JP2016169288A - Antifogging agent composition and antifogging article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifogging agent composition excellent in long lasting of antifogging performance.SOLUTION: An antifogging agent composition consists of a copolymer (A), a polyfunctional block isocyanate compound (B) and a surfactant (C). The copolymer (A) is constituted by 35 to 90 pts.wt. of a monomer (A-1), 5 to 60 pts.wt. of a monomer (A-2) and 5 to 30 pts.wt. of the monomer (A-3) based on 100 pts.wt. of the copolymer (A). A NCO//OH ratio which is a ratio of isocyanate group content (NCO) of the polyfunctional block isocyanate compound (B) and hydroxyl group content (OH) of the copolymer (A) is in a range of 0.1 to 1.5. The surfactant (C) contains 1.00 to 10.0 pts.wt. of a fluorine-based anionic surfactant (C-1) and 0.01 to 3.00 pts.wt. of a betaine-based surfactant (C-2) based on 100 pts.wt. of the copolymer (A).SELECTED DRAWING: None

Description

  The present invention relates to an antifogging agent composition having excellent antifogging performance and an antifogging article using the same.

  2. Description of the Related Art A lighting device such as an automobile headlamp is configured such that a transparent member made of glass or plastic is disposed in front of a light source, and light emitted from the light source is irradiated to the outside through the transparent member. . In such an illuminating device, for example, when fogging occurs on the inside of the transparent member, the intensity of the irradiation light may decrease and the aesthetic appearance of the irradiation light may be impaired.

Patent Document 1 discloses an antifogging agent composition that can be used to prevent the occurrence of fogging in the lighting device as described above. This anti-fogging agent composition contains the following components.
Monomer (A): Non-crosslinkable water-soluble vinyl monomer Monomer (B): Non-crosslinkable water-insoluble vinyl monomer Monomer (C): Has a hydroxyl group Vinyl monomer / crosslinking agent having isocyanate group (D)
・ Surfactant (E)

  In the antifogging agent composition described in Patent Document 1, antifogging performance is obtained based on the properties of the monomer (A), and good adhesion and water resistance are obtained based on the properties of the monomer (B). And good antifogging performance is obtained by the function of the surfactant (E).

JP 2010-150351 A

  In the anti-fogging film obtained from the anti-fogging agent composition described in Patent Document 1, the surfactant (E) gradually flows out in applications such as automobile headlamps used in an environment where repeated condensation occurs. End up. Therefore, in the antifogging article in which the antifogging agent composition described in Patent Document 1 is used, the antifogging performance (water film forming ability) may decrease with use.

  In view of the circumstances as described above, an object of the present invention is to provide an antifogging agent composition excellent in sustainability of antifogging performance and an antifogging article using the same.

…（１）
（一般式（１）中、Ｒ^１は、水素原子、又はメチル基であり、Ｒ^２ _は、炭素数１〜４の直鎖もしくは分岐のアルキル基、−Ｃ（ＣＨ_３）_２ＣＨ_２ＣＯＣＨ_３、−Ｃ_２Ｈ_４Ｎ（ＣＨ_３）_２、又は−Ｃ_３Ｈ_６Ｎ（ＣＨ_３）_２であり、Ｒ^３は、水素原子、又は直鎖もしくは分岐の炭素数１〜４のアルキル基である。）

…（２）
（一般式（２）中、Ｒ^４は、水素原子、又はメチル基である。）

…（３）
（一般式（３）中、Ｒ^５は、水素原子、又はメチル基であり、Ｒ^６は、炭素数１〜１６の直鎖、分岐、又は環状のアルキル基である。）

…（４）
（一般式（４）中、Ｒ^７は、水素原子、又はメチル基であり、Ｒ^８は、炭素数２〜４の直鎖もしくは分岐のアルキレン基、又は−Ｃ_２Ｈ_４（ＯＣＯ（ＣＨ_２）_５）_ｎ−（ｎは１〜５の整数である。）である。）

…（５）
（一般式（５）中、Ｒ^９は、水素原子、又はメチル基であり、Ｒ^１０は、炭素数１〜４の直鎖又は分岐のアルキレン基である。）
上記単量体（Ａ−１）、上記単量体（Ａ−２）、及び上記単量体（Ａ−３）の合計１００重量部に対して、上記単量体（Ａ−１）が３５〜９０重量部で、上記単量体（Ａ−２）が５〜６０重量部で、上記単量体（Ａ−３）が５〜３０重量部である。
上記多官能ブロックイソシアネート化合物（Ｂ）のイソシアネート基含有量（ＮＣＯ）と、上記共重合体（Ａ）の水酸基含有量（ＯＨ）との比であるＮＣＯ／ＯＨ比が０．１〜１．５の範囲内である。
上記界面活性剤（Ｃ）は、上記共重合体（Ａ）１００重量部に対して、１．００〜１０．０重量部のフッ素系アニオン系界面活性剤（Ｃ−１）と、０．０１〜３．００重量部のベタイン系界面活性剤（Ｃ−２）とを含む。 In order to achieve the above object, an antifogging agent composition according to one embodiment of the present invention comprises a copolymer (A), a polyfunctional blocked isocyanate compound (B), and a surfactant (C).
The copolymer (A) includes a monomer (A-1) represented by the following general formula (1) or (2) and a monomer (A-2) represented by the following general formula (3). ) And a monomer (A-3) represented by the following general formula (4) or (5).

... (1)
(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, 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} ) is _2, ^{R 3} is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms is there.)

... (2)
(In General Formula (2), R ⁴ is a hydrogen atom or a methyl group.)

... (3)
(In General Formula (3), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms.)

... (4)
(In General Formula (4), R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a linear or branched alkylene group having 2 to 4 carbon atoms, or —C ₂ H ₄ (OCO (CH _{2 5} ) _n- (n is an integer of 1 to ₅ ).)

... (5)
(In General Formula (5), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 1 to 4 carbon atoms.)
The monomer (A-1) is 35 with respect to a total of 100 parts by weight of the monomer (A-1), the monomer (A-2), and the monomer (A-3). The amount of the monomer (A-2) is 5 to 60 parts by weight, and the amount of the monomer (A-3) is 5 to 30 parts by weight.
The NCO / OH ratio, which is the ratio of the isocyanate group content (NCO) of the polyfunctional blocked isocyanate compound (B) and the hydroxyl group content (OH) of the copolymer (A), is 0.1 to 1.5. Is within the range.
The surfactant (C) is 1.00 to 10.0 parts by weight of a fluorine-based anionic surfactant (C-1) with respect to 100 parts by weight of the copolymer (A), and 0.01 To 3.00 parts by weight of a betaine surfactant (C-2).

  In this configuration, the combined use of the fluoroanionic surfactant (C-1) and the betaine surfactant (C-2) makes it difficult for the surfactant to flow out due to moisture caused by condensation. . For this reason, in this anti-fogging agent composition, the anti-fogging performance (water film forming ability) is not easily lowered with use, and the excellent anti-fogging performance is maintained.

An antifogging article according to one embodiment of the present invention includes a base material and an antifogging film.
The antifogging film is formed by heat-curing the antifogging composition applied to the substrate.
With this configuration, an antifogging article having an antifogging film in which the antifogging performance (water film forming ability) hardly decreases with use and the excellent antifogging performance is sustained is obtained.

  It is possible to provide an antifogging agent composition and an antifogging article having excellent antifogging performance.

Hereinafter, embodiments of the present invention will be described.
One embodiment of the present invention relates to a technique for providing an antifogging film on the surface of a base material to which an antifogging performance is imparted, such as a transparent member used for an automotive headlamp. The antifogging film according to this embodiment is formed by heat curing an antifogging agent composition that is a mixture of a plurality of types of materials. The component of the antifogging agent composition is determined so that the durability of the antifogging performance can be satisfactorily obtained in the antifogging film after heat curing.

[Anti-fogging agent composition]
The antifogging agent composition according to the present embodiment has a copolymer (A), a polyfunctional blocked isocyanate compound (B), and a surfactant (C).

(Surfactant (C))
In the antifogging agent composition according to the present embodiment, a fluorine-based anionic surfactant (C-1) and a betaine-based surfactant (C-2) are used in combination as the surfactant (C). In this configuration, the anion of the fluorine-based anionic surfactant (C-1) and the cation of the betaine-based surfactant (C-2) form an ion pair. As a result, the fluorine-based anionic surfactant (C-1) and the betaine-based surfactant (C-2) are unlikely to flow out due to moisture caused by condensation.

  Therefore, in the anti-fogging film obtained from the anti-fogging agent composition according to the present embodiment, the use of the fluorine-based anionic surfactant (C-1) and the betaine surfactant (C-2) is accompanied by use. Decrease in antifogging performance (water film forming ability) hardly occurs, and excellent antifogging performance is sustained.

  It is preferable that the quantity of a fluorine-type anionic surfactant (C-1) exists in the range of 1.00-10.00 weight part with respect to 100 weight part of copolymers (A). When the amount of the fluorine-based anionic surfactant (C-1) is less than 1.00 parts by weight, the anti-fogging performance in the anti-fogging film is lowered and the anti-fogging performance after the heat test is lowered. . On the other hand, when the amount of the fluorine-based anionic surfactant (C-1) exceeds 10.00 parts by weight, water dripping marks are easily noticeable on the antifogging film.

  The amount of the betaine surfactant (C-2) is preferably within a range of 0.01 to 3.00 parts by weight with respect to 100 parts by weight of the copolymer (A). When the amount of the betaine surfactant (C-2) is less than 0.01 parts by weight, the durability of the antifogging performance in the antifogging film is lowered. On the other hand, when the amount of the fluorine-based anionic surfactant (C-1) exceeds 3.00 parts by weight, water dripping marks are easily noticeable on the antifogging film.

(Copolymer (A))
A copolymer (A) is comprised from a monomer (A-1), a monomer (A-2), and a monomer (A-3). The monomer (A-1) is represented by the following general formula (1) or (2). The monomer (A-2) is represented by the following general formula (3). The monomer (A-3) is represented by the following general formula (4) or (5).

…（１）
一般式（１）中、Ｒ^１は、水素原子、又はメチル基であり、Ｒ^２は、炭素数１〜４の直鎖もしくは分岐のアルキル基、−Ｃ（ＣＨ_３）_２ＣＨ_２ＣＯＣＨ_３、−Ｃ_２Ｈ_４Ｎ（ＣＨ_３）_２、又は−Ｃ_３Ｈ_６Ｎ（ＣＨ_３）_２であり、Ｒ^３は、水素原子、又は直鎖もしくは分岐の炭素数１〜４のアルキル基である。

... (1)
In General Formula (1), R ¹ is a hydrogen atom or a methyl group, 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} ) is _2, ^{R 3} is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms .

…（２）
一般式（２）中、Ｒ^４は、水素原子、又はメチル基である。

... (2)
In general formula (2), R ⁴ is a hydrogen atom or a methyl group.

…（３）
一般式（３）中、Ｒ^５は、水素原子、又はメチル基であり、Ｒ^６は、炭素数１〜１６の直鎖、分岐、又は環状のアルキル基である。

... (3)
In General Formula (3), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms.

…（４）
一般式（４）中、Ｒ^７は、水素原子、又はメチル基であり、Ｒ^８は、炭素数２〜４の直鎖もしくは分岐のアルキレン基、又は−Ｃ_２Ｈ_４（ＯＣＯ（ＣＨ_２）_５）_ｎ−（ｎは１〜５の整数である。）である。

... (4)
In General Formula (4), R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a linear or branched alkylene group having 2 to 4 carbon atoms, or —C ₂ H ₄ (OCO (CH ₂ ) ₅ ) _n- (n is an integer of 1 to ₅ ).

…（５）
一般式（５）中、Ｒ^９は、水素原子、又はメチル基であり、Ｒ^１０は、炭素数１〜４の直鎖又は分岐のアルキレン基である。

... (5)
In General Formula (5), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 1 to 4 carbon atoms.

  When the monomer (A-1) is dialkyl (meth) acrylamide, the adhesion of the antifogging film obtained from the antifogging agent composition to the substrate is particularly excellent.

  The amount of the monomer (A-1) is 35 to 35 parts by weight based on a total of 100 parts by weight of the monomer (A-1), the monomer (A-2), and the monomer (A-3). It is preferably within the range of 90 parts by weight. When the amount of the monomer (A-1) is less than 35 parts by weight, the durability of the antifogging performance in the antifogging film is lowered. On the other hand, when the amount of the monomer (A-1) exceeds 90 parts by weight, water dripping traces are easily noticeable on the antifogging film.

  When the monomer (A-2) is a (meth) acrylate having 1 to 16 carbon atoms, the antifogging performance after the heat resistance and moisture resistance test of the antifogging film obtained from the antifogging agent composition is particularly excellent. When the number of carbon atoms is more than 16, the antifogging performance after the heat resistance and moisture resistance test of the antifogging film obtained from the antifogging agent composition is lowered.

  The amount of the monomer (A-2) is 5 to 5 parts by weight with respect to a total of 100 parts by weight of the monomer (A-1), the monomer (A-2), and the monomer (A-3). It is preferably within the range of 60 parts by weight. When the amount of the monomer (A-2) is less than 5 parts by weight, water dripping marks are easily noticeable on the antifogging film. On the other hand, when the amount of the monomer (A-2) exceeds 60 parts by weight, the durability of the antifogging performance in the antifogging film is lowered.

  When the monomer (A-3) is hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide, the durability of the antifogging performance in the antifogging film obtained from the antifogging agent composition is particularly excellent.

  The amount of the monomer (A-3) is 5 to 5 parts by weight based on 100 parts by weight of the monomer (A-1), the monomer (A-2), and the monomer (A-3). It is preferably within the range of 30 parts by weight. When the amount of the monomer (A-3) is less than 5 parts by weight, the water resistance in the antifogging film is lowered, and water dripping marks are easily noticeable in the antifogging film. On the other hand, when the amount of the monomer (A-3) exceeds 30 parts by weight, the adhesion of the antifogging film to the substrate is lowered.

(Polyfunctional blocked isocyanate compound (B))
When the polyfunctional blocked isocyanate compound (B) is diethyl malonate blocked isocyanate, the antifogging composition is cured well at a low temperature (about 120 ° C.) without adding a catalyst.

  When the isocyanate group content in the polyfunctional block isocyanate compound (B) is “NCO” and the hydroxyl group content of the copolymer (A) is “OH”, the isocyanate group content NCO is converted into the copolymer (A). The NCO / OH ratio obtained by dividing by the hydroxyl group content OH is preferably in the range of 0.1 to 1.5.

  When the NCO / OH ratio is less than 0.1, the water resistance of the antifogging film is lowered, and water dripping marks are easily noticeable on the antifogging film. On the other hand, when the NCO / OH ratio exceeds 1.5, the durability of the antifogging performance of the antifogging film is lowered.

[Anti-fogging article]
In the antifogging article according to the present embodiment, an antifogging agent composition is applied to the surface of an article that is a base material to which antifogging performance is imparted, and the antifogging agent composition on the surface of the article is heated and cured. Can be manufactured. Articles to which the present embodiment is applicable are not particularly limited.

  However, since the anti-fogging article according to the present embodiment has high anti-fogging performance and sustainability, the present embodiment can be more suitably applied to an article used in an environment where condensation is likely to occur. Examples of such articles include automobile headlamps.

1. Preparation of antifogging agent composition (1-1) Synthesis of copolymer (A) Using a reaction vessel equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube, 213 parts by weight of t-, which is an organic solvent The amyl alcohol was heated to 80 ° C. while blowing nitrogen gas. The following solution (a) and solution (b) were dropped into this reaction vessel over 2 hours.

Solution (a): 50 parts by weight of N, N-dimethylacrylamide (monomer (A-1)), 35 parts by weight of butyl acrylate (monomer (A-2)), and 15 parts by weight of 2 -Hydroxyacrylate (monomer (A-3)) mixed solution / solution (b): 0.5 parts by weight of t-hexylperoxypivalate (radical polymerization initiator) [manufactured by NOF Corporation Product name: Perhexyl PV (active ingredient 70% by weight)] dissolved in 20 parts by weight of t-amyl alcohol

  The solution of the copolymer (A) was obtained by stirring the solution in the reaction vessel after dropping the solution (a) and the solution (b) for 1 hour. The polymerization conversion rate of the charged monomer of the copolymer (A) measured by gas chromatography was 100%. Moreover, the weight average molecular weight of the copolymer (A) measured by gel permeation chromatography was 93,000.

Moreover, the hydroxyl value of the copolymer (A) was calculated according to the following formula.
[Hydroxyl value] (mgKOH / g)
= [Parts by weight of monomer (A-3) in 100.0 parts by weight of copolymer (A)] (g) / [Mole weight of monomer (A-3)] (g / mol) × KOH (mg)
= 0.15 (g) /116.12 (g / mol) x 56100 (mgKOH)
= 72.5 (mgKOH / g)

(1-2) Preparation of antifogging agent composition (when malonate block isocyanate is used)
100 parts by weight of polypropylene glycol monomethyl ether, 200 parts by weight of diacetone alcohol, 100 parts by weight of 333 parts by weight of a solid content 30.0% polymerization solution corresponding to 100 parts by weight of copolymer (A) Methyl isobutyl ketone and 267 parts by weight of n-butanol were added to adjust the solid content to 10.0% by weight.

  As the polyfunctional blocked isocyanate compound (B), 83.5 parts by weight of a hexamethylene diisocyanate malonate block isocyanate having an NCO / OH ratio of 1.0 (trade name: Duranate MF-, manufactured by Asahi Kasei Chemicals Corporation) K60B (NCO concentration 6.5 wt%)] was used.

  As the fluorine-based anionic surfactant (C-1), 5.0 parts by weight of a fluorine-based sodium sulfonate [trade name: manufactured by Neos Co., Ltd .: Footent 100 (active ingredient 100% by weight)] was used. .

  As betaine surfactant (C-2), 0.01 part by weight of lauryldimethylaminoacetic acid betaine [trade name: NISSAN ANON BL-SF (available from NOF Corporation) (active ingredient 33.5 to 38.5) % By weight)].

  As a leveling agent, 0.01 part by weight of a polyether-modified polydimethylsiloxane [trade name: BYK333 manufactured by Big Chemie Japan Co., Ltd.] was used.

  The above copolymer (A), polyfunctional blocked isocyanate compound (B), fluorine-based anionic surfactant (C-1), betaine-based surfactant (C-2), and leveling agent are mixed, An antifogging composition was obtained.

(1-3) Preparation of anti-fogging agent composition (when using other than malonate blocked isocyanate)
100 parts by weight of polypropylene glycol monomethyl ether, 200 parts by weight of diacetone alcohol, 100 parts by weight of 333 parts by weight of a solid content 30.0% polymerization solution corresponding to 100 parts by weight of copolymer (A) Methyl isobutyl ketone and 267 parts by weight of n-butanol were added to adjust the solid content to 10.0% by weight.

  As the polyfunctional block isocyanate compound (B), 51.7 parts by weight of a dimethylpyrazole block isocyanate body of hexamethylene diisocyanate having an NCO / OH ratio of 1.0 (trade name: Sumika Bayer Urethane Co., Ltd. Module 3575/1 (NCO concentration 10.5 wt%)] was used.

  As a fluorine-based anionic surfactant (C-1), a fluorine-based carboxylate equivalent to 5.0 parts by weight [trade name: Surflon S-211 manufactured by AGC Seimi Chemical Co., Ltd. (active ingredient 50% by weight)] Was used.

  As betaine surfactant (C-2), 3.0 parts by weight of fluorine betaine [trade name: Footage 400SW (active ingredient 50% by weight) manufactured by Neos Co., Ltd.] was used.

  As a catalyst, 1.0 part by weight of dibutyltin dilaurate was used.

  As a leveling agent, 0.01 part by weight of a polyether-modified polydimethylsiloxane [trade name: BYK333 manufactured by Big Chemie Japan Co., Ltd.] was used.

  The above copolymer (A), polyfunctional blocked isocyanate compound (B), fluorine-based anionic surfactant (C-1), betaine-based surfactant (C-2), catalyst, and leveling agent are mixed. Thus, an antifogging agent composition was obtained.

2. Production of antifogging film A polycarbonate resin plate was used as a base material for forming the antifogging film. The antifogging agent composition was applied to a polycarbonate resin plate by a spray coating method so that the film thickness of the antifogging film after curing was 5 μm. And the anti-fogging agent composition was heat-hardened by hold | maintaining the polycarbonate resin board with which the anti-fogging agent composition was apply | coated at 130 degreeC for 30 minutes. Thereby, an antifogging film test piece having an antifogging film was obtained.

3. Performance evaluation of anti-fogging film (3-1) Anti-fogging performance (a) Sustainability test The anti-fogging film is placed under the anti-fogging film test piece at a height of 2 cm from the surface of the warm water bath maintained at 80 ° C. By installing so as to face, steam irradiation of the antifogging film test piece with a warm water bath was performed on the antifogging film, and then the antifogging film test piece was dried for 1 hour at room temperature in a state where the antifogging film test piece was set up vertically. After repeating this 50 times, the presence or absence of fogging 10 seconds after the steam irradiation was visually evaluated in the following four stages.

A: A water film is formed immediately after the steam irradiation and does not become cloudy.
○: Instantaneous clouding is recognized immediately after steam irradiation, but a water film is formed immediately and the cloudiness is eliminated.
Δ: Clouding is observed immediately after steam irradiation, but a water film is formed and the clouding is eliminated.
X: A clean water film is not formed after steam irradiation, or a water film is not formed and cloudiness is recognized.

  The anti-fogging film formed on the anti-fogging film test piece has no practical problem as long as it is evaluated as ◯ or higher, and is preferable if it is ◎.

(B) Steam test The antifogging film test piece is prevented by placing the antifogging film test piece at a position 2 cm above the surface of the hot water bath maintained at 80 ° C. so that the antifogging film faces downward. The cloud film was irradiated with steam in a warm water bath, and the presence or absence of fogging 10 seconds after the steam irradiation was visually evaluated in the following four stages.

A: A water film is formed immediately after the steam irradiation and does not become cloudy.
○: Instantaneous clouding is recognized immediately after steam irradiation, but a water film is formed immediately and the cloudiness is eliminated.
Δ: Clouding is observed immediately after steam irradiation, but a water film is formed and the clouding is eliminated.
X: Cloudiness is recognized immediately after steam irradiation, and a water film is not formed.

  The antifogging film formed on the antifogging film test piece has no practical problem as long as the evaluation is Δ or more, preferably ○, and more preferably ◎.

(C) Steam test after moisture resistance test The antifogging film specimen was allowed to stand for 240 hours under conditions of 50 ° C. and 95% RH, and further allowed to stand at room temperature for 1 hour. Thereafter, the antifogging film test piece was placed on the antifogging film on the antifogging film by placing the antifogging film test piece at a position 2 cm above the surface of the warm water bath maintained at 80 ° C. Steam irradiation in a warm water bath was performed, and the presence or absence of clouding 10 seconds after the steam irradiation was visually evaluated in the following four stages.

A: A water film is formed immediately after the steam irradiation and does not become cloudy.
○: Instantaneous clouding is recognized immediately after steam irradiation, but a water film is formed immediately and the cloudiness is eliminated.
Δ: Clouding is observed immediately after steam irradiation, but a water film is formed and the clouding is eliminated.
X: A clean water film is not formed after steam irradiation, or a water film is not formed and cloudiness is recognized.

  The antifogging film formed on the antifogging film test piece has no practical problem as long as the evaluation is Δ or more, preferably ○, and more preferably ◎.

(D) Steam test after heat resistance test The antifogging film test piece was allowed to stand at 120 ° C. for 240 hours, and further allowed to stand at room temperature for 1 hour. Thereafter, the antifogging film test piece is placed on the antifogging film by placing the antifogging film test piece at a position 2 cm above the water surface of the warm water bath maintained at 80 ° C. Steam irradiation in a warm water bath was performed, and the presence or absence of clouding 10 seconds after the steam irradiation was visually evaluated in the following four stages.

A: A water film is formed immediately after the steam irradiation and does not become cloudy.
○: Instantaneous clouding is recognized immediately after steam irradiation, but a water film is formed immediately and the cloudiness is eliminated.
Δ: Clouding is observed immediately after steam irradiation, but a water film is formed and the clouding is eliminated.
X: A clean water film is not formed after steam irradiation, or a water film is not formed and cloudiness is recognized.

  The antifogging film formed on the antifogging film test piece has no practical problem as long as the evaluation is Δ or more, preferably ○, and more preferably ◎.

(3-2) Water spilling trace By installing the antifogging film test piece so that the antifogging film faces downward at a position 2 cm above the surface of the hot water bath maintained at 80 ° C., the antifogging film test is performed. After irradiating the piece of anti-fogging film with steam in a warm water bath, the anti-fogging film test piece was dried vertically at room temperature for 1 hour. The presence or absence of water dripping marks on the antifogging film test piece after drying was visually evaluated in the following four stages.

A: The dripping trace is not conspicuous.
○: Water dripping marks are hardly noticeable.
Δ: Water dripping marks are slightly noticeable.
X: Water dripping marks are conspicuous.

  The antifogging film formed on the antifogging film test piece has no practical problem as long as the evaluation is Δ or more, preferably ○, and more preferably ◎.

(3-3) Adhesiveness According to JIS K 5600-5-6, the presence or absence of peeling of the antifogging film in the antifogging film test piece was visually evaluated in the following three stages.

(Double-circle): Peeling is not recognized at all.
○: Partial peeling is observed.
X: All peeled off.

  The antifogging film formed on the antifogging film test piece has no practical problem if the evaluation is ◯ or higher, and is more preferable if it is ◎.

(3-4) Water resistance The antifogging membrane test piece was allowed to stand in warm water at 40 ° C. for 240 hours, and further allowed to stand at room temperature for 1 hour. Thereafter, the appearance of the antifogging film of the antifogging film test piece was visually evaluated in the following four stages.

A: There is no change in the appearance before the test.
○: The coating film surface is slightly rough.
(Triangle | delta): The coating-film surface is rough or slight whitening and a spot are recognized.
X: Part or all of the coating film is dissolved, or whitening or spots are clearly observed.

  The antifogging film formed on the antifogging film test piece has no practical problem as long as the evaluation is Δ or more, preferably ○, and more preferably ◎.

4). Evaluation results of antifogging film (4-1) Examples 1 to 9
In Examples 1 to 9, the types and amounts of the fluorine-based anionic surfactant (C-1) and the betaine-based surfactant (C-2) were mainly examined. All the antifogging film test pieces according to Examples 1 to 9 are produced by the same method as described above. Table 1 shows the composition (parts by weight) of the antifogging agent composition according to Examples 1 to 9 and the evaluation results of the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition. Show.

なお、表１中の各物質の省略表記については後述する。

In addition, the abbreviation notation of each substance in Table 1 will be described later.

  As shown in Table 1, in Examples 1 to 9, good performance of the antifogging film was confirmed. In the antifogging film according to Example 2, particularly good performance was obtained.

  More specifically, in the sustainability test, good evaluation results were obtained in any of the examples, and particularly good evaluation results were obtained in Examples 2, 3, and 6-9. From this evaluation result, it is understood that further improvement of the antifogging durability can be obtained by the kind and amount of the fluorine-based anionic surfactant (C-1) and the betaine-based surfactant (C-2). It was.

  In the steam test, an evaluation result having no practical problem is obtained in any of the examples, and among them, good evaluation results are obtained in Examples 1, 5, and 6, and further, in Examples 2, 3, 7 to 9 Particularly good evaluation results were obtained. From this evaluation result, it was found that the durability against steam irradiation can be further improved depending on the types and amounts of the fluorine-based anionic surfactant (C-1) and the betaine-based surfactant (C-2). .

  In the water dripping test, an evaluation result having no practical problem is obtained in any of the examples, and among them, good evaluation results are obtained in Examples 3, 6 to 8, and further, Examples 1, 2, 4, Particularly good evaluation results were obtained in FIG. From this evaluation result, the betaine surfactant (C-2) is Nissan Anone BL-SF or Softazoline LPB-R, and the amount of the fluorine-based anionic surfactant (C-1) is suppressed to a certain extent. It was found that the occurrence of sagging marks can be further suppressed.

  In the adhesion test and the water resistance test, particularly good evaluation results were obtained in any of the examples. From this evaluation result, it was found that particularly good adhesion and water resistance can be obtained by adopting the configuration of the present invention.

(4-2) Examples 10 to 21
In Examples 10 to 21, the types of the monomer (A-1), the monomer (A-2), and the monomer (A-3) were mainly examined. All the anti-fogging film test pieces according to Examples 10 to 21 are produced by the same method as described above. Table 2 shows the composition (parts by weight) of the antifogging agent composition according to Examples 10 to 21 and the evaluation result of the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition. Show.

なお、表２中の各物質の省略表記については後述する。

In addition, the abbreviation notation of each substance in Table 2 will be described later.

  As shown in Table 2, in Examples 10 to 21, good performance of the antifogging film was confirmed.

  More specifically, in the sustainability test, good evaluation results were obtained in any of the examples, and particularly good evaluation results were obtained in Examples 10 to 19 among them. From this evaluation result, it has been found that further improvement of the antifogging durability can be obtained by using any of HEA, HEMA, and HEAA as the monomer (A-3).

  In the steam test, good evaluation results were obtained in any of the examples, and particularly good evaluation results were obtained in Examples 10 to 16 and 18 to 21. From this evaluation result, it can be seen that further improvement of durability against steam irradiation can be obtained by using any one of MMA (C1), BA (C4), and CHA (C6) as the monomer (A-2). all right.

  In the water dripping test, good evaluation results were obtained in any of the examples, and particularly good evaluation results were obtained in Examples 10 to 14 and 16 to 21. From this evaluation result, it is understood that the occurrence of dripping traces can be further suppressed by setting the monomer (A-2) to one of BA (C4), CHA (C6), and CA (C16). It was.

  In the adhesion test, good evaluation results were obtained in any of the examples, and particularly good evaluation results were obtained in Examples 10 and 15 to 20. From this evaluation result, it was found that a further improvement in adhesion can be obtained by using DMMA or DEMA as the monomer (A-1).

  In the water resistance test, particularly good evaluation results were obtained in any of the examples. From this evaluation result, it was found that particularly good water resistance can be obtained by adopting the constitution of the present invention.

(4-3) Examples 22 to 26
In Examples 22 to 26, the amount of monomer (A-1), monomer (A-2), monomer (A-3), and polyfunctional blocked isocyanate compound (B) was mainly examined. did. All of the antifogging film test pieces according to Examples 22 to 26 are produced by the same method as described above. Table 3 shows the composition (parts by weight) of the antifogging agent composition according to Examples 22 to 26 and the evaluation result of the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition. Show.

なお、表３中の各物質の省略表記については後述する。

In addition, the abbreviation notation of each substance in Table 3 will be described later.

  As shown in Table 3, in Examples 22 to 26, good performance of the antifogging film was confirmed.

  More specifically, in the sustainability test, good evaluation results were obtained in any of the examples, and particularly good evaluation results were obtained in Examples 22, 24, and 25 among them. From this evaluation result, it was found that the polyfunctional blocked isocyanate compound (B) was diethyl malonate blocked isocyanate and the NCO / OH ratio was kept small to a certain extent, thereby further improving the antifogging durability.

  In the steam test, particularly good evaluation results were obtained in any of the examples. From this evaluation result, it was found that by using the configuration of the present invention, particularly good durability against steam irradiation can be obtained.

  In the water dripping test, an evaluation result having no practical problem is obtained in any of the examples, and among them, a good evaluation result is obtained in Example 23, and furthermore, a particularly good evaluation result is obtained in Examples 24 and 26. Obtained. From this evaluation result, it was found that the occurrence of dripping traces can be further suppressed by using diethyl malonate blocked isocyanate as the polyfunctional blocked isocyanate compound (B) and increasing the amount thereof to some extent.

  In the adhesion test, good evaluation results were obtained in any of the examples, and particularly good evaluation results were obtained in Examples 22, 23, 25, and 26. From this evaluation result, it was found that the adhesiveness was further improved by setting the amount of the monomer (A-2) to be equal to or greater than the amount of the monomer (A-3).

In the water resistance test, an evaluation result having no practical problem is obtained in any of the examples, and among them, a good evaluation result is obtained in Example 23, and further, particularly good evaluation results are obtained in Examples 24 and 26. It was. From this evaluation result, it was found that the polyfunctional blocked isocyanate compound (B) is diethyl malonate blocked isocyanate, and the water resistance can be further improved by increasing the amount to some extent.
5. Comparative Example Table 4 shows the composition (parts by weight) of the antifogging agent composition according to Comparative Examples 1 to 7 and the evaluation results of the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition It shows. All of the antifogging film test pieces according to Comparative Examples 1 to 7 are produced by the same method as described above.

なお、表４中の各物質の省略表記については後述する。

In addition, the abbreviation notation of each substance in Table 4 is mentioned later.

  Unlike the embodiment of the present invention, the antifogging agent composition according to Comparative Example 1 does not contain a betaine surfactant (C-2). As a result, the antifogging film according to Comparative Example 1 could not obtain sufficient antifogging performance.

  Unlike the embodiment of the present invention, the antifogging agent composition according to Comparative Example 2 does not contain a fluorine-based anionic surfactant (C-1). As a result, the antifogging film according to Comparative Example 2 could not obtain sufficient antifogging performance. Moreover, in the anti-fogging film | membrane which concerns on the comparative example 2, the anti-fogging property after a heat test was a little low.

  Unlike the embodiment of the present invention, the antifogging agent composition according to Comparative Examples 3 and 4 is an anionic surfactant (C-1 ′) instead of the fluorinated anionic surfactant (C-1). Is used. As a result, the anti-fogging film according to Comparative Examples 3 and 4 did not have sufficient sustainability of the anti-fogging performance. Further, in the antifogging film according to Comparative Example 4, the water dripping trace was slightly noticeable.

  Unlike the embodiment of the present invention, the antifogging agent composition according to Comparative Example 5 is a nonionic surfactant instead of the fluorine-based anionic surfactant (C-1) and the betaine-based surfactant (C-2). Surfactant (C-3) is used. As a result, the antifogging film according to Comparative Example 5 could not obtain sufficient antifogging performance. Moreover, in the anti-fogging film | membrane which concerns on the comparative example 5, the anti-fogging property after a heat test was a little low.

  Unlike the embodiment of the present invention, the antifogging agent composition according to Comparative Example 6 uses a nonionic surfactant (C-3) instead of the betaine surfactant (C-2). . As a result, the antifogging film according to Comparative Example 6 could not obtain sufficient antifogging performance. Further, in the antifogging film according to Comparative Example 6, water dripping marks were easily noticeable.

  Unlike the embodiment of the present invention, the antifogging agent composition according to Comparative Example 7 uses a nonionic surfactant (C-3) instead of the fluorine-based anionic surfactant (C-1). ing. As a result, the antifogging film according to Comparative Example 7 could not obtain sufficient antifogging performance. Moreover, in the anti-fogging film | membrane which concerns on the comparative example 5, the anti-fogging property after a heat test was a little low, and the water dripping trace was a little conspicuous.

6). Substance Abbreviations The names corresponding to the substance abbreviations used in Tables 1 to 4 are summarized below.

(6-1) Monomer (A-1)
DMAA: N, N-dimethylacrylamide DEMA: N, N-diethylmethacrylamide IPAA: N-isopropylacrylamide,
DAAA: diacetone acrylamide DMAPAA: dimethylaminopropyl acrylamide ACMO: N-acryloylmorpholine

(6-2) Monomer (A-2)
MMA: methyl methacrylate BA: n-butyl acrylate CHA: cyclohexyl acrylate CA: cetyl acrylate

(6-3) Monomer (A-3)
HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate HEAA: hydroxyethyl acrylamide PLACEL FA2D: 2-hydroxyethyl acrylate caprolactone 2 mol adduct PLACEL FA5: 2-hydroxyethyl acrylate caprolactone 5 mol adduct

(6-4) Polyfunctional blocked isocyanate compound (B)
Duranate MF-K60B: Malonate block isocyanate [trade name: Duranate MF-K60B manufactured by Asahi Kasei Chemicals Corporation]
Desmodur BL3575 / 1: Dimethylpyrazole block isocyanate [trade name: Desmodur BL3575 / 1 manufactured by Sumitomo Bayer Urethane Co., Ltd.]
Sumidur BL3175: methyl ethyl ketoxime block isocyanate [trade name: Sumidur BL3175 manufactured by Sumitomo Bayer Urethane Co., Ltd.]

(6-5) Fluorine-based anionic surfactant (C-1)
Footage 100: Sodium fluorinated sulfonate [manufactured by Neos Co., Ltd. (active ingredient 100% by weight)]
Surflon S-211: Fluorine-based carboxylate [manufactured by AGC Seimi Chemical Co., Ltd. (active ingredient 50% by weight)]

(6-5 ')
Anionic surfactant (C-1 ′)
Lapisol A-80: sodium di (2-ethylhexyl) sulfosuccinate [manufactured by NOF Corporation (active ingredient 80% by weight)]

(6-6) Betaine surfactant (C-2)
NS
Softazoline LPB-R: lauric acid amidopropyl betaine [manufactured by Kawaken Fine Chemical Co., Ltd. (active ingredient 30% by weight)]
Footage 400SW: Fluorine-based betaine [manufactured by Neos (active ingredient 50% by weight)]
Surflon S-232: Fluorine-based betaine [manufactured by AGC Seimi Chemical Co., Ltd. (active ingredient 30% by weight)]

(6-7) Nonionic surfactant (C-3)
Neugen EA-140: polyoxyethylene alkylphenyl ether [Daiichi Kogyo Seiyaku Co., Ltd. (active ingredient 100% by weight)]

[Others]
The embodiment of the present invention has been described above, but the present invention is not limited to the above-described embodiment, and it is needless to say that various modifications can be made without departing from the gist of the present invention.

Claims (2)

Consists of a copolymer (A), a polyfunctional blocked isocyanate compound (B) and a surfactant (C),
The copolymer (A) is
The monomer (A-1) represented by the following general formula (1) or (2), the monomer (A-2) represented by the following general formula (3), and the following general formula (4) Or a monomer (A-3) represented by (5),

... (1)
(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, 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} ) is _2, ^{R 3} is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms is there.)

... (2)
(In General Formula (2), R ⁴ is a hydrogen atom or a methyl group.)

... (3)
(In General Formula (3), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms.)

... (4)
(In General Formula (4), R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a linear or branched alkylene group having 2 to 4 carbon atoms, or —C ₂ H ₄ (OCO (CH _{2 5} ) _n- (n is an integer of 1 to ₅ ).)

... (5)
(In General Formula (5), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 1 to 4 carbon atoms.)
The monomer (A-1) is 35 with respect to a total of 100 parts by weight of the monomer (A-1), the monomer (A-2), and the monomer (A-3). -90 parts by weight, the monomer (A-2) is 5-60 parts by weight, and the monomer (A-3) is 5-30 parts by weight,
The NCO / OH ratio, which is the ratio of the isocyanate group content (NCO) of the polyfunctional blocked isocyanate compound (B) and the hydroxyl group content (OH) of the copolymer (A), is 0.1 to 1.5. Within the range of
The surfactant (C) is 1.00 to 10.0 parts by weight of a fluorine-based anionic surfactant (C-1) with respect to 100 parts by weight of the copolymer (A), and 0.01 An anti-fogging agent composition comprising -3.00 parts by weight of a betaine surfactant (C-2). A substrate;
An antifogging article comprising: an antifogging film obtained by heat-curing the antifogging composition according to claim 1 applied to the substrate.