JP2015137342A - Anti-fogging coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-fogging coating agent which is excellent in an anti-fogging property and persistence thereof, strength of a coating film, and adhesiveness to glass.SOLUTION: An anti-fogging coating agent comprises: a (co)polymer (A) comprising as a constituent unit a (co)polymer containing only a polymerizable unsaturated monomer (a) having a carboxyl group and/or an acid anhydride group, and/or a (co)polymer of the monomer (a) and a polymerizable unsaturated monomer not containing a carboxylic acid and/or an acid anhydride group; a crosslinking agent having at least two functional groups which can react with the carboxyl group and/or an acid anhydride group in (A) to form covalent bonds; a hydroxide of an alkali metal and/or an alkaline earth metal; and water and/or an organic solvent.

Description

  The present invention relates to an antifogging coating agent. More specifically, the present invention relates to an antifogging coating agent that is particularly excellent in adhesion to glass.

The reason why the substrate such as glass and plastic becomes cloudy is that when the surface temperature falls below the dew point, moisture in the air adheres as fine water droplets, and light is irregularly reflected on the substrate surface. Therefore, clouding can be prevented by preventing formation of water droplets on the surface of the substrate.
Conventionally, as a method of imparting antifogging properties, a method of applying an antifogging agent containing a polyvinyl acetal resin (Patent Document 1) and a method of coating a surface with a mixture of a plurality of surfactants (Patent Document 2) are known. It has been. Further, a method using a coating film made of a silicone component (Patent Document 3) has been proposed.

Japanese Patent Laid-Open No. 06-157794 JP 2003-201355 A JP 2009-256472 A

However, in Patent Document 1, the strength of the coating film is insufficient, and in Patent Document 2, the antifogging effect is short, and in Patent Document 3, the antifogging effect is sustained, but the antifogging effect is insufficient. It was a thing.
An object of this invention is to provide the anti-fogging coating agent excellent in anti-fogging property and its durability, the intensity | strength of a coating film, and adhesiveness with glass.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to the (co) polymer (A1) and / or the monomer (a) and the carboxyl group having only the polymerizable unsaturated monomer (a) having a carboxyl group and / or an acid anhydride group as a constituent unit. And / or a (co) polymer (A2) comprising a (co) polymer (A2) having a polymerizable unsaturated monomer (b) having no acid anhydride group as a structural unit, a carboxyl group in (A) And / or a crosslinking agent (B) having at least two functional groups capable of reacting with an acid anhydride group to form a covalent bond, an alkali metal and / or alkaline earth metal hydroxide (C), and water and / or Or it is anti-fogging coating agent (X) containing an organic solvent (D).

The antifogging coating agent (X) of the present invention has the following effects.
(1) Excellent antifogging property and durability.
(2) Excellent coating film strength and moisture resistance.
(3) Excellent adhesion to glass.

[(Co) polymer (A)]
The (co) polymer (A) in the present invention is composed of the (co) polymer (A1) having only a polymerizable unsaturated monomer (a) having a carboxyl group and / or an acid anhydride group as a constituent unit and / or It consists of (co) polymer (A2) which has (a) and the polymerizable unsaturated monomer (b) which does not have a carboxyl group and / or an acid anhydride group as a structural unit. Among (A), (A1) is preferable from an industrial viewpoint.

  (A) polymerizes a polymerizable unsaturated monomer (a) having a carboxyl group and / or an acid anhydride group, or (a) and a carboxyl group and / or an acid anhydride group other than (a) It can be obtained by copolymerizing the polymerizable unsaturated monomer (b) that is not present. Examples of (a) include the following and mixtures thereof:

  Among (a), the polymerizable unsaturated monomer (a1) having a carboxyl group is an unsaturated monocarboxylic acid [(meth) acrylic acid (acrylic acid and / or Methacrylic acid, the same shall apply hereinafter), crotonic acid, cinnamic acid, vinylbenzoic acid, alkenoic acid [C4-20 (preferably C4-13) such as vinylacetic acid, 3-methyl-3-butenoic acid, 3 -Pentenoic acid, 4- and 5-hexenoic acid], monoalkyl (C1-8) esters of unsaturated dicarboxylic acids [C4-16, such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, citraconic acid monoalkyl esters] , Monoesters of unsaturated dicarboxylic acids [C5-20, eg ethyl carbitol monoester of maleic acid, ethyl fumaric acid Ruby tall monoesters, itaconic acid glycol monoester], etc.], C4-20 (preferably C4～16) unsaturated dicarboxylic acids [maleic acid, fumaric acid, citraconic acid, and itaconic acid] and the like.

Among (a), as the polymerizable unsaturated monomer (a2) having an acid anhydride group, an anhydride of the unsaturated dicarboxylic acid [C4-20 (preferably C4-16)] in (a1), for example, anhydrous Examples include maleic acid and itaconic anhydride.
Of the above (a1) and (a2), (a1) is preferable from the viewpoint of the curing rate of the antifogging coating agent (X), and acrylic acid is more preferable.

Examples of the polymerizable unsaturated monomer (b) having no carboxyl group and / or acid anhydride group include the following C2-30.
(1) Amide monomer C3-18, such as (meth) acrylamide, N-alkyl (C1-5) (meth) acrylamide, alkoxy (C1-4) alkyl (C1-5) (meth) acrylamide, N, N-dialkyl (C1-5) (meth) acrylamide, aminoalkyl (C1-5) (meth) acrylamide, N-alkyl (C1-5) aminoalkyl (C1-5) (meth) acrylamide, N, N-dialkyl (C1 5) Aminoalkyl (C1-5) (meth) acrylamide, diacetone (meth) acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone;

(2) Acrylate monomers C3-30, such as alkyl (C1-18) (meth) acrylates and their lower alkyl (C1-4) ethers, hydroxyalkyl (C1-5) (meth) acrylates, aminoalkyl (C1-5) ) (Meth) acrylate, N-alkyl (C1-5) aminoalkyl (C1-5) (meth) acrylate, N, N-dialkyl (C1-5) (meth) acrylate, N-alkyl (C1-5) amino Alkyl (C1-5) aminoalkyl (C1-5) (meth) acrylate;

(3) Vinyl monomer C3-30, such as vinylalkyl (C1-20) ether, N-alkyl (C1-5) vinylamine, N, N-dialkyl (C1-5) vinylamine, N-vinylpyridine, N-vinylimidazole N- (alkyl) aminoalkyl (C1-5) vinylamine;
(4) Allyl monomer C3-10, such as N-allylamine, N-alkyl (C1-5) allylamine, N, N-dialkyl (C1-5) allylamine;
(5) Nitrile monomer C3-10, such as (meth) acrylonitrile;

(6) Aliphatic unsaturated hydrocarbon monomer C2-30, such as ethylene, propylene, isobutylene, isoprene, butadiene, etc .;
(7) C8-30 styrene monomer Styrene, α-methylstyrene, p-methoxystyrene, vinyltoluene, p-hydroxystyrene, p-acetoxystyrene, and the like;
(8) C3-30 vinyl ester monomer Vinyl acetate, vinyl propionate and the like.
The above (b) may be used alone or in combination of two or more.

  Of the above (b), preferred are (2), (3), (6) and (7), and (2) are more preferred from the viewpoints of the strength of the coating film, adhesion to glass and stability. Particularly preferred are alkyl (C1-18) (meth) acrylates.

The proportion (% by weight) of each monomer constituting (A) is usually 60% or more, preferably from 70 to 100%, more preferably from 80 to 100% from the viewpoint of durability and coating strength. ; (B) is usually 40% or less, preferably 30% or less, more preferably 20% or less from the viewpoint of durability and coating strength.
As (a), each of (a1) and (a2) may be used alone or in combination.
The weight ratio [(a1) / (a2)] when used in combination is preferably 50/50 to 90/10, more preferably 70/30 to 85/5, from the viewpoints of curing speed and coating strength. .

Weight average molecular weight of (A) [hereinafter abbreviated as Mw. The measurement is based on a gel permeation chromatography (GPC) method described later. ] Is preferably 10,000 to 250,000, more preferably 15,000 to 200,000, and particularly preferably 20,000 to 150 from the viewpoints of antifogging property, durability, coating strength, and productivity. , 000.
The GPC measurement conditions of Mw in the present invention and the number average molecular weight (hereinafter abbreviated as Mn. The measurement is according to the GPC method described later) are as follows.
<GPC measurement conditions>
[1] Apparatus: Gel permeation chromatography
“HLC-8120GPC”, manufactured by Tosoh Corporation.
[2] Column: “TSKgel G6000PWxl”, “TSKgel”
G3000PWxl "[both manufactured by Tosoh Corporation] are connected in series.
[3] Eluent: 0.5% by weight of sodium acetate in methanol / water = 30/70 (volume ratio)
Um dissolved.
[4] Reference material: polyethylene glycol (hereinafter abbreviated as PEG)
[5] Injection conditions: sample concentration 0.25%, column temperature 40 ° C.

  The number of carboxyl groups and / or acid anhydride groups in (A) is at least 2, preferably 3 to 2,000, more preferably 5 to 1,000, and particularly preferably 10 to 500. . If the number of the carboxyl groups and / or acid anhydride groups is less than 2, the strength of the coating film is deteriorated.

(A) can be produced by a known solution polymerization method, and an aqueous solution polymerization method is preferred from the viewpoint of productivity. When an organic solvent is used, it may be removed after polymerization or may be used as it is without removing the solvent.
Examples of the organic solvent include ketones [methyl ethyl ketone (hereinafter abbreviated as MEK) and the like], alcohols [isopropanol and the like] and the like. From the viewpoint of productivity, ketones are preferable, and MEK is more preferable.
The (A) is usually obtained as a solution (preferably an aqueous solution), and the content (% by weight) of (A) in the solution is determined in terms of productivity and handling during production of the antifogging coating agent (X) in the subsequent step. From the viewpoint of property, it is preferably 5 to 80%, more preferably 10 to 70%, and particularly preferably 20 to 60%.

The polymerization temperature is preferably 0 to 200 ° C. from the viewpoint of productivity and (A) molecular weight control.
The polymerization time is preferably 1 to 10 hours from the viewpoint of reducing the residual monomer content in the product and productivity.
The end point of the polymerization reaction can be confirmed by the amount of residual monomer. The amount of residual monomer is preferably 5% or less, more preferably 3% or less from the viewpoint of the strength of the coating film. The amount of residual monomer can be measured by gas chromatography.

[Crosslinking agent (B)]
The crosslinking agent (B) in the present invention is a compound having at least two functional groups that can react with the carboxyl group and / or acid anhydride group in (A) to form a covalent bond.
Examples of the functional group include an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.

  Examples of (B) include amino alcohol (B1), polyamine (B2), polyol (B3), polyepoxide (B4), polyisocyanate (B5), polycarbodiimide (B6), and polyoxazoline (B7).

  Examples of amino alcohol (B1) include C2-20 hydroxylamine, amine alkylene oxide (hereinafter abbreviated as AO) adducts, and mixtures thereof.

  Hydroxylamine includes C2-20, for example having one hydroxyl group [having an amino group [for example, monoethanolamine, isopropanolamine], having an amino group and an imino group [for example, 2- (2-aminoethylamino ) Ethanol] and the like, and those having two hydroxyl groups [those having an imino group (for example, diisopropanolamine, diethanolamine, etc.)].

  AO adducts of amines include those having C3 or more and Mn 3,000 or less, such as aliphatic amines [C1-10, such as methylamine, ethylamine, n- and i-propylamine, ethylenediamine, diethylenetriamine], aromatic amines [ C6-12, eg aniline, toluidine, xylylenediamine], alicyclic amines [C4-10, eg cyclopentylamine, cyclohexylamine], heterocycle containing amines [C4-10, eg piperazine] and AO addition of said hydroxylamines Things. The number of moles of AO addition is preferably 1 to 20 moles. Many of these amine AO adducts have an imino group.

  AO includes C2-12 or higher (preferably C2-4) AO such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran. And 3-methyl-tetrahydrofuran), 1,3-propylene oxide, isobutylene oxide, C5-12 α-olefin oxide, substituted AO, such as styrene oxide, and combinations of two or more thereof (random addition and / or block addition) ) Is included.

  Among these (B1), from the viewpoint of the stability of the curable and antifogging coating agent (X), preferred are C2-20 hydroxylamine, more preferred are monoethanolamine, diethanolamine, isopropanolamine, Preference is given to diethanolamine. These may be used alone or in combination of two or more.

  Examples of the polyamine (B2) include alkylene diamine, polyalkylene polyamine, alicyclic polyamine, heterocyclic polyamine, and mixtures thereof.

  As alkylene diamine, it is alkylene diamine containing a C1-10 grade alkylene group, for example, ethylene diamine, propylene diamine, hexamethylene diamine etc. are mentioned.

  The polyalkylene polyamine is a product obtained by decondensing an alkylene diamine and condensing it, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, 3-azahexane-1,6- Examples include diamines.

  Examples of the alicyclic polyamine include isophorone diamine, bis (aminomethyl) cyclohexane, 4,7-diazadecane-1,10-diamine, and the like.

  The heterocyclic polyamine usually includes a heterocyclic ring which is an alicyclic hydrocarbon group containing at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom in the molecule, and a primary amino group and / Or an amine having at least two secondary amino groups. For example, heterocyclic diamines [eg piperazine, homopiperazine, N-methylpiperazine, N-ethylpiperazine, N-propylpiperazine, N-acetylpiperazine, 1- (chlorophenyl) piperazine, etc.], heterocyclic amines containing aminoalkyl [For example, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylpiperazine, N-aminopropylpiperazine, N-aminoethylmorpholine, N-aminopropylmorpholine, N-aminopropyl-2-pipecoline, N-amino Propyl-4-pipecholine and 1,4-bis (aminopropyl) piperazine etc.] and the like.

  Of these (B2), from the viewpoint of the stability of the curable and antifogging coating agent (X), alkylenediamine and polyalkylenepolyamine are preferable, ethylenediamine and diethylenetriamine are more preferable, and ethylenediamine is particularly preferable. is there. These may be used alone or in combination of two or more.

  Examples of the polyol (B3) include polyhydric alcohols, polyhydric phenols, and mixtures thereof.

  Examples of the polyhydric alcohol include C2-18 dihydric alcohol [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4- and 1,3-butanediol, 1,6-hexanediol, and neopentyl glycol. Etc.], C3-18 (preferably 3-12) 3-5 valent polyhydric alcohol [alkane polyol and its intramolecular or intermolecular dehydrate, such as glycerin, trimethylolpropane, pentaerythritol, sorbitan, diglycerin Sugars and derivatives thereof, such as a-methylglucoside, xylitol, glucose, fructose; etc.], and C5-18 (preferably 5-12) 6-10 valent or higher polyhydric alcohol [6-10 valent; Alkane polyol and polyhydric alcampo Intramolecular or intermolecular dehydrates of riol, such as dipentaerythritol; saccharides and derivatives thereof, such as sorbitol, mannitol, sucrose; and the like].

  As polyhydric phenol, bivalent phenol [monocyclic polyhydric phenol (hydroquinone, etc.), bisphenol (bisphenol A, bisphenol F, etc.)], 3-5 polyhydric phenol [monocyclic polyphenol (pyrogallol, Phloroglucin, etc.), formalin low condensate of phenolic compound (3-5 valence) (number average molecular weight 1000 or less) (novolak resin, intermediate of resol), etc.], 6-10 valent or higher polyhydric phenol [phenolic compound Formalin low condensate (hexavalent or higher) (number average molecular weight 1000 or less) (novolak resin, intermediate of resol) and the like], condensate of phenol and alkanolamine (Mannich polyol) and the like.

  Of these (B3), polyhydric alcohols are preferred from the viewpoints of the curability and stability of the antifogging coating agent (X) and the transparency of the cured product, and glycerin and pentaerythritol are particularly preferred. Is glycerin. These may be used alone or in combination of two or more.

  Examples of the polyepoxide (B4) include glycidyl ethers of polyhydric alcohols, glycidyl esters of polybasic acids, and mixtures thereof.

  Polyglycol glycidyl ethers include polyethylene glycol diglycidyl ether, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether Etc.

  Examples of the glycidyl ester of polybasic acid include phthalic acid diglycidyl ester.

  Of these (B4), glycidyl ethers of polyhydric alcohols are preferred, and polyethylene glycol diglycidyl is more preferred from the viewpoints of the curability and stability of the antifogging coating agent (X) and the transparency of the cured product. Ether, glycerin triglycidyl ether, sorbitol hexaglycidyl ether, and particularly preferred is glycerin triglycidyl ether. These may be used alone or in combination of two or more.

  The polyisocyanate (B5) is polyisocyanate or a blocked polyisocyanate compound obtained by blocking the isocyanate group of the polyisocyanate with an active hydrogen-containing compound.

  Examples of the polyisocyanate constituting (B5) include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- or 1,4- Diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (also known as isophorone diisocyanate; IPDI), dicyclohexylmethane-4,4′-diisocyanate (also known as hydrogenated MDI), 2- or 4- Isocyanatocyclohexyl-2′-isocyanatocyclohexylmethane, 1,3- or 1,4-bis- (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methylcyclohexyl) methane, 1,3- or 1,4-α, α, α ′, α′-tetramethylxylylene diisocyanate, 2,4- or 2,6-diisocyanatotoluene, 2,2′-, 2,4′- or 4,4′-diisocyanatodiphenylmethane (MDI) 1,5-naphthalene diisocyanate, p- or m-phenylene diisocyanate, xylene diisocyanate, diphenyl-4,4′-diisocyanate and the like. Polyisocyanate may be used alone or in combination of two or more.

  Among these polyisocyanates, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (1,6-tetramethylene diisocyanate (1,6) are preferred from the viewpoints of curability, stability of the antifogging coating agent (X) and transparency of the cured product. HDI), 1,12-dodecamethylene diisocyanate, more preferably 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI). These may be used alone or in combination of two or more.

The active hydrogen-containing compound (blocking agent) used in (B5) is not particularly limited, and is —OH group (alcohols, phenols, etc.), ═N—OH group (oximes, etc.), ═N—H group. Examples thereof include compounds having (amines, amides, imides, lactams, etc.), compounds having a —CH ₂ — group (active methylene group), and azoles.
For example, phenol, cresol, xylenol, ε-caprolactam, δ-valerolactam, γ-butyrolactam, methanol, ethanol, n-, i-, or t-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol mono Examples thereof include ethyl ether, propylene glycol monomethyl ether, benzyl alcohol, formamide oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexane oxime, dimethyl malonate, ethyl acetoacetate, acetylacetone, and pyrazole.

  Among these blocking agents, methyl ethyl ketoxime and dimethyl malonate are preferable from the viewpoint of the dissociation temperature of isocyanate and the transparency of the cured product. These may be used alone or in combination of two or more.

  Examples of the carbodiimide (B6) include a monocarbodiimide compound and a polycarbodiimide compound. For example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, and the like can be given.

  Among these (B6), from the viewpoint of curability, stability of the antifogging coating agent (X) and transparency of the cured product, a polycarbodiimide compound is preferable. For example, commercially available products are manufactured by Nittobo Co., Ltd. Carbodilite V-02 and Carbodilite E-01. (B6) may be used alone or in combination of two or more.

  As polyoxazoline (B7), 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline) 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline), 2,2′-hexamethylene-bis- (2-oxazoline), 2, 2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2- Oxazoline), 2,2'-m-phenylene-bis- (4,4'-dimethyl-2-oxazoline), bis- (2-oxazolinylcyclohexane) sulfide and bis- (2-oxazolinyl norbo Nan) and sulfide, 2-vinyl-2-oxazoline, aqueous resins obtained by polymerization of unsaturated oxazoline with other unsaturated compounds such as 2-isopropenyl-2-oxazoline.

  Of these (B7), polymers having an acrylic main chain are preferable from the viewpoints of the curability and stability of the antifogging coating agent (X) and the transparency of the cured product. Examples of the product include Epocross WS-500 and Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd. (B7) may be used alone or in combination of two or more.

  Of the above (B), preferred are (B1) and (B2) from the viewpoints of antifogging property, adhesion to glass, curability, stability of the antifogging coating agent (X) and transparency of the cured product. , (B3), (B4), more preferably (B1).

[Alkali metal and / or alkaline earth metal hydroxide (C)]
Examples of the alkali metal and / or alkaline earth metal hydroxide (C) in the present invention include an alkali metal hydroxide (C1) and an alkaline earth metal hydroxide (C2). Examples of (C) include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like.
Of these (C), sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide are preferred from the viewpoint of antifogging and industrial use, and sodium hydroxide and potassium hydroxide are more preferred. . These may be used alone or in combination of two or more.

[Water and / or organic solvent (D)]
The water and / or organic solvent (D) in the present invention is preferably water from the viewpoint of the productivity of (A). Examples of the organic solvent include ketones [methyl ethyl ketone (hereinafter abbreviated as MEK) and the like], alcohols [isopropanol and the like] and the like. From the viewpoint of productivity, ketones are preferable, and MEK is more preferable.

[Anti-fogging coating agent (X)]
The antifogging coating agent (X) of the present invention comprises the (co) polymer (A), the crosslinking agent (B), an alkali metal and / or alkaline earth metal hydroxide (C), and water and / or Or an organic solvent (D), the carboxyl group in (A) in (B) with respect to the number of moles of the carboxyl group in (A) and / or the carboxyl group derived from the acid anhydride group, and The ratio (γ1) of the total number of moles of the functional group capable of reacting with the carboxyl group derived from the acid anhydride group is preferably 0.1 from the viewpoint of antifogging property and moisture resistance of (X) after curing. It is -0.9, More preferably, it is 0.15-0.7, Most preferably, it is 0.2-0.5.
The ratio (γ2) of the number of moles of hydroxide ions derived from (C) to the number of moles of carboxyl groups derived from the carboxyl group and / or the acid anhydride group in (A) is (( From the viewpoint of antifogging property and moisture resistance of X), it is preferably 0.1 to 0.9, more preferably 0.15 to 0.7, and particularly preferably 0.2 to 0.5.
Furthermore, the sum of the ratio (γ1) and the ratio (γ2) is preferably 0.2 to 1.2, more preferably 0.3 to 1.0, and particularly preferably 0.4 to 0.9.

The ratio (γ1) is obtained by measuring the 1,2-secondary amine equivalent (12Ameq) of (B) by the measurement method described later, the hydroxyl value of (B) and its equivalent (OHeq), the acid value of (A) and The equivalent (Aeq) was measured according to JIS K-0070 “Testing Method for Acid Value and Hydroxyl Group of Chemical Products” and the calculation method described later, and the epoxy equivalent (Eeq) was attached to JIS C-2105. From the results measured in accordance with “Test method not based on IEC” 4 and the isocyanate equivalent (Ieq), JIS K-1603-1 “Plastic-polyurethane raw material aromatic isocyanate test method—Determining the isocyanate group content rate” The carbodiimide equivalent (Keq) and the oxazoline equivalent (Oeq) are determined from the results of the measurement based on the “method”, from the analytical values and calculated values of the commercial products, Formula can be obtained using.

Ratio (γ1) = [[weight of (B1)] / [(B1) (1,2 secondary amine equivalent)]
+ [Weight of (B1)] / [(hydroxyl equivalent of (B1)]]
+ [Weight of (B2)] / [(1,2 amine equivalent of (B2)]]
+ [Weight of (B3)] / [(hydroxyl equivalent of (B3)]]
+ [Weight of (B4)] / [(epoxy equivalent of (B4)]]
+ [Weight of (B5)] / [(isocyanate equivalent) of (B5)]
+ [Weight of (B6)] / [(carbodiimide equivalent of (B6))]
+ [(B7) weight] / [(B7) (oxazoline equivalent)]]]
/ [[Weight of (A)] / (Aeq)]

<Method of measuring (B) 1st, 2nd amine value>
(B) [1] Total amine value (total Am), [2] 2, tertiary amine value (23 Am), [3] tertiary amine value (3 Am) were measured by the method described below, and the following formula From the above, the primary and secondary amine values (12 Am) are obtained.

(12 Am) = (total Am) − (3 Am)

[1] Method for measuring total amine value (total Am) Total amine value is the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize primary, secondary and tertiary amines contained in 1 g of a sample. Say. Measured by the following method according to ASTM D2074.
(1) Weigh accurately the sample. (Sample amount: S ₁ g)
(2) Add and dissolve 30 mL of neutral ethanol [neutralized bromcresol green (BCG)].
(3) Titrate with 0.2 mol / L ethanolic hydrochloric acid solution (titer: f ₁ ), and the point at which the color changed from green to yellow is the end point. (Titration volume: A ₁ mL)
(4) The total amine value (total Am) is calculated from the following formula.

Total amine number (total Am) = A ₁ × f ₁ × 0.2 × 56.108 / S ₁

[2] Method for measuring 2, tertiary amine value (23Am) 2, tertiary amine value (23Am) is the amount of hydroxide equivalent to the hydrochloric acid required to neutralize the secondary or tertiary amine contained in 1 g of the sample. Refers to the number of mg of potassium. Measured by the following method according to ASTM D2074.
(1) Weigh accurately the sample. (Sample amount: S ₂ g)
(2) Neutral ethanol [Bromocresol Green (BCG, the same shall apply hereinafter) Neutral] 30 m
Add L and dissolve.
(3) Add 5 mL of 25% salicylaldehyde in ethanol and leave at room temperature for about 30 minutes.
(4) Titrate with 0.2 mol / L ethanolic hydrochloric acid solution (titer: f ₂ ), and the point at which the color changed from green to yellow is the end point. (Titration volume: A ₂ mL)
(5) The secondary and tertiary amine values (23 Am) are calculated from the following formula.

2, tertiary amine value (23 Am) = A ₂ × f ₂ × 0.2 × 56.108 / S ₂

[3] Method for measuring tertiary amine value (3Am) The tertiary amine value (3Am) is the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the tertiary amine contained in 1 g of a sample. Say. Measured by the following method according to ASTM D2073.
(1) Weigh accurately the sample. (Sample amount: S ₃ g)
(2) Add 20 mL of acetic anhydride / acetic acid mixed solution (9/1) to dissolve, and let stand at room temperature for 3 hours.
(3) Add 30 mL of acetic acid, and titrate with a 0.1 mol / L perchloric acid / acetic acid solution (titer: f ₃ ) with a potentiometric titrator. (Titration volume: A ₃ mL)
(4) A blank test is performed as described above. (Titration volume: B ₁ mL)
(5) The tertiary amine value (3Am) is calculated from the following formula.

Tertiary amine value (3Am) = (A ₃ −B ₁ ) × f ₃ × 0.1 × 56.108 / S ₃

<Calculation method of 1,2-secondary amine equivalent of (B)>
From the following formula, the first and second amine equivalents (12Ameq) are determined.

(12Ameq) = 56108 / (12Am)

<Calculation method of hydroxyl equivalent of (B)>
From the hydroxyl value of (B) measured in accordance with JIS K-0070, the hydroxyl equivalent (OHeq) is determined from the following formula.

(OHeq) = 56108 / [Hydroxyl value of (B)]

<Calculation method of acid equivalent of (A)>
From the acid value of (A) measured according to JIS K-0070, the acid equivalent (Aeq) is determined from the following calculation formula.
(Aeq) = 56108 / [acid value of (A)]

The ratio (γ2) can be obtained using the following calculation formula.

Ratio (γ2) = {[[weight of each (C)] / [hydroxide ion equivalent of each (C)]]}
/ [[Weight of (A)] / [acid equivalent of (A)]]

However, the hydroxide ion equivalent of each (C) is as follows.
(C1): [Molecular weight of (C1)]
(C2): 0.5 × [molecular weight of (C2)]

  The total content of (A), (B) and (C) in the antifogging coating agent (X) of the present invention is preferably from 2 to 80% by weight, more preferably from the viewpoint of productivity and coatability. It is 3 to 70% by weight, particularly preferably 4 to 60% by weight.

  The anti-fogging coating agent (X) of the present invention is necessary within a range that does not impair the effects of the present invention, and is a curing accelerator, an adhesion improver, a viscosity modifier, an antioxidant, an ultraviolet absorber, a stabilizer, a plasticizer. One or more other additives selected from the group consisting of agents, waxes, pigments or dyes, antistatic agents, antibacterial agents, antifungal agents, fragrances, flame retardants, dispersants, film-forming aids, and wetting agents You may use an agent (E) together.

The total amount of the additive (E) used is usually 50% or less based on the total weight of (A) and (B), from the viewpoint of the additive effect of each additive, the strength of the coating film, and the adhesion to glass. Preferably it is 0.5 to 20%.
In addition, the amount of each additive used based on the total weight of (A) and (B) is usually 10 for each of a curing accelerator, an antioxidant, an ultraviolet absorber, a stabilizer, an antibacterial agent, a fungicide and a fragrance. % Or less, preferably 0.5 to 5% from the same viewpoint as described above; plasticizers, waxes, pigments or dyes, antistatic agents, flame retardants, dispersants, film-forming aids and wetting agents are each usually 10%. Hereinafter, it is preferably 1 to 5% from the same viewpoint as described above.

  The production method of the antifogging coating agent (X) of the present invention includes (co) polymer (A), crosslinking agent (B), alkali metal and / or alkaline earth metal hydroxide (C), and There is no particular limitation as long as it is a method that can mix and disperse water and / or organic solvent (D) and, if necessary, additive (E). The mixing time is usually from 30 minutes to 3 hours, and uniform mixing of the antifogging coating agent (X) can be visually confirmed.

[Anti-fogging coating film, anti-fogging article]
The antifogging coating agent (X) of the present invention is suitably used as an antifogging article formed by coating, baking, and heat-curing on a plate glass or the like, or an antifogging coating film obtained by forming (X) itself into a film. .
Examples of the coating method include dip coating, roll coating, spin coating, spray coating, and the like, but are not particularly limited thereto.
The heat-curing temperature during baking is preferably 50 ° C to 250 ° C, and more preferably 80 ° C to 200 ° C from the viewpoint of productivity and transparency of the coating film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following, parts and% represent parts by weight and% by weight, respectively.

The (co) polymer (A) used in Examples and Comparative Examples is as follows.
(A-1): Polyacrylic acid aqueous solution
[Mw 50,000, acid equivalent: 74 g / eq, nonvolatile content 50%]
(A-2): Acrylic acid / hydroxyethyl methacrylate (weight ratio = 90/6)
Copolymer aqueous solution
[Mw 48,000, acid equivalent: 77 g / eq, nonvolatile content 50%]
(A-3): Polymethacrylic acid MEK solution
[Mw 60,000, acid equivalent: 88 g / eq, non-volatile content 50%]

The crosslinking agent (B) used in Examples and Comparative Examples is as follows.
(B-1): Diethanolamine
[1,2 amine equivalent: 105 g / eq, hydroxyl equivalent: 53 g / eq]
(B-2): Ethylenediamine
[1,2 amine equivalent: 30 eq / eq]
(B-3): Glycerin [Hydroxyl equivalent: 31 g / eq]
(B-4): Glycerin triglycidyl ether
[Product name “Denacol EX-313”, manufactured by Nagase ChemteX Corporation,
Epoxy equivalent: 141 g / eq]
(B-5): 1,4-tetramethylene diisocyanate
[Isocyanate equivalent: 86 g / eq]
(B-6): Carbodiimide group-containing polymer
[Product name “Carbodilite V-04”, manufactured by Nisshinbo Co., Ltd.,
Carbodiimide equivalent: 335 g / eq]
(B-7): Oxazoline group-containing acrylic polymer
[Product name "Epocross WS-500", manufactured by Nippon Shokubai Co., Ltd.
Oxazoline equivalent: 220 g / eq]

The alkali metal and / or alkaline earth metal hydroxides (C) used in the examples and comparative examples are as follows.
(C-1): Sodium hydroxide (C-2): Potassium hydroxide

The water and / or organic solvent (D) used in the examples and comparative examples are as follows.
(D-1): Ion exchange water (D-2): Methyl ethyl ketone

Examples 1-12, Comparative Examples 1-2
An antifogging coating agent (X) was prepared according to the composition (parts) shown in Table 1. Using (X), the glass was coated in the following manner and evaluated by the methods described below. The results are shown in Table 1.

[Formation of anti-fogging coating film]
The antifogging coating agent (X) prepared according to the composition (parts) shown in Table 1 was spin-coated on a 3 mm thick, 100 mm square float glass plate polished with ceria fine particles, brushed and dried. It was applied evenly. The glass plate coated with (X) was heat-treated for 30 minutes with a circulating air dryer at 180 ° C. to obtain an antifogging article having an antifogging coating having a thickness of about 25 μm.
[Film thickness measurement]
The film thickness of the anti-fogging coating film formed on the glass plate was measured using a stylus type surface roughness meter (manufactured by Kosaka Laboratory, Surfcoder ET-4000A).

[Anti-fogging test]
The antifogging coating film surface held for 1 hour in a constant temperature and humidity chamber maintained at 20 ° C. and 50% relative humidity is held on a warm water bath at 35 ° C. for 20 cm, and the time until cloudiness is observed is measured. did. The test results were evaluated according to the following criteria.
<Evaluation criteria>
Time until cloudiness occurs ◎: 60 seconds or more ○: 30 to 60 seconds Δ: 10 to 30 seconds ×: 10 seconds or less

[Heat resistance test] (Evaluation of anti-fogging durability)
The antifogging coating film was held for 1000 hours in a thermostatic bath maintained at 100 ° C., and the change in appearance and the rate of decrease in the antifogging test were evaluated according to the following criteria.
<Evaluation criteria>
○: No change in appearance, decrease rate of anti-fogging test is 30% or less Δ: Change in appearance, or decrease rate of anti-fogging test is 30% or more ×: Change in appearance and anti-fogging property Decrease rate of test is 30% or more <Decrease rate of antifogging test>

[(T1)-(t2)] × 100 / (t1)

However, (t1): Anti-fogging test result (time) of coating film before heat resistance test
(T2): Anti-fogging test result (time) of coating film after heat resistance test

[Abrasion resistance test] (Evaluation of coating strength)
This was performed in accordance with JIS R 3212 (inside the vehicle). A wear wheel CS-10F was used on a Taber 5130 type abrasion tester. A wear wheel was brought into contact with the surface of the anti-fogging coating film, rotated 100 times with a load of 4.90 N, the change in haze value ΔH (%) was measured, and evaluated based on the following evaluation criteria.
<Evaluation criteria>
○: ΔH is 4% or less Δ: ΔH is over 4% or part of the anti-fogging coating film is peeled ×: ΔH is over 4% and part of the anti-fogging coating film is peeled off

[Adhesion test] (Evaluation of adhesion to glass)
A cross-cut test was performed on the anti-fogging coating surface in accordance with JIS K5600-5-6, and evaluation was performed according to the following criteria.
<Evaluation criteria>
◎: No peeling of the grids and no peeling at the intersection of the crosscuts ○: No peeling of the grids and slight peeling at the intersections of the crosscuts △: Peeling of 1 to 10 squares in 100 squares ×: 100 There is peeling of 11 squares or more in the square

[Moisture resistance test]
Hold the anti-fogging coating film in a constant temperature and humidity chamber maintained at 20 ° C and 50% relative humidity for 350 hours, confirm changes in the appearance of the coating surface (discoloration, blistering, peeling, etc.). evaluated.
<Evaluation criteria>
○: No change in appearance Δ: Slight change in appearance ×: Significant change in appearance seen

  From the results of Table 1, the anti-fogging coating agent of the present invention is superior in anti-fogging property and its durability, strength of the coating film, and adhesion to glass compared with the comparative ones, and is cured. Is excellent in moisture resistance.

  The anti-fogging coating agent of the present invention is excellent in anti-fogging property and its durability, the strength of the coating film, and the adhesion to glass. Therefore, visibility such as glass for automobiles, washstands, and mirrors for baths is necessary. It can be used widely for various glass applications and is extremely useful.

Claims (6)

  (Co) polymer (A1) having only a polymerizable unsaturated monomer (a) having a carboxyl group and / or an acid anhydride group as a constituent unit and / or the monomer (a) and a carboxyl group and / or an acid anhydride A (co) polymer (A2) comprising a (co) polymer (A2) having a polymerizable unsaturated monomer (b) having no group as a structural unit, a carboxyl group and / or an acid anhydride in (A) Crosslinker (B) having at least two functional groups capable of reacting with groups to form covalent bonds, alkali metal and / or alkaline earth metal hydroxides (C), and water and / or organic solvents (D) An antifogging coating agent (X) comprising   (B) is at least selected from the group consisting of amino alcohol (B1), polyamine (B2), polyol (B3), polyepoxide (B4), polyisocyanate (B5), polycarbodiimide (B6) and polyoxazoline (B7). The antifogging coating agent according to claim 1, which is one type.   The total moles of functional groups in (B) that can react with the carboxyl groups in (A) and form covalent bonds with respect to the number of moles of carboxyl groups derived from the carboxyl groups and / or acid anhydride groups in (A). The antifogging coating agent according to claim 1 or 2, wherein the number ratio (γ1) is 0.1 to 0.9.   The ratio (γ2) of the number of moles of the hydroxide ion derived from (C) to the number of moles of the carboxyl group derived from the carboxyl group and / or the acid anhydride group in (A) is 0.1 to 0.9. The antifogging coating agent according to any one of claims 1 to 3.   An antifogging article obtained by applying the antifogging coating agent according to claim 1 and curing by heating.   The anti-fogging coating film formed by heat-hardening the anti-fogging coating agent in any one of Claims 1-4.