerization initiator is added to the reaction solution with respect to the total molar amount of all monomers. it can.

  In the production method of the present invention, a radical polymerization initiator is added to a reaction solution containing (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′), glycidyl (meth) acrylate (2 ′) and a solvent, at room temperature or The copolymerization reaction is carried out by adding an appropriate stirring operation under heating conditions. The polymerization temperature is preferably -100 to 80 ° C. The polymerization time is preferably 1 to 100 hours.

  In the production method of the present invention, the use amount of the aminoalkoxysilane (ia) can be 10 to 200 mol% with respect to the epoxy group in the glycidyl (meth) acrylate (2 '), and 20 to 100 mol% can be exemplified. Preferably, 30-100 mol% is more preferable, and 40-100 mol% is further more preferable.

In the production method of the present invention, the aminoalkoxysilane (iii) is a (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′), glycidyl (meth) acrylate (2 ′), and before or after polymerization. / Or mixed with a reaction solution containing these copolymers. Especially, it is preferable to mix with the reaction liquid after superposition | polymerization since a reaction liquid becomes low viscosity compared with the case where it mixes before superposition | polymerization or during superposition | polymerization.
As another embodiment of the production method of the present invention, a copolymer (i) synthesized using (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) and glycidyl (meth) acrylate (2 ′) as raw materials is started. As a substance, aminoalkoxysilane (iii) may be mixed in a solution containing this copolymer.

In the production method of the present invention, after the aminoalkoxysilane (ia) and the reaction liquid are mixed, the amino group in the aminoalkoxysilane (ia) and the glycidyl (meth) acrylate (2 ′) and / or the copolymer To form a covalent bond.
When the reaction solution before or during polymerization in the step (a) of the production method of the present invention and aminoalkoxysilane (ia) are mixed, for example, at a reaction temperature of 25 to 80 ° C., 15 to 30 hours. The reaction and the copolymerization reaction of the epoxy group and the amino group can be caused to proceed at the same time by carrying out the reaction.
On the other hand, when the reaction liquid after polymerization in the step (a) and aminoalkoxysilane (ia) are mixed, the mixture is heated after being mixed with the epoxy group in aminoalkoxysilane (ia). The reaction with the amino group in the polymer can proceed. Here, as reaction temperature, 25 degreeC or more can be illustrated, 25-100 degreeC is preferable, 30-80 degreeC is more preferable, and 35-70 degreeC is further more preferable. Moreover, 15-30 hours can be illustrated as reaction time.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited at all by these Examples.

  First, the measurement method of the contact angle of the glass which received the average degree of polymerization of the reaction material and surface treatment which were obtained in the Example and the comparative example is shown.

[Average polymerization degree]
The average degree of polymerization of the reactant is obtained by dividing the weight average molecular weight of the reactant by the molecular weight of each constituent unit constituting the copolymer as the reactant and the weighted average molecular weight of the constituent unit calculated from the molar ratio thereof. I asked for it.
Here, the weight average molecular weight (Mw) of the reaction product was measured by gel permeation chromatography (GPC method) using Hitachi L-6000 type high performance liquid chromatograph. The eluent flow path pump is Hitachi L-6000, the detector is a Shodex RI-101 differential refractive index detector, and the column is a water gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS of Shodex Asahi Pack. -620HQ (exclusion limit molecular weight 2 million) connected in series was used. Samples were prepared with an eluent to a concentration of 0.5 g / 100 ml, and 20 μl was used. As an eluent, a 0.4 mol / liter sodium chloride aqueous solution was used. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve is obtained using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard substance, and the weight average molecular weight of the copolymer ( Mw) was determined.

[Contact angle]
The contact angle was measured by using DM-301 manufactured by Kyowa Interface Science Co., Ltd. with respect to 1 μL of water on the dried glass surface.
In general, the smaller the contact angle, the higher the hydrophilicity of the substrate surface.

[Example 1]
(I) Synthesis of copolymer of methacryloylaminopropyltrimethylammonium chloride (75 mol%) and glycidyl methacrylate (25%) First, methacryloylamino was added to a 100 mL three-necked flask equipped with a thermometer, stirrer and condenser. 20.27 g (corresponding to MAPTAC 0.09 mol) of a 98% solution of propyltrimethylammonium chloride (manufactured by Wako Chemical Co., Ltd .; hereinafter sometimes referred to as MAPTAC), glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.); Hereinafter, 4.26 g (sometimes referred to as GMA) of 4.26 g (corresponding to 0.03 mol of GMA) and 35.79 g of ethanol (corresponding to adjustment of monomer concentration of 40 wt%) are added and heated to 60 ° C. in a water bath. did.
Then, a radical polymerization initiator to obtain a monomer concentration of 40 wt% solution of dimethyl 2,2 ^'- azobis (2-methylpropionate) (Wako Pure Chemical Industries, Ltd., hereinafter sometimes to be referred to as V-601 ) 1.24 g (corresponding to 4 mol% relative to the monomer) was added and polymerized to obtain a copolymer of MAPTAC and GMA (hereinafter sometimes referred to as P (MAPTAC / GMA)). Since the obtained P (MAPTAC / GMA) solution was highly viscous, it was diluted by adding 20.1 g of ethanol.
In addition, the obtained P (MAPTAC / GMA) solution had a solid content concentration of 30 wt%, and the reprecipitation yield in an acetone solvent was 95%. The obtained P (MAPTAC / GMA) had a weight average molecular weight of 99000 and an average degree of polymerization of 490.
In the IR spectrum (FIG. 1) of the reprecipitate, absorption near 900 cm ⁻¹ derived from an epoxy group was observed, confirming that the copolymerization reaction of MAPTAC and GMA was in progress. In addition, due to the nature of this reaction, it was estimated that the copolymerization ratio almost coincided with the monomer charge.

(Ii) Synthesis of reaction product of P (MAPTAC / GMA) and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane First, in a 100 mL three-necked flask equipped with a thermometer, a stirrer, and a condenser tube, 21.17 g of the P (MAPTAC / GMA) solution obtained in (i) and 31.72 g of ethanol were added and mixed at room temperature.
Next, 1.87 g of a 95% solution of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; hereinafter sometimes referred to as AEAPTMS) was added to the resulting liquid. P (MAPTAC / GMA) is added, and the reaction is carried out at 40 ° C. for 24 hours, and a reaction product of P (MAPTAC / GMA) and AEAPTMS (hereinafter referred to as P (MAPTAC / GMA)). -It may be described as -AEAPTMS).
The obtained P (MAPTAC / GMA) -AEAPTMS solution had a solid content concentration of 16 wt%.
The movement of the TLC spot was observed in the solution after the completion of the reaction, and the absorption of 1064 cm ⁻¹ derived from Si—O—C was observed from the IR spectrum (FIG. 2) of the reprecipitation with acetone solvent. From this, it was confirmed that the reaction was progressing.

(Iii) Preparation of surface-treated glass First, the solid content concentration of the P (MAPTAC / GMA) -AEAPTMS solution obtained in (ii) is 5.0 wt%, 35% concentrated hydrochloric acid (manufactured by Nacalai Tesque) 2.5 wt% %, Water was 92.5 wt%, water, hydrochloric acid, and P (MAPTAC / GMA) -AEAPTMS solution were mixed in this order, and allowed to stand at room temperature for 1 hour to prepare a glass treatment solution. The pH of the glass treatment solution was 2.6 as measured with a pH meter (manufactured by HORIBA) under room temperature conditions (23 ± 5 ° C.).
Next, the slide glass (manufactured by AS ONE Co., Ltd.) was dipped in a glass treatment solution for 10 seconds, pulled up, heated at 130 ° C. for 15 minutes and dried, and the slide glass was coated with a surface treatment agent.

[Example 2]
Example 1 except that 0.94 g of AEAPTMS 95% solution (corresponding to 50 mol% with respect to GMA in P (MAPTAC / GMA)) was used instead of 1.87 g of AEAPTMS 95% solution in Example (ii). A surface-treated glass was prepared in the same manner as in 1.
The obtained P (MAPTAC / GMA) -AEAPTMS solution had a solid content of 16%.

[Example 3]
In Example 1 (i), 13.51 g of MAPTAC 98% solution (corresponding to MAPTAC 0.06 mol) was used instead of 20.27 g of MAPTAC 98% solution, and 2.84 g of GMA 100% solution was used instead of 4.26 g of GMA 100% solution. (GMA equivalent to 0.02 mol), instead of ethanol 35.79 g, ethanol 37.27 g (monomer concentration 30 wt% adjustment equivalent) was used. Further, the obtained P (MAPTAC / GMA) solution was not diluted.
In Example (ii), in place of 21.17 g of P (MAPTAC / GMA) solution and 31.72 g of ethanol, 17.73 g of P (MAPTAC / GMA) solution and 21.93 g of ethanol were used. Further, instead of 1.87 g of AEAPTMS 95% solution, 1.41 g of AEAPTMS 95% solution (corresponding to 100 mol% with respect to GMA in P (MAPTAC / GMA)) was used.
Otherwise, a surface-treated glass was prepared in the same manner as in Example 1.
In addition, the obtained P (MAPTAC / GMA) solution had a solid content concentration of 27 wt%, and the reprecipitation yield in the acetone solvent was 93%. The obtained P (MAPTAC / GMA) had a weight average molecular weight of 30,000 and an average degree of polymerization of 150.
Moreover, the obtained P (MAPTAC / GMA) -AEAPTMS solution had a solid content of 14 wt%.

[Example 4]
In Example 1 (i), 315.68 g of ethanol (monomer concentration adjusted to 60 wt%) was used instead of 35.79 g of ethanol. In addition, since the viscosity of the reaction solution is increased, 20.1 g of ethanol was added in portions during the copolymerization reaction and diluted, and the resulting P (MAPTAC / GMA) solution was further diluted with 20.1 g of ethanol. .
In Example (ii), 20.05 g of P (MAPTAC / GMA) solution and 32.84 g of ethanol were used instead of 21.17 g of P (MAPTAC / GMA) solution and 31.72 g of ethanol. Further, 1.87 g of AEAPTMS 95% solution (corresponding to 100 mol% with respect to GMA in P (MAPTAC / GMA)) was used.
Otherwise, a surface-treated glass was prepared in the same manner as in Example 1.
In addition, the obtained P (MAPTAC / GMA) solution had a solid content concentration of 32 wt%, and the reprecipitation yield in the acetone solvent was 93%. The obtained P (MAPTAC / GMA) had a weight average molecular weight of 320,000 and an average degree of polymerization of 1600.
Further, the obtained P (MAPTAC / GMA) -AEAPTMS solution had a solid content concentration of 15 wt%.

[Example 5]
In Example 1 (i), instead of 20.27 g of the MAPTAC 98% solution, 18.02 g of MAPTAC 98% solution (corresponding to MAPTAC 0.08 mol) was used, and instead of 4.26 g of the GMA 100% solution, 5.69 g of the GMA 100% solution. (GMA equivalent to 0.04 mol), ethanol 34.66 g (monomer concentration 40% adjustment equivalent) was used instead of 35.79 g of ethanol. Further, the obtained P (MAPTAC / GMA) solution was not diluted. V601 used was 1.86 g (corresponding to 6 mol% with respect to the monomer).
In Example 1 (ii), instead of 21.17 g of P (MAPTAC / GMA) solution and 31.72 g of ethanol, 5.61 g of P (MAPTAC / GMA) solution and 15.47 g of ethanol were used. Further, 0.94 g of AEAPTMS 95% solution (corresponding to 100 mol% with respect to GMA in P (MAPTAC / GMA)) was used instead of 1.87 g of AEAPTMS 95% solution.
Otherwise, a surface-treated glass was prepared in the same manner as in Example 1.
The obtained P (MAPTAC / GMA) solution had a solid content of 43% and a reprecipitation yield in an acetone solvent of 95%. The obtained P (MAPTAC / GMA) had a weight average molecular weight of 52,000 and an average degree of polymerization of 270.
The obtained P (MAPTAC / GMA) -AEAPTMS solution had a solid content of 17%.

[Example 6]
In Example 1 (i), 20.27 g of MAPTAC 98% solution (corresponding to MAPTAC 0.09 mol) was used, and instead of 4.26 g of GMA 100% solution, 1.42 g of GMA 100% solution (corresponding to 0.01 mol of GMA), Instead of 35.79 g of ethanol, 31.53 g of ethanol (monomer concentration adjusted to 40%) was used. Further, the obtained P (MAPTAC / GMA) solution was diluted with 27.6 g of ethanol.
In Example (ii), instead of 21.17 g of P (MAPTAC / GMA) solution and 31.72 g of ethanol, 24.13 g of P (MAPTAC / GMA) solution and 29.91 g of ethanol were used. Further, instead of 0.935 g of AEAPTMS 95% solution, 0.82 g of AEAPTMS 95% solution (corresponding to 100 mol% with respect to GMA in P (MAPTAC / GMA)) was used.
Otherwise, a surface-treated glass was prepared in the same manner as in Example 1.
The obtained P (MAPTAC / GMA) had a solid concentration of 31%, and the reprecipitation yield in an acetone solvent was 105%. The obtained P (MAPTAC / GMA) had a weight average molecular weight of 99000 and an average degree of polymerization of 470.
The obtained P (MAPTAC / GMA) -AEAPTMS had a solid content of 15%.

[Example 7]
In (ii) of Example 1, instead of 1.87 g of the AEAPTMS 95% solution, 3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter sometimes referred to as APTMS) 97% solution A surface-treated glass was prepared in the same manner as in Example 1 except that 48 g (corresponding to 100 mol% with respect to GMA in P (MAPTAC / GMA)) was used.
The obtained P (MAPTAC / GMA) -APTMS had a solid content concentration of 14%.
The movement of the TLC spot was observed in the solution after the completion of the reaction, and the absorption of 1064 cm ⁻¹ derived from Si—O—C was observed from the IR spectrum (FIG. 3) of the reprecipitate in the acetone solvent. From this, it was confirmed that the reaction was progressing.

[Example 8]
In (ii) of Example 1, instead of 1.87 g of the AEAPTMS 95% solution, 3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter sometimes referred to as APTMS) 97% solution Surface-treated glass was prepared in the same manner as in Example 1 except that 74 g (corresponding to 50 mol% with respect to GMA in P (MAPTAC / GMA)) was used.
The obtained P (MAPTAC / GMA) -APTMS had a solid content concentration of 15%.

[Comparative Example 1]
In (iii) of Example 1, in place of the P (MAPTAC / GMA) -AEAPTMS solution, the P (MAPTAC / GMA) solution obtained in the same manner as in (i) of Example 1 was used for the surface-treated glass. Created.

[Comparative Example 2]
Polyallylamine (manufactured by Nittobo Co., Ltd .; polyallylamine ethanol solution having a concentration of 20.6%, weight average molecular weight 3000; hereinafter, may be referred to as PAA, and allylamine may also be referred to as AA) 27. 72 g and 84.11 g of ethanol were added, and the mixture was heated to 30 ° C. using a water bath with stirring.
Next, 2.36 g (10 mol% with respect to the amino group of PAA) of 3-glycidpropylpropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; hereinafter sometimes referred to as GPTMS) was added to the resulting liquid. It was dripped. After completion of the dropwise addition, the reaction is carried out at 30 ° C. for 24 hours, whereby a polymer compound containing GPMS (10 mol%) and AA (90%) having a solid content concentration of 6% (sometimes referred to as P (GPTMS / AA)). Got.
Subsequently, in (iii) of Example 1, it replaced with the P (MAPTAC / GMA) -AEAPTMS solution, and produced the surface treatment glass using the obtained P (GPTMS / AA) solution.
Here, P (GPTMS / AA) is a polymer having particularly excellent hydrophilicity because it has a primary amino group having a particularly high hydrophilicity among hydrophilic groups among various hydrophilic polymers according to the prior art. Presumed to be. Therefore, in this specification, this P (GPTMS / AA) was used as a comparative example.

[Hydrophilicity and water resistance evaluation test]
In the surface-treated glass obtained in Examples 1 to 8 and Comparative Examples 1 and 2, it was determined whether or not hydrophilicity was imparted to the surface-treated glass by measuring the contact angle of the surface-treated glass when not washed. evaluated.
Next, the surface-treated glass was immersed in water at room temperature (23 ± 5 ° C.) for 2 days. Thereafter, the surface-treated glass was pulled up from the water and the contact angle was measured to evaluate whether the surface treatment applied to the surface-treated glass had water resistance.
In addition, the same evaluation was performed about the untreated slide glass as the comparative example 3.
The evaluation results of hydrophilicity and water resistance are shown in Table 1.

  In Table 1, when the silane compound is AEAPTMS or APTMS, the reactive group mol% is a value relative to the epoxy group of GMA in P (MAPTAC / GMA), and when the silane compound is GPTMS, PAA is It is the value for the amino group it has.

As shown in Table 1, P (MAPTAC / GMA) -AEAPTMS or P (MAPTAC / which is a polymer compound having a hydrophilic group (quaternary amino group) and a hydrolyzable silyl group (alkoxysilyl group) in the side chain. The surface-treated glass of Examples 1 to 8 treated with a surface treatment agent containing GMA) -APTMS showed high hydrophilicity. Furthermore, the surface-treated glass of Examples 1 to 8 is the surface of Comparative Example 1 treated with a surface treatment agent containing P (MAPTAC / GMA), which is a polymer compound having only hydrophilic groups (quaternary amino groups). It showed much higher water resistance than the treated glass.
On the other hand, Comparative Example 2 treated with a surface treating agent containing P (GPTMS / AA), which is a polymer compound having a hydrophilic group (primary amino group) and a hydrolyzable silyl group (alkoxysilyl group) in the side chain. The surface-treated glass did not show water resistance.
Moreover, the untreated slide glass of Comparative Example 3 did not show hydrophilicity and water resistance.

  From these results, it was confirmed that a hydrophilic coating excellent in water resistance can be applied to the substrate using P (MAPTAC / GMA) -AEAPTMS or P (MAPTAC / GMA) -APTMS. Further, P (MAPTAC / GMA) -AEAPTMS or P (MAPTAC / GMA) -APTMS is a polymer compound having a hydrophilic group and a hydrolyzable silyl group in the side chain, in particular, hydrophilicity and water resistance to the substrate. It was confirmed that the application was excellent.

  From comparison of Examples 1-8, P (MAPTAC / GMA) is MAPTAC: GMA = 3: 1, the monomer concentration is 30 to 60%, and the addition amount of AEAPTMS is P (MAPTAC / GMA). On the other hand, it was confirmed that the surface treatment agent containing P (MAPTAC / GMA) -AEAPTMS that is 50 to 100 mol% can impart particularly excellent hydrophilicity and water resistance to the surface-treated glass.

[Evaluation test for hot water resistance]
The surface-treated glass obtained in Examples 1, 3-6 and Comparative Examples 1-2 was immersed in warm water at 50 ° C. for 15 days. Whether or not the surface treatment applied to the surface-treated glass has hot water resistance by raising the surface-treated glass from the water and measuring the contact angle when 5 days and 15 days have passed since the immersion in warm water Was evaluated.
The evaluation results of hydrophilicity and hot water resistance are shown in Table 2.

  In Table 2, mol% for reactive groups is a value relative to the epoxy group of GMA in P (MAPTAC / GMA) when the silane compound is AEAPTMS, and PAA has when the silane compound is GPTMS. Values for amino groups.

  As shown in Table 2, the surface-treated glass treated with the surface treatment agent of the present invention containing a polymer compound having a hydrophilic group (quaternary amino group) and a hydrolyzable silyl group (alkoxysilyl group) in the side chain is It was confirmed that the water resistance was extremely high compared to the comparative example.

  Further, from the comparison of Examples 1, 3, and 4 to 6, when MAPTAC: GMA = 3: 1 in P (MAPTAC / GMA) and the monomer concentration is 40 to 60%, particularly excellent hot water resistance It was confirmed that can be imparted to the surface-treated glass.

By using the surface treating agent composition of the present invention, high hydrophilicity can be imparted to the substrate surface, and the resulting hydrophilized surface has excellent durability, especially water resistance. Along with this, antifouling properties, antifogging properties, and weather resistance can be imparted to the substrate by using the surface treating agent composition of the present invention. Therefore, the surface treatment agent composition of the present invention can be used as, for example, a hydrophilic treatment agent, an antifogging agent, and an antifouling coating agent. Moreover, the surface treatment agent composition of this invention can be utilized as an antibacterial agent or a fungicide by making the surface treatment agent composition of this invention contain the additive for antibacterial or mold prevention.
On the other hand, the surface-treated substrate of the present invention is, for example, a bathroom or toilet mirror, a mirror such as a vehicle mirror, and an optical article such as a spectacle lens or an optical lens, which require antifouling properties or antifogging properties. Etc. can be used.

Claims (11)

As a structural unit, the following general formula (I)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} each independently represents an alkyl group having 1 to 3 carbon atoms, ^{X a -} represents a counter ion, a is shown the valency of the counter ion)
At least one structural unit (1) represented by:
The following general formula (II)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A copolymer (i) containing at least one structural unit (2) represented by:
An aminosilane compound (ii) containing at least one amino group capable of reacting with a hydrolyzable silyl group and an epoxy group in the copolymer (i), and a solvent (iii)
A surface treatment composition comprising: The aminosilane compound (ii) is represented by the following general formula (III)

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ are each independently carbon. An alkyl group having 1 to 3 carbon atoms, and A represents an alkylene group having 2 to 5 carbon atoms)
The surface treating agent composition of Claim 1 which is aminoalkoxysilane (ia) represented by these.   The surface treating agent composition according to claim 1 or 2, wherein an epoxy group in the copolymer (i) and an amino group in the aminosilane compound (ii) are reacted to form a covalent bond. As a structural unit, the following general formula (I)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} are independently an alkyl group having 1 to 3 carbon ^{atoms, X a-} Represents a counter ion, and a represents the valence of the counter ion)
At least one structural unit (1) represented by:
The following general formula (IV)

(Where q represents an integer of 1 to 3, r represents an integer of 2 to 5, s represents an integer of 0 to 2, and Z represents —NH—, —NH—A—NH— or —NH (A -NH ₂₎ - indicates, ^{R 5} represents a hydrogen atom or a methyl group, ^{R 6,} and ^{R 7} independently represent an alkyl group having 1 to 3 carbon atoms, a is an alkylene group having 2 to 5 carbon atoms Show)
The copolymer containing at least 1 sort (s) of structural units (4) represented by these. As a structural unit, the following general formula (II)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
The copolymer of Claim 4 containing at least 1 sort (s) of structural units (2) represented by these.   A surface treating agent composition comprising the copolymer according to claim 4 or 5 and a solvent (iii).   The surface treatment agent composition according to claim 3 or 6, wherein the surface treatment is a treatment for imparting hydrophilicity to the substrate surface.   A surface treatment method for a substrate, wherein the surface treatment agent composition according to claim 3, 6 or 7 is applied on the substrate and then dried to form a coating layer on the substrate surface.   A surface-treated substrate provided with a coating layer comprising the copolymer according to claim 4 or 5. In the presence of a radical polymerization initiator in a solvent, the following general formula (V)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} are independently an alkyl group having 1 to 3 carbon ^{atoms, X a-} Represents a counter ion, and a represents the valence of the counter ion)
At least one (meth) acryloylaminoalkyl quaternary ammonium salt (1 ′) represented by:
The following general formula (VI)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A step (a) of copolymerizing at least one glycidyl (meth) acrylate (2 ′) represented by
The reaction solution before, during or after polymerization in the step (a), and the following general formula (III)

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ are each independently carbon. An alkyl group having 1 to 3 carbon atoms, and A represents an alkylene group having 2 to 5 carbon atoms)
The epoxy group in the copolymer obtained by the said glycidyl (meth) acrylate (2 ') and / or the said process (a) and the said amino alkoxysilane ( a step of reacting with an amino group in ia) to form a covalent bond (a),
It has these, The manufacturing method of the copolymer of Claim 4 or 5 characterized by the above-mentioned. As a structural unit, the following general formula (I)

(Here, p represents an integer of 1 to 6, ^{R 1} represents a hydrogen atom or a methyl ^group, R 2, ^{R 3,} and ^{R 4} each independently represents an alkyl group having 1 to 3 carbon atoms, ^{X a -} represents a counter ion, a is shown the valency of the counter ion)
At least one structural unit (1) represented by:
The following general formula (II)

(Wherein, ^{R 5} represents a hydrogen atom or a methyl group, q is an integer of 1 to 3)
A copolymer (i) containing at least one structural unit (2) represented by the general formula (III):

(Wherein r represents an integer of 2 to 5, s represents an integer of 0 to 2, Y represents NH ₂ — or NH ₂ —A—NH—, and R ⁶ and R ⁷ are each independently carbon. An alkyl group having 1 to 3 carbon atoms, and A represents an alkylene group having 2 to 5 carbon atoms)
And a step of reacting an epoxy group in the copolymer (i) with an amino group in the aminoalkoxysilane (ia) to form a covalent bond ( The method for producing a copolymer according to claim 4 or 5, wherein the copolymer has a).

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