JP2017179174A - Catalyst for antifogging agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for an antifogging agent composition having antifogging performance generally required for a vehicle lighting tool and forming an antifogging coated film of which water sagging mark is extremely inconspicuous even after drying water sagging, an antifogging agent composition containing the same and a resin member having the antifogging coated film formed therefrom.SOLUTION: There is provided a catalyst (A) for antifogging composition which is a (meth)acrylate copolymer formed from a monomer mixture containing a vinyl monomer having a sulfonic group (a1), a (meth)acrylamide monomer (a2), a methoxy ethylene glycol group-containing (meth)acrylate monomer (a3) and an alkyl group-containing (meth)acrylate monomer (a4) with (a) of 4 to 19 wt.%, (a2) and (a3) of total 40 to 80 wt.% and (a4) of 10 to 48 wt.% based on the monomer mixture of the (a1) to (a4) component.SELECTED DRAWING: None

Description

  The present invention relates to a catalyst for an antifogging agent composition, an antifogging agent composition containing the same, and a resin member having an antifogging coating film formed therefrom.

  In vehicle lamps such as automobile headlamps, high humidity air may enter the lamp chamber, the lens may be cooled by outside air, rain, or the like, and moisture may condense on the inner surface of the lens, resulting in cloudiness. As a result, the brightness of the vehicle light decreases and the aesthetic appearance of the lens surface may be impaired, which may cause discomfort to the user. In order to prevent such fogging of the inner surface of the lens, a method of coating an antifogging agent composition on the inner surface of the lens to form an antifogging coating film is known.

  As an antifogging agent composition, an antifogging agent composition containing a block or graft copolymer composed of a hydrophilic polymer part and a hydrophobic polymer part, and an acidic phosphoric acid alkyl ester catalyst is known. (Patent Document 1).

JP 2003-105255 A

  In general, in a vehicle lamp such as a lamp provided with an anti-fogging coating, when the inside of the lamp is filled with high-humidity air, a water film is formed on the anti-fogging coating to prevent fogging of the lens inner surface. it can. However, at this time, if the inside of the lamp is filled with excessively high-humidity air, the thickness of the water film increases and water sagging may occur on the lens inner surface. And after this water sauce dried, the phenomenon which the coating film of this part whitened as a water sauce trace may be recognized.

  When the present inventors examined the cause of the water sagging trace, after the low molecular weight compound such as the catalyst contained in the antifogging agent composition was eluted into the water film and the water sagging part was dried, these compounds were coated. I found out that it would agglomerate on the surface.

  The present invention provides an antifogging agent composition that has an antifogging performance generally required for vehicle lamps such as lamps, and that can form an antifogging coating film in which water dripping traces are very inconspicuous even after drying the water dripping. It aims at providing the resin member which has the catalyst for objects, the anti-fogging agent composition containing this, and the anti-fogging coating film formed from this.

  As a result of intensive investigations to solve the above problems, the present inventors have made the catalyst used in the antifogging agent composition a (meth) acrylate copolymer formed from a specific monomer mixture. The anti-fogging coating film obtained from the anti-fogging agent composition containing the same has been found to have excellent anti-fogging properties and performance in which water dripping traces are not very noticeable.

［前記一般式（１）中、Ｒ^１は水素原子又はメチル基、ＸはＯ又はＮＨ、Ｒ^２は炭素数１〜４の直鎖又は分岐鎖アルキレン基である。］、
下記一般式（２）で表される（メタ）アクリルアミド系単量体（ａ２）

［前記一般式（２）中、Ｒ^３は水素原子又はメチル基、Ｒ^４は水素原子又は炭素数１〜４の直鎖アルキル基であり、Ｒ^５は炭素数１〜４の直鎖アルキル基であり、Ｒ^４及びＲ^５はそれぞれ同一でもよく、異なっていてもよい。］、
下記一般式（３）で表されるメトキシエチレングリコール基含有（メタ）アクリレート系単量体（ａ３）

［前記一般式（３）中、Ｒ^６は水素原子又はメチル基、ｎはオキシエチレン基の平均付加モル数を示す１〜９である。］、及び
下記一般式（４）で表されるアルキル基含有（メタ）アクリレート系単量体（ａ４）

［前記一般式（４）中、Ｒ^７は水素原子又はメチル基、Ｒ^８は炭素数１〜４の直鎖又は分岐鎖アルキル基である。］を含む、単量体混合物から形成される（メタ）アクリレート共重合体であり、
前記（ａ１）〜（ａ４）成分の単量体混合物に対し、スルホン酸基を有するビニル系単量体（ａ１）を４〜１９重量％、（メタ）アクリルアミド系単量体（ａ２）及びメトキシエチレングリコール基含有（メタ）アクリレート系単量体（ａ３）の合計を４０〜８０重量％、並びにアルキル基含有（メタ）アクリレート系単量体（ａ４）を１０〜４８重量％含む、防曇剤組成物用の触媒、に関する。 That is, the present invention is a catalyst (A) used in an antifogging agent composition,
The catalyst (A) is a vinyl monomer (a1) having a sulfonic acid group represented by the following general formula (1)

[In the general formula (1), R ¹ is a hydrogen atom or a methyl group, X is O or NH, and R ² is a linear or branched alkylene group having 1 to 4 carbon atoms. ],
(Meth) acrylamide monomer (a2) represented by the following general formula (2)

[In the general formula (2), R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and R ⁵ is a linear alkyl group having 1 to 4 carbon atoms. R ⁴ and R ⁵ may be the same or different. ],
Methoxyethylene glycol group-containing (meth) acrylate monomer (a3) represented by the following general formula (3)

[In the general formula (3), R ⁶ is a hydrogen atom or a methyl radical, n is 1-9 showing an average addition molar number of oxyethylene groups. And an alkyl group-containing (meth) acrylate monomer (a4) represented by the following general formula (4)

[In the general formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms. A (meth) acrylate copolymer formed from a monomer mixture,
4 to 19% by weight of vinyl monomer (a1) having a sulfonic acid group, (meth) acrylamide monomer (a2) and methoxy with respect to the monomer mixture of the components (a1) to (a4). Antifogging agent comprising 40 to 80% by weight of total of ethylene glycol group-containing (meth) acrylate monomer (a3) and 10 to 48% by weight of alkyl group-containing (meth) acrylate monomer (a4) Relates to a catalyst for the composition.

  The weight average molecular weight (Mw) of the catalyst (A) for the antifogging agent composition of the present invention is preferably 5,000 or more and 100,000 or less.

  The present invention includes a catalyst (A) for the antifogging agent composition, a block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion, and a surfactant (C). The present invention relates to an antifogging agent composition.

  The antifogging composition of the present invention is a copolymer in which the hydrophilic polymer portion is formed from a monomer mixture containing a vinyl monomer having an N-methylol group and / or an N-alkoxymethylol group. A hydrophilic polymer portion consisting of

  In the antifogging agent composition of the present invention, the catalyst (A) is added in an amount of 5 to 35 wt% with respect to 100 wt parts of the block or graft copolymer (B) having the hydrophilic polymer portion and the hydrophobic polymer portion. It is preferable to include a part.

  The anti-fogging agent composition of the present invention is a block or graft copolymer in which the anti-fogging agent composition further contains a solvent and has the catalyst (A), the hydrophilic polymer portion and the hydrophobic polymer portion. It is preferable that the solvent is contained in an amount of 200 to 2000 parts by weight with respect to 100 parts by weight in total of (B).

  The present invention relates to a resin member having a cured coating film formed from the antifogging agent composition.

  According to the catalyst for an antifogging agent composition of the present invention, the antifogging coating film obtained by the antifogging agent composition containing the same exhibits excellent antifogging properties and the occurrence of water dripping traces is extremely high. Since it is not conspicuous, it is possible to provide a catalyst for an antifogging agent composition that can impart an effect of preventing water dripping to the antifogging coating film.

  The mechanism of action of the present invention is that the catalyst (A) for the antifogging agent composition is a (meth) acrylate copolymer formed from a specific monomer mixture, and thus includes an antifogging agent composition. In the water film formed on the anti-fogging coating film obtained from the above, since the catalyst (A) is not easily eluted, even when water sagging occurs, the water sagging trace of the coating film becomes very inconspicuous. ,It is estimated to be.

  Moreover, since the said specific monomer mixture contains a specific amount of monomer (a1)-(a4), the (meth) acrylate copolymer formed from these is the main component of an antifogging agent composition. Since the structure is similar to the block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion, the antifogging coating film obtained from the antifogging agent composition containing these is It is estimated that antifogging performance generally required for vehicle lamps such as headlamps can be developed.

  Furthermore, the hydrophilic polymer portion of the block or graft copolymer is a copolymer formed from a monomer mixture containing a vinyl monomer having an N-methylol group and / or an N-alkoxymethylol group. In this case, it is presumed that the catalyst (A) promotes these dehydration or dealcohol condensation condensation reactions.

  The catalyst (A) used in the antifogging agent composition of the present invention is a (meth) acrylate copolymer formed from a monomer mixture containing specific amounts of monomers (a1) to (a4).

［前記一般式（１）中、Ｒ^１は水素原子又はメチル基、ＸはＯ又はＮＨ、Ｒ^２は炭素数１〜４の直鎖又は分岐鎖アルキレン基である。］ <Monomer (a)>
The monomer (a1) of the present invention is a vinyl monomer having a sulfonic acid group represented by the following general formula (1), and improves the function as an acid catalyst and the hydrophilicity of the antifogging coating film. It has a function.

[In the general formula (1), R ¹ is a hydrogen atom or a methyl group, X is O or NH, and R ² is a linear or branched alkylene group having 1 to 4 carbon atoms. ]

  In the monomer (a1), examples of the compound represented by the general formula (1) include 2- (meth) acrylamido-2-methylpropanesulfonic acid, 2-((meth) acryloyloxy) ethanesulfonic acid, 3-((meth) acryloyloxy) -1-propanesulfonic acid and the like. As the monomer (a1), at least one type may be used, and two or more types may be used in combination.

  The monomer (a1) is 2- (meth) acrylamide in which X in the general formula (1) is NH from the viewpoint of high effect as an acid catalyst and high hydrophilic effect of the antifogging coating film. -2-Methylpropanesulfonic acid is preferred.

［前記一般式（２）中、Ｒ^３は水素原子又はメチル基、Ｒ^４は水素原子又は炭素数１〜４の直鎖アルキル基であり、Ｒ^５は炭素数１〜４の直鎖アルキル基であり、Ｒ^４及びＲ^５はそれぞれ同一でもよく、異なっていてもよい。］ <Monomer (a2)>
The monomer (a2) of the present invention is a (meth) acrylamide monomer represented by the following general formula (2), and has a function of increasing the hydrophilicity of the antifogging coating film.

[In the general formula (2), R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and R ⁵ is a linear alkyl group having 1 to 4 carbon atoms. R ⁴ and R ⁵ may be the same or different. ]

  In the monomer (a2), examples of the compound represented by the general formula (2) include (meth) acrylamide, N-methylacrylamide, N, N-dimethyl (meth) acrylamide, and N-ethyl (meth) acrylamide. N, N-diethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide and the like. Monomer (b) should just use at least 1 type and can be used in combination of 2 or more type.

  The monomer (a2) is preferably N, N-dimethyl (meth) acrylamide or N, N-diethyl (meth) acrylamide from the viewpoint of a high effect of enhancing the hydrophilicity of the antifogging coating film.

［前記一般式（３）中、Ｒ^６は水素原子又はメチル基、ｎはオキシエチレン基の平均付加モル数を示す１〜９である。］ <Monomer (a3)>
The monomer (a3) of the present invention is a methoxyethylene glycol group-containing (meth) acrylate monomer represented by the following general formula (3), and has a function of increasing the hydrophilicity of the antifogging coating film.

[In the general formula (3), R ⁶ is a hydrogen atom or a methyl radical, n is 1-9 showing an average addition molar number of oxyethylene groups. ]

  In the monomer (a3), examples of the compound represented by the general formula (3) include methoxypolyethylene glycol (meth) acrylate having an oxyethylene group having an average addition mole number of 1 to 9. As the monomer (a3), at least one type may be used, and two or more types may be used in combination.

［前記一般式（４）中、Ｒ^７は水素原子又はメチル基、Ｒ^８は炭素数１〜４の直鎖又は分岐鎖アルキル基である。］ <Monomer (a4)>
The monomer (a4) of the present invention is an alkyl group-containing (meth) acrylate monomer represented by the following general formula (4), and has a hydrophilic polymer portion and a hydrophobic polymer portion described later. It has a function of increasing the compatibility with the block or graft copolymer (B) and a function of preventing abnormal appearance of the antifogging coating film in the steam antifogging test.

[In the general formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms. ]

  In the monomer (a4), the compound represented by the general formula (4) includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate and the like. As the monomer (a4), at least one type may be used, and two or more types may be used in combination.

  The monomer (a4) has an effect of increasing the compatibility of the block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion, which will be described later, and an anti-fogging property in a steam antifogging test. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate are preferred from the viewpoint of a high effect of preventing appearance abnormality of the cloudy coating film.

<Other monomers>
As other monomers other than (a1) to (a4), known monomers other than (a1) to (a4) can be used. However, a vinyl monomer having a functional group that undergoes a crosslinking reaction due to the acid catalyst function of (a1), such as a vinyl monomer having an N-methylol group or an N-alkoxymethylol group, is a catalyst (A). From the viewpoint of enhancing the storage stability of the monomer mixture, it is preferably not contained in the monomer mixture.

  Below, in the catalyst (A) of this invention, the ratio of each monomer component in the monomer mixture which forms a (meth) acrylate copolymer is demonstrated. Each monomer in the monomer mixture forms a (meth) acrylate copolymer at the following predetermined ratio, and this (meth) acrylate copolymer has the above-described function of each monomer. In addition, it can also have a function of making the water drip trace of the anti-fogging coating very inconspicuous.

  The ratio of the monomer (a1) to the monomer mixture of the components (a1) to (a4) is 4 to 19% by weight. The ratio of the monomer (a1) to the monomer mixture of the components (a1) to (a4) greatly increases the effect of the catalyst (A) as an acid catalyst, and the water dripping trace of the antifogging coating film. From the viewpoint of enhancing the effect of making it less noticeable, 5% by weight or more is preferable, and 8% by weight or more is more preferable. The ratio of the monomer (a1) to the monomer mixture of the components (a1) to (a4) is preferably 17% by weight or less from the viewpoint of preventing appearance abnormality of the antifogging coating film in the steam antifogging test. 15% by weight or less is more preferable.

  The total ratio of the monomers (a2) and (a3) to the monomer mixture of the components (a1) to (a4) is 40 to 80% by weight. The total ratio of the monomers (a2) and (a3) to the monomer mixture of the components (a1) to (a4) is 45 from the viewpoint of enhancing the effect of making the water spill marks of the antifogging coating very inconspicuous. % By weight or more is preferable, and 50% by weight or more is more preferable. The total ratio of the monomers (a2) and (a3) to the monomer mixture of the components (a1) to (a4) is 75% by weight from the viewpoint of enhancing the effect of making the water spill marks of the antifogging coating very inconspicuous. % Or less is preferable, and 70% by weight or less is more preferable.

  The ratio of the monomer (a2) to the monomer mixture of the components (a1) to (a4) is 10% by weight or more from the viewpoint of enhancing the effect of making the water sagging trace of the antifogging coating very inconspicuous. Preferably, 12 weight% or more is more preferable. The ratio of the monomer (a2) to the monomer mixture of the components (a1) to (a4) is preferably 50% by weight or less from the viewpoint of enhancing the effect of making the water drip trace of the antifogging coating very inconspicuous. 40% by weight or less is more preferable.

  The ratio of the monomer (a3) to the monomer mixture of the components (a1) to (a4) is 20% by weight or more from the viewpoint of enhancing the effect of making the water sagging marks of the antifogging coating very inconspicuous. Preferably, 25 weight% or more is more preferable. The ratio of the monomer (a3) to the monomer mixture of the components (a1) to (a4) is preferably 50% by weight or less from the viewpoint of enhancing the effect of making the water spillage of the antifogging coating very inconspicuous. 45% by weight or less is more preferable.

  The ratio of the monomer (a4) to the monomer mixture of the components (a1) to (a4) is 10 to 48% by weight. The ratio of the monomer (a4) to the monomer mixture of the components (a1) to (a4) is the effect of preventing the appearance abnormality of the antifogging coating film in the steam antifogging test, and the water of the antifogging coating film From the viewpoint of enhancing the effect of making the sagging trace very inconspicuous, the content is preferably 12% by weight or more, and more preferably 15% by weight or more. The ratio of the monomer (a4) to the monomer mixture of the components (a1) to (a4) is preferably 45% by weight or less from the viewpoint of enhancing the effect of making the water spill marks of the antifogging coating very inconspicuous. 40% by weight or less is more preferable.

<Method for producing (meth) acrylate copolymer>
The (meth) acrylate copolymer can be obtained by copolymerizing the monomer mixture. The structure of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, but an antifogging agent composition including antifogging properties. The random copolymer is preferable from the viewpoint that the effect of the antifogging agent composition can be easily prepared. As a polymerization method for obtaining a copolymer, various known polymerization methods such as a radical polymerization method, a cationic polymerization method, an anion living polymerization method, and a cation living polymerization method are adopted. The radical polymerization method is preferred from the viewpoint of performance over many meanings. As the radical polymerization method, a normal bulk polymerization method, suspension polymerization method, solution polymerization method, emulsion polymerization method, etc. are adopted, but the solution polymerization method can be used as it is for the antifogging agent composition after polymerization. Is preferred.

  In the solution polymerization method, a solvent having a remarkably high boiling point with respect to the polymerization solvent may impair the adhesion of the coating film to the substrate due to the residual solvent during drying and heat curing of the coating film. It is preferable to use a solvent having Examples of such a polymerization solvent include alcohol solvents such as methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, s-butanol, t-butanol, diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol Alcohol ether solvents such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Ketone solvents such as tetrahydrofuran, dioxane, etc .; methyl acetate, ethyl acetate, N-butyl acetate, isobutyl acetate, t-butyl acetate, milk An ester solvent such as methyl acid or ethyl lactate; an aromatic solvent such as benzene, toluene or xylene; an amide solvent such as formamide or dimethylformamide; water or the like is used. These polymerization solvents should just use at least 1 sort (s), and can use them in combination of 2 or more sorts.

  The monomer mixture of the components (a1) to (a4) is easy to carry out industrial production by suppressing polymerization heat generation in a total of 100 parts by weight of the monomer mixture (a1) to (a4) and the polymerization solvent. Therefore, the amount is preferably 50 parts by weight or less, and more preferably 40 parts by weight or less.

  As the radical polymerization initiator used in the radical polymerization method, generally used organic peroxides, azo compounds, and the like can be used. Organic peroxides include benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-hexanoate, t-butylperoxypivalate, t-hexylperoxypi Valate etc. are mentioned. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and the like. It is preferable that the usage-amount of a radical polymerization initiator is 0.01-5 weight part with respect to 100 weight part of monomer mixtures of (a1)-(a4). The radical polymerization initiator is preferably polymerized while being dropped into the reaction vessel in terms of easy control of the heat generated by polymerization. Although the temperature which performs a polymerization reaction is suitably changed with the kind of radical polymerization initiator to be used, when manufacturing industrially, it is preferably 30-150 degreeC, More preferably, it is 40-100 degreeC.

  The weight average molecular weight (Mw) of the (meth) acrylate copolymer is preferably 5,000 or more, more preferably 8,000 or more, and further preferably 10,000 or more. The weight average molecular weight (Mw) of the (meth) acrylate copolymer is preferably 100,000 or less, and more preferably 50,000 or less.

  The antifogging agent composition of the present invention comprises a catalyst (A), a block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion, and a surfactant (C).

<Hydrophilic polymer portion forming block or graft copolymer (B)>
The hydrophilic polymer portion of the present invention is preferably a copolymer formed from a monomer mixture containing a water-soluble vinyl monomer, and has an N-methylol group and / or an N-alkoxymethylol group. It is preferably a copolymer formed from a monomer mixture containing a vinyl monomer having

<Water-soluble vinyl monomer>
Examples of the water-soluble vinyl monomer include (meth) acrylamide, N-methylacrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -Propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (2-dimethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, diacetone (meth) acrylamide, N -Nitrogen-containing vinyl monomers such as (meth) acryloylpiperidine, N- (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, 4-vinylpyridine; methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (Meta) Acry Over DOO, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) alkoxy alkylene glycol group-containing vinyl monomers such as acrylate. As the water-soluble vinyl monomer, at least one kind may be used, and two or more kinds may be used in combination.

  The water-soluble vinyl monomer is N, N-dimethyl (meth) acrylamide, N, N-diethylacrylamide, oxyethylene having an average addition mole number of 1 to 10 from the viewpoint of enhancing the antifogging property of the antifogging coating film. A methoxypolyethylene glycol (meth) acrylate having a group and a methoxypolypropylene glycol (meth) acrylate having an oxypropylene group having an average addition mole number of 1 to 10 are preferred.

  The proportion of the water-soluble vinyl monomer in the monomer mixture forming the hydrophilic polymer portion is preferably 50% by weight or more and 95% by weight or less from the viewpoint of improving the antifogging property of the antifogging coating film. It is more preferably 55% by weight or more and 80% by weight.

<Vinyl monomer having an N-methylol group and / or an N-alkoxymethylol group>
Examples of the vinyl monomer having an N-methylol group and / or an N-alkoxymethylol group include N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N -Butoxymethyl (meth) acrylamide etc. are mentioned. As the vinyl monomer having an N-methylol group and / or an N-alkoxymethylol group, at least one type may be used, and two or more types may be used in combination.

  From the viewpoint of improving the antifogging property of the antifogging coating film, the vinyl monomer having the N-methylol group and / or the N-alkoxymethylol group is N-methylol (meth) acrylamide, N-methoxymethyl (meth). Acrylamide is preferred.

  The proportion of the vinyl monomer having an N-methylol group and / or N-alkoxymethylol group in the monomer mixture forming the hydrophilic polymer portion is preferably 5% by weight or more and 50% by weight or less. More preferably, the weight percent is 20% by weight or more.

<Other monomers>
As other monomers other than the vinyl monomer having a water-soluble vinyl monomer, N-methylol group and / or N-alkoxymethylol group forming the hydrophilic polymer part, a known single monomer The body can be used. From the viewpoint of allowing dehydration or dealcoholization condensation crosslinking reaction with the vinyl monomer having the N-methylol group and / or N-alkoxymethylol group, it is preferable to use a vinyl monomer having a hydroxyl group. From the viewpoint of increasing the hardness of the cloudy coating film, it is preferable to use a vinyl monomer having a linear or branched alkyl group having 1 to 4 carbon atoms.

  Examples of the vinyl monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. -Vinyl monomers added with 1 mol of caprolactone may be mentioned. As the vinyl monomer having a hydroxyl group, at least one kind may be used, and two or more kinds may be used in combination.

  Examples of the (meth) acrylate monomer having a linear or branched alkyl group having 1 to 4 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Examples include butyl (meth) acrylate, isobutyl (meth) acrylate, and tertiary butyl (meth) acrylate. At least one kind of the linear or branched alkyl group-containing vinyl monomer having 1 to 4 carbon atoms may be used, and two or more kinds may be used in combination.

<Hydrophobic polymer portion forming block or graft copolymer (B)>
The hydrophobic polymer portion of the present invention is preferably a copolymer formed from a monomer mixture containing a water-insoluble vinyl monomer.

  Examples of the water-insoluble vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tertiary. Linear or branched alkyl group-containing vinyl monomers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; styrene, vinyltoluene, α-methyl Aromatic vinyl monomers such as styrene; acrylonitrile and the like. As the water-insoluble vinyl monomer, at least one kind may be used, and two or more kinds may be used in combination.

  The water-insoluble vinyl monomer is preferably methyl (meth) acrylate or ethyl (meth) acrylate from the viewpoint of improving the adhesion between the antifogging coating film and the substrate.

  The proportion of the water-insoluble vinyl monomer in the monomer mixture forming the hydrophobic polymer portion is 85% by weight or more and 99% by weight from the viewpoint of improving the adhesion between the antifogging coating film and the substrate. The following are preferable, and 90 to 98 weight% is more preferable.

<Other monomers>
As other monomers other than the water-insoluble vinyl monomer, known monomers other than the water-insoluble vinyl monomer can be used. From the viewpoint of enhancing the transparency of the antifogging coating film, it is preferable to use a vinyl monomer containing an acid group.

  Examples of the vinyl monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, 2-sulfoethyl (meth) acrylate, 2-acrylamido-2-methylsulfonic acid, and the like. As the vinyl monomer containing an acid group, at least one kind may be used, and two or more kinds may be used in combination.

  The proportion of the vinyl monomer containing an acid group in the monomer mixture forming the hydrophobic polymer portion is preferably 1% by weight to 15% by weight, and more preferably 2% by weight to 12% by weight. preferable.

<Block or graft copolymer (B)>
The block or graft copolymer (B) of the present invention is a copolymer having the hydrophilic polymer portion and the hydrophobic polymer portion.

  The content of the monomer mixture forming the hydrophilic polymer portion is a viewpoint of improving the antifogging property of the antifogging coating film with respect to 100 parts by weight of the monomer mixture forming the block or graft copolymer. Therefore, 40 parts by weight or more is preferable, and 50 parts by weight or more is more preferable. The content of the monomer mixture forming the hydrophilic polymer portion is such that the adhesion between the antifogging coating and the substrate is 100 parts by weight of the monomer mixture forming the block or graft copolymer. From the viewpoint of increasing, 80 parts by weight or less is preferable, and 70 parts by weight or less is more preferable.

  The content of the monomer mixture forming the hydrophobic polymer portion is such that the adhesion between the antifogging coating film and the substrate is 100 parts by weight of the monomer mixture forming the block or graft copolymer. From the viewpoint of increasing the amount, 20 parts by weight or more is preferable, and 30 parts by weight or more is more preferable. The content of the monomer mixture forming the hydrophobic polymer portion is from the viewpoint of increasing the antifogging property of the antifogging coating film with respect to 100 parts by weight of the monomer mixture forming the block or graft copolymer. 60 parts by weight or less is preferable, and 50 parts by weight or less is more preferable.

<Method for producing block copolymer>
The block copolymer of the present invention can be carried out by various known polymerization methods such as radical polymerization, cationic polymerization, anion living polymerization, and cation living polymerization.

The radical solution polymerization method using the polymer peroxide is a radical in which at least one polymer peroxide compound having a structure represented by the following general formulas (I), (II), and (III) is used as a polymerization initiator. The polymerization method is preferable from the viewpoint of industrially producing the block copolymer in large quantities and efficiently.
General formula (I): [—CO (CH ₂ ) ₄ COO (C ₂ H ₄ O) ₃ CO (CH ₂ ) ₄ CO—OO—] _p
Formula (II): [—CO (CH ₂ ) ₇ CO—OO—] _q
Formula (III): [—CO (CH ₂ ) ₆ CH (CH ₂ CH ₃ ) (CH ₂ ) ₉ CO—OO—] _r
[In the general formulas (I) to (III), p, q and r are all integers of 2 to 20. ]

  In the radical solution polymerization method using the polymeric peroxide, first, a polymerization solvent is added to a reactor equipped with a stirrer and a thermometer and heated at a temperature of 60 to 80 ° C. Next, either one of the polymeric peroxide compound and a monomer mixture forming a hydrophilic polymer part or a monomer mixture forming a hydrophobic polymer part is added over 30 minutes to 3 hours, Furthermore, a polymerization reaction is performed for 30 minutes to 3 hours to synthesize a block copolymer precursor. Then, the temperature is raised by 5 to 20 ° C., and the monomer mixture forming the other polymer portion is added over 30 minutes to 3 hours, and the polymerization reaction is further carried out for 30 minutes to 5 hours. How to get.

<Method for producing graft copolymer>
The graft copolymer of the present invention can be carried out by various known polymerization methods such as radical polymerization, cationic polymerization, anion living polymerization, and cation living polymerization.

The radical polymerization method using the vinyl monomer having a peroxide bond is a radical polymerization method using a vinyl monomer having a structure represented by the following general formula (IV) or (V). From the viewpoint that the copolymer can be produced industrially in large quantities and efficiently, it is preferable.
Formula ^{_{(IV): CH 2 = CR}} 12 -COO-CH 2 CH 2 OCO-OOC (CH 3) 3
Formula ^{_{(V): CH 2 = CR}} 13 -CH 2 OCO-OOC (CH 3) 3
[In the formulas (IV) and (V), R ¹² and R ¹³ are a hydrogen atom or a methyl group. ]

  In the radical polymerization method using a vinyl monomer having a peroxide bond, a polymerization solvent is first added to a reactor equipped with a stirrer and a thermometer, and heated at a temperature of 70 to 90 ° C. Next, a vinyl monomer having a peroxide bond, a radical polymerization initiator, a monomer mixture forming a hydrophilic polymer part, or a monomer forming a hydrophobic polymer part (B) Either one of the mixture is added over 30 minutes to 3 hours, and a polymerization reaction is further performed for 30 minutes to 3 hours to synthesize a graft copolymer precursor. The polymerization reaction at this time is based on the decomposition of only the radical polymerization initiator, and it is necessary to set a temperature condition that does not cause the decomposition of the peroxide bond of the vinyl monomer having a peroxide bond. Then, the temperature is increased by 10 to 30 ° C., and the monomer mixture that forms the other polymer portion is taken for 30 minutes to 3 hours under the condition that the peroxide bond of the vinyl monomer having a peroxide bond is decomposed. And a polymerization reaction is further performed for 30 minutes to 5 hours to obtain a graft copolymer.

  The weight average molecular weight (Mw) of the block or graft copolymer (B) having the hydrophilic polymer portion and the hydrophobic polymer portion reduces the elution component from the antifogging coating film, From the viewpoint of enhancing the effect of making the mark very inconspicuous, 5,000 or more is preferable, and 8,000 or more is more preferable. The weight average molecular weight (Mw) of the block or graft copolymer is preferably 100,000 or less, and more preferably 50,000 or less.

The weight average molecular weight (Mw) of the block or graft copolymer (B) having the hydrophilic polymer portion and the hydrophobic polymer portion can be determined by the GPC method. The sample can be measured under the following conditions using a sample prepared by dissolving the sample in THF to obtain a 0.3 wt% solution and filtering through a 0.25 μm membrane filter.
<Measurement of weight average molecular weight (Mw)>
・ Analyzer: TOSOH HLC-8320GPC
Columns 1 and 2: TSKgel SuperMultibipore HZ-M
-Column 3: TSKgel Super H-RC
-Column size: 15 cm x 4.6 mmφ (all three)
・ Eluent: THF
・ Flow rate: 35 ml / min
・ Detector: RI
-Column temperature: 40 ° C
Standard sample: polystyrene

  Since the block or graft copolymer (B) having the hydrophilic polymer portion and the hydrophobic polymer portion is composed of polymer portions having different properties such as a hydrophilic polymer portion and a hydrophobic polymer portion, As the polymerization solvent, it is preferable to use an organic solvent having an affinity for both the polymer portions. The organic solvent is preferably an organic solvent having a boiling point of less than 180 ° C. from the viewpoint of preventing a decrease in adhesion between the antifogging coating film and the substrate due to the residual organic solvent in low temperature drying.

  Examples of the polymerization solvent for the block or graft copolymer (B) having the hydrophilic polymer portion and the hydrophobic polymer portion include alcohol solvents such as methanol, ethanol, isopropanol, diacetone alcohol; ethylene glycol monomethyl ether Alcohol ether solvents such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol; methyl ethyl ketone, methyl isobutyl ketone, Examples include ketone solvents such as cyclohexanone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as methyl acetate, ethyl acetate, methyl lactate, and ethyl lactate. As the polymerization solvent, at least one kind may be used, and two or more kinds may be used in combination.

  The content of the catalyst (A) is preferably 5 to 35 parts by weight with respect to 100 parts by weight of the block or graft copolymer (B) having a hydrophilic polymer part and a hydrophobic polymer part. The content of the catalyst (A) is a block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion from the viewpoint of preventing abnormal appearance of the antifogging coating film in the steam antifogging test. ) 6 parts by weight or more is preferable with respect to 100 parts by weight, and 10 parts by weight or more is more preferable. The content of the catalyst (A) is a block or graft copolymer having a hydrophilic polymer portion and a hydrophobic polymer portion (from the viewpoint of expressing the antifogging property of the antifogging coating film in the steam antifogging test). B) 30 parts by weight or less is preferable with respect to 100 parts by weight, and 28 parts by weight or less is more preferable.

<Surfactant (C)>
The surfactant (C) of the present invention is a component for improving the antifogging property by reducing the surface tension of water adhering to the coating film surface and forming a water film on the coating film surface. As the surfactant (C), all conventionally known surfactants can be used, such as nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants. Can be mentioned. As the surfactant (C), at least one kind may be used, and two or more kinds may be used in combination. Among these, it is preferable that at least one or more anionic surfactants are contained from the viewpoint of durability of the effect, and a combination of a nonionic surfactant and an anionic surfactant is more preferable.

  Examples of the nonionic surfactant include polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenol. Polyoxyethylene alkyl aryl ethers, polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate, polypropylene glycol ethylene oxide adducts, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, etc. Ethylene sorbitan fatty acid esters, alkyl phosphate esters, polyoxyethylene alkyl ether phosphate esters, etc. Phosphate esters, sugar esters, cellulose ethers are used.

  Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium oleate, higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzenes such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate. Sulfonates and alkyl naphthalene sulfonates, naphthalene sulfonic acid formalin condensates, dialkyl sulfosuccinates, dialkyl phosphate salts, polyoxyethylene sulfate salts such as sodium polyoxyethylene alkylphenyl ether sulfate, and the like are used.

  Examples of the cationic surfactant include ethanolamines, laurylamine acetate, triethanolamine monoformate, amine salts such as stearamide ethyl diethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dilauryldimethylammonium. Quaternary ammonium salts such as chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride are used.

  Examples of the zwitterionic surfactant include fatty acid type zwitterionic surfactants such as dimethylalkyl lauryl betaine and dimethylalkyl stearyl betaine, sulfonic acid type zwitterionic surfactants such as dimethylalkylsulfobetaine, and alkylglycine. Is used.

  The content of the surfactant (C) is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the block or graft copolymer (B) from the viewpoint of improving the antifogging property of the antifogging coating film. More preferred are parts by weight. The content of the surfactant (C) is 100 parts by weight of the block or graft copolymer (B) from the viewpoint of increasing the transparency of the antifogging coating film and from the viewpoint of increasing the adhesion between the antifogging coating film and the substrate. The amount is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less.

  As a mixing method of the surfactant (C) and the block or graft copolymer (B), the block or graft copolymer (B) is dissolved in a solvent described later and the surfactant (C ) Or a surfactant (C) may be added together with the production of the block or graft copolymer (B).

  The antifogging composition of the present invention preferably further contains a solvent.

  The solvent includes a polymerization solvent for the catalyst (A), a polymerization solvent for the block or graft copolymer (B) having the hydrophilic polymer portion and the hydrophobic polymer portion, and a dilution solvent. The dilution solvent is used for the purpose of adjusting the solid content and viscosity suitable for coating the antifogging agent composition. As the diluting solvent, it is preferable to use a polymerization solvent for the catalyst (A) and / or a polymerization solvent for the block or graft copolymer (B) having the hydrophilic polymer portion and the hydrophobic polymer portion.

  The content of the solvent is preferably 200 to 2000 parts by weight with respect to 100 parts by weight in total of the catalyst (A) and the block or graft copolymer (B) having a hydrophilic polymer part and a hydrophobic polymer part. . The content of the solvent is a total of 100 weights of the catalyst (A) and the block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion from the viewpoint of enhancing the handling properties of the antifogging agent composition. 300 parts by weight or more is preferable with respect to parts, and 400 parts by weight or more is more preferable. The content of the solvent is a total of 100 weights of the catalyst (A) and the block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion from the viewpoint of improving the paintability of the antifogging agent composition. The amount is preferably 1500 parts by weight or less, more preferably 1000 parts by weight or less, and still more preferably 800 parts by weight or less.

<Other ingredients>
The anti-fogging agent composition of the present invention can contain various conventional additives such as a leveling agent, an antioxidant, an ultraviolet absorber, and a light stabilizer as necessary as other components.

<Manufacture of anti-fogging agent composition>
The antifogging agent composition of the present invention comprises, for example, a catalyst (A) and a block or graft copolymer (B) having a hydrophilic polymer portion and a hydrophobic polymer portion, and a solid content and viscosity adjustment suitable for coating. For the purpose, it can be prepared by adding the solvent (the polymerization solvent or the diluting solvent) and dissolving, dispersing or diluting. The solid content and viscosity suitable for coating differ depending on the coating method, but in the case of the spray coating method, the catalyst (A) and the block or graft having a hydrophilic polymer portion and a hydrophobic polymer portion in the antifogging agent composition The total proportion of the copolymer (B) is preferably 2% by weight or more, more preferably 5% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less.

<Anti-fog coating>
The anti-fogging agent composition of the present invention can form an anti-fogging coating film on the surface of a resin member by coating the resin member by a coating method performed in a normal paint, followed by drying and heat curing.

  As the resin member, a known resin base material can be used regardless of the type, and polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS. Examples of the base material include resins, polyester resins, and polyamide resins.

  When coating the resin member, it is possible to remove adhering foreign matter, degrease, and wash the surface of the resin member before coating for the purpose of increasing the wettability of the antifogging agent composition to the resin member and preventing repellency. preferable. Specific examples include dust removal with high-pressure air or ionized air, ultrasonic cleaning with an aqueous detergent solution or an alcohol solvent, wiping using an alcohol solvent, cleaning with ultraviolet rays and ozone, and the like. As the coating method, a dipping method, a flow coating method, a roll coating method, a bar coating method, a spray coating method and the like are suitable.

  The drying is a step of evaporating and drying the solvent contained in the coating film at a temperature of 20 to 50 ° C. for 0.5 to 5 minutes. The heating temperature is usually 60 to 150 ° C. for 5 to 60 minutes, preferably 70 to 130 ° C. for 10 to 40 minutes. However, it is necessary to set the curing temperature below the heat deformation temperature of the resin member.

  The film thickness of the antifogging coating film is preferably 0.5 μm or more and more preferably 1.0 μm or more from the viewpoint of enhancing the antifogging property of the antifogging coating film. The film thickness of the antifogging coating film is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint of enhancing the smoothness of the antifogging coating film.

  The resin member on which the antifogging coating film is formed is preferably used for a vehicle lamp. Specific vehicle lights include headlamps, auxiliary headlamps, vehicle width lights, number lights, tail lights, parking lights, brake lights, reverse lights, direction indicators, auxiliary direction indicators, emergency flashing indicators, etc. Can be mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these implementation.

<Raw material>
The compounds used in Examples or Comparative Examples are shown below.
<Catalyst (A)>
<Monomer (a1)>
2-acrylamido-2-methylpropanesulfonic acid (AMPS)
2- (Methacryloyloxy) ethanesulfonic acid (MAES)
<Monomer (a2)>
N, N-dimethylacrylamide (DMAA)
N, N-diethylmethacrylamide (DEMAA)
<Monomer (a3)>
Methoxy polyethylene glycol methacrylate (average number of moles of ethylene glycol added 2) (M-20G)
Methoxypolyethylene glycol acrylate (average added mole number of ethylene glycol 9) (AM-90G)
<Monomer (a4)>
Methyl methacrylate (MMA)
Ethyl acrylate (EA)
Butyl acrylate (BA)

<Block or graft copolymer (B)>
<Hydrophilic polymer part>
<Water-soluble vinyl monomer>
N, N-dimethylacrylamide (DMAA)
Methoxy polyethylene glycol methacrylate (average number of moles of ethylene glycol added 2) (M-20G)
<Vinyl monomer having an N-methylol group and / or an N-alkoxymethylol group>
N-methylolacrylamide (N-MAAm)
<Other monomers>
2-Hydroxyethyl methacrylate (2-HEMA)
Methyl methacrylate (MMA)

<Hydrophobic polymer part>
<Water-insoluble monomer>
Methyl methacrylate (MMA)
<Other monomers>
Acrylic acid (AA)
<Polymerization initiator>
Polymeric peroxide (general formula: HO — [— CO (CH ₂ ) ₄ COO (C ₂ H ₄ O) ₃ CO (CH ₂ ) ₄ CO—OO—] ₁₀ —H
t-hexyl peroxyneodecanoate (diluted hydrocarbon (active ingredient 80% by weight), manufactured by NOF Corporation, perhexyl ND)
t- butylperoxy allyl monocarbonate (general _{formula: CH 2 = CH-CH 2} OCO-OOC (CH 3) 3)
<Solvent>
Propylene glycol monomethyl ether (PGM)
<Low molecular catalyst>
Phosphoric acid alkyl ester p-toluenesulfonic acid dodecylbenzenesulfonic acid <surfactant>
Sodium dioctylsulfosuccinate (manufactured by NOF Corporation, trade name: Rapisol A80)
Polyoxyethylene octyl phenyl ether (manufactured by NOF Corporation, trade name: Nonion HS-210)
<Leveling agent>
Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF351-A)

<Measurement of weight average molecular weight (Mw) of catalyst (A)>
The weight average molecular weight (Mw) of the following catalyst (A) was determined by the GPC method. The sample was measured under the following conditions using a catalyst (A) (solution) dissolved in THF to give a 0.3 wt% (solid content) solution filtered through a 0.25 μm membrane filter.
<Measurement of weight average molecular weight (Mw)>
Analyzer: TOSOH HLC-8320GPC
Column 1, 2: TSKgel SuperMultibipore HZ-M
Column 3: TSKgel Super H-RC
Column size: 15 cm x 4.6 mmφ (all three)
Eluent: THF
Flow rate: 35 ml / min
Detector: RI
Column temperature: 40 ° C
Standard sample: Polystyrene

<Example 1>
<Manufacture of catalyst A1 (solution)>
A reactor equipped with a thermometer and a stirrer was charged with 224 parts by weight of PGM as a polymerization solvent, and heated to 80 ° C. while blowing nitrogen gas. The monomer (a1) is 10.0 parts by weight of AMPS, the monomer (b) is 28.2 parts by weight of DMAA, the monomer (c) is 29.3 parts by weight of M-20G, the monomer (D) Mixing of 32.5 parts by weight of MMA, 1 part by weight of hydrocarbon-diluted t-hexylperoxyneodecanoate as a polymerization initiator, and 5 parts by weight of polymeric peroxide dissolved in 9 parts by weight of PGM The liquid was added dropwise over 2 hours. Further, a polymerization reaction was carried out for 1.5 hours to obtain a catalyst A1 (solution) (solid content 30% by weight) comprising a (meth) acrylate copolymer.

<Production of block copolymer B1 (solution)>
A reactor equipped with a thermometer and a stirrer was charged with 233 parts by weight of PGM as a polymerization solvent, and heated to 70 ° C. while blowing nitrogen gas. 2.5 parts by weight of polymeric peroxide as a polymerization initiator, 20 parts by weight of DMAA and 20 parts by weight of M-20G as a water-soluble vinyl monomer forming a hydrophilic polymer part, N-methylol group and / or A mixed solution in which 5 parts by weight of N-MAAm as a vinyl monomer having an N-alkoxymethylol group and 10 parts by weight of MMA as another monomer was dissolved was added dropwise over 2 hours. Furthermore, a polymerization reaction was performed for 2 hours to obtain a block copolymer precursor.
Thereafter, a mixture of 37 parts by weight of MMA as the water-insoluble vinyl monomer forming the hydrophobic polymer portion and 3 parts by weight of AA as the other monomer was added dropwise for 1 hour, Was carried out for 3 hours to obtain a block copolymer B1 (solution) (solid content 30 wt%).

<Manufacture of anti-fogging agent composition>
13.2 parts by weight of catalyst A1 (solution) (4.0 parts by weight of solid), 100 parts by weight of block copolymer B1 (solution) (30 parts by weight of solid), and sodium dioctylsulfosuccinate as a surfactant ( Rapisol A80) 2.3 parts by weight, polyoxyethylene octylphenyl ether (nonion HS-210) 0.45 parts by weight, silicone oil (KF351) as leveling agent 0.09 parts by weight, and PGM as diluent solvent 70 parts by weight was mixed to obtain an antifogging agent composition 1 of Example 1.

<Examples 2 to 15>
<Manufacture of catalyst A2-12 (solution)>
Except having changed into the monomer of Table 1, the catalyst A2-12 (solution) was obtained by the method of Example 1.

<Production of block copolymer B2-3>
Block copolymers B2-3 were obtained by the method described in Example 1 except that the monomers listed in Table 3 were changed.

<Production of graft copolymer B4>
A reactor equipped with a thermometer and a stirrer was charged with 233 parts by weight of PGM as a polymerization solvent, and heated to 85 ° C. while blowing nitrogen gas. 0.5 parts by weight of t-butylperoxyoctanoate and 2 parts by weight of t-butylperoxyallyl monocarbonate as a polymerization initiator, and M-20G as a water-soluble vinyl monomer forming a hydrophilic polymer part 30 parts by weight, 12.5 parts by weight of N-HAAm as a vinyl monomer having an N-methylol group and / or N-alkoxymethylol group, and 7.5 parts by weight of 2-HEMA as another monomer A mixed solution in which 7.5 parts by weight of MMA was dissolved was dropped over 2 hours. Further, a polymerization reaction was performed for 2 hours to obtain a graft copolymer precursor.
Thereafter, a mixture of 37 parts by weight of MMA as a water-insoluble vinyl monomer forming a hydrophobic polymer portion and 3 parts by weight of AA as another monomer was added dropwise over 1 hour, and the temperature was 110 ° C. The polymerization reaction was carried out for 5 hours to obtain a graft copolymer B4 (solution) (solid content 30% by weight).

<Manufacture of anti-fogging agent composition>
The antifogging agent compositions of Examples 2 to 15 were the same as in Example 1 except that the catalyst (A) (solution) and the block or graft copolymer (B) (solution) described in Table 4 were used. I got a thing.

(0) Evaluation of storage stability of catalyst The catalysts A1 to 12 (solution) obtained above were stored at 30 ° C for 7 days, and the liquid state was evaluated visually. The case where no abnormality was observed in the liquid viscosity or the like was rated as ◎, and the case where an increase in the liquid viscosity was recognized as ◯. If the evaluation is ◎, it is more preferable from the viewpoint of practical storage stability. The results are shown in Table 4.

<Creation of anti-fogging coating film>
Each antifoggant composition obtained above is applied to a polycarbonate resin plate by a spray coating method so that the film thickness after curing is 2 to 3 μm, and heat-cured at 120 ° C. for 10 minutes, A test piece of an antifogging coating film was obtained. About these anti-fogging coating films, evaluation of following (1)-(5) was performed. The results are shown in Table 4.

(1) Evaluation of coating film appearance The appearance of the antifogging coating film was visually evaluated. A sample that was colorless and transparent and did not show any abnormalities was marked with ◯, and a sample that showed some abnormalities was marked with ×.

(2) Evaluation of breath anti-fogging property The test piece of the anti-fogging coating film was returned to room temperature, breath was blown at room temperature, and the presence or absence of cloudiness was visually evaluated. The case where cloudiness was not recognized was rated as ◯, and the case where cloudiness was observed was rated as x.

(3) Evaluation of steam appearance Return the test piece of the anti-fogging coating film to room temperature, and place the test piece at a height of 5 cm from the water surface of a warm water bath maintained at 80 ° C. with the coating film surface facing down. Then, the coating film was continuously irradiated with steam from the hot water bath for 10 seconds, and the appearance of the water film forming portion 10 seconds after the irradiation was visually evaluated. A colorless and transparent sample with no abnormalities was marked with ◯, and a sample with whitening was marked with ×.

(4) Evaluation of steam antifogging property Return the test piece of the anti-fogging coating film to room temperature and place the test piece on the surface of the hot water bath kept at 40 ° C. at a height of 5 cm. The film was continuously irradiated with steam from a hot water bath for 5 minutes, and the state of water film formation at that time was visually evaluated. Those that form a uniform water film without passing through cloudiness, ◎, those that form a water film after passing through the cloud only at the interface where the water film is formed (clouding duration less than 1 second) ○, via temporary cloudy After forming a water film (clouding duration of 1 second or more), or a film that does not form a uniform water film was evaluated as x. In addition, if evaluation is (circle), there is no practical problem, and (double-circle) is more preferable.

(5) Evaluation of water sagging trace Return the test piece of the anti-fogging coating film to room temperature, and place the test piece at a height of 5 cm from the water surface of the warm water bath maintained at 80 ° C. Then, the coating film was continuously irradiated with steam from a hot water bath for 10 seconds. Next, the test piece was set up vertically, and the formed water film was hung downward to form a water sauce. Thereafter, the test piece was left to dry the water sauce, and the water sauce trace was visually evaluated. The outline and the inside of the water dripping trace are transparent and very inconspicuous ◎, the outline and the inside of the water dripping trace are transparent and inconspicuous ○, the outline of the water dripping trace is transparent, The whitening was observed in the inside of the film, and the case that was slightly conspicuous was indicated by Δ. In addition, if evaluation is (circle), there is no practical problem, and (double-circle) is more preferable. A triangle indicates that it is the same level as the prior art.

Comprehensive evaluation In any of the evaluations (0) to (5), in any evaluation, Δ or x, and the storage stability of the catalyst, the steam antifogging property, and the water sagging trace are ◎, There is no △ or × in the evaluation, and the case where the steam antifogging property and the water sagging trace are ◯ and ◎ (or ◎ and ◯) is ◯, and at least any evaluation is △, at least any In the evaluation of, the case where x is indicated as x, and the case where the overall evaluation is ◯ has no practical problem, and ◎ is more preferable.

<Comparative Examples 1-12>
<Manufacture of catalyst A'13-18 (solution)>
Except having changed into the monomer of Table 2, the catalyst A'12-18 of the comparative example was obtained by the method as described in Example 1. FIG. The obtained catalysts A′12 to 18 were evaluated in the above (0). The results are shown in Table 5.

<Manufacture of anti-fogging agent composition>
Comparative Example 1 except that the catalyst (A ′) (solution), low molecular weight catalyst, and block or graft copolymer (B) (solution) described in Table 5 were used. -12 antifogging agent compositions were obtained.

<Creation of anti-fogging coating film>
The test piece of the anti-fogging coating film of Comparative Examples 1-12 was obtained by the method as described in an Example. About these anti-fogging coating films, evaluation of said (1)-(5) was performed. The results are shown in Table 5.

  It was confirmed that the anti-fogging coating films obtained from the anti-fogging agent compositions of Examples 1 to 15 were less noticeable or less noticeable than the conventional anti-fogging coating films (evaluation). (5)). It was also confirmed that the obtained anti-fogging coating film had anti-fogging performance (evaluation (1) to (4)) required for vehicle lamps such as headlamps. Therefore, according to the catalyst (A) for the antifogging agent composition of Examples 1 to 15, the antifogging coating film obtained by the antifogging agent composition containing the antifogging coating composition is very inconspicuous, or It was found that the catalyst (A) of the present invention is a catalyst capable of imparting the effect of preventing dripping of water to the anti-fogging coating film because it is not noticeable and exhibits excellent anti-fogging properties.

  Moreover, from the viewpoint of the storage stability of the catalyst, the catalysts A1 to 11 used in Examples 1 to 14 are more practically preferable than the catalyst A12 used in Example 15.

  The anti-fogging coating film obtained from the anti-fogging agent composition of Comparative Examples 1 to 6 does not satisfy the contents of the monomers (a1) to (a4) necessary for forming the catalyst (A). It is the coating film obtained by (A '). Since these antifogging coating films of Comparative Examples 1 to 6 cannot satisfy the performance of water dripping trace or steam appearance, the catalyst (A ′) for the antifogging agent composition of Comparative Examples 1 to 6 is It has been found that the problems of the invention cannot be achieved.

The anti-fogging coating film obtained from the anti-fogging agent composition of Comparative Examples 7-12 is a coating film obtained using the low molecular catalyst currently used by the prior art instead of the catalyst (A). Since these antifogging coating films of Comparative Examples 7 to 12 cannot satisfy at least the performance of water sag, the low molecular catalyst for the antifogging agent composition of Comparative Examples 7 to 12 achieves the object of the present invention. I found it impossible.

Claims (7)

A catalyst (A) used in the antifogging agent composition,
The catalyst (A) is a vinyl monomer (a1) having a sulfonic acid group represented by the following general formula (1)

[In the general formula (1), R ¹ is a hydrogen atom or a methyl group, X is O or NH, and R ² is a linear or branched alkylene group having 1 to 4 carbon atoms. ],
(Meth) acrylamide monomer (a2) represented by the following general formula (2)

[In the general formula (2), R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and R ⁵ is a linear alkyl group having 1 to 4 carbon atoms. R ⁴ and R ⁵ may be the same or different. ],
Methoxyethylene glycol group-containing (meth) acrylate monomer (a3) represented by the following general formula (3)

[In the general formula (3), R ⁶ is a hydrogen atom or a methyl radical, n is 1-9 showing an average addition molar number of oxyethylene groups. And an alkyl group-containing (meth) acrylate monomer (a4) represented by the following general formula (4)

[In the general formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms. A (meth) acrylate copolymer formed from a monomer mixture,
4 to 19% by weight of vinyl monomer (a1) having a sulfonic acid group, (meth) acrylamide monomer (a2) and methoxy with respect to the monomer mixture of the components (a1) to (a4). Antifogging agent comprising 40 to 80% by weight of total of ethylene glycol group-containing (meth) acrylate monomer (a3) and 10 to 48% by weight of alkyl group-containing (meth) acrylate monomer (a4) Catalyst for the composition.   The catalyst for an antifogging composition according to claim 1, wherein the catalyst (A) has a weight average molecular weight (Mw) of 5,000 or more and 100,000 or less.   The catalyst (A) for the antifogging agent composition according to claim 1 or 2, a block or graft copolymer (B) having a hydrophilic polymer part and a hydrophobic polymer part, and a surfactant (C) An antifogging composition comprising:   The hydrophilic polymer portion is a hydrophilic polymer portion made of a copolymer formed from a monomer mixture containing a vinyl monomer having an N-methylol group and / or an N-alkoxymethylol group. The anti-fogging agent composition according to claim 3.   The catalyst (A) is contained in 5 to 35 parts by weight with respect to 100 parts by weight of the block or graft copolymer (B) having the hydrophilic polymer part and the hydrophobic polymer part. Antifogging composition. The antifogging composition further contains a solvent,
The solvent is included in an amount of 200 to 2000 parts by weight based on 100 parts by weight of the catalyst (A) and the total of 100 parts by weight of the block or graft copolymer (B) having the hydrophilic polymer part and the hydrophobic polymer part. The antifogging agent composition in any one of 3-5. The resin member which has a cured coating film formed from the antifogging agent composition in any one of Claims 3-6.