JP6212370B2 - 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 discloses a hydrophilic slipping surface treatment agent containing a hydrophilic vinyl monomer having a cationic functional group having a specific structure and a copolymer composed of a silicon macromer having a specific structure and, if necessary, a hydrophobic vinyl monomer. Has been.

JP 2001-181601 A JP-T-2006-514150 JP 2012-25820 A JP 2002-80831 A

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 is derived from an unsaturated monomer-derived polymer segment A-1 containing a repeating unit derived from a hydrophobic unsaturated monomer as a main chain and an unsaturated monomer having a sulfobetaine group as a side chain. The present invention relates to a hydrophilic treatment agent comprising a graft polymer A having a polymer segment A-2 derived from an unsaturated monomer containing a repeating unit.
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 graft polymer A.
The graft polymer A is derived from an unsaturated monomer-derived polymer segment A-1 containing a repeating unit derived from a hydrophobic unsaturated monomer as a main chain and an unsaturated monomer having a sulfobetaine group as a side chain. It has a polymer segment A-2 derived from an unsaturated monomer containing a repeating unit.

[Main chain polymer segment A-1]
(Configuration of main chain polymer segment A-1)
The main chain 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 structural unit derived by polymerizing an unsaturated monomer represented by the following general formula (4) (hereinafter also referred to as an unsaturated monomer a). In the general formulas (1) and (4), R ¹ , R ² , R ³ , R ⁴ and Y ¹ are all synonymous.

In formula (1) and formula (4), from the viewpoint of availability of unsaturated monomers, from the viewpoint of polymerizability of monomers and from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent, R ¹ and R ² are A hydrogen atom is preferred. 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 linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a benzyl group, and more preferably a linear or branched chain having 1 to 12 carbon atoms or benzyl group. A branched alkyl group, an alkenyl group, or a benzyl group, more preferably a linear or branched 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, 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, ( It is one or more selected from n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate and n-hexyl (meth) acrylate, more preferably It is 1 type, or 2 or more types chosen from methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate n-butyl.
In the present specification, “(meth) acryl” means acrylic, methacrylic, or both.

From the viewpoint of production of the graft polymer A, the main chain polymer segment A-1 is an unsaturated monomer having a reactive functional group capable of reacting with a reactive functional group of the side chain polymer segment B-2 described later ( Hereinafter, it is preferably obtained from main chain polymer segment B-1 containing a repeating unit derived from unsaturated monomer b).
Examples of the reactive functional group of the unsaturated monomer b include an epoxy group, an isocyanate group, a carboxy group, a phosphoric acid group, a sulfonic acid group, an amino group, and a hydroxy group.

As unsaturated monomer b containing an epoxy group, (meth) acrylic acid ester such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc. , (Meth) acrylamides such as N-glycidyl (meth) acrylamide, allyl ethers such as allyl glycidyl ether, 1,2-epoxy-5-hexene, and the like.
Examples of the unsaturated monomer b containing an isocyanate group include isocyanate monomers. Specifically, 2-methacryloyloxyethyl isocyanate (product name: Karenz MOI), 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (product name: Karenz MOI-BP), methacrylic acid 2- ( [1′-methylpropylideneamino] carboxyamino) ethyl (product name: Karenz MOI-BM), 2-acryloyloxyethyl isocyanate (product name: Karenz AOI) and the like. All product names are from Showa Denko.

Examples of the unsaturated monomer b containing a carboxy group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, and the like.
Examples of the unsaturated monomer b containing a phosphoric acid group include mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, and the like.
Examples of the unsaturated monomer b containing a sulfonic acid group include acrylamide 2-methylpropanesulfonic acid.
As the unsaturated monomer b containing an amino group, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like can be mentioned.
Examples of the unsaturated monomer b containing a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene glycol, polypropylene glycol, And monoesters of polyether polyols such as polybutylene glycol and unsaturated carboxylic acids such as (meth) acrylic acid.

  Among these, from the viewpoint of improving the productivity of the reaction in Step 3 described later, an unsaturated monomer b containing an epoxy group is preferred, a (meth) acrylic acid ester containing a glycidyl group is more preferred, and glycidyl (Meth) acrylate is more preferred.

The unsaturated monomer constituting the main chain polymer segment B-1 preferably contains an unsaturated monomer a and an unsaturated monomer b.
The content of the unsaturated monomer a in the unsaturated monomer constituting the main chain polymer segment B-1 is preferably 10% by mass or more from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent. Preferably it is 30% by mass, more preferably 40% by mass, more preferably 50% by mass, preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass. % Or less.

  The content of the unsaturated monomer b in the unsaturated monomer constituting the main chain polymer segment B-1 is preferably 10% by mass or more from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent. Preferably it is 20 mass%, more preferably 25 mass%, more preferably 30 mass%, preferably 90 mass% or less, more preferably 70 mass% or less, more preferably 60 mass% or less, more preferably 50 mass%. % Or less.

The total content of the unsaturated monomer a and the unsaturated monomer b in the unsaturated monomer constituting the main chain polymer segment B-1 is from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment agent. Preferably it is 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably substantially 100% by mass. And 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 and the repeating unit derived from the unsaturated monomer b is contained in the main chain polymer segment B-1 of the present invention. It means to include the case of inevitably mixed.

  The number average molecular weight of the main chain polymer segment A-1 or the main chain polymer segment B-1 is preferably 500 or more, more preferably 2000 or more, more preferably from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment agent. From the same viewpoint, it is preferably 50000 or less, more preferably 10,000 or less, and even more preferably 7000 or less. This number average molecular weight can be measured by the method described in Examples.

  The content of the polymer segment A-1 of the main chain in the graft polymer A is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of improving the hydrophilization performance of the hydrophilizing agent. From the same viewpoint, it is preferably 15% by mass or less, more preferably 10% by mass or less, more preferably 8% by mass or less, more preferably 7% by mass or less, and more preferably 6% by mass or less.

[Side chain polymer segment A-2]
(Configuration of side chain polymer segment A-2)
Side chain 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 the 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, and R ⁸ is preferably an alkylene group having 2 or 3 carbon atoms, more preferably a dimethylene group having 2 carbon atoms from the same viewpoint. 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 quaternary reaction, and includes a propylene group, a butylene group, A 2-hydroxypropylene group is more preferable, and a propylene group is more preferable.

Side chain polymer segment A-2 is a side chain polymer segment having a reactive functional group capable of reacting with the reactive functional group of main chain polymer segment B-1 at one end from the viewpoint of production of graft polymer A. It is preferably obtained from (for example, side chain polymer segment B-2 described later).
Examples of the functional group capable of reacting with the reactive functional group of the main chain polymer segment B-1 include a carboxy group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, and a phosphoric acid group. It can be selected as appropriate in consideration of the type of the reactive functional group of B-1.

When the reactive functional group of the main chain polymer segment B-1 is an epoxy group, the side chain polymer segment is a polymer having a carboxy group at one end (one-end carboxylic acid type polymer) or at one end. A polymer having an amino group (one-terminal amino group type polymer) is preferred.
When the reactive functional group of the main chain polymer segment B-1 is an isocyanate group, the side chain polymer segment is a polymer having a hydroxyl group at one end (one-end hydroxyl group type polymer) or at one end. A polymer having an amino group (one-terminal amino group type polymer) is preferred.
When the reactive functional group of the main chain polymer segment B-1 is a carboxy group, the side chain polymer segment is a polymer having a hydroxyl group at one end (a polymer at one end hydroxyl type) or an amino group at one end. A polymer having a group (one-terminal amino group type polymer) is preferred.
When the reactive functional group of the main chain polymer segment B-1 is a hydroxy group, the side chain polymer segment is a polymer having a carboxy group at one end (one-end carboxy type polymer) or an isocyanate at one end. It is preferably a polymer having a group (one-end isocyanate group type polymer).
When the reactive functional group of the main chain polymer segment B-1 is an amino group, the side chain polymer segment is a polymer having a carboxy group at one end (one-end carboxy type polymer) or an isocyanate at one end. It is preferably a polymer having a group (one-end isocyanate group type polymer).
When the reactive functional group of the main chain polymer segment B-1 is a phosphate group, the side chain polymer segment is a polymer having a hydroxyl group at one end (polymer of one end hydroxyl group type). Is preferred.
When the reactive functional group of the main chain polymer segment B-1 is a sulfonic acid group, the side chain polymer segment is a polymer having a hydroxyl group at one end (polymer of one end hydroxyl group type). Is preferred.
Here, the side chain polymer segment is a side chain weight having a reactive functional group at one end capable of reacting with the reactive functional group of the main chain polymer segment B-1, which becomes the side chain polymer segment A-2. It is a coalesced segment.

From the viewpoint of the productivity of the graft polymer A, the reactive functional group of the main chain polymer segment B-1 is an epoxy group and becomes the side chain polymer segment A-2. The reaction of the main chain polymer segment B-1 It is preferable that the reactive functional group of the side chain polymer segment having a reactive functional group capable of reacting with the functional functional group at one end is a carboxy group.
The side chain polymer segment having a reactive functional group at one end is in the presence of a polymerization initiator or a chain transfer agent containing a reactive functional group capable of reacting with the reactive functional group of the main chain polymer segment B-1. It can be obtained by polymerizing an unsaturated monomer.

The content of the repeating unit derived from the unsaturated monomer having a sulfobetaine group in the side chain polymer segment A-2 is preferably 70% by mass or more from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent. More preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably substantially 100% by mass, and even more preferably 100% by mass. % By mass.
In addition, substantially 100 mass% is a case where the structural unit other than the repeating unit derived from the unsaturated monomer having a sulfobetaine group is inevitably mixed in the side chain polymer segment A-2 of the present invention. Including meaning.

  The number average molecular weight of the side chain polymer segment A-2 is preferably 1000 or more, more preferably 3000 or more, more preferably 4000 or more, from the same viewpoint, from the viewpoint of improving the hydrophilization performance of the hydrophilic treatment agent. , Preferably 200000 or less, more preferably 50000 or less, more preferably 15000 or more. This number average molecular weight can be calculated by the method described in Examples.

[Graft polymer A]
In the graft polymer A, the number of side chains per main chain is preferably 5 or more, more preferably 6 or more, from the viewpoint of improving the hydrophilization performance of the hydrophilic treatment agent, and from the same viewpoint, Preferably it is 20 or less, more preferably 14 or less, more preferably 12 or less.

  The number average molecular weight of the graft polymer A is preferably 40,000 or more, more preferably 50,000 or more, preferably 300,000 or less, more preferably 200,000 or less, from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment agent. More preferably, it is 160,000 or less. This number average molecular weight can be calculated by the method described in Examples.

(Method for producing graft polymer A)
Examples of the method for producing the graft polymer A include the following production methods.
(I) A method of polymerizing an unsaturated monomer having a sulfobetaine group on a main chain segment having a radical reactive group and containing a repeating unit derived from a hydrophobic unsaturated monomer.
(Ii) A method of polymerizing a macromonomer containing a repeating unit derived from an unsaturated monomer having a sulfobetaine group and a hydrophobic unsaturated monomer.
(Iii) A main chain segment containing a repeating unit derived from a hydrophobic unsaturated monomer, having a reactive functional group capable of reacting with the reactive functional group of the side chain segment, and an unsaturated monomer having a sulfobetaine group A method of reacting a side chain segment containing a repeating unit derived from and having a reactive functional group capable of reacting with a reactive functional group of a main chain segment at one end.
Further, (i-1) includes a method in which an unsaturated monomer having an amino group is polymerized instead of a sulfobetaine group, and further converted to a sulfobetaine group by reacting with a quaternizing agent.
Similarly, as (iii-1), a side chain segment containing a repeating unit derived from an unsaturated monomer having an amino group instead of a sulfobetaine group is reacted, and further a quaternizing agent is reacted to obtain a sulfobetaine. The method of converting into a group is mentioned.
From the viewpoint of increasing the productivity of the production of the graft polymer A, the production method of the graft polymer A is preferably the method (iii), more preferably the method (iii-1).

As a method for producing the graft polymer A of the present invention, a method including the following steps 1 to 4 may be mentioned. Therefore, the graft polymer A of the present invention includes a graft polymer obtained by a production method including the following steps 1 to 4. This method belongs to the above production method (iii-1).
Step 1: Unsaturation having a reactive functional group capable of reacting with a hydrophobic functional monomer (unsaturated monomer a) and the reactive functional group of the side chain polymer segment B-2 prepared in Step 2 A step of polymerizing an unsaturated monomer containing a monomer (unsaturated monomer b) to obtain main chain polymer segment B-1.
Step 2: Unsaturated monomer having an amino group (unsaturated in the presence of a polymerization initiator or a chain transfer agent containing a reactive functional group capable of reacting with the reactive functional group of the main chain polymer segment B-1 A step of polymerizing an unsaturated monomer containing monomer c) to obtain a side chain polymer segment B-2.
Process 3: The process of obtaining the graft polymer B by making the main chain polymer segment B-1 obtained at the process 1 and the side chain polymer segment B-2 obtained at the process 2 react.
Step 4: A step of obtaining graft polymer A by reacting graft polymer B with a quaternizing agent.
In addition, the amino group of the unsaturated monomer in the process 2 becomes a precursor of a sulfobetaine group.

[Step 1: Production of main chain polymer segment B-1]
Step 1 is a step of polymerizing an unsaturated monomer containing unsaturated monomer a and unsaturated monomer b to produce main chain polymer ment B-1.

  The content of the unsaturated monomer b in the unsaturated monomer for producing the main chain polymer segment B-1 is preferably 10% by mass or more from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent. Preferably it is 20 mass%, more preferably 25 mass%, more preferably 30 mass%, preferably 90 mass% or less, more preferably 70 mass% or less, more preferably 60 mass% or less, more preferably 50 mass%. % Or less.

The total content of the unsaturated monomer a and the unsaturated monomer b in the unsaturated monomer for producing the main chain polymer segment B-1 is from the viewpoint of enhancing the hydrophilization performance of the hydrophilic treatment agent. Preferably it is 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably substantially 100% by mass. And 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 and the repeating unit derived from the unsaturated monomer b is contained in the main chain polymer segment B-1 of the present invention. It means to include the case of inevitably mixed.

(Method for producing main chain polymer segment B-1)
The polymerization method is not particularly limited, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method and the like can be adopted, but a solution polymerization method is preferable. Solvents used in the solution polymerization method include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane and cyclohexane, diethyl ether and tetrahydrofuran. Examples thereof include aromatic compounds such as ether, benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform.
Examples of the polymerization initiator include azo-based initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), and peroxides such as lauroyl peroxide and benzoyl peroxide. Examples thereof include oxide-based initiators and persulfuric acids such as ammonium persulfate. Moreover, a chain transfer agent etc. can also be used as needed. Examples of chain transfer agents include mercaptans such as dodecyl mercaptan, mercaptoethanol, mercaptopropionic acid.
The reaction temperature can be appropriately selected depending on the polymerization initiator used, the type of solvent, and the like, but is usually preferably in the range of 50 ° C or higher and 100 ° C or lower.

[Step 2: Production of side chain polymer segment B-2]
Unsaturated monomer containing an unsaturated monomer having an amino group in the presence of a polymerization initiator or a chain transfer agent containing a reactive functional group capable of reacting with the reactive functional group of the main chain polymer segment B-1 This is a step of polymerizing the body (unsaturated monomer c) to obtain a side chain polymer segment B-2. The side chain polymer segment B-2 contains a reactive functional group capable of reacting with the reactive functional group of the main chain polymer segment B-1 at one end, including a repeating unit derived from an unsaturated monomer having an amino group. Have.

(Polymerization initiator or chain transfer agent containing a reactive functional group capable of reacting with the reactive functional group of the main chain polymer segment B-1)
In order to introduce a carboxylic acid into one end of the side chain polymer segment B-2, a polymerization initiator containing an azo group such as 4,4′-azobis (4-cyanobutyric acid) and a carboxylic acid, mercaptopropionic acid, etc. It is preferable to use a chain transfer agent containing a mercapto group and a carboxylic acid, and in order to introduce an amino group at one end, a chain transfer agent containing a mercapto group such as aminoethanethiol and an amino group, a hydroxyl group at one end In order to introduce, it is preferable to use a chain transfer agent such as mercaptoethanol containing a mercapto group and a hydroxy group.

(Unsaturated monomer c having an amino group)
As the unsaturated monomer c, from the viewpoint of improving the productivity of the reaction in Step 4 and the availability of the unsaturated monomer, the unsaturated monomer c-1 represented by the general formula (5) Is preferred. By using the unsaturated monomer c-1, the side chain polymer segment B-2 contains a repeating unit represented by the general formula (3).

[In Formula (3) and (5),
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 , and R ¹¹ represents a hydrogen atom or a hydrocarbon group having 4 to 4 carbon atoms. ]

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, and R ⁸ is preferably an alkylene group having 2 or 3 carbon atoms, and preferably a dimethylene group having 2 carbon atoms from the same viewpoint. From the same viewpoint, R ⁹ and R ¹⁰ are preferably a methyl group or an ethyl group, and more preferably a methyl group.
Specifically, from the same viewpoint, the unsaturated monomer c-1 is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, N, N- Dimethylaminoethyl (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide are preferred.

The content of the unsaturated monomer c in the unsaturated monomer for producing the side chain polymer segment B-2 is preferably 70% by mass or more from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent. More preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably substantially 100% by mass, and even more preferably 100% by mass. % By mass.
In addition, substantially 100 mass% is meant to include the case where a structural unit other than the repeating unit derived from the unsaturated monomer c is inevitably mixed in the side chain polymer segment B-2 of the present invention. .

(Production of side chain polymer segment B-2)
The production can be carried out in the same manner as in the production of the main chain polymer segment B-1, except that the polymerization initiator or chain transfer agent and the unsaturated monomer c are used.

[Step 3: Production of graft polymer B]
Step 3 is a step of obtaining graft polymer B by reacting main chain polymer segment B-1 and side chain polymer segment B-2.
In the reaction, a catalyst may be used. From the viewpoint of improving the productivity in Step 3, it is preferable to add a catalyst in the case of a reaction between an epoxy group and a carboxy group or a reaction between an isocyanate group and a hydroxyl group.

Examples of the catalyst for the reaction between the epoxy group and the carboxy group include quaternary ammonium salts, tertiary amines, alkali metal hydroxides, inorganic acids, sulfonic acids, carboxylic acids, solid acids, solid bases and the like.
Examples of the quaternary ammonium salt include halides such as tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodide, tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride. Include triethylamine, dimethylbutylamine, diisopropylethylamine, 2,2,6,6-tetramethylpiperidine and the like.
Among the above catalysts, from the viewpoint of improving the productivity in Step 3, a quaternary ammonium salt and a tertiary amine are preferable, a quaternary ammonium halide is more preferable, and tetrabutylammonium bromide is more preferable.
In the case of the reaction between an epoxy group and a carboxy group, the amount of the catalyst added is not particularly limited, but is preferably 0.5 mol% or more and 200 mol% or less with respect to the carboxy group.

  Examples of the catalyst for the reaction between an isocyanate group and a hydroxyl group include amines such as pyridine and organic metals such as dibutyltin dilaurate. Although there is no restriction | limiting in particular about the addition amount of a catalyst, 0.05 mol% or more and 200 mol% or less are preferable with respect to an isocyanate group.

The solvent is not particularly limited as long as it dissolves the main chain polymer segment B-1 and the side chain polymer segment B-2. A solvent can be used individually or in combination of 2 or more types.
Although there is no restriction | limiting in particular in the density | concentration of a reaction system, The total amount of the main chain polymer segment B-1 and side chain polymer segment B-2 in the whole quantity is a viewpoint which suppresses a viscosity raise and advances a reaction uniformly, and From the viewpoint of shortening the reaction time, it is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 70% by mass or less, more preferably 50% by mass or less. The reaction temperature is not particularly limited, but is preferably 60 ° C. or higher from the viewpoint of the reaction rate.
The progress of the reaction can be confirmed by quantifying each reactive functional group. For example, when the main chain polymer segment B-1 having an epoxy group and the side chain polymer segment B-2 having a carboxy group are used, the progress of the reaction can be determined by measuring the acid value and epoxy group in the reaction system. I can confirm.
In addition, it is also possible to hydrolyze unreacted reactive functional groups (such as epoxy groups) remaining in the main chain polymer segment B-1 by adding a small amount of water to the obtained graft polymer B and heating it. Is possible.

[Step 4: Production of Graft Polymer A]
Step 4 is a step of obtaining graft polymer A by reacting the side chain amino group of graft polymer B with a quaternizing agent to change to a sulfobetaine group.
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 can dissolve the graft polymer B. A solvent can be used individually or in combination of 2 or more types. Specifically, ethyl acetate etc. are mentioned.

<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. More preferably, it is 0.05% by mass or more, and from the viewpoint of preventing the adsorption of the graft polymer A to the solid surface and preventing the hydrophilization performance from decreasing, it is preferably 30% by mass or less, preferably 20% by mass or less. More preferably, it is 10 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.

[Polyvalent organic acid]
The hydrophilic treatment composition of the present invention preferably further contains a polyvalent organic acid from the viewpoint of enhancing the hydrophilic performance of the hydrophilic treatment composition.
The polyvalent organic acid is a compound having two or more acidic groups in one molecule, and the acidic group means a carboxy group, a sulfonic acid group, a phosphoric acid group, or the like.
Examples of the polyvalent organic acid include oxalic acid, maleic acid, citric acid, adipic acid, sebacic acid, malic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, and poly-2-acrylamide. -2-Methylpropane sulfonic acid, poly p-styrene sulfonic acid and the like. Among these, one or two or more selected from ethylenediaminetetraacetic acid, citric acid, and polyacrylic acid are preferable from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing agent composition.
The polyvalent organic acid may be in the form of a salt. Examples of the salt of the polyvalent organic acid include alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts. Among these, from the viewpoint of enhancing the solubility of the polyvalent organic acid in water and the hydrophilization performance of the hydrophilizing agent composition, an alkali metal salt or an ammonium salt is preferable, and a sodium salt, a potassium salt, or More preferred is an ammonium salt.

[Other ingredients]
The hydrophilic treatment agent composition of the present invention includes a lower alcohol such as ethyl alcohol and isopropyl alcohol; a solubilizer such as toluene sulfonate, xylene sulfonate and urea; clay within a range not impairing the object of the present invention; Viscosity modifiers such as minerals and water-soluble polymer compounds (excluding graft polymer A); water-insoluble abrasives such as calcite, silica, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon, polystyrene; glycerin, sorbitol, etc. Moisturizing agent; feel improver such as cationized cellulose (excluding graft polymer A); alkali builder such as sodium carbonate and sodium silicate; enzyme, dye, fragrance, antiseptic / antifungal agent and the like can be added.

[Production of hydrophilizing agent composition]
The hydrophilic treatment agent composition of the present invention is obtained by adding the graft polymer A, 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. As the mixing device, for example, a homogenizer, an ultrasonic disperser, a high-pressure disperser, or the like can be used.
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 or more per 10 cm ^{2 in} the case of a hydrophilizing agent composition having a graft polymer A content of 0.5% by mass. 0.1 mL or less.
In the method (iii), it is preferably used in the form of a cleaning composition containing the graft 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) Number average molecular weight of main chain polymer segment A-1 The number average molecular weight of main chain polymer segment A-1 is the same as the number average molecular weight of main chain polymer segment B-1 produced in Step 1 by gel permeation chromatography. Measurement was performed under the following conditions using a graph (polystyrene equivalent).
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) Number average molecular weight of side chain polymer segment A-2 The number average molecular weight of side chain polymer segment A-2 was determined by the following method.
The number average molecular weight (M1) of the side chain polymer segment B-2 produced in Step 2 was measured in the same manner as the number average molecular weight of the main chain segment.
The molecular weight (M2) increased in Step 4 was determined by multiplying the difference between the number of amino groups contained in the side chain polymer segment B-2 and the molecular weight of the amino group with the sulfobetaine group in Step 3.
From the sum of the number average molecular weight (M1) of the side chain polymer segment B-2 and the molecular weight (M2) increased in Step 4, the number average molecular weight of the side chain polymer segment A-2 was determined.

(3) Number of side chain segments A-2 per main chain segment A-1 The amount of epoxy groups in main chain segment B-1 and the amount of carboxy groups in side chain segment B-2 were determined in advance by the following method. . Before the ligation reaction, the number of side chain segments A-2 per main chain segment A-1 was set from the ratio between the amount of epoxy groups in the main chain B-1 and the amount of carboxy groups in the side chain. The amount of carboxy groups in the mixture before the reaction for connecting the main chain and the side chain and the amount of carboxyl groups after the reaction were measured, and the reduction rate of the amount of carboxy groups was defined as the reaction rate. The reaction rate was calculated by multiplying the set number of side chain segments per main chain segment.
The number of side chain segments A-2 per main chain segment A-1 is shown in the table as “number of segments”.
(I) Measurement of the amount of epoxy groups The polymer was precisely weighed and dissolved in a toluene solvent. Hydrochloric acid, pyridine and phenolphthalein were added to the polymer solution, and the amount consumed by chlorohydrination was determined by titration with potassium hydroxide.
(Ii) Measurement of carboxy group amount A precisely weighed polymer or reaction solution was dissolved in a toluene / ethanol mixed solvent, phenolphthalein was added, and the amount was determined from the amount of potassium hydroxide required for neutralization.

(4) Content of main chain segment A-1 in graft polymer A Using (1) to (3) above, the number average molecular weight of graft polymer A was determined from the following formula, and the main chain segment determined in (1) It was determined by dividing the number average molecular weight of the chain polymer segment A-1 by the number average molecular weight of the graft polymer A.
Number average molecular weight of graft polymer A = number average molecular weight of main chain polymer segment A-1 + number average molecular weight of side chain polymer segment A-2 × number of side chain segments A-2 per main chain segment A-1

Production Example 1 (Production of Polymer A1)
(Process 1)
75.1 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device, and the temperature was raised to 77 ° C. by replacing with nitrogen. There, 56.0 g of butyl methacrylate (hereinafter referred to as “BMA”), 24.0 g of glycidyl methacrylate (hereinafter referred to as “GMA”), 50.0 g of ethanol, 2,2′-azobis (2,4-dimethylvalero) Nitrile) (manufactured by Wako Pure Chemical Industries, Ltd., azo polymerization initiator, trade name: V-65B) was added over a period of 2 hours to a solution in which 3.49 g was mixed. After completion of dropping, the mixture was stirred for 3 hours while maintaining at 77 ° C. and cooled to room temperature to obtain an ethanol solution of poly (BMA-GMA). Thereafter, the obtained ethanol solution was dropped into a water-methanol mixture (mass ratio 1: 1), and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a polymer solid as a main chain.
(Process 2)
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 48.2 g of ethyl acetate, and the temperature was raised to 77 ° C. by replacing with nitrogen. There, 117.4 g of dimethylaminoethyl methacrylate (hereinafter referred to as “DMAEMA”), 2.6 g of 3-mercaptopropionic acid, 32.1 g of ethyl acetate, 2,2′-azobis (2,4-dimethylvaleronitrile) 0.49 g was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining at 77 ° C. and cooled to room temperature to obtain an ethyl acetate solution of poly (DMAEMA). Thereafter, the obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried for 24 hours in a 70 ° C. vacuum dryer to obtain a polymer solid as a side chain. The number average molecular weight was 4300.
(Process 3)
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 3.0 g of poly (BMA-GMA), 11.6 g of poly (DMAEMA), 0.437 g of tetrabutylammonium bromide, and 82.6 g of ethyl acetate. The temperature was raised to 77 ° C. After reacting for 6 hours, the mixture was cooled to room temperature to obtain an ethyl acetate solution of the graft polymer. The obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a graft polymer solid. The reaction rate was 74.3%.
(Process 4)
In a recovery flask equipped with a three-way cock, 3.0 g of a graft polymer and 12 g of 2,2,2, -trifluoroethanol were added to dissolve the polymer. While heating to 50 ° C., 2.2 g of 1,3-propane sultone was added dropwise. After reacting for 5 hours, the reaction mixture was cooled, added dropwise to methanol, and the precipitate was filtered off. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a solid of a graft type polymer A1.

Production Example 2 (Production of polymer A2)
(Process 1)
The same main chain as in Production Example 1 (Polymer A1) was used.
(Process 2)
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 48.1 g of ethyl acetate, followed by nitrogen substitution, and the temperature was raised to 77 ° C. Thereto, 118.9 g of DMAEMA, 1.1 g of 3-mercaptopropionic acid, 32.1 g of ethyl acetate, and 0.20 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining at 77 ° C. and cooled to room temperature to obtain an ethyl acetate solution of poly (DMAEMA). Thereafter, the obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried for 24 hours in a 70 ° C. vacuum dryer to obtain a polymer solid as a side chain. The number average molecular weight was 7700.
(Process 3)
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 1.5 g of poly (BMA-GMA), 11.2 g of poly (DMAEMA), 0.510 g of tetrabutylammonium bromide, and 72.2 g of ethyl acetate. The temperature was raised to 77 ° C. After reacting for 8 hours, the mixture was cooled to room temperature to obtain an ethyl acetate solution of the graft polymer. The obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a graft polymer solid. The reaction rate was 82.6%.
(Process 4)
In a recovery flask equipped with a three-way cock, 1.5 g of a graft polymer, 3 g of 2,2,2, -trifluoroethanol, and 3 g of acetone were added to dissolve the polymer. While heating at 50 ° C., 1.1 g of 1,3-propane sultone was added dropwise. After reacting for 5 hours, the reaction mixture was cooled, added dropwise to methanol, and the precipitate was separated by filtration. The precipitate separated by filtration was dried for 24 hours at 70 ° C. under reduced pressure to obtain a graft polymer A2 solid.

Production Example 3 (Production of polymer A3)
(Process 1)
75.1 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device, and the temperature was raised to 77 ° C. by replacing with nitrogen. A solution prepared by mixing 40.0 g of BMA, 40.0 g of GMA, 50.1 g of ethanol, and 3.49 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added over 2 hours. After completion of dropping, the mixture was stirred for 3 hours while maintaining at 77 ° C. and cooled to room temperature to obtain an ethanol solution of poly (BMA-GMA). Thereafter, the obtained ethanol solution was dropped into a water-methanol mixture (mass ratio 1: 1), and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a polymer solid as a main chain.
(Process 2)
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device was charged with 48.4 g of ethyl acetate, and the temperature was raised to 77 ° C. by replacing with nitrogen. Thereto, 114.8 g of DMAEMA, 5.2 g of 3-mercaptopropionic acid, 32.3 g of ethyl acetate, and 0.96 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining at 77 ° C. and cooled to room temperature to obtain an ethyl acetate solution of poly (DMAEMA). Thereafter, the obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried for 24 hours in a 70 ° C. vacuum dryer to obtain a polymer solid as a side chain. The number average molecular weight was 2500 (polystyrene conversion).
(Process 3)
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 2.0 g of poly (BMA-GMA), 11.92 g of poly (DMAEMA), 0.278 g of tetrabutylammonium bromide, and 81.0 g of ethyl acetate. The temperature was raised to 77 ° C. After reacting for 8 hours, the mixture was cooled to room temperature to obtain an ethyl acetate solution of the graft polymer. The obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a graft polymer solid. The reaction rate was 87.5%.
(Process 4)
In an eggplant flask equipped with a three-way cock, 7.0 g of the graft polymer and 28 g of 2,2,2, -trifluoroethanol were added to dissolve the polymer. While heating to 50 ° C., 4.90 g of 1,3-propane sultone was added dropwise. After reacting for 5 hours, the reaction mixture was cooled, added dropwise to methanol, and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a solid of graft type polymer A3.

Production Example 4 (Production of Polymer A4)
(Process 1)
The same main chain as in Production Example 3 (Polymer A3) was used.
(Process 2)
The same side chain as in Production Example 1 (Polymer A1) was used.
(Process 3)
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 1.0 g of poly (BMA-GMA), 10.8 g of poly (DMAEMA), 0.359 g of tetrabutylammonium bromide, and 67.1 g of ethyl acetate. The temperature was raised to 77 ° C. After reacting for 6 hours, the mixture was cooled to room temperature to obtain an ethyl acetate solution of the graft polymer. The obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a graft polymer solid. The reaction rate was 89.8%.
(Process 4)
In a recovery flask equipped with a three-way cock, 3.0 g of the graft polymer and 12.0 g of 2,2,2, -trifluoroethanol were added to dissolve the polymer. While heating at 50 ° C., 2.30 g of 1,3-propane sultone was added dropwise. After reacting for 5 hours, the reaction mixture was cooled, added dropwise to methanol, and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a solid of graft type polymer A4.

Production Example 5 (Production of polymer b)
(Process 1)
75.1 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device, and the temperature was raised to 77 ° C. by replacing with nitrogen. A solution prepared by mixing 40.0 g of BMA, 40.0 g of GMA, 50.1 g of ethanol, and 3.49 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added over 2 hours. After completion of dropping, the mixture was stirred for 3 hours while maintaining at 77 ° C. and cooled to room temperature to obtain an ethanol solution of poly (BMA-GMA). Thereafter, the obtained ethanol solution was dropped into a water-methanol mixture (mass ratio 1: 1), and the precipitate was separated by filtration. The precipitate separated by filtration was dried for 24 hours at 70 ° C. under reduced pressure to obtain a main polymer solid.
(Process 2)
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device was charged with 48.4 g of ethyl acetate, and the temperature was raised to 77 ° C. by replacing with nitrogen. Thereto, 114.8 g of DMAEMA, 5.2 g of 3-mercaptopropionic acid, 32.3 g of ethyl acetate, and 0.96 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining at 77 ° C. and cooled to room temperature to obtain an ethyl acetate solution of poly (DMAEMA). Thereafter, the obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried for 24 hours in a 70 ° C. vacuum dryer to obtain a polymer solid as a side chain. The number average molecular weight was 2500.
(Process 3)
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 2.0 g of poly (BMA-GMA), 11.92 g of poly (DMAEMA), 0.278 g of tetrabutylammonium bromide, and 81.0 g of ethyl acetate. The temperature was raised to 77 ° C. After reacting for 8 hours, the mixture was cooled to room temperature to obtain an ethyl acetate solution of the graft polymer. The obtained ethyl acetate solution was added dropwise to n-hexane, and the precipitate was separated by filtration. The precipitate separated by filtration was dried in a vacuum dryer at 70 ° C. for 24 hours to obtain a graft-type polymer b solid. The reaction rate was 93.0%.

Production Example 6 (Production of polymer c)
In a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen introduction tube and a stirring device, 49 g of dimethylaminoethyl methacrylate, 1.9 g of t-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 2, 0.31 g of 2′-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. 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) was added to the obtained polymerization reaction solution, and the mixture was sufficiently stirred. And 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 c.

  Table 1 shows the number average molecular weight and content of the main chain polymer segment A-1 of the obtained polymers A1 to A4, polymer b and polymer c, and the number average molecular weight and number of segments of the side chain polymer segment A-2. .

Examples 1-4, Comparative Examples 1-2
Using the polymers A1 to A4, the polymer b, and the polymer c (collectively referred to as test polymers), the following hydrophilizing treatment compositions 1 and 2 were prepared, and the contact angles were measured.
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 static contact angle with respect to the ion-exchanged water of the treated part of the surface of this test piece was adjusted to the conditions after 10 seconds of addition and 6 seconds after addition. Measured.
The measurement was performed 5 times per test piece using 2 test pieces, and the average value of 10 measurements was used.
The static contact angle of the test piece before the treatment was 85 °.

Composition of hydrophilizing agent composition 1 Test polymer: 0.5% by mass
Linear alkyl group having 12 to 16 carbon atoms, polyoxyethylene alkyl ether sulfate sodium salt having an average addition mole number of ethylene oxide of 1.0: 0.03% by mass
Diethylene glycol monobutyl ether: 2.5% by mass
Water: composition of the remaining hydrophilizing agent composition 2 Test polymer: 0.5% by mass
Water: remainder (test polymer aqueous solution)

  The smaller the contact angle, the better the hydrophilization performance. The results are shown in Table 2.

  As is clear from Table 2, the hydrophilization treatment composition of Examples 1 to 4 can lower the contact angle and is excellent in hydrophilization performance as compared with the hydrophilization treatment composition of Comparative Example. .

Claims (9)

The polymer segment A-1 derived from an unsaturated monomer containing a repeating unit derived from a hydrophobic unsaturated monomer as the main chain, and the repeating unit derived from an unsaturated monomer having a sulfobetaine group as the side chain A hydrophilic treatment agent comprising a graft polymer A having a polymer segment A-2 derived from an unsaturated monomer ,
The repeating unit derived from the hydrophobic unsaturated monomer in the graft polymer A is a structural unit represented by the general formula (1).
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 is} O or NR ¹¹ , and R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
Indicates. ] The hydrophilic treatment agent according to claim 1, wherein the repeating unit derived from an unsaturated monomer having a sulfobetaine group in the graft 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 claim 1 or 2 , wherein the number average molecular weight of the side chain polymer segment A-2 in the graft polymer A is 1,000 or more and 200,000 or less. The hydrophilization treatment agent according to any one of claims 1 to 3 , wherein the content of the polymer segment A-1 in the graft polymer A is 1% by mass or more and 15% by mass or less. The hydrophilic treatment agent according to any one of claims 1 to 4 , wherein the number of side chains per main chain in the graft polymer A is 5 or more and 20 or less. The hydrophilic treatment agent according to any one of claims 1 to 5 , wherein the graft polymer A is a graft polymer obtained by a production method including the following steps 1 to 4.
Step 1: having a reactive functional group capable of reacting with the hydrophobic unsaturated monomer represented by the following general formula (4) and the reactive functional group of the side chain polymer segment B-2 prepared in Step 2 A step of polymerizing an unsaturated monomer containing an unsaturated monomer to obtain a main chain polymer segment B-1.
Step 2: In the presence of a polymerization initiator or a chain transfer agent containing a reactive functional group capable of reacting with the reactive functional group of the main chain polymer segment B-1, an unsaturated monomer containing an amino group is contained. A step of polymerizing a saturated monomer to obtain a side chain polymer segment B-2.
Process 3: The process of obtaining the graft polymer B by making the main chain polymer segment B-1 obtained at the process 1 and the side chain polymer segment B-2 obtained at the process 2 react.
Step 4: A step of obtaining graft polymer A by reacting graft polymer B with a quaternizing 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 is} O or NR ¹¹ , and R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
Indicates. ] The hydrophilic treatment agent according to claim 6 , wherein the unsaturated monomer having an amino group is a monomer represented by the general formula (5).

[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 , and R ¹¹ represents a hydrogen atom or a hydrocarbon group having 4 to 4 carbon atoms. ] A hydrophilic treatment composition comprising the hydrophilic treatment agent according to any one of claims 1 to 7 and water. Furthermore, the hydrophilization treatment agent composition of Claim 8 containing surfactant.