JP6351960B2 - Hydrophilic treatment agent - Google Patents

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 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, and both amphiphilic block copolymers are formed from a hydrophilic block having a specific structure and an ethylenically unsaturated hydrophobic monomer. Disclosed is a method for improving the wettability / hydrophilicity of a hydrophobic support containing a modified hydrophobic block.

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

However, there are surprisingly few products that apply hydrophilization technology, and it cannot be said that they are widely spread. This is due to the absence of a hydrophilizing agent that has a sufficiently satisfactory effect.
This invention makes it a subject to provide the hydrophilic treatment agent which exhibits the outstanding hydrophilization capability, and the hydrophilic treatment agent composition containing it.

The present invention includes an unsaturated monomer-derived polymer segment A-1 containing a repeating unit derived from a hydrophobic unsaturated monomer, and an unsaturated containing a repeating unit derived from an unsaturated monomer having a sulfobetaine group. A hydrophilization treatment agent comprising a block polymer A having a monomer segment-derived polymer segment A-2 and a content of the polymer segment A-1 of 0.05% by mass or more and 75% by mass or less. About.
Moreover, this invention relates to the hydrophilic treatment agent composition containing the hydrophilic treatment agent of the said invention and water.

  The hydrophilic treatment composition containing the hydrophilic treatment agent of the present invention is excellent in hydrophilic performance (hereinafter also referred to as the effect of the present invention).

<Hydrophilic treatment agent>
The hydrophilic treatment agent of the present invention comprises a specific block polymer A.
The block polymer A includes a polymer segment A-1 derived from an unsaturated monomer containing a repeating unit derived from a hydrophobic unsaturated monomer, and a repeating unit derived from an unsaturated monomer having a sulfobetaine group. It has polymer segment A-2 derived from an unsaturated monomer, and the content of polymer segment A-1 is 0.05% by mass or more and 75% by mass or less.

[Polymer segment A-1]
(Content of polymer segment A-1)
The content of the polymer segment A-1 in the block polymer A is 0.05% by mass or more, preferably 0.1% by mass or more, more preferably, from the viewpoint of improving the hydrophilization performance of the hydrophilic treatment agent. Is 0.2% by mass or more, more preferably 1.0% by mass or more, more preferably 2.0% by mass or more, more preferably 2.5% by mass or more, and from the same viewpoint, 75% by mass or less. Yes, preferably 60% by mass or less, more preferably 50% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass or less, more Preferably it is 11 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is 4.8 mass% or less.

(Configuration of polymer segment A-1)
Polymer segment A-1 contains a repeating unit derived from a hydrophobic unsaturated monomer. From the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent, the hydrophobic unsaturated monomer is preferably 10 g or less, more preferably 1 g or less, more preferably 0, at 20 ° C. with respect to 100 g of water. .1 g or less.

  The repeating unit derived from the hydrophobic unsaturated monomer is preferably a structural unit represented by the general formula (1) from the viewpoint of enhancing the hydrophilization performance of the 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 hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms 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 general formula (1 ′) are all synonymous.

In the formula (1) and the formula (1 ′), R ¹ and R ² from the viewpoint of availability of the unsaturated monomer, the polymerizability of the monomer, and the hydrophilization performance of the hydrophilizing agent. Is preferably a hydrogen atom. 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 a hydrocarbon group having 1 to 7 carbon atoms. More preferred. Examples of the hydrocarbon group for R ⁴ include an alkyl group, an alkenyl group, and a benzyl group. Examples of R ⁴ include a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, and a benzyl group, preferably a linear or branched alkyl group having 1 to 12 carbon atoms or An alkenyl group and a benzyl group, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms and a benzyl group.

  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, behenyl (meth) acrylate and benzyl (meth) acrylate, N -Ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide N, N-diethyl (meth) include (meth) acrylamides such as acrylamide.

From the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent, the unsaturated monomer a is preferably a (meth) acrylate, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, ( From n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, and benzyl (meth) acrylate 1 or more selected, more preferably 1 selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and benzyl (meth) acrylate It is a seed or two or more kinds.
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 unsaturated monomer a in the unsaturated monomer constituting the polymer segment A-1 is preferably 70% by mass or more from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent. Preferably it is 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, still more preferably substantially 100% by weight, and even more preferably 100% by weight. It is.
In addition, substantially 100 mass% is the meaning including the case where structural units other than the repeating unit derived from the unsaturated monomer a are inevitably mixed in the polymer segment A-1 of this invention.

  The weight average molecular weight of the polymer segment A-1 is preferably 1500 or more, more preferably 2000 or more, from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent, and compoundability (suppression of increase in viscosity of the blend, etc.). From this viewpoint, it is preferably 50000 or less, more preferably 10,000 or less, more preferably 8000 or less, and more preferably 6000 or less. This weight average molecular weight can be measured by the method described in Examples.

[Polymer segment A-2]
(Configuration of polymer segment A-2)
Polymer segment A-2 contains a repeating unit derived from an unsaturated monomer having a sulfobetaine group. The repeating unit derived from the unsaturated monomer having a sulfobetaine group is preferably a structural unit represented by the general formula (2) from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent.

[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 and R ¹⁰ : the same or different, and having 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom or 1 or more carbon atoms, and 4 or less hydrocarbon group X ² : 2 or more carbon atoms optionally having a hydroxyl group 4 The following alkylene groups are shown. ]

In formula (2), R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of unsaturated monomers, from the viewpoint of polymerizability of the monomers, and from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment agent. 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 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 an alkylene group having 3 or 4 carbon atoms which may have a hydroxyl group from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent and the ease of the quaternization reaction, and includes a propylene group and a butylene group. 2-hydroxypropylene group is more preferable, and propylene group and 2-hydroxypropylene group are more preferable.

  The polymer segment B may contain a structural unit derived from a monomer other than the unsaturated monomer having a sulfobetaine group within a range not impairing the effects of the present application. As the monomer other than the unsaturated monomer having a sulfobetaine group, an unsaturated monomer other than the unsaturated monomer a is preferable, and (meth) acrylic acid, hydroxyethyl (meth) acrylate, oxyethylene chain More preferred are hydrophilic unsaturated monomers such as acrylate, acrylamide, and dimethylacrylamide.

The content of the repeating unit derived from the unsaturated monomer having a sulfobetaine group in the polymer segment A-2 is preferably 70% by mass or more from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent. Preferably it is 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, still more preferably substantially 100% by weight, and even more preferably 100% by weight. It is.
In addition, substantially 100 mass% means that the structural unit other than the repeating unit derived from the unsaturated monomer having a sulfobetaine group is inevitably mixed in the polymer segment A-2 of the present invention. It is.

[Block polymer A]
The weight average molecular weight of the block polymer A is preferably 2500 or more, more preferably 3500 or more, more preferably 6000 or more, more preferably 10,000 or more, more preferably 25000, from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment agent. From the viewpoint of compoundability, it is preferably 500000 or less, more preferably 400000 or less, more preferably 300000 or less, more preferably 200000 or less, and more preferably 150,000 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 A- The repeating structure of B-A-B-A-B ... is mentioned, and from the viewpoint of manufacturability, the structure of the block of AB is preferable.

(Method for producing block polymer A)
The production method of the block polymer A used in the present invention is not particularly limited and can be produced by a known method. For example, a monomer can be polymerized by living polymerization to obtain a block polymer. Examples of living polymerization include living radical polymerization, living anion polymerization, and living cation polymerization. Living radical polymerization is preferable from the viewpoint of simplicity of the polymerization operation.
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 polymerization of the second block after being isolated and purified, or the first polymer is not isolated and purified, and the first polymer can be subjected to the first polymerization during or after the polymerization of the first polymer. The block can be polymerized by adding a second monomer to the polymerization. Isolation and purification can be performed by a well-known method, for example, by adding a polymerization solution to a polymer poor solvent to precipitate a polymer, followed by filtration and drying.

Examples of the block polymer A of the present invention include block polymers obtained by a production method having a step of quaternizing the following block polymer A ′.
Block polymer A ′: a block polymer having a polymer segment A-1 and a polymer segment having an amino group, which is a precursor polymer segment of the polymer segment A-2

  As a manufacturing method of the block polymer of this invention, polymer segment A-1 containing the repeating unit of general formula (1) is manufactured previously, and the polymer segment containing the repeating unit of the following general formula (2-1) (Precursor polymer segment of polymer segment A-2) and quaternization method (production method (1)), and polymer segment (polymer segment) containing the repeating unit of general formula (2-1) A-2 (precursor polymer segment) is produced first, polymer segment A-1 is produced and quaternized (production method (2)), and the hydrophilization performance of the hydrophilizing agent From the viewpoint of improvement, production method (1) is preferred.

[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 and R ¹⁰ : the same or different, and having 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ¹¹ , R ¹¹ 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 step 1 and step 2. Therefore, the block polymer A of the present invention includes a block polymer obtained by the production method including the steps 1 and 2.

Step 1: The unsaturated monomer represented by the following general formula (1 ′) is polymerized, preferably living polymerized, and then the unsaturated monomer represented by the following general formula (2 ′) is polymerized, preferably The process of carrying out living polymerization and obtaining block polymer A '.

[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 hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms 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 and R ¹⁰ : the same or different, and having 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ¹¹ , R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

Step 2: A step of obtaining block polymer A by reacting block polymer A '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 is Cl or Br, preferably Cl, X ² is an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, preferably a 2-hydroxypropylene group, M represents Na or K. .)

In Formula (2 ′), R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of unsaturated monomers, from the viewpoint of polymerizability of the monomers, and from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment agent. . 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 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.
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, block 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 2 is a step in which the side chain amino group of the block polymer A ′ is reacted with the quaternizing agent of the general formula (B1) or (B2) to obtain a block polymer A 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 block polymer A ′. 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 hydrophilizing agent in the hydrophilizing agent composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving the hydrophilizing performance of the hydrophilizing agent composition. More preferably, the content is 0.2% by mass or more, and preferably 5% by mass or less, preferably 2.0% by mass from the viewpoint of preventing a uniform treatment by thickening and preventing the hydrophilization performance from deteriorating. Hereinafter, it is 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 enhancing the hydrophilic performance of the hydrophilic treatment composition. By using the surfactant, the hydrophilic treatment composition is easily wetted and spread on the solid surface, and the hydrophilic 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 hydrophilization performance is improved.
The content of the surfactant in the hydrophilizing agent composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent composition. Preferably, the content is 0.05% by mass or more, and is preferably 30% by mass or less, preferably 20% by mass from the viewpoint of preventing the adsorption of the block polymer A to the solid surface and preventing the hydrophilization performance from being lowered. Hereinafter, it is more preferably 10% 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 (sodium laureth-2 sulfate) are used from the viewpoint of improving the hydrophilic performance of the hydrophilic treatment composition. ) And the like, 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), Is sulfosuccinic acid alkyl ester salt such as sodium laureth-2 sulfosuccinate, acyl glutamate such as sodium N-acyl-L-glutamate (sodium cocoyl glutamate), acyl isethionate, and acylmethyl taurate? One or more preferably chosen, 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 oxyalkylene (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, polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, and alkylglycoside are selected from the viewpoint of improving the hydrophilization 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, 1 is selected from imidazoline-based betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and alkylhydroxysulfobetaines from the viewpoint of improving the hydrophilization performance of the hydrophilizing composition. A seed | species or 2 or more types is 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 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. Examples thereof include ammonium salts, pyridinium salts, and 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 hydrophilization performance of the hydrophilizing agent 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 acid such as acid, polymethacrylic acid, polymaleic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, poly-p-styrenesulfonic acid; lower alcohol such as ethyl alcohol and isopropyl alcohol; solvent such as diethylene glycol monobutyl ether A salt that improves the solubility of a hydrophilizing agent such as NaCl in water; a solubilizer such as toluene sulfonate, xylene sulfonate, or urea; a viscosity modifier such as clay mineral or water-soluble polymer compound ( Except for block polymer A); calcite, silica, calcium phosphate, zeolite, charcoal Water-insoluble abrasives such as calcium, polyethylene, nylon and polystyrene; Moisturizers such as glycerin and sorbitol; Touch improvers such as cationized cellulose (excluding block polymer A); Alkali builders such as sodium carbonate and sodium silicate Enzymes, pigments, fragrances, preservatives and fungicides can be added.

[Production of hydrophilizing agent composition]
The hydrophilic treatment agent composition of the present invention is agitated and mixed by a known method by adding the block polymer A, water and other components such as the surfactant and polyvalent organic acid as necessary. 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 hydrophilic 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 solid surface is hydrophilized with the hydrophilizing agent composition is preferably 5 ° C. or more, more preferably from the viewpoint of enhancing the hydrophilizing performance of the hydrophilizing agent composition and the ease of the treating method. Is 10 ° C or higher, more preferably 15 ° C or higher, preferably 50 ° C or lower, more preferably 40 ° C or lower, more preferably 30 ° C or lower.
In the method (i), the immersion time is preferably 0.5 minutes or more, more preferably 1 minute or more, from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment composition and from the viewpoint of economy. Preferably it is 60 minutes or less, More preferably, it is 50 minutes or less.
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, for example, 0.01 mL per 10 cm ^{2 in} the case of a hydrophilizing agent composition in which the content of the block polymer A is 0.5% by mass. It is 0.1 mL or less.
In the method (iii), it is preferably used in the form of a cleaning composition containing the block polymer A and a surfactant and brought into contact with a solid surface. In the case of the form of such a cleaning composition, the pH is preferably 4 or more, preferably 10 or less, more preferably 8 or less, from the viewpoints of handling safety and prevention of damage to the solid surface.
As the surfactant, those described above can be used.

The static contact angle with respect to water of the solid surface hydrophilized by the hydrophilizing composition of the present invention is preferably 50 ° or less, more preferably 40 ° or less, more preferably 30 ° or less, more preferably It is 25 degrees or less.
Moreover, it is preferable that the solid surface hydrophilized by the hydrophilizing composition of the present invention is uniformly treated from the viewpoint of enhancing the hydrophilization performance. The uniformity of the surface 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) It measured by the weight average molecular weight gel permeation chromatography (polystyrene conversion) of polymer segment A-1.
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 °
Solvent: trifluoroethanol

(3) Content of polymer segment A-1 in block polymer Using the weight average molecular weight of polymer segment A-1 determined in the above (1) and (2), the weight average molecular weight of the block polymer, It calculated | required from the following formula.
Content (%) of polymer segment A-1 in block polymer = weight average molecular weight of polymer segment A-1 / weight average molecular weight of block polymer × 100

Production Example 1 (Production of Polymer A1)
(Process 1)
In an eggplant flask, 30 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 1.169 g of ethyl 2-bromoisobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4′-dinonyl-2,2′-dipyridyl ( 3.67 g (manufactured by Sigma Aldrich) and 45 g of anisole were added, stoppered with a three-way cock, and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip, 0.297 g of copper chloride (I) (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.201 g of copper chloride (II) (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in another eggplant flask. After plugging with a cock and purging with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 3 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Subsequently, the polymerization solution was dropped while stirring a mixed solution of 200 mL of water and 600 mL of methanol to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, in an eggplant flask, 20 g of 2- (dimethylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.85 g of the polymer solid obtained above, 1,1,4,7,10,10-hexamethyl A monomer solution was prepared by adding 0.07 g of triethylenetetramine (manufactured by Sigma Aldrich) and 8.6 g of anisole, stoppered with a three-way cock, and bubbling with nitrogen for 15 minutes. Next, a stirrer chip and 0.028 g of copper (I) chloride were put into another eggplant flask, and the mixture was stoppered with a three-way cock and purged with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 14 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
3 g of the polymer obtained in an eggplant flask and 12 g of 2,2,2-trifluoroethanol (manufactured by Sigma-Aldrich) were added to dissolve the polymer. 2.4 g of 1,3-propane sultone (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise while heating to 50 ° C. with a three-way cock. 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 solid of polymer A1 was obtained by filtration and drying.

Production Example 2 (Production of polymer A2)
(Process 1)
Place 15 g of methyl methacrylate, 1.46 g of ethyl 2-bromoisobutyrate, 4.6 g of 4,4'-dinonyl-2,2'-dipyridyl and 35 g of anisole in an eggplant flask, stopper with a three-way cock, and perform nitrogen bubbling for 15 minutes. A monomer solution was prepared. Next, a stirrer chip, 0.371 g of copper (I) chloride, and 0.252 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 2.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, the polymerization solution was dropped while stirring hexane to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, in the eggplant flask, 5 g of 2- (dimethylamino) ethyl methacrylate, 0.636 g of the polymer solid obtained above, 0.11 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 11.67 g of anisole were added. Then, it was stoppered with a three-way cock and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip and 0.0314 g of copper (I) chloride were put into another eggplant flask, and the mixture was stoppered with a three-way cock and purged with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 8 hours, the polymerization solution was cooled with ice while being exposed to air, to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 2.3 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. The mixture was allowed to react for 5 hours and then cooled. While stirring 500 mL of methanol, the polymer solution was added dropwise to precipitate the polymer, and the polymer A2 solid was obtained by filtration and drying.

Production Example 3 (Production of polymer A3)
(Process 1)
Place 15 g of methyl methacrylate, 1.46 g of ethyl 2-bromoisobutyrate, 4.6 g of 4,4'-dinonyl-2,2'-dipyridyl and 35 g of anisole in an eggplant flask, stopper with a three-way cock, and perform nitrogen bubbling for 15 minutes. A monomer solution was prepared. Next, a stirrer chip, 0.371 g of copper (I) chloride, and 0.252 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 2.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, the polymerization solution was dropped while stirring hexane to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, in the eggplant flask, 5 g of 2- (dimethylamino) ethyl methacrylate, 1.06 g of the polymer solid obtained above, 0.183 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine and 11.67 g of anisole were added. Then, it was stoppered with a three-way cock and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip and 0.0524 g of copper (I) chloride were put into another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 3 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 2 g of the polymer obtained and 8 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 1.5 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. The mixture was allowed to react for 5 hours and then cooled. While stirring 500 mL of methanol, the polymer solution was added dropwise to precipitate the polymer, and a solid of polymer A3 was obtained by filtration and drying.

Production Example 4 (Production of Polymer A4)
(Process 1)
Place 15 g of methyl methacrylate, 1.46 g of ethyl 2-bromoisobutyrate, 4.6 g of 4,4'-dinonyl-2,2'-dipyridyl and 35 g of anisole in an eggplant flask, stopper with a three-way cock, and perform nitrogen bubbling for 15 minutes. A monomer solution was prepared. Next, a stirrer chip, 0.371 g of copper (I) chloride, and 0.252 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 2.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, the polymerization solution was dropped while stirring hexane to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, in the eggplant flask, 5 g of 2- (dimethylamino) ethyl methacrylate, 2.12 g of the polymer solid obtained above, 0.37 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine and 20.0 g of anisole were added. Then, it was stoppered with a three-way cock and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip, 0.105 g of copper (I) chloride and 0.0285 g of copper (II) chloride were placed in another eggplant flask, and the monomer solution was added after plugging with a three-way cock and replacing with nitrogen. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 3.8 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
1.36 g of the polymer obtained in an eggplant flask and 5.4 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was capped with a three-way cock, and 0.8 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. 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 A4 solid was obtained by filtration and drying.

Production Example 5 (Production of polymer A5)
(Process 1)
Place 15 g of methyl methacrylate, 1.46 g of ethyl 2-bromoisobutyrate, 4.6 g of 4,4'-dinonyl-2,2'-dipyridyl and 35 g of anisole in an eggplant flask, stopper with a three-way cock, and perform nitrogen bubbling for 15 minutes. A monomer solution was prepared. Next, a stirrer chip, 0.371 g of copper (I) chloride, and 0.252 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 2.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, the polymerization solution was dropped while stirring hexane to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, add 2 g of 2- (dimethylamino) ethyl methacrylate, 1.6 g of the polymer solid obtained above, 0.274 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 8 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip, 0.0787 g of copper (I) chloride, and 0.0427 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 1.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 1.205 g of the obtained polymer and 4.9 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 0.55 g of 1,3 propane sultone was added dropwise while heating to 50 ° C. 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, followed by filtration and drying to obtain a solid of polymer A5.

Production Example 6 (Production of polymer A6)
(Process 1)
Place 15 g of methyl methacrylate, 1.46 g of ethyl 2-bromoisobutyrate, 4.6 g of 4,4'-dinonyl-2,2'-dipyridyl and 35 g of anisole in an eggplant flask, stopper with a three-way cock, and perform nitrogen bubbling for 15 minutes. A monomer solution was prepared. Next, a stirrer chip, 0.371 g of copper (I) chloride, and 0.252 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 2.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, the polymerization solution was dropped while stirring hexane to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, in the eggplant flask, 1.5 g of 2- (dimethylamino) ethyl methacrylate, 1.6 g of the polymer solid obtained above, 0.292 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 8.5 g of anisole And stoppered with a three-way cock and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip, 0.0787 g of copper (I) chloride, and 0.0534 g of copper (II) chloride were put into another eggplant flask, and after replacing with nitrogen with a three-way cock, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 2 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 1.205 g of the obtained polymer and 4.9 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 0.3 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. The mixture was allowed to react for 5 hours and then cooled. While stirring 500 mL of methanol, the polymer solution was added dropwise to precipitate the polymer, and the polymer A6 solid was obtained by filtration and drying.

Production Example 7 (Production of polymer B1)
(Process 1)
In an eggplant flask, put 30 g of n-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.823 g of ethyl 2-bromoisobutyrate, 2.58 g of 4,4'-dinonyl-2,2'-dipyridyl and 45 g of anisole. The monomer solution was prepared by stoppering with a cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip, 0.209 g of copper (I) chloride, and 0.141 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 6 hours, the polymerization solution was ice-cooled while being exposed to air to complete the polymerization. Next, a polymerization solution was dropped while stirring a mixed solution of 500 mL of ion-exchanged water and 1500 mL of methanol to precipitate a polymer, and a polymer solid was obtained by decantation and drying. Next, add 30 g of 2- (dimethylamino) ethyl methacrylate, 2.83 g of the polymer solid obtained above, 0.146 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 30 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip and 0.0629 g of copper (I) chloride were put into another eggplant flask, and the mixture was stoppered with a three-way cock and replaced with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 7.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 2 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 2.2 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, and a solid of polymer B1 was obtained by filtration and drying.

Production Example 8 (Production of polymer B2)
(Process 1)
Put 15g of n-butyl methacrylate, 1.03g of ethyl 2-bromoisobutyrate, 3.23g of 4,4'-dinonyl-2,2'-dipyridyl and 35g of anisole into an eggplant flask, stopper with a three-way cock, and bubbling with nitrogen for 15 minutes To prepare a monomer solution. Next, a stirrer chip, 0.261 g of copper (I) chloride, and 0.177 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 4 hours, the polymerization solution was ice-cooled while being exposed to air to complete the polymerization. Next, a polymerization solution was dropped while stirring a mixed solution of 500 mL of ion-exchanged water and 1500 mL of methanol to precipitate a polymer, and a polymer solid was obtained by decantation and drying. Next, in an eggplant flask was charged 30 g of 2- (dimethylamino) ethyl methacrylate, 0.174 g of the polymer solid obtained above, 0.0293 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 12.9 g of anisole. Then, it was stoppered with a three-way cock and nitrogen bubbling was performed for 15 minutes to prepare a monomer solution. Next, a stirrer chip and 0.0126 g of copper (I) chloride were put into another eggplant flask, and the inside was replaced with nitrogen with a three-way cock, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 27 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 2 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 27 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 2.6 g of 1,3 propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, and a solid of polymer B2 was obtained by filtration and drying.

Production Example 9 (Production of polymer B3)
(Process 1)
Put 15g of n-butyl methacrylate, 1.03g of ethyl 2-bromoisobutyrate, 3.23g of 4,4'-dinonyl-2,2'-dipyridyl and 35g of anisole into an eggplant flask, stopper with a three-way cock, and bubbling with nitrogen for 15 minutes To prepare a monomer solution. Next, a stirrer chip, 0.261 g of copper (I) chloride, and 0.177 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 4 hours, the polymerization solution was ice-cooled while being exposed to air to complete the polymerization. Next, a polymerization solution was dropped while stirring a mixed solution of 500 mL of ion-exchanged water and 1500 mL of methanol to precipitate a polymer, and a polymer solid was obtained by decantation and drying. Next, add 30 g of 2- (dimethylamino) ethyl methacrylate, 1.73 g of the polymer solid obtained above, 0.293 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 70 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip and 0.126 g of copper (I) chloride were placed in another eggplant flask, and the mixture was stoppered with a three-way cock and purged with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 5 hours, the polymerization solution was ice-cooled while exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 2 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 2.5 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, and a solid of polymer B3 was obtained by filtration and drying.

Production Example 10 (Production of polymer B4)
(Process 1)
Put 15g of n-butyl methacrylate, 1.03g of ethyl 2-bromoisobutyrate, 3.23g of 4,4'-dinonyl-2,2'-dipyridyl and 35g of anisole into an eggplant flask, stopper with a three-way cock, and bubbling with nitrogen for 15 minutes To prepare a monomer solution. Next, a stirrer chip, 0.261 g of copper (I) chloride, and 0.177 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 4 hours, the polymerization solution was ice-cooled while being exposed to air to complete the polymerization. Next, a polymerization solution was dropped while stirring a mixed solution of 500 mL of ion-exchanged water and 1500 mL of methanol to precipitate a polymer, and a polymer solid was obtained by decantation and drying. Next, add 15 g of 2- (dimethylamino) ethyl methacrylate, 1.74 g of the polymer solid obtained above, 0.293 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 35 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip and 0.063 g of copper (I) chloride were put into another eggplant flask, and the mixture was stoppered with a three-way cock and purged with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 2.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 2.3 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, and a solid of polymer B4 was obtained by filtration and drying.

Production Example 11 (Production of polymer B5)
(Process 1)
Put 15g of n-butyl methacrylate, 1.03g of ethyl 2-bromoisobutyrate, 3.23g of 4,4'-dinonyl-2,2'-dipyridyl and 35g of anisole into an eggplant flask, stopper with a three-way cock, and bubbling with nitrogen for 15 minutes To prepare a monomer solution. Next, a stirrer chip, 0.261 g of copper (I) chloride, and 0.177 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 4 hours, the polymerization solution was ice-cooled while being exposed to air to complete the polymerization. Next, a polymerization solution was dropped while stirring a mixed solution of 500 mL of ion-exchanged water and 1500 mL of methanol to precipitate a polymer, and a polymer solid was obtained by decantation and drying. Next, add 10 g of 2- (dimethylamino) ethyl methacrylate, 2.32 g of the polymer solid obtained above, 0.39 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 40 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip and 0.084 g of copper (I) chloride were put into another eggplant flask, and the mixture was stoppered with a three-way cock and purged with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 2.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock, and 2.0 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, followed by filtration and drying to obtain a solid of polymer B5.

Production Example 12 (Production of polymer B6)
(Process 1)
In an eggplant flask, n-butyl methacrylate 5.0 g, iodine (I2) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.45 g, 2,2'-azobis (isobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.58 g, 0.035 g of cyclohexadiene (manufactured by Wako Pure Chemical Industries, Ltd.), 5.0 g of ethanol and a stirrer chip were placed, and a three-way cock and a reflux tube were attached. Nitrogen bubbling was performed for 15 minutes, and then the mixture was heated to 80 ° C. to initiate polymerization of n-butyl methacrylate. Next, 49.8 g of 2- (dimethylamino) ethyl methacrylate, 2,72'-azobis (0.072 g of isobutyronitrile, and 49.8 g of ethanol) were placed in another eggplant flask, and nitrogen bubbling was performed for 15 minutes. Four hours after the start of n-butyl polymerization, the above-mentioned 2- (dimethylamino) ethyl methacrylate solution was added to the n-butyl methacrylate polymerization solution, and the reaction was further continued for 5 hours. The polymer solution was dropped while stirring 5 L of hexane to precipitate a polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 2.5 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was added dropwise with stirring of 500 mL of methanol to precipitate a polymer, followed by filtration and drying to obtain a solid of polymer B6.

Production Example 13 (Production of polymer C1)
(Process 1)
Put 15g lauryl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.575g ethyl 2-bromoisobutyrate, 1.81g 4,4'-dinonyl-2,2'-dipyridyl and 35g anisole in an eggplant flask. The monomer solution was prepared by stoppering and nitrogen bubbling for 15 minutes. Next, a stirrer chip, 0.146 g of copper (I) chloride, and 0.099 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 8 hours, the polymerization solution was cooled with ice while being exposed to air, to complete the polymerization. Next, the polymerization solution was dropped while stirring 1500 mL of methanol to precipitate a polymer, and a polymer solid was obtained by decantation and drying. Next, add 10 g of 2- (dimethylamino) ethyl methacrylate, 0.539 g of the polymer solid obtained above, 0.0488 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 10 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip and 0.021 g of copper (I) chloride were put into another eggplant flask, and the mixture was stoppered with a three-way cock and purged with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 5.3 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by an activated alumina column treatment, a polymer solution was dropped while stirring 1 L of ion-exchanged water to precipitate a polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was capped with a three-way cock and 2.7 g of 1,3 propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, and a solid of polymer C1 was obtained by filtration and drying.

Production Example 14 (Production of polymer D1)
(Process 1)
In a recovery flask, put 15 g of benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.83 g of ethyl 2-bromoisobutyrate, 2.61 g of 4,4'-dinonyl-2,2'-dipyridyl, and 35 g of anisole. The monomer solution was prepared by stoppering and nitrogen bubbling for 15 minutes. Next, a stirrer chip, 0.211 g of copper (I) chloride, and 0.143 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, and then polymerization was performed by heating to 62 ° C. After reacting for 6 hours, the polymerization solution was ice-cooled while being exposed to air to complete the polymerization. Next, a polymerization solution was dropped while stirring a mixed solution of 500 mL of ion-exchanged water and 1500 mL of methanol to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, add 30 g of 2- (dimethylamino) ethyl methacrylate, 2.15 g of the polymer solid obtained above, 0.293 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 70 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip and 0.126 g of copper (I) chloride were placed in another eggplant flask, and the mixture was stoppered with a three-way cock and purged with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After reacting for 5 hours, the polymerization solution was ice-cooled while exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 2 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock and 2.5 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After reacting for 5 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, and a solid of polymer D1 was obtained by filtration and drying.

Production Example 15 (Production of polymer E1)
(Process 1)
In a recovery flask, place 5.0 g of n-butyl methacrylate, 0.45 g of iodine (I2), 0.58 g of 2,2'-azobis (isobutyronitrile), 0.035 g of cyclohexadiene, 5.0 g of ethanol, and a stirrer chip. A reflux tube was attached. Nitrogen bubbling was performed for 15 minutes, and then the mixture was heated to 80 ° C. to initiate polymerization of n-butyl methacrylate. Next, 49.8 g of 2- (dimethylamino) ethyl methacrylate, 2,72'-azobis (0.072 g of isobutyronitrile, and 49.8 g of ethanol) were placed in another eggplant flask, and nitrogen bubbling was performed for 15 minutes. Four hours after the start of n-butyl polymerization, the above-mentioned 2- (dimethylamino) ethyl methacrylate solution was added to the n-butyl methacrylate polymerization solution, and the reaction was further continued for 5 hours. The polymer solution was dropped while stirring 5 L of hexane to precipitate a polymer, and a polymer solid was obtained by filtration and drying.
(Process 2)
The eggplant flask was charged with 3 g of the obtained polymer, 12 g of 2,2,2-trifluoroethanol, 6 g of ion-exchanged water, and 4.2 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate (manufactured by Sigma-Aldrich). It was plugged with a three-way cock and heated to 80 ° C. After reacting for 24 hours, the mixture was cooled, and a polymer solution was dropped while stirring 500 mL of methanol to precipitate a polymer, followed by filtration and drying to obtain a solid of polymer E1.

Production Example 16 (Production of polymer F1)
In a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen introduction tube and a stirring device, dimethylaminoethyl methacrylate 49 g, t-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 1.9 g, 2,2 0.31 g of '-azobis (2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethanol were charged, and the reaction was performed at 80 ° C. for 4 hours while blowing nitrogen. After adding a solution obtained by dissolving 67.5 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate in 70 g of ethanol / water (= 50/50 mass ratio) to the obtained polymerization reaction solution, and sufficiently stirring, Heated to 80 ° C. After reacting for 24 hours, the mixture was cooled, filtered to remove the precipitate, and dried to obtain a solid of polymer F1.

Production Example 17 (Production of polymer F2)
A separable flask equipped with a cooling reflux tube, a thermometer, a nitrogen introduction tube and a stirrer was charged with N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium (Sigma). 28.39 g (manufactured by Aldrich), 1.61 g of n-butyl methacrylate, and 67.48 g of trifluoroethanol were mixed and mixed uniformly and stirred for 30 minutes in a nitrogen atmosphere. After the temperature of this solution was raised to about 70 ° C., 0.28 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.52 g of trifluoroethanol were added for 6 hours. The polymerization was carried out while holding. Next, the polymer solution was dropped while stirring 4 L of methanol to precipitate a polymer, and a solid of polymer F2 was obtained by filtration and drying.

Production Example 18 (Production of polymer F3)
In a separable flask equipped with a cooling reflux tube, a thermometer, a nitrogen introduction tube and a stirrer, 24.63 g of N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium Then, 5.37 g of n-butyl methacrylate and 67.18 g of trifluoroethanol were added, mixed uniformly, and stirred for 30 minutes under a nitrogen atmosphere. After the temperature of this solution was raised to about 70 ° C., 0.32 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 2.82 g of trifluoroethanol were added, and polymerization was carried out by maintaining for 6 hours. Next, the polymer solution was dropped while stirring 4 L of methanol to precipitate a polymer, and a solid of polymer F3 was obtained by filtration and drying.

  Weight average molecular weight and content of polymer segment A-1 of obtained polymers A1 to A6, polymers B1 to B6, polymer C1, polymer D1, polymer E1, and polymers F1 to F3, and block polymer A Is shown in Table 1.

* 1 Content of the structural unit represented by general formula (1) in the polymer

Examples 1-15, Comparative Examples 1-3
Using the polymers obtained in the above production examples, the hydrophilic treatment agent compositions were prepared so as to have the compositions shown in Table 2, and the hydrophilic treatment agent compositions of Examples 1 to 15 and Comparative Examples 2 and 3 were obtained. It was. In Comparative Example 1, nothing other than water was blended. In addition, ion-exchange water was used for water.
The following evaluation was used using the hydrophilic treatment agent compositions of Examples 1 to 15, water of Comparative Example 1, and the hydrophilic treatment agent compositions of Comparative Examples 2 and 3.

[Test method (evaluation of hydrophilic surface)]
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 lightly with about 200 mL of ion-exchange water, and air-dried.
Using the automatic contact angle meter “DM-500” (manufactured by Kyowa Interface Science Co., Ltd.), the amount of 10 μL added and the condition 6 seconds after the addition were used for the static contact angle with respect to ion-exchanged water on the surface of the treated part of this test piece 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 hydrophilization performance. The results are shown in Table 2.

* 1 Content of the structural unit represented by the general formula (1) in the polymer In the table, the symbol of the monomer has the following meaning (the same applies hereinafter).
SBMA: N- (3-sulfopropyl) -N-methacryloxyethyl-N, N-dimethylammonium betaine SB (OH) MA: N- (3-sulfo-2-hydroxypropyl) -N-methacryloxyethyl -N, N-dimethylammonium betaine-MMA: methyl methacrylate-BMA: n-butyl methacrylate-LMA: lauryl methacrylate-BzMA: benzyl methacrylate-tBMA: t-butyl methacrylate

  As is clear from Table 2, the hydrophilic treatment compositions of Examples 1 to 15 can lower the contact angle and make the surface hydrophilic as compared with the hydrophilic treatment compositions of Comparative Examples 2 and 3. Excellent performance.

Examples 16 to 27, Comparative Examples 4 to 6
Using the polymers obtained in the above production examples, a hydrophilic treatment agent composition was prepared so as to have the composition shown in Table 3, and the hydrophilic treatment agent compositions of Examples 16 to 27 and Comparative Examples 4 to 6 were obtained. It was.
The surfactants and solvents used for the preparation of the hydrophilic treatment composition are as follows.
Surfactant: C12-16 straight chain alkyl group, ethylene oxide average addition mole number 4.0 polyoxyethylene alkyl ether sulfate sodium salt Solvent: Diethylene glycol monobutyl ether

  Using the hydrophilic treatment agent compositions of Examples 16 to 27 and Comparative Examples 4 to 6, a hydrophilic surface formation test was conducted in the same manner as in Example 1. The results are shown in Table 3.

* 1 Content of the structural unit represented by general formula (1) in the polymer

  As is clear from Table 3, the hydrophilic treatment compositions of Examples 16 to 27 can reduce the contact angle and make the surface hydrophilic, compared with the hydrophilic treatment compositions of Comparative Examples 4 to 6. Excellent performance.

Example 28, Comparative Examples 7 and 8
Using the polymer B3 and the polymer F3, a hydrophilic treatment composition was prepared so as to have the composition shown in Table 4, and the hydrophilic treatment compositions of Example 28 and Comparative Example 8 were obtained.
The surfactant and solvent used for the preparation of the hydrophilic treatment composition are the same as those in Example 16.

Using the hydrophilic treatment agents of Example 28, Comparative Example 7 and Comparative Example 8, a hydrophilic surface formation test was conducted in the same manner as described above except that 2 mL of the polymer solution was dropped only when the glass substrate was used. The substrate used for the test is as follows.
Stainless steel: "Stainless steel test piece" (manufactured by Engineering Test Service Co., Ltd., material: JIS G 4305 SUS304, 25 mm x 75 mm)
Glass: “Glass test piece” (Akebono Shokai, Material: Glass plate (square cutting), 60 mm x 60 mm)
PMMA: “PMMA test piece” (manufactured by Engineering Test Service Co., Ltd., material: polymethyl methacrylate, 25 mm × 75 mm)
PET: “PET test piece” (manufactured by Engineering Test Service, material: polyethylene terephthalate, 25 mm × 75 mm)
FRP: “FRP test piece” (manufactured by Engineering Test Service Co., Ltd., material: fiber reinforced plastic, 25 mm × 75 mm)
Vinyl chloride: “vinyl chloride test piece” (manufactured by Engineering Test Service Co., Ltd., material: rigid polyvinyl chloride, 25 mm × 75 mm)
The results are shown in Table 4.

* 1 Content of the structural unit represented by general formula (1) in the polymer

  As is clear from Table 4, the hydrophilization treatment composition of Example 28 can lower the contact angle compared to the hydrophilization treatment composition of Comparative Example 7 and Comparative Example 8, and the hydrophilization performance. Are better.

Claims (8)

Polymer segment A-1 derived from unsaturated monomer containing repeating unit derived from hydrophobic unsaturated monomer, and derived from unsaturated monomer containing repeating unit derived from unsaturated monomer having sulfobetaine group Polymer segment A-2, and the content of polymer segment A-1 is 0.05% by mass or more and 30 % by mass or less, and a hydrophilizing treatment agent. The hydrophilic treatment agent according to claim 1, wherein the repeating unit derived from the hydrophobic unsaturated monomer in the block polymer A is a structural unit represented by the 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 hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms is shown. ] The hydrophilic treatment agent according to claim 1 or 2, wherein the repeating unit derived from the unsaturated monomer having a sulfobetaine group in the block polymer A is a structural unit represented by the general formula (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 and R ¹⁰ : the same or different, and having 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom or 1 or more carbon atoms, and 4 or less hydrocarbon group X ² : 2 or more carbon atoms optionally having a hydroxyl group 4 The following alkylene groups are shown. ]   The hydrophilic treatment agent according to any one of claims 1 to 3, wherein the block polymer A has a weight average molecular weight of 2500 or more and 500,000 or less. The hydrophilic treatment agent according to any one of claims 1 to 4, wherein the block polymer A is a block polymer obtained by a production method including a step of quaternizing the following block polymer A '.
Block polymer A ′: a block polymer having a polymer segment A-1 and a polymer segment having an amino group, which is a precursor polymer segment of the polymer segment A-2 The hydrophilization treatment agent according to any one of claims 1 to 4, wherein the block polymer A is a block polymer obtained by a production method including the following step 1 and step 2.
Step 1: After the unsaturated monomer represented by the following general formula (1 ′) is polymerized, the unsaturated monomer represented by the following general formula (2 ′) is polymerized to form a block polymer A ′. Obtaining step.

[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 hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms 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 and R ¹⁰ : the same or different, and having 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ¹¹ , R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
Step 2: A step of obtaining block polymer A by reacting block polymer A ′ 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.