TWI696691B - Anti-fog coating composition and anti-fog transparent sheet using the coating composition - Google Patents

Abstract

The present invention provides an anti-fog coating composition and an anti-fog transparent sheet using the same. The anti-fog coating composition contains: one or both of hydrophilic bisphenol A acrylate and hydrophilic bisphenol A methacrylate, component A, reactive nonionic surfactant, component C, and component C That is, reactive ionic liquid and component D, that is, a polymerization initiator. The anti-fog coating composition preferably further contains either or both of E component, pentaerythritol acrylate and pentaerythritol methacrylate, and F component, either urethane acrylate resin and urethane methacrylate resin. One or two parties. The anti-fog transparent sheet includes a transparent base material and an anti-fog coating film composed of the anti-fog coating composition disposed on the surface of the base material.

Description

Anti-fog coating composition and anti-fog transparent sheet using the coating composition

The present invention relates to an anti-fog coating composition and an anti-fog transparent sheet using the same.

When the surface temperature of the base material is lower than the dew point of the surrounding air, water droplets adhere to the surface of the base material and become blurred. In transparent substrates such as lenses, glass windows, transparent films, and reflective materials such as mirrors, blurring of the surface causes damage to the visibility of transmitted or reflected images. For this reason, a method of forming a coating that imparts an anti-fog effect on the surface of a substrate to prevent fog is proposed. For example, the following method has been disclosed: by forming an anti-fog coating on the surface of a transparent substrate, increasing the hydrophilicity of the surface of the substrate or reducing the contact angle of the lens with water to prevent the formation of water droplets on the surface of the substrate, thereby preventing Base material blur (for example, Patent Document 1, Patent Document 2, etc.).

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2004-83846.

Patent Document 2: Japanese Patent Application Publication No. 2007-137937.

Anti-fog properties are sought on various occasions. Especially in an environment accompanied by rapid temperature changes, the anti-fog properties are also sought. Furthermore, an anti-fog coating is sought, which not only has excellent initial anti-fog properties immediately after the anti-fog coating is formed, but also has excellent anti-fog continuity in which the anti-fog effect can last for a long time. For example, an anti-fog coating film with an anti-fog property that continues to be exposed to water and warm water and an anti-fog transparent sheet provided with such an anti-fog film are sought.

Therefore, one of the objects of the present invention is to provide an anti-fog coating composition capable of forming an anti-fog coating film that is excellent not only in initial anti-fog properties but also in anti-fog effects that can last for a long time, and anti-fog properties using the same Transparent sheet.

The anti-fog coating composition according to the first aspect of the present invention contains: (A) a hydrophilic bisphenol A type (meth)acrylate, (B) a reactive nonionic surfactant, (C) a reactive ionic liquid and (D) Polymerizable initiator.

In addition, the anti-fog transparent sheet according to the second aspect of the present invention includes a transparent base material and an anti-fog coating film composed of the anti-fog coating composition disposed on the surface of the base material.

According to the present invention, it is possible to provide an anti-fog coating composition capable of forming not only an initial anti-fog property, but also an anti-fog film having excellent anti-fog durability that can last for a long time, and an anti-fog transparent sheet having excellent anti-fog properties material.

[Description of embodiment of the present invention]

First, the embodiments of the present invention are listed and explained. The anti-fog coating composition according to the present invention contains: (A) hydrophilic bisphenol A (meth)acrylate, (B) reactive nonionic surfactant, (C) reactive ionic liquid, and (D) polymerization Sexual initiator.

The anti-fog coating composition containing (A) hydrophilic bisphenol A type (meth)acrylate, (B) reactive nonionic surfactant and (C) reactive ionic liquid immediately after forming the anti-fog coating film Excellent anti-fog properties. Among them, there is an effect of exerting anti-fog properties (low-temperature anti-fog properties) especially in a low-temperature environment. In addition, such an anti-fog coating composition has an effect of continuing the hydrophilicity of the surface of the base material after the anti-fog coating is formed. By imparting such continuous hydrophilicity (hydrophilic continuity) to the base material, an anti-fog coating film excellent in anti-fog continuity can be formed.

In addition, (B) the reactive nonionic surfactant and (C) the reactive ionic liquid also have the effect of reducing the contact angle of the substrate surface. By reducing the contact angle of the substrate surface, the anti-fog effect is further improved. Furthermore, by containing (D) a polymerizable initiator, it is possible to provide an anti-fog coating film having a large molecular weight and excellent retention on the surface of the substrate. As a result, it is possible to form an anti-fog coating film having excellent anti-fog continuity with an anti-fog effect that can last for a long time.

By containing the components (A) to (D) in this way, an anti-fog coating composition capable of forming an anti-fog coating film that is excellent in initial anti-fog properties and that can maintain anti-fog effects for a long period of time is also excellent. Thing.

In the above anti-fog coating composition, (C) the reactive ionic liquid may be a liquid composed of ammonium sulfonate. By containing such a reactive ionic liquid, it is possible to more reliably obtain an anti-fog coating film that is excellent not only in initial anti-fog properties but also in anti-fog effects that can last for a long time and has excellent anti-fog properties.

The anti-fog coating composition may further contain (E) pentaerythritol (meth)acrylate. By containing the (E) component, the anti-fog coating film described later can be improved in washing resistance, and the anti-fog coating film can be given flexibility.

The anti-fog coating composition may further contain (F) urethane (meth) acrylate resin. By containing the (F) component, the anti-fog coating film to be described later can be improved in washing resistance, and the anti-fog coating film can be given flexibility.

In the above anti-fog coating composition, the content of the component (B) may be more than 2 parts by mass and 20 parts by mass or less with respect to 100 parts by mass of the component (A). By setting the content of the component (B) to more than 2 parts by mass relative to 100 parts by mass of the component (A), an anti-fog coating composition capable of forming an anti-fogging film with high transparency of the film more stably can be obtained. In addition, even if the content of the component (B) exceeds 20 parts by mass relative to 100 parts by mass of the component (A), the transparency and anti-fogging properties will not be improved due to saturation of the effect, but the cost will increase. Therefore, the content of the component (B) is preferably 20 parts by mass or less relative to 100 parts by mass of the component (A).

In the anti-fog coating composition, the content of the component (C) may be 1 part by mass or more and 5 parts by mass or less relative to 100 parts by mass of the component (A). As long as the content of the (C) component is 1 part by mass or more, the effect of improving the anti-fog characteristics by the (C) component can be more clearly exhibited. In addition, even if the content of the component (C) exceeds 5 parts by mass relative to 100 parts by mass of the component (A), the transparency and anti-fogging properties will not be improved due to saturation of the effect, but the cost will increase. Therefore, the content of the component (C) is preferably 5 parts by mass or less with respect to 100 parts by mass of the component (A).

The content ratio (B)/(C) of the component (B) to the component (C) may be 1 or more and 10 or less. By setting the ratio (B)/(C) to 1 or more, it is possible to provide an anti-fog coating film having more excellent anti-fog characteristics. In addition, even if the above ratio exceeds 10, since the effect is saturated, the transparency and anti-fog characteristics will not change any more, so the upper limit is preferably 10.

The anti-fog coating composition may further contain a leveling agent. By containing a leveling agent, the coating properties of the anti-fog coating composition can be improved. Furthermore, the contact angle between the base material and water can be reduced, so that water droplets are not easily generated. Therefore, it helps to improve the anti-fog effect.

In the above anti-fog coating composition, the polymerizable initiator may be a photopolymerization initiator. By using the polymerizable initiator as a photopolymerization initiator, the curing after applying the anti-fog coating composition can be relatively easily performed.

The anti-fog transparent sheet according to the invention of the present application includes a transparent base material and an anti-fog coating film composed of the anti-fog coating composition disposed on the surface of the base material. The anti-fog transparent sheet provided with the anti-fog coating composed of the anti-fog coating composition has excellent transparency and anti-fog properties.

The base material may be a base material made of polyethylene terephthalate. Since polyethylene terephthalate is excellent in transparency, it is possible to obtain an anti-fog transparent sheet with high transparency throughout the sheet. In addition, since polyethylene terephthalate has excellent processability, it is possible to obtain an anti-fog transparent sheet that can be applied to various applications.

[Detailed description of embodiments of the invention]

Next, an embodiment of the anti-fog coating composition of the present invention will be described. The anti-fog coating composition according to this embodiment contains: (A) hydrophilic bisphenol A type (meth)acrylate (also referred to as "(A) component" in this specification and patent application), (B) Reactive nonionic surfactant (also referred to as "(B) component" in this specification and patent application), (C) reactive ionic liquid (also referred to as "(C) in this specification and patent application "Component") and (D) a polymerizable initiator (also referred to as "(D)component" in this specification and patent application). In this specification, "(meth)acrylate" means either or both of acrylate and methacrylate.

[(A) Hydrophilic bisphenol A (meth)acrylate]

The anti-fog coating composition of the present invention contains a hydrophilic bisphenol A type (meth)acrylate as (A) component. The hydrophilic bisphenol A type (meth)acrylate is the main component of the anti-fog coating composition, and imparts hydrophilicity to the base material coated with the anti-fog coating composition, which helps to improve the anti-fog effect. In addition, the anti-fog coating composition containing the hydrophilic bisphenol A type (meth)acrylate and the ionic liquid containing the anti-fogging coating formed of the anti-fog coating composition has just formed an anti-fogging coating In particular, the low-temperature anti-fogging property and the hydrophilic sustainability are good. "Hydrophilic" means a resin that does not undergo phase separation when added to water and can be dispersed or dissolved in water.

The above-mentioned hydrophilic bisphenol A type (meth)acrylate has a structure in which two hydroxyl groups of bisphenol A are substituted with a reactive group having a (meth)acrylate group. Examples of the hydrophilic bisphenol A type (meth)acrylate include compounds having a structure represented by the following general formula (1).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and m and n each independently represent an integer of 0 or more. The value of m+n is 0 or more, preferably 4 or more, and more preferably 10 the above.)

As shown in the above formula (1), in this specification, the hydrophilic bisphenol A type (meth)acrylate preferably contains an alkylene oxide-modified bisphenol A type (meth)acrylate. The alkylene oxide modified bisphenol A type (meth)acrylate includes, for example, ethylene oxide modified bisphenol A type (meth)acrylate, propylene oxide modified bisphenol A type (meth) Base) acrylate and the like. In formula (1), the larger the value of m+n, the higher the hydrophilicity of the hydrophilic bisphenol A type (meth)acrylate. As described above, the value of m+n is preferably 4 or more, and more preferably 10 or more. As a preferable example of such a compound, for example, a compound represented by the following formula (2) can be mentioned.

(In the formula, m and n independently represent integers of 0 or more, for example, m+n=20)

As an example of a commercially available product of hydrophilic bisphenol A type (meth)acrylate, New Frontier (R) BPE-4 (in formula (1), R ¹ and R ² is a hydrogen atom, m+n=4), New Frontier(R) BPE-10 (in formula (1), R ¹ and R ² are hydrogen atoms, m+n=10), New Frontier(R) BPE-20 (in formula (1), R ¹ and R ² are hydrogen atoms, m+n=20), New Frontier (R) BPEM-4 (in formula (1), R ¹ and R ² are A Base, m+n=4), New Frontier(R)BPEM-10 (in formula (1), R ¹ and R ² are methyl, m+n=10) and other New Frontier(R) series.

The ratio of the hydrophilic bisphenol A type (meth)acrylate to 100% by mass of the total solid content of the anti-fog coating composition in terms of solid content is preferably 50% by mass or more, and more preferably 60% by mass or more. By containing a hydrophilic bisphenol A type (meth)acrylate of 50% by mass or more in terms of solid content, an anti-fog coating that can form anti-fog properties, especially excellent in low-temperature anti-fog properties and hydrophilic continuity can be obtained Anti-fog coating composition. The upper limit of the above ratio is not particularly limited, but the upper limit is, for example, 90% by mass in terms of solid content.

[(B) Reactive nonionic surfactant]

The anti-fog coating composition of the present invention contains a reactive nonionic surfactant as the (B) component. Reactive non-ionic surfactants mainly help to improve the low-temperature anti-fog properties of anti-fog coatings, improve the sustainability of hydrophilicity and reduce the contact angle.

The nonionic surfactant (nonionic surfactant) is a surfactant having a hydrophilic group that does not ionize in a state of being dissolved in water. Among them, "reactive nonionic surfactant" is a nonionic surfactant having a reactive functional group in the molecule. Examples of the above-mentioned reactive functional group include groups containing unsaturated bonds such as vinyl and (meth)acryloyl, especially groups containing ethylenic unsaturated bonds.

Examples of the reactive nonionic surfactant contained in the anti-fog coating composition of the present application include compounds having a structure represented by the following formula (3).

(In the formula, R ³ represents a carbon atom having 8 to 36 carbon atoms, and a monovalent branched aliphatic hydrocarbon group or a branched aliphatic acyl group having 3 or more methyl groups, and AO represents a carbon atom having 2 to 4 carbon atoms. Alkyl group, L represents a group represented by the following formula (4), z represents a number from 1 to 10, X represents a hydrogen atom or the following anionic hydrophilic group or cationic hydrophilic group (preferably a hydrogen atom ), m represents a number from 0 to 1000, n represents a number from 0 to 1000.)

(In the formula, R ⁴ and R ⁵ represent a hydrogen atom or a methyl group, x represents a number from 0 to 12, and y represents a number of 0 or 1.)

Anionic hydrophilic group: -SO ₃ M, -R ⁶ -SO ₃ M, -R ⁷ -COOM, -PO ₃ M ₂ , -PO ₃ MH, or -CO-R ⁸ -COOM (where M represents hydrogen Atom, alkali metal atom, alkaline earth metal atom or ammonium (among them, alkaline earth metal atom is 1/2), R ⁶ and R ⁷ represent alkylene group, R ⁸ represents the residue after removing carboxyl group from dibasic acid or its anhydride base.)

Cationic hydrophilic group: -R ⁹ -NR ¹⁰ R ¹¹ R ¹² . Y or -Z-NR ¹⁰ R ¹¹ R ¹² . Y (wherein R ⁹ represents an alkylene group, R ¹⁰ to R ¹² represent an alkyl group having 1 to 4 carbon atoms, an alkanol group or a benzyl group having 2 to 4 carbon atoms, and Y represents a halogen atom or a methyl group Sulfuric acid group, Z represents a group represented by -CH ₂ CH(OH)CH ₂ -or -CH(CH ₂ OH)CH ₂ -.)

The above L is preferably a group having a structure represented by the following formula (5).

Formula (5) -CH ₂ -CH=CH ₂ (5)

Specific examples of the compound having the structure represented by the above formula (3) include compounds having the structure represented by the following formula (6).

(In the formula, EO is ethylene oxide, and m is a number from 0 to 1000.)

Typically, m in the above formula (6) is an integer of 5 or more and 50 or less, for example, m=10, 20, 30, or 40.

Among the nonionic surfactants which are compounds having the structure represented by the above formula (3), examples of commercially available products include Adekarea Soap ER-10, Adekarea Soap ER-20, Adekarea Soap ER-30, Adekarea Soap ER-40, Adekarea Soap SR series and Adekarea Soap SE series (all made by ADEKA Corporation), etc.

The content of the component (B) is preferably more than 2 parts by mass and 20 parts by mass or less relative to 100 parts by mass of the component (A). By containing more than 2 parts by mass of the (B) component relative to 100 parts by mass of the (A) component, an anti-fogging film with high film transparency can be formed more stably. In addition, even if the content of the component (B) exceeds 20 parts by mass relative to 100 parts by mass of the component (A), the transparency and anti-fog properties will not be improved due to saturation of the effect, but the cost will increase. Therefore, the content of the component (B) is preferably 20 parts by mass or less relative to 100 parts by mass of the component (A). The upper limit of the content of (B) component is more preferably 18 parts by mass relative to 100 parts by mass of (A) component.

[(C) Reactive ionic liquid]

The anti-fog coating composition of the present invention contains a reactive ionic liquid as (C) component. An ionic liquid is a substance in which ions composed of cations and anions exist as a liquid. Ionic liquids are salts and have a low melting point and are in a liquid state near room temperature. In addition, "reactive ionic liquid" is a substance containing a cation having a reactive functional group. Examples of the reactive functional group include unsaturated bond-containing groups such as vinyl groups and (meth)acryloyl groups, and particularly groups containing ethylenic unsaturated bonds.

Examples of the reactive ionic liquid of the above component (C) include reactive ionic liquids containing ion-binding salts having reactive groups represented by the following chemical formula (7) or the following chemical formula (8).

(In the formula, R ¹³ and R ¹⁴ independently represent a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted carbon atom has 6 to 30 carbon atoms Aryl groups; substituted or unsubstituted aralkyl groups having 7 to 31 carbon atoms, A ¹ and A ² are straight or branched chain alkylene groups having 2 to 4 carbon atoms, n is 0 Integer to 50, Q1 ⁺ and Q2 ⁺ independently represent an ammonium ion having an ethylenically unsaturated bond, an imidazolium ion having an ethylenically unsaturated bond, a pyridinium ion having an ethylenically unsaturated bond, Pyrrolidinium ion having an ethylenically unsaturated bond, pyrrolium ion having an ethylenically unsaturated bond, pyridinium ion having an ethylenically unsaturated bond, pyrazinium ion having an ethylenically unsaturated bond, having ethylene Pyrimidinium ion with unsaturated bond, triazolium ion with ethylenic unsaturated bond, triazineium ion with ethylenic unsaturated bond, quinolinium ion with ethylenic unsaturated bond, ethylenic unsaturated bond Isoquinolinium ions, indolium ions with ethylenic unsaturated bonds, quinoxalinium ions with ethylenic unsaturated bonds, pyrazinium ions with ethylenic unsaturated bonds, ethylenic unsaturated bonds At least one of the group consisting of an oxazolinium ion, a thiazolinium ion having an ethylenically unsaturated bond, and a morpholinium ion having an ethylenically unsaturated bond.)

The content of the component (C) is preferably 1 part by mass or more and 5 parts by mass or less relative to 100 parts by mass of the component (A). By containing 1 part by mass or more of (C) component with respect to 100 parts by mass of (A) component, the anti-fog properties and hydrophilic sustainability of the obtained anti-fog coating film become a sufficient level. In addition, even if the content of the component (C) exceeds 5 parts by mass relative to 100 parts by mass of the component (A), the transparency and anti-fogging properties will not be improved due to the saturation of the effect, but the cost will increase. Therefore, the content of the component (C) is preferably 5 parts by mass or less relative to 100 parts by mass of the component (A). The lower limit of the content of the component (C) is more preferably 1.5 parts by mass relative to 100 parts by mass of (A). The upper limit is more preferably 3 parts by mass.

The content ratio (B)/(C) of the component (B) to the component (C) is preferably 1 or more and 10 or less. By making the content of the component (B) relative to the content of the component (C) at least 1 in mass ratio, it is possible to more surely obtain antifogging properties that can form antifogging properties, in particular, excellent antifogging properties at low temperatures and hydrophilic sustainability Anti-fog coating composition for fog coating. In addition, even if the content ratio (B)/(C) exceeds 10, since the effect is saturated, the transparency and anti-fog characteristics will not change any more, so the preferred upper limit is 10.

[(D) polymerization initiator]

The anti-fog coating composition according to this embodiment contains a polymerization initiator as the component (D). Examples of the polymerization initiator include thermal polymerization initiators and photopolymerization initiators. Among them, a photopolymerization initiator is preferred because it can be easily cured after applying the anti-fog coating composition. Furthermore, the photopolymerization initiator is preferably a photopolymerization initiator cured by ultraviolet rays. One kind of polymerization initiator may be used alone, or two or more kinds may be used in combination.

The amount of the polymerization initiator can be appropriately set as needed. For example, it is preferably set appropriately so that the amount of the polymerization initiator of component (D) is 1 part by mass or more and 50 parts by mass with respect to 100 parts by mass of hydrophilic bisphenol A type (meth)acrylate of component (A). It is preferably within a range of 5 parts by mass or more and 30 parts by mass or less.

[(E)Pentaerythritol (meth)acrylate]

In addition to the aforementioned components (A) to (D), the anti-fog coating composition may further contain (E) pentaerythritol (meth)acrylate.

(E) The component pentaerythritol (meth)acrylate helps reduce the contact angle of the anti-fog coating surface. The synergistic effect of the above-mentioned components (B) and (C) can improve the anti-fog property after wiping off the water when the surface of the anti-fog coating film is washed with hot water and then wiped with a cloth. Furthermore, component (E) contributes to improvement of curing reactivity and surface hardness.

Examples of pentaerythritol (meth)acrylate of component (E) include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Methacrylate, hexanediol (meth)acrylate, etc. In addition, since it is possible to impart hydrophilicity, the pentaerythritol (meth)acrylate as the component (E) is preferably an alkylene oxide-modified pentaerythritol (meth)acrylate.

Examples of commercially available (E) pentaerythritol (meth)acrylates include KAYARAD DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), KAYARAD DPEA12 (ethylene oxide modified dipentaerythritol hexaacrylate), KAYARAD D-330 (dipentaerythritol triacrylate), KAYARAD D-320 (dipentaerythritol tetraacrylate) and KAYARAD D-310 (dipentaerythritol pentaacrylate) (all manufactured by Nippon Kayaku Co., Ltd.), etc. Among them, KAYARAD DPEA12 (ethylene oxide-modified dipentaerythritol hexaacrylate) modified with alkylene oxide is preferred.

The content of the (E) component is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more relative to 100 parts by mass of the hydrophilic bisphenol A type (meth)acrylate of the component (A). By containing more than 5 parts by mass of the (E) component relative to 100 parts by mass of the hydrophilic bisphenol A type (meth)acrylate, it can further contribute to reducing the contact angle and improving wiping off water After the anti-fogging properties and the softness of the anti-fog coating. The upper limit is not particularly limited, and is, for example, 30 parts by mass.

[(F) Urethane acrylate resin]

The anti-fog coating composition may further contain the urethane (meth)acrylate resin of the component (F). The urethane acrylate resin can improve the curing reactivity of the anti-fog coating composition.

Examples of urethane (meth)acrylate resins include reaction products of polyol compounds and organic polyisocyanates.

Examples of the polyol compound include ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, and 2 -Ethyl-2-butyl-1,3-propanediol, trimethylolpropane, diethylene glycol, dipropylene glycol, polypropylene glycol, 1,4-dimethylolcyclohexane, bisphenol A polyethoxylate Polyols such as base diol and polytetramethylene glycol; as the above-mentioned polyols and succinic acid, maleic acid, itaconic acid, adipic acid, hydrogenated dibasic acid, phthalic acid, m-phthalic acid Polyester polyols such as reaction products of polybasic acids such as dicarboxylic acid and terephthalic acid or their anhydrides; polycaprolactone polyols as reaction products of the above polyols and ε-caprolactone; Reaction products of ε-caprolactone of alcohols and the aforementioned polybasic acids or their anhydrides; polycarbonate polyols; polymer polyols, etc.

Examples of the organic polyisocyanate include toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentyl diisocyanate, and hexamethylene Diisocyanate, 2,4,4'-trimethylhexamethylene diisocyanate, 2,2'-4-trimethylhexamethylene diisocyanate, etc.

The urethane (meth)acrylate resin preferably contains a urethane (meth)acrylate oligomer. The weight average molecular weight of the urethane (meth)acrylate oligomer is preferably 300 or more and 5000 or less, and more preferably 300 or more and 3000 or less.

Examples of commercially available urethane (meth)acrylate resins of the above (F) component include Art Resin series (manufactured by Negami Industry Co., Ltd.).

The content of the component (F) is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more with respect to 100 parts by mass of the hydrophilic bisphenol A type (meth)acrylate of the component (A). By containing 2 parts by mass or more of (F) component relative to 100 parts by mass of hydrophilic bisphenol A type (meth)acrylate, it can greatly contribute to imparting anti-fog coating scratch resistance (hard Coating), or to improve the reactivity of the anti-fog coating composition. The upper limit is not particularly limited, and is, for example, 10 parts by mass. In addition, the component (F) is more preferably used in combination with the component (E) described above.

〔Leveling agent〕

The anti-fog coating composition according to this embodiment may contain other added components within a range that does not impair the effects of the invention. For example, the anti-fog coating composition according to this embodiment may further contain a leveling agent. By containing a leveling agent, the coating properties of the anti-fog coating composition can be improved. Furthermore, the contact angle between the anti-fog coating and the water can be reduced, and water droplets are not easily generated. Therefore, it helps to improve the anti-fog effect.

Examples of the above-mentioned leveling agent include a silicon-based leveling agent, a fluorine-based leveling agent, an acrylic-based leveling agent, an ethylene-based leveling agent, and a leveling agent that combines fluorine and acrylic. One kind of leveling agent may be used alone, or two or more kinds may be used in combination.

The amount of the leveling agent can be appropriately set as needed. For example, it is appropriately set so that the amount of the leveling agent relative to 100 parts by mass of the hydrophilic bisphenol A type (meth)acrylate of component (A) is 1 part by mass or more and 50 parts by mass or less, preferably 5 Within the range of 30 parts by mass or more.

[Compatibilizer]

The anti-fog coating composition may contain a compatibilizer as needed. The above-mentioned compatibilizer can be appropriately selected according to the compatibility of the above-mentioned components. Examples of the compatibilizer include aliphatic (meth)acrylate, alicyclic (meth)acrylate, aromatic (meth)acrylate and the like. The aliphatic (meth)acrylate, alicyclic (meth)acrylate, and aromatic (meth)acrylate may contain functional groups such as hydroxyl, amino, glycidyl, carboxylic acid (carboxy), and phosphate groups Or polyethylene glycol chain and other modified groups. Examples of commercially available compatibilizers include Light-Ester series and Light-Acrylate series (all manufactured by Kyoeisha Chemical Co., Ltd.). The amount of the compatibilizer can be appropriately adjusted in consideration of the solubility of each component.

[Solvent]

If necessary, the anti-fog coating composition according to this embodiment may contain a solvent. Examples of the solvent include ketone solvents such as methyl ethyl ketone and acetone; ester solvents; glycol ether solvents such as PGM (propylene glycol monomethyl ether); organic solvents such as alcohol solvents; and water. These solvents can be appropriately selected in consideration of the solubility of the added component.

In addition, the ratio of the solvent of the anti-fog coating composition is set in consideration of the solubility of each component, the applicability of the composition, and the like. Among them, when the amount of the solvent is too large, the curing of the coating film tends to become insufficient. In addition, when the amount of the solvent is too small, the transparency of the anti-fog coating tends to decrease. The proportion of the solvent in the anti-fog coating composition is not particularly limited, but it is typically 50% by mass or more and 80% by mass or less of the total amount of the anti-fog coating composition, preferably 50% by mass or more and 70% by mass or less, more preferably It is 55% by mass or more and 65% by mass or less.

[Other added ingredients]

Furthermore, according to the desired characteristics, the anti-fog coating composition according to this embodiment may further contain a film-forming aid, a foam inhibitor, a stabilizer, a filler, an adhesion promoter, a curing agent, a curing accelerator other than the above-mentioned components , Plasticizers, thixotropic agents, pigments, antioxidants and other well-known additives.

[Anti-fog coating composition]

The anti-fog coating composition according to this embodiment can be prepared by the following method: adding (A) hydrophilic bisphenol A type (meth)acrylate to a solvent such as methyl ethyl ketone (MEK), and (B) reacting Nonionic surfactant, (C) reactive ionic liquid, (D) polymerization initiator, (E) ethylene oxide modified dipentaerythritol hexaacrylate, (F) urethane (meth)acrylic acid Ester resin, leveling agent and other required ingredients, and put into the mixer to stir. The order of inputting each component is not particularly limited, and those with ordinary knowledge in the technical field can adjust it arbitrarily according to the technical common sense.

In this embodiment, the preferable anti-fog coating composition is relative to 100 parts by mass of (A) hydrophilic bisphenol A type (meth)acrylate, and contains: 1 part by mass or more and 20 parts by mass or less, preferably 1.5 parts by mass or more and 18 parts by mass or less (B) reactive nonionic surfactant; 1 part by mass or more and 5 parts by mass or less, preferably 1.5 parts by mass or more and 3 parts by mass or less (C) reactive ionic liquid; and (D) The polymerizable initiator is 1 part by mass or more and 50 parts by mass or less, preferably 5 parts by mass or more and 30 parts by mass or less. The content ratio of (B) component to (C) component (B)/(C) is more preferably 1 or more and 10 or less.

In this embodiment, the other preferable anti-fog coating composition is relative to 100 parts by mass of (A) hydrophilic bisphenol A type (meth)acrylate, containing: 1 part by mass or more, preferably 1.5 parts by mass 18 parts by mass or more (B) reactive nonionic surfactant; 1 part by mass or more and 5 parts by mass or less, preferably 1.5 parts by mass or more and 3 parts by mass or less (C) reactive ionic liquid; 1 part by mass More than 50 parts by mass or less, preferably 5 parts by mass or more and 30 parts by mass or less (D) a polymerizable initiator; 5 parts by mass or more, more preferably 10 parts by mass or more and 30 parts by mass or less (E) ethylene oxide Modified dipentaerythritol hexaacrylate; and (F) urethane (meth)acrylate resin of 2 parts by mass or more, more preferably 3 parts by mass or more and 10 parts by mass or less. The content ratio (B)/(C) of the component (B) relative to the component (C) is more preferably 1 or more and 10 or less.

[Anti-fog transparent sheet]

Next, the anti-fog transparent sheet according to this embodiment will be described. The anti-fog transparent sheet of the present embodiment includes a transparent base material and an anti-fog coating film composed of the anti-fog coating composition disposed on the surface of the base material.

The anti-fog transparent anti-fog coating film can be formed by coating the above-mentioned coating composition on a substrate and drying the coating film. In addition, when the anti-fog coating composition contains a photopolymerization initiator, after coating, the curing of each component can be promoted by irradiating light such as ultraviolet rays to form an anti-fog coating film.

As the above-mentioned base material, a transparent base material such as glass, resin (plastic) sheet or film is preferable. Examples of the transparent substrate include resin-made transparent sheets or transparent films selected from transparent resins such as polyethylene terephthalate (PET), polycarbonate, and poly(meth)acrylate.

Furthermore, the anti-fog coating film has excellent high-temperature anti-fog properties and low-temperature anti-fog properties. Therefore, the anti-fog effect can be exerted in a wide temperature environment. In addition, since the coating film is also excellent in transparency, it can be used as a coating film that does not impair the appearance of the base material and the visibility of the external scenery image transmitted through the base material.

[Use]

The anti-fog coating agent according to the present embodiment can exhibit the anti-fog effect in a wide range of temperature environments, and is excellent in the continuity of the anti-fog effect and the transparency of the coating. Therefore, it is possible to form an anti-fog coating film having high adhesion to plastic molded products, plastic films, and especially materials made of PET.

Furthermore, an anti-fog transparent sheet provided with an anti-fog coating composed of the anti-fog coating agent can also be used as an anti-fog material with a base material that is an inorganic glass lens or a building window , Bathroom windows, mirrors, windows for vehicles such as cars or trains, airplanes, ships, goggles for skiing, swimming, etc., protective covers for face masks, motorcycle helmets, etc.

Examples

Hereinafter, the present invention will be described more specifically with reference to examples. The scope of the present invention is not limited to the description of these examples.

The components blended in the following examples and comparative examples are as follows.

(A) Hydrophilic bisphenol A type (meth)acrylate (trade name New Frontier BPE20G, manufactured by Daiichi Pharmaceutical Co., Ltd.)

(B) Reactive nonionic surfactant (trade name Adekarea Soap ER10, manufactured by ADEKA Corporation)

(C) Reactive ionic liquid (trade name JI62C01, manufactured by Japan Emulsifier Co., Ltd.)

(D) Polymerization initiator (trade name DAROCUR(R) 4265 (50% by mass 2,4,6-trimethylbenzyl diphenylphosphine oxide and 50% by mass 2-hydroxy-2-methyl-1 -Mixture of phenyl-1-acetone), manufactured by BASF JAPAN Co., Ltd.)

(E) Pentaerythritol (meth)acrylate

Ethylene oxide (EO) modified dipentaerythritol hexaacrylate (KAYARAD DPEA12, manufactured by Nippon Kayaku Co., Ltd.).

(F) Urethane (meth) acrylic resin

Urethane acrylate oligomer, reactive urethane polymer mixture (trade name Artresin H135, manufactured by Negami Industry Co., Ltd.)

-Compatibilizer

2-Hydroxyethyl methacrylate (trade name Light-Ester HO250N, manufactured by Kyoeisha Chemical Co., Ltd.)

-Solvent

MEK (methyl ethyl ketone)

-Leveling agent A

BYK3560 (polyether macromer modified acrylate, manufactured by BYK Chemie JAPAN Corporation)

-Leveling agent B

DOW CORNING(R)67 ADDITIVE (3-(polyoxyethylene)propyl heptamethyltrisiloxane, solid content concentration 70% by mass to 80% by mass, manufactured by Toray Dow Corning Corporation)

[Preparation of anti-fog coating composition and formation of anti-fog coating]

According to the compounding shown in Table 1 to Table 2, a predetermined amount of the above-mentioned various components are put into a kneader, and an anti-fog coating composition is obtained by kneading. The obtained anti-fog coating composition was coated on a transparent sheet of polyethylene terephthalate (PET) as a base material so that the film thickness after drying became approximately 10 μm, and was performed at 80° C. for 10 minutes. Heat and dry to form a coating film. By using a high-pressure mercury lamp with an output density of 120 W/cm, the coating film formed at a position of 12 cm under the light source is irradiated with ultraviolet rays at a cumulative light amount of 1000 mJ/cm 2 to cure the coating film to form an anti-fog coating. The compounding shown in Table 2 is different from the compounding shown in Table 1 in that it further contains (E) pentaerythritol (meth)acrylate and (F) urethane (meth)acrylate resin.

[Evaluation of anti-fog coating]

Next, the sheet formed with the anti-fog coating was evaluated according to the following evaluation items. The evaluation items and their evaluation sequence are as follows.

(1) Film transparency

The transparency of the film was evaluated by visual observation of the sheet on which the anti-fog film was formed. In the evaluation, the transparency and the presence or absence of haze were observed by visual observation. In Table 1 and Table 2, the mark that is transparent to the coating is "+", and the mark that is found to be fuzzy and turbid on the coating is "-".

(2) Evaluation of anti-fog properties

(2-1) Evaluation of anti-fog properties under normal conditions

Prepare the open container above and inject warm water at 50°C to 60°C. A composite sheet to be evaluated is prepared, the open surface of the container is covered with the composite sheet, and the side of the anti-fogging film faces downward. At this time, the distance between the surface of the anti-fog coating and the surface of warm water is 100 mm ± 5 mm. Keep it still and visually observe the change of the membrane surface after 2 minutes. In Table 1 and Table 2, the result of visual observation is that the composite sheet is entirely transparent, and the exterior scene on the opposite side of the sheet is visible through the sheet as "+"; the sheet is blurred and the sheet is transparent The outside scene on the opposite side of the invisible sheet is marked with "-".

(2-2) Evaluation of low-temperature anti-fog properties

The composite sheet of the evaluation object was left in an environment of -15°C for 10 minutes, and then taken out to an environment of 20°C ± 5 at room temperature. Observe the blur of the surface of the anti-fog coating after 60 seconds after removal from the room temperature environment. In Table 1 and Table 2, the result of visual observation is that the composite sheet is entirely transparent, and the exterior scene on the opposite side of the sheet is visible through the sheet as "+"; the sheet is blurred and the sheet is transparent The outside scene on the opposite side of the invisible sheet is marked with "-".

(2-3) Evaluation of high-temperature anti-fog properties

(i) Standard

Prepare the open container above and fill it with warm water at 80°C±5. A composite sheet to be evaluated is prepared, the open surface of the container is covered with the composite sheet, and the side of the anti-fogging film faces downward. At this time, the distance between the surface of the anti-fog coating and the surface of warm water is 100 mm ± 5 mm. Keep it still and observe the change of the membrane surface after 2 minutes. In Table 1 and Table 2, the result of visual observation is that the composite sheet is transparent as a whole, and the exterior view of the opposite side of the sheet is visible as "+" through the sheet, the sheet is blurred, and the sheet is transparent The outside scene on the opposite side of the invisible sheet is marked with "-" (the same applies to (ii) and (iii) below).

(ii) Evaluation of high-temperature anti-fog properties in water resistance test 1

The composite sheet of the evaluation article was immersed in room temperature water at 20°C to 30°C, and allowed to stand for 2 hours. Remove the sheet from room temperature water and let it dry. After drying, the high-temperature anti-fog properties of the sheet were evaluated in the order shown in the "(i) standard" above.

(iii) Evaluation of high-temperature anti-fog properties in water resistance test 2

The composite sheet of the evaluation article was immersed in warm water at 75°C to 85°C, and allowed to stand for 2 hours. Remove the sheet from warm water and let it dry. After drying, the high-temperature anti-fog properties of the sheet were evaluated in the order shown in the "(i) standard" above.

Table 1 and Table 2 show the evaluation results of the blending of Comparative Examples 1, 2 and Examples 1 to 14 and the film transparency and anti-fogging properties. The number described in the column of compounding indicates mass parts.

＊1)雖然是允許範圍，但多少有點模糊

＊1) Although it is within the allowable range, it is somewhat vague

As shown in the evaluation results in Table 1, in Comparative Example 1 in which neither (B) the reactive nonionic surfactant or (C) the reactive ionic liquid is contained, the evaluation of the film transparency is transparent, but if The evaluation results of the anti-fogging property show that almost no anti-fogging effect is seen.

In addition, in Comparative Example 2, which further contains (C) a reactive ionic liquid and a compatibilizing agent that promotes compatibility of each component with respect to the compounding of Comparative Example 1, the anti-fogging effect is hardly seen.

In contrast, in Examples 1 to 14 containing both (B) a reactive nonionic surfactant and (C) a reactive ionic liquid, the evaluation of each antifogging property exhibited good antifogging properties .

In Examples 1 to 14, in Example 1 (with respect to 100 parts by mass of (A) hydrophilic bisphenol A type (meth)acrylate, (B) the amount of reactive nonionic surfactant is 2 parts by mass In Example), in the evaluation of the film transparency, the film was somewhat blurred. In the other examples (Examples 2 to 14), all the films are transparent. When the amount of (B) reactive nonionic surfactant is 2 parts by mass, an anti-fog coating film with insufficient transparency of the coating film may be obtained. From this result, it is known that in order to exhibit high anti-fog properties and to form an anti-fog coating with high transparency of the coating more stably, it is preferably relative to 100 parts by mass of (A) hydrophilic bisphenol A type (meth)acrylate, (B ) The amount of reactive nonionic surfactant is more than 2 parts by mass, more preferably 4 parts by mass or more.

In this way, it can be seen that the anti-fog coating film obtained from the anti-fog coating composition of the present invention and the anti-fog transparent sheet provided with the anti-fog coating film have excellent anti-fogging properties (all anti-fogging properties at normal temperature, low temperature, and high temperature). Furthermore, by making the amount of (B) reactive nonionic surfactant exceed 2 parts by mass, an anti-fogging film with high film transparency can be formed more stably.

(3) Evaluation of washing resistance

The composite sheet to be evaluated was prepared, and the surface of the anti-fog coating was rubbed by hand in warm water at 30°C to 40°C for 10 times, and then wiped off with a cloth to dry the sheet. Next, prepare a container opened above and inject warm water at 50°C to 60°C. Prepare the dried sheet, cover the open surface of the container with the composite sheet, and the side of the anti-fog coating facing down. At this time, the distance between the surface of the anti-fog coating and the surface of warm water is 100 mm ± 5 mm. Keep it still and visually observe the change of the membrane surface after 2 minutes. The anti-fogging properties were evaluated in four stages (level A→B→C→D) in the order of less blur. Levels A to C are allowed levels. Level D is due to blurring and the sheet is opaque and cannot withstand practical standards. The evaluation results are shown in Table 3 and Table 4. The combination shown in Table 3 is the same as Table 1. In addition, the combination shown in Table 4 is the same as Table 2.

As shown in the evaluation results in Table 3, Comparative Example 1 which does not contain either (B) reactive nonionic surfactant and (C) reactive ionic liquid, or does not contain (B) reactive nonionic surfactant In Example 2, the washing resistance was D level, which was insufficient. In contrast to this, in Examples 1 to 7 containing both (B) a reactive nonionic surfactant and (C) a reactive ionic liquid, the washing resistance was improved to C to B level.

In addition, as shown in Table 4, by further including (E) pentaerythritol (meth)acrylate and (F) urethane (meth)acrylate-based resin, the washing resistance is improved. In particular, it contains 6 parts by mass or more and 10 parts by mass or less of (B) a reactive nonionic surfactant and 2 parts by mass relative to 100 parts by mass of (A) hydrophilic bisphenol A type (meth)acrylate. C) Reactive ionic liquid, 8 parts by mass (D) polymerizable initiator, 10 parts by mass (E) pentaerythritol (meth)acrylate and 4 parts by mass (F) urethane (meth)acrylate resin ( Examples 10 to 12) show excellent water-wash resistance of grade A. That is, since it is clear that the water washing resistance is improved, it is preferable to further include the above-mentioned components (E) and (F) in addition to the above-mentioned components (A) to (D).

(4) Hardness of anti-fog coating

For the anti-fog coating compositions of Examples 8 to 14 containing the above-mentioned (E) component and (F) component, the surface hardness of the anti-fogging coating film further formed from the anti-fogging coating composition was evaluated. For evaluation, the pencil hardness of the surface of the anti-fog coating was measured. The results are shown in Table 5.

As shown in Table 5, when the amount of the (B) reactive nonionic surfactant is increased in the state of containing the (E) component and (F) component, the surface of the anti-fog coating gradually becomes soft. From the viewpoint of the surface hardness of the anti-fog coating, it is particularly preferable to contain 4 parts by mass or more and 8 parts by mass or less (B) of reactivity with respect to 100 parts by mass of (A) hydrophilic bisphenol A type (meth)acrylate. Nonionic surfactant, 2 parts by mass (C) reactive ionic liquid, 8 parts by mass (D) polymerizable initiator, 10 parts by mass (E) pentaerythritol (meth)acrylate and 4 parts by mass (F) urethane (Meth)acrylate resins (Examples 9 to 11).

(to sum up)

From the above results, it can be seen that the anti-fog coating composition having a specific composition according to the invention of the present application can form not only an initial anti-fog property (eg, high-temperature anti-fog property, low-temperature anti-fog property) immediately after the anti-fog coating is formed, The anti-fog effect is an anti-fog coating that can last for a long time and has excellent anti-fog durability. In addition, by containing the components (E) and (F) in addition to the components (A) to (D) described above, an anti-fogging film having excellent washing resistance and imparting flexibility can be obtained.

The embodiments and examples disclosed in the present invention are all examples, and it should be understood that the scope of the invention is not limited in any way. The scope of the present invention is not limited to the above-mentioned meanings, but also includes the meanings equivalent to the scope of the patent application and all the changes within the scope.

[Industry availability]

The anti-fog coating composition and the anti-fog transparent sheet of the present invention can be advantageously used in various fields in which the anti-fog effect can be sustained for a long time.

Claims (9)

An anti-fog coating composition comprising: component A, which is either or both of hydrophilic bisphenol A acrylate and hydrophilic bisphenol A methacrylate, relative to 100% by mass of the aforementioned anti-fog The total solid content of the coating composition, the content of the aforementioned component A is 50% by mass or more and 90% by mass or less in terms of solid content; the component B, which is a reactive nonionic surfactant, relative to 100 parts by mass of the aforementioned component A, The content of the component B is more than 2 parts by mass to 20 parts by mass or less; the component C is a reactive ionic liquid, and the content of the component C is 100 parts by mass or more to 5 parts by mass or less with respect to 100 parts by mass of the component A. And component D, which is a polymerizable initiator, and the content of the component D is 100 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the component A. The anti-fog coating composition according to claim 1, wherein the component C is a liquid composed of an ammonium sulfonate. The anti-fog coating composition according to claim 1 or 2, further comprising component E, which is either or both of pentaerythritol acrylate and pentaerythritol methacrylate. The anti-fog coating composition according to claim 1 or 2, further comprising component F, which is either or both of urethane acrylate resin and urethane methacrylate resin. The anti-fog coating composition according to claim 1 or 2, wherein the content ratio of the component B to the component C is B component/C component in a mass ratio of 1 or more to 10 or less. The anti-fog coating composition according to claim 1 or 2, further comprising a leveling agent. The anti-fog coating composition according to claim 1 or 2, wherein the polymerizable initiator is a photopolymerization initiator. An anti-fog transparent sheet comprising: a transparent base material; and an anti-fog coating film composed of the anti-fog coating composition described in claim 1 or 2 disposed on the surface of the base material. The anti-fog transparent sheet according to claim 8, wherein the substrate is a substrate made of polyethylene terephthalate.