JP6880503B2 - Anti-fog composition, anti-fog article with anti-fog coating - Google Patents

Description

The present invention relates to an antifogging agent composition and an antifogging article having an antifogging coating film.

In vehicle lighting equipment such as automobile headlamps, high-humidity air may enter the lighting chamber, the lens may be cooled by outside air or rainfall, and moisture may condense on the inner surface to cause fogging. As a result, the brightness of the vehicle light is reduced and the aesthetic appearance of the lens surface is impaired, which may cause discomfort to the user. In order to prevent such fogging of the lens, a method of applying an antifogging agent to a part where fogging occurs (inside the lens) to form an antifogging coating film (dry coating film or cured coating film) is known. (Patent Documents 1 to 3).

In Patent Document 1, a monomer mixture containing a vinyl-based monomer having an N-methylol group or an N-alkoxymethylol group, a vinyl-based monomer having a sulfonic acid group, and an alkyl (meth) acrylate-based monomer. A copolymer formed from, a basic compound having a sulfonic acid group, and an antifogging agent composition containing a surfactant are disclosed.

Further, Patent Document 2 discloses an antifogging agent composition containing a specific (meth) acrylate copolymer, a polyfunctional blocked isocyanate compound, and a surfactant.

Further, Patent Document 3 discloses an antifogging agent composition containing a specific block or graft copolymer, a fluorine-based surfactant, and an acidic phosphoric acid alkyl ester.

Japanese Unexamined Patent Publication No. 2011-140589 International Publication No. 2016/047430 Japanese Unexamined Patent Publication No. 2004-250601

Usually, a polycarbonate (PC) resin is used as a headlamp lens and a polymethylmethacrylate (PMMA) resin is used as a rear combination lens for a lens used for a vehicle lamp from the viewpoint of high transparency and excellent impact resistance. The thermal deformation temperature of the PC resin is about 130 to 140 ° C., whereas the thermal deformation temperature of the PMMA resin is about 65 to 90 ° C. due to the influence of the molecular weight and additives of PMMA constituting the resin. As the antifogging agent composition used for the resin, for example, one that can be cured (low temperature curing) at a temperature of about 60 ° C. or lower is required. Further, from the viewpoint of increasing production efficiency, there is a demand for an antifogging agent composition that can be cured in as short a time as possible, for example, 40 minutes or less.

Further, as disclosed in Patent Document 1 or Patent Document 2, the antifogging agent composition for vehicle lighting fixtures has good antifogging durability, antifogging property after moisture resistance test, and antifogging property after heat resistance test. There is a demand for an antifogging coating film that has fogging properties, is less likely to cause water dripping marks, and has adhesiveness and water resistance. In particular, in recent years, there has been a demand for a device having better anti-fog durability so that it can exhibit anti-fog properties even in various usage environments of vehicle lamps.

However, the antifogging coating film obtained by low-temperature curing the antifogging agent composition disclosed in Patent Documents 1 to 3 can satisfy the high antifogging durability required for the above vehicle lighting equipment. There was a concern that it could not be done.

The present invention has been made in view of the above circumstances, and forms an anti-fog coating film having the performance required for a vehicle lamp (particularly, excellent in anti-fog durability) under low temperature and short-time conditions. It is an object of the present invention to provide an antifogging agent composition capable of providing an antifogging agent composition, and an antifogging article having the antifogging coating film.

（一般式（１）中、Ｒ^１は、水素原子、またはメチル基であり、Ｒ^２は、炭素数１〜４の直鎖もしくは分岐鎖のアルキル基、−Ｃ（ＣＨ_３）_２ＣＨ_２ＣＯＣＨ_３、−Ｃ_２Ｈ_４Ｎ（ＣＨ_３）_２、またはＣ_３Ｈ_６Ｎ（ＣＨ_３）_２であり、Ｒ^３は、水素原子、または炭素数１〜４の直鎖もしくは分岐鎖のアルキル基である。）で表される単量体、
一般式（２）：

（一般式（２）中、Ｒ^４は、水素原子、またはメチル基、Ａは−Ｃ_２Ｈ_４ＯＣ_２Ｈ_４−、または−Ｃ_３Ｈ_６Ｃ（＝Ｏ）−である。）で表される単量体、および
一般式（３）：ＣＨ_２＝ＣＲ^５−ＣＯＯ−（ＡＯ）_ｎ−Ｒ^６・・・（３）
（一般式（３）中、Ｒ^５は、水素原子、またはメチル基、ＡＯは炭素数２〜３のアルキレンオキシ基、Ｒ^６は、炭素数１〜３の直鎖または分岐鎖のアルキル基、ｎはアルキレンオキシ基の平均付加モル数を示す１〜１０である。）で表される単量体からなる群より選ばれる１種以上の単量体（Ａ−１）と、
一般式（４）：

（一般式（４）中、Ｒ^７は、水素原子、またはメチル基であり、Ｒ^８は、炭素数１〜１６の直鎖、分岐鎖、もしくは環状のアルキル基、またはベンジル基である。）で表される単量体（Ａ−２）と、
一般式（５）：

（一般式（５）中、Ｒ^９は、水素原子、またはメチル基であり、Ｒ^１０は、炭素数２〜４の直鎖もしくは分岐鎖のアルキレン基、またはＣ_２Ｈ_４（ＯＣＯ（Ｃ_２Ｈ_４）_５）_ｎ−であり、ｎは１〜４である。）で表される単量体、および
一般式（６）：

（一般式（６）中、Ｒ^１１は、水素原子、またはメチル基であり、Ｒ^１２は、炭素数２〜４の直鎖または分岐鎖のアルキレン基である。）で表される単量体からなる群より選ばれる１種以上の単量体（Ａ−３）と、
一般式（７）：

（一般式（７）中、Ｒ^1３は、水素原子、またはメチル基であり、Ｒ^１４は、水素原子、または炭素数１〜４の直鎖もしくは分岐鎖のアルキル基である。）で表される単量体（Ａ−４）を含み、
前記酸触媒（Ｂ）は、硫酸および／またはスルホン酸系化合物を含み、
前記界面活性剤（Ｃ）は、アニオン系界面活性剤（Ｃ−１）とカチオン系界面活性剤（Ｃ−２）を含み、
前記単量体混合物中、前記単量体（Ａ−１）の割合が１０〜６０重量％、前記単量体（Ａ−２）の割合が２０〜８０重量％、前記単量体（Ａ−３）が２〜２０重量％、および前記単量体（Ａ−４）が０．５〜１５重量％であることを特徴とする防曇剤組成物、に関する。 That is, the present invention is an antifogging agent composition containing a copolymer (A), an acid catalyst (B) and a surfactant (C), and the copolymer (A) is made from a monomer mixture. The obtained (meth) acrylate copolymer, and the monomer mixture is a general formula (1):

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a linear or branched alkyl group having 1 to 4 carbon atoms, −C (CH ₃ ) ₂ CH ₂ COCH. ₃ , -C ₂ H ₄ N (CH ₃ ) ₂ , or C ₃ H ₆ N (CH ₃ ) ₂ , where R ³ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. The monomer represented by)
General formula (2):

Table in (which is in the general formula (2), ^{R 4} is a hydrogen atom or a methyl group,, A is _{-C 2 H 4 OC 2 H 4} - -, or _{-C 3 H 6 C (= O} ).) Monomer to be used, and general formula (3): CH ₂ = CR ^5- COO- (AO) _n- R ⁶ ... (3)
(In the general formula (3), R ⁵ is a hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, and R ⁶ is a linear or branched alkyl group having 1 to 3 carbon atoms. n is one or more monomers (A-1) selected from the group consisting of monomers represented by (1 to 10) indicating the average number of moles of alkyleneoxy groups added.
General formula (4):

(In the general formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a linear, branched or cyclic alkyl group or benzyl group having 1 to 16 carbon atoms.) The monomer (A-2) represented by
General formula (5):

(In the general formula (5), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 4 carbon atoms, or C ₂ H ₄ (OCO (C _2). H ₄ ) ₅ ) _n −, n is 1 to 4), and the general formula (6) :.

(In the general formula (6), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is a linear or branched alkylene group having 2 to 4 carbon atoms.) One or more monomers (A-3) selected from the group consisting of
General formula (7):

(In the general formula (7), R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.) Contains the monomer (A-4)
The acid catalyst (B) contains sulfuric acid and / or a sulfonic acid-based compound.
The surfactant (C) contains an anionic surfactant (C-1) and a cationic surfactant (C-2).
In the monomer mixture, the proportion of the monomer (A-1) is 10 to 60% by weight, the proportion of the monomer (A-2) is 20 to 80% by weight, and the monomer (A-). 3) is 2 to 20% by weight, and the monomer (A-4) is 0.5 to 15% by weight.

The present invention also relates to an antifogging article having an antifogging coating film formed from the antifogging agent composition.

In the present invention, the following mechanism of action is presumed.

The antifogging coating film formed from the antifogging agent composition of the present invention exhibits good antifogging properties mainly based on the properties of the monomer (A-1) constituting the copolymer (A). Then, good adhesion to the substrate and water resistance are exhibited based on the properties of the monomer (A-2), and the properties of the monomer (A-3) and the monomer (A-4) are changed. Based on this, crosslinks of the coating film are formed. Then, in the cross-linking reaction, the curing reaction is promoted by the acid catalyst (B). Further, since the antifogging agent composition of the present invention has an acid catalyst (B) added externally, the curing reaction at a low temperature is good, so that the antifogging coating has the performance required for a vehicle lamp at a low temperature and in a short time. It is advantageous for forming a film.

In the antifogging agent composition of the present invention, an anionic surfactant (C-1) and a cationic surfactant (C-2) are used in combination as the surfactant (C). The anionic surfactant (C-1) and the cationic surfactant (C-2) form an ion pair in the coating film, which makes it difficult to elute from the coating film. The anti-fog coating film is less likely to deteriorate in anti-fog performance over a long period of use, and good anti-fog performance is maintained.

Further, the antifogging agent composition of the present invention further forms a water film on the antifogging coating film by using a nonionic surfactant (C-3) as the surfactant (C). It is possible to make the generated water dripping traces inconspicuous. The water dripping mark refers to a mark that is visually recognized by the components eluted on the surface of the coating film being dried after the antifogging coating film forms a water film.

Therefore, according to the antifogging agent composition of the present invention, the antifogging agent composition has the performance required for vehicle lighting equipment by thermosetting under low temperature and short time conditions as compared with the conventional antifogging agent composition (particularly, antifogging durability). It is possible to provide an antifogging coating film (excellent in the above) and an antifogging article having an antifogging coating film.

The antifogging agent composition of the present invention contains a copolymer (A), an acid catalyst (B) and a surfactant (C).

<Copolymer (A)>
The copolymer (A) of the present invention is a (meth) acrylate copolymer obtained from a monomer mixture, and the monomer mixture is at least the following monomers (A-1) to (A). -4) is included.

（一般式（１）中、Ｒ^１は、水素原子、またはメチル基であり、Ｒ^２は、炭素数１〜４の直鎖もしくは分岐鎖のアルキル基、−Ｃ（ＣＨ_３）_２ＣＨ_２ＣＯＣＨ_３、−Ｃ_２Ｈ_４Ｎ（ＣＨ_３）_２、またはＣ_３Ｈ_６Ｎ（ＣＨ_３）_２であり、Ｒ^３は、水素原子、または炭素数１〜４の直鎖もしくは分岐鎖のアルキル基である。）で表される単量体、一般式（２）：

（一般式（２）中、Ｒ^４は、水素原子、またはメチル基、Ａは−Ｃ_２Ｈ_４ＯＣ_２Ｈ_４−、または−Ｃ_３Ｈ_６Ｃ（＝Ｏ）−である。）で表される単量体、および一般式（３）：
ＣＨ_２＝ＣＲ^５−ＣＯＯ−（ＡＯ）ｎ−Ｒ^６・・・（３）
（一般式（３）中、Ｒ^５は、水素原子、またはメチル基、ＡＯは炭素数２〜３のアルキレンオキシ基、Ｒ^６は、炭素数１〜３の直鎖または分岐鎖のアルキル基、ｎはアルキレンオキシ基の平均付加モル数を示す１〜１０である。）で表される単量体からなる群より選ばれる１種以上の単量体である。 <Monomer (A-1)>
The monomer (A-1) of the present invention has a general formula (1):

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a linear or branched alkyl group having 1 to 4 carbon atoms, −C (CH ₃ ) ₂ CH ₂ COCH. ₃ , -C ₂ H ₄ N (CH ₃ ) ₂ , or C ₃ H ₆ N (CH ₃ ) ₂ , where R ³ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. The monomer represented by), the general formula (2) :.

Table in (which is in the general formula (2), ^{R 4} is a hydrogen atom or a methyl group,, A is _{-C 2 H 4 OC 2 H 4} - -, or _{-C 3 H 6 C (= O} ).) Monomer to be used, and general formula (3):
CH ₂ = CR ^5- COO- (AO) n-R ⁶ ... (3)
(In the general formula (3), R ⁵ is a hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, and R ⁶ is a linear or branched alkyl group having 1 to 3 carbon atoms. n is one or more monomers selected from the group consisting of monomers represented by (1 to 10) indicating the average number of moles of alkyleneoxy groups added.

The monomer (A-1) mainly has a function of expressing water absorption in the copolymer (A) and enhancing the antifogging property of the antifogging coating film.

Examples of the monomer (A-1) include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-n-propyl (meth) acrylamide, and N-isopropyl (meth) acrylamide; N, N-dialkyl (meth) acrylamide-based monomers such as N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide; N-dimethylaminoethyl (meth) acrylamide, N- (3-dimethylamino) Propyl) (meth) acrylamide, diacetone (meth) acrylamide, (meth) acroylmorpholin, N-vinyl-2-pyrrolidone, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, (where the number of ethylene oxides) 1 to 10 is preferable, 2 to 8 is more preferable), methoxypolypropylene glycol (meth) acrylate (here, the number of propylene oxides is preferably 1 to 10, more preferably 2 to 8) and the like. The monomer (A-1) is preferably an N, N-dialkyl (meth) acrylamide-based monomer, preferably N, N, from the viewpoint of excellent adhesion between the coating film and the substrate as well as antifogging property. -Dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide are particularly preferred. At least one type of the monomer (A-1) may be used, and two or more types may be used in combination.

（一般式（４）中、Ｒ^７は、水素原子、またはメチル基であり、Ｒ^８は、炭素数１〜１６の直鎖、分岐鎖、もしくは環状のアルキル基、またはベンジル基である。）で表される単量体である。 <Monomer (A-2)>
The monomer (A-2) of the present invention has a general formula (4):

(In the general formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a linear, branched or cyclic alkyl group or benzyl group having 1 to 16 carbon atoms.) It is a monomer represented by.

The monomer (A-2) mainly has a function of enhancing the adhesion of the antifogging coating film to the substrate and enhancing the water resistance.

Examples of the monomer (A-2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl ( Examples thereof include meta) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and benzyl (meth) acrylate. The monomer (A-2) may have a linear or branched alkyl group from the viewpoint of enhancing the adhesion between the coating film and the substrate, water resistance, and enhancing the antifogging property of the coating film. It is preferable, and the number of carbon atoms is preferably 1 to 12, more preferably 1 to 8. At least one type of the monomer (A-2) may be used, and two or more types may be used in combination.

Further, the monomer (A-2), from the viewpoint of improving the anti-fogging property and water resistance, it is preferable to use a combination of two or more, R ⁸ carbon atoms in the general formula (4) 1 It is more preferable to use a monomer having an alkyl group of 3 (A-2-1) and a monomer having an alkyl group in which R ⁸ has 4 to 16 carbon atoms (A-2-2) in combination. The weight ratio ((A-2-1) / (A-2-2)) of the monomer (A-2-1) to the monomer (A-2-2) is 100/5 or more. It is preferably 100/10 or more, more preferably 100/80 or less, and more preferably 100/70 or less.

（一般式（５）中、Ｒ^９は、水素原子、またはメチル基であり、Ｒ^１０は、炭素数２〜４の直鎖もしくは分岐鎖のアルキレン基、またはＣ_２Ｈ_４（ＯＣＯ（Ｃ_２Ｈ_４）_５）_ｎ−であり、ｎは１〜４である。）で表される単量体、および一般式（６）：

（一般式（６）中、Ｒ^１１は、水素原子、またはメチル基であり、Ｒ^１２は、炭素数２〜４の直鎖または分岐鎖のアルキレン基である。）で表される単量体からなる群より選ばれる１種以上の単量体である。 <Monomer (A-3)>
The monomer (A-3) of the present invention has a general formula (5):

(In the general formula (5), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 4 carbon atoms, or C ₂ H ₄ (OCO (C _2). H ₄ ) ₅ ) _n −, n is 1 to 4), and the general formula (6) :.

(In the general formula (6), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is a linear or branched alkylene group having 2 to 4 carbon atoms.) One or more monomers selected from the group consisting of.

The monomer (A-3) mainly has a function of forming a crosslinked structure with the monomer (A-4) described later.

Examples of the monomer (A-3) include 2-hydroxyethyl (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (4). Examples thereof include a caprolactone adduct of a meta) acrylate and a hydroxyethyl acrylate. The monomer (A-3) is 2-hydroxyethyl (meth) acrylate or N- (2-hydroxyethyl) (meth) acrylamide from the viewpoint of excellent water resistance of the coating film and excellent antifogging durability. , 4-Hydroxybutyl (meth) acrylate is preferred. At least one type of the monomer (A-3) may be used, and two or more types may be used in combination.

（一般式（７）中、Ｒ^１３は、水素原子、またはメチル基であり、Ｒ^１４は、水素原子または炭素数１〜４の直鎖または分岐鎖のアルキル基である。）で表される単量体である。 <Monomer (A-4)>
The monomer (A-4) of the present invention has a general formula (7):

(In the general formula (7), R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.) It is a monomer.

The monomer (A-4) mainly contains a dehydration condensation reaction between N-methylol groups and N-methylol ether groups, and a dealcohol condensation reaction between N-methylol groups and N-methylol ether groups and hydroxyl groups. It has a function of cross-linking between molecules to form a cross-linked structure in the copolymer. In addition, this condensation reaction is promoted by an acid catalyst.

Examples of the monomer (A-4) include N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N. -Isobutoxymethyl (meth) acrylamide and the like. The monomer (A-3) is preferably N-methylol (meth) acrylamide from the viewpoint of excellent water resistance of the coating film and excellent heat curability at low temperature. At least one type of the monomer (A-4) may be used, and two or more types may be used in combination.

The ratio of each monomer component in the monomer mixture forming the copolymer (A) of the present invention will be described below.

The proportion of the monomer (A-1) in the monomer mixture is 10 to 60% by weight. From the viewpoint of improving the antifogging property, the proportion of the monomer (A-1) is preferably 20% by weight or more, more preferably 30% by weight or more, and more preferably 30% by weight or more in the monomer mixture. From the viewpoint of improving water resistance and suppressing dripping marks, the content is preferably 50% by weight or less, more preferably 40% by weight or less.

The proportion of the monomer (A-2) in the monomer mixture is 20 to 80% by weight. The proportion of the monomer (A-2) is preferably 30% by weight or more, more preferably 40% by weight or more in the monomer mixture from the viewpoint of improving water resistance and adhesion. It is preferable, and from the viewpoint of improving the antifogging property, it is preferably 70% by weight or less, and more preferably 60% by weight or less.

The proportion of the monomer (A-3) in the monomer mixture is 2 to 20% by weight. The proportion of the monomer (A-3) is preferably 3% by weight or more, preferably 5% by weight or more, in the monomer mixture from the viewpoint of improving water resistance and suppressing dripping marks. From the viewpoint of improving adhesion, it is preferably 17% by weight or less, and more preferably 15% by weight or less.

The proportion of the monomer (A-4) in the monomer mixture is 0.5 to 15% by weight. The proportion of the monomer (A-4) is preferably 1% by weight or more, preferably 1.5% by weight, in the monomer mixture from the viewpoint of improving water resistance and suppressing dripping marks. % Or more is more preferable, and from the viewpoint of improving adhesion, it is preferably 10% by weight or less, and more preferably 8% by weight or less.

The total ratio of the monomers (A-1) to (A-4) in the monomer mixture is preferably 85% by weight or more, more preferably 90% by weight or more, and 95% by weight or more. It is more preferably 7% by weight or more, further preferably 97% by weight or more, and even more preferably 99% by weight or more.

In the monomer mixture, aromatic vinyl such as styrene, vinyl toluene, α-methylstyrene and the like can be used as other monomers other than the monomers (A-1) to (A-4). System monomer; Vinyl-based monomer containing a quaternary ammonium salt such as (meth) acryloyloxyethyl trimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride; phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth). ) Acrylate-based monomers such as acrylates and isobornyl (meth) acrylates; carboxy group-containing monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, and maleic acid, and ammonium salts and organic amine salts thereof. , Alkali metal salt; sulfonic acid group-containing vinyl-based single amount such as styrene sulfonic acid, vinyl sulfonic acid, metharyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate. The body, and these ammonium salts, organic amine salts, alkali metal salts; phosphate group-containing vinyl-based monomers such as 2- (meth) acryloyloxyethyl acid phosphate, and these ammonium salts, organic amine salts, alkali metals. Salts; 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerinji (meth) ) Acrylate, bifunctional (meth) acrylate such as N, N'-methylenebis [(meth) acrylamide]; trimethylolpropanthry (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. Polyfunctional vinyl-based monomer; vinyl-based monomer having an alkoxysilyl group such as γ- (meth) acryloxipropyltrimethoxysilane, γ- (meth) acryloxipropyltriethoxysilane, vinyltrimethoxysilane; Vinyl-based monomers having an epoxy group such as glycidyl (meth) acrylate, vinyl glycidyl ether, and allyl glycidyl ether can be used.

<Method for producing copolymer (A)>
The copolymer (A) of the present invention 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 property. A random copolymer is preferable from the viewpoint that the effect of the above can be improved and 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 anionic living polymerization method, and a cationic living polymerization method are adopted, but industrial productivity is particularly easy. The radical polymerization method is preferable from the viewpoint of performance in a wide range of meanings. As the radical polymerization method, a usual bulk polymerization method, suspension polymerization method, solution polymerization method, emulsion polymerization method and the like are adopted, but the solution polymerization method is that it can be used as it is as an antifogging agent composition after polymerization. Is preferable.

Examples of the polymerization solvent used in the solution polymerization method include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, and diacetone alcohol; ethylene glycol monomethyl. Alcohol ether solvents such as ether, ethylene glycol 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 Ketone solvents such as isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate and ethyl lactate; benzene , Aromatic solvents such as toluene and xylene, amide solvents such as formamide and dimethylformamide; water and the like are used. At least one type of the polymerization solvent may be used, and two or more types may be used in combination.

As for the polymerization solvent, a solvent having a remarkably high boiling point may impair the adhesion of the coating film to the substrate due to residual solvent during drying and heat curing of the coating film, and is 180 at 1 atm. It is preferable to use a solvent having a boiling point of less than ° C.

As the radical polymerization initiator, commonly used organic peroxides, azo compounds and the like can be used. Examples of the organic peroxide include benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-hexanoatelate, t-butylperoxypivalate, and t-hexyl. Peroxypivalate and the like can be mentioned. Examples of the azo compound include 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile. At least one type of the radical polymerization initiator may be used, and two or more types may be used in combination.

The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer mixture. It is preferable to carry out the polymerization of the radical polymerization initiator while dropping it in a reaction vessel because it is easy to control the heat generation of the polymerization. The temperature at which the polymerization reaction is carried out varies depending on the type of radical polymerization initiator used, but is preferably 30 to 150 ° C., more preferably 40 to 100 ° C. for industrial production.

The weight average molecular weight (Mw) of the copolymer (A) is preferably 20,000 or more, and more preferably 30,000 or more, from the viewpoint of imparting water resistance to the antifogging coating film. The weight average molecular weight (Mw) of the copolymer (A) is preferably 120,000 or less, more preferably 110,000 or less, from the viewpoint of enhancing the coatability and handleability of the antifogging agent composition.

The weight average molecular weight (Mw) of the copolymer (A) 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 dimethylformamide to prepare a 0.2% by weight solution and filtering with a 0.45 μm membrane filter.
<Measurement of weight average molecular weight (Mw)>
Analyzer: HLC-8320GPC (manufactured by Tosoh)
Column: Series connection of KD-802.5 (manufactured by Showa Denko), KD-803 (manufactured by Showa Denko), KD-80M (manufactured by Showa Denko) Column size: 8.0 x 300 mm
Eluent: Dimethylformamide Flow rate: 1.0 ml / min
Detector: Differential refractometer Column temperature: 40 ° C
Standard sample: polystyrene

Further, from the viewpoint of improving the adhesion, the copolymer (A) preferably has an acid value of 20 mgKOH / g or less, more preferably 15 mgKOH / g or less, and 12 mgKOH / g or less. It is even more preferable, and it is even more preferable that it is 9 mgKOH / g or less. The acid value of the copolymer (A) is set in 1 g of the solid content of the copolymer having an acid group such as a carboxy group, a sulfone group, and a phosphoric acid group, based on the amount of the raw material (monomer) charged. It refers to the theoretical acid value calculated from the number of mg of KOH required to neutralize the contained acid group.

<Acid catalyst (B)>
The acid catalyst (B) of the present invention is a sulfuric acid and / or sulfonic acid-based compound, and serves as a catalyst for accelerating the condensation reaction of the monomers (A-3) and (A-4) at a low temperature. Has a function.

Examples of the acid catalyst (B) include sulfuric acid; fluorosulfonic acid; methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, and other alkylsulfonic acid-based compounds; benzenesulfonic acid, dodecylbenzenesulfonic acid, p-. Toluene sulfonic acid, 4-ethylbenzene sulfonic acid, p-chlorobenzene sulfonic acid, m-xylene-4-sulfonic acid, 3-pyridine sulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalenedisulfonic acid, 1-pyrene sulfonic acid, etc. Examples thereof include aryl sulfonic acid-based compounds. The acid catalyst (B) includes alkyl sulfonic acid compounds having 1 to 3 carbon atoms and aryl sulfonic acid compounds having a benzyl structure or a naphthalene structure from the viewpoint of excellent curability and inconspicuous water dripping marks. preferable. At least one type of acid catalyst (B) may be used, and two or more types may be used in combination.

The acid catalyst (B) is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the copolymer (A). The acid catalyst (B) is 0.2 parts by weight or more with respect to 100 parts by weight of the copolymer (A) from the viewpoint of improving water resistance and antifogging performance and suppressing water dripping marks. It is preferably 0.3 parts by weight or more, more preferably 4 parts by weight or less, and more preferably 3 parts by weight or less.

The acid catalyst (B) is a value represented by the formula (1): {weight of acid catalyst (B) with respect to 100 parts by weight of copolymer (A) × 1,000} / molecular weight of acid catalyst (B). However, it is preferably 9 or less, more preferably 8 or less, preferably 1 or more, and more preferably 2 or more. For example, when 0.35 parts by weight of methanesulfonic acid (molecular weight: 96.11) is used as the acid catalyst (B) with respect to 100 parts by weight of the copolymer (A), the formula (1) is {0. .35 × 1,000} /96.11=3.6.

<Surfactant (C)>
The surfactant (C) of the present invention contains at least an anionic surfactant (C-1) and a cationic surfactant (C-2).

As the anionic surfactant (C-1), all conventionally known surfactants can be used, and for example, fatty acid salts such as sodium oleate and potassium oleate; higher grades such as sodium lauryl sulfate and ammonium lauryl sulfate. Alcohol sulfate esters; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate and alkylnaphthalene sulfonates; dialkyl phosphate salts of naphthalene sulfonic acid, marine condensates, dialkyl sulfosuccinates, dialkyl phosphate salts, poly Examples thereof include polyoxyethylene sulfate salts such as sodium oxyethylene alkylphenyl ether sulfate. Examples of the anionic surfactant (C-1) include fluorine-containing anionic surfactants such as perfluoroalkyl carboxylic acid salt, perfluoroalkyl sulfonate, and perfluoroalkyl phosphate ester. Be done. The anionic surfactant (C-1) is preferably a dialkylsulfosuccinate or a dialkylphosphate salt from the viewpoint of excellent antifogging performance and antifogging durability. At least one type of the anionic surfactant (C-1) may be used, and two or more types may be used in combination.

As the cationic surfactant (C-2), all conventionally known ones can be used, and for example, ethanolamines, laurylamine acetate, triethanolamine monoammonium acidate, stearamide ethyl diethylamine acetate. Amine salts such as; alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride; dialkyldimethylammonium salts such as dilauryldimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride. And so on. Further, examples of the cationic surfactant (C-2) include a fluorine-containing cationic surfactant such as a perfluoroalkyltrimethylammonium salt. The cationic surfactant (C-2) is preferably an alkyltrimethylammonium salt or a dialkyldimethylammonium salt from the viewpoint of long-lasting antifogging and inconspicuous water dripping marks. At least one type of the anionic surfactant (C-2) may be used, and two or more types may be used in combination.

The surfactant (C) further contains a nonionic surfactant (C-3) from the viewpoint of making the water dripping marks generated after forming the water film on the antifogging coating film inconspicuous. Is preferable.

As the nonionic surfactant (C-3), all conventionally known ones can be used, and for example, polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol; polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate; polypropylene glycol ethylene oxide adducts, polyoxyethylene sorbitan monolaurate, Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate; phosphoric acid esters such as alkyl phosphoric acid esters and polyoxyethylene alkyl ether phosphoric acid esters; sugar esters, cellulose ethers and the like. Examples of the nonionic surfactant (C-3) include perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer having perfluoroalkyl group and hydrophilic group, perfluoroalkyl group and lipophilicity. Examples thereof include fluorine-containing nonionic surfactants such as oligomers having a group, oligomers having a perfluoroalkyl group and an oil-based group, and oligomers having a perfluoroalkyl group and a hydrophilic group and an oil-based group. As the nonionic surfactant (C-3), polyoxyethylene higher alcohol ethers are preferable from the viewpoints of long-lasting anti-fog and inconspicuous water dripping marks. The anionic surfactant (C-3) can be used in combination of two or more.

The surfactant (C) may contain a betaine-based surfactant. Examples of the betaine-based surfactant include fatty acid-type betaine-based surfactants such as dimethylalkyllauryl betaine and dimethylalkylstearyl betaine; sulfonic acid-type betaine-based surfactants such as dimethylalkylsulfobetaine; alkylglycine; Examples thereof include fluorine-containing betaine surfactants such as fluoroalkyl betaine.

The amount of the anionic surfactant (C-1) is preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the copolymer (A). From the viewpoint of improving the antifogging property, the anionic surfactant (C-1) is more preferably 1 part by weight or more with respect to 100 parts by weight of the copolymer (A), and 2 parts by weight. The above is more preferable, and from the viewpoint of suppressing the trace of water dripping, it is more preferably 12 parts by weight or less, and further preferably 10 parts by weight or less.

The amount of the cationic surfactant (C-2) is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the copolymer (A). The cationic surfactant (C-2) is 0.1 part by weight with respect to 100 parts by weight of the copolymer (A) from the viewpoint of improving the antifogging durability and the antifogging property after the moisture resistance test. It is more preferably 0.2 parts by weight or more, and more preferably 2 parts by weight or less from the viewpoint of improving water resistance and suppressing dripping marks. It is more preferably 1.5 parts by weight or less.

The weight ratio ((C-1) / (C-2)) of the anionic surfactant (C-1) and the cationic surfactant (C-2) is 100/50 (= 2) or more. It is preferably 100/40 (= 2.5) or more, more preferably 100/10 (= 10) or less, and 100/12 (= 8) or less. Is more preferable.

When the surfactant (C) further contains a nonionic surfactant (C-3), the nonionic surfactant (C-3) is 100 parts by weight of the copolymer (A). On the other hand, it is preferably 0.5 to 15 parts by weight. The nonionic surfactant (C-3) is more preferably 1 part by weight or more with respect to 100 parts by weight of the copolymer (A) from the viewpoint of suppressing water dripping marks. The above is more preferable, and it is more preferably 12 parts by weight or less, and further preferably 10 parts by weight or less.

When the surfactant (C) contains a nonionic surfactant (C-3), the weight ratio of the anionic surfactant (C-1) to the nonionic surfactant (C-3). ((C-1) / (C-3)) is preferably 100/300 (= 0.3) or more, more preferably 100/250 (= 0.4) or more, and It is preferably 100/50 (= 2) or less, and more preferably 100/66 (= 1.5) or less.

The antifogging agent composition of the present invention can further contain a diluting solvent.

The diluting 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 the polymerization solvent of the copolymer (A). The solid content and viscosity suitable for coating differ depending on the coating method, but in the case of the spray coating method, the copolymer (A) is preferably 3% by weight or more in the antifogging agent composition, and 5% by weight. % Or more, more preferably 30% by weight or less, and even more preferably 20% by weight or less.

In the antifogging agent composition of the present invention, various conventional additives such as a leveling agent, an antioxidant, an ultraviolet absorber, and a light stabilizer can be added as other components, if necessary. The amount of the other components added can be a conventional amount for each additive, but is usually 10 parts by weight or less with respect to 100 parts by weight of the copolymer (C).

<Anti-fog article>
In the antifogging article of the present invention, the antifogging agent composition is applied to an object to be coated by a coating method used in ordinary paints and heat-cured to form an antifogging coating film on the surface of the object to be coated. It was done. A drying step can be provided before the heat curing step for the purpose of volatilizing and drying the solvent contained in the coating film immediately after painting.

As the object to be coated, a known resin base material can be used regardless of the type. For example, polymethylmethacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, etc. Examples thereof include acetate resin, ABS resin, polyester resin and polyamide resin.

When painting the object to be coated, it is preferable to remove foreign substances adhering to the surface of the object to be coated before painting for the purpose of enhancing the wettability of the antifogging agent composition on the object to be coated and preventing repelling. .. Examples include dust removal with high-pressure air or ionized air, ultrasonic cleaning with an aqueous detergent solution or alcohol solvent, wiping with an alcohol solvent, and cleaning with ultraviolet rays and ozone. Examples of the coating method include a dipping method, a flow coating method, a roll coating method, a bar coating method, and a spray coating method.

The drying is usually carried out at a temperature of 20 to 50 ° C. for 0.5 to 5 minutes.

In the heating, when the base material is a resin member, it is necessary to set the heating temperature to be equal to or lower than the thermal deformation temperature of the resin member. However, from the viewpoint of preventing slight deformation of the resin member, the thermal deformation of the resin member is performed. The temperature is preferably 5 ° C. or lower, preferably 10 ° C. or lower. For example, when the resin member is a polymethylmethacrylate resin, the temperature is preferably 60 ° C. or lower, and when the resin member is a polycarbonate resin, the temperature is preferably 110 ° C. or lower. For example, when the heating temperature is 60 ° C., the heating time is preferably 10 minutes or more, more preferably 15 minutes or more. For example, when the heating temperature is 110 ° C., the heating time is preferably 5 minutes or longer, more preferably 10 minutes or longer.

The film thickness of the antifogging coating film is preferably about 0.5 to 10 μm, more preferably about 1 to 5 μm, from the viewpoint of obtaining good antifogging properties and the appearance of the coating film.

The use of the anti-fog article is not limited in any way, but it can be used, for example, in a vehicle lamp of an automobile. Examples of the vehicle lighting equipment include headlights, auxiliary headlights, side lights, number lights, tail lights, parking lights, backward lights, direction indicator lights, auxiliary direction indicator lights, and emergency flashing displays.

Hereinafter, the present invention will be described with reference to Examples and the like, but the present invention is not limited to these.

<Example 1>
<Manufacturing of copolymer (A)>
In a reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube, 213 parts by weight of n-propyl alcohol was charged as a polymerization solvent, and the mixture was heated to 80 ° C. while blowing nitrogen gas. Next, as the monomer (A-1), 35 parts by weight of N, N-dimethylacrylamide, 30 parts by weight of methyl methacrylate and 20 parts by weight of butyl acrylate as the monomer (A-2), and the monomer (monomer (A-2)). A solution obtained by mixing 10 parts by weight of 2-hydroxyethyl acrylate as A-3), 5 parts by weight of N-methylolacrylamide as a monomer (A-4), and 15 parts by weight of n-propyl alcohol, and a radical polymerization initiator. 2 parts of t-hexyl peroxypivalate (manufactured by Nichiyu Co., Ltd., trade name "perhexyl PV" (70% by weight of active ingredient)) equivalent to 1.0 part by weight dissolved in 20 parts by weight of n-propyl alcohol. Dropped over time. After completion of the dropping, the mixture was stirred as it was for 1 hour and then cooled to produce a solution of the copolymer (A). When the polymerization conversion rate of the charged monomer of the copolymer (A) was measured by gas chromatography, it was 100%. The weight average molecular weight of the copolymer (A) was measured by gel permeation chromatography and found to be 70,000. The solid content of the solution of the copolymer (A) was 30.0% by weight. The acid value (theoretical acid value) of the copolymer (A) is 0 mgKOH / g.

<Manufacturing of antifogging agent composition>
70 parts by weight of diacetone alcohol and 297 parts by weight of n-propyl alcohol are added to 333 parts by weight of the solution of 100 parts by weight (solid content 30%) of the copolymer (A) obtained above to add the copolymer (A). ) Was adjusted to 13.0% by weight. Next, 0.35 parts by weight of methanesulfonic acid was used as the acid catalyst (B), and di (2-ethylhexyl) sodium sulfosuccinate as the anionic surfactant (C-1) (manufactured by Nichiyu Co., Ltd., trade name "Lapisol"). 4.0 parts by weight of "A80" (active ingredient 80% by weight)) as a cationic surfactant (C-2), dodecyltrimethylammonium chloride (manufactured by Nichiyu Co., Ltd., trade name "Nissan Cation BB" (active ingredient) 30 parts by weight)) is equivalent to 1.0 part by weight, and 0.1 part by weight of polyether-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd., trade name "BYK333") is mixed as a leveling agent to form an antifogging agent composition. Manufactured.

<Making anti-fog articles>
In an environment set at 25 ° C. and a relative humidity of 30% RH, the antifogging agent composition obtained above was applied to a polymethylmethacrylate (PMMA) resin plate, and the film thickness of the coating film after curing was about 2 to 3 μm. The coating was carried out by a spray coating method and heat-cured at 60 ° C. for 20 minutes to prepare an antifogging article (test piece) having an antifogging coating film.

Table 1 shows the results obtained by the following evaluation methods (1-1) to (1-4) and (2) to (4) using the test pieces obtained above.

<(1) Evaluation of anti-fog performance>
<(1-1) Sustainability test>
The test piece was placed at a height of 2 cm from the water surface of the hot water bath kept at 80 ° C. so that the coating film surface was on the bottom, and steam from the hot water bath was continuously irradiated to the coating film for 10 seconds. The test piece was dried at room temperature for 1 hour with the test piece standing vertically. After repeating this 30 times, the presence or absence of fogging 10 seconds after the steam irradiation was visually evaluated in the following four stages. If the evaluation is Δ or higher, there is no problem in practical use, if it is ◯, it is preferable, and if it is ⊚, it is more preferable.
⊚: A water film is formed immediately after steam irradiation and does not become cloudy.
◯: Momentary cloudiness is observed immediately after steam irradiation, but a water film is formed immediately and no cloudiness occurs.
Δ: Cloudiness is observed immediately after steam irradiation, but a water film is formed and the cloudiness does not occur.
X: A clean water film is not formed after steam irradiation, or no water film is formed and cloudiness is observed.

<(1-2) Steam test>
The test piece was placed at a height of 2 cm from the water surface of the hot water bath kept at 60 ° C. so that the coating film surface was facing down, and steam from the hot water bath was continuously irradiated to the coating film for 10 seconds after the irradiation. The presence or absence of subsequent fogging was visually evaluated in the following four stages. If the evaluation is Δ or higher, there is no problem in practical use, if it is ◯, it is preferable, and if it is ⊚, it is more preferable.
⊚: A water film is formed immediately after steam irradiation and does not become cloudy.
◯: Momentary cloudiness is observed immediately after steam irradiation, but a water film is formed immediately and no cloudiness occurs.
Δ: Cloudiness is observed immediately after steam irradiation, but a water film is formed and the cloudiness does not occur.
X: Cloudiness is observed immediately after steam irradiation, and no water film is formed.

<(1-3) Steam test after moisture resistance test>
The test piece was allowed to stand at 50 ° C. and 95% RH for 240 hours, and then allowed to stand at room temperature for 24 hours. After that, the test piece was placed at a height of 2 cm from the water surface of the hot water bath kept at 60 ° C. so that the coating film surface was facing down, and steam from the hot water bath was continuously irradiated to the coating film. The presence or absence of cloudiness after 10 seconds was visually evaluated in the following four stages. If the evaluation is Δ or higher, there is no problem in practical use, if it is ◯, it is preferable, and if it is ⊚, it is more preferable.
⊚: A water film is formed immediately after steam irradiation and does not become cloudy.
◯: Momentary cloudiness is observed immediately after steam irradiation, but a water film is formed immediately and no cloudiness occurs.
Δ: Cloudiness is observed immediately after steam irradiation, but a water film is formed and the cloudiness does not occur.
X: A clean water film is not formed after steam irradiation, or no water film is formed and cloudiness is observed.

<(1-4) Steam test after heat resistance test>
The test piece was allowed to stand at 80 ° C. for 240 hours and then allowed to stand at room temperature for 24 hours. After that, the test piece was placed at a height of 2 cm from the water surface of the hot water bath kept at 60 ° C. so that the coating film surface was facing down, and steam from the hot water bath was continuously irradiated to the coating film. The presence or absence of cloudiness after 10 seconds was visually evaluated in the following four stages. If the evaluation is Δ or higher, there is no problem in practical use, if it is ◯, it is preferable, and if it is ⊚, it is more preferable.
⊚: A water film is formed immediately after steam irradiation and does not become cloudy.
◯: Momentary cloudiness is observed immediately after steam irradiation, but a water film is formed immediately and no cloudiness occurs.
Δ: Cloudiness is observed immediately after steam irradiation, but a water film is formed and the cloudiness does not occur.
X: A clean water film is not formed after steam irradiation, or no water film is formed and cloudiness is observed.

<(2) Adhesion>
The presence or absence of peeling of the coating film was visually evaluated in the following three stages in accordance with JIS K 5400 8.5.1. If the evaluation is ◯ or higher, there is no problem in practical use, and if it is ⊚, it is more preferable.
⊚: No peeling is observed.
◯: Peeling is observed in some parts.
X: All are peeled off.

<(3) Water resistance>
The test piece was allowed to stand in warm water at 40 ° C. for 240 hours and then allowed to stand at room temperature for 1 hour, and then the appearance of the coating film was visually evaluated in the following four stages. If the evaluation is Δ or higher, there is no problem in practical use, if it is ◯, it is preferable, and if it is ⊚, it is more preferable.
⊚: There is no change in appearance from before the test.
◯: The surface of the coating film is slightly rough.
Δ: The surface of the coating film is rough, or slight whitening or stains are observed.
X: Part or all of the coating film is dissolved, or whitening or stains are clearly observed.

<(4) Water dripping marks>
The test piece was placed at a height of 2 cm from the water surface of the hot water bath kept at 80 ° C. so that the coating film surface was on the bottom, and steam from the hot water bath was continuously irradiated to the coating film for 10 seconds before the test. The pieces were allowed to stand vertically and dried at room temperature for 1 hour. After drying, the presence or absence of water dripping marks was visually evaluated in the following four stages. If the evaluation is Δ or higher, there is no problem in practical use, if it is ◯, it is preferable, and if it is ⊚, it is more preferable.
⊚: Water dripping marks are not noticeable.
◯: Water dripping marks are hardly noticeable.
Δ: Water dripping marks are slightly noticeable.
X: Water dripping marks are conspicuous.

<Examples 2-27>
<Manufacturing of copolymer (A)>
The copolymers (A) of Examples 2 to 27 were subjected to the same operations as in Example 1 except that the monomers of Example 1 were changed to the raw materials and their ratios shown in Tables 1 to 3. The solution was produced.

<Manufacture of anti-fog composition and production of anti-fog article>
The antifogging agent composition of Examples 2 to 27 was produced by the same operation as in Example 1 except that the raw materials of Example 1 were changed to the raw materials shown in Tables 1 to 3 and their ratios. Further, an antifogging article (test piece) having the antifogging coating film of Examples 2 to 27 was produced by the same operation as in Example 1.

Tables 1 to 3 show the results obtained by the evaluation methods (1-1) to (1-4) and (2) to (4) above using the test pieces obtained above.

<Comparative example 1>
<Manufacturing of copolymer (A)>
In a reaction vessel equipped with a stirrer, a nitrogen introduction tube and a cooling tube, 223 parts by weight of n-propanol as a polymerization solvent, 17 parts by weight of N, N-dimethylacrylamide (DMAA) as a monomer (a1), and a monomer (monomer (a1)). 50 parts by weight of methyl methacrylate (MMA) as a2), 17 parts by weight of n-butyl acrylate (BA), 8 parts by weight of N-methylol acrylamide (N-MAA) as monomer (a4), 2-acrylamide-2-methyl 8 parts by weight of propanesulfonic acid (AMPS) and 4.03 g of triethanolamine as a basic compound (amount corresponding to 70 mol% with respect to the sulfonic acid group of the AMPS, calculation method; {AMPS charged parts by weight} ÷ APPS Molar mass × 70% ÷ 100 × {molar mass of triethanolamine} = 8 ÷ 207.4 × 70 ÷ 100 × 149.2 = 4.03) was charged and heated to 65 ° C. while blowing nitrogen gas. 1.0 part by weight of t-hexylperoxypivalate hydrocarbon diluted product (manufactured by Nichiyu Co., Ltd., trade name "Perhexyl PV") as a radical polymerization initiator is dissolved in 20 parts by weight of n-propanol. Was added dropwise over 3 hours. After further polymerizing for 5 hours, the temperature was raised to 80 ° C., and polymerization was carried out at that temperature for 1 hour to obtain a solution of the acrylic copolymer (A). When the polymerization conversion rate of the charged monomer of the copolymer (A) was measured by gas chromatography, it was 100%. The weight average molecular weight of the copolymer (A) was measured by gel permeation chromatography and found to be 170,000. The solid content of the solution of the copolymer (A) was 30.0% by weight.

<Comparative example 2>
<Manufacturing of copolymer (A)>
The copolymer (A) of Comparative Example 2 was subjected to the same operation as in Comparative Example 1 except that the monomer and triethanolamine of Comparative Example 1 were changed to the raw materials and their ratios shown in Table 4. The solution was produced.

<Comparative Examples 3 to 11>
The solution of the copolymer (A) of Comparative Examples 3 to 11 was prepared in the same manner as in Example 1 except that the monomer of Example 1 was changed to the raw materials shown in Table 4 and their ratios. Manufactured.

<Manufacture of anti-fog composition and production of anti-fog article>
The antifogging agent compositions of Comparative Examples 1 to 11 were produced in the same manner as in Example 1 except that the raw materials of Example 1 were changed to the raw materials shown in Table 4 and their ratios. Further, the antifogging article (test piece) having the antifogging coating film of Comparative Examples 1 to 11 was subjected to the same operation as in Example 1 except that the curing temperature and curing time were changed to those shown in Table 4. Made.

Table 4 shows the results obtained by the evaluation methods (1-1) to (1-4) and (2) to (4) above using the test pieces obtained in the above comparative example.

In Tables 1 to 4, as monomers (A-1) to (A-4),
DMAA is N, N-dimethylacrylamide;
DAAA is diacetone acrylamide;
ACMO is N-acryloyl morpholine;
M-20G is methoxypolyethylene glycol methacrylate (average number of moles of ethylene glycol added 2, manufactured by Shin Nakamura Chemical Industry Co., Ltd.);
MMA is methyl methacrylate;
BA is n-butyl acrylate;
EHA is 2-ethylhexyl acrylate;
LA is lauryl acrylate;
HEA is 2-hydroxyethyl acrylate;
HEMA is 2-hydroxyethyl methacrylate;
HEAA is hydroxyethyl acrylamide;
HBA is 4-hydroxybutyl acrylate;
PLAXEL FA2D is a caprolactone 2 mol adduct of hydroxyethyl acrylate (manufactured by Daicel Corporation);
N-MAA is N-methylolacrylamide;
N-BMA is N-butoxymethylacrylamide;
N-MMM indicates N-methoxymethylmethacrylamide;
Also, as other monomers,
AMPS indicates 2-acrylamide-2-methylpropanesulfonic acid;

In Tables 1 to 4, as the acid catalyst (B),
H ₂ SO ₄ is a 5 wt% aqueous solution of sulfuric acid;
MSA is methanesulfonic acid;
PTS is p-toluenesulfonic acid;
DBS is dodecylbenzene sulfonic acid;
DNNDSA indicates dinonylnaphthalene sulfonic acid;
Also, as another catalyst,
NACURE4054J represents a phosphoric acid alkyl ester (manufactured by King Industries Inc.);

In Tables 1 to 4, as the surfactant (C),
Lapizol A80 is a sulfosuccinic acid diester salt (manufactured by NOF CORPORATION, active ingredient 80% by weight);
Persoft SK is an alkyl sulfate sodium salt (manufactured by NOF CORPORATION, active ingredient 30% by weight);
Futergent 100 is a fluorine-containing sulfonate (manufactured by Neos Co., Ltd., 100% by weight of active ingredient);
Nissan Cation BB is a monoalkyl quaternary ammonium salt (manufactured by NOF CORPORATION, active ingredient 30% by weight);
Nissan Cation 2DB500E is a dialkyl quaternary ammonium salt (manufactured by NOF CORPORATION, active ingredient 50% by weight);
Futergent 300 is a fluorine-containing cationic surfactant (manufactured by Neos Co., Ltd., 100% by weight of active ingredient).
Nonion L-4 represents polyoxyethylene monolaurate (manufactured by NOF CORPORATION, active ingredient 100% by weight);
Nonion EH-208 is a polyoxyethylene-2-ethylhexyl ether (manufactured by NOF CORPORATION, active ingredient 100% by weight);
Nonion ID-203 represents polyoxyethylene isodecyl ether (manufactured by NOF CORPORATION, active ingredient 100% by weight);

The main considerations of the results of the above Examples and Comparative Examples are shown below.

From the results of Examples 1 to 5, it was found that among the monomers (A-1), DMAA is preferable from the viewpoint of improving the adhesion. From the results of Examples 1 and 6 to 7, it was found that among the monomers (A-2), those having an alkyl chain having 1 to 8 carbon atoms are preferable from the viewpoint of improving the antifogging property. It was. From the results of Examples 1 and 8 to 11, the molecular chain of the monomer (A-3) is shorter than that of the caprolactone 2 mol adduct of hydroxyethyl acrylate from the viewpoint of improving antifogging property and water resistance. It turned out that the one was preferable. From the results of Examples 1 and 12 to 13, it was found that among the monomers (A-4), N-MAA is preferable from the viewpoint of improving antifogging property and water resistance.

From the results of Examples 1 and 14 to 19, the preferable ratios of the monomers (A-1) to (A-4) in the copolymer (A) for expressing each performance in a well-balanced manner were found. Further, from the results of Examples 1 and 20 to 21, a preferable blending amount of the acid catalyst (B) was found. Furthermore, from the results of Examples 1 and 22 to 27, a preferable blending amount of the surfactant (C) for improving the antifogging property was found.

On the other hand, Comparative Examples 1 to 4, 7 to 11 are inferior in anti-fog durability as compared with Examples because they do not use the surfactants (C-1) and / or (C-2). I found out.
Comparative Example 4 was carried out because a monomer having an acid group was used as the monomer constituting the copolymer and no acid catalyst (B) of sulfuric acid and / or a sulfonic acid compound was used. It was found that the antifogging durability and water resistance were inferior to those of the examples. In Comparative Example 5, a phosphoric acid system was used as a catalyst, but it was found that the antifogging durability and water resistance were inferior to those of the examples. Since Comparative Example 6 did not use the monomer (A-3), it was found that the antifogging durability and water resistance were inferior to those of Examples.

Claims (6)

An antifogging agent composition containing a copolymer (A), an acid catalyst (B), and a surfactant (C).
The copolymer (A) is a (meth) acrylate copolymer of a random copolymer obtained from a monomer mixture.
The monomer mixture has a general formula (1):

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a linear or branched alkyl group having 1 to 4 carbon atoms, −C (CH ₃ ) ₂ CH ₂ COCH. ₃ , -C ₂ H ₄ N (CH ₃ ) ₂ , or C ₃ H ₆ N (CH ₃ ) ₂ , where R ³ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. The monomer represented by)
General formula (2):

Table in (which is in the general formula (2), ^{R 4} is a hydrogen atom or a methyl group,, A is _{-C 2 H 4 OC 2 H 4} - -, or _{-C 3 H 6 C (= O} ).) Monomer to be used, and general formula (3): CH ₂ = CR ^5- COO- (AO) _n- R ⁶ ... (3)
(In the general formula (3), R ⁵ is a hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, and R ⁶ is a linear or branched alkyl group having 1 to 3 carbon atoms. n is one or more monomers (A-1) selected from the group consisting of monomers represented by (1 to 10) indicating the average number of moles of alkyleneoxy groups added.
General formula (4):

(In the general formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a linear, branched or cyclic alkyl group or benzyl group having 1 to 16 carbon atoms.) The monomer (A-2) represented by
General formula (5):

(In the general formula (5), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 4 carbon atoms, or C ₂ H ₄ (OCO (C _2). H ₄ ) ₅ ) _n −, n is 1 to 4), and the general formula (6) :.

(In the general formula (6), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is a linear or branched alkylene group having 2 to 4 carbon atoms.) One or more monomers (A-3) selected from the group consisting of
General formula (7):

(In the general formula (7), R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.) Contains the monomer (A-4)
The acid catalyst (B) contains sulfuric acid and / or a sulfonic acid-based compound.
The surfactant (C) contains an anionic surfactant (C-1) and a cationic surfactant (C-2).
In the monomer mixture, the proportion of the monomer (A-1) is 10 to 60% by weight, the proportion of the monomer (A-2) is 20 to 80% by weight, and the monomer (A-). An antifogging agent composition comprising 2 to 20% by weight of 3) and 0.5 to 15% by weight of the monomer (A-4). With respect to 100 parts by weight of the copolymer (A), 0.5 to 15 parts by weight of the anionic surfactant (C-1) and 0.05 to 0.05 parts by weight of the cationic surfactant (C-2). The antifogging agent composition according to claim 1, wherein the composition is 3 parts by weight. The antifogging agent composition according to claim 1 or 2, wherein the acid catalyst (B) is 0.1 to 5 parts by weight with respect to 100 parts by weight of the copolymer (A). The prevention according to any one of claims 1 to 3, wherein the acid catalyst (B) is at least one selected from the group consisting of sulfuric acid, an aryl sulfonic acid compound, and an alkyl sulfonic acid compound. Clouding agent composition. The surfactant (C) contains a nonionic surfactant (C-3), and the surfactant (C) contains a nonionic surfactant (C-3).
The invention according to any one of claims 1 to 4, wherein the amount of the nonionic surfactant (C-3) is 0.5 to 15 parts by weight with respect to 100 parts by weight of the copolymer (A). Antifogging agent composition. An antifogging article having an antifogging coating film formed from the antifogging agent composition according to any one of claims 1 to 5.