JP2022155530A - Hydrophilic film-forming composition, laminate having film, and method for forming film - Google Patents

Abstract

To provide a hydrophilic film-forming composition, a laminate having a film, and a method for forming a film.SOLUTION: The hydrophilic film-forming composition contains: a polymer (A) which contains a radically polymerizable monomer having a carboxy group and/or its salt (a-1) as a reaction component; and a carboxyalkyl cellulose and/or its salt (B). The mass ratio [(A)/(B)] of the component (A) to the component (B) in terms of solid content is 15/85-99/1. An aqueous solution in which the concentration of the total solid content of the component (A) and the component (B) is 1% has a pH of 2.0-5.0.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to a hydrophilic film-forming composition, a laminate having a film, and a method of forming a film.

Conventionally, frost, dew, ice, and the like adhere to the surface of articles at low temperatures, causing problems. For example, there is a problem that if ice or snow accumulates on the surface of a signal, the signal becomes invisible, mainly in a snowy area. Especially in recent years, the number of traffic signals using LEDs that generate less heat during operation is increasing, and the importance of this problem is increasing. In addition, fins that use metal plates as fins in the heat exchangers of air conditioners have condensed water that adheres to the fins during heating operation. There is a problem that the heat exchange performance is lowered. In addition, a defrosting operation is required to remove ice and frost from the fins, increasing the energy required for the heat exchanger. Furthermore, there is a problem that frost, dew condensation, or icing on the window glass of an automobile makes the window glass opaque, making it impossible to drive safely.

In order to solve this problem, techniques have been developed to reduce the formation of frost, condensation, and ice by coating the surface of articles with various resins. Examples of such resins include resins containing polyvinyl alcohol and polyvinylpyrrolidone (Patent Document 1). However, the resin of Patent Literature 1 has the disadvantage that it deteriorates significantly over time. In particular, when the fins are repeatedly heated and cooled by the defrosting operation of the air conditioner, the resin is deteriorated, the hydrophilicity of the film is deteriorated, and frosting and icing tend to increase.

JP-A-5-302042

The problem to be solved by the present disclosure is to provide a composition for forming a hydrophilic film that has good hydrophilicity and is resistant to the formation of ice and frost, a laminate having the film, and a method for forming the film. It is to be.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a predetermined hydrophilic film-forming composition, a laminate having a film, and a film-forming method.

The following items are provided by this disclosure.
(Item 1)
a polymer (A) containing a radically polymerizable monomer having a carboxy group and/or a salt thereof (a-1) as a reaction component;
and carboxyalkyl cellulose and / or a salt thereof (B),
The solid content-equivalent mass ratio [(A)/(B)] of the component (A) and the component (B) is 15/85 to 99/1,
A composition for forming a hydrophilic film, wherein the pH of an aqueous solution having a concentration of solid content of 1% in which the components (A) and (B) are combined has a pH of 2.0 to 5.0.
(Item 2)
2. The composition for forming a hydrophilic film according to item 1, wherein the viscosity (mPa·s/25° C.) of component (B) at a solid content concentration of 1% is 1 to 155.
(Item 3)
3. The hydrophilic film-forming composition according to item 1 or 2, wherein the component (B) has a degree of etherification of 0.4 to 1.5.
(Item 4)
The group in which component (a-1) consists of (meth)acrylic acid, (meth)acrylic acid salts, itaconic acid, itaconic acid salts, itaconic acid monoesters, itaconic acid monoester salts, and itaconic anhydride 4. The hydrophilic film-forming composition according to any one of items 1 to 3, comprising one or more selected from
(Item 5)
Component (A) is poly(meth)acrylic acid, a copolymer of (meth)acrylic acid and (meth)acrylamide, or a copolymer of (meth)acrylic acid and an anionic monomer other than (meth)acrylic acid. , a copolymer of (meth)acrylic acid, (meth)acrylamide, and an anionic monomer other than (meth)acrylic acid, and one or more selected from salts thereof, according to any one of items 1 to 4. A composition for forming a hydrophilic film.
(Item 6)
6. The hydrophilic film-forming composition according to any one of Items 1 to 5, wherein component (B) contains one or more selected from sodium carboxymethylcellulose, potassium carboxymethylcellulose, and ammonium carboxymethylcellulose.
(Item 7)
7. The composition for forming a hydrophilic film according to any one of items 1 to 6, wherein the component (B) has a viscosity (mPa·s/25°C) of 1 to 300 at a solid content concentration of 10%.
(Item 8)
8. The composition for forming a hydrophilic film according to any one of items 1 to 7, wherein component (a-1) is 29 mol % or more as a monomer constituting the polymer of component (A).
(Item 9)
A laminate having a film of the hydrophilic film-forming composition according to any one of Items 1 to 8 on at least one side of a substrate.
(Item 10)
A method for forming a film, comprising the step of applying the hydrophilic film-forming composition according to any one of Items 1 to 8 to the surface of a substrate.
(Item 11)
Component (A) is a polymer (α) of component (a-1), a copolymer (β) of component (a-1) and an anionic monomer other than component (a-1), (a-1) ) and a copolymer (γ) of a nonionic monomer, and a copolymer (δ) of a component (a-1), an anionic monomer other than the component (a-1), and a nonionic monomer. 9. The hydrophilic film-forming composition according to any one of items 1 to 8, which is one or more of
(Item 12)
The molar ratio of the component (a-1), the anionic monomer other than the component (a-1), and the nonionic monomer [component (a-1) / anionic monomer other than the component (a-1) / nonionic 12. The composition for forming a hydrophilic film according to item 11, wherein the monomer] is from 29 to 100/0 to 25/0 to 70.
(Item 13)
Component (A) contains component (a-1) and a monomer other than component (a-1) as reaction components, and the molar ratio [(component (a-1)) / (component other than component (a-1) Monomer)] is 29/71 to 99.9/0.1.

When the film is formed on the surface of a substrate or article by the hydrophilic film-forming composition, the laminate having the film, and the method for forming the film provided by the present disclosure, not only does it exhibit good hydrophilicity, but also , ice and frost are less likely to form on the article surface.

Throughout the present disclosure, the range of numerical values for each physical property value, content, etc. can be set as appropriate (for example, by selecting from the upper and lower limit values described in each item below). Specifically, when the lower limit of the numerical value α is A1, A2, A3, etc., and the upper limit of the numerical value α is B1, B2, B3, etc., the range of the numerical value α is A1 or more, A2 or more, A3 or more, B1 or less, B2 or less, B3 or less, A1-B1, A1-B2, A1-B3, A2-B1, A2-B2, A2-B3, A3-B1, A3-B2, A3-B3 etc. are exemplified. In the present disclosure, "~" is used to mean including the numerical values before and after it as lower and upper limits.

<(A) Component>
Component (A) is a polymer containing a radically polymerizable monomer having a carboxyl group and/or a salt thereof (a-1) (also referred to as "(a-1) component" in the present disclosure) as a reaction component. . A radically polymerizable monomer refers to a monomer having a radically polymerizable functional group. Examples of the radically polymerizable functional group include a group having a carbon-carbon double bond and a group having a carbon-carbon triple bond. Specific examples of the radically polymerizable functional group include a (meth)acryloyl group and a vinyl group.

Examples of monomers constituting the polymer of component (A) include anionic monomers, cationic monomers, and nonionic monomers. As the anionic monomer, a radically polymerizable monomer having a carboxy group and/or a salt thereof (a-1), a radically polymerizable monomer having a sulfonic acid group (sulfo group) and/or a salt thereof (a-2) (the present disclosure , also referred to as "component (a-2)"), a radical polymerizable monomer having a phosphoric acid group and/or a salt thereof (a-3) (also referred to as "component (a-3)" in the present disclosure). ) and the like are exemplified. Examples of cationic monomers include radically polymerizable monomers having an amino group and/or salts thereof (a-4) (also referred to as “(a-4) component” in the present disclosure). As nonionic monomers, a radically polymerizable monomer having a hydroxy group (a-5) (also referred to as "component (a-5)" in the present disclosure), a radically polymerizable monomer having an amide group (a-6) ( In the present disclosure, also referred to as “(a-6) component”), a radically polymerizable monomer having an ester bond (a-7) (also referred to as “(a-7) component” in the present disclosure), a nitrile group (also referred to as “(a-8) component” in the present disclosure) and the like. In the present disclosure, an anionic monomer and a cationic monomer refer to a monomer that is negatively ionized when the monomer is dissolved in water and ionized, and a positively charged monomer is referred to as a cationic monomer. . In the present disclosure, a nonionic monomer refers to a monomer that does not become ions even when dissolved in water.

By including the component (a-1) as a monomer constituting the polymer of the component (A), it is possible to form a film having good water resistance when combined with the component (B). As component (a-1), a radical polymerizable monomer having one carboxy group, a radical polymerizable monomer having two carboxy groups, an anhydride of a radical polymerizable monomer having two carboxy groups, and two carboxy groups Examples include monoesters of radically polymerizable monomers, salts of the above monomers, and salts of monoesters of the above monomers. Examples of radically polymerizable monomers having one carboxy group include (meth)acrylic acid, carboxyethyl (meth)acrylate, 2-(trifluoromethyl)(meth)acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid, and the like. are exemplified. Examples of radical polymerizable monomers having two carboxy groups include maleic acid, itaconic acid, fumaric acid, citraconic acid, and chloromaleic acid. Examples of anhydrides of radically polymerizable monomers having two carboxy groups include maleic anhydride, itaconic anhydride, citraconic anhydride, and chloromaleic anhydride. Examples of monoesters of radical polymerizable monomers having two carboxy groups include monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, and monobutyl itaconate. be. Salts of the present disclosure include metal salts, onium salts (eg, ammonium salts, phosphonium salts, etc.), and the like. Examples of metal salts of the present disclosure include alkali metal salts (eg, lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (eg, magnesium salts, calcium salts, etc.), and the like. In the present disclosure, the salt is not limited to those in which all of the functional groups (e.g., carboxy group, etc.) in the component form a salt, and some functional groups contained in the component form a salt. It may be formed. Component (a-1) is preferably (meth)acrylic acid, a salt of (meth)acrylic acid, itaconic acid, or a salt of itaconic acid, because good water resistance can be exhibited by combining the component (a-1) with the component (B). , itaconic acid monoester, salt of itaconic acid monoester, and itaconic anhydride.

(a-2) components as sulfoethyl (meth)acrylate, sulfopropyl (meth)acrylate, styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxy-1- Examples include propanesulfonic acid, methallylsulfonic acid, 3-((meth)acryloyloxy)propanesulfonic acid, salts of the above monomers, and the like. Of the components (a-2), methallylsulfonic acid is preferred because it can be used as a chain transfer agent and the viscosity can be easily controlled.

Examples of component (a-3) include vinylphosphonic acid, 2-(meth)acryloyloxyethyl acid phosphate, salts of the above monomers, and the like.

2-(dimethylamino)ethyl (meth)acrylate hydrochloride, 2-aminoethyl (meth)acrylate hydrochloride, N-(3-aminopropyl)(meth)acrylate hydrochloride as component (a-4) , [3-((meth)acryloylamino)propyl]trimethylammonium chloride solution, [2-((meth)acryloyloxy)ethyl]trimethylammonium chloride, (meth)acrylamidopropyltrimethylammonium chloride, 2-aminoethyl (meth) acrylamide hydrochloride, N-(3-aminopropyl)-(meth)acrylamide hydrochloride, diallyldimethylammonium chloride, allylamine hydrochloride, vinylimidazolium hydrochloride, vinylpyridinium hydrochloride, vinylbenzyltrimethylammonium chloride, 2-(( Examples include meth)acryloyloxy)ethyltrimethylammonium methylsulfate, 3-((meth)acrylamido)propyltrimethylammonium methylsulfate and the like.

Examples of component (a-5) include vinyl alcohol, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

(a-6) components as (meth)acrylamide, vinylacetamide, N-methoxymethyl(meth)acrylamide, Nn-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, Nt- Butyl (meth)acrylamide, Nt-octyl (meth)acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N'-methylenebis(meth)acrylamide, 1,3,5-triacrylamide Hexahydro-1,3,5-triazine is exemplified. Of the component (a-6), it can be used as a crosslinkable polyfunctional monomer, and from the viewpoint of easy viscosity control, preferably N,N'-methylenebis(meth)acrylamide and/or 1,3,5-tri It is acryloylhexahydro-1,3,5-triazine, and preferably (meth)acrylamide because of its good hydrophilicity.

Examples of component (a-7) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate and vinyl acetate.

(a-8) is exemplified by (meth)acrylonitrile and the like.

The substances exemplified as the monomers constituting the polymer of component (A) and the known monomers constituting the polymer of component (A) can be used alone or in combination of two or more.

(A) A component can be obtained by a conventionally well-known method. For example, it is conceivable to put one or more of the above monomers in a container, stir the mixture, and then carry out a radical polymerization reaction at 50 to 100° C. for 30 minutes to 10 hours. Before the stirring, before the reaction, or after the reaction, one or more selected from the group consisting of a solvent, a polymerization initiator, an acidic substance and a basic substance may be added as appropriate. Solvents are exemplified by those detailed below. As an example of a preferable solvent, a solvent having a chain transfer effect such as isopropanol is exemplified because it enables viscosity adjustment and the like. As polymerization initiators, persulfate initiators (e.g., ammonium persulfate, potassium persulfate, etc.), azo initiators (e.g., 2,2-azobis-(2-amidinopropane) dihydrochloride, etc.), peroxides Hydrogen, ascorbic acid and the like are exemplified. Examples of basic substances include amine compounds, alkali metal hydroxides, alkaline earth metal hydroxides, basic amino acids, and ammonia. Examples of amine compounds include triethanolamine, diethanolamine, monoethanolamine, ethylamine, butylamine, and benzylamine. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide. Arginine etc. are illustrated as a basic amino acid.

(A) Component may be a commercially available product. As such products, polyacrylic acid (product name “Aqualic HL”, manufactured by Nippon Shokubai Co., Ltd.) (product name “Aron A-10H”, “Jerimer AC-10LHPK”, “Jerimer AC-10SHP”, Toagosei ( Co., Ltd.), sodium polyacrylate (product names “Aqualic DL”, “Aqualic IH”, “Aqualic FH”, “Aqualic MH”, manufactured by Nippon Shokubai Co., Ltd.) (product name “Aron A- 20L”, “Aron A-7100”, manufactured by Toagosei Co., Ltd.) (product name “Sodium polyacrylate”, manufactured by Hayashi Pure Chemical Industries, Ltd.), ammonium polyacrylate (product name “Aron A-30” , manufactured by Toagosei Co., Ltd.), acrylic acid / sodium acrylate copolymer (product names "Viscomate NP-800", "Viscomate NP-700", "Viscomate NP-600", manufactured by Showa Denko Co., Ltd.), Acrylic acid/maleic acid copolymer salt (product name “Aqualic TL”, manufactured by Nippon Shokubai Co., Ltd.), acrylic acid/sulfonic acid monomer copolymer salt (product name “Aqualic GL”, Japan Co., Ltd. Catalyst), carboxylic acid copolymers (product names “Aron A-7185”, “Aron A-7195”, “Aron A-7075”, manufactured by Toagosei Co., Ltd.) and the like.

The substances exemplified as component (A) and those known as component (A) can be used alone or in combination of two or more. Component (A) is preferably
(α) the polymer of component (a-1),
(β) a copolymer of the component (a-1) and an anionic monomer other than the component (a-1),
(γ) a copolymer of component (a-1) and a nonionic monomer, and (δ) a copolymer of component (a-1), an anionic monomer other than component (a-1), and a nonionic monomer It is one or more selected from polymers.
The anionic monomer other than component (a-1) is preferably component (a-2).
The nonionic monomer is preferably component (a-6).

The upper limits of the number of radically polymerizable functional groups, carboxy groups, sulfonic acid groups, phosphoric acid groups, amino groups, hydroxy groups and amide groups possessed by the monomers constituting the polymer of component (A) are 6, 5, and 5, respectively. 4, 3, 2, etc. are exemplified, and the lower limit is exemplified as 5, 4, 3, 2, 1, etc. In one embodiment, the number of radically polymerizable functional groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups, hydroxy groups, and amide groups possessed by the monomers constituting the polymer of component (A) is About 1 to 6 is preferable.

The upper limit of the molecular weight of the monomer constituting the polymer of component (A) is 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250. , 200, 150, 100, 50, etc., and the lower limits are 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100 , 50, 25, etc. are exemplified. As one embodiment, the molecular weight of the monomer constituting the polymer of component (A) is preferably about 25 to 1,000. In the present disclosure, the term "molecular weight" simply refers to a value calculated on an atomic weight basis.

The upper limit of the pH of component (A) at a solid content concentration of 1% is exemplified by 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit is 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 are exemplified. In one embodiment, the pH of component (A) at a solid content concentration of 1% is preferably about 1-12.

(A) The upper limit of the solid content concentration (%) of the component is 100, 99, 97, 95, 93, 91, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35 , 30, 25, 20, 15, 10, 5, 3, 1, 0.5, etc., and the lower limits are 99, 97, 95, 93, 91, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 3, 1, 0.5, 0.1 and the like are exemplified. In one embodiment, the solid content concentration (%) of component (A) is preferably about 0.1 to 100.

The upper limit of the viscosity (mPa s/25°C) when the solid content concentration of component (A) is 15% is 150,000, 100,000, 90,000, 80,000, 70,000, 60,000 , 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2 , 000, 1,000, 500, 100, 50, 40, 30, 20, etc., and the lower limits are 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40 ,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000 , 500, 100, 50, 40, 30, 20, 10 are exemplified. In one embodiment, the viscosity (mPa·s/25° C.) when the solid concentration of component (A) is 15% is preferably about 10 to 150,000. The viscosity is a value when the solid content concentration is 15% by diluting with water or the like. As a method for measuring viscosity, a method using a viscometer described in JIS K 7117-1:1999 is exemplified.

When using a monomer other than the component (a-1) and the component (a-1) as a monomer constituting the polymer of the component (A), the molar ratio [((a-1) component) / ((a- 1) Monomers other than components)] are 100/0, 99.9/0.1, 99.5/0.5, 99/1, 95/5, 90/10, 85/15, 80/ 20, 79/21, 75/25, 70/30, 69/31, 65/35, 60/40, 55/45, 50/50, 49/51, 45/55, 40/60, 35/65, 30/70, 29/71, 25/75, 20/80, 15/85, 10/90, etc. are exemplified, and the lower limits are 99.9/0.1, 99.5/0.5, 99/1 , 95/5, 90/10, 85/15, 80/20, 79/21, 75/25, 70/30, 69/31, 65/35, 60/40, 55/45, 50/50, 49 /51, 45/55, 40/60, 35/65, 30/70, 29/71, 25/75, 20/80, 15/85, 10/90, 5/95 and the like. In one embodiment, the molar ratio of the component (a-1) and the monomer other than the component (a-1) [(component (a-1))/(monomer other than the component (a-1))] is About 5/95 to 100/0 is preferable, about 29/71 to 100/0 is more preferable, about 49/51 to 100/0 is even more preferable, and about 69/31 to 100/0 is particularly preferable. A higher ratio of component (a-1) is preferable because water resistance becomes better when combined with component (B).

When an anionic monomer and a nonionic monomer are used as monomers constituting the polymer of component (A), the upper limit of the molar ratio [(anionic monomer)/(nonionic monomer)] is 100/0,99. 9/0.1, 99.5/0.5, 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, etc., and the lower limit is 99.9 /0.1, 99.5/0.5, 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55 /45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95 and the like. In one embodiment, the molar ratio of the anionic monomer and the nonionic monomer [(anionic monomer)/(nonionic monomer)] is preferably about 5/95 to 100/0.

The molar ratio of the component (a-1), which is a monomer constituting the polymer of the component (A), the anionic monomer other than the component (a-1), and the nonionic monomer [component (a-1) / ( a-1) anionic monomer other than component/nonionic monomer)] is preferably from 29 to 100/0 to 25/0 to 70, more preferably from 49 to 100/0 to 20/0 to 50, Still more preferably 69-100/0-15/0-30, particularly preferably 79-100/0-5/0-20. A higher ratio of component (a-1) is preferable because the water resistance becomes better when combined with component (B).

The upper limit of the content (in terms of solid content) of component (A) in 100% by mass of the hydrophilic film-forming composition of the present disclosure is 99, 97, 95, 90, 85, 80, 75, 70, 65, 60. , 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 3% by mass, etc., and the lower limits are 97, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 3, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (A) in 100% by mass of the hydrophilic film-forming composition of the present disclosure is preferably about 1 to 99% by mass.

<(B) Component>
(B) A component is carboxyalkyl cellulose and/or its salt. Examples of salts of carboxyalkyl cellulose include metal salts, onium salts and the like. Specific examples of carboxyalkyl cellulose include carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose and the like.

The component (B) may be a commercially available product or a commercially available product whose viscosity is adjusted with a commercially available enzyme or the like. Examples of such products include carboxymethyl cellulose (product name “FINNFIX”, manufactured by Sansho Co., Ltd.), carboxymethyl cellulose sodium (“Sunrose (registered trademark)”, manufactured by Nippon Paper Industries Co., Ltd.), (product name “CMC Daicel 1110” , "CMC Daicel 1120", "CMC Daicel 1130", "CMC Daicel 1140", "CMC Daicel 1150", "CMC Daicel 1160", "CMC Daicel 1170", "CMC Daicel 1180", "CMC Daicel 1190", " CMC Daicel 1220", "CMC Daicel 1240", "CMC Daicel 1250", "CMC Daicel 1260", "CMC Daicel 1330", "CMC Daicel 1350", "CMC Daicel 1380", "CMC Daicel 1390", "CMC Daicel 2200", "CMC Daicel 2260", manufactured by Daicel Miraise Co., Ltd.), (product names "Serogen 5A", "Serogen 6A", "Serogen 7A", "Serogen PR", "Serogen WS-A", "Serogen PL -15”, “Serogen WS-C”, “Serogen WS-D”, “Serogen BS”, “Serogen HH-T”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), (product name “Kimika CMC F-2” , "Kimica CMC F-2E", "Kimica CMC F-10", "Kimica CMC F-30", "Kimica CMC F-100", "Kimica CMC PL-4", "Kimica CMC P-1", " Kimika CMC P-3”, “Kimica CMC P-10”, “Kimica CMC SYL-1”, “Kimica CMC SYL-1W”, manufactured by Kimika Co., Ltd.), (“Blanose (registered trademark) REF CMC”, Ashland ), etc., and for adjusting the viscosity of the component (B), cellulase (“Cellulizer ACE”, “Cellulizer FP”, “Cellulase SS”, “Cellulase XL-531”, “Cellulase Nagase”, Nagasechem Tex Co., Ltd.), "Cellulose AC40", "Cellulosine AL8", "Cellulosine TF", HBI Co., Ltd.), "Sucrase (registered trademark) C", Mitsubishi Chemical Corporation), "Cellulase A" Amano" 3", "Cellulase T "Amano" 4", Amano Enzyme Co., Ltd.) are exemplified.

The substances exemplified as component (B) and those known as component (B) can be used alone or in combination of two or more. Component (B) is preferably a salt of carboxymethylcellulose, more preferably a metal salt and/or an onium salt of carboxymethylcellulose, and even more preferably selected from sodium carboxymethylcellulose, potassium carboxymethylcellulose, and ammonium carboxymethylcellulose. is one or more.

The upper limit of the number of carbon atoms in the alkyl group of the carboxyalkyl cellulose is exemplified by 5, 4, 3, 2, etc., and the lower limit is exemplified by 4, 3, 2, 1, etc. In one embodiment, the number of carbon atoms in the alkyl group of carboxyalkyl cellulose is preferably about 1 to 5.

The upper limit of the pH of component (B) at a solid concentration of 1% is 12, 11, 10, 9, 8, 7.7, 7.6, 7.5, 7.4, 7.3, 7.2, 7.1, 7.0, 6.9, 6.8, 6.7, 6.6, 6.5, 6.4, 6.3, 6.2, 6.1, 6.0, 5. 8, 5.6, 5.4, 5.2, 5.0, 4, 3, 2, etc. are exemplified, and the lower limits are 11, 10, 9, 8, 7.7, 7.6, 7.5, 7.4, 7.3, 7.2, 7.1, 7.0, 6.9, 6.8, 6.7, 6.6, 6.5, 6.4, 6.3, 6. 2, 6.1, 6.0, 5.8, 5.6, 5.4, 5.2, 5.0, 4, 3, 2, 1 are exemplified. In one embodiment, the pH of component (B) at a solid concentration of 1% is preferably about 1-12.

The upper limit of the viscosity (mPa s/25°C) of component (B) when the solid content concentration diluted with water is 1% is 20,000, 15,000, 10,000, 5,000, 4,000 , 3,000, 2,000, 1,000, 900, 800, 700, 600, 550, 500, 450, 400, 350, 300, 250, 220, 200, 155, 150, 125, 100, 90, 80 , 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3 , 2, etc., and the lower limits are 15,000, 10,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 550, 500, 450, 400, 350, 300, 250, 220, 200, 155, 150, 125, 100, 90, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 are exemplified. In one embodiment, the viscosity (mPa s/25° C.) of component (B) when diluted with water to a solid concentration of 1% is preferably about 1 to 220, more preferably about 1 to 155. About 1 to 10 is even more preferable. As a method for measuring the viscosity, the same measuring method as for the component (A) is exemplified. The lower the viscosity of the component (B) is, the better the freezing resistance and frost resistance are, so it is preferable.

The upper limit of the viscosity (mPa s/25°C) of component (B) when the solid content concentration diluted with water is 10% is 2,000,000, 1,000,000, 500,000, 200,000 , 100,000, 50,000, 20,000, 15,000, 10,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 550 , 500, 450, 400, 350, 300, 250, 220, 200, 155, 150, 125, 100, 90, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25 , 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limits are 1,000,000, 500,000, 200, 000, 100,000, 50,000, 20,000, 15,000, 10,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 550, 500, 450, 400, 350, 300, 250, 220, 200, 155, 150, 125, 100, 90, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 are exemplified. In one embodiment, the viscosity (mPa·s/25° C.) of the component (B) when diluted with water to a solid concentration of 10% is particularly preferably about 1 to 300. As a method for measuring the viscosity, the same measuring method as for the component (A) is exemplified. The lower the viscosity of the component (B) is, the better the freezing resistance and frost resistance are, so it is preferable.

The upper limit of the degree of etherification (DS) of component (B) is 2.0, 1.7, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9. , 0.8, 0.7, 0.6, 0.5, etc., and the lower limits are 1.7, 1.5, 1.4, 1.3, 1.2, 1.1, 1.1. 0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4 and the like are exemplified. In one embodiment, the degree of etherification (DS) of component (B) is preferably about 0.4 to 1.7, more preferably about 0.4 to 1.5, and about 0.4 to 1.0. It is even more preferable, and about 0.4 to 0.9 is particularly preferable. When the degree of etherification (DS) is 0.4 or more, the solubility of the component (B) in a solvent such as water becomes good, and when it is 0.4 or more and the degree of etherification is lower, freezing resistance is improved. It is preferable because it has particularly good properties, frost resistance, and durability of hydrophilicity. As a method for measuring the degree of etherification (DS), an ashing titration method or the like is exemplified. Degree of etherification (DS) refers to the degree of substitution of carboxymethyl groups per anhydroglucose unit.

The upper limit of the mass ratio (in terms of solid content) of component (A) and component (B) [(A) component/(B) component] is 99/1, 95/5, 90/10, 85/15, 80/ 20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80 etc. are exemplified, and the lower limits are 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55 , 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, and the like. In one embodiment, the mass ratio of component (A) and component (B) (in terms of solid content) [(A) component/(B) component] is preferably from 15/85 to 99/1, and from 20/80 to 90/10 is more preferred, 30/70 to 80/20 is even more preferred, and 35/65 to 70/30 is particularly preferred. The higher the ratio of component (B), the better the freezing resistance and the frost resistance. When the film formed from the hydrophilic film-forming composition is immersed in water or adheres to water, the components are eluted, resulting in a decrease in freezing resistance, frost resistance, and hydrophilicity sustainability. I will stay. When the ratio of component (A)/component (B) is in the range of 35/65 to 80/20, the water resistance is particularly excellent, and when the coating formed from the hydrophilic coating composition is immersed in water, Since the elution of the components when attached is further suppressed, the deterioration of freezing resistance, frost resistance, and hydrophilicity sustainability can be further suppressed. Therefore, the higher the ratio of the component (B) and the better the water resistance, the better the freezing resistance, frost resistance, and hydrophilicity sustainability.

The upper limit of the content (in terms of solid content) of component (B) in 100% by mass of the hydrophilic film-forming composition of the present disclosure is 85, 80, 75, 70, 65, 60, 55, 50, 45, 40. , 35, 30, 25, 20, 15, 10, 5, 3% by mass, etc., and the lower limits are 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 3, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (B) in 100% by mass of the hydrophilic film-forming composition of the present disclosure is preferably about 1 to 85% by mass.

<Other agents that can be added>
The hydrophilic film-forming composition of the present disclosure may further contain a cross-linking agent, an antibacterial agent, a surfactant, an antiseptic agent, an anticorrosive agent, a viscosity modifier, a pH adjuster, Various additives such as pigments, dyes, lubricants, leveling agents, catalysts, antifoaming agents, photosensitizers (amines, quinones, etc.), organic particles, etc. may also be incorporated. When the hydrophilic film-forming composition of the present disclosure does not contain organic particles such as polyamide-based particles, the dispersibility and the like are improved, so it is preferable not to contain such particles.

Examples of the cross-linking agent of the present disclosure include a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide, a cross-linking agent having an oxazoline group, a cross-linking agent having a cyclocarbonate group, a cross-linking agent having a hydroxy group, a cross-linking agent having an isocyanate group, a carboxy Examples include cross-linking agents having groups, cross-linking agents having acid anhydride groups, amino resins, phenol resins, amines, organic peroxides, melamine resins, silane coupling agents, organic metals, and the like. Including a cross-linking agent in the hydrophilic film-forming composition of the present disclosure is preferable because the film of the hydrophilic film-forming composition is less likely to come off from the substrate. The substances exemplified as cross-linking agents and known cross-linking agents can be used alone or in combination of two or more.

As a cross-linking agent having an epoxy group, phenol novolak type epoxide, cresol novolak type epoxide, bisphenol A type epoxide, bisphenol F type epoxide, bisphenol S type epoxide, hydrogenated bisphenol A type epoxide, hydrogenated bisphenol F type epoxide, stilbene type epoxide. , triazine skeleton-containing epoxide, fluorene skeleton-containing epoxide, linear aliphatic epoxide, alicyclic epoxide, glycidylamine-type epoxide, triphenolmethane-type epoxide, alkyl-modified triphenolmethane-type epoxide, biphenyl-type epoxide, dicyclopentadiene skeleton-containing Examples include epoxides, naphthalene skeleton-containing epoxides, arylalkylene type epoxides, tetraglycidylxylylenediamine, dimer acid-modified epoxides which are dimer acid-modified epoxides, dimer acid diglycidyl esters, and the like.

Examples of cross-linking agents having carbodiimide include 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1,3-diisopropylcarbodiimide, bis(2,6-diisopropylphenyl)carbodiimide and the like.

Examples of the cross-linking agent having an oxazoline group include 2-isopropenyl-2-oxazoline polymer, 2-vinyl-2-oxazoline polymer, product name "Epocross" (Nippon Shokubai Co., Ltd.), and the like.

Examples of cross-linking agents having hydroxy groups include polyether polyol, polybutadiene polyol, polycaprolactone polyol, tris(2-hydroxyethyl) isocyanurate and the like.

Examples of cross-linking agents having isocyanate groups include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and isocyanatoethyl methacrylate. As the cross-linking agent having an isocyanate group, an adduct, polymer or block of the above-mentioned cross-linking agent having an isocyanate group may be used.

As the cross-linking agent having a carboxy group, an ester resin having a carboxy group, an aliphatic dicarboxylic acid (for example, dodecanedioic acid, etc.), and the like are exemplified.

Examples of cross-linking agents having acid anhydride groups include phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyrrolimethic anhydride, benzophenonetetracarboxylic anhydride, and maleic anhydride-styrene copolymers.

Amino resins are resins obtained by addition condensation of amino compounds (eg, melamine, benzoguanamine, urea, etc.) with formaldehyde or alcohol. Examples of amino resins include melamine resin, benzoguanamine, tetraalkoxymethyl glycoluril, and urea resin. Examples of melamine resins include fully alkylated melamine resins and partially alkylated melamine resins.

Examples of phenolic resins include novolak-type phenolic resins and resol-type phenolic resins. Examples of novolak-type phenolic resins include product names "Sandpond 4860SK", "Sandpond 4740SK", and "Sandpond 4650" (Lignite Co., Ltd.). Examples of resol-type phenolic resins include product names "Sandpond H3-PC", "Sandpond LT-H", and "Sandpond LT-15" (Lignite Co., Ltd.).

Amines include polymethylenediamine, dimethylaminopropylamine, diethylenetriamine, bishexamethylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, polyetherdiamine, diaminocyclohexane, diaminodiphenylmethane, diaminodiphenylsulfone, bis(O-toluidine), Examples include phenylenediamine, methylpiperazine, morpholine, triethanolamine, dialkylaminoethanol and the like.

Organic peroxides such as di(4-methylbenzoyl) peroxide, dibenzoyl peroxide, di(t-butylperoxy)cyclohexane, butylperoxy-2-ethylhexyl monocarbonate, butyl-4,4-di(t -butylperoxy)valerate, dicumyl peroxide, di(t-hexylperoxy)cyclohexane and the like.

Examples of organic metals include organic titanium, organic zirconium, and organic aluminum. Examples of organic titanium include titanium alkoxide and titanium chelate. Examples of organic zirconium include zirconium alkoxide and zirconium chelate. Examples of organic aluminum include aluminum alkoxide and aluminum chelate.

Other cross-linking agents are exemplified by oxadridine, hydroxypropylcarbamate and the like.

Examples of antibacterial agents include imidazole antibacterial agents (e.g., 2-(4-thiazolyl)benzimidazole, carbamine methyl 2-benzimidazolate, etc.), thiazole antibacterial agents (e.g., 1,2-benzisothiazolin-3-one, 2 -n-octyl-4-isothiazolin-3-one, etc.), iodine antibacterial agents (e.g., 3-iodo-2-propargylbutylcarbamate, 4-chlorophenyl-3-iodopropargyl formal, etc.), nitrile antibacterial agents agents (e.g., 2,3,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroisophthalonitrile, etc.), phenolic antibacterial agents (e.g., p-chloro-m-cresol , 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.), haloalkylthio antibacterial agents (e.g., N-(fluorodichloromethylthio)phthalimide, N,N-dimethyl-N'-(dichlorofluoromethylthio)- N'-phenylsulfamide, N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide, etc.), pyridine-based antibacterial agents (e.g., 2-pyridinethiol-1-oxide sodium, 2-pyridinethiol -1-zinc oxide, etc.), triazine antibacterial agents (e.g., hexahydro-1,3,5-tris(2-hydroxyethyl) S-triazine, hexahydro-1,3,5-triethyl-S-triazine, etc.), Bromine-based antibacterial agents (e.g., 2-bromo-2-nitro-1,3-propanediol, 1,2-dibromo-2,4-dicyanobutane, etc.), inorganic antibacterial agents (e.g., silver-zeolite, zinc zeolite , barium metaborate, copper borate, zinc borate, zeolite (aluminosilicate), etc.), halo diallylurea antibacterial agents (e.g., trichlorcarban, etc.), guanidine antibacterial agents (e.g., chlorohexadine gluconate, polyhexamethylene (piguanidine hydrochloride, etc.), dithiocarbamate antibacterial agents (e.g., bis(dimethylthiocarbamoyl) disulfide, etc.), fatty acid ester antibacterial agents (e.g., propyl glycol monofatty acid ester, glycerol fatty acid ester, etc.), polymer-coordinated metal agents Examples include antibacterial agents (eg, cellulose copper, copper-crosslinked acrylonitrile-acrylic acid copolymer, etc.), other antibacterial agents (eg, 10,10′-oxybisphenoxyarsine, 8-oxyquinoline copper, etc.). The substances exemplified as antibacterial agents and known antibacterial agents can be used alone or in combination of two or more.

The hydrophilic film-forming composition of the present disclosure may contain a surfactant to such an extent that the freezing resistance and frost resistance are not excessively lowered. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Nonionic surfactants include aliphatic alcohol alkylene oxide adducts, (poly)oxyalkylene higher fatty acid esters, polyhydric alcohol fatty acid esters, (poly)oxyalkylene polyhydric alcohol higher fatty acid esters, fatty acid alkanolamides, (poly) Oxyalkylenealkylphenyl ethers, (poly)oxyalkylenealkylaminoethers, alkyldialkylamine oxides and the like are exemplified. Examples of anionic surfactants include hydrocarbon ether carboxylic acids or salts thereof, hydrocarbon sulfate salts, hydrocarbon sulfonates, hydrocarbon phosphate salts, fatty acid salts, and acylated amino acid salts. be. Examples of cationic surfactants include alkylsulfuric acid higher fatty acid aminoalkyltrialkylammonium salts and amine salt types. Examples of amphoteric surfactants include betaine amphoteric surfactants and amino acid amphoteric surfactants.

Examples of pH adjusters include acidic substances (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.) and basic substances (sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc.).

Examples of rust preventives include zirconium compounds, vanadium compounds, titanium compounds, niobium compounds, phosphorus compounds, cerium compounds, chromium compounds, and the like.

If necessary, the hydrophilic film-forming composition of the present disclosure can be used by adding a solvent to adjust the viscosity. Water, an organic solvent, etc. are illustrated as a solvent. Various known organic solvents may be used. Examples of organic solvents include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, amide solvents and the like.

Examples of ketone solvents include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like.

Examples of aromatic solvents include toluene and xylene.

Examples of alcohol solvents include methanol, ethanol, n-propanol, isopropanol, butanol and the like.

Examples of glycol solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and the like.

Glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Examples include ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether and the like.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and the like.

Examples of petroleum solvents include Solvesso #100 (manufactured by Exxon), Solvesso #150 (manufactured by Exxon) and the like.

Chloroform etc. are illustrated as a haloalkane solvent.

Examples of amide solvents include dimethylformamide and the like.

The substances exemplified as organic solvents and known organic solvents can be used alone or in combination of two or more.

The upper limit of the content of the solvent with respect to 100% by mass in terms of solid content of the components constituting the hydrophilic film-forming composition of the present disclosure is 100,000, 50,000, 25,000, 20,000, 15,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,900, 1,800, 1,700, 1, 600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 500, 100, 50, 25% by mass, etc., and the lower limits are 50,000, 25,000 , 20,000, 15,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,900, 1 , 800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 500, 100, 50, 25, 10% by mass, etc. be. In one embodiment, the content of the solvent with respect to 100% by mass of the components constituting the hydrophilic film-forming composition of the present disclosure is preferably about 10 to 100,000% by mass, and 500 to 20,000% by mass. About % by mass is more preferable.

<Composition for forming a hydrophilic film>
The hydrophilic film-forming composition of the present disclosure contains components (A) and (B) and, if necessary, the additives (basic substances, acidic substances, antibacterial agents, preservatives, solvents, cross-linking agents, etc.). Obtained by mixing. The hydrophilic film-forming composition of the present disclosure can be prepared as appropriate without any particular limitation on the mixing order or the like. For example, the components (A) and (B) and, if necessary, the additives may be mixed at room temperature and stirred for 0.1 to 24 hours, or may be mixed in advance with the additives if necessary. Component (A) may be mixed with a liquid obtained by mixing component (A) with stirring at room temperature for 0.5 to 24 hours, or component (B) may be mixed with the additive previously mixed as necessary. The liquid mixed with stirring for 0.5 to 24 hours may be mixed with the component (A), or the liquid mixed with stirring the components (A) and (B) at room temperature for 0.5 to 24 hours. You may mix the said additive mixed as needed with.

The upper limit of the pH of the aqueous solution at which the concentration of the solid content of the combined components (A) and (B) is 1% is 5.0, 4.9, 4.8, 4.7, 4.6, 4. 5, 4.4, 4.3, 4.2, 4.1, 4.0, 3.9, 3.8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, etc. and the lower limits are 4.9, 4.8, 4.7, 4.6, 4.5, 4.4, 4.3, 4.2, 4.1, 4.0, 3.9, 3. 8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0 and the like are exemplified. The pH of the aqueous solution at which the concentration of the solid content of the combined components (A) and (B) is 1% is preferably 2.0 to 5.0, more preferably 2.0 to 4.8, and 2.0 ~4.5 is more preferred. If the pH is less than 2.0, the substrate may be corroded by the action of the hydrophilic film-forming composition, which is not preferable. When the pH exceeds 5.0, the water resistance is significantly reduced, and when the film formed from the hydrophilic film-forming composition is immersed in water or when water adheres, the components are eluted, and the freeze resistance and adhesion resistance are reduced. It is not preferable because it cannot maintain ice frost property and hydrophilicity persistence. When the pH is in the range of 2.0 to 4.5, the water resistance of the film formed from the hydrophilic film-forming composition is particularly excellent, and the elution of components when immersed in water or when water adheres is further suppressed. As a result, the deterioration of freezing resistance, frost resistance, and hydrophilicity persistence can be further suppressed, and the freezing resistance, frost resistance, and hydrophilicity sustainability are further improved, which is preferable. The pH is measured after adding water or the like to the hydrophilic film-forming composition so that the concentration of the solid content of the combined components (A) and (B) is 1%.

<Laminate>
The present disclosure provides films of hydrophilic film-forming compositions. Further, the present disclosure provides a laminate having a film of a hydrophilic film-forming composition on at least one side of a substrate. The present disclosure also provides a method for forming a film of a hydrophilic film-forming composition, which comprises applying the hydrophilic film-forming composition to the surface of a substrate.

Examples of substrates to which the hydrophilic film-forming composition of the present disclosure is applied include glass substrates, metal substrates, plastic substrates, and the like. Metal substrates include gold, silver, copper, tin, nickel, aluminum, titanium, molybdenum, zinc, cobalt, nickel, chromium iron-nickel-cobalt alloy, tungsten, copper-tungsten, invar, galvalume steel plate (registered trademark), A ZAM steel plate etc. are illustrated. Examples of plastic substrates include thermoplastic plastic substrates, thermosetting plastic substrates, and the like. Examples of thermoplastic plastic substrates include general-purpose plastic substrates, engineering plastic substrates, and the like. Examples of general-purpose plastic substrates include olefin-based, polyester-based, acrylic-based, vinyl-based, polystyrene-based, and the like. Examples of olefin-based materials include polyethylene, polypropylene, norbornene, and the like. Examples of polyester-based materials include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of acrylic materials include polymethyl methacrylate (PMMA). Examples of vinyl-based materials include polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. Examples of polystyrene-based resins include polystyrene (PS) resin, styrene-acrylonitrile (AS) resin, styrene-butadiene-acrylonitrile (ABS) resin, and the like. Examples of engineering plastic substrates include general-purpose engineering plastics, super engineering plastics, and the like. Examples of general-purpose engineering plastics include polycarbonate and polyamide (nylon). Examples of super engineering plastics include polyetheretherketone (PEEK). Examples of thermosetting plastic substrates include polyimide, epoxy resin, and melamine resin. Examples of other plastic substrates include triacetyl cellulose resin and the like. The substrate may be subjected to surface treatment (corona discharge, metal vapor deposition, plating treatment, etc.), rust prevention treatment, chemical conversion treatment. A specular surface treatment is exemplified as the antirust treatment. Examples of the surface treatment include plating treatment using a plating solution containing Ni, Zn, Sn, etc., treatment with zirconium phosphate, chromate treatment, and the like. The chromate treatment is exemplified by using chromate phosphate and chromate chromate. Other layers (e.g., easy-adhesion layer, anchor layer, etc.) may be provided between the film formed by the hydrophilic film-forming composition of the present disclosure provided on one or both sides of the substrate. . The substrate is preferably a metal substrate or a plastic substrate, more preferably aluminum, Galvalume steel sheet (registered trademark), ZAM steel sheet or thermoplastic, still more preferably aluminum, Galvalume steel sheet (registered trademark), ZAM steel plate or general-purpose plastic, particularly preferably aluminum, Galvalume steel plate (registered trademark), ZAM steel plate or polyester. The substrate to which the hydrophilic film-forming composition of the present disclosure is applied is preferably a metal substrate, and more preferably aluminum, since the film of the present disclosure easily adheres to the substrate. The thickness of the base material is not particularly limited, and is exemplified from about 1 μm to 2 mm.

Examples of methods for applying the hydrophilic film-forming composition of the present disclosure onto a substrate include roll coater coating, reverse roll coater coating, bar coater coating, Mayer bar coating, air knife coating, gravure coating, and reverse coating. Gravure coating, offset printing, flexographic printing, screen printing and the like are exemplified. Although the coating amount is not particularly limited, it is usually in the range where the mass after drying is 0.1 to 10.0 g/m ² , preferably 0.1 to 5.0 g/m ² . It is preferably 0.1 to 2.0 g/m ² , still more preferably 0.1 to 1.0 g/m ² . The film thickness of the hydrophilic film-forming composition of the present disclosure is about 0.1 to 10 μm.

After applying the hydrophilic film-forming composition to the surface of the substrate, a drying step may be performed as necessary. The drying step of the present disclosure only needs to dry the hydrophilic film-forming composition applied to the substrate. As the drying process of the present disclosure, for example, drying at about 60 to 350° C. for about 10 seconds to 60 minutes is exemplified. The drying process of the present disclosure is preferably performed at 100 to 250° C., more preferably at 100 to 200° C. for about 10 seconds to 5 minutes.

Since the film of the composition for forming a hydrophilic film of the present disclosure is excellent in freezing resistance and frost resistance, it can be used as an anti-icing and frosting treatment agent. In addition, since the film of the hydrophilic film-forming composition of the present disclosure easily adheres to metals, it can be used as a hydrophilic film-forming composition for metal substrates and as an anti-icing and frosting agent for metal substrates. preferably. Specific examples of application include use in aluminum fins for air conditioning, vehicle bodies, and traffic signals.

In addition, it is conceivable that the composition for forming a hydrophilic film of the present disclosure may be used for various applications in which the effect of the hydrophilic film-forming composition can be exhibited.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, all parts and percentages are based on mass unless otherwise specified.

<Synthesis Example 1: Synthesis of component (A-1)>
186.8 parts of 80% acrylic acid aqueous solution (solid content: 149.4 parts) and 776.6 parts of ion-exchanged water were charged into a reaction apparatus equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. , oxygen was removed from the reaction system through nitrogen gas. The inside of the system was heated to 60° C., and 0.54 parts of ammonium persulfate (product name: "ammonium persulfate", manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dissolved in 10.6 parts of ion-exchanged water as a polymerization initiator while stirring. . After raising the temperature to 90° C., the temperature was maintained for 2 hours. After the temperature was maintained, 25.5 parts of ion-exchanged water was added to obtain component (A-1) having a solid content concentration of 15% by mass and a viscosity (25°C) of 40,000 mPa·s. Table 1 shows the monomer composition and the physical properties of the obtained component (A-1). The viscosity was measured using a Brookfield viscometer (product name "VISCOMETER TVB-10M" manufactured by Toki Sangyo Co., Ltd.) at 25°C. 4 rotors were used, and the measurement was carried out under the conditions of a rotation speed of 6 rpm.

<Synthesis Example 2: Synthesis of component (A-2)>
A reaction apparatus equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and two dropping funnels was charged with 50.6 parts of ion-exchanged water, and nitrogen gas was passed through the reaction system to remove oxygen. It was heated to °C. Into one dropping funnel were added 249.0 parts of an 80% aqueous acrylic acid solution (solid content: 199.2 parts), 2.64 parts of sodium methallylsulfonate, 0.129 parts of N,N'-methylenebisacrylamide, and ion exchange. 325.3 parts of water are added. Also, 0.283 parts of ammonium persulfate and 180.0 parts of ion-exchanged water were put into the other dropping funnel. Next, the monomer and catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of dropping, 0.20 parts of ammonium persulfate was dissolved in 10.0 parts of deionized water and added. After keeping the temperature for 1 hour, 194.2 parts of ion-exchanged water was added to obtain component (A-2) having a solid content concentration of 20% by mass and a viscosity (25°C) of 6,000 mPa·s. Table 1 shows the monomer composition and the physical properties of the obtained component (A-2). In addition, the viscosity of the rotor, No. Measurement was performed in the same manner as in Synthesis Example 1, except that 3 rotors and the rotation speed were changed to 12 rpm.

<Synthesis Example 3: Synthesis of component (A-3)>
277.1 parts of ion-exchanged water was added to a reaction apparatus equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and two dropping funnels, and nitrogen gas was passed through the reaction system to remove oxygen. It was heated to °C. 367.7 parts of an 80% acrylic acid aqueous solution (solid content: 294.2 parts), 5.86 parts of sodium methallylsulfonate, and 226.5 parts of ion-exchanged water were added to one dropping funnel. 0.60 parts of ammonium persulfate and 90 parts of ion-exchanged water were added to the other dropping funnel. Next, the monomer and catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of dropping, 0.30 part of ammonium persulfate was dissolved in 10 parts of deionized water and added. After keeping the temperature for 1 hour, 25.0 parts of ion-exchanged water was added to obtain component (A-3) having a solid content concentration of 30% by mass and a viscosity (25°C) of 3,000 mPa·s. Table 1 shows the monomer composition and the physical properties of the obtained component (A-3). In addition, the viscosity of the rotor, No. Measurement was performed in the same manner as in Synthesis Example 1, except that 3 rotors and the rotation speed were changed to 12 rpm.

<Synthesis Examples 4 to 9 and Comparative Synthesis Example 1: Synthesis of Components (A-4) to (A-9) and Components (A-C1)>
Synthesis Examples 4 to 9 and Comparative Synthesis Example 1 were performed in the same manner as in Synthesis Example 2 except that the composition was changed to that shown in Table 1, and a solution of component (A-4) to component (A-9) were prepared. and a solution of component (A-C1) were obtained. Table 1 summarizes the concentrations of the components (A-4) to (A-9) and (A-C1), which are the obtained polymers, and the viscosity (mPa·s) at 25°C. The viscosities of the components (A-4) to (A-5), (A-7) to (A-9), and (A-C1) are determined by the rotor. Measurement was performed in the same manner as in Synthesis Example 1, except that 3 rotors and the rotation speed were changed to 12 rpm. Incidentally, the viscosity of the component (A-6) is determined by measuring the rotor. Measurement was performed in the same manner as in Synthesis Example 1, except that 2 rotors and the rotation speed were changed to 30 rpm.

<Synthesis Example 10: Synthesis of component (A-10)>
Synthesis Example 10 was carried out in the same manner as in Synthesis Example 1 except that the composition was changed to that shown in Table 1 to obtain a solution of component (A-10). Table 1 summarizes the concentration of component (A-10), which is the polymer obtained, and the viscosity (mPa·s) at 25°C. Incidentally, the viscosity of the component (A-10) is determined by measuring the rotor. Measurement was performed in the same manner as in Synthesis Example 1, except that 2 rotors and the rotation speed were changed to 30 rpm.

The meanings of the terms in Table 1 are as follows.
AA: acrylic acid (product name "80% acrylic acid", manufactured by Osaka Organic Chemical Industry Co., Ltd.)
IA: itaconic acid (product name “purified itaconic acid”, manufactured by Fuso Chemical Industry Co., Ltd.)
MAA: methacrylic acid (product name "methacrylic acid 80", manufactured by Mitsubishi Chemical Corporation)
SMAS: sodium methallyl sulfonate (product name: sodium methallyl sulfonate, purchased from Maruzen Yuka Shoji Co., Ltd.)
AM: acrylamide (product name “acrylamide (50% aqueous solution)”, manufactured by Mitsubishi Chemical Corporation)
MBAA: N,N'-methylenebisacrylamide (product name "N,N'-methylenebisacrylamide", manufactured by MCC Unitec Co., Ltd.)

<Example: Preparation of hydrophilic film-forming composition>
In Example 1, 50 parts of component (A-1) in terms of solid content and 50 parts of sodium carboxymethyl cellulose (product name “Celogen 7A”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in terms of solid content were blended. A hydrophilic film-forming composition (1) was prepared by diluting with ion-exchanged water so that the content was 5%. Examples 2 to 67 and Comparative Examples 1 to 46 were carried out in the same manner as in Example 1, except that the compositions were changed to those shown in Tables 2 to 6. Hydrophilic film-forming compositions (2) to (67) and (C1)-(C46) were obtained. In addition, about the Example and the comparative example which add a pH adjuster, after adding (B) component, a pH adjuster was added.

<Evaluation Example: Production of Laminate>
In Evaluation Example 1, the hydrophilic film-forming composition (1) was applied to an aluminum substrate (thickness: 100 μm) treated with chromate phosphate using a bar coater No. 1. 14 (film thickness after drying: 1 μm) and dried at 200° C. for 1 minute to obtain a laminate (1). In Evaluation Examples 2 to 67 and Comparative Evaluation Examples 1 to 46, hydrophilic film-forming composition (1) was changed to hydrophilic film-forming composition (2) to (67) or (C1) to (C46). Then, the laminates (2) to (67) and (C1) to (C46) were obtained in the same manner as in Evaluation Example 1 except that the substrates were changed to those shown in Tables 2 to 6.

<Performance evaluation (1): Freezing resistance test>
The obtained laminate was immersed in running tap water at a flow rate of 1.0 L/min for 2 hours, air-dried at room temperature for 12 hours, dried at 80°C for 1 hour, and dried at 23°C and 50% humidity for 1 hour. Let it stand for a while. After that, a handy painter (product name “Wagner Handy Painter HP-W330 60Hz”, Wagner Japan Co., Ltd.) was applied to the laminate horizontally arranged with respect to the ground so that the surface coated with the hydrophilic film-forming composition was the upper surface. 160 g/m ² of ultrapure water was applied using a spray tech (manufactured by Spraytech Co., Ltd.), and then the laminate was placed vertically on the ground for 20 seconds to remove excess moisture on the laminate. After that, in a small environmental tester (product name "Small environmental tester SH-241", manufactured by ESPEC Co., Ltd.), the laminate is placed horizontally against the ground, stored at a predetermined temperature and time, and laminated. The presence or absence of freezing of water on the body surface layer was confirmed visually and by touch. Even when the laminate was placed vertically to the ground in a small environmental tester and the same evaluation was performed, the same evaluation result as the horizontal evaluation was obtained.
The measurement results were evaluated according to the following criteria.
AAA: Freezes after storage at -10°C for 2 minutes and storage at -8°C for 30 minutes AA: Freezes after storage at -10°C for 2 minutes, but does not freeze after storage at -8°C for 30 minutes A: Below -8°C Freezes after 30 minutes of storage, but does not freeze after 30 minutes of storage at -6°C B: Freezes after 30 minutes of storage at -6°C

<Performance evaluation (2): hydrophilicity test>
The obtained laminate was immersed in running tap water at a flow rate of 1.0 L/min for 2 hours, air-dried at room temperature for 12 hours, dried at 80°C for 1 hour, and dried at 23°C and 50% humidity for 1 hour. Let it stand for a while. After that, 1 μL of ultrapure water was applied to the film surface of the hydrophilic film-forming composition of the laminate placed horizontally with respect to the ground. 10 seconds after the liquid is applied, the contact angle of the water droplet on the film surface of the hydrophilic film-forming composition of the laminate is measured by a device (product name “Contact Angle Meter DM-500”, manufactured by Kyowa Interface Science Co., Ltd.). was measured using The measurement results were evaluated according to the following criteria.
AAA: 0° or more and less than 11° AA: 11° or more and less than 21° A: 21° or more and less than 41° B: 41° or more

<Performance evaluation (3): Hydrophilic persistence test>
The obtained laminate was immersed in running tap water at a flow rate of 1.0 L/min for 2 hours, air-dried at room temperature for 12 hours, dried at 80°C for 1 hour, and dried at 23°C and 50% humidity for 1 hour. Let it stand for a while. After that, it is immersed in running tap water with a flow rate of 1.0 L/min for 8 hours, air-dried at room temperature for 12 hours, dried at 80°C for 1 hour, and left to stand at 23°C and 50% humidity for 1 hour. as one cycle, 15 cycles were carried out. Thereafter, 1 μL of ultrapure water was applied to the film surface of the hydrophilic film-forming composition of the laminate placed horizontally with respect to the ground. 10 seconds after the liquid is applied, the contact angle of the water droplet on the film surface of the hydrophilic film-forming composition of the laminate is measured by a device (product name “Contact Angle Meter DM-500”, manufactured by Kyowa Interface Science Co., Ltd.). was measured using The measurement results were evaluated according to the following criteria.
AAA: 0° or more and less than 11° AA: 11° or more and less than 21° A: 21° or more and less than 41° B: 41° or more

<Performance evaluation (4): water resistance test>
The obtained laminate was immersed in running tap water at a flow rate of 1.0 L/min for 2 hours, air-dried at room temperature for 12 hours, dried at 80°C for 1 hour, and dried at 23°C and 50% humidity for 1 hour. Let it stand for a while. After that, it is immersed in running tap water with a flow rate of 1.0 L/min for 8 hours, air-dried at room temperature for 12 hours, dried at 80°C for 1 hour, and left to stand at 23°C and 50% humidity for 1 hour. as one cycle, 15 cycles were carried out. After that, from the change in the weight of the laminate, the remaining film ratio of the film was calculated according to the following formula. The measurement results were evaluated according to the following criteria.
(Weight of laminate after 15 cycles (g) - Weight of substrate before coating (g)) ÷ (Weight of laminate before test (g) - Weight of substrate before coating (g)) × 100 = Remaining film rate (%)
AAA: 80% or more AA: 60% or more and less than 80% A: 40% or more and less than 60% B: less than 40%

<Performance Evaluation (5): Ice and Frost Resistance Test>
The laminate thus obtained was immersed in ultrapure water for 30 minutes, air-dried at room temperature for 12 hours, dried at 80° C. for 1 hour, and allowed to stand at 23° C. and humidity of 50% for 1 hour. After that, at 23 ° C. and 50% humidity, a plate of a Peltier kit (product name “Sakaguchi Peltier Kit II SPE-UC-200”, manufactured by Sakaguchi Electric Heat Co., Ltd.) is placed perpendicular to the ground. is set to 23 ° C., and after the temperature of the plate stabilizes at 23 ° C., the laminate is attached with tape so that the film surface of the hydrophilic film-forming composition is on the front side, and the laminate is applied to the ground. was placed vertically. After that, the set temperature of the plate was set to -7.5°C, and after the temperature of the plate reached -7.5°C, the presence or absence of freezing of condensed water adhering to the surface layer of the laminate and frost formation were visually confirmed. The measurement results were evaluated according to the following criteria.
AAA: 10 minutes after the plate temperature reaches -7.5°C, no condensation or frost formation on the surface of the laminate AA: 5 minutes after the plate temperature reaches -7.5°C, on the surface of the laminate Freezing or frosting of condensed water was observed on the laminate surface within 10 minutes after the plate temperature reached -7.5°C without freezing or frosting. A: Plate temperature was -7. For 2 minutes after reaching 5°C, no condensation water freezes or frost forms on the surface of the laminate, and within 5 minutes after the plate temperature reaches -7.5°C, condensation water freezes or frost forms on the surface of the laminate. B: Before the plate temperature reached −7.5° C. or within 2 minutes after the plate temperature reached −7.5° C., freezing of condensed water or frost formation was observed on the laminate surface. was taken

The meanings of terms in Tables 2 to 6 are as follows.
In the table, numerical values relating to constituent elements indicate parts by mass.
AL: Aluminum base material treated with chromate phosphate (thickness: 100 μm)
ZAM: ZAM steel plate (thickness 1.2 mm, manufactured by Nippon Test Panel Co., Ltd.)
GL: Galvalume steel plate (registered trademark) (thickness 0.5 mm, manufactured by Nippon Test Panel Co., Ltd.)
Celogen 7A: Sodium carboxymethyl cellulose (product name "Celogen 7A", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., degree of etherification: 0.7 to 0.8, viscosity at solid content concentration of 1% (mPa s/25°C ): 6.8, pH at 1% solids concentration: 6.9, Viscosity at 10% solids concentration (mPa s / 25 ° C.): 3,260)
Celogen 6A: Sodium carboxymethyl cellulose (product name "Celogen 6A", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., degree of etherification: 0.7 to 0.8, viscosity at solid content concentration of 1% (mPa s/25°C ): 4.6, pH at solid content concentration of 1%: 6.5, viscosity at solid content concentration of 10% (mPa s / 25 ° C.): 556)
Celogen 5A: Sodium carboxymethyl cellulose (product name "Celogen 5A", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., degree of etherification: 0.7 to 0.8, viscosity at solid content concentration of 1% (mPa s/25°C ): 4.1, pH at solid content concentration of 1%: 6.4, viscosity at solid content concentration of 10% (mPa s / 25 ° C.): 223)
Cellogen PR: Sodium carboxymethyl cellulose (product name “Celogen PR”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., degree of etherification: 0.6 to 0.7, viscosity at solid content concentration of 1% (mPa s/25°C ): 14.7, pH at solid content concentration of 1%: 7.2, viscosity at solid content concentration of 10% (mPa s / 25 ° C.): 10,000 or more)
Cellogen WS-C: Sodium carboxymethyl cellulose (product name “Cellogen WS-C”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., degree of etherification: 0.6 to 0.7, viscosity at solid content concentration of 1% (mPa・s/25°C): 216, pH at 1% solids concentration: 7.0, Viscosity at 10% solids concentration (mPa s/25°C): 10,000 or more)
CMC1110: Sodium carboxymethyl cellulose (product name "CMC1110", manufactured by Daicel Miraise Co., Ltd., degree of etherification: 0.6 to 0.8, viscosity at solid content concentration of 1% (mPa s/25°C): 11. 8, pH when solid content concentration is 1%: 6.7, Viscosity when solid content concentration is 10% (mPa s / 25 ° C.): 10,000 or more)
CMC1120: Sodium carboxymethylcellulose (product name "CMC1120", manufactured by Daicel Miraise Co., Ltd., degree of etherification: 0.6 to 0.8, viscosity at 1% solid concentration (mPa s/25°C): 36. 0, pH at 1% solids concentration: 6.8, Viscosity at 10% solids concentration (mPa s/25°C): 10,000 or more)
CMC1220: Sodium carboxymethyl cellulose (product name "CMC1220", manufactured by Daicel Miraise Co., Ltd., degree of etherification: 0.8 to 1.0, viscosity at solid content concentration of 1% (mPa s/25°C): 14. 0, pH at 1% solids concentration: 7.0, Viscosity at 10% solids concentration (mPa s/25°C): 10,000 or more)
CMC1330: Sodium carboxymethylcellulose (product name "CMC1330", manufactured by Daicel Miraise Co., Ltd., degree of etherification: 1.0 to 1.5, viscosity at solid content concentration of 1% (mPa·s/25°C): 63. 0, pH at 1% solids concentration: 6.8, Viscosity at 10% solids concentration (mPa s/25°C): 10,000 or more)
Kimika CMC PL-4: Sodium carboxymethylcellulose (product name "Kimika CMC PL-4", manufactured by Kimika Co., Ltd., degree of etherification: 0.7 to 1.1, viscosity at solid content concentration of 1% (mPa s /25°C): 12.3, pH at 1% solids concentration: 7.6, Viscosity at 10% solids concentration (mPa s/25°C): 10,000 or more)
Kimika CMC F-2: Sodium carboxymethylcellulose (product name "Kimika CMC F-2", manufactured by Kimika Co., Ltd., degree of etherification: 0.5 to 0.9, viscosity at solid content concentration of 1% (mPa s /25°C): 153.9, pH at 1% solids concentration: 7.5, Viscosity at 10% solids concentration (mPa s/25°C): 10,000 or more)
Kimika CMC P-3: Sodium carboxymethylcellulose (product name "Kimika CMC P-3", manufactured by Kimika Co., Ltd., degree of etherification: 1.4 to 1.7, viscosity at solid content concentration of 1% (mPa s /25°C): 36.0, pH at 1% solids concentration: 7.7, Viscosity at 10% solids concentration (mPa s/25°C): 10,000 or more)
Blanose (registered trademark) REF CMC 7ULC: Sodium carboxymethylcellulose (product name "Blanose (registered trademark) REF CMC 7ULC", manufactured by Ashland, degree of etherification: 0.65 to 0.9, viscosity at solid content concentration of 1% ( mPa s/25°C): 2.1, pH at 1% solids concentration: 5.6, Viscosity at 10% solids concentration (mPa s/25°C): 46.7)
Sodium alginate: sodium alginate (product name “Sodium Alginate 80-120”, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
Methyl cellulose: methyl cellulose (product name "Metolose SM-15", manufactured by Shin-Etsu Chemical Co., Ltd.)
Hydroxypropyl cellulose: Hydroxypropyl cellulose (product name “Hydroxypropyl cellulose 6.0-10.0”, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
Hydroxypropyl methylcellulose: Hydroxypropyl methylcellulose (product name “Metolose 60SH-03”, manufactured by Shin-Etsu Chemical Co., Ltd.)
Hydroxyethyl cellulose: Hydroxyethyl cellulose (product name “HEC Daicel SP200”, manufactured by Daicel Miraise Co., Ltd.)
Sodium hydroxide: sodium hydroxide (product name "liquid caustic soda", manufactured by Nippon Soda Co., Ltd.)
Potassium hydroxide: potassium hydroxide (product name “liquid caustic potash”, manufactured by AGC Inc.)
Ammonia: Ammonia (product name "28% ammonia water", manufactured by Taisei Kako Co., Ltd.)
Sulfuric acid: Sulfuric acid (product name “50 degrees sulfuric acid”, manufactured by Furukawa Chemicals Co., Ltd.)
Hydrochloric acid: Hydrochloric acid (product name “hydrochloric acid”, manufactured by Kaname Yakuhin Co., Ltd.)
Phosphoric acid: Phosphoric acid (product name “Phosphoric acid (special grade)”, manufactured by Kishida Chemical Co., Ltd.)
pH: pH of an aqueous solution with a combined solid concentration of components (A) and (B) of 1%. pH is measured at 25° C. using a pH meter (product name “desktop pH meter F-71”, manufactured by Horiba Advanced Techno Co., Ltd.) based on the pH measurement method described in JIS Z 8802:2011. did.

Claims (10)

a polymer (A) containing a radically polymerizable monomer having a carboxy group and/or a salt thereof (a-1) as a reaction component;
and carboxyalkyl cellulose and / or a salt thereof (B),
The solid content-equivalent mass ratio [(A)/(B)] of the component (A) and the component (B) is 15/85 to 99/1,
A composition for forming a hydrophilic film, wherein the pH of an aqueous solution having a concentration of solid content of 1% in which the components (A) and (B) are combined has a pH of 2.0 to 5.0. 2. The hydrophilic film-forming composition according to claim 1, wherein the component (B) has a viscosity (mPa·s/25° C.) of 1 to 155 at a solid content concentration of 1%. 3. The hydrophilic film-forming composition according to claim 1, wherein the component (B) has a degree of etherification of 0.4 to 1.5. The group in which component (a-1) consists of (meth)acrylic acid, (meth)acrylic acid salts, itaconic acid, itaconic acid salts, itaconic acid monoesters, itaconic acid monoester salts, and itaconic anhydride The hydrophilic film-forming composition according to any one of claims 1 to 3, comprising one or more selected from Component (A) is poly(meth)acrylic acid, a copolymer of (meth)acrylic acid and (meth)acrylamide, or a copolymer of (meth)acrylic acid and an anionic monomer other than (meth)acrylic acid. , a copolymer of (meth)acrylic acid, (meth)acrylamide and an anionic monomer other than (meth)acrylic acid, and one or more selected from salts thereof, according to any one of claims 1 to 4 The hydrophilic film-forming composition as described. 6. The hydrophilic film-forming composition according to any one of claims 1 to 5, wherein component (B) contains one or more selected from carboxymethylcellulose sodium, carboxymethylcellulose potassium, and carboxymethylcellulose ammonium. 7. The hydrophilic film-forming composition according to any one of claims 1 to 6, wherein the viscosity (mPa·s/25°C) of component (B) at a solid content concentration of 10% is 1 to 300. 8. The composition for forming a hydrophilic film according to any one of claims 1 to 7, wherein component (a-1) accounts for 29 mol% or more of the monomer constituting the polymer of component (A). A laminate having a film of the hydrophilic film-forming composition according to any one of claims 1 to 8 on at least one side of a substrate. A method for forming a film, comprising the step of applying the hydrophilic film-forming composition according to any one of claims 1 to 8 to the surface of a substrate.