JP2019006891A - Antifogging coating composition and antifogging transparent sheet using the same - Google Patents

Abstract

To provide an antifogging coating composition that can form an antifogging film excellent in not only initial antifogging properties but also antifogging durability having an antifogging effect lasting over a long period of time, and to provide an antifogging transparent sheet using the antifogging coating composition.SOLUTION: An antifogging coating composition comprises (A) a hydrophilic bisphenol A type (meth)acrylate, (B) a reactive nonionic surfactant, (C) reactive ionic liquid and (D) a polymerizable initiator. Preferably, the antifogging coating composition further includes (E) a pentaerythritol (meth)acrylate and (F) a urethane (meth)acrylate-based resin. The antifogging transparent sheet comprises a transparent base material and an antifogging film comprising the antifogging coating composition disposed on a surface of the base material.SELECTED DRAWING: None

Description

  The present invention relates to an antifogging coating composition and an antifogging transparent sheet using the same.

  When the surface temperature of the base material becomes lower than the dew point of the surrounding air, water droplets adhere to the surface of the base material and cloudiness occurs. In a transparent base material such as a lens, a glass window, or a transparent film, and a reflective material such as a mirror, the visibility of a transmitted image or a reflected image is impaired due to fogging on the surface. Therefore, a method for preventing fogging by forming a coating that imparts an antifogging effect on the surface of the substrate has been proposed. For example, an anti-fogging film is formed on the surface of a transparent substrate to prevent the formation of water droplets on the substrate surface by increasing the hydrophilicity of the substrate surface or reducing the contact angle between the lens and water. Methods for preventing fogging have already been disclosed (for example, Patent Document 1 and Patent Document 2).

JP 2004-83846 A JP 2007-137937 A

  Antifogging is required in various situations. In particular, it is required to exhibit antifogging properties even in an environment with a sudden temperature change. Furthermore, there is a need for an antifogging film that not only has excellent initial antifogging properties immediately after the formation of the antifogging film, but also has excellent antifogging durability that maintains the antifogging effect over a long period of time. For example, there is a need for an antifogging film that maintains antifogging properties even in an environment exposed to water or warm water, and an antifogging transparent sheet having such an antifogging film.

  Accordingly, an anti-fogging coating composition capable of forming an anti-fogging film excellent not only in initial anti-fogging property but also in anti-fogging sustaining property in which anti-fogging effect is maintained for a long period of time, and an anti-fogging transparent sheet using the same Is one of the purposes.

  The antifogging coating composition according to the first aspect of the present invention comprises (A) a hydrophilic bisphenol A type (meth) acrylate, (B) a reactive nonionic surfactant, (C) a reactive ionic liquid, (D) a polymerizable initiator.

  Moreover, the antifogging transparent sheet which concerns on 2nd aspect of this invention is equipped with a transparent base material and the antifogging film | membrane which consists of the said antifogging coating composition arrange | positioned on the surface of the base material.

  According to the present invention, the antifogging coating composition capable of forming an antifogging film excellent not only in the initial antifogging property but also in the antifogging sustaining property in which the antifogging effect is sustained over a long period of time, and the antifogging property It becomes possible to provide an excellent antifogging transparent sheet.

[Description of Embodiment of Present Invention]
First, embodiments of the present invention will be listed and described. The anti-fogging coating composition according to the present invention comprises (A) a hydrophilic bisphenol A type (meth) acrylate, (B) a reactive nonionic surfactant, (C) a reactive ionic liquid, and (D) a polymerizable property. And an initiator.

  The antifogging coating composition containing (A) a hydrophilic bisphenol A type (meth) acrylate, (B) a reactive nonionic surfactant, and (C) a reactive ionic liquid is obtained immediately after the antifogging film is formed. Excellent initial anti-fogging property. Especially, it has the effect of exhibiting the antifogging property (low temperature antifogging property) especially in a low temperature environment. Further, such an antifogging coating composition has an effect of maintaining the hydrophilicity of the substrate surface on which the antifogging film is formed. By imparting such persistent hydrophilicity (hydrophilic persistence) to the substrate, an antifogging film having excellent antifogging durability can be formed.

  Further, (B) the reactive nonionic surfactant and (C) the reactive ionic liquid also have an effect of reducing the contact angle of the substrate surface. The antifogging effect is further improved by reducing the contact angle of the substrate surface. Further, by including (D) a polymerizable initiator, an antifogging film having a high molecular weight and excellent retention on the substrate surface can be provided. As a result, it is possible to form an antifogging film excellent in antifogging durability in which the antifogging effect is sustained over a long period of time.

  By including the components (A) to (D) as described above, the antifogging film is excellent in initial antifogging property and can form an antifogging film excellent in antifogging durability that has a long antifogging effect. It becomes possible to provide a coating composition.

  In the antifogging coating composition, the reactive ionic liquid (C) may be a liquid made of a sulfonic acid ammonium salt. By containing such a reactive ionic liquid, it is possible not only to have excellent initial antifogging properties, but also to more reliably obtain an antifogging film having excellent antifogging durability in which the antifogging effect is sustained over a long period of time. .

  The antifogging coating composition may further contain (E) pentaerythritol (meth) acrylate. By containing (E) component, the water-washing tolerance of the anti-fogging film mentioned later can be improved, and softness can be provided to the anti-fogging film.

  The anti-fogging coating composition may further contain (F) urethane (meth) acrylate resin. By including (F) component, the water-washing tolerance of the anti-fogging film mentioned later can be improved, and softness can be provided to the anti-fogging film.

  In the antifogging 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). An anti-fogging coating composition capable of more stably forming an anti-fogging film having a high film transparency when the content of the component (B) is more than 2 parts by mass with respect to 100 parts by mass of the component (A). can get. Moreover, even if the content of the component (B) exceeds 20 parts by mass with respect to 100 parts by mass of the component (A), the transparency and antifogging properties are not further improved due to saturation of the effect, but the cost is increased. Therefore, it is preferable that content of (B) component is 20 mass parts or less with respect to 100 mass parts of (A) component.

  In the antifogging coating composition, the content of the component (C) may be 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component (A). If content of (C) component is 1 mass part or more, the improvement effect of the anti-fogging property by (C) component will be exhibited more clearly. Moreover, even if the content of the component (C) exceeds 5 parts by mass with respect to 100 parts by mass of the component (A), the transparency and antifogging properties are not further improved due to saturation of the effect, but rather the cost increases. Therefore, it is preferable that content of (C) component is 5 mass parts or less with respect to 100 mass parts of (A) component.

  The content ratio (B) / (C) of the component (B) to the component (C) may be 1 or more and 10 or less. When the ratio (B) / (C) is 1 or more, an antifogging film having more excellent antifogging properties can be provided. In addition, even if the ratio exceeds 10, the effect is saturated, and the transparency and antifogging properties do not change any more, so the upper limit is preferably 10.

  The antifogging coating composition may further contain a leveling agent. By including the leveling agent, the coating property of the antifogging coating composition can be improved. Furthermore, the contact angle between the substrate and water can be reduced, and water droplets can be made difficult to occur. Therefore, it contributes to the improvement of the anti-fogging effect.

  In the antifogging coating composition, the polymerizable initiator may be a photopolymerization initiator. When the polymerizable initiator is a photopolymerization initiator, curing after applying the antifogging coating composition can be performed relatively easily.

  The anti-fogging transparent sheet concerning this invention is equipped with a transparent base material and the anti-fogging film | membrane which consists of the said anti-fogging coating composition arrange | positioned on the surface of a base material. The antifogging transparent sheet provided with the antifogging film comprising the antifogging coating composition has excellent transparency and antifogging properties.

  The substrate may be a polyethylene terephthalate substrate. Since polyethylene terephthalate is excellent in transparency, an anti-fogging transparent sheet having high transparency as the whole sheet can be obtained. Moreover, since polyethylene terephthalate is excellent in processability, an antifogging transparent sheet applicable to many uses can be obtained.

[Details of the embodiment of the present invention]
Next, an embodiment of the antifogging coating composition of the present invention will be described. The antifogging coating composition according to the present embodiment comprises (A) a hydrophilic bisphenol A type (meth) acrylate (also referred to as “component (A)” in the present specification and claims), and (B) a reaction. Nonionic surfactant (also referred to as “component (B)” in the present specification and claims) and (C) reactive ionic liquid (referred to as “component (C)” in the present specification and claims) And (D) a polymerizable initiator (also referred to as “component (D)” in the present specification and claims). In the present specification, “(meth) acrylate” means one or both of acrylate and methacrylate.

[(A) hydrophilic bisphenol A type (meth) acrylate]
The antifogging coating composition of the present invention contains hydrophilic bisphenol A type (meth) acrylate as the component (A). The hydrophilic bisphenol A type (meth) acrylate is a main component of the antifogging coating composition, imparts hydrophilicity to the substrate on which the antifogging coating composition is applied, and contributes to the improvement of the antifogging effect. The antifogging coating composition containing the ionic liquid of the antifogging film formed from the antifogging coating composition by containing the hydrophilic bisphenol A type (meth) acrylate, Immediately after the formation of the cloud film, the low-temperature anti-fogging property and the hydrophilic durability are particularly good. “Hydrophilic” means a resin that does not phase separate when added to water and can be dispersed in water or dissolved in water.

（式中、Ｒ^１及びＲ^２はそれぞれ独立に、水素、またはメチル基であり、ｍ及びｎはそれぞれ独立に０以上の整数である。ｍ＋ｎの値は０以上、好ましくは４以上、より好ましくは１０以上である。） The hydrophilic bisphenol A type (meth) acrylate has a structure in which two hydroxy 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).

Wherein R ¹ and R ² are each independently hydrogen or a methyl group, and m and n are each independently an integer of 0 or more. The value of m + n is 0 or more, preferably 4 or more, more preferably Is 10 or more.)

（式中、ｍ及びｎはそれぞれ独立に０以上の整数であり、例えばｍ＋ｎ＝２０である）
で表される化合物が挙げられる。 As shown in the above formula (1), in the present specification, the hydrophilic bisphenol A type (meth) acrylate preferably contains an alkylene oxide-modified bisphenol A type (meth) acrylate. Examples of the alkylene oxide-modified bisphenol A type (meth) acrylate include ethylene oxide-modified bisphenol A type (meth) acrylate and propylene oxide-modified bisphenol A type (meth) acrylate. In formula (1), the greater 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, more preferably 10 or more. Preferred examples of such a compound include, for example, the following formula (2):

(In the formula, m and n are each independently an integer of 0 or more, for example, m + n = 20)
The compound represented by these is mentioned.

As an example of a commercial product of hydrophilic bisphenol A type (meth) acrylate, New Frontier (R) BPE-4 (in formula (1), R ¹ and R ² are commercially available from Daiichi Kogyo Seiyaku Co., Ltd. Hydrogen, m + n = 4), new frontier (R) BPE-10 (in formula (1), R ¹ and R ² are hydrogen, m + n = 10), new frontier (R) BPE-20 (in formula (1), R ¹ and R ² are hydrogen, m + n = 20), New Frontier (R) BPEM-4 (in Formula (1), R ¹ and R ² are methyl groups, m + n = 4), New Frontier (R) BPEM-10 (In the formula (1), New Frontier (R) series such as R ¹ and R ² are methyl groups, m + n = 10) can be mentioned.

  The ratio of the hydrophilic bisphenol A type (meth) acrylate to 100% by mass of the total solid content of the antifogging coating composition is preferably 50% by mass or more, more preferably 60% by mass or more in terms of solid content. An anti-fogging coating composition capable of forming an anti-fogging film excellent in anti-fogging properties, particularly low-temperature anti-fogging properties and hydrophilic sustainability by containing 50% by mass or more of hydrophilic bisphenol A type (meth) acrylate in terms of solid content can get. Although the upper limit of the said ratio is not specifically limited, For example, an upper limit is 90 mass% in conversion of solid content.

[(B) Reactive nonionic surfactant]
The antifogging coating composition of the present invention contains a reactive nonionic surfactant as the component (B). The reactive nonionic surfactant mainly contributes to improvement of the low temperature antifogging property of the antifogging film, improvement of hydrophilic sustainability, and reduction of the contact angle.

  A nonionic surfactant (nonionic surfactant) is a surfactant having a hydrophilic group that is not ionized when dissolved in water. Among these, the “reactive nonionic surfactant” is a nonionic surfactant having a reactive functional group in the molecule. Examples of the reactive functional group include unsaturated bond-containing groups such as vinyl groups and (meth) acryloyl groups, particularly ethylenically unsaturated bond-containing groups.

（式中、Ｒ^３は炭素数８〜３６であり、且つ、３個以上のメチル基を有する一価の分岐脂肪族炭化水素基又は分岐の脂肪族アシル基を表し、ＡＯは炭素数２〜４のオキシアルキレン基を表し、Ｌは下記式（４）で表わされる基を表し、ｚは１〜１０の数を表し、Ｘは水素原子又は下記のアニオン性親水基又はカチオン性親水基（好ましくは水素原子）を表し、ｍは０〜１，０００の数を表し、ｎは０〜１，０００の数を表す。）

（式中、Ｒ^４及びＲ^５は水素原子又はメチル基を表し、ｘは０〜１２の数を表し、ｙは０又は１の数を表す。）
アニオン性親水基：−ＳＯ_３Ｍ、−Ｒ^６−ＳＯ_３Ｍ、−Ｒ^７−ＣＯＯＭ、−ＰＯ_３Ｍ_２、−ＰＯ_３ＭＨ又は−ＣＯ−Ｒ^８−ＣＯＯＭ（式中、Ｍは水素原子、アルカリ金属原子、アルカリ土類金属原子又はアンモニウム（但し、アルカリ土類金属原子は１／２）を表わし、Ｒ^６及びＲ^７はアルキレン基を表わし、Ｒ^８は２塩基酸又はその無水物からカルボキシル基を除いた残基を表わす。）
カチオン性親水基：−Ｒ^９−ＮＲ^１０Ｒ^１１Ｒ^１２・Ｙ、又は−Ｚ−ＮＲ^１０Ｒ^１１Ｒ^１２・Ｙ
（式中、Ｒ^９はアルキレン基を表わし、Ｒ^１０〜Ｒ^１２は炭素数１〜４のアルキル基、炭素数２〜４のアルカノール基又はベンジル基を表わし、Ｙはハロゲン原子又はメチル硫酸基を表わし、Ｚは−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−又は−ＣＨ（ＣＨ_２ＯＨ）ＣＨ_２−で表わされる基を表わす。）］ As an example of the reactive nonionic surfactant which the anti-fogging coating composition of this application contains, the compound which has a structure represented by following formula (3) is mentioned.

(In the formula, R ³ represents a monovalent branched aliphatic hydrocarbon group or a branched aliphatic acyl group having 8 to 36 carbon atoms and having 3 or more methyl groups, and AO represents 2 to 2 carbon atoms. 4 represents an oxyalkylene group, L represents a group represented by the following formula (4), z represents a number of 1 to 10, and X represents a hydrogen atom or the following anionic hydrophilic group or cationic hydrophilic group (preferably Represents a hydrogen atom), m represents a number of 0 to 1,000, and n represents a number of 0 to 1,000.)

(Wherein, ^{R 4} and ^{R 5} represents a hydrogen atom or a methyl group, x is a number from 0 to 12, y is 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 (wherein M is a hydrogen atom) Represents an alkali metal atom, an alkaline earth metal atom or ammonium (wherein the alkaline earth metal atom is 1/2), R ⁶ and R ⁷ represent an alkylene group, and R ⁸ represents a dibasic acid or an anhydride thereof. Represents a residue excluding the carboxyl group.)
Cationic hydrophilic group: —R ⁹ —NR ¹⁰ R ¹¹ R ¹² · Y, or —Z—NR ¹⁰ R ¹¹ R ¹² · Y
(In the formula, R ⁹ represents an alkylene group, R ^{10 to} R ¹² represent an alkyl group having 1 to 4 carbon atoms, an alkanol group having 2 to 4 carbon atoms, or a benzyl group, and Y represents a halogen atom or a methyl sulfate group. Z represents a group represented by —CH ₂ CH (OH) CH ₂ — or —CH (CH ₂ OH) CH ₂ —)]

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

（式中、ＥＯはエチレンオキシドであり、ｍは０〜１，０００である。） Specific examples of the compound having the structure represented by the above formula (3) include a compound having a structure represented by the following formula (6).

(In the formula, EO is ethylene oxide and m is 0 to 1,000.)

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

  Among nonionic surfactants which are compounds having a structure represented by the above formula (3), examples of commercially available products include Adeka Soap ER-10, Adeka Soap ER-20, Adekalia Soap ER-30, Examples include ADEKA rear soap ER-40, ADEKA rear soap SR series, and ADEKA rear soap SE series (all manufactured by ADEKA Corporation).

  It is preferable that content of (B) component is more than 2 mass parts and 20 mass parts or less with respect to 100 mass parts of (A) component. By containing more than 2 parts by mass of component (B) with respect to 100 parts by mass of component (A), an antifogging film having high film transparency can be formed more stably. Moreover, even if the content of the component (B) exceeds 20 parts by mass with respect to 100 parts by mass of the component (A), the transparency and antifogging properties are not further improved due to saturation of the effect, but the cost is increased. Therefore, it is preferable that content of (B) component is 20 mass parts or less with respect to 100 mass parts of (A) component. As for the upper limit of content of (B) component with respect to 100 mass parts of (A) component, 18 mass parts is more preferable.

[(C) Reactive ionic liquid]
The antifogging coating composition of the present invention contains a reactive ionic liquid as the component (C). An ionic liquid is a substance in which ions composed of cations and anions are present as a liquid. An ionic liquid is a substance that has a low melting point and takes a liquid state around room temperature while being a salt. The “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, particularly ethylenically unsaturated bond-containing groups.

（式中、Ｒ^１３およびＲ^１４は、それぞれ独立して、置換又は無置換の炭素数１〜３０の直鎖状、分枝状、もしくは環状のアルキル基、置換又は無置換の炭素数６〜３０のアリール基、または置換されているかもしくは非置換の炭素数７〜３１のアリールアルキル基であり、Ａ^１およびＡ^２は炭素数２〜４の直鎖状または分枝状のアルキレン基であり、ｎは０〜５０の整数であり、Ｑ１^＋およびＱ２^＋は、それぞれ独立して、エチレン性不飽和結合を有するアンモニウムイオン、エチレン性不飽和結合を有するイミダゾリウムイオン、エチレン性不飽和結合を有するピリジニウムイオン、エチレン性不飽和結合を有するピロリジニウムイオン、エチレン性不飽和結合を有するピロリニウムイオン、エチレン性不飽和結合を有するピペリジニウムイオン、エチレン性不飽和結合を有するピラジニウムイオン、エチレン性不飽和結合を有するピリミジニウムイオン、エチレン性不飽和結合を有するトリアゾリウムイオン、エチレン性不飽和結合を有するトリアジニウムイオン、エチレン性不飽和結合を有するキノリニウムイオン、エチレン性不飽和結合を有するイソキノリニウムイオン、エチレン性不飽和結合を有するインドリニウムイオン、エチレン性不飽和結合を有するキノキサリニウムイオン、エチレン性不飽和結合を有するピペラジニウムイオン、エチレン性不飽和結合を有するオキサゾリニウムイオン、エチレン性不飽和結合を有するチアゾリニウムイオン、およびエチレン性不飽和結合を有するモルホリニウムイオンからなる群より選択される少なくとも１種である。） Examples of the reactive ionic liquid of the component (C) include a reactive ionic liquid containing an ion-binding salt having a reactive group represented by the following chemical formula (7) or the following chemical formula (8).

(Wherein R ¹³ and R ¹⁴ each independently represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 6 to 6 carbon atoms, 30 aryl groups, or substituted or unsubstituted arylalkyl groups having 7 to 31 carbon atoms, and A ¹ and A ² are linear or branched alkylene groups having 2 to 4 carbon atoms. , N is an integer of 0 to 50, and Q1 ⁺ and Q2 ⁺ each independently represent an ammonium ion having an ethylenically unsaturated bond, an imidazolium ion having an ethylenically unsaturated bond, or an ethylenically unsaturated bond. Pyridinium ion having ethylenically unsaturated bond, pyrrolidinium ion having ethylenically unsaturated bond, pyrrolium ion having ethylenically unsaturated bond, piperidy having ethylenically unsaturated bond Ion, pyrazinium ion having ethylenically unsaturated bond, pyrimidinium ion having ethylenically unsaturated bond, triazolium ion having ethylenically unsaturated bond, triazinium ion having ethylenically unsaturated bond, ethylenically unsaturated Quinolinium ion with saturated bond, isoquinolinium ion with ethylenically unsaturated bond, indolinium ion with ethylenically unsaturated bond, quinoxalinium ion with ethylenically unsaturated bond, ethylenically unsaturated Selected from the group consisting of a piperazinium ion having a bond, an oxazolinium ion having an ethylenically unsaturated bond, a thiazolinium ion having an ethylenically unsaturated bond, and a morpholinium ion having an ethylenically unsaturated bond At least one.

  It is preferable that content of (C) component is 1 to 5 mass parts with respect to 100 mass parts of (A) component. By containing 1 part by mass or more of component (C) with respect to 100 parts by mass of component (A), the antifogging properties and hydrophilic sustainability of the resulting antifogging film are at a sufficient level. Moreover, even if the content of the component (C) exceeds 5 parts by mass with respect to 100 parts by mass of the component (A), the transparency and antifogging properties are not further improved due to saturation of the effect, but rather the cost increases. Therefore, it is preferable that content of (C) component is 5 mass parts or less with respect to 100 mass parts of (A) component. The lower limit of the content of the component (C) with respect to 100 parts by mass of the component (A) is more preferably 1.5 parts by mass. 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. When the content of the component (B) with respect to the content of the component (C) is 1 or more in terms of mass ratio, an antifogging film having more excellent antifogging properties, particularly low temperature antifogging properties and hydrophilic sustainability, can be obtained. An antifogging coating composition that can be formed is obtained. In addition, even if the content mass ratio (B) / (C) exceeds 10, the effect is saturated and the transparency and antifogging properties do not change any more, so the upper limit is preferably 10.

[(D) Polymerization initiator]
The antifogging coating composition according to the present embodiment contains a polymerization initiator as the component (D). Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. Among these, a photopolymerization initiator is preferable because it can be easily cured after the antifogging coating composition is applied. Further, among the photopolymerization initiators, photopolymerization initiators that are cured by ultraviolet rays are preferable. A polymerization initiator may be used independently and may be used in combination of 2 or more type.

  The amount of the polymerization initiator is appropriately set as necessary. For example, with respect to 100 parts by mass of the hydrophilic bisphenol A type (meth) acrylate of the component (A), the amount of the polymerization initiator of the component (D) 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. It is preferable to set appropriately within the following range.

[(E) pentaerythritol (meth) acrylate]
The antifogging coating composition may further contain (E) pentaerythritol (meth) acrylate in addition to the components (A) to (D).

  The (E) component pentaerythritol (meth) acrylate contributes to the reduction of the contact angle on the antifogging film surface. Due to the synergistic effect with the component (B) and the component (C), the antifogging property after wiping off the water when the surface of the antifogging film is washed with hot water and then wiped off with a cloth can be improved. Furthermore, (E) component contributes to the improvement of hardening reactivity and surface hardness.

  Examples of pentaerythritol (meth) acrylate as component (E) include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include hexanediol (meth) acrylate. In addition, as the (E) component pentaerythritol (meth) acrylate, alkylene oxide-modified pentaerythritol (meth) acrylate is preferable because hydrophilicity can be imparted.

  Examples of commercially available (E) pentaerythritol (meth) acrylates include KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), KAYARAD DPEA12 (ethylene oxide-modified dipentaerythritol hexaacrylate), and KAYARAD D-330 (di). Pentaerythritol triacrylate), KAYARAD D-320 (dipentaerythritol tetraacrylate), and KAYARAD D-310 (dipentaerythritol pentaacrylate) (all manufactured by Nippon Kayaku Co., Ltd.). Of these, KAYARAD DPEA 12 (ethylene oxide-modified dipentaerythritol hexaacrylate) modified with alkylene oxide is preferable.

  The content of the component (E) is preferably 5 parts by mass or more and more preferably 10 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 including 5 parts by mass or more of the component (E) with respect to 100 parts by mass of the hydrophilic bisphenol A type (meth) acrylate of the component (A), the contact angle is reduced, the antifogging property after wiping with water is improved, and It can greatly contribute by imparting softness to the antifogging film. Although there is no restriction | limiting in particular in an upper limit, For example, it is 30 mass parts.

[(F) Urethane acrylate resin]
The anti-fogging coating composition may further contain a urethane (meth) acrylate resin as component (F). The urethane acrylate resin increases the curing reactivity of the antifogging coating composition.

  Examples of the urethane (meth) acrylate resin include a reaction product of a polyol compound and an organic polyisocyanate.

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 polyethoxydiol, polytetramethylene glycol and other polyols, the above polyols and succinic acid , Polyester polyols which are reaction products with polybasic acids such as maleic acid, itaconic acid, adipic acid, hydrogenated dimer acid, phthalic acid, isophthalic acid, terephthalic acid, etc., or their anhydrides, the above polyols Polycaprolactone polyols are the reaction product of ε- caprolactone, the polyols and polybasic acids or a reaction product of ε- caprolactone these acid anhydrides, polycarbonate polyols, polymer polyols and the like.

  Examples of the organic polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, hexamethylene diisocyanate, 2,4,4′-trimethylhexamethylene diisocyanate. 2,2'-4-trimethylhexamethylene diisocyanate and the like.

  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 the commercially available urethane (meth) acrylate resin of the component (F) include Art Resin series (manufactured by Negami Industrial 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 adding 2 parts by mass or more of the component (F) to 100 parts by mass of the hydrophilic bisphenol A type (meth) acrylate of the component (A), the antifogging film is given scratch resistance (hard coat property), Moreover, it can contribute more greatly to increase the reactivity of the antifogging coating composition. Although there is no restriction | limiting in particular in an upper limit, For example, it is 10 mass parts. The component (F) is more preferably used in combination with the above-described component (E).

[Leveling agent]
The anti-fogging coating composition in the present embodiment may contain other additive components as long as the effects of the invention are not impaired. For example, the antifogging coating composition according to the present embodiment may further contain a leveling agent. By containing a leveling agent, the coating properties of the antifogging coating composition can be improved. Furthermore, the contact angle between the antifogging film and water can be reduced, and water droplets can be made difficult to occur. Therefore, it contributes to the improvement of the anti-fogging effect.

  Examples of the leveling agent include a silicone leveling agent, a fluorine leveling agent, an acrylic leveling agent, a vinyl leveling agent, and a leveling agent in which a fluorine type and an acrylic type are combined. A leveling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the leveling agent is appropriately set as necessary. For example, with respect to 100 parts by mass of the hydrophilic bisphenol A type (meth) acrylate of component (A), the amount of the leveling agent is in the range of 1 to 50 parts by mass, preferably 5 to 30 parts by mass. It is set as appropriate.

[Compatibilizer]
The anti-fogging coating composition may contain a compatibilizer as necessary. The compatibilizer is appropriately selected according to the compatibility of the above components. Examples of the compatibilizer include aliphatic (meth) acrylate, alicyclic (meth) acrylate, and aromatic (meth) acrylate. The aliphatic (meth) acrylate, alicyclic (meth) acrylate, and aromatic (meth) acrylate are functional groups such as hydroxy group, amino group, glycidyl group, carboxylic acid group (carboxy group), and phosphate ester group, Alternatively, it may contain a modifying group such as a polyethylene glycol chain. Examples of commercially available compatibilizers include the light ester series and the light acrylate series (both manufactured by Kyoeisha Chemical Co., Ltd.). The amount of the compatibilizer can be appropriately adjusted in consideration of the solubility of each component.

[solvent]
The anti-fogging coating composition according to the present embodiment may contain a solvent as necessary. 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 are appropriately selected in consideration of the solubility of the added component.

  The proportion of the solvent in the anti-fogging coating composition is set in consideration of the solubility of each component, composition coating property, and the like. However, when the amount of the solvent is too large, the coating tends to be insufficiently cured. Moreover, when there is too little quantity of a solvent, there exists a tendency for the transparency of an anti-fogging film to fall easily. The proportion of the solvent in the anti-fogging coating composition is not particularly limited, but is typically 50% by mass or more and 80% by mass or less, preferably 50% by mass or more and 70% by mass or less, based on the total amount of the anti-fog coating composition. Preferably they are 55 mass% or more and 65 mass% or less.

[Other additive components]
Furthermore, the anti-fogging coating composition according to the present embodiment has a film-forming aid, a foam inhibitor, a stabilizer, a filler, an adhesion promoter, a curing agent, and a curing accelerator, in addition to the above components, depending on desired properties. Known additives such as an agent, a plasticizer, a thixotropic agent, a pigment, and an antioxidant may be included.

[Anti-fogging coating composition]
The antifogging coating composition according to the present embodiment comprises (A) a hydrophilic bisphenol A type (meth) acrylate, (B) a reactive nonionic surfactant, (C) in a solvent such as methyl ethyl ketone (MEK). ) Reactive ionic liquid, (D) polymerizable initiator, (E) ethylene oxide modified dipentaerythritol hexaacrylate, (F) urethane (meth) acrylate resin, leveling agent, and other as required Necessary components can be prepared by putting them into a stirrer and stirring them. The order in which the components are added is not particularly limited, and can be arbitrarily adjusted by those skilled in the art in light of common technical knowledge.

  In the present embodiment, the preferred antifogging coating composition is 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 with respect to 100 parts by mass of (A) hydrophilic bisphenol A type (meth) acrylate. 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) a reactive ionic liquid and 1 part by mass or more 50 parts by mass or less, preferably 5 parts by mass or more and 30 parts by mass or less (D) polymerizable initiator. The content ratio (B) / (C) of the component (B) to the component (C) is more preferably 1 or more and 10 or less.

  In the present embodiment, another preferred anti-fogging coating composition is (A) 1 part by mass or more, preferably 1.5 parts by mass or more and 18 parts by mass with respect to 100 parts by mass of the hydrophilic bisphenol A type (meth) acrylate. The following (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) a reactive ionic liquid and 1 part by mass or more and 50 parts by mass Part or less, preferably 5 parts by weight or more and 30 parts by weight or less (D) polymerizable initiator and 5 parts by weight or more, more preferably 10 parts by weight or more and 30 parts by weight or less (E) ethylene oxide modified dipenta. It contains erythritol hexaacrylate and 2 parts by mass or more, more preferably 3 parts by mass or more and 10 parts by mass or less (F) urethane (meth) acrylate resin. The content ratio (B) / (C) of the component (B) to the component (C) is more preferably 1 or more and 10 or less.

[Anti-fogging transparent sheet]
Next, the antifogging transparent sheet according to the present embodiment will be described. The antifogging transparent sheet of this Embodiment contains a transparent base material and the antifogging film which consists of the said antifogging coating composition arrange | positioned on the surface of the base material.

  The antifogging transparent antifogging film can be formed by applying the coating composition on a substrate and drying the coating film. Further, when the antifogging coating composition contains a photopolymerization initiator, it is possible to form an antifogging film while promoting curing of each component by irradiating light such as ultraviolet rays after application.

  The substrate is preferably a transparent substrate such as glass or resin (plastic) sheet or film. Examples of the transparent substrate include a resin-made transparent sheet or transparent film selected from transparent resins such as polyethylene terephthalate (PET), polycarbonate, and poly (meth) acrylate.

  Further, the antifogging film has excellent high temperature antifogging properties and low temperature antifogging properties. Therefore, the anti-fogging effect can be exhibited under a wide temperature environment. Moreover, since it is excellent also in film | membrane transparency, it can be used as a film | membrane which does not impair the external appearance of a base material, or the visibility of the image of the outside scene through a base material.

[Usage]
The antifogging coating agent according to the present embodiment can exhibit an antifogging effect under a wide range of temperature environments, and is excellent in durability of the antifogging effect and film transparency. Therefore, it is possible to form an antifogging film having high adhesion to plastic molded products and plastic films, particularly materials made of PET.

  Further, the antifogging transparent sheet provided with the antifogging film comprising the above antifogging coating agent is an inorganic glass lens, a window of a building, a window of a bathroom, a mirror, a window of a vehicle such as an automobile or a train, an aircraft, a ship, etc. It can also be used as an anti-fogging material provided with a base material such as a goggle used for skiing and swimming, a mask, a shield used for motorcycle helmets, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. The scope of the present invention is not construed as being limited by 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 Kogyo Seiyaku Co., Ltd.)
(B) Reactive nonionic surfactant (trade name ADEKA rear soap ER10, manufactured by ADEKA Corporation)
(C) Reactive ionic liquid (trade name JI62C01, manufactured by Nippon Emulsifier Co., Ltd.)
(D) Polymerization initiator (trade name DAROCUR® 4265 (50% by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 50% by mass of 2-hydroxy-2-methyl-1-phenyl-1-propanone) Mixture, manufactured by BASF Japan Ltd.)
(E) Pentaerythritol (meth) acrylate Ethylene oxide (EO) modified dipentaerythritol hexaacrylate (KAYARAD DPEA12, manufactured by Nippon Kayaku Co., Ltd.)
(F) Urethane (meth) acrylate resin Urethane acrylate oligomer / reactive urethane polymer mixture (trade name Art Resin H135, manufactured by Negami Kogyo 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 Big Chemie Japan Co., Ltd.)
-Leveling agent B
DOW CORNING (R) 67 ADDITIVE (3- (polyoxyethylene) propylheptamethyltrisiloxane, solid content concentration 70-80% by mass, manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of antifogging coating composition and formation of antifogging film]
Based on the formulations shown in Tables 1 and 2, predetermined amounts of the above-described various components were charged into a kneader and kneaded to obtain an antifogging coating composition. The obtained anti-fogging coating composition was applied on a transparent sheet of polyethylene terephthalate (PET) as a base material so that the film thickness after drying was about 10 μm, and heated and dried at 80 ° C. for 10 minutes. A coating film was formed. 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 of 1,000 mJ / cm ² in terms of accumulated light quantity, thereby curing the coating film, Formed. The formulation shown in Table 2 differs from the formulation shown in Table 1 in that it further includes (E) pentaerythritol (meth) acrylate and (F) urethane (meth) acrylate resin.

[Evaluation of anti-fogging film]
Next, the sheet on which the antifogging film was formed was evaluated based on the following evaluation items. Evaluation items and evaluation procedures are shown below.

(1) Film transparency The transparency of the film was visually evaluated on the sheet on which the antifogging film was formed. In the evaluation, the presence of transparency and haze was examined visually. In Tables 1 and 2, a film with a transparent film was indicated as “+”, and a film with cloudiness or turbidity was indicated as “−”.

(2) Evaluation of anti-fogging property (2-1) Evaluation of anti-fogging property under general conditions A container having an open upper surface was prepared, and hot water at 50 ° C to 60 ° C was added. A composite sheet to be evaluated was prepared, and the open surface of the container was covered with the composite sheet with the antifogging film side down. At this time, the distance between the surface of the antifogging film and the hot water surface was set to 100 mm ± 5 mm. The film was allowed to stand as it was, and the film surface change after 2 minutes was visually observed. In Tables 1 and 2, as a result of visual observation, the composite sheet as a whole was transparent, and the outside view on the opposite side of the sheet was visible through the sheet was “+”. Those whose outside scenery could not be visually recognized were indicated as “−”.

(2-2) Evaluation of low-temperature antifogging property The composite sheet to be evaluated was placed in an environment at -15 ° C for 10 minutes, and then taken out into an environment at room temperature of 20 ° C ± 5. After taking out to room temperature environment, the cloudiness of the surface of the anti-fogging film after 60 seconds was observed. In Tables 1 and 2, as a result of visual observation, the composite sheet as a whole was transparent, and the outside view on the opposite side of the sheet was visible through the sheet was “+”. Those whose outside scenery could not be visually recognized were indicated as “−”.

(2-3) Evaluation of anti-fogging property at high temperature (i) Standard A container having an open upper surface was prepared, and hot water at 80 ° C. ± 5 was added. A composite sheet to be evaluated was prepared, and the open surface of the container was covered with the composite sheet with the antifogging film side down. At this time, the distance between the surface of the antifogging film and the hot water surface was set to 100 mm ± 5 mm. The film was allowed to stand as it was, and the film surface change after 2 minutes was observed. In Tables 1 and 2, as a result of visual observation, the composite sheet as a whole was transparent, and the outside view on the opposite side of the sheet was visible through the sheet was “+”. Those in which the outside scene could not be visually recognized were indicated as “−” (the same applies to (ii) and (iii) below).

(Ii) Evaluation of high-temperature anti-fogging property in water resistance test 1 The composite sheet to be evaluated was immersed in room temperature water at 20 ° C. to 30 ° C. and allowed to stand for 2 hours. The sheet was taken out from room temperature water and dried. After drying, the sheet was evaluated for high-temperature antifogging property according to the procedure shown in the above “(i) standard”.

(Iii) Evaluation of high-temperature anti-fogging property of water resistance test 2 The composite sheet to be evaluated was immersed in warm water of 75 ° C. to 85 ° C. and allowed to stand for 2 hours. The sheet was removed from the hot water and dried. After drying, the sheet was evaluated for high-temperature antifogging property according to the procedure shown in the above “(i) standard”.

  Tables 1 and 2 show the formulations in Comparative Examples 1 and 2 and Examples 1 to 14 and the evaluation results of film transparency and antifogging properties. In addition, the number described in the column of a mixing | blending represents a mass part.

＊１）許容範囲だが、わずかに曇り

* 1) Acceptable range, but slightly cloudy

  As shown in the evaluation results of Table 1, in Comparative Example 1 which did not contain either (B) a reactive nonionic surfactant or (C) a reactive ionic liquid, the film transparency was transparent. As shown in the evaluation results for antifogging properties, almost no antifogging effect was observed.

  Moreover, the antifogging effect was hardly seen also in the comparative example 2 which contains the (C) reactive ionic liquid and the compatibilizer which promotes compatibility of each component with respect to the mixing | blending of the comparative example 1.

  On the other hand, in Examples 1-14 containing both (B) reactive nonionic surfactant and (C) reactive ionic liquid, in each evaluation of antifogging property, all exhibit favorable antifogging properties. did.

  Among Examples 1 to 14, in Example 1 (example where the amount of (B) reactive nonionic surfactant is 2 parts by mass with respect to 100 parts by mass of (A) hydrophilic bisphenol A type (meth) acrylate). In the evaluation of film transparency, it was observed that the film was slightly cloudy. In the other examples (Examples 2 to 14), all the films were transparent. Thus, when the amount of (B) the reactive nonionic surfactant is 2 parts by mass, an antifogging film with insufficient film transparency may be obtained. From this result, in order to exhibit high anti-fogging property and more stably form an anti-fogging film with high film transparency, (A) with respect to 100 parts by mass of hydrophilic bisphenol A type (meth) acrylate ( B) It can be seen that the amount of reactive nonionic surfactant is preferably more than 2 parts by mass, more preferably 4 parts by mass or more.

  As described above, the antifogging film obtained from the antifogging coating composition of the present invention and the antifogging transparent sheet provided with the antifogging film have excellent antifogging properties (all antifogging properties at room temperature, low temperature and high temperature). ). Furthermore, when the amount of (B) the reactive nonionic surfactant is more than 2 parts by mass, an antifogging film with high film transparency can be formed more stably.

(3) Evaluation of water-washing resistance Prepare a composite sheet to be evaluated, wash the surface of the anti-fogging film 10 times in warm water at 30 ° C to 40 ° C, and then wipe the moisture with a cloth and dry the sheet. I let you. Next, a container having an open upper surface was prepared, and hot water of 50 ° C to 60 ° C was added. A dried sheet was prepared, and the open surface of the container was covered with the composite sheet with the antifogging film side down. At this time, the distance between the surface of the antifogging film and the hot water surface was set to 100 mm ± 5 mm. The film was allowed to stand as it was, and the film surface change after 2 minutes was visually observed. The anti-fogging property was evaluated in four stages in the order of less fogging (Rank A → B → C → D. Ranks A to C are acceptable levels. Rank D is a level in which the sheet becomes opaque due to fogging and cannot be practically used. The evaluation results are shown in Table 3 and Table 4. The composition shown in Table 3 is the same as that in Table 1. The composition shown in Table 4 is the same as that in Table 2.

  As shown in the evaluation results of Table 3, Comparative Example 1 containing neither (B) a reactive nonionic surfactant and (C) a reactive ionic liquid, or (B) containing a reactive nonionic surfactant. In Comparative Example 2 that was not present, the water washing resistance was D rank, which was insufficient. On the other hand, in Examples 1-7 containing both (B) reactive nonionic surfactant and (C) reactive ionic liquid, the water-washing resistance improved to C-B rank.

  Moreover, as shown in the result of Table 4, the water-washing tolerance improved by further including (E) pentaerythritol (meth) acrylate and (F) urethane (meth) acrylate type resin. In particular, 6 parts by mass or more and 10 parts by mass or less of (B) reactive nonionic surfactant and 2 parts by mass of (C) reactive ionic liquid with respect to 100 parts by mass of (A) hydrophilic bisphenol A type (meth) acrylate And 8 parts by mass of (D) polymerizable initiator, 10 parts by mass of (E) pentaerythritol (meth) acrylate, 4 parts by mass and (F) urethane (meth) acrylate resin Examples 10 to 12), A rank excellent water-washing resistance was shown. That is, it has been clarified that it is preferable to further include the components (E) and (F) in addition to the components (A) to (D) in terms of enhancing the resistance to washing with water.

(4) Hardness of antifogging film About the antifogging coating composition of Examples 8-14 containing the said (E) component and (F) component, the surface of the antifogging film formed from the antifogging coating composition further The hardness was evaluated. For evaluation, the pencil hardness of the antifogging film surface 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 the (F) component, the surface of the antifogging film becomes gradually softer. From the viewpoint of the hardness of the surface of the antifogging film, in particular, (A) 4 to 8 parts by mass of (B) reactive nonionic surfactant with respect to 100 parts by mass of hydrophilic bisphenol A type (meth) acrylate 2 parts by weight of (C) reactive ionic liquid, 8 parts by weight of (D) polymerizable initiator, 10 parts by weight of (E) pentaerythritol (meth) acrylate, 4 parts by weight and (F) urethane (Examples 9 to 11) containing a (meth) acrylate resin are preferable.

(Summary)
From the above results, the antifogging coating composition having a specific composition according to the present invention is not only excellent in initial antifogging property immediately after the formation of the antifogging film (for example, high temperature antifogging property, low temperature antifogging property), It is possible to form an antifogging film excellent in antifogging durability in which the antifogging effect is sustained over a long period. Moreover, in addition to said (A)-(D) component, by containing (E) component and (F) component, it is excellent in water-washing resistance, and the anti-fogging film | membrane with which softness was provided can be obtained.

  It should be understood that the embodiments and examples disclosed herein are illustrative in all respects and are not restrictive in any respect. The scope of the present invention is defined by the terms of the claims, rather than the meaning described above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The antifogging coating composition and the antifogging transparent sheet of the present application can be particularly advantageously applied in various fields where an antifogging effect that is sustained over a long period is required.

Claims (11)

(A) hydrophilic bisphenol A type (meth) acrylate,
(B) a reactive nonionic surfactant;
(C) a reactive ionic liquid;
(D) An antifogging coating composition containing a polymerizable initiator.   The antifogging coating composition according to claim 1, wherein the (C) reactive ionic liquid is a liquid comprising an ammonium sulfonate.   The antifogging coating composition according to claim 1 or 2, further comprising (E) pentaerythritol (meth) acrylate.   The antifogging coating composition according to any one of claims 1 to 3, further comprising (F) a urethane (meth) acrylate-based resin.   The anti-fogging coating composition according to any one of claims 1 to 4, wherein a content of the component (B) is more than 2 parts by mass and not more than 20 parts by mass with respect to 100 parts by mass of the component (A). object.   The anti-fog coating composition of any one of Claims 1-5 whose content of the said (C) component is 1 mass part or more and 5 mass parts or less with respect to 100 mass parts of said (A) components. object.   The content mass ratio of the component (B) to the component (C) is such that (B) / (C) is 1 or more and 10 or less, and is antifogging according to any one of claims 1 to 6. Coating composition.   The antifogging coating composition according to any one of claims 1 to 7, further comprising a leveling agent.   The anti-fogging coating composition according to any one of claims 1 to 8, wherein the polymerizable initiator is a photopolymerization initiator. A transparent substrate,
An antifogging film comprising the antifogging coating composition according to any one of claims 1 to 9, disposed on the surface of the substrate,
An anti-fogging transparent sheet.   The anti-fogging transparent sheet according to claim 10, wherein the base material is a base material made of polyethylene terephthalate.