JP6953290B2 - Hydrophilization treatment agent composition - Google Patents

Description

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

Conventionally, as a method for imparting antifouling property to a solid surface, different methods of water repellent treatment and hydrophilic treatment are known.
The water-repellent treatment is a technique for subjecting a solid surface such as glass, metal, or fiber to have water repellency to prevent dirt contained in water from adhering to the surface. For example, it is widely practiced to wash clothes and then treat them with a soft finish, spray ski wear with a water repellent to give a waterproof effect, and wax the painted surface of an automobile. ..
However, it is difficult to completely make the surface water-repellent by the water-repellent treatment, and the dirt contained in the water accumulates on the solid surface due to repeated contact with water, so that a sufficient antifouling effect is exhibited. Is difficult.

On the other hand, when the solid surface is hydrophilized, that is, the contact angle of the solid surface with water is lowered to make the solid surface wet easily with water, the dirt adhering to the solid surface after the treatment is easily removed during cleaning. In addition to being expected to have the effect of preventing recontamination of dirt, antifogging effect of glass, mirrors, etc., antistatic, prevention of frost formation of aluminum fins of heat exchangers, addition of antifouling properties to bathtubs and toilet surfaces, etc. Can be expected.

Several proposals have been made as a hydrophilizing agent and a method for a solid surface.
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 describes hydrophilicity containing an acrylic resin obtained by copolymerizing a polymerizable unsaturated monomer having a specific betaine structure and a specific polymerizable unsaturated monomer, hydrophilic crosslinked polymer particles, and a crosslinking agent. The treatment agent composition is disclosed. Patent Document 4 includes the step of applying a composition containing an amphipathic block copolymer to a support, wherein the amphipathic block copolymer is formed from a hydrophilic block having a specific structure and an ethylenically unsaturated hydrophobic monomer. Methods for improving the wettability / hydrophilicity of hydrophobic supports containing hydrophobic blocks have been disclosed. 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 consisting of a block polymer A having a polymer segment A-2 derived from an unsaturated monomer and having a polymer segment A-1 content of 0.05% by mass or more and 75% by mass or less. The treatment agent is disclosed. Patent Document 6 discloses a surface treatment agent composed of a copolymer containing a specific structural unit (A) having a betaine group and a specific structural unit (B) having a cationic group.

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

However, there are surprisingly few products that apply hydrophilic technology, and it is hard to say that they are widely used. This is due to the lack of a hydrophilic agent that has a sufficiently satisfactory effect. Further, even if the solid surface immediately after being treated with the hydrophilic agent shows 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 hydrophilic treatment agent composition that exhibits excellent hydrophilization ability for a long period of time.

The present invention relates to 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, and an anionic surfactant (hereinafter referred to as component A). , Component B) and water (hereinafter referred to as component C).

[In the formula,
R ^11a , R ^12a , R ^13a : same or different, hydrogen atom or alkyl group having 1 or 2 carbon atoms R ^14a : alkylene group having 1 to 4 carbon atoms, or −Y ¹ −OPO ₃ ⁻ −Y ² −
Y ¹ , Y ² : Same or different alkylene group with 1 or more and 4 or less carbon atoms R ^15a , R ^16a : Same or different hydrocarbon group with 1 or more and 4 or less carbon atoms X ¹ : O or NR ^17a . , ^{R 17a} is a hydrogen atom or a C 1 to 4 hydrocarbon group X ^2: a hydrogen atom, 1 to 4 of the hydrocarbon group having a carbon ^{number, R} 18a SO ₃ ^-, or ^R 18a COO ^- shows the. Provided ^that 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, R 14a} is When −Y ¹ −OPO ₃ ⁻ −Y ²⁻ , X ² is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. ]

The present invention also relates to a hydrophilization treatment method for applying the hydrophilization treatment agent composition of the present invention to a solid surface.

According to the present invention, there is provided a hydrophilic treatment agent composition that exhibits excellent hydrophilization ability for a long period of time.

<Hydrophilic treatment agent composition>
By applying the hydrophilic treatment agent composition of the present invention to a solid surface, the hydrophilicity of the solid surface can be maintained for a long period of time even when exposed to a high humidity environment or an environment wet with water for a long time.
The details of the action mechanism of the hydrophilizing agent composition according to the present invention are not clear, but it is considered as follows.
The component A, which is a hydrophilizing agent, is a copolymer, and is a solid by containing a structural unit (A1) represented by the formula (a1) and a structural unit (A2) having an aromatic group in the structural unit. Adsorbs to the surface and makes the solid surface hydrophilic. However, while making the solid surface hydrophilic, it also dissolves in water due to its high affinity with water, so in an environment exposed to water for a long period of time, it separates from the solid surface and the solid surface It may be difficult to maintain hydrophilicity. However, in the present invention, the cationic component A and the anionic component B function as a combination, and these are mixed in advance to form a complex, whereby this complex and the solid surface are combined. 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. Further, it is presumed that by containing water, the concentration can be easily adjusted when applied to a solid surface, and the handleability is improved.

[Component A]
The copolymer of the component A contains a structural unit (A1) represented by the above formula (a1) and a 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 , and X ² are all synonymous.

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

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

Z-X _2- SO ₃ M (a1 "-3)
(In the formula, Z represents Cl or Br, preferably Cl, X ² represents an alkylene group having 2 or more and 4 or less 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 of the copolymer of component A after the hydrophilization treatment, the proportion of the structural unit (A1) in all the structural units is preferably 80 mol% or more, more preferably 85 mol% or more, and further. It is preferably 88 mol% or more, 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)) is used. Can be mentioned. The structural unit (A2) is preferably the structural unit (a21) represented by the following formula (a2).

[In the formula,
R ^21a , R ^22a , R ^23a : Same or different, hydrogen atom or alkyl group having 1 or 2 carbon atoms R ^24a : Hydrocarbon group having a total carbon number of 6 to 22 having an aromatic group Z ¹ : O or NR ^25a , where R ^25a represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less 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 an unsaturated monomer a2'), and is a structural unit of the formula (a2'). ^{R 21a} , R ^22a , R ^23a and Z ¹ in a2) and the formula (a2') are all synonymous.

^{In the formulas (a2) and (a2'), R 21a} and R ^{22a are used} from the viewpoint of availability of unsaturated monomer, polymerizability of monomer, and enhancement of hydrophilization performance of hydrophilization treatment agent. Is preferably a hydrogen atom. From the same viewpoint, R ^23a is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. Z ¹ is preferably O from the same viewpoint. The total number of carbon atoms 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 with one or more hydroxyl groups. ^Examples of R 24a include an aralkyl group such as a benzyl group, a phenethyl group and a 3,4-dihydroxyphenethyl group, an aryl group such as a phenyl group, and an alkyl-substituted aryl group. 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 addition, in this specification, "(meth) acrylic" means acrylic, methacryl, or both.

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

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

From the viewpoint of improving durability after the hydrophilization treatment, the total ratio of the structural units (A1) and the structural units (A2) in the total structural units of the copolymer of the component A is preferably 80 mol% or more. It is preferably 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 the component A can further contain a structural unit (A3) represented by the following formula (a3).

[In the formula,
^{R 31a, R 32a, R 33a} : the same or different, an alkyl group to ^Q 1 hydrogen atom or C 1 or 2: O or NH group ^{R 34a:} alkylene group having 1 to 4 carbon atoms ^{Q 2: N} + R ^35a R ^36a R ^37a · Q ³ or NR ^38a R ^39a , and R ^35a , R ^36a , R ^37a , R ^38a , and R ^39a are the same or different, hydrogen atoms or hydrocarbon groups having 1 or more and 4 or less carbon atoms. , ^{Q 3} represents an anion. ]

The structural unit (A3) is a structural unit derived by polymerizing an unsaturated monomer represented by the following formula (a3'), and R ^31a in the formulas (a3) and (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'), which is the structural unit (A3), include unsaturated monomers such as methacryloyloxyethyl dimethyl ethyl ammonium ethyl sulfate (MOEDES).

In the formulas (a3) and (a3'), from the viewpoint of availability of unsaturated monomer, polymerizability of monomer, and enhancement of hydrophilization performance of the hydrophilization treatment agent, the formula (a3) is used. , R ^31a , R ^32a , and R ^33a are preferably hydrogen atoms or methyl groups. Q ¹ is, O is preferred. 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 ratio of the structural unit (A3) to all the structural units is preferably 10 mol% or less, more preferably 8 mol% or less, still more preferably 5 mol% or less.

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

The component A contains a constituent unit (A1), a constituent unit (A2), and a constituent unit other than the constituent unit (A3) (hereinafter referred to as a constituent unit (A4)) as long as the effect of the present invention is not impaired. May be good. Other monomers that serve as the structural unit (A4) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and (meth). ) T-butyl acrylate, n-hexyl (meth) acrylate, -cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate , (Meta) lauryl acrylate, (meth) myristyl acrylate, (meth) palmityl acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate and benzyl (meth) acrylate (meth) acrylate esters Examples thereof include (meth) acrylamides such as N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-t-butyl (meth) acrylamide, and N, N-diethyl (meth) 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, and manufacturability from the viewpoint of enhancing hydrophilicity performance. From the viewpoint of improving (viscosity of the formulation, etc.), it is preferably 1 million 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 Examples.

[Component B]
Component B is an anionic surfactant. The anionic surfactant is not particularly limited, and any anionic surfactant may be used. The component B is at least one kind of anionic surfactant, and may be two or more kinds.

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 sulfate ester 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 or more and 22 or less carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid and salts thereof, (12) polyoxyethylene lauryl ether carboxylic acid, Carboxylic acid of alcohols having 8 or more and 22 or less carbon atoms such as polyoxyethylene myristyl ether carboxylic acid and polyoxyethylene oleyl ether carboxylic acid Average 1 mol or more and 10 mol or less Carboxylic acid-based surface activity of additives such as carboxylic acids and salts thereof Agent;
(2) (21) Sulfonic acid mono or diester of alcohol having 6 or more and 24 or less carbon atoms and its salt, (22) Sulfonic oxide of α-olefin having 8 or more and 24 or less carbon atoms and its salt, (23) Number of carbon atoms Sulfonic acid-based surfactants such as alkylbenzene sulfonic acids having 8 or more and 14 or less alkyl groups and salts thereof, (24) petroleum sulfonates and salts thereof;
(3) (31) Sulfate ester of alcohol having 8 or more and 22 carbon atoms and its salt, (32) Sulfate ester of alcohol having 8 or more and 22 carbon atoms and its salt on average 1 mol or more and 10 mol or less , (33) Sulfated oil and its salt, (34) Sulfated fatty acid ester and its salt, (35) Sulfated olefin and its salt and other sulfate ester-based surfactants;
(4) (41) Phosphoric acid mono or diester of alcohol having 8 or more and 24 or less carbon atoms and a salt thereof, (42) Phosphoric acid mono or diester of an alcohol alkylene oxide adduct having 8 or more carbon atoms and 24 or less carbon atoms and a salt thereof, etc. Phosphate ester-based surfactant;
And so on.

In addition, as a polymer-type surfactant such as a polymer composed of repeating units by polycondensation or the like,
(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 } Carboxymethylated products, carboxymethyl cellulose, carboxymethyl methyl cellulose, carboxymethyl ethyl cellulose, benzoic acid formaldehyde condensates, benzoic acid-phenol-formaldehyde condensates and polymers of these, polymeric carboxylic acid-based surfactants;
(6) Polystyrene sulfonic acid, styrene / styrene sulfonic acid copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / (meth) acrylic acid copolymer, 2- (meth) acryloylamino- High of 2,2-dimethylethanesulfonic acid / (meth) acrylic acid / acrylamide copolymer, naphthalenesulfonic acid formaldehyde condensate, methylnaphthalenesulfonic acid formaldehyde condensate, dimethylnaphthalenesulfonic acid formaldehyde condensate, etc. and salts thereof. Molecular sulfonic acid-based surfactant;
(7) Poly {2-hydroxyethyl (meth) acrylate sulfate ester}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate sulfate ester copolymer, poly {2-hydroxyethyl (meth) acrylate } Sulfate esters, etc. and high-molecular-weight sulfate ester-based surfactants such as salts thereof;
(8) Poly {(meth) acryloyloxyethyl phosphonic acid}, 2-hydroxyethyl (meth) acrylate / (meth) acryloyloxyethyl phosphonic acid copolymer, naphthalenephosphonic acid formaldehyde condensate, etc. Molecular phosphonic acid-based surfactant;
(9) Poly {2-hydroxyethyl (meth) acrylate phosphate}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate phosphate copolymer, poly {2-hydroxyethyl (meth) ) Acrylate} phosphoric acid esterified products and high molecular weight phosphoric acid ester-based surfactants such as salts thereof;
And so on.

The component B preferably has a molecular weight of 200 or more and 100,000 or less from the viewpoint of improving durability after the hydrophilic treatment. This molecular weight may be the weight average molecular weight when the component B is a polymer. The weight average molecular weight of component B was measured under the following conditions using a gel permeation chromatography (hereinafter, also referred to as “GPC”) method. When the component B is a polymer, the weight average molecular weight is preferably 3000 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 (manufactured by Tosoh Corporation)
Eluent: 0.2M 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
Standard substance: Polyethylene glycol equivalent

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

Specifically, the component B is an alkylene oxide 1 of an alcohol having 6 or more and 24 or less carbon atoms such as sodium dioctyl sulfosuccinate, a sulfosuccinic acid diester salt of an alcohol having 6 or more and 24 or less carbon atoms, and an alcohol having 8 or more and 22 or less carbon atoms such as sodium polyoxyethylene lauryl ether sulfate. Alkylbenzene sulfone having an alkyl group having 8 or more and 14 or less carbon atoms, such as a sulfate ester salt of an adduct of molar or more and 10 mol or less, a sulfate ester salt of an alcohol having 8 or more and 22 or less carbon atoms such as sodium lauryl sulfate, and sodium dodecylbenzene sulfonate or the like. Fatty acid salts having hydrocarbon groups having 8 to 22 carbon atoms such as acid salts, sodium oleate, potassium oleate, sodium polyacrylate, sodium polymethacrylate, sodium (meth) acrylic acid / maleic acid copolymer Poly (meth) acrylic acid-based polymer such as salt, sodium salt of maleic acid / diisobutylene copolymer, maleic acid-based polymer such as sodium salt of maleic acid / styrene copolymer, sodium β-naphthalene sulfonate Examples thereof include sulfonic acid group-containing polymers such as formaldehyde condensates.
Among these, from the viewpoint of improving durability after hydrophilization treatment, sodium dioctyl sulfosuccinate, polyoxyethylene (for example, average addition molar number 3) sodium lauryl ether sulfate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, oleic acid Selected from maleic acid-based polymers such as potassium, sodium polyacrylate, sodium salt of maleic acid / diisobutylene copolymer, sodium salt of maleic acid / styrene copolymer, and formaldehyde condensate of sodium β-naphthalene sulfonate. One or more anionic surfactants are preferable, and from the viewpoint of improving durability against aluminum, sodium dioctyl sulfosuccinate, polyoxyethylene (for example, average addition molar number 3) sodium lauryl ether sulfate, sodium lauryl sulfate, dodecylbenzene sulfonic acid. More preferably, one or more anionic surfactants selected from sodium salts of sodium, sodium polyacrylate, maleic acid / diisobutylene copolymers and formaldehyde condensates of sodium β-naphthalene sulfonate, sodium lauryl sulfate, dodecyl. One or more anionic surfactants selected from sodium benzenesulfonate, sodium polyacrylate, sodium salt of maleic acid / diisobutylene copolymer and formaldehyde condensate of sodium β-naphthalene sulfonate are more preferable, and lauryl sulfate is more preferable. More preferably, one or more anionic surfactants selected from sodium salts of sodium and maleic acid / diisobutylene copolymers.
From the viewpoint of improving durability against polycarbonate, sodium dioctyl sulfosuccinate, polyoxyethylene (for example, average addition molar number 3) sodium lauryl ether sulfate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyacrylate, maleic acid / One or more anionic surfactants selected from maleic acid-based 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 molar number 3) sodium lauryl ether sulfate, sodium polyacrylate, sodium salt of maleic acid / diisobutylene copolymer and formaldehyde condensation of sodium β-naphthalene sulfonate. One or more anionic surfactants selected from the above are more preferable, and one or more selected from polyoxyethylene (for example, an average addition molar number of 3) sodium lauryl ether sulfate and a sodium salt of a maleic acid / diisobutylene copolymer. Anionic surfactants are more preferred.

[Composition, optional ingredients, etc.]
In the hydrophilization treatment 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 more preferably 30% by mass or more from the viewpoint of improving storage efficiency, transport efficiency and handleability. Is even more preferable, 35% by mass or more is further preferable, and from the viewpoint of storage stability and handleability, 80% by mass or less is more preferable, 70% by mass or less is more preferable, 60% by mass or less is further preferable, and 50% by mass is used. % Or less is even more preferable.

In the hydrophilization treatment 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 viewpoint of improving storage efficiency, transport efficiency, and handleability. 0.3% by mass or more is further preferable, 0.5% by mass or more is further preferable, and from the viewpoint of storage stability and handleability, 8% by mass or less is more preferable, 7% by mass or less is more preferable, and 6% by mass is used. % 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 durability after the hydrophilization treatment. From the same viewpoint, the mass ratio of component A / component B is more preferably 11 or more, further preferably 12 or more, further preferably 13 or more, still more preferably 80 or less, further preferably 60 or less, and further preferably 50 or less. Is even more preferable.

In the hydrophilizing treatment agent composition of the present invention, the water of the component C is used in an amount that becomes the balance of the composition. In the hydrophilization treatment composition of the present invention, the content of the component C is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and from the viewpoint of handleability, and From the viewpoint of improving storage efficiency and transportation efficiency, it is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.

The hydrophilic 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 hydrophilic treatment and the aesthetic 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 aesthetics of improving durability after the hydrophilization treatment. The above is further preferable, 0.5% by mass or more is further preferable, 0.9% by mass or more is further preferable, and 5.0% by mass or less is preferable from the viewpoint of the aesthetic appearance of the solid surface after treatment. It is more preferably 0.0% by mass or less, further preferably 2.0% by mass or less, further preferably 1.5% by mass or less, still more preferably 1.0% by mass or less.
Further, 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 improving the durability after the hydrophilic treatment and the aesthetic appearance of the solid surface after the treatment. preferable. In the treatment liquid, the content of component B is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and more preferably 0.01% by mass, from the viewpoint of aesthetics of improving durability after the hydrophilization treatment. The above is further preferable, 0.05% by mass or more is further preferable, 0.1% by mass or more is further preferable, and 1.0% by mass or less is preferable from the viewpoint of the aesthetic appearance of the solid surface after treatment, and 0. It is more preferably 7% by mass or less, further preferably 0.5% by mass or less, further preferably 0.3% by mass or less, still more preferably 0.2% by mass or less.
Further, 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 improving the durability after the hydrophilic treatment and the aesthetic appearance of the solid surface after the treatment. Is preferable. 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, and more preferably 0.3, from the viewpoint of improving the durability after the hydrophilization treatment. By mass% or more is further preferable, 0.5% by mass or more is further preferable, and from the viewpoint of the aesthetic appearance of the solid surface after treatment, 5.0% by mass or less is more preferable, and 3.0% by mass or less is more preferable. 2.0% by mass or less is further preferable, 1.5% by mass or less is further preferable, and 1.2% by mass or less is further preferable.
When used, the hydrophilization treatment composition of the present invention is preferably used at a concentration in which the total of component A and component B is 0.05% by mass or more and 5.0% by mass or less. More specifically, the hydrophilization treatment composition of the present invention comprises a treatment liquid containing component A, component B and water, and further a treatment liquid containing the component A having the above content, the component B having the content and water. It is preferable to be used as.

The hydrophilization treatment composition of the present invention contains carboxylic acids such as oxalic acid, maleic acid, citric acid, adipic acid, sebacic acid, malic acid, ethylenediamine tetraacetic 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 that improve the solubility of hydrophilization agents such as NaCl in water; Solubilizer; viscosity modifier for clay minerals, water-soluble polymer compounds, etc. (excluding copolymers of the present invention); water-insoluble for lithofite, siliceous stone, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon, polystyrene, etc. Abrasives; Moisturizers such as glycerin and sorbitol; Tactile improvers such as cationized cellulose (excluding copolymers of the present invention); Alkaline builders such as sodium carbonate and sodium silicate; Enzymes, pigments, fragrances, antiseptic / Antifungal agents and the like can be added.

The hydrophilization treatment composition of the present invention can be obtained by adding component A, component B, water and, if necessary, other components described above, and stirring and mixing by a known method. The composition ratio of the hydrophilic treatment agent composition can be appropriately adjusted according to the type of solid surface and the purpose of treatment. It is also possible to prepare a concentrated solution and dilute it at the time of use.

The pH of the obtained hydrophilic treatment agent composition at 20 ° C. is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, and 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, and more preferably 8 or less. Examples of the pH adjuster include 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, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Examples thereof include inorganic alkaline compounds such as ammonia and derivatives thereof, and alkaline agents such as organic alkaline compounds such as monoethanolamine, diethanolamine and triethanolamine. Further, an acid agent and an alkaline agent can be combined and used as a buffer system.

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

<Hydrophilic treatment method>
The present invention provides a hydrophilization treatment method for applying the hydrophilization treatment agent composition of the present invention to a solid surface.
Here, the "solid" of the "solid surface" is not particularly limited, and is limited to glass, pottery, porcelain, amber, tile, ceramics; metals such as aluminum, stainless steel, and brass; polycarbonate, polyethylene, polypropylene, melamine resin, and polyamide resin. , ABS resin, synthetic resin such as FRP; natural fiber such as cotton, silk, wool; synthetic fiber such as polyester, nylon, layon; solid such as hair, nails, teeth.
Suitable solid surfaces to which the method of the present invention can be applied include hydrophobic hard surfaces 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 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 Examples.
The hydrophilization method of the present invention preferably targets 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 liquid described in the hydrophilic treatment agent composition of the present invention. In the hydrophilization treatment method of the present invention, it is preferable that the treatment liquid described in the hydrophilization treatment agent composition of the present invention is brought into contact with the solid surface.

The method of contacting the solid surface with the hydrophilic treatment agent composition is not particularly limited. For example, the following methods (i) to (iii) can be mentioned.
(I) Method of immersing a solid in the hydrophilizing agent composition (ii) Method of spraying or applying the hydrophilizing agent composition to the solid surface (iii) Cleaning the solid surface with the hydrophilizing 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 higher, more preferably from the viewpoint of enhancing the hydrophilizing performance of the hydrophilizing agent composition and the ease of the treatment method. Is 10 ° C. or higher, more preferably 15 ° C. or higher, preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and 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 hydrophilization treatment agent composition and from the viewpoint of economic efficiency. It is preferably 60 minutes or less, more preferably 50 minutes or less.
In the method (ii), the method of spraying or applying the hydrophilic treatment agent composition to the solid surface can be appropriately selected depending on the size (area) of the hard surface and the like. A method in which the hydrophilic treatment agent composition is sprayed onto a solid surface by a spray or the like and then dried is preferable. If necessary, it may be sprayed and then rinsed with water. Further, after spraying, it may be spread thinly with a sponge or the like.
The amount of the hydrophilizing agent composition sprayed or applied to the solid surface is, for example, 0 per ^{10 cm 2 in} the case of the hydrophilizing agent composition having a copolymer content of component A of 0.5% by mass. It is 0.01 mL or more and 0.1 mL or less.
In the method (iii) above, it is preferable to use it in the form of a detergent composition containing a copolymer of component A and an anionic surfactant of component B and bring it into contact with a solid surface. In the form of such a cleaning agent composition, the pH is preferably 4 or more, preferably 10 or less, and more preferably 8 or less from the viewpoint of handling safety and prevention of damage to the solid surface.

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

<Ingredient 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)
46.40 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd., the same applies hereinafter) was placed in a 1000 mL four-necked flask, 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) ethyldiethyl sulfate (manufactured by Kao Co., Ltd./90% aqueous solution), benzyl methacrylate. (Wako Pure Chemical Industries, Ltd.) 9.340 g, ethanol 20.90 g mixed solution, 2,2'-azobis (2-methylbutyronitrile) (Wako Pure Chemical Industries, Ltd.) 2.080 g, ethanol 10.00 The solution in which g was mixed was added dropwise over 2 hours. 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. 106.4 g of 1,3-propane sulton (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto over 2 hours to carry out the reaction. 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) / structural unit (A2) / structural unit (A3) = SBMA / BzMA / MOEDES = 90/5/5 (molar ratio), and has a weight average molecular weight of 100,000. rice field. Here, the symbol of the constituent unit means the following monomer. The structural unit in the copolymer A1 is a structural unit 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)
Eggplant flask 100 mL, [2-(methacrylonitrile Iruo) ethyl]-dimethyl-- (3-sulfopropyl) ammonium hydroxide [[2- (Methacryloyloxy) ethyl] dimethy l- (3-sulfopropyl) ammoniumhydroxide ] (manufactured by Aldrich ) 9.345g, benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.655g, V-65B (manufactured by Wako Pure Chemical Industries, Ltd.) 0.092g, trifluoroethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 23.24g, nitrogen Degassing was performed by bubbling. The oil bath was set at 65 ° C., an eggplant flask was set, and polymerization was started. Polymerization was completed 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.
The copolymer A2 had a structural unit (A1) / structural unit (A2) = SBMA / BzMA = 90/10 (molar ratio), and had a weight average molecular weight of 120,000.

<Measurement of weight average molecular weight>
The weight average molecular weights of the copolymers A1 and A2 were measured 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 producing a Zimm-prot. The refractive index increment required 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 every 10 ° from 30 ° to 150 °.
Average temperature: 25 ° C
Solvent: Trifluoroethanol

<Ingredient B>
-Anionic surfactant B1: Sodium dioctyl sulfosuccinate (Kao Corporation, Perex OTP, molecular weight: 444)
-Anionic surfactant B2: Polyoxyethylene (average number of moles added 3) Sodium lauryl ether sulfate (Kao Corporation, Emar 20C, weight average molecular weight: 420)
-Anionic surfactant B3: Sodium lauryl sulfate (Kao Corporation, Emar O, molecular weight: 288)
-Anionic surfactant B4: Sodium dodecylbenzene sulfonate (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: Maleic acid / diisobutylene (1/1 molar ratio) Sodium salt of copolymer (weight average molecular weight: 20,000)

<Component C>
-Water: Pure water with an electrical conductivity of 1 μS / cm or less manufactured by the pure water device G-10DSTSET manufactured by Organo Corporation.

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

[Examples 1 to 12 and Comparative Examples 1 to 5]
<Manufacturing of hydrophilizing agent composition>
Each component was used as it was or mixed so as to have a mass% shown in Table 1 to obtain an aqueous solution. The obtained aqueous solution was used for the following evaluation as a hydrophilic treatment agent composition.

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

<Evaluation board>
An aluminum plate (manufactured by TP Giken Co., Ltd., pure aluminum plate "A1050P") or a polycarbonate plate (manufactured by Taiyu Kikai Co., Ltd., polycarbonate transparent PS610 160 mm x 80 mm x 1.0 mm) cut out to a length of 70 mm x width of 25 mm is used as an evaluation substrate. Using.

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

<Contact angle measurement method>
The contact angles of the evaluation substrate after the coating step, the rinsing step, and 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.

<Observation of substrate surface after hydrophilization treatment>
The state of the evaluation substrate after the coating process, the rinsing process, and the durability test was visually observed and evaluated based on the following criteria. The results are shown in Table 2. Table 2 also shows the results of Example 6.
1: No deposit 2: Precipitated on the edge 3: Precipitated on the entire surface

Claims (10)

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, and an anionic surfactant (hereinafter referred to as component B). ) And water (hereinafter referred to as component C) .
Component B is a polymer-type surfactant having a weight average molecular weight of 10,000 or more and 100,000 or less.
Hydrophilization treatment agent composition .

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

[In the formula,
R ^21a , R ^22a , R ^23a : Same or different, hydrogen atom or alkyl group having 1 or 2 carbon atoms R ^24a : Hydrocarbon group having a total carbon number of 6 to 22 having an aromatic group Z ¹ : O or NR ^25a , where R ^25a represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. ] The hydrophilization treatment agent composition according to claim 1 or 2, wherein the component A further contains a structural unit (A3) represented by the following formula (a3).

[In the formula,
^{R 31a, R 32a, R 33a} : the same or different, an alkyl group to ^Q 1 hydrogen atom or C 1 or 2: O or NH group ^{R 34a:} alkylene group having 1 to 4 carbon atoms ^{Q 2: N} + R ^35a R ^36a R ^37a · Q ³ or NR ^38a R ^39a , and R ^35a , R ^36a , R ^37a , R ^38a , and R ^39a are the same or different, hydrogen atoms or hydrocarbon groups having 1 or more and 4 or less carbon atoms. , ^{Q 3} represents an anion. ] The hydrophilization treatment composition according to any one of claims 1 to 3 , wherein the component B is a sodium salt and / or a potassium salt. The hydrophilization treatment composition according to any one of claims 1 to 4 , wherein the mass ratio of component A to component B (component A / component B) is 10 or more and 100 or less. The hydrophilization treatment composition according to any one of claims 1 to 5 , wherein the 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. A method for hydrophilizing treatment, wherein the hydrophilizing treatment agent composition according to any one of claims 1 to 6 is applied to a solid surface. The hydrophilization treatment method according to claim 7 , wherein the solid surface is a solid surface containing aluminum and / or polycarbonate. The hydrophilization treatment method according to claim 7 or 8 , wherein the treatment liquid containing the hydrophilic treatment agent composition and water is applied to a solid surface. The hydrophilization treatment method according to claim 9 , wherein the total content of the component A and the component B in the treatment liquid is 0.05% by mass or more and 5.0% by mass or less.