JP2019094434A - Hydrophilization treatment agent composition - Google Patents

Abstract

To provide a hydrophilization treatment agent composition containing a hydrophilization treatment agent that exhibits an excellent hydrophilization ability for a long time.SOLUTION: A hydrophilization treatment agent composition contains a copolymer (component A) containing a specific constitutional unit (A1) having a betaine group and a constitutional unit (A2) having an aromatic group, an anionic surfactant (component B) and water (component C).SELECTED DRAWING: None

Description

  The present invention relates to a hydrophilization treatment composition and a hydrophilization method.

Conventionally, as a method of imparting antifouling properties to a solid surface, different methods of water repelling treatment and hydrophilizing treatment are known.
The water repelling treatment is a technique for performing surface treatment to give water repellence to a solid surface such as glass, metal, fiber and the like so that dirt contained in water is not attached. For example, after washing clothes, they are treated with a softener, sprayed with a water repellent on ski wear, etc. to have a waterproof effect, or waxed on the painted surface of a car. .
However, in water repellent treatment, it is difficult to make the surface completely water repellent, and due to repeated contact with water, dirt contained in water accumulates on the solid surface, thus exhibiting a sufficient antifouling effect. Is difficult.

  On the other hand, if the solid surface is rendered hydrophilic, that is, the contact surface of the solid surface with water is reduced to make the solid surface easy to wet with water, the dirt adhering to the solid surface after the treatment tends to fall off during cleaning. In addition to being expected to have the effect of preventing soil re-contamination, anti-fogging effect of glass and mirror, antistatic prevention, prevention of frost formation on aluminum fins of heat exchanger, anti-soiling property of bath and toilet surfaces etc. Can be expected.

Several proposals have been made for hydrophilic surface treatment agents and methods for solid surfaces.
For example, Patent Document 1 discloses an aqueous antifouling composition containing an amphoteric polyelectrolyte. Patent Document 2 discloses a cleaning or rinsing composition containing a surfactant and a specific polybetaine. Patent Document 3 discloses a hydrophilic resin containing an acrylic resin obtained by copolymerizing a polymerizable unsaturated monomer having a specific betaine structure and a specific polymerizable unsaturated monomer, a hydrophilic crosslinked polymer particle and a crosslinking agent. A treatment composition has been disclosed. U.S. Pat. No. 5,959,059 comprises applying to the support a composition comprising an amphiphilic block copolymer, wherein the amphiphilic block copolymer is formed from a hydrophilic block of a particular structure and an ethylenically unsaturated hydrophobic monomer. A method is disclosed to improve the wettability / hydrophilicity of hydrophobic supports containing hydrophobic blocks. Patent Document 5 includes a polymer segment A-1 derived from an unsaturated monomer containing a repeating unit derived from a hydrophobic unsaturated monomer, and a repeating unit derived from an unsaturated monomer having a sulfobetaine group. Hydrophilization comprising a block polymer A having a polymer segment A-2 derived from an unsaturated monomer and having a content of the polymer segment A-1 of 0.05% by mass or more and 75% by mass or less Treatment agents are disclosed. Patent Document 6 discloses a surface treatment agent comprising a copolymer comprising a specific structural unit (A) having a betaine group and a specific structural unit (B) having a cationic group.

JP 2001-181601 A Japanese Patent Application Publication No. 2006-514150 JP, 2012-25820, A Japanese Patent Application Publication No. 2009-545642 JP, 2015-105313, A JP, 2017-190381, A

  However, the product to which the hydrophilization technology is applied is surprisingly small, and it can not be said that it is widely and widely used. This is due to the lack of a hydrophilizing agent having a sufficiently satisfactory effect. In addition, even if the solid surface immediately after the treatment with a hydrophilizing agent exhibits hydrophilicity, the hydrophilicity may decrease when exposed to a high humidity environment or an environment wet with water for a long time. The hydrophilic agent is required to have high durability.

  The present invention provides a hydrophilization treatment agent composition that exhibits excellent hydrophilization ability for a long time.

  The present invention is a copolymer containing a structural unit (A1) represented by the following formula (a1) and a structural unit (A2) having an aromatic group (hereinafter referred to as component A), an anionic surfactant (hereinafter referred to as , Component B) and water (hereinafter referred to as component C).

[In the formula,
^{R 11a, R 12a, R 13a} : the same or different, an alkyl group R ^14a a hydrogen atom or a C 1 or 2: 1 to 4 alkylene group having a carbon number, or ^-Y 1 -OPO ₃ ^{- -Y 2 -}
Y ¹ and Y ^{2 are the} same or different and each is an alkylene group having 1 to 4 carbon atoms, R ^15a , R ^16a : the same or different, a hydrocarbon group having 1 to 4 carbon atoms, X ¹ : O or NR ^17a And R ^17a represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R ^18a SO ₃ ⁻ or R ^18a COO ⁻ . However, when R ^14a is an alkylene group having 1 to 4 carbon atoms, X ² is R ^18a SO ₃ ⁻ or R ^18a COO ⁻ , R ^18a is an alkylene group having 1 to 4 carbon atoms, and R ^14a is When -Y ¹ -OPO ₃ ^-- Y ^2- , X ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

  Further, the present invention relates to a method of hydrophilizing treatment, wherein the above-mentioned hydrophilizing treatment composition of the present invention is applied to a solid surface.

  ADVANTAGE OF THE INVENTION According to this invention, the hydrophilization treatment agent composition which exhibits the outstanding hydrophilization ability for a long time is provided.

<Hydrophilizing treatment composition>
The hydrophilic treatment agent composition of the present invention can maintain the hydrophilicity of the solid surface for a long period of time by being applied to a solid surface, even when exposed to a high humidity environment or an environment wet with water for a long time.
Although the detail of the action mechanism of the hydrophilization treatment agent composition according to the present invention is not clear, it is considered as follows.
The component A which is a hydrophilization treatment agent is a copolymer, and it is a solid by including the structural unit (A1) represented by the formula (a1) and the structural unit (A2) having an aromatic group in the structural units. It adsorbs to the surface and hydrophilizes the solid surface. However, while the solid surface is hydrophilized, it also dissolves in water because it has a high affinity to water, so it will separate from the solid surface in an environment exposed to water for a long period of time, causing the solid surface to It may be difficult to maintain hydrophilization. However, in the present invention, the component A, which is cationic, and the component B, which is anionic, function as a combination, and these are mixed beforehand to form a complex, thereby forming this complex and the solid surface. It is presumed that, even if it is exposed to a high humidity environment or an environment wet with water for a long time, it does not easily separate from the solid surface and can maintain hydrophilicity. Moreover, it is presumed that concentration can be easily adjusted when applying on a solid surface by containing water, and the handleability is improved.

[Component A]
The copolymer of the component A includes the structural unit (A1) represented by the formula (a1) and the structural unit (A2) having an aromatic group.

The structural unit (A1) is a structural unit having a sulfobetaine group, a carbobetaine group, or a phosphobetaine group.
The structural unit (A) is, for example, a structural unit derived by polymerizing an unsaturated monomer represented by the following formula (a1 ′), and R in the formulas (a1) and (a1 ′) ^{11a, R 12a, R 13a,} R 14a, R 15a, R 16a, X 1, X 2 are all synonymous.

In formulas (a1) and (a1 ′), from the viewpoint of the availability of unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment agent, R ^11a and R ^12a are A hydrogen atom is preferred. From the same point of view, R ^13a is preferably a hydrogen atom or a methyl group, more preferably a methyl group. X ¹ is preferably O from the same viewpoint. From the same point of view, R ^14a is preferably a C 2 or C 3 alkylene group, more preferably a C 2 ethylene group. From the same point of view, R ^15a and R ^16a are preferably a methyl group or an ethyl group, and more preferably a methyl group.
In formulas (a1) and (a1 ′), R ^14a is an alkylene group having 1 to 4 carbon atoms, and X ² is preferably R ^18a SO ₃ ⁻ or R ^18a COO ⁻ , and R ^14a is an alkylene group having 1 to 4 carbon atoms, ^{X 2} is ^R 18a SO ₃ ^- and more preferably.

When the structural unit (A1) is a structural unit having a sulfobetaine group, for example, after the unsaturated monomer represented by the following formula (a1 ′ ′-1) is polymerized, the following formula (a1 ′ ′) R ^11a , R ^12a , R ^13a , R in the formula (a1 ′ ′) can be obtained by reacting the compound represented by the formula 2) or the compound represented by the following formula (a1′′3) ^14a , R ^15a , R ^16a and X ¹ are all synonymous with the formula (a1), and preferred embodiments are also the same as the formula (a1).

_{Z-X 2 -SO 3 M (} a1 "-3)
(Wherein, Z represents Cl or Br, preferably Cl, X ² represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, preferably a 2-hydroxypropylene group, and M represents Na or K) .)

  From the viewpoint of improving the durability after the hydrophilization treatment, the proportion of the constituent unit (A1) in all constituent units of the copolymer of Component A is preferably 80 mol% or more, more preferably 85 mol% or more, and further preferably Preferably, it is 88 mol% or more, and preferably 99 mol% or less, more preferably 95 mol% or less, still more preferably 92 mol% or less.

  The structural unit (A2) is a structural unit having an aromatic group. The aromatic group of the structural unit (A2) may have a substituent such as a hydroxyl group. As the structural unit (A2), a structural unit represented by the following formula (a2) (hereinafter, also referred to as a structural unit (a21)) and / or a structural unit derived from styrene (hereinafter, also referred to as a structural unit (a22)) It can be mentioned. The structural unit (A2) is preferably a structural unit (a21) represented by the following formula (a2).

[In the formula,
R ^21a , R ^22a , R ^23a : identical or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ^24a : an aromatic group having 6 to 22 carbon atoms in total hydrocarbon group Z ¹ : O or NR is ^{25a, R 25a} represents a 4 or less hydrogen atom or a hydrocarbon group having 1 or more carbon atoms. ]

The structural unit (a21) is a structural unit derived by polymerizing an unsaturated monomer represented by the following formula (a2 ′) (hereinafter, also referred to as unsaturated monomer a2 ′), and R ^21a , R ^22a , R ^23a and Z ¹ in a2) and formula (a2 ′) are all synonymous.

In the formulas (a2) and (a2 ′), R ^21a and R ^22a from the viewpoint of the availability of unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment agent. Is preferably a hydrogen atom. From the same point of view, R ^23a is preferably a hydrogen atom or a methyl group, more preferably a methyl group. Z ¹ is preferably O from the same viewpoint. The total carbon number of the hydrocarbon group of R ^24a is 6 or more and 22 or less, preferably 18 or less. The aromatic group of R ^24a may be substituted by one or more hydroxyl groups. R ^24a includes aralkyl groups such as benzyl group, phenethyl group and 3,4-dihydroxyphenethyl group, aryl groups such as phenyl group, and alkyl substituted aryl groups. R ^24a is preferably an aralkyl group from the viewpoint of enhancing the adsorptivity to the surface.

  Examples of the unsaturated monomer a2 'include benzyl (meth) acrylate and N- (3,4-dihydroxyphenylethyl) (meth) acrylamide. In the present specification, “(meth) acrylic” means acrylic, methacrylic or both of them.

  From the viewpoint of improving the durability after the hydrophilization treatment, the proportion of the structural unit (A2) in all the structural units of the copolymer of component A is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably Preferably, it is 3 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less.

  The copolymer of component A is preferably structural unit (A) / structural unit (A2) having a molar ratio of structural unit (A1) to structural unit (A2) from the viewpoint of improving durability after hydrophilization treatment. Is 3 or more, more preferably 5 or more, further preferably 8 or more, and preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less.

  From the viewpoint of improving the durability after the hydrophilization treatment, in the copolymer of Component A, the ratio of the total of the structural unit (A1) and the structural unit (A2) in all the structural units is preferably 80 mol% or more, more preferably Preferably, it is 85 mol% or more, more preferably 90 mol% or more, and preferably 100 mol% or less, more preferably 98 mol% or less, still more preferably 95 mol% or less.

  The copolymer of component A can further contain a structural unit (A3) represented by the following formula (a3).

[In the formula,
R ^31a , R ^32a , R ^33a : identical or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms Q ¹ : O or NH group R ^34a : an alkylene group having 1 to 4 carbon atoms Q ² : N ⁺ R ^35a R ^36a R ^37a · Q ³ or NR ^38a R ^39a , wherein R ^35a , R ^36a , R ^37a , R ^38a and R ^39a are the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms , Q ³ show anions. ]

The structural unit (A3) is a structural unit derived by polymerizing an unsaturated monomer represented by the following formula (a3 ′), and R ^31a in formula (a3) and formula (a3 ′) R ^32a , R ^33a , Q ¹ , R ^34a and Q ² are all synonymous. Examples of the unsaturated monomer represented by the following formula (a3 ′) to be the structural unit (A3) include unsaturated monomers such as methacryloyloxyethyldimethylethylammonium ethyl sulfate (MOEDES).

In the formula (a3) and the formula (a3 ′), from the viewpoint of the availability of unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment agent, in the formula (a3) ^Each of R ^31a , R ^32a and R ^33a is preferably a hydrogen atom or a methyl group. Q ¹ is preferably O. R ^34a is preferably an ethylene group. Q ^{2 is, R 35a} and ^{R 36a} is ^{methyl, R 37a} is ethyl, ^{Q 3} is dimethylethyl ammonium ethylsulfate is preferably ethylsulfate.

  The proportion of the structural unit (A3) in all the structural units is preferably 10 mol% or less, more preferably 8 mol% or less, and still more preferably 5 mol% or less.

  When the copolymer of component A contains the structural unit (A3), the structural unit (A1), the structural unit (A2) and the structural unit (A3) in all the structural units from the viewpoint of improving the durability after the hydrophilization treatment The ratio of the total of is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less, more preferably 99 mol% or less, still more preferably 98 It is less than mol%.

  Component A contains a structural unit (A1), a structural unit (A2), and a structural unit (hereinafter referred to as a structural unit (A4)) other than the structural unit (A3) within the range not impairing the effects of the present invention It is also good. As the monomer to be the structural unit (A4), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, (meth ) T-butyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate (Meth) acrylic acid esters such as lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate and benzyl (meth) acrylate Or N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-t-butyl (meth) ac Ruamido, N, N-diethyl (meth) include (meth) acrylamides such as acrylamide.

  The weight average molecular weight of the copolymer of component A is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, from the viewpoint of enhancing the hydrophilization performance, and manufacturability From the viewpoint of improving (the viscosity of the composition, etc.), it is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 400,000 or less, still more preferably 300,000 or less. This weight average molecular weight can be measured by the method described in the examples.

[Component B]
Component B is an anionic surfactant. There is no particular limitation on the anionic surfactant, and any anionic surfactant may be used. Component B is at least one anionic surfactant, and may be two or more.

  The anionic surfactant of Component B is preferably an anionic surfactant having at least one group selected from the group consisting of a sulfonic acid group, a sulfuric acid ester group, a carboxylic acid group, a carboxylic acid group, a phosphonic acid group and a phosphoric acid ester group. .

As component B, for example,
(1) (11) fatty acids having a hydrocarbon group having 8 to 22 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid and salts thereof, (12) polyoxyethylene lauryl ether carboxylic acid, Surfactants of carboxylic acids such as carboxylic acids and salts thereof of alkylene oxides of 1 to 10 moles of alkylene oxide of an alcohol having 8 to 22 carbon atoms such as polyoxyethylene myristyl ether carboxylic acid and polyoxyethylene oleyl ether carboxylic acid. Agents;
(2) (21) sulfosuccinic acid mono- or diesters of alcohols having 6 to 24 carbon atoms and salts thereof, (22) sulfones of α-olefins having 8 to 24 carbon atoms and salts thereof, and (23) carbon atoms Alkyl benzene sulfonic acid and its salt which have an alkyl group of 8 or more and 14 or less, (24) sulfonic acid type surfactant such as petroleum sulfonate and its salt;
(3) (31) sulfuric acid ester of alcohol having 8 to 22 carbon atoms and a salt thereof, and (32) alkylene oxide of alcohol having alcohol number of 8 to 22 carbon atoms and an average of 1 to 10 mol sulfuric acid ester of an adduct and a salt thereof (33) Sulfated oils and salts thereof (34) Sulfated fatty acid esters and salts thereof (35) Sulfated ester surfactants such as sulfated olefins and salts thereof
(4) (41) phosphoric acid mono- or diesters of alcohols having 8 to 24 carbon atoms and salts thereof, (42) mono- or diesters of phosphoric acid mono- or diesters of alkylene oxide adducts of alcohols having 8 to 24 carbon atoms and salts thereof Phosphate ester surfactant;
Etc.

In addition, as a polymer type surfactant such as a polymer consisting of repeating units by polycondensation etc.,
(5) Poly (meth) acrylic acid, (meth) acrylic acid-maleic acid copolymer, (meth) acrylic acid-itaconic acid copolymer, (meth) acrylic acid-fumaric acid copolymer, (meth) acrylic Acid / vinyl acetate copolymer, 2-hydroxyethyl methacrylate / (meth) acrylic acid copolymer, maleic acid / diisobutylene copolymer, maleic acid / styrene copolymer, poly {2-hydroxyethyl (meth) acrylate Polymeric carboxylic acid surfactants such as carboxymethylated products, carboxymethylcelluloses, carboxymethylcelluloses, carboxymethylethylcelluloses, formaldehyde condensates of benzoic acid, benzoic acid-phenol-formaldehyde condensates, and salts thereof;
(6) polystyrene sulfonic acid, styrene / styrene sulfonic acid copolymer, 2- (meth) acryloylamino-2,2-dimethylethane sulfonic acid / (meth) acrylic acid copolymer, 2- (meth) acryloylamino- 2,2-Dimethylethane sulfonic acid / (meth) acrylic acid / acrylamide copolymer, naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, dimethyl naphthalene sulfonic acid formaldehyde condensate etc. and salts thereof etc. Molecular type sulfonic acid surfactant;
(7) Poly {2-hydroxyethyl (meth) acrylate sulfuric acid ester}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate sulfuric acid ester copolymer, poly {2-hydroxyethyl (meth) acrylate And the like, and high molecular type sulfuric acid ester surfactants such as sulfuric acid esters and the like and salts thereof;
(8) Poly {(meth) acryloyloxyethyl phosphonic acid}, 2-hydroxyethyl (meth) acrylate / (meth) acryloyloxyethyl phosphonic acid copolymer, naphthalene phosphonic acid formaldehyde condensate, etc. and salts thereof etc. Molecular type phosphonic acid surfactant;
(9) Poly {2-hydroxyethyl (meth) acrylate phosphoric acid ester}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate phosphoric acid ester copolymer, poly {2-hydroxyethyl (meth) acrylate A polymeric ester of a phosphoric acid ester of an acrylate} and salts thereof etc .;
Etc.

Component B preferably has a molecular weight of 200 or more and 100,000 or less from the viewpoint of improving the durability after the hydrophilization treatment. This molecular weight may be a weight average molecular weight when component B is a polymer. The weight average molecular weight of the component B is measured under the following conditions using gel permeation chromatography (hereinafter also referred to as "GPC") method. When Component B is a polymer, the weight average molecular weight is preferably 3,000 or more, more preferably 10,000 or more, and preferably 50,000 or less, more preferably 30,000 or less.
[GPC conditions]
Column: G4000PWXL + G2500PWXL (made by Tosoh Corporation)
Eluent: 0.2 M phosphate buffer / CH ₃ CN = 9/1 (volume ratio)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.5 mg / mL
Reference substance: Polyethylene glycol equivalent

  Component B is preferably an alkali metal salt, more preferably a sodium salt and / or a potassium salt, from the viewpoint of improving the durability after the hydrophilization treatment.

Specifically, Component B is a sulfosuccinic acid diester salt of an alcohol having 6 to 24 carbon atoms such as sodium dioctyl sulfosuccinate, or an alkylene oxide 1 of an alcohol having 8 to 22 carbon atoms such as sodium polyoxyethylene lauryl ether sulfate 1 Alkyl ester sulfone having an alkyl group having a carbon number of 8 to 14 such as a sulfuric acid ester salt of an adduct of 10 to 10 mol and a sulfuric acid ester of an alcohol having 8 to 22 carbon atoms such as sodium lauryl sulfate or sodium dodecylbenzene sulfonate Acid salt, fatty acid salt having hydrocarbon group having 8 to 22 carbon atoms such as sodium oleate and potassium oleate, sodium polyacrylate, sodium polymethacrylate, sodium of (meth) acrylic acid / maleic acid copolymer Salt and so on Maleic acid polymers such as (meth) acrylic acid polymers, sodium salts of maleic acid / diisobutylene copolymers, sodium salts of maleic acid / styrene copolymers, formaldehyde condensates of sodium β-naphthalene sulfonate, etc. And sulfonic acid group-containing polymers.
Among these, sodium dioctyl sulfosuccinate, polyoxyethylene (for example, average addition mole number 3) sodium lauryl ether sulfate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, oleic acid from the viewpoint of improving durability after hydrophilization treatment. It is selected from maleic acid polymers such as potassium, sodium polyacrylate, sodium salt of maleic acid / diisobutylene copolymer, sodium salt of maleic acid / styrene copolymer, and formaldehyde condensates of sodium β-naphthalene sulfonate One or more anionic surfactants are preferable, and from the viewpoint of improving the durability against aluminum, sodium dioctyl sulfosuccinate, polyoxyethylene (for example, average addition mole number 3) sodium lauryl ether sulfate, lauryl sulfate One or more anionic surfactants selected from sodium, sodium dodecyl benzene sulfonate, sodium polyacrylate, sodium salt of maleic acid / diisobutylene copolymer and formaldehyde condensate of sodium β-naphthalene sulfonate are more preferable And one or more anionic surfactants selected from sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyacrylate, sodium salt of maleic acid / diisobutylene copolymer and formaldehyde condensate of sodium β-naphthalenesulfonate Is more preferred, and one or more anionic surfactants selected from sodium lauryl sulfate and sodium salt of maleic acid / diisobutylene copolymer are more preferred.
In addition, from the viewpoint of improving the durability to polycarbonate, sodium dioctyl sulfosuccinate, polyoxyethylene (for example, average addition mole number 3) sodium lauryl ether sulfate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyacrylate, maleic acid / At least one anionic surfactant selected from maleic acid polymers such as sodium salt of diisobutylene copolymer, sodium salt of maleic acid / styrene copolymer and formaldehyde condensate of sodium β-naphthalene sulfonate More preferably, sodium dioctyl sulfosuccinate, polyoxyethylene (eg, average addition mole number 3) sodium lauryl ether sulfate, sodium polyacrylate, sodium of maleic acid / diisobutylene copolymer Further preferred is one or more anionic surfactant selected from formaldehyde condensates of sodium salt and sodium β-naphthalene sulfonate, polyoxyethylene (eg, average addition mole number 3) sodium lauryl ether sulfate and maleic acid / diisobutylene More preferred are one or more anionic surfactants selected from sodium salts of copolymers.

[Composition, optional components, etc.]
In the hydrophilization treatment agent composition of the present invention, the content of component A is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more from the viewpoint of storage efficiency and transport efficiency improvement and handleability. Is more preferably 35% by mass or more, and from the viewpoint of storage stability and handling, 80% by mass or less is preferable, 70% by mass or less is more preferable, 60% by mass or less is more preferable, and 50% by mass % Or less is even more preferable.

  In the hydrophilization treatment agent composition of the present invention, the content of component B is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, from the viewpoints of storage efficiency, transport efficiency improvement, and handleability. 0.3 mass% or more is further preferable, 0.5 mass% or more is further more preferable, and from the viewpoint of storage stability and handleability, 8 mass% or less is preferable, 7 mass% or less is more preferable, 6 mass% % Or less is more preferable, and 5% by mass or less is even more preferable.

  In the hydrophilization treatment agent composition of the present invention, the mass ratio of component A to component B (component A / component B) is preferably 10 or more and 100 or less from the viewpoint of improving the durability after the hydrophilization treatment. From the same viewpoint, the mass ratio of component A / component B is preferably 11 or more, more preferably 12 or more, still more preferably 13 or more, and still more preferably 80 or less, still more preferably 60 or less, 50 or less Is even more preferred.

  In the hydrophilization treatment agent composition of the present invention, the water of component C is used in an amount to be the balance of the composition. In the hydrophilic treatment agent composition of the present invention, the content of component C is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more from the viewpoint of handleability. From the viewpoint of storage efficiency and transport efficiency improvement, it is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.

The hydrophilization treatment agent composition of the present invention is preferably used as a treatment liquid diluted with water. In the treatment liquid, the content of the component A is preferably 0.01% by mass or more and 5.0% by mass or less from the viewpoint of improving the durability after the hydrophilization treatment and the appearance of the solid surface after the treatment. In the treatment liquid, the content of the component A is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass from the viewpoint of the appearance of durability improvement after the hydrophilization treatment. The content is more preferably 0.5% by mass or more, still more preferably 0.9% by mass or more, and 5.0% by mass or less from the viewpoint of the appearance of the solid surface after treatment, 3 The content is preferably not more than 0% by mass, more preferably 2.0% by mass or less, still more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less.
In the treatment liquid, the content of the component B is 0.001% by mass or more and 1.0% by mass or less from the viewpoint of the improvement of durability after the hydrophilization treatment and the appearance of the solid surface after the treatment. preferable. In the treatment liquid, the content of the component B is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass from the viewpoint of the appearance of durability improvement after the hydrophilization treatment. The content is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and 1.0% by mass or less from the viewpoint of the appearance of the solid surface after treatment, 0 .7 mass% or less is more preferable, 0.5 mass% or less is more preferable, 0.3 mass% or less is further more preferable, 0.2 mass% or less is still more preferable.
In the treatment liquid, the total content of the component A and the component B is 0.05% by mass or more and 5.0% by mass or less from the viewpoint of durability improvement after the hydrophilization treatment and appearance of the solid surface after the treatment. Is preferred. In the treatment liquid, the total content of the component A and the component B is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving the durability after the hydrophilization treatment. % By mass or more is more preferable, and 0.5% by mass or more is still more preferable, and from the viewpoint of the appearance of the solid surface after treatment, 5.0% by mass or less is preferable, and 3.0% by mass or less is more preferable. 2.0 mass% or less is further preferable, 1.5 mass% or less is further more preferable, and 1.2 mass% or less is still more preferable.
The hydrophilic treatment agent composition of the present invention is preferably used at a concentration of 0.05% by mass or more and 5.0% by mass or less of the total of the component A and the component B at the time of use. More specifically, the hydrophilization treatment agent composition of the present invention comprises a treatment liquid containing component A, component B and water, and a treatment liquid containing component A of the above content, component B of the above content and water. Preferably used as

  The hydrophilizing agent composition of the present invention may be selected from carboxylic acids such as oxalic acid, maleic acid, citric acid, adipic acid, sebacic acid, malic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid, as long as the object of the present invention is not impaired. Acids; Lower alcohols such as ethyl alcohol and isopropyl alcohol; solvents such as diethylene glycol monobutyl ether; salts for improving the solubility of hydrophilic treatment agents such as NaCl; to water; toluene sulfonates, xylene sulfonates, ureas, etc. Solubilizers; viscosity modifiers such as clay minerals and water-soluble polymer compounds (but excluding the copolymer of the present invention); calcite, silica stone, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon, water-insoluble substances such as polystyrene Abrasives; Humectants such as glycerin and sorbitol; Feelings of cationized cellulose etc. Agents (except the copolymer of the present invention); sodium carbonate, alkali builders such as sodium silicate; enzymes can be added dyes, perfumes, preservatives and antifungal agents.

  The hydrophilization treatment agent composition of the present invention can be obtained by adding Component A, Component B, water and, if necessary, the other components described above, and stirring and mixing according to a known method. The composition ratio of the hydrophilization treatment agent composition can be appropriately adjusted in accordance with the type of solid surface and the treatment purpose. In addition, concentrated solutions can be prepared and diluted before use.

  The pH of the resulting hydrophilized treatment composition at 20 ° C. is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, from the viewpoint of safety in handling and prevention of damage to the solid surface, preferably Is 11 or less, more preferably 10 or less, more preferably 8 or less. As pH adjusters, inorganic acids such as hydrochloric acid and sulfuric acid; acid agents such as the above-mentioned organic acids; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate And alkali agents such as ammonia and derivatives thereof, and organic alkali compounds such as monoethanolamine, diethanolamine and triethanolamine. Moreover, an acid agent and an alkali agent can be combined and used as a buffer system.

  The hydrophilizing treatment composition of the present invention can be applied to solid surfaces of various substances. The solid surface is preferably a solid surface comprising aluminum and / or polycarbonate.

<Hydrophilization treatment method>
The present invention provides a hydrophilization treatment method of applying the hydrophilization treatment composition of the present invention to a solid surface.
Here, "solid" of "solid surface" is not particularly limited, and glass, ceramics, porcelain, tiles, tiles, ceramics; metals such as aluminum, stainless steel, brass, etc .; polycarbonate, polyethylene, polypropylene, melamine resin, polyamide resin Synthetic resins such as ABS resin and FRP; natural fibers such as cotton, silk and wool; synthetic fibers such as polyester, nylon and rayon; and solids such as hair, nails and teeth.
Suitable solid surfaces to which the method of the present invention can be applied include hydrophobic hard surfaces, and further, one or more hydrophobic hard surfaces selected from ceramics, metals and synthetic resins. Here, a hydrophobic hard surface means that the static contact angle to water is 70 ° or more, and a hydrophilic hard surface means that it is less than 70 °. In addition, a stationary contact angle can be measured by the method as described in an Example.
The hydrophilization treatment method of the present invention is preferably directed to a solid surface containing aluminum and / or polycarbonate.

  In the hydrophilization treatment method of the present invention, the hydrophilization treatment agent composition is preferably an aqueous solution from the viewpoint of handling stability. The aqueous solution may be the treatment solution described in the hydrophilic treatment composition of the present invention. In the hydrophilization treatment method of the present invention, it is preferable to bring the treatment liquid described in the hydrophilization treatment composition of the present invention into contact with a solid surface.

The method of contacting the solid surface with the hydrophilizing treatment composition is not particularly limited. For example, the following methods (i) to (iii) may be mentioned.
(I) A method of immersing the solid in the hydrophilizing treatment composition (ii) a method of spraying or applying the hydrophilizing treatment composition onto the solid surface (iii) washing the solid surface according to a conventional method with the hydrophilizing treatment composition The temperature at which the solid surface is subjected to the hydrophilization treatment with the hydrophilization treatment agent composition is preferably 5 ° C. or more, more preferably from the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment agent composition and easiness of the treatment method. Is 10 ° C. or more, more preferably 15 ° C. or more, preferably 50 ° C. or less, more preferably 40 ° C. or less, more preferably 30 ° C. or less.
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 hydrophilization treatment composition and from the economical viewpoint. 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 treatment composition to a solid surface can be appropriately selected depending on the size (area) of the hard surface and the like. It is preferable to spray the hydrophilic treatment composition on a solid surface by a method such as spraying, and then to dry it. If necessary, after spraying, it may be rinsed with water. Moreover, after spraying, you may apply thinly using sponge etc.
The amount of the hydrophilizing treatment composition to be sprayed or applied onto the solid surface is preferably, for example, 0 per 10 cm ² of the hydrophilizing treatment composition in which the content of the copolymer of component A is 0.5% by mass. .01 mL or more and 0.1 mL or less.
In the method of (iii) above, it is preferable to use in the form of a detergent composition containing the copolymer of Component A and the anionic surfactant of Component B, and to contact the solid surface. In the form of such a detergent composition, the pH is preferably 4 or more, preferably 10 or less, and more preferably 8 or less, from the viewpoint of safety in handling and prevention of damage to the solid surface.

  In the following synthesis examples, examples and comparative examples, "%" means "% by mass" unless otherwise specified.

<Component A>
Copolymer A1: Copolymer obtained in Synthesis Example 1 below Copolymer A2: Copolymer obtained in Synthesis Example 2 below

Synthesis Example 1 (Production of Copolymer A1)
(Step 1)
In a 1000 mL four-necked flask, 46.40 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd., the same applies hereinafter) was charged, and the temperature was raised to 78 ° C. to reflux. Here, 128.0 g of 2- (dimethylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 14.12 g of 2- (dimethylamino) ethyl diethyl sulfate methacrylate (manufactured by Kao Corporation / 90% aqueous solution), benzyl methacrylate (Wako Pure Chemical Industries, Ltd.) A solution of 9.340 g of ethanol and 20.90 g of ethanol mixed with 2,2'-azobis (2-methylbutyronitrile) (Wako Pure Chemical Industries, Ltd.) 2.080 g of ethanol 10.00 The solution which mixed g was dripped over 2 hours, respectively. After aging for 4 hours, it was cooled to obtain a polymer solution.
(Step 2)
230.8 g of the obtained polymer solution, 6.837 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 310.7 g of water were added to a 1000 mL four-necked flask, and the temperature was raised to 50 ° C. The reaction was carried out by dropping 106.4 g of 1,3-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.) over 2 hours. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain an aqueous solution containing the copolymer A1.
The copolymer A1 has a structural unit (A1) / a structural unit (A2) / a structural unit (A3) = SBMA / BzMA / MOEDES = 90/5/5 (molar ratio), and has a weight average molecular weight of 100,000. The Here, the symbol of the structural unit has the meaning of the following monomers. The constituent units in the copolymer A1 are constituent units corresponding to these monomers (the same applies hereinafter).
SBMA: N- (3-sulfopropyl) -N-methacryloxyethyl-N, N-dimethylammonium betaine BzMA: benzyl methacrylate MOEDES: methacryloyloxyethyl dimethylethylammonium ethyl sulfate

Synthesis Example 2 (Production of Copolymer A2)
[2- (Methacryloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide [[2- (Methacryloyloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide (manufactured by Aldrich) 9.345 in a 100 mL eggplant flask. Add 0.655 g of benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.092 g of V-65B (manufactured by Wako Pure Chemical Industries, Ltd.), 23.24 g of trifluoroethanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and boil with nitrogen Degassed. The oil bath was set to 65 ° C. and the eggplant flask was set to initiate polymerization. The polymerization was terminated after 6 hours, and reprecipitation was carried out with an acetone (manufactured by Wako Pure Chemical Industries, Ltd.) solvent. The precipitated polymer was vacuum dried at 80 ° C. to obtain a copolymer A2.
Copolymer A2 was structural-unit (A1) / structural-unit (A2) = SBMA / BzMA = 90/10 (molar ratio), and the weight average molecular weight was 120,000.

<Measurement of weight average molecular weight>
The weight average molecular weight of copolymer A1 and A2 measured the molecular weight by SLS (static light scattering method). The weight average molecular weight (Mw) was calculated by measuring static light scattering under the following conditions using a light scattering photometer "DLS-7000" (manufactured by Otsuka Electronics Co., Ltd.) and preparing Zimm-plot. Moreover, the refractive index increment required for calculation of 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 10 ° intervals from 30 ° to 150 °.
Average temperature: 25 ° C
Solvent: trifluoroethanol

<Component B>
Anionic surfactant B1: sodium dioctyl sulfosuccinate (manufactured by Kao Corporation, Perex OTP, molecular weight: 444)
Anionic surfactant B2: polyoxyethylene (average number of added moles: 3) sodium lauryl ether sulfate (manufactured by Kao Corporation, Emar 20C, weight average molecular weight: 420)
Anionic surfactant B3: sodium lauryl sulfate (manufactured by Kao Corporation, Emar O, molecular weight: 288)
Anionic surfactant B4: sodium dodecyl benzene sulfonate (manufactured by Kao Corporation, Neoperex G-65, molecular weight: 348)
Anionic surfactant B5: potassium oleate (manufactured by Kao Corporation, FR-14, molecular weight: 320)
・ Anionic surfactant B6: Sodium polyacrylate (weight average molecular weight: 25,000)
Anionic surfactant B7: sodium salt of maleic acid / diisobutylene (1/1 molar ratio) copolymer (weight average molecular weight: 20,000)

<Component C>
Water: pure water having an electrical conductivity of 1 μS / cm or less manufactured by using a pure water device G-10DSTSET manufactured by Organo Corporation

<Other ingredients>
Nonionic surfactant: polyoxyethylene (average added mole number 6) dodecyl ether cationic surfactant: stearylamine acetate (manufactured by Kao Corporation, acetamine 86)
Sodium sulfate: manufactured by Nacalai Tesque, Inc., sodium sulfate decahydrate, JIS reagent special grade

[Examples 1 to 12 and Comparative Examples 1 to 5]
<Production of Hydrophilizing Treatment Composition>
Each component was mixed as it is or was mixed so as to be the mass% shown in Table 1 to obtain an aqueous solution. The obtained aqueous solution was used for the following evaluation as a hydrophilization treatment agent composition.

<Preparation of test solution>
Each hydrophilic treatment composition was diluted with water to a solid content (component other than water) concentration of 1.00 mass% to prepare a test solution.
Preparation of Test Solution (Examples 13 to 15)
The hydrophilization treatment agent composition of Example 6 was diluted with water to a solid content concentration of 0.10 mass%, 0.30 mass% or 2.00 mass% to prepare a test solution.

<Evaluation board>
An aluminum plate (TP Giken Co., Ltd., pure aluminum plate “A1050P”) cut out to 70 mm long × 25 mm wide or a polycarbonate plate (polycarbonate transparent PS610 160 mm × 80 mm × 1.0 mm manufactured by Taiyo Engineering Co., Ltd.) as a substrate for evaluation Using.

<Coating process>
The entire evaluation substrate was immersed in the test solution at 20 ° C., and after 20 seconds, it was removed from the test solution and left to stand vertically for 1 hour.
<Rinse process>
After the coating step, the substrate for evaluation was rinsed with water twice using a washing bottle, and then left to stand vertically for 1 hour. The amount of water used to flush the substrate was approximately 50 mL per run.
<Durability test>
After the rinsing step, the substrate for evaluation was allowed to stand vertically in a 20 ° C. water bath with the whole being immersed, removed from the water bath after 1 hour, and allowed to stand vertically for 1 hour.

<Contact angle measurement method>
After the application step, the contact angles of the substrate for evaluation after the rinse step and after the durability test were measured using a contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Tables 1 and 2. Table 2 also shows the results of Example 6.

<Substrate surface observation after hydrophilization treatment>
The state of the substrate for evaluation after the application step, after the rinse step and after the endurance test was visually observed and evaluated based on the following. The results are shown in Table 2. Table 2 also shows the results of Example 6.
1: No precipitate 2: There is a precipitate at the edge 3: 3: There is a precipitate on the entire surface

Claims (11)

A copolymer (hereinafter referred to as component A) containing a structural unit (A1) represented by the following formula (a1) and a structural unit (A2) having an aromatic group, an anionic surfactant (hereinafter referred to as component B) And a water (hereinafter referred to as component C).

[In the formula,
^{R 11a, R 12a, R 13a} : the same or different, an alkyl group R ^14a a hydrogen atom or a C 1 or 2: 1 to 4 alkylene group having a carbon number, or ^-Y 1 -OPO ₃ ^{- -Y 2 -}
Y ¹ and Y ^{2 are the} same or different and each is an alkylene group having 1 to 4 carbon atoms, R ^15a , R ^16a : the same or different, a hydrocarbon group having 1 to 4 carbon atoms, X ¹ : O or NR ^17a And R ^17a represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R ^18a SO ₃ ⁻ or R ^18a COO ⁻ . However, when R ^14a is an alkylene group having 1 to 4 carbon atoms, X ² is R ^18a SO ₃ ⁻ or R ^18a COO ⁻ , R ^18a is an alkylene group having 1 to 4 carbon atoms, and R ^14a is When -Y ¹ -OPO ₃ ^-- Y ^2- , X ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ] The hydrophilic treatment agent composition according to claim 1, wherein the constituent unit (A2) having an aromatic group in the component A is a constituent unit represented by the following formula (a2) and / or a constituent unit derived from styrene.

[In the formula,
R ^21a , R ^22a , R ^23a : identical or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ^24a : an aromatic group having 6 to 22 carbon atoms in total hydrocarbon group Z ¹ : O or NR is ^{25a, R 25a} represents a 4 or less hydrogen atom or a hydrocarbon group having 1 or more carbon atoms. ] The hydrophilization treatment agent composition of Claim 1 or 2 in which the component A contains the structural unit (A3) further represented by a following formula (a3).

[In the formula,
R ^31a , R ^32a , R ^33a : identical or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms Q ¹ : O or NH group R ^34a : an alkylene group having 1 to 4 carbon atoms Q ² : N ⁺ R ^35a R ^36a R ^37a · Q ³ or NR ^38a R ^39a , wherein R ^35a , R ^36a , R ^37a , R ^38a and R ^39a are the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms , Q ³ show anions. ]   The hydrophilization treatment agent composition in any one of Claims 1-3 whose molecular weight of component B is 200 or more and 100,000 or less.   The hydrophilization treatment agent composition in any one of Claims 1-4 whose component B is a sodium salt and / or potassium salt.   The hydrophilization treatment agent composition in any one of Claims 1-5 whose mass ratio (component A / component B) of the component A and the component B is 10 or more and 100 or less.   The hydrophilic treatment agent composition according to any one of claims 1 to 6, wherein a total of component A and component B is used at a concentration of 0.05% by mass or more and 5.0% by mass or less at the time of use.   The hydrophilization processing method which apply | coats the hydrophilization processing agent composition in any one of Claims 1-7 to a solid surface.   The hydrophilization treatment method according to claim 8, wherein the solid surface is a solid surface containing aluminum and / or polycarbonate.   The hydrophilization treatment method according to claim 8 or 9, wherein a treatment liquid containing the hydrophilization treatment agent composition and water is applied to a solid surface.   The hydrophilization treatment method according to claim 10, wherein the total content of component A and component B in the treatment liquid is 0.05% by mass or more and 5.0% by mass or less.