JP6401582B2 - 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 fact that there is no hydrophilic agent having a sufficiently satisfactory effect, the hydrophilic agent is insufficiently soluble in water, and it is difficult to perform the blending operation stably.
It is an object of the present invention to provide a hydrophilic treatment agent having a hydrophilic effect on a solid surface and its sustainability, and also having excellent solubility in water, and a hydrophilic treatment composition containing the same. To do.

The present invention includes a polymer segment A-1 containing a repeating unit derived from an unsaturated monomer having a sulfobetaine group as a main chain, and a polymer segment containing a repeating unit derived from a hydrophobic unsaturated monomer as a side chain A hydrophilic treatment agent comprising a graft polymer A having A-2,
The content of the repeating unit derived from the unsaturated monomer having a sulfobetaine group in the graft polymer A is 60% by mass or more,
The content of the polymer segment A-2 in the graft polymer A is 5% by mass or less.
The present invention relates to a hydrophilic treatment agent.
Moreover, this invention relates to the hydrophilic treatment agent composition containing the hydrophilic treatment agent of the said invention and water.

  The hydrophilization treatment agent of the present invention is excellent in the effect of hydrophilizing the solid surface and its sustainability, and is also excellent in solubility in water.

<Hydrophilic treatment agent>
The hydrophilic treatment agent of the present invention comprises a specific graft polymer A.
Graft polymer A is a polymer segment A-1 containing a repeating unit derived from an unsaturated monomer having a sulfobetaine group as a main chain, and a polymer containing a repeating unit derived from a hydrophobic unsaturated monomer as a side chain And segment A-2.

[Main chain polymer segment A-1]
(Configuration of main chain polymer segment A-1)
Main chain polymer segment A-1 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 (1) from the viewpoint of reducing the contact angle and improving the solubility.

[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 : an alkylene group having 1 to ⁴ carbon atoms R ⁵ , R ⁶ : the same or different, 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ⁷ , R ⁷ is a hydrogen atom or 1 or more carbon atoms, 4 or less hydrocarbon group X ² : 2 or more carbon atoms that may have a hydroxyl group, 4 The following alkylene groups are shown. ]

In the general formula (1), the viewpoint of availability of unsaturated monomers, the viewpoint of polymerizability of the monomers, the viewpoint of reducing the contact angle of the hydrophilizing agent, the solubility and the water film durability are improved. From the viewpoint, R ¹ and R ² are preferably hydrogen atoms.
From the same viewpoint, R ³ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
X ¹ is preferably O from the same viewpoint.
From the same viewpoint, R ⁴ 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 ⁵ and R ⁶ are preferably a methyl group or an ethyl group, and more preferably a methyl group.
From the same viewpoint, R ⁷ is preferably a hydrogen atom or a methyl 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 same viewpoint and the ease of the quaternization reaction, and includes a propylene group, a butylene group, and a 2-hydroxypropylene group. The selected group is more preferable, and a propylene group or a 2-hydroxypropylene group is more preferable.

  The content of the structural unit derived from the unsaturated monomer having a sulfobetaine group in the graft polymer A is 60% by mass or more from the viewpoint of reducing the contact angle, solubility and water film sustainability. , Preferably 65% by mass or more, more preferably 70% by mass or more, and still more preferably 75% by mass, and preferably 98% by mass or less from the viewpoint of reducing the contact angle and improving the water film sustainability. More preferably 95% by mass or less, still more preferably 90% by mass or less, and still more preferably 85% by mass or less.

The polymer segment A-1 of the main chain can contain a constitutional unit other than a constitutional unit derived from an unsaturated monomer having a sulfobetaine group. In this case, the polymer segment A-1 of the main chain may be either a random polymer or a block polymer, but a random polymer is preferable.
The polymer segment A-1 of the main chain preferably contains a repeating unit derived from a hydrophobic unsaturated monomer from the viewpoint of reducing the contact angle, improving the solubility and water film durability, It is more preferable that the structural unit represented by (2) is included.

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹² and R ¹² is hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms is shown. ]

The structural unit represented by the general formula (2) is a structural unit derived by polymerizing the unsaturated monomer represented by the general formula (3) (hereinafter, unsaturated monomer a), In the formula (2) and the general formula (3), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and Y ¹ are all synonymous.

In general formula (2) and general formula (3), the viewpoint of availability of unsaturated monomers, the viewpoint of polymerizability of monomers, the viewpoint of reducing the contact angle, and the solubility and water film sustainability are improved. From the point of view, R ⁸ and R ⁹ are preferably hydrogen atoms. From the same viewpoint, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group. Y ¹ is preferably O from the same viewpoint. From the same viewpoint, R ¹¹ 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 straight chain having 1 to 12 carbon atoms or a 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, and more preferably a linear or branched chain having 1 to 4 carbon atoms. It is an alkyl group. From the same viewpoint, R ¹² is preferably a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

  Specific examples of the unsaturated monomer a derived from the general formula (2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. iso-butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylate-cyclohexyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth (Meth) acrylic esters such as n-decyl acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate Is mentioned.

The unsaturated monomer a derived from the general formula (2) is preferably a (meth) acrylic acid ester, more preferably from the viewpoint of reducing the contact angle, improving the solubility and water film durability. Is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate and n-hexyl (meth) acrylate It is 1 type, or 2 or more types chosen from, More preferably, it is 1 type, or 2 or more types chosen from methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate. .
In the present specification, “(meth) acryl” means acrylic, methacrylic, or both.

  The content of the repeating unit derived from the hydrophobic unsaturated monomer in the polymer segment A-1, preferably the constituent unit represented by the general formula (2), reduces the contact angle, and maintains the water film. From the viewpoint of improving the viscosity, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and still more preferably 15% by mass or more. From the viewpoint of improving the property and water film durability, it is preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 27% by mass or less, still more preferably 25.5% by mass or less, and still more preferably. Is 21% by mass or less.

  The content of the repeating unit derived from the unsaturated monomer having a sulfobetaine group in the polymer segment A-1, preferably the constituent unit represented by the general formula (1), reduces the contact angle, solubility. And from the viewpoint of improving water film persistence, it is preferably 65% by mass or more, more preferably 70% by mass or more, still more preferably 73% by mass or more, still more preferably 74.5% by mass or more, and still more preferably. 79% by mass or more, from the viewpoint of reducing the contact angle, and from the viewpoint of improving the water film sustainability, preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, More preferably, it is 85 mass% or less.

  It is derived from an unsaturated monomer having a sulfobetaine group in polymer segment A-1 and preferably from a hydrophobic unsaturated monomer with respect to the content of the structural unit represented by the general formula (1). The ratio of the content of the repeating unit, preferably the structural unit represented by the general formula (2), is preferably 10% by mass or more, more preferably from the viewpoint of reducing the contact angle and improving the water film sustainability. Is 15% by mass or more, more preferably 18% by mass or more, and preferably 55% by mass or less, more preferably 40% by mass or less, from the viewpoint of reducing the contact angle, from the viewpoint of improving solubility and water film sustainability. More preferably, it is 34 mass% or less, More preferably, it is 33 mass% or less, More preferably, it is 25 mass% or less.

  The content of the polymer segment A-1 in the graft polymer A is 95% by mass or more, preferably 98% by mass or more, more preferably from the viewpoint of reducing the contact angle, improving the solubility and water film sustainability. It is preferably 98.7% by mass or more, and preferably 99.5% by mass or less, more preferably 99.2% by mass or less, and still more preferably 99% from the viewpoint of reducing the contact angle and improving the water film sustainability. 0.0 mass% or less.

  Repeating unit derived from unsaturated monomer having sulfobetaine group in polymer segment A-1, preferably content of structural unit represented by general formula (1) and repeating from hydrophobic unsaturated monomer The total content of the units, preferably the constituent units represented by the general formula (2), is preferably 95% by mass from the viewpoint of reducing the contact angle of the hydrophilizing agent and improving the water film sustainability. As mentioned above, More preferably, it is 98 mass% or more, More preferably, it is 99 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%. In addition, substantially 100% by mass means a repeating unit derived from an unsaturated monomer having a sulfobetaine group in the polymer segment A-1 of the present invention, preferably a structural unit represented by the general formula (1) And a repeating unit derived from a hydrophobic unsaturated monomer, preferably a case where a structural unit other than the structural unit represented by the general formula (2) is inevitably mixed.

  The main chain polymer segment A-1 is a repeating unit derived from an unsaturated monomer having a sulfobetaine group, preferably a structural unit represented by the general formula (1) and a hydrophobic group, as long as the effects of the present invention are not impaired. A repeating unit derived from a polymerizable unsaturated monomer, preferably a structural unit derived from a monomer other than the structural unit represented by the general formula (2) may be contained. A repeating unit derived from an unsaturated monomer having a sulfobetaine group, preferably a structural unit represented by the general formula (1) and a repeating unit derived from a hydrophobic unsaturated monomer, preferably represented by the general formula (2). Examples of the monomer other than the structural unit include hydrophilic unsaturated monomers such as hydroxyethyl (meth) acrylate, acrylate having an oxyethylene chain, acrylamide, and dimethylacrylamide.

[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 a hydrophobic unsaturated monomer from the viewpoint of reducing the contact angle and improving the water film durability. The amount of the hydrophobic unsaturated monomer dissolved in 100 g of water at 20 ° C. is preferably 10 g or less, more preferably 1 g or less, still more preferably 0.1 g or less. In the present invention, the hydrophobic unsaturated monomer does not include an unsaturated monomer having a sulfobetaine group.

  The repeating unit derived from the hydrophobic unsaturated monomer is preferably a structural unit represented by the general formula (2) from the viewpoint of reducing the contact angle and improving the sustainability of the water film.

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹² and R ¹² is hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms is shown. ]

In the general formula (2), from the viewpoint of availability of unsaturated monomers, the viewpoint of polymerizability of the monomers, the viewpoint of reducing the contact angle, and the viewpoint of improving solubility and water film sustainability, R ⁸ And R ⁹ is preferably a hydrogen atom. From the same viewpoint, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group. Y ¹ is preferably O from the same viewpoint. From the same viewpoint, R ¹¹ 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 straight chain having 1 to 12 carbon atoms or a benzyl group. A branched alkyl group, an alkenyl group, or a benzyl group, more preferably a straight chain or branched chain alkyl group having 1 to 6 carbon atoms, and still more preferably a straight chain having 1 to 4 carbon atoms or It is a branched alkyl group. From the same viewpoint, R ¹² is preferably a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

  The side chain polymer segment A-2 is preferably obtained by polymerizing a monomer having a structure represented by the general formula (4) or a monomer having a structure represented by the general formula (5). . These are high molecular weight monomers having polymerizable functional groups, and are sometimes referred to as macromonomers.

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms R ¹³ , R ¹⁴ : the same or different, a hydrogen atom or C 1 or 2 alkyl group R ¹⁵ : hydrocarbon group Y ¹ or more and 22 or less hydrocarbon group Y ¹ : O or NR ¹² , R ¹² is a hydrogen atom or a hydrocarbon group Y having 1 or more and 4 or less carbon atoms ² : O or NR ¹⁶ ; R ¹⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms R ¹³ , R ¹⁴ : the same or different, a hydrogen atom or C 1 or 2 alkyl group R ¹⁷ : hydrogen atom or C 1 or 2 alkyl group Y ¹ : O or NR ¹² , R ¹² is a hydrogen atom or a hydrocarbon group Y having 1 to 4 carbon atoms ² : O, OR ¹⁸ , or NR ¹⁶ , R ¹⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁸ represents an alkylene group having 1 to 6 carbon atoms. ]

  The monomer having the structure represented by the general formula (4) or the monomer having the structure represented by the general formula (5) can be produced using the aforementioned unsaturated monomer a. it can.

  Examples of the monomer having a structure represented by the general formula (4) include “AA-6” manufactured by Toa Gosei Co., Ltd.

  As a monomer which has a structure represented by General formula (5), it can manufacture with the following method, for example.

  The unsaturated monomer a derived from the monomer having the structure represented by the general formula (5) is polymerized using an alcohol having a sulfyl group at one end as an initiator, and the resulting polymer and isocyanate group By reacting with a reactive monomer having, a macromonomer having an unsaturated bond at the terminal can be obtained.

Formula (4) or general formula (5) in the ^{- [C (R 8) (} R 9) -C (R 10) (CO-Y 1 -R 11)] - moiety represented by the repeating unit Yes, the number can be determined in consideration of the weight average molecular weight of the side chain polymer segment A-2 described later, but can be selected from 10 or more and 300 or less.

  As the unsaturated monomer a derived from the monomer having the structure represented by the general formula (4) or the monomer having the structure represented by the general formula (5), specifically, ) Methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, (meta ) Acrylic acid-cyclohexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-decyl, (meth) acrylic acid lauryl, (meth) acrylic acid myristyl, (meth) Examples include (meth) acrylic acid esters such as palmityl acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.

  The unsaturated monomer a derived from the monomer having the structure represented by the general formula (4) or the monomer having the structure represented by the general formula (5) has a viewpoint of reducing the contact angle, From the viewpoint of improving the solubility and water film durability, preferably a (meth) acrylate, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, One or more selected from iso-butyl (meth) acrylate, t-butyl (meth) acrylate and n-hexyl (meth) acrylate, more preferably methyl (meth) acrylate, ( One or more selected from ethyl (meth) acrylate and n-butyl (meth) acrylate.

  The content of the side chain polymer segment A-2 in the graft polymer A is 5% by mass or less, more preferably 2% by mass or less from the viewpoint of reducing the contact angle, and improving the solubility and water film durability. More preferably, it is 1.3% by mass or less, and from the viewpoint of reducing the contact angle and improving the water film sustainability, it is more than 0% by mass, preferably 0.3% by mass or more, more preferably 0.5%. It is at least mass%, more preferably at least 0.8 mass%, even more preferably at least 1.0 mass%.

  The weight average molecular weight of the side chain polymer segment A-2 is preferably 2000 or more, more preferably 3000 or more, and still more preferably 4000 or more, from the viewpoint of reducing the contact angle and improving the water film sustainability. From the viewpoint of improving the solubility, it is preferably 50000 or less, more preferably 20000 or less, and still more preferably 15000 or less. This weight average molecular weight can be measured by the method described in Examples.

[Graft polymer A]
The weight average molecular weight of the graft polymer A is preferably 50,000 or more, more preferably 80,000 or more, and still more preferably 100,000 or more, from the viewpoint of reducing the contact angle and improving the water film durability. And from a viewpoint of improving productivity, Preferably it is 200,000 or less, More preferably, it is 180,000 or less, More preferably, it is 150,000 or less. This weight average molecular weight can be calculated by the method described in the Examples.

The repeating unit derived from the hydrophobic unsaturated monomer in the side chain polymer segment A-2 and the main chain polymer segment A-1 in the graft polymer A, preferably the structural unit represented by the general formula (2) is It contributes to the adsorptivity of the graft polymer A to the solid surface. The side chain polymer segment A-2 contributes to improvement of the adsorptivity to the solid surface by about 5 times compared with the repeating unit derived from the hydrophobic unsaturated monomer in the main chain polymer segment A-1. It is thought that there is.
The graft polymer A of the present invention has a hydrophilization index of preferably 45 or less, more preferably 40 or less, and still more preferably 38 or less, from the viewpoint of reducing the contact angle and improving solubility. From the viewpoint of reducing and improving the water film sustainability, it is preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more.
Here, the hydrophilization index is obtained by multiplying the content (% by mass) of the side chain polymer segment A-2 in the graft polymer A by 5 times and the hydrophobicity of the main chain polymer segment A-1 in the graft polymer A. It is the total of the number of repeating units derived from the unsaturated monomer, preferably the content (mass%) of the structural unit represented by the general formula (2).

(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 a hydrophobic unsaturated monomer on a main chain segment having a radical reactive group, which includes a repeating unit of an unsaturated monomer having a sulfobetaine group.
(Ii) derived from a hydrophobic unsaturated monomer comprising a main chain segment containing a reactive functional group capable of reacting with a reactive functional group of a side chain segment, comprising a repeating unit of an unsaturated monomer having a sulfobetaine group The side chain segment which has a reactive functional group which can react with the reactive functional group of the main chain segment in one terminal is included.
(Iii) A method of polymerizing a macromonomer containing a repeating unit derived from a hydrophobic unsaturated monomer and an unsaturated monomer having a sulfobetaine group.
Further, as (iii-1), instead of the unsaturated monomer having a sulfobetaine group, an unsaturated monomer having an amino group (unsaturated monomer b) is polymerized, and a quaternizing agent is further added. The method of making it react and converting into a sulfobetaine group is mentioned. From the viewpoint of improving the productivity of the production of the graft polymer A, the method of producing 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 and 2 can 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 and 2. This method belongs to the above method (iii-1).
Step 1: A step of obtaining a graft polymer B by polymerizing an unsaturated monomer having an amino group and an unsaturated monomer containing an unsaturated monomer having a side chain polymer segment A-2.
Step 2: 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 1 becomes a precursor of a sulfobetaine group.

[Step 1: Production of graft polymer B]
In Step 1, an unsaturated monomer having an amino group (unsaturated monomer b) and an unsaturated monomer containing a macromonomer containing a repeating unit of a hydrophobic unsaturated monomer are polymerized to produce graft polymer B. It is a manufacturing process.
(Unsaturated monomer b having an amino group)
As the unsaturated monomer b, the unsaturated monomer b-1 represented by the general formula (6) from the viewpoint of improving the productivity of the reaction in Step 2 and the availability of the unsaturated monomer. Is preferred. By using the unsaturated monomer b-1, the main chain polymer segment B-1 contains a repeating unit represented by the general formula (7).

[In General Formula (6) and General Formula (7),
R ^{1 to} R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : an alkylene group having 1 to ⁴ carbon atoms R ⁵ , R ⁶ : the same or different, 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ⁷ , and R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

In general formula (6) and general formula (7), the viewpoint of availability of unsaturated monomers, the viewpoint of polymerizability of monomers, the viewpoint of reducing the contact angle, solubility and water film durability are improved. From the viewpoint, R ¹ and R ² are preferably hydrogen atoms. From the same viewpoint, R ³ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X ¹ is preferably O from the same viewpoint, and R ⁴ 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 ⁵ and R ⁶ are preferably a methyl group or an ethyl group, and more preferably a methyl group.
Specifically, from the same viewpoint, the unsaturated monomer b-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 b contained in the main chain polymer segment B-1, preferably the constituent unit derived from the unsaturated monomer b-1, is the viewpoint of reducing the contact angle, solubility and water film durability. From the viewpoint of improving the water content, it is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 65% by mass or more, from the viewpoint of reducing the contact angle and the viewpoint of improving water film sustainability. Therefore, it is preferably 99% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less.

  The unsaturated monomer having the side chain polymer segment A-2 is preferably a monomer having a structure represented by the general formula (4) or a single unit having a structure represented by the general formula (5). A monomer is mentioned.

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 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and the like. Examples thereof include azo initiators, peroxide initiators such as lauroyl peroxide and benzoyl peroxide, and persulfates 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 graft polymer A]
Step 2 is a step of obtaining graft polymer A by reacting the amino group of the main chain 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. Specific examples include 2,2,2-trifluoroethanol and ethyl acetate.

<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 being lowered, 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 oxyethylene (hardened) castor oil and polyhydric alcohol type nonionic surfactants such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkylglycoside, and the like And fatty acid alkanolamides.
Among these nonionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, and alkyl glycoside are 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. Moisturizer; Feeling improver such as cationized cellulose (excluding graft polymer A); Alkali builder such as sodium carbonate and sodium silicate; Solubilizer such as sodium chloride, calcium chloride and potassium chloride; Enzyme, dye and fragrance Antiseptic and fungicides 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.

Moreover, the static contact angle with respect to the water of the solid surface hydrophilized by the hydrophilizing agent composition of this invention becomes like this. Preferably it is 50 degrees or less, More preferably, it is 40 degrees or less, More preferably, it is 35 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) Weight average molecular weight of polymer segment A-2 The weight average molecular weight of the unsaturated monomer having the polymer segment A-2, that is, the macromonomer used for the production of the graft polymer A, is determined by the polymer segment A-2. The weight average molecular weight of
The weight average molecular weight of the macromonomer was measured by gel permeation chromatography (polystyrene conversion).
Two columns: K-804L (manufactured by Showa Denko KK) were connected in series and used.
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 graft polymer A The weight average molecular weight (Mw) was measured for static light scattering under the following conditions using a light scattering photometer “DLS-7000” (manufactured by Otsuka Electronics Co., Ltd.) It calculated by producing 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) Constituent units represented by general formula (1) and general formula (2) of polymer segment A-1 in graft polymer A, and the content of polymer segment A-2 As described in Examples and Comparative Examples The content of each component was shown in the production examples. Calculated from the amount charged. At that time, in each production example (except production example 18), it corresponds to the monomer having an amino group corresponding to the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). Since the monomer and macromonomer to be used were used, the calculation was performed as follows.
The amount of the monomer having an amino group corresponding to the structural unit represented by the general formula (1) of the polymer segment A-1 corresponds to the structural unit represented by S1 (g) and the general formula (2). The amount of monomer to be charged is S2 (g), and the amount of macromonomer corresponding to the structural unit of polymer segment A-2 is S3 (g). S1 was divided by the molecular weight of the monomer having an amino group and multiplied by the molecular weight of the monomer having a corresponding sulfobetaine group to obtain S1 ′ (g), and was obtained from the following formula.
The content P1 of the structural unit represented by the general formula (1) of the polymer segment A-1 was determined by the following formula.
P1 = [S1 ′ / (S1 ′ + S2 + S3)] × 100 (%)
The content P2 of the structural unit represented by the general formula (2) of the polymer segment A-1 was determined by the following formula.
P2 = [S2 / (S1 ′ + S2 + S3)] × 100 (%)
The content P3 of the polymer segment A-2 was determined by the following formula.
P3 = [S3 / (S1 ′ + S2 + S3)] × 100 (%)

Production Example 1 (Production of Macromonomer C2)
(Process i)
12.10 g of methyl ethyl ketone was placed in a glass separable flask having an internal volume of 300 mL, and stirred at about 80 ° C. for 30 minutes in a nitrogen atmosphere. A monomer solution prepared by mixing 28.30 g of methyl methacrylate and 1.700 g of mercaptopropanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.180 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and methyl ethyl ketone An initiator solution mixed with 8.000 g was dropped simultaneously over 2 hours to carry out polymerization. Thereafter, the mixture was aged by being held at 80 ° C. for 3 hours, cooled with ice while being exposed to air, the polymer solution was dropped into 1 L of hexane with stirring, the polymer was precipitated, and a polymer solid was obtained by decantation and drying.
(Process ii)
Stirrer tip on eggplant flask, polymer 15.00 g obtained in step i, 2-methacryloyloxyethyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.330 g, N, N, N ′, N ″, N ′ '-Pentamethyldiethylenetriamine (manufactured by Wako Pure Chemical Industries, Ltd.) (0.026 g) was added tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) (15.00 g), and the reaction was performed by heating to 50 ° C. After reacting for 24 hours, the solution was ice-cooled while exposed to air, and the polymer solution was added dropwise to 1 L of hexane with stirring to precipitate the polymer, followed by decantation and drying to obtain macromonomer C2. The weight average molecular weight of the macromonomer C2 was 4000.

Production Example 2 (Production of Macromonomer C3)
In step i of Production Example 1, 48.50 g of methyl methacrylate, 1.500 g of mercaptopropanol (manufactured by Wako Pure Chemical Industries, Ltd.), 0 of 2,2′-azobis (2,4-dimethylvaleronitrile) The macromonomer C3 was obtained in the same manner as in Production Example 1 except that the amount of the polymer obtained in the step i was changed to 30.00 g in the step ii. The weight average molecular weight of the macromonomer C3 was 8000.

The monomers used for polymer production are shown below.
Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
N-Butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
2- (dimethylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
Macromonomer C1 Methyl methacrylate macromonomer “AA-6” (manufactured by Toa Gosei Co., Ltd.)
Macromonomer C2 Macromonomer produced in Production Example 1 Macromonomer C3 Macromonomer produced in Production Example 2 Macromonomer C4 Silicone Macromonomer “Silaplane FM-0711” (manufactured by Chisso Corporation)

Production Example 3 (Production of Polymer A1)
(Process 1)
In an eggplant flask, a stirrer chip, 9.362 g of methyl methacrylate, 15.00 g of 2- (dimethylamino) ethyl methacrylate, 0.191 g of macromonomer C1, 2,2′-azobis (2-methylbutyronitrile) (sum 0.183 g (manufactured by Kojun Pharmaceutical Co., Ltd.) and 24.55 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and nitrogen bubbling was performed for 30 minutes to prepare a monomer solution. Then, it superposed | polymerized by heating to 67 degreeC. After reacting for 8 hours, the reaction solution was ice-cooled while exposed to air, and polymer B1 was obtained by drying.
(Process 2)
In an eggplant flask, 4.00 g of the polymer B1 obtained in step 1, 16.00 g of 2,2,2-trifluoroethanol (manufactured by Sigma Aldrich), 1,3-propane sultone (Wako Pure Chemical Industries, Ltd.) 2.089 g) was added to dissolve the polymer. The mixture was heated to 50 ° C., reacted for 5 hours, cooled, and dried to obtain a polymer (polymer A1) solid.

Production Example 4 (Production of Polymer A2)
In Step 1 of Production Example 3, 10.00 g of methyl methacrylate, 16.53 g of 2- (dimethylamino) ethyl methacrylate, 0.526 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.202 g, methyl ethyl ketone was 27.05 g, and in Step 2, the same procedure as in Production Example 3 was carried out except that the amount of 1,3-propane sultone was 2.088 g, to obtain polymer A2.

Production Example 5 (Production of polymer A3)
In Step 1 of Production Example 3, 10.00 g of methyl methacrylate, 17.45 g of 2- (dimethylamino) ethyl methacrylate, 1.111 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.213 g, methyl ethyl ketone was 28.56 g, and the amount of 1,3-propane sultone in Step 2 was changed to 2.088 g to obtain Polymer A3.

Production Example 6 (Production of polymer A4)
In Step 1 of Production Example 3, methyl methacrylate was not added, 20.00 g of 2- (dimethylamino) ethyl methacrylate, 0.327 g of macromonomer C1, and 2,2′-azobis (2-methylbutyronitrile) ) 0.125 g, methyl ethyl ketone 20.30 g, and the amount of 1,3-propane sultone in Step 2 was changed to 3.364 g to obtain polymer A4.

Production Example 7 (Production of polymer A5)
In Step 1 of Production Example 3, 1.061 g of methyl methacrylate, 20.00 g of 2- (dimethylamino) ethyl methacrylate, 0.354 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.136 g, methyl ethyl ketone was 21.42 g, and the amount of 1,3-propane sultone in Step 2 was changed to 3.193 g to obtain polymer A5.

Production Example 8 (Production of polymer A6)
In Step 1 of Production Example 3, 15.00 g of methyl methacrylate, 59.95 g of 2- (dimethylamino) ethyl methacrylate, 1.364 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.210 g, methyl ethyl ketone was 74.32 g, and the amount of 1,3-propane sultone in Step 2 was changed to 2.464 g to obtain Polymer A6.

Production Example 9 (Production of polymer A7)
In Step 1 of Production Example 3, 15.00 g of methyl methacrylate, 37.69 g of 2- (dimethylamino) ethyl methacrylate, 1.000 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.384 g, methyl ethyl ketone was 78.53 g, and the amount of 1,3-propane sultone in Step 2 was changed to 2.400 g to obtain Polymer A7.

Production Example 10 (Production of polymer A8)
In Step 1 of Production Example 3, 15.00 g of methyl methacrylate, 16.38 g of 2- (dimethylamino) ethyl methacrylate, 0.652 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.251 g, methyl ethyl ketone was 32.04 g, and the amount of 1,3-propane sultone in Step 2 was changed to 1.749 g to obtain Polymer A8.

Production Example 11 (Production of Polymer A9)
In Step 1 of Production Example 3, 10.00 g of methyl methacrylate, 25.12 g of 2- (dimethylamino) ethyl methacrylate, 0.667 g of macromonomer C2 instead of macromonomer C1, and 2,2′-azobis Polymer A9 was obtained in the same manner as in Production Example 3, except that 0.256 g of (2-methylbutyronitrile), 35.79 g of methyl ethyl ketone, and 2.400 g of 1,3-propane sultone in Step 2 were used. It was.

Production Example 12 (Production of polymer A10)
In Step 1 of Production Example 3, 10.00 g of methyl methacrylate, 25.12 g of 2- (dimethylamino) ethyl methacrylate, 0.667 g of macromonomer C3 instead of macromonomer C1, and 2,2′-azobis Polymer A10 was obtained in the same manner as in Production Example 3 except that 0.256 g of (2-methylbutyronitrile), 35.79 g of methyl ethyl ketone, and 2.400 g of 1,3-propane sultone in Step 2 were used. It was.

Production Example 13 (Production of polymer A11)
In Step 1 of Production Example 3, instead of methyl methacrylate, 3.753 g of n-butyl methacrylate, 15.00 g of 2- (dimethylamino) ethyl methacrylate, 0.341 g of macromonomer C1, 2,2 ′ Polymer A11 was prepared in the same manner as in Production Example 3 except that 0.120 g of azobis (2-methylbutyronitrile), 19.09 g of methyl ethyl ketone, and 2.666 g of 1,3-propane sultone in Step 2 were used. Got.

Production Example 14 (Production of polymer a1)
In Step 1 of Production Example 3, 9.553 g of methyl methacrylate, 15.00 g of 2- (dimethylamino) ethyl methacrylate, and 2,2′-azobis (2-methylbutyronitrile) were not added. ) 0.183 g, methyl ethyl ketone 24.55 g, and the amount of 1,3-propane sultone in Step 2 was 2.089 g, to obtain polymer a1.

Production Example 15 (Production of polymer a2)
In Step 1 of Production Example 3, 7.642 g of methyl methacrylate, 15.00 g of 2- (dimethylamino) ethyl methacrylate, 1.911 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.183 g, methyl ethyl ketone was 24.55 g, and the amount of 1,3-propane sultone in Step 2 was 2.089 g, to give polymer a2.

Production Example 16 (Production of polymer a3)
In Step 1 of Production Example 3, 20.00 g of methyl methacrylate, 13.96 g of 2- (dimethylamino) ethyl methacrylate, 0.741 g of macromonomer C1, 2,2′-azobis (2-methylbutyro (Nitrile) was 0.285 g, methyl ethyl ketone was 34.70 g, and the amount of 1,3-propane sultone in Step 2 was changed to 1.375 g to obtain polymer a3.

Production Example 17 (Production of polymer a4)
In Step 1 of Production Example 3, methyl methacrylate was not added, 20.00 g of 2- (dimethylamino) ethyl methacrylate, 1.415 g of macromonomer C1, and 2,2′-azobis (2-methylbutyronitrile) ) 0.136 g, methyl ethyl ketone 21.42 g, and the amount of 1,3-propane sultone in Step 2 was 3.193 g to obtain polymer a4.

Production Example 18 (Production of polymer a5)
In Step 1 of Production Example 3, methyl methacrylate was not added, 16.00 g of 2- (dimethylamino) ethyl methacrylate, 4.000 g of macromonomer C4, 2,2′-azobis (2-methylbutyronitrile) ) 0.140 g and methyl ethyl ketone 19.90 g, except that step 2 was not performed, the same as in Production Example 3 to obtain polymer a5.

  Table 1 shows the structure of the structural unit of the obtained polymer.

Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-5
Using polymers A1 to A11 and polymers a1 to a5 (in the following formulation, these were collectively used as a test polymer), a hydrophilizing agent composition 1 having the composition shown below was prepared. Specifically, each component was blended according to the blending amounts described below, and stirred at 25 ° C. for 30 minutes to obtain a hydrophilic treatment agent composition 1. About the compounding quantity of the component described below, the compounding quantity as each effective part is shown.
(mass%)
Test polymer 0.3
Sodium chloride 1.0
Ion-exchanged water balance (total) 100

Examples 2-1 to 2-11
A hydrophilic treatment agent composition 2 having the following composition was prepared using the polymers A1 to A11. Specifically, each component was blended according to the blending amounts described below, and stirred at 25 ° C. for 30 minutes to obtain surface treating agent composition 2. About the compounding quantity of the component described below, the compounding quantity as each effective part is shown.
(mass%)
Test polymer 0.3
Polyoxyethylene (4) sodium lauryl ether sulfate ^(*) 0.1
Diethylene glycol monobutyl ether ^(**) 5.0
Sodium chloride 1.0
Ion-exchanged water balance (total) 100
(*) ES-4K; manufactured by Kao Corporation 60%
(**) BDG-NS; manufactured by Nippon Emulsifier Co., Ltd. Effective content 99.71%

  The following evaluation was performed using the obtained hydrophilic treatment composition 1 and 2. The results of Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-5 are shown in Table 2. The results of Examples 2-1 to 2-11 are shown in Table 3. Tables 2 and 3 show the structure and content of the repeating unit of the graft polymer used, the structure and content and weight average molecular weight of the polymer segment A-2, and the weight average molecular weight of the graft polymer.

[Evaluation method]
Test Example 1 (Measurement of contact angle)
A test piece “vinyl chloride test piece” (manufactured by Engineering Test Service Co., Ltd., material: hard polyvinyl chloride, 25 mm × 75 mm), which has been cleaned in advance, is fixed horizontally, and 1 mL of a hydrophilizing agent composition is added dropwise to 5 After standing for a minute, about 200 mL of ion-exchanged water was added dropwise, rinsed 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 static contact angle of the test piece before the treatment was 85 °.

Test Example 2 (Measurement of transmittance)
The transmittance of each hydrophilic treatment composition was measured. Using a UV-visible spectrophotometer “UV-2550” (manufactured by Shimadzu Corporation), the transmittance of light at a wavelength of 600 nm at 25 ° C. was measured, and the relative transmittance when the transmittance of the composition with no polymer added was taken as 100%. The rate was determined. The greater the transmittance, the better the solubility or dispersibility of the hydrophilic treatment agent.

Test Example 3 (Measurement of water film durability)
The test piece surface treatment was performed in the same way as in Test Example 1, and the time from immediately after rinsing with ion-exchanged water until the water remaining on the test piece flowed down and the surface of the test piece began to be exposed was the duration of the water film. It was. The longer the water film lasts, the less likely the lipophilic dirt will come into contact with the surface and the better the antifouling performance. A water film having a duration of 10 seconds or more was designated as A, and a film having a duration of less than 10 seconds was designated as B.

* 1 Repeating unit derived from an unsaturated monomer having a sulfobetaine group * 2 Repeating unit derived from a hydrophobic unsaturated monomer * 3 Content (% by mass) in the graft polymer
* 4 Since the undissolved residue was observed in the prepared composition, the contact angle, transmittance, and water film durability were not evaluated.

Claims (12)

Polymer segment A-1 containing a repeating unit derived from an unsaturated monomer having a sulfobetaine group as a main chain, and Polymer segment A-2 containing a repeating unit derived from a hydrophobic unsaturated monomer as a side chain; A hydrophilic treatment agent comprising a graft polymer A having
The content of the repeating unit derived from the unsaturated monomer having a sulfobetaine group in the graft polymer A is 60% by mass or more,
The content of the polymer segment A-2 in the graft polymer A is 5% by mass or less.
Hydrophilizing agent. The hydrophilic treatment agent according to claim 1, wherein the repeating unit derived from the unsaturated monomer having a sulfobetaine group in the graft 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 : an alkylene group having 1 to ⁴ carbon atoms R ⁵ , R ⁶ : the same or different, 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ⁷ , R ⁷ is a hydrogen atom or 1 or more carbon atoms, 4 or less hydrocarbon group X ² : 2 or more carbon atoms that may have a hydroxyl group, 4 The following alkylene groups are shown. ] The hydrophilic treatment agent according to claim 1 or 2, wherein the repeating unit derived from the hydrophobic unsaturated monomer of the polymer segment A-2 in the graft polymer A is a structural unit represented by the general formula (2). .

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹² and R ¹² is hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms is shown. ] The hydrophilic treatment agent in any one of Claims 1-3 in which the polymer segment A-1 in the graft polymer A contains the structural unit represented by General formula (2).

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹² and R ¹² is hydrogen An atom or a hydrocarbon group having 1 to 4 carbon atoms is shown. ]   The hydrophilization treatment agent according to any one of claims 1 to 4, wherein the content of the structural unit derived from the unsaturated monomer having a sulfobetaine group in the graft polymer A is 70% by mass or more and 90% by mass or less. .   The hydrophilic treatment agent according to any one of claims 1 to 5, wherein the graft polymer A has a weight average molecular weight of 50,000 or more and 200,000 or less. The polymer segment A-2 in the graft polymer A is obtained by polymerizing a monomer having a structure represented by the general formula (4) or a monomer having a structure represented by the general formula (5). The hydrophilization treatment agent according to any one of claims 1 to 6, wherein

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms R ¹³ , R ¹⁴ : the same or different, a hydrogen atom or C 1 or 2 alkyl group R ¹⁵ : hydrocarbon group Y ¹ or more and 22 or less hydrocarbon group Y ¹ : O or NR ¹² , R ¹² is a hydrogen atom or a hydrocarbon group Y having 1 or more and 4 or less carbon atoms ² : O or NR ¹⁶ ; R ¹⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

[Where,
R ^{8 to} R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ¹¹ : a hydrocarbon group having 1 to 22 carbon atoms R ¹³ , R ¹⁴ : the same or different, a hydrogen atom or C 1 or 2 alkyl group R ¹⁷ : hydrogen atom or C 1 or 2 alkyl group Y ¹ : O or NR ¹² , R ¹² is a hydrogen atom or a hydrocarbon group Y having 1 to 4 carbon atoms ² : O, OR ¹⁸ , or NR ¹⁶ , R ¹⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁸ represents an alkylene group having 1 to 6 carbon atoms. ] The hydrophilic treatment agent according to any one of claims 1 to 7, wherein the graft polymer A is a graft polymer obtained by a production method including the following steps 1 and 2.
Step 1: A step of obtaining a graft polymer B by polymerizing an unsaturated monomer having an amino group and an unsaturated monomer containing an unsaturated monomer having a side chain polymer segment A-2.
Step 2: A step of obtaining graft polymer A by reacting graft polymer B with a quaternizing agent.   The unsaturated monomer having the side chain polymer segment A-2 has a structure represented by the monomer represented by the general formula (4) according to claim 7 or the structure represented by the general formula (5). The hydrophilic treatment agent according to claim 8, which is a monomer monomer. The hydrophilic treatment agent according to claim 8 or 9, wherein the unsaturated monomer having an amino group is a monomer represented by the general formula (6).

[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 : an alkylene group having 1 to ⁴ carbon atoms R ⁵ , R ⁶ : the same or different, 1 or more carbon atoms 4 or less hydrocarbon group X ¹ : O or NR ⁷ , and R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]   The hydrophilic treatment agent composition containing the hydrophilic treatment agent of any one of Claims 1-10, and water.   Furthermore, the hydrophilic treatment agent composition of Claim 11 containing surfactant.