JP2016113471A - Hydrophilization treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilization treatment agent excellent in ability of hydrophilizing a solid surface, enabling slippage of the solid surface after being treated to be suppressed and excellent in dissolubility and dispersibility into water, and a hydrophilization treatment agent composition containing the hydrophilization treatment agent.SOLUTION: The hydrophilization treatment agent is provided which is composed of a block polymer having a polymer segment A composed of a special constituent unit (1) derived from a hydrophobic unsaturated monomer and a polymer segment B composed of a random polymer containing the special constituent unit (1) derived from a hydrophobic unsaturated monomer and a specific constituent unit (2) derived from a sulfobetaine group, the content of the polymer segment A in the block polymer being 2 mass% to 14 mass% and the content of the constituent unit (1) in the polymer segment B being 5 mass% to 30 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a hydrophilic treatment agent and a hydrophilic treatment agent composition.

Conventionally, as a method for imparting antifouling properties to a solid surface, different methods of water repellent treatment and hydrophilic treatment are known.
The water repellency treatment is a technique for applying a surface repellency to a solid surface of glass, metal, fiber, or the like so that dirt contained in water does not adhere. For example, after washing clothes, they are treated with a soft finish, sprayed with water repellent on skiwear, etc. to give a waterproof effect, and painted surfaces of automobiles are waxed. .
However, with water-repellent treatment, it is difficult to make the surface completely water-repellent, and due to repeated contact with water, dirt contained in the water accumulates on the solid surface, so it exhibits a sufficient antifouling effect Is difficult.

  On the other hand, when the surface of the solid surface is hydrophilized, that is, when the surface of the solid surface is decreased in contact angle with water, and the surface of the solid surface is easily wetted with water, dirt attached to the solid surface after the processing is easily removed during cleaning. Anti-fogging effect of glass and mirrors, anti-fogging effect, anti-frosting of aluminum fins of heat exchanger, anti-fouling property of bath and toilet surfaces, etc. it can.

Several proposals have been made for a hydrophilic treatment agent and a hydrophilic treatment method for a solid surface.
For example, Patent Document 1 discloses an aqueous antifouling composition containing an amphoteric polymer electrolyte. Patent Document 2 discloses a cleaning or rinsing composition containing a surfactant and a specific polybetaine. Patent Document 3 discloses hydrophilization containing an acrylic resin obtained by copolymerizing a polymerizable unsaturated monomer having a specific betaine structure and a specific polymerizable unsaturated monomer, hydrophilic cross-linked polymer particles, and a cross-linking agent. A treating agent composition is disclosed. Patent Document 4 includes a step of applying a composition containing an amphiphilic block copolymer to a support, wherein the amphiphilic block copolymer is formed from a hydrophilic block having a specific structure and an ethylenically unsaturated hydrophobic monomer. A method for improving the wettability / hydrophilicity of a hydrophobic support containing a hydrophobic block is disclosed.

JP 2001-181601 A JP-T-2006-514150 JP 2012-25820 A Special table 2009-545642

However, there are surprisingly few products that apply hydrophilic treatment technology, and it is difficult to say that they are widely spread. This is due to the absence of a hydrophilic treatment agent having a sufficiently satisfactory effect.
The present invention provides a hydrophilizing agent excellent in hydrophilizing ability on a solid surface, capable of suppressing slippage of the solid surface after treatment, and excellent in solubility or dispersibility in water, and a hydrophilizing agent containing the same. A composition is provided.

The present invention is a hydrophilic treatment agent comprising a block polymer having a polymer segment A and a polymer segment B,
The polymer segment A is a block polymer segment composed of a structural unit represented by the general formula (1),
Polymer segment B is a random polymer segment composed of a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2),
The content of the polymer segment A in the block polymer is 2% by mass or more and 14% by mass or less,
The content of the structural unit represented by the general formula (1) in the polymer segment B is 5% by mass or more and 30% by mass or less.
The present invention relates to a hydrophilic treatment agent.

[Where,
R ^{1 to} R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom Or a C1-C4 hydrocarbon group is shown. ]

[Where,
R ^{5 to} R ⁷ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁸ : an alkylene group having 1 to 4 carbon atoms R ⁹ , R ¹⁰ : the same or different, 1 to 4 carbon atoms The following hydrocarbon group X ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group Indicates. ]

  Moreover, this invention relates to the hydrophilic treatment agent composition containing the hydrophilic treatment agent of the said invention and water.

  According to the present invention, a hydrophilizing agent excellent in hydrophilizing ability of a solid surface, capable of suppressing slippage of the solid surface after treatment, and having excellent solubility or dispersibility in water and hydrophilization containing the same. A treating agent composition is provided.

<Hydrophilic treatment agent>
The hydrophilic treatment agent of the present invention comprises a specific block polymer. Hereinafter, the term “block polymer” refers to a block polymer that serves as a hydrophilic treatment agent of the present invention unless otherwise specified. The block polymer comprises a polymer segment A composed of the structural unit represented by the general formula (1), a random unit composed of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). The polymer segment A has a polymer segment B, the content of the polymer segment A in the polymer is 2% by mass or more and 14% by mass or less, and the content of the structural unit represented by the general formula (1) in the polymer segment B is It is 5 mass% or more and 30 mass% or less. Since the polymer according to the present invention has a group of polymer segments A and a group of different polymer segments B, the present invention blocks such a polymer. It is expressed as a polymer.

[Polymer segment A]
(Content of polymer segment A)
From the viewpoint of improving the adsorption amount, the content of the polymer segment A in the block polymer is 2% by mass or more, preferably 4% by mass or more, more preferably 4.5% by mass or more, and the contact angle. From the viewpoint of reducing the solubility and improving the solubility, it is 14% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 7% by mass or less, thereby improving the adsorption amount. From the viewpoint, it is more preferably 6.5% by mass or less, and still more preferably 5.5% by mass or less.

(Configuration of polymer segment A)
The polymer segment A is composed of a structural unit represented by the general formula (1) from the viewpoint of improving the adsorption amount.

[Where,
R ^{1 to} R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom Or a C1-C4 hydrocarbon group is shown. ]
The structural unit represented by the general formula (1) is a structure derived by polymerizing an unsaturated monomer represented by the following general formula (1 ′) (hereinafter also referred to as an unsaturated monomer a). R ¹ , R ² , R ³ , R ⁴ and Y ¹ in the general formula (1) and the general formula (1 ′) are all synonymous.

In the formula (1) and formula (1 ′), the viewpoint of availability of unsaturated monomers, the viewpoint of polymerizability of the monomers, the viewpoint of reducing the contact angle, the adsorptivity and the solubility, From the viewpoint of providing a dynamic coefficient of friction, R ¹ and R ² are preferably hydrogen atoms. From the same viewpoint, R ³ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. Y ¹ is preferably O from the same viewpoint. From the same viewpoint, R ⁴ is preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 7 carbon atoms. Examples of the hydrocarbon group for R ⁴ include an alkyl group and an alkenyl group. Examples of R ⁴ include a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, preferably a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms, More preferably, it is a linear alkyl group having 1 to 6 carbon atoms.

  Specific examples of the unsaturated monomer a include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and (meth) acrylic acid. t-butyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid-cyclohexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-decyl, (meta ) (Meth) acrylate esters such as lauryl acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate, and N-ethyl (meth) acrylamide N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-diethyl (meth) (Meth) acrylamides such as acrylamide and the like.

  The unsaturated monomer a is preferably a (meth) acrylic acid ester from the viewpoint of reducing the contact angle, excellent adsorbability to the solid surface, excellent solubility, and imparting an appropriate dynamic friction coefficient. Preferably methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, n- (meth) acrylate One or more selected from hexyl and lauryl (meth) acrylate, more preferably selected from methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate 1 type or 2 types or more. In the present specification, “(meth) acryl” means acrylic, methacrylic, or both.

  In the polymer segment A, you may contain the structural unit derived from monomers other than the unsaturated monomer a in the range which does not impair the effect of this application. As the monomer other than the unsaturated monomer a, an unsaturated monomer other than the unsaturated monomer having a sulfobetaine group is preferable, and a hydrophobic unsaturated monomer such as styrene is more preferable.

  The content of the structural unit represented by the general formula (1) in the polymer segment A is preferably from the viewpoint of reducing the contact angle, improving the adsorptivity and solubility, and imparting an appropriate dynamic friction coefficient. Is 90% by mass or more, more preferably 95% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass. In addition, substantially 100 mass% means that the structural unit other than the repeating unit derived from the unsaturated monomer a is inevitably mixed in the polymer segment A of the present invention.

  The weight average molecular weight of the polymer segment A is preferably 2000 or more, more preferably 3000 or more, further preferably from the viewpoint of reducing the contact angle, improving the adsorptivity and solubility, and imparting an appropriate dynamic friction coefficient. Is 4000 or more, and preferably 20000 or less, more preferably 15000 or less, still more preferably 10,000 or less, and even more preferably 8000, from the viewpoints of blendability and solubility of the hydrophilizing agent composition. It is as follows. This weight average molecular weight can be measured by the method described in Examples.

[Polymer segment B]
(Content of polymer segment B)
The content of the polymer segment B in the block polymer is 86% by mass or more, preferably 90% by mass or more, more preferably 92% by mass or more, from the viewpoint of reducing the contact angle and improving the solubility. More preferably, it is 93% by mass or more, from the viewpoint of improving the adsorption amount, more preferably 93.5% by mass or more, still more preferably 94.5% by mass or more, from the viewpoint of improving the adsorption amount, It is 98 mass% or less, Preferably it is 96 mass% or less, More preferably, it is 95.5 mass% or less.

(Configuration of polymer segment B)
From the viewpoints of reducing the contact angle, improving the adsorptivity and solubility, and imparting an appropriate dynamic friction coefficient, the polymer segment B has the structural unit represented by the general formula (1) and the following general formula ( It is a random polymer segment consisting of the structural unit represented by 2).

[Where,
R ^{5 to} R ⁷ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁸ : an alkylene group having 1 to 4 carbon atoms R ⁹ , R ¹⁰ : the same or different, 1 to 4 carbon atoms The following hydrocarbon group X ¹ : O or NR ¹² , R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group Indicates. ]

In the general formula (2), the viewpoint of availability of unsaturated monomers, the viewpoint of the polymerizability of the monomers, the viewpoint of reducing the contact angle, the viewpoint of improving the adsorptivity and solubility, and an appropriate dynamic friction coefficient In view of the above, R ⁵ and R ⁶ are preferably hydrogen atoms. From the same viewpoint, R ⁷ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X ¹ is preferably O from the same viewpoint. When X ¹ is NR ¹² , R ¹² is preferably a hydrogen atom. From the same viewpoint, R ⁸ is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably a dimethylene group having 2 carbon atoms. From the same viewpoint, R ⁹ and R ¹⁰ are preferably a methyl group or an ethyl group, and more preferably a methyl group. X ² is preferably a C 3 or C 4 alkylene group which may have a hydroxyl group, more preferably a propylene group, a butylene group or a 2-hydroxypropylene group, from the viewpoint of ease of quaternization reaction, and a propylene group 2-hydroxypropylene group is more preferable. Specific examples of the structural unit represented by the general formula (2) include a structural unit derived from sulfobetaine methacrylate and a structural unit derived from sulfobetaine hydroxymethacrylate. A structural unit derived from sulfobetaine hydroxymethacrylate is preferable from the viewpoint of not lowering, and a structural unit derived from sulfobetaine methacrylate is preferable from the viewpoint of improving the adsorption amount.

  The preferred embodiment of the structural unit represented by the general formula (1) in the polymer segment B is the same as that described in the polymer segment A.

  The content of the structural unit represented by the general formula (1) in the polymer segment B is 5% by mass or more, preferably 10% by mass or more, more preferably from the viewpoint of imparting an appropriate dynamic friction coefficient. Is 15% by mass or more, more preferably 18% by mass or more, and is 30% by mass or less, preferably 28% by mass or less from the viewpoint of reducing the contact angle and from the viewpoint of improving solubility and adsorption amount. More preferably, it is 25 mass% or less, More preferably, it is 23 mass% or less.

  In the polymer segment B, a structural unit derived from a monomer other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is included within a range not impairing the effects of the present application. You may contain. As the monomer other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), an unsaturated monomer other than the unsaturated monomer a is preferable, and hydroxyethyl ( More preferred are hydrophilic unsaturated monomers such as (meth) acrylate, acrylate having an oxyethylene chain, acrylamide, and dimethylacrylamide.

  The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the polymer segment B is improved in view of reducing the contact angle, adsorbability and solubility. From the viewpoint of providing an appropriate dynamic friction coefficient, it is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably substantially 100% by mass, and still more preferably 100% by mass. %. Note that substantially 100% by mass means that the structural unit other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is unavoidable in the polymer segment B of the present invention. This includes the case where it is mixed.

  The weight average molecular weight of the polymer segment B is preferably 50000 or more, more preferably 70000 or more, further preferably from the viewpoint of reducing the contact angle, improving the adsorptivity and solubility, and imparting an appropriate dynamic friction coefficient. Is 90000 or more, and preferably 200000 or less, more preferably 150,000 or less, still more preferably 130,000 or less, and still more preferably 100000 or less, from the viewpoints of blendability and solubility of the hydrophilic treatment agent composition. is there. This weight average molecular weight can be calculated by (molecular weight of block polymer) − (molecular weight of segment A).

[Block polymer]
The weight average molecular weight of the block polymer is preferably 20000 or more, more preferably 50000 or more, and still more preferably from the viewpoint of reducing the contact angle, improving the adsorptivity and solubility, and imparting an appropriate dynamic friction coefficient. 70000 or more, more preferably 90000 or more, and from the viewpoint of improving compoundability and improving solubility, preferably 220,000 or less, more preferably 200000 or less, further preferably 150,000 or less, and even more preferably 130,000 or less. . This weight average molecular weight can be measured by the method described in Examples.

  As the structure of the block polymer, when the polymer segment A is represented by A and the polymer segment B is represented by B, the structure of AB, ABA, BAB, or ABAA- A repeating structure of B-A-B ... is mentioned, and from the viewpoint of ease of production, a structure of AB, A-B-A, or B-A-B is preferable, and a structure of AB Is more preferable. The block polymer is preferably composed of one or more polymer segments A and one or more polymer segments B. The block polymer is preferably composed of one or two polymer segments A and one or two polymer segments B. The block polymer is more preferably composed of one polymer segment A and one polymer segment B.

(Method for producing polymer segment A)
The production method of the polymer segment A used in the present invention is not particularly limited and can be produced by a known method. For example, the monomer is polymerized by living polymerization or chain transfer to form a block polymer. Can do. Examples of living polymerization include living radical polymerization, living anion polymerization, and living cation polymerization. Living radical polymerization methods include atom transfer radical polymerization (ATRP) method, iodine transfer radical polymerization method, polymerization using nitroxy radical (NMP) method, reversible addition-fragmentation chain transfer polymerization (RAFT) method, reversible chain transfer catalytic polymerization. (RTCP) method, reversible complex formation mediated polymerization (RCMP) method and the like can be used, and from the viewpoint of catalyst availability and polymerization control, ATRP method, RAFT method, RTCP method and RCMP method are preferable. The ATRP method is described in Chemical Reviews, 2001, 101, 2921-2990. The RAFT method is described in the document Chemical Reviews, 2009, 109, 5402-5436. The RTCP method is described in Patent Document WO2010 / 027093. The RCMP method is described in Patent Document WO2011 / 016166.

  In the case of a block polymer comprising two types of blocks, for example, the block polymer can be obtained by a method including a step of polymerizing the first block and a step of polymerizing the second block. More specifically, for example, after polymerizing the first block, the block polymer can be obtained by polymerizing the second block in the presence of the obtained first polymer. The first polymer can be subjected to the polymerization of the second block after being isolated and purified, or the first polymer is not isolated and purified, and during the polymerization of the first polymer or at the completion of the polymerization, By adding a second monomer to the first polymerization, the block can be polymerized. Isolation and purification can be performed by a well-known method, for example, filtration and drying after adding the reaction solution to the poor solvent of the polymer to precipitate the polymer.

  The block polymer according to the present invention is a step of quaternizing the following block polymer having a polymer segment A and a polymer segment B ′ having an amino group and a precursor polymer segment of the polymer segment B The block polymer obtained by the manufacturing method which has this is mentioned.

  As a method for producing a block polymer according to the present invention, a polymer segment A containing a repeating unit of the general formula (1) is first produced, and the repeating unit of the general formula (1) and the following general formula (2-1) A polymer segment (precursor polymer segment B ′ of polymer segment B) containing a random number of repeating units, and a quaternization method (production method (1)), a repeating unit of the general formula (1) and A method of first producing a polymer segment (precursor polymer segment B ′ of polymer segment B) containing random repeating units of the general formula (2-1), producing polymer segment A, and quaternizing ( Production method (2)), and the production method (1) is preferred from the viewpoint of improving the effects of the present invention.

[Wherein, R ^{5 to} R ^{7 are the} same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁸ : an alkylene group having 1 to 4 carbon atoms R ⁹ , R ¹⁰ : the same or different, carbon The hydrocarbon group X ¹ having a number of 1 or more and 4 or less is O ¹ or NR ¹² , and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

  Specifically, the manufacturing method (1) includes a manufacturing method including the following steps 1 to 3. Therefore, the block polymer according to the present invention includes a block polymer obtained by the production method including the steps 1 to 3.

Step 1: A step of obtaining a polymer A by polymerizing an unsaturated monomer represented by the following general formula (1 ').

[Where,
R ^{1 to} R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom Or a C1-C4 hydrocarbon group is shown. ]

Step 2: In the presence of the polymer A, the unsaturated monomer represented by the general formula (1 ′) and the unsaturated monomer represented by the following general formula (2 ′) are randomly polymerized and segmented A step of obtaining a block polymer containing B ′.

[Wherein, R ^{5 to} R ^{7 are the} same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁸ : an alkylene group having 1 to 4 carbon atoms R ⁹ , R ¹⁰ : the same or different, carbon The hydrocarbon group X ¹ having a number of 1 or more and 4 or less is O ¹ or NR ¹² , and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
Step 3: A step of obtaining a block polymer by reacting the polymer obtained in Step 2 with a compound represented by the following general formula (B1) or a compound represented by the following general formula (B2).

_{^{Z-X 2 -SO 3 M (}} B2)
(In the formula, Z represents Cl or Br, X ² represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and M represents Na or K.)

In the formula (2 ′), the viewpoint of availability of the unsaturated monomer, the viewpoint of the polymerizability of the monomer, the viewpoint of reducing the contact angle, the viewpoint of improving the adsorptivity and solubility, and an appropriate dynamic friction coefficient are imparted. From the viewpoint, R ⁵ and R ⁶ are preferably hydrogen atoms. From the same viewpoint, R ⁷ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X ¹ is preferably O from the same viewpoint. From the same viewpoint, R ⁸ is preferably an alkylene group having 2 or 3 carbon atoms, and is preferably a dimethylene group having 2 carbon atoms. From the same viewpoint, R ⁹ and R ¹⁰ are preferably a methyl group or an ethyl group, and more preferably a methyl group.
Specific examples of the unsaturated monomer represented by the general formula (2 ′) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, N , N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide.

  In step 1, the polymer A can be obtained by a known method. For example, the living polymerization method can be employed. The solvent is not particularly limited as long as it can dissolve monomers and polymers. A solvent can be used individually or in combination of 2 or more types. Specific examples include anisole and ethanol.

  Step 3 is a step in which the amino group of the block polymer obtained in Step 2 is reacted with the quaternizing agent of the general formula (B1) or (B2) to obtain a block polymer by changing to a sulfobetaine group. is there. A known method can be used as a production method in which an amino group is reacted with a quaternizing agent to convert it into a sulfobetaine group, and examples thereof include a method described in JP-T-2006-514150.

  The quaternizing agent is preferably at least one selected from 1,3-propane sultone, 1,4-butane sultone and sodium 3-chloro-2-hydroxypropane sulfonate from the viewpoint of reactivity. The solvent is not particularly limited as long as it dissolves the polymer. A solvent can be used individually or in combination of 2 or more types. Specific examples include 2,2,2-trifluoroethanol.

<Hydrophilic treatment agent composition>
The hydrophilic treatment agent composition of the present invention contains the hydrophilic treatment agent of the present invention and water. One or more hydrophilic treatment agents can be used.
The content of the hydrophilic treatment agent in the hydrophilic treatment agent composition is 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of reducing the contact angle of the hydrophilic treatment agent composition. From the viewpoint of preventing a uniform treatment from being increased by thickening and preventing the contact angle from being increased, the content is preferably 5% by mass or less, more preferably 1.0% by mass or less.

[Surfactant]
The hydrophilic treatment composition of the present invention preferably contains a surfactant from the viewpoint of improving the contact angle reduction performance of the hydrophilic treatment composition. By using the surfactant, the hydrophilizing agent composition tends to wet and spread on the solid surface, and the contact angle reduction performance is improved. In addition, when a dirt substance, in particular, an oily dirt substance having a high hydrophobic property is attached to the solid surface, the surfactant is used to remove the highly hydrophobic dirt substance by the surfactant, Surface contact angle reduction performance is improved. From the viewpoint of reducing the contact angle of the hydrophilic treatment agent composition, the content of the surfactant in the hydrophilic treatment agent composition is 0.01% by mass or more, more preferably 0.03% by mass or more, and the block. From the viewpoint of preventing the adsorption of the polymer to the solid surface and preventing the contact angle lowering performance from deteriorating, it is preferably 30% by mass or less, and preferably 20% by mass or less. Further, from the viewpoint of foam suppression, it is preferably 1% by mass or less, more preferably less than 0.5% by mass, further preferably 0.3% by mass or less, and still more preferably 0.1% by mass or less.

  The surfactant to be used is not particularly limited as long as it is a surfactant that is usually used for a liquid detergent. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. From the above viewpoint, the surfactant preferably has an alkyl group or an alkenyl group as a hydrophobic site, and the carbon number thereof is preferably 8 or more, more preferably 10 or more, and the upper limit is preferably Is 20 or less, more preferably 16 or less.

(Anionic surfactant)
The anionic surfactant is preferably one or more selected from sulfate ester salts, sulfonate salts, carboxylate salts, phosphate ester salts, and amino acid salts having a hydrophobic site. Specifically, sulfate esters having a hydrophobic site such as alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates; sulfosuccinic acid Alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, alkane sulfonates, internal olefin sulfonates, acyl isethionates, sulfonates having a hydrophobic site such as acyl methyl taurate; 8 to 16 carbon atoms Higher fatty acid salts, carboxylates having a hydrophobic site such as polyoxyalkylene alkyl ether acetates; phosphoric acid ester salts having a hydrophobic site such as alkyl phosphates, polyoxyalkylene alkyl ether phosphates; Glutamic acid salts, alanine derivatives, glycine derivatives, amino acid salts and the like having a hydrophobic moiety, such as arginine derivatives.

  Among these anionic surfactants, alkyl sulfates such as sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate (laureth-2 sulfate) are used from the viewpoint of improving the contact angle reduction performance of the hydrophilic treatment composition. Sodium) polyoxyethylene alkyl ether sulfates, higher fatty acid salts such as potassium laurate and sodium myristate, polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene lauryl acetate (sodium laureth-4,5 acetate) Sulfosuccinic acid alkyl ester salts such as sodium laureth-2 sulfosuccinate, acyl glutamates such as sodium N-acyl-L-glutamate (sodium cocoyl glutamate), acyl isethionate, and acylmethyl tauree One or more preferably selected from, one or more selected from polyoxyethylene alkyl ether sulfuric acid salts and higher fatty acid salts are more preferred.

(Nonionic surfactant)
Nonionic surfactants include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, Polyethylene glycol type nonionic surfactants such as oxyethylene (hardened) castor oil and polyhydric alcohol type nonionic surfactants such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkylglycoside, and the like And fatty acid alkanolamides. Among these nonionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, and alkyl glycoside are used from the viewpoint of improving the contact angle reduction performance of the hydrophilizing agent composition. 1 type or 2 types or more selected are preferable, and 1 type or 2 types or more selected from polyoxyethylene alkyl ether and alkyl glucoside are more preferable.

(Amphoteric surfactant)
Examples of amphoteric surfactants include betaine surfactants such as imidazoline betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and sulfobetaines, and amine oxide surfactants such as alkyldimethylamine oxides. Among these amphoteric surfactants, imidazoline-based betaine, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, and alkylhydroxysulfobetaine are selected from the viewpoint of improving the contact angle reducing performance of the hydrophilizing agent composition. 1 type or 2 types or more are preferable and fatty-acid amide propyl betaines, such as lauric acid amidopropyl-N, N- dimethyl-acetic acid betaine, are more preferable.

(Cationic surfactant)
As the cationic surfactant, a quaternary ammonium salt having a hydrocarbon group having 12 to 28 carbon atoms, preferably 16 to 22 carbon atoms, which may be separated by an amide group, an ester group or an ether group. , Pyridinium salts, or salts of tertiary amine mineral acids or organic acids. Specifically, long-chain alkyltrimethylammonium salts such as cetyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, okdadecyloxypropyltrimethylammonium salt; long-chain alkyldimethylbenzylammonium salt such as stearyldimethylbenzylammonium salt Di-long chain alkyl dimethyl ammonium salts such as distearyl dimethyl ammonium salt and diisotetradecyl dimethyl ammonium salt; mono long chain alkyl dimethyl amine salts such as stearyl dimethylamine, behenyl dimethylamine and octadecyloxypropyl dimethylamine acid salts Is mentioned. Among these cationic surfactants, a long-chain alkyldimethylbenzylammonium salt is preferable from the viewpoint of improving the contact angle reduction performance of the hydrophilic treatment composition.

[Other ingredients]
The hydrophilizing agent composition of the present invention includes oxalic acid, maleic acid, citric acid, adipic acid, sebacic acid, malic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, polyacrylic acid as long as the object of the present invention is not impaired. Polycarboxylic acids such as acid, polymethacrylic acid and polymaleic acid; sulfonic acids such as poly-2-acrylamido-2-methylpropane sulfonic acid and poly p-styrene sulfonic acid; lower alcohols such as ethyl alcohol and isopropyl alcohol; diethylene glycol mono Solvents such as butyl ether; salts that improve the solubility of hydrophilic agents such as NaCl in water; solubilizers such as toluene sulfonate, xylene sulfonate, urea; clay minerals, water-soluble polymer compounds, etc. Viscosity modifier (however, excluding the block polymer according to the present invention); calcite, silica, phosphate Water-insoluble abrasives such as calcium, zeolite, calcium carbonate, polyethylene, nylon and polystyrene; moisturizers such as glycerin and sorbitol; touch improvers such as cationized cellulose (excluding the block polymer according to the present invention); carbonic acid Alkali builders such as sodium and sodium silicate; enzymes, dyes, fragrances, antiseptic / antifungal agents and the like can be added.

[Production of hydrophilizing agent composition]
The hydrophilic treatment agent composition of the present invention is obtained by adding a block polymer, water and other components such as the surfactant and polyvalent organic acid as necessary, and stirring and mixing by a known method. Can be obtained. The composition ratio of the hydrophilizing agent composition can be appropriately adjusted according to the type of solid surface and the purpose of treatment. In addition, a concentrated solution can be prepared and diluted at the time of use.

  The pH at 20 ° C. of the obtained hydrophilizing agent composition is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, from the viewpoint of handling safety and prevention of damage to the solid surface. Is 11 or less, more preferably 10 or less, more preferably 8 or less. Examples of pH regulators include inorganic acids such as hydrochloric acid and sulfuric acid, and acid agents such as the aforementioned organic acids; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate Inorganic alkali compounds such as ammonia and derivatives thereof, and alkali agents such as organic alkali compounds such as monoethanolamine, diethanolamine, and triethanolamine. Also, a combination of an acid agent and an alkali agent can be used as a buffer system.

<Hydrophilic treatment method>
In the method for hydrophilizing a solid surface of the present invention, the solid surface is brought into contact with the hydrophilizing composition of the present invention.
Here, the “solid” of the “solid surface” is not particularly limited, and glass, ceramic, porcelain, glazed, tile, ceramics; metals such as aluminum, stainless steel, brass; polyethylene, polypropylene, melamine resin, polyamide resin, ABS Synthetic resins such as resin and FRP; natural fibers such as cotton, silk and wool; synthetic fibers such as polyester, nylon and rayon; solids such as hair, nails and teeth.
Suitable solid surfaces to which the method of the present invention can be applied include a hydrophobic hard surface, and one or more hydrophobic hard surfaces selected from ceramics, metals, and synthetic resins. Here, the hydrophobic hard surface means that the static contact angle with respect to water is 70 ° or more, and the treated hard surface means less than 70 °. The static contact angle can be measured by the method described in the examples.
In addition, the hydrophilizing agent composition is preferably an aqueous solution from the viewpoint of handling stability.

The method for contacting the solid surface with the hydrophilizing agent composition is not particularly limited. For example, the following methods (i) to (iii) may be mentioned.
(I) A method of immersing a solid in a hydrophilic treatment agent composition (ii) A method of spraying or applying a hydrophilic treatment agent composition to a solid surface (iii) A solid surface is washed with a hydrophilic treatment agent composition according to a conventional method The temperature at which the surface of the solid is surface-treated with the hydrophilizing agent composition is reduced from the viewpoint of reducing the contact angle, from the viewpoint of improving dissolution and adsorption, from the viewpoint of imparting an appropriate dynamic friction coefficient, and from the viewpoint of ease of processing. Therefore, it is preferably 5 ° C or higher, more preferably 10 ° C or higher, still more preferably 15 ° C or higher, preferably 50 ° C or lower, more preferably 40 ° C or lower, and further preferably 30 ° C or lower.
In the method (i), the dipping time is preferably 0.5 minutes or more, more preferably 1 minute or more, preferably 60 minutes or less, more preferably 50 minutes or less from the same viewpoint.
In the method (ii), the method of spraying or applying the hydrophilizing agent composition onto the solid surface can be appropriately selected according to the width (area) of the hard surface. A method in which the hydrophilizing agent composition is sprayed on the solid surface by spraying and then dried is preferable. If necessary, rinse with water after spraying. Further, after spraying, it may be thinly applied using a sponge or the like.
The amount of the hydrophilizing agent composition sprayed or applied to the solid surface is preferably 0.01 mL or more per 10 cm ^{2 in} the case of a hydrophilizing agent composition having a block polymer content of 0.5% by mass, for example. 0.1 mL or less.
In the method (iii), it is preferably used in the form of a cleaning composition containing a block polymer and a surfactant and brought into contact with a solid surface. In the case of such a detergent composition, the pH is preferably 4 or more, and preferably 10 or less, more preferably 8 or less, from the viewpoint of safety in handling and prevention of damage to the solid surface.
As the surfactant, those described above can be used.

Moreover, the static contact angle with respect to water of the solid surface hydrophilized by the hydrophilizing composition of the present invention is 60 ° or less, preferably 50 ° or less, more preferably 40 ° or less, and still more preferably 30 ° or less. More preferably, the angle is 25 ° or less.
Moreover, it is preferable that the solid surface hydrophilized by the hydrophilization treatment agent composition of this invention is processed uniformly from a viewpoint of improving the effect of this invention. The uniformity of the hydrophilic treatment can be judged by visually observing the solid surface after the treatment.

  In the following production examples, examples and comparative examples, “%” means “mass%”. Various physical properties and the like were measured by the following methods.

(1) The polymer segment A was measured by weight average molecular weight gel permeation chromatography (polystyrene conversion).
Two columns: K-804L (manufactured by Showa Denko KK) were used in series.
Column temperature: 40 ° C
Eluent: 1 mmol / L dimethyl lauryl amine / CHCl ₃ (dimethyl lauryl amine: Farmin DM2098: manufactured by Kao Corporation)
Flow rate: 1.0 ml / min Detector: Differential refractometer

(2) Weight average molecular weight of block polymer Molecular weight was measured by SLS (static light scattering method). The weight average molecular weight (Mw) was calculated by measuring the static light scattering under the following conditions using a light scattering photometer “DLS-7000” (manufactured by Otsuka Electronics Co., Ltd.) and preparing a Zimm-plot. . Further, the refractive index increment necessary for calculating the molecular weight was measured using a differential refractometer “DRM3000” (manufactured by Otsuka Electronics Co., Ltd.).
Wavelength: 632.8 nm (helium-neon laser)
Scattering angle: measured at intervals of 10 ° from 30 ° to 150 °.
Average temperature: 25 ° C
Solvent: 2,2,2-trifluoroethanol

(3) Content of polymer segment A in block polymer Using the weight average molecular weight of the polymer segment A and the weight average molecular weight of the block polymer determined in the above (1) and (2), Asked.
Content (%) of polymer segment A in block polymer = weight average molecular weight of polymer segment A / weight average molecular weight of block polymer × 100

(4) Content of structural unit represented by general formula (1) in polymer segment B The reaction solution of Step 2 is obtained by using gas chromatograph (GC) 6850 (manufactured by Agilent) of anisole as a solvent. From the ratio of the integral value of the monomer peak of the structural unit represented by the general formula (1) and the integral value of the monomer peak of the structural unit represented by the general formula (2) to the integrated value of the peak The reaction rate was measured. From these, the content of the structural unit represented by the general formula (1) in the polymer segment B was determined.
Detector: FID
Column: DB-1
Temperature (oven): 50-200 ° C, 10 ° C / min
Inlet temperature: 200 ° C
Split ratio: 50: 1
Gas type: Helium detector Temperature: 250 ° C
H2 flow rate: 40.0 ml / min
Air flow rate: 400.0 ml / min
Total flow rate: 45.0 ml / min

The acquisition source of the monomer (1 ′) for deriving the structural unit of segment A and the monomer (2 ′) for deriving the structural unit of segment B used in the production of the polymer is shown.
N-Butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
N-Butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
Methacrylic acid-2- (dimethylamino) ethyl (manufactured by Wako Pure Chemical Industries, Ltd.)
Dimethylaminopropylacrylamide (manufactured by KJ Chemicals)
N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium (manufactured by Sigma-Aldrich)

Production Example 1 (Production of polymer P1)
(Process 1)
2. In an eggplant flask, 40.00 g of n-butyl methacrylate, 1.097 g of ethyl 2-bromoisobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4′-dinonyl-2,2′-dipyridyl (manufactured by Sigma-Aldrich) 45 g and 60.00 g of anisole were added, and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip, 0.278 g of copper chloride (I) (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.189 g of copper chloride (II) (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in another eggplant flask. After purging with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by heating to 70 ° C. After reacting for 320 minutes, the reaction solution was ice-cooled while being exposed to air to complete the polymerization. Next, the reaction solution was dropped into a mixed solution of 400 mL of water and 1200 mL of methanol while stirring to precipitate a polymer, followed by decantation and drying to obtain a polymer (polymer A) constituting the polymer segment A. .

(Process 2)
Next, in a recovery flask, 14.00 g of 2- (dimethylamino) ethyl methacrylate, 1.60 g of n-butyl methacrylate, 0.946 g of the polymer A obtained in Step 1, 1,1,4,7,10,10 -0.081 g of hexamethyltriethylenetetramine (manufactured by Sigma-Aldrich) and 21.00 g of anisole were added, and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip and 0.035 g of copper (I) chloride were placed in another eggplant flask, and the atmosphere was replaced with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by heating to 70 ° C. After reacting for 840 minutes, the reaction solution was ice-cooled while exposed to air to complete the polymerization. Next, after removing the copper complex by the activated alumina column treatment, the polymer solution is dropped into 1 L of hexane while stirring to precipitate the polymer, followed by decantation and drying, and polymer segment A and polymer segment B ′ are separated. A polymer (polymer AB ′) was obtained.

(Process 3)
The eggplant flask was charged with 3.00 g of the polymer AB ′ obtained in Step 2 and 12.00 g of 2,2,2-trifluoroethanol (manufactured by Sigma-Aldrich) to dissolve the polymer. While heating at 50 ° C., 2.33 g of 1,3-propane sultone (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After reacting for 5 hours, it was cooled. While stirring in 500 mL of methanol, the reaction solution was added dropwise to precipitate a polymer, followed by filtration and drying to obtain a polymer (polymer P1) solid.

Production Example 2 (Production of polymer P2)
In Step 2 of Production Example 1, 0.932 g of Polymer A, 12.00 g of 2- (dimethylamino) ethyl methacrylate, and 3.16 g of n-butyl methacrylate were used, and 1,3- A polymer P2 was obtained in the same manner as in Production Example 1 except that the amount of propane sultone was changed to 2.04 g.

Production Example 3 (Production of polymer P3)
In Step 2 of Production Example 1, 1.08 g of Polymer A, 12.00 g of 2- (dimethylamino) ethyl methacrylate, and 5.43 g of n-butyl methacrylate were used. In Step 3, 1,3-propane sultone was used. A polymer P3 was obtained in the same manner as in Production Example 1 except that the amount of was 1.84 g.

Production Example 4 (Production of polymer P4)
A polymer P4 was obtained in the same manner as in Production Example 3 except that Step 3 in Production Example 3 was carried out as follows.
(Process 3)
In a recovery flask, 3.00 g of polymer AB ′, 12.00 g of 2,2,2-trifluoroethanol, 6.00 g of ion-exchanged water, sodium 3-chloro-2-hydroxy-1-propanesulfonate (Sigma Aldrich) 2.66 g). The mixture was heated to 80 ° C. and reacted for 16 hours. Subsequently, 0.48 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate (manufactured by Sigma Aldrich) and 0.21 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were added and reacted for 10 hours, followed by cooling. did. The reaction solution was added dropwise to 500 mL of methanol while stirring to precipitate a polymer, followed by filtration and drying to obtain polymer P4.

Production Example 5 (Production of polymer P5)
(Process 1)
In an eggplant flask, 7.15 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.91 g of iodine (manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylbutyronitrile) ( 1.37 g of Wako Pure Chemical Industries, Ltd. and 7.15 g of ethanol were added, and nitrogen bubbling was performed for 20 minutes. The mixture was heated to 70 ° C. and reacted for 310 minutes.

(Process 2)
Separately, 78.56 g of 2- (dimethylamino) ethyl methacrylate, 14.30 g of methyl methacrylate, 0.17 g of 2,2′-azobis (2-methylbutyronitrile), and 92.85 g of ethanol are placed in an eggplant flask. The solution subjected to nitrogen bubbling for 20 minutes was added to the reaction solution in Step 1 and reacted at 70 ° C. for 300 minutes. The reacted solution was dried under reduced pressure at 80 ° C. to obtain a polymer AB ′.

(Process 3)
In a recovery flask, 3.00 g of the polymer AB ′ obtained in Step 2, 12.00 g of 2,2,2-trifluoroethanol, 6 g of ion-exchanged water, 3-chloro-2-hydroxy-1-propanesulfonic acid 3.00 g of sodium was added. The mixture was heated to 80 ° C. and reacted for 16 hours. Subsequently, 0.59 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate and 0.25 g of sodium hydrogen carbonate were added and reacted for 10 hours, followed by cooling. A polymer (polymer P5) solid was obtained by drying under reduced pressure.

Production Example 6 (Production of polymer P6)
In Step 1 of Production Example 5, methyl methacrylate was 7.45 g, in Step 2, 2- (dimethylamino) ethyl methacrylate was 70.20 g, and methyl methacrylate was 22.35 g. Polymer P6 was obtained in the same manner as in Production Example 5 except that the sodium 3-chloro-2-hydroxy-1-propanesulfonate was added to 2.89 g and 0.53 g, respectively.

Production Example 7 (Production of polymer P7)
In Step 1 of Production Example 5, 0.49 g of iodine, 7.78 g of methyl methacrylate, and 0.90 g of 2,2′-azobis (2-methylbutyronitrile) were used. In Step 2, 2- (methacrylic acid 2- ( 3-Chloro-2, which is added in portions in Step 3, with 61.09 g of dimethylamino) ethyl, 31.13 g of methyl methacrylate, and 0.11 g of 2,2′-azobis (2-methylbutyronitrile). Polymer P7 was obtained in the same manner as in Production Example 5 except that sodium 2-hydroxy-1-propanesulfonate was changed to 2.52 g and 0.46 g, respectively.

Production Example 8 (Production of polymer P8)
In Step 1 of Production Example 5, 0.74 g of iodine, 5.84 g of methyl methacrylate, 1.12 g of 2,2′-azobis (2-methylbutyronitrile), and 2- (dimethyl methacrylate) in Step 2 91.64 g of amino) ethyl, 52.57 g of methyl methacrylate mixed therewith, and 2.52 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate added in portions in Step 3, respectively. The same procedure as in Production Example 5 was repeated except that the amount was changed to .46 g, to obtain a polymer P8.

Production Example 9 (Production of polymer P9)
In Step 1 of Production Example 5, 0.98 g of iodine, 7.78 g of methyl methacrylate, and 1.49 g of 2,2′-azobis (2-methylbutyronitrile) were used. In Step 2, 2- (dimethyl methacrylate) was used. Amino) ethyl (61.09 g), methyl methacrylate (31.13 g), and 2,2′-azobis (2-methylbutyronitrile) (0.19 g) were added in portions in 3-chloro-2-chloro-2- A polymer P9 was obtained in the same manner as in Production Example 5, except that sodium hydroxy-1-propanesulfonate was changed to 2.52 g and 0.46 g, respectively.

Production Example 10 (Production of polymer P10)
(Process 1)
In an eggplant flask, n-butyl acrylate 60.00 g, 2-bromoisotrithiocarbonate bis {4- [ethyl- (2-hydroxyethyl) carbamoyl] benzyl} (manufactured by Wako Pure Chemical Industries, Ltd.) 2.438 g, 2 , 2′-Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) (0.077 g) and dimethylformamide (90.00 g) were added, and nitrogen bubbling was performed for 15 minutes, followed by heating to 65 ° C. After reacting for 60 minutes, the reaction solution was ice-cooled while exposed to air to complete the polymerization. Next, the reaction solution was dropped into a mixed solution of 400 mL of water and 1200 mL of methanol while stirring to precipitate a polymer, followed by decantation and drying to obtain a polymer (polymer A) constituting the polymer segment A. .

(Process 2)
Next, put 20.00 g of dimethylaminopropylacrylamide, 7.36 g of n-butyl acrylate, 1.93 g of the above polymer, 0.015 g of 2,2′-azobisisobutyronitrile, and 30.0 g of methyl ethyl ketone in an eggplant flask. Nitrogen bubbling was performed for 20 minutes. After heating to 65 ° C. and reacting for 80 minutes, the reaction solution was ice-cooled to complete the polymerization. Next, the polymer solution is dropped into 1 L of hexane while stirring to precipitate the polymer, followed by decantation and drying, and a polymer having a polymer segment A and a polymer segment B ′ (polymer AB- A) was obtained.

(Process 3)
The eggplant flask was charged with 3.00 g of the polymer AB′-A obtained in Step 2 and 12.00 g of 2,2,2-trifluoroethanol to dissolve the polymer. While heating at 50 ° C., 1.81 g of 1,3-propane sultone was added dropwise. After reacting for 5 hours, the mixture was cooled, and while stirring 500 mL of methanol, the polymer solution was added dropwise to precipitate the polymer, and a polymer (polymer P10) solid was obtained by filtration and drying.

Production Example 11 (Production of polymer P11)
A polymer P11 was obtained in the same manner as in Production Example 10 except that Step 3 in Production Example 10 was carried out as follows.
(Process 3)
In a recovery flask, 3.00 g of the polymer AB′-A obtained in Step 2, 12.0 g of 2,2,2-trifluoroethanol, 6.00 g of ion-exchanged water, 3-chloro-2-hydroxy-1- 1.94 g of sodium propanesulfonate was added. The mixture was heated to 80 ° C. and reacted for 16 hours. Subsequently, 0.51 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate and 0.21 g of sodium hydrogen carbonate were added and reacted for 10 hours, followed by cooling. The reaction solution was added dropwise to 500 mL of methanol while stirring to precipitate a polymer, followed by filtration and drying to obtain a polymer (polymer P11) solid.

Production Example 12 (Production of polymer P12)
(Process 1)
In an eggplant flask, n-butyl methacrylate 80.00 g, bis (2-bromoisobutyric acid) ethylene 0.380 g (manufactured by Sigma-Aldrich), 4,4-dinonyl 2,2-bipyridine (manufactured by Sigma-Aldrich) 0.647 g, anisole 22 0.5 g was added and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip, 0.052 g of copper (I) chloride, and 0.035 g of copper (II) chloride were placed in another eggplant flask, and after replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by heating to 70 ° C. After reacting for 240 minutes, the reaction solution was ice-cooled while being exposed to air to complete the polymerization. Next, the polymerization solution was dropped into a mixed solution of 1200 mL of water and 1200 mL of methanol with stirring to precipitate a polymer, and a polymer was obtained by decantation and drying.

(Process 2)
In an eggplant flask, 1-2.00 g of 2- (dimethylamino) ethyl methacrylate, 5.43 g of n-butyl methacrylate, 0.824 g of the polymer obtained in Step 1, 1,1,4,7,10,10-hexa Methyltriethylenetetramine (0.110 g) and anisole (28.2 g) were added, and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip and 0.047 g of copper (I) chloride were placed in another eggplant flask, and after replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by heating to 70 ° C. After reacting for 120 minutes, the reaction solution was ice-cooled while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution is dropped into 1 L of hexane with stirring to precipitate the polymer, and the polymer segment A and polymer segment B ′ having a polymer segment B ′ are decanted and dried. A polymer (polymer B′-AB ′) was obtained.

(Process 3)
The eggplant flask was charged with 2.00 g of the polymer B′-AB ′ obtained in Step 2 and 8.00 g of 2,2,2-trifluoroethanol to dissolve the polymer. While heating at 50 ° C., 1.82 g of 1,3-propane sultone was added dropwise. After reacting for 5 hours, it was cooled. The reaction solution was added dropwise to 500 mL of methanol with stirring to precipitate a polymer, and a polymer (polymer P12) solid was obtained by filtration and drying.

Production Example 13 (Production of polymer P13)
A polymer P13 was obtained in the same manner as in Production Example 12 except that Step 3 was carried out as follows in Production Example 12.
(Process 3)
In an eggplant flask, 2.00 g of the polymer B′-AB ′ obtained in Step 2, 8.00 g of 2,2,2-trifluoroethanol, 4.00 g of ion-exchanged water, 3-chloro-2-hydroxy- 2.01 g of sodium 1-propanesulfonate was added. Heated to 80 ° C. The reaction was performed for 16 hours. Subsequently, 0.40 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate and 0.25 g of sodium bicarbonate were added and reacted for 10 hours. After cooling, the reaction solution was added dropwise to 500 mL of methanol with stirring to form a polymer. The polymer (polymer P13) was obtained as a solid by filtration and drying.

Production Example 14 (Production of Polymer Q1) (Block Polymer)
In Step 2 of Production Example 1, 30.00 g of 2- (dimethylamino) ethyl methacrylate was used, 1.73 g of the polymer obtained in Step 1 was used, and 0.126 g of copper (I) chloride was used. A solid polymer (polymer Q1) was obtained in the same manner as in Production Example 1 except that butyl was not used and the reaction time was 5 hours.

Production Example 15 (Production of polymer Q2)
In Step 1 of Production Example 1, n-butyl methacrylate was replaced with 80.00 g, 4,4′-dinonyl-2,2′-dipyridyl, 1,1,4,7,10,10-hexamethyltriethylene 1.56 g of tetramine, 80 g of anisole, 0.446 g of copper (I) chloride, and 0.303 g of copper (II) chloride. In step 2, 0.284 g of polymer A and 1,3-propane in step 3 Polymer Q2 was obtained in the same manner as in Production Example 1 except that the amount of sultone was changed to 2.12 g.

Production Example 16 (Production of polymer Q3)
In Step 2 of Production Example 1, the same procedure as in Production Example 1 was conducted, except that Polymer A was 0.280 g, 2- (dimethylamino) ethyl methacrylate was 5.03 g, and n-butyl methacrylate was 9.67 g. Polymer Q3 was obtained.

Production Example 17 (Production of Polymer R1) (Random Polymer)
N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium 28. In a separable flask equipped with a cooling reflux tube, a thermometer, a nitrogen introduction tube and a stirrer. 39 g, 1.61 g of n-butyl methacrylate, and 67.48 g of 2,2,2-trifluoroethanol were added, mixed uniformly, and stirred for 30 minutes in a nitrogen atmosphere. After the temperature of this solution was raised to about 70 ° C., 0.22 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 2.52 g of 2,2,2-trifluoroethanol were added, and the reaction was performed for 6 hours. went. Next, the reaction solution was dropped into 4 L of methanol while stirring to precipitate a polymer, and a solid of polymer R1 was obtained by filtration and drying.

  Weight average molecular weight (weight average molecular weight per polymer segment A) of the obtained polymer P1 to P13, polymer Q1 to Q3 and polymer R1 of polymer segment A, and content, formula (1 Tables 1 and 2 show the content of the structural unit represented by) and the weight average molecular weight of the block polymer.

* 1 Content of constituent unit of general formula (1) in the whole test polymer

<Examples 1 to 13 and Comparative Examples 1 to 4>
Using polymers P1 to P13, polymers Q1 to Q3, and polymer R1 (in the following formulation, these were collectively used as test polymers), a hydrophilizing agent composition having the composition shown below was prepared. 13, The hydrophilic treatment agent composition of Comparative Examples 1-4 was obtained. Specifically, each component was blended according to the blending amounts described below, and stirred at 25 ° C. for 30 minutes to produce a hydrophilic treatment composition. About the compounding quantity of the component described below, the compounding quantity as each effective part is shown.
(mass%)
Test polymer 0.1
Polyoxyethylene (2) ammonium lauryl ether sulfate ^(*) 0.03
Diethylene glycol monobutyl ether ^(**) 2.5
Ion-exchanged water balance (total) 100
(*) ES-125A; manufactured by Kao Corporation 25%
(**) BDG-NS; manufactured by Nippon Emulsifier Co., Ltd. Effective content 99.71%

  The following evaluation was performed using the hydrophilic treatment agent composition of Examples 1-13 and Comparative Examples 1-4. The results are shown in Table 3.

[Evaluation method]
Test Example 1 (Measurement of contact angle)
A test piece “vinyl chloride test piece” (manufactured by Engineering Test Service Co., Ltd., material: hard polyvinyl chloride, 25 mm × 75 mm), which has been cleaned in advance, is fixed horizontally, and 1 mL of a hydrophilizing agent composition is added dropwise to 5 After leaving still for a minute, it rinsed with about 200 mL ion-exchange water, and air-dried.
The static contact angle with respect to the ion-exchanged water on the surface of the treated part of the test piece was set to 10 μL of the sample using an automatic contact angle meter “DM-500” (manufactured by Kyowa Interface Science Co., Ltd.), and 6 seconds after the addition It was measured. The measurement was performed 5 times per test piece using 2 test pieces, and the average value of 10 measurements was used. The smaller the contact angle, the better the contact angle reduction performance.
The static contact angle of the test piece before the treatment was 85 °.

Test Example 2 (Measurement of adsorption amount)
The adsorption amount of each hydrophilic treatment agent composition was measured. The amount of polymer adsorbed on the hydrophobic surface was measured with a quartz crystal microbalance (QCM) measuring device (manufactured by AFFINIX). The measuring method is as follows.
A gold substrate for QCM measurement treated with a 1 mM octadecanethiol solution was obtained. The frequency was stabilized by adding 720 μL of pure water to a measuring instrument equipped with a gold substrate for QCM measurement. 80 μL of the hydrophilizing agent composition was added thereto, and the change in frequency was measured. The adsorption amount on the surface was calculated from the value of the frequency change by the following formula.
Adsorption amount [mg / m ² ] = ΔF × 0.03 / 4.9
(ΔF: frequency change [Hz] before and after the addition of the hydrophilizing agent composition)

Test Example 3 (Measurement of transmittance)
The transmittance of each hydrophilic treatment composition was measured. With a UV-visible spectrophotometer “UV-2550” (manufactured by Shimadzu Corporation), the transmittance of light having a wavelength of 600 nm at 25 ° C. was measured, and the transmittance of the composition to which no polymer was added as a hydrophilizing agent was 100%. The relative transmittance was determined. It shows that it is excellent in the solubility or dispersibility of a hydrophilic treatment agent, so that the transmittance | permeability is large.

Test Example 4 (Measurement of dynamic friction coefficient)
The dynamic friction coefficient of each hydrophilic treatment agent composition was measured. The dynamic friction coefficient was measured using a surface property tester (HEIDON-14D: manufactured by Shinto Chemical Co., Ltd.). The friction element uses pig skin and the measurement area is 1 cm ² . The test piece and the friction piece treated in the same manner as in Test Example 1 were immersed in water for 5 minutes, and then the dynamic friction coefficient was measured in water. The vertical load was 100 g, and the measurement speed was 100 mm / min. It shows that it is excellent in suppression of slip, so that a dynamic friction coefficient is large.

* 2 Content of structural unit of general formula (1) in the whole test polymer

  As is clear from Table 3, the hydrophilization treatment agent compositions of Examples 1 to 13 can lower the contact angle as compared with the hydrophilization treatment agent compositions of Comparative Examples 1 to 4, and the adsorption amount and permeation amount. The rate is high, and the performance of suppressing the reduction of the dynamic friction coefficient is excellent.

Claims (8)

A hydrophilic treatment agent comprising a block polymer having a polymer segment A and a polymer segment B,
The polymer segment A is a block polymer segment composed of a structural unit represented by the general formula (1),
Polymer segment B is a random polymer segment composed of a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2),
The content of the polymer segment A in the block polymer is 2% by mass or more and 14% by mass or less,
The content of the structural unit represented by the general formula (1) in the polymer segment B is 5% by mass or more and 30% by mass or less.
Hydrophilizing agent.

[Where,
R ^{1 to} R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom Or a C1-C4 hydrocarbon group is shown. ]

[Where,
R ^{5 to} R ⁷ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁸ : an alkylene group having 1 to 4 carbon atoms R ⁹ , R ¹⁰ : the same or different, 1 to 4 carbon atoms The following hydrocarbon group X ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group Indicates. ]   The hydrophilic treatment agent according to claim 1, wherein the block polymer has a weight average molecular weight of 20,000 or more and 220,000 or less.   The hydrophilic treatment agent according to claim 1 or 2, wherein the block polymer comprises a polymer segment A and a polymer segment B.   The block polymer represents the polymer segment A as A and the polymer segment B as B, and has a structure of any one of A-B, A-B-A, and B-A-B. The hydrophilic treatment agent according to any one of the above.   The block polymer is a block polymer obtained by quaternizing a block polymer which is a polymer segment A and a polymer segment B ′ which is a precursor polymer segment of the polymer segment B and has an amino group. The hydrophilization treatment agent according to any one of claims 1 to 4. The hydrophilization treatment agent according to any one of claims 1 to 5, wherein the block polymer is a block polymer obtained by a production method including the following steps 1 to 3.
Step 1: A step of obtaining a polymer A by polymerizing an unsaturated monomer represented by the following general formula (1 ′).
Step 2: In the presence of the polymer A, an unsaturated monomer represented by the following general formula (1 ′) and an unsaturated monomer represented by the following general formula (2 ′) are randomly polymerized. A step of obtaining a block polymer containing segment B ′.

[Where,
R ^{1 to} R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom Or a C1-C4 hydrocarbon group is shown. ]

[Where,
R ^{5 to} R ⁷ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁸ : an alkylene group having 1 to 4 carbon atoms R ⁹ , R ¹⁰ : the same or different, 1 to 4 carbon atoms The following hydrocarbon groups X ¹ : O or NR ¹² , and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
Step 3: A step of obtaining a block polymer by reacting the polymer obtained in Step 2 with a compound represented by the following general formula (B1) or a compound represented by the following general formula (B2).

_{^{Z-X 2 -SO 3 M (}} B2)
(In the formula, Z represents Cl or Br, X ² represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and M represents Na or K.)   The hydrophilization treatment agent composition containing the hydrophilization treatment agent and water of any one of Claims 1-6.   Furthermore, the hydrophilic treatment agent composition of Claim 7 containing surfactant.