JP7160638B2 - Resin composition and anti-fogging film - Google Patents

Description

The present invention relates to a resin composition and an antifogging film.

2. Description of the Related Art Conventionally, transparent substrates such as plate glass and lenses made of glass, plastic, or the like may be cooled to a temperature below the dew point depending on the temperature and humidity to which the substrate is exposed. In that case, dew condensation occurs on the surface of the base material that is below the dew point, resulting in fogging. Therefore, lenses of cameras and eyeglasses, windows of houses, automobiles and aircraft, mirrors, etc. may be made less foggy by imparting hydrophilicity or water absorbency with a coating agent or film. .

Hydrophilic or water-absorbing resins are used for antifogging coating agents and films. For example, coatings and films made of coating agents containing surfactants, etc. are exposed to light and heat for a long period of time, because the surfactants decompose, deteriorate, and bleed over time. , the anti-fogging performance may be significantly reduced.

For example, in Patent Document 1, a copolymer represented by a specific general formula and a polyfunctional epoxy compound having a solubility in water at 25° C. of 40 to 100% by mass are combined with a quaternary ammonium salt or a quaternary phosphonium. An anti-fogging film-forming material obtained by reacting in the presence of a salt is described.

Japanese Patent Application Laid-Open No. 2014-114430 (published on June 26, 2014)

The resin composition described in Patent Document 1 attempts to improve heat resistance by cross-linking a copolymer represented by a specific general formula with a polyfunctional epoxy compound, but the antifogging property is not sufficient. There is a problem. Further, a resin composition having higher heat resistance than the resin composition of Patent Document 1 is desired.

The present invention has been made in view of the above problems, and provides a resin composition capable of imparting high antifogging properties to a substrate and forming a coating with high heat resistance, and related arts thereof. With the goal.

In order to solve the above problems, the following aspects are included.
<1> A resin composition containing polyvinylpyrrolidone, at least one polyol resin selected from the group consisting of polyester polyols and polycarbonate polyols, and an isocyanate cross-linking agent.
<2> The resin composition according to <1>, wherein the polyester polyol is polycaprolactone polyol.
<3> The resin composition according to <1> or <2>, wherein the isocyanate-based cross-linking agent is a cross-linking agent derived from an alicyclic isocyanate.
<4> The resin composition according to any one of <1> to <3>, further comprising a cross-linking agent derived from an aliphatic isocyanate as the isocyanate-based cross-linking agent.
<5> The resin composition according to <4>, wherein the aliphatic isocyanate-derived cross-linking agent is a bifunctional cross-linking agent derived from an aliphatic isocyanate compound.
<6> The resin composition according to any one of <1> to <5>, wherein the number of equivalents of the functional group of the cross-linking agent to the hydroxyl group of the polyol resin is within the range of 0.5 to 2.3 equivalents.
<7> The resin composition according to any one of <1> to <6>, wherein the number of equivalents of the functional group of the cross-linking agent to the hydroxyl group of the polyol resin is within the range of 0.7 to 2.3 equivalents.
<8> The resin composition according to any one of <1> to <7>, further comprising a melamine cross-linking agent.
<9> An anti-fogging film comprising a film and an anti-fogging layer formed on the film, wherein the anti-fogging layer is formed from the resin composition according to any one of <1> to <8>. the film.

ADVANTAGE OF THE INVENTION According to the resin composition which concerns on 1 aspect of this invention, it is effective in the ability to provide a base material with high antifogging property, and to form a film with high heat resistance.

In this specification, the numerical range indicated using "to" indicates the range including the numerical values before and after "to" as the minimum and maximum values, respectively.

<Resin composition>
A resin composition according to an aspect of the present invention contains polyvinylpyrrolidone, at least one polyol resin selected from the group consisting of polyester polyols and polycarbonate polyols, and an isocyanate cross-linking agent.

According to the above configuration, it is possible to obtain a resin composition capable of forming a coating (antifogging layer) having high antifogging properties and high heat resistance. Moreover, according to the above configuration, it is possible to form a coating having high total light transmittance and low haze value while providing high antifogging properties and high heat resistance. Therefore, it is suitably used for imparting anti-fogging properties to transparent resin substrates such as acrylic resins and polycarbonate resins, as well as to glass substrates. In particular, since the resin composition according to one aspect of the present invention has high heat resistance, it is suitably used for anti-fogging windshields and the like of vehicles in which the temperature is extremely high due to direct sunlight in summer.

The resin composition of the present invention may be directly applied to a substrate, or a film may be previously coated with the resin composition and the film may be attached to glass or the like.

[Polyvinylpyrrolidone]
Polyvinylpyrrolidone is a water-soluble polymer that contributes to the antifogging properties of the coating formed from the resin composition.

The weight average molecular weight (Mw) of the polyvinylpyrrolidone contained in the resin composition of the present invention is not particularly limited, but is preferably in the range of 8000 to 3 million, more preferably in the range of 20,000 to 2 million. and most preferably within the range of 40,000 to 1,500,000. Within the weight average molecular weight range of 8,000 to 3,000,000 polyvinylpyrrolidone, the smaller the weight average molecular weight, the higher the antifogging property, and the larger the weight average molecular weight, the higher the heat resistance (resisting yellowing caused by heat). resistance) is obtained.

The content of polyvinylpyrrolidone in the resin composition is preferably in the range of 15 to 80 parts by mass, more preferably in the range of 28 to 78 parts by mass, with respect to 100 parts by mass in total of polyvinylpyrrolidone and the polyol resin described later. and most preferably within the range of 38 to 65 parts by mass. Within the range of 15 to 80 parts by mass, the higher the content of polyvinylpyrrolidone, the higher the antifogging property, and the lower the content, the higher the water resistance. In particular, when the content of polyvinylpyrrolidone is in the range of 38 to 65 parts by mass with respect to 100 parts by mass of the total of polyvinylpyrrolidone and polyol resin in the resin composition, the antifogging property is dramatically improved. It is possible to obtain a resin composition capable of forming a film having high water resistance while improving water resistance.

Commercial products of polyvinylpyrrolidone include, for example, Pittscol (registered trademark), Crejas (registered trademark) and Eyefact (registered trademark) (all manufactured by Daiichi Pharmaceutical Co., Ltd.), and Kollidon (registered trademark) (BASF Japan Co., Ltd.) and the like. Commercial products of polyvinylpyrrolidone may be used in powder form or in solution form. Moreover, for example, two or more kinds of polyvinylpyrrolidone having different weight average molecular weights may be used in combination.

Polyvinylpyrrolidone is typically a polymer composed of vinylpyrrolidone alone, but it may be a copolymer of vinylpyrrolidone and other monomers as long as the effects of the present invention are not impaired. Other monomers include, for example, acrylic acid esters and acrylic acid, methacrylic acid esters and methacrylic acid, as well as styrene and vinyl acetate. Polyvinylpyrrolidone may be, for example, a block polymer or a graft polymer of a vinylpyrrolidone block and a polyvinylalcohol block of another monomer.

[Polyol resin]
The polyol resin is a resin that reacts with a cross-linking agent, which will be described later, and has a hydroxyl group as a functional group that reacts with the cross-linking agent. The number of hydroxyl groups possessed by one molecule of the polyol resin is preferably 2 to 6, more preferably 2 to 4. The polyol resin is typically at least one polyol resin selected from the group consisting of polyester polyols and polycarbonate polyols. Here, the polyester polyol is more preferably polycaprolactone polyol. By blending polyester polyol and/or polycarbonate polyol with polyvinylpyrrolidone, the resin composition of the present invention can suppress deterioration of antifogging properties due to heat and form a film with a low haze value.

The hydroxyl value of the polyol resin is preferably in the range of 30 to 350 KOHmg/g, and more preferably in the range of 80 to 250 KOHmg/g from the viewpoint of improving water resistance, and further abrasion resistance. is most preferably within the range of 100 to 250 KOHmg/g.

Polycaprolactone polyol is obtained by reacting a compound having multiple hydroxyl groups in the molecule with polycaprolactone. A commercially available polycaprolactone polyol may also be used.

Examples of commercially available polycaprolactone polyols include Plaxel (registered trademark) manufactured by Daicel Corporation, and its product number is #205 (number average molecular weight (Mn) 530, number of hydroxyl groups 2, hydroxyl value 212 KOHmg/g ), #208 (Mn830, number of hydroxyl groups: 2), #210 (Mn1000, number of hydroxyl groups: 2), #212 (Mn1250, number of hydroxyl groups: 2), #220 (Mn2000, number of hydroxyl groups: 2, hydroxyl groups #305 (Mn530, number of hydroxyl groups: 3, hydroxyl value: 305 KOHmg/g), #308 (Mn850, number of hydroxyl groups: 3), #309 (Mn900, number of hydroxyl groups: 3), #312 (Mn 1250, 3 hydroxyl groups), #320 (Mn 2000, 3 hydroxyl groups) and #410 (Mn 1000, 4 hydroxyl groups). Commercially available polycaprolactone polyols include CAPA2085 (Mn 830, number of hydroxyl groups: 2), CAPA2100 (Mn: 1000, number of hydroxyl groups: 2), CAPA2121 (Mn: 1250, number of hydroxyl groups: 2) manufactured by Perstorp Japan, CAPA2125 (Mn1250, number of hydroxyl groups: 2), CAPA2200 (Mn2000, number of hydroxyl groups: 2), CAPA2201 (Mn2000, number of hydroxyl groups: 2), CAPA2205 (Mn2000, number of hydroxyl groups: 2), CAPA2209 (Mn2000, number of hydroxyl groups: 2) 2), CAPA3091 (Mn900, 3 hydroxyl groups), CAPA3121J (Mn1200, 3 hydroxyl groups), CAPA3201 (Mn2000, 3 hydroxyl groups) and CAPA4101 (Mn1000, 4 hydroxyl groups). be done. One type of polycaprolactone polyol may be used alone, or two or more types may be used in combination.

A polycarbonate polyol is a polycarbonate diol or is a polycarbonate polyol. The polycarbonate polyol is obtained by reacting the polycarbonate diol with a compound having a plurality of hydroxyl groups in the molecule. Moreover, a polycarbonate polyol may use a commercial item.

Examples of commercially available polycarbonate polyols include DURANOL (registered trademark) manufactured by Asahi Kasei Corporation, and the product numbers thereof include, for example, T6002 (Mn 2000, number of hydroxyl groups: 2, hydroxyl value 51 to 61 KOHmg/g), T6001 ( Mn1000, number of hydroxyl groups: 2, hydroxyl value: 100-120 KOHmg/g), T5652 (Mn2000, number of hydroxyl groups: 2, hydroxyl value: 51-61 KOHmg/g), T5651 (Mn1000, number of hydroxyl groups: 2, hydroxyl value: 100- 120KOHmg/g), T5650J (Mn500, number of hydroxyl groups: 2, hydroxyl value: 112KOHmg/g), T5650E (Mn500, number of hydroxyl groups: 2, hydroxyl value: 200-250KOHmg/g), T4672 (Mn2000, number of hydroxyl groups: 2 , hydroxyl value 45 to 56 KOH mg / g), T4671 (Mn 1000, number of hydroxyl groups 2, hydroxyl value 100 to 120 KOH mg / g), T4692 (Mn 2000, number of hydroxyl groups 2, hydroxyl value 51 to 61 KOH mg / g), T4691 ( Mn1000, 2 hydroxyl groups, hydroxyl value 100 to 120 KOHmg/g), G3452 (Mn2000, 2 hydroxyl groups, hydroxyl value 51 to 61 KOHmg/g) and G3450J (Mn800, 2 hydroxyl groups, hydroxyl value 130~ 150 KOH mg/g) and the like.

Moreover, as the polyol resin, polyether polyol may be used in combination with polycaprolactone polyol and/or polycarbonate polyol as long as the effects of the present invention are not impaired. Polyether polyols include, for example, polyether diols such as polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol (PTMG), and such polyether diols with multiple hydroxyl groups in the molecule. It is a polyether polyol obtained by reacting a compound having

[Crosslinking agent]
The amount of the cross-linking agent added in the present invention is preferably such that the functional group of the cross-linking agent is within the range of 0.3 to 3.3 equivalents, particularly 0.5, with respect to the hydroxyl groups of the polyol resin. It is preferably added so that the number of equivalents is within the range of up to 2.3, more preferably within the range of 0.7 to 2.3 equivalents. By setting the functional groups of the cross-linking agent to 0.5 to 2.3 equivalents with respect to the hydroxyl groups possessed by the polyol resin, it is possible to impart hot water resistance to the film formed by the resin composition while maintaining antifogging properties. Abrasion resistance of the coating formed from the resin composition can be improved by adjusting the equivalent weight to 0.7 to 2.3. In addition, when using a plurality of types of cross-linking agents, the total number of functional groups possessed by each cross-linking agent with respect to the hydroxyl groups possessed by the polyol resin should be within the range of 0.3 to 3.3 equivalents. should be added.

As a cross-linking agent, an isocyanate-based cross-linking agent is typically used. Further, other cross-linking agents may be used together with the isocyanate-based cross-linking agent. Examples of other cross-linking agents include melamine-based cross-linking agents, benzoguanamine-based cross-linking agents, urea-based cross-linking agents, metal chelate-based cross-linking agents, organosilane-based cross-linking agents, epoxy-based cross-linking agents, and acid anhydride-based cross-linking agents. It is particularly preferable to use a melamine cross-linking agent together.

[Isocyanate-based cross-linking agent]
The cross-linking agent is a compound having a functional group that reacts with the hydroxyl group of the polyol resin, and is typically an isocyanate-based cross-linking agent. By using an isocyanate-based cross-linking agent, it is possible to suppress deterioration of the antifogging properties of the coating formed from the resin composition due to heat. Such an effect is said to be brought about by the fact that the isocyanate-based cross-linking agent reacts with the polyol resin to cross-link, and the urethane bond, allophanate bond, etc. formed by this cross-linking pseudo-cross-links with the carbonyl portion of polyvinylpyrrolidone. guessed.

Examples of isocyanate-based cross-linking agents include isocyanate compounds and cross-linking agents derived from such isocyanate compounds, and it is sufficient that an isocyanate group is bonded to an organic compound having about 1 to 1,000 carbon atoms. Examples of isocyanate compounds include polymeric MDIs such as xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), and triphenylmethane triisocyanate; aromatic isocyanate compounds such as tolylene diisocyanate (TDI); ), heptamethylene diisocyanate, isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate (hydrogenated XDI) such as 1,4-cyclohexanebismethyl isocyanate, hydrogenated diphenylmethane diisocyanate such as 4,4-methylenebiscyclohexyl isocyanate ( and aliphatic or alicyclic isocyanate compounds such as hydrogenated MDI). Cross-linking agents derived from isocyanate compounds include, for example, dimers or trimers of isocyanate compounds, that is, uretdione or isocyanurate, prepolymers of isocyanate compounds and polyol resins, isocyanate compounds, and propylene glycol (2 functional alcohol), butylene glycol (bifunctional alcohol), trimethylolpropane (TMP, trifunctional alcohol), glycerin (trifunctional alcohol), polyhydric alcohol compounds such as pentaerythritol (tetrafunctional alcohol), adducts with urea compounds, etc. A body etc. are mentioned. Examples of such adducts include tolylene diisocyanate-trifunctional alcohol adduct, isophorone diisocyanate-difunctional alcohol adduct, isophorone diisocyanate-trifunctional alcohol adduct, hexamethylene diisocyanate-difunctional alcohol adduct, and hexamethylene diisocyanate. −3-functional alcohol adducts. Other isocyanate-based cross-linking agents include dimethylsilicon diisocyanate and monomethylsilicon triisocyanate. The isocyanate-based cross-linking agent may also contain n-butyl isocyanate, n-hexyl isocyanate, trimethyl silicon isocyanate, and the like. These isocyanate-based cross-linking agents may be used in combination of two or more.

From the viewpoint of further improving the heat resistance (resistance to yellowing) of the coating formed by the resin composition of the present invention, the isocyanate-based cross-linking agent includes an aliphatic isocyanate compound and an alicyclic isocyanate compound, and an aliphatic Alternatively, an isocyanate-based cross-linking agent derived from an alicyclic isocyanate is more preferable. In particular, by using an isocyanate-based cross-linking agent derived from an alicyclic isocyanate, the resin composition can be suitably formed into a film regardless of the mixing ratio of the polyvinylpyrrolidone and the polyol resin. In particular, by using an isocyanurate-type isocyanate-based cross-linking agent derived from an alicyclic isocyanate compound, the antifogging property can be further improved.

Furthermore, by using both an isocyanate-based cross-linking agent derived from an aliphatic isocyanate compound and an isocyanate-based cross-linking agent derived from an alicyclic isocyanate compound, the heat resistance and water resistance of the coating can be maintained while antifogging properties are improved. can improve. From the viewpoint of improving antifogging properties, it is more preferable to use a bifunctional isocyanate-based cross-linking agent derived from an aliphatic isocyanate.

[Melamine-based cross-linking agent]
A melamine-based cross-linking agent can also be used in the resin composition according to the present invention in combination with an isocyanate-based cross-linking agent. By reacting a polyol resin with a melamine-based cross-linking agent in the presence of polyvinylpyrrolidone, a coating formed from the resin composition can be imparted with high antifogging properties and high water resistance. Such an effect is brought about by the fact that the melamine cross-linking agent reacts with the polyol resin to cross-link, cross-links the melamine cross-linking agents with each other, and pseudo-cross-links the melamine cross-linking agent with the carbonyl moiety of polyvinylpyrrolidone. presumed to be

Examples of melamine cross-linking agents include melamine, methylolated melamine derivatives obtained by condensing melamine and formaldehyde, compounds obtained by reacting methylolated melamine with a lower alcohol to partially or completely etherify, or mixtures thereof. etc. can be used. The melamine-based cross-linking agent may be either a monomer or a condensate of dimers or higher polymers, or a mixture thereof. More specific examples include imino group-type methylated melamine resins, methylol group-type melamine resins, methylol group-type methylated melamine resins, and completely alkyl-type methylated melamine resins.

The melamine-based cross-linking agent is represented, for example, by general formula (I) below.

(Here, R ¹ to R ⁵ are each independently a hydrogen atom, R ⁷ —OCH ₂ —, or a melamine residue represented by formula (II) or formula (III), and R ⁷ is hydrogen atom, an alkyl group of 1 to 4 carbons, or a glycidyl group, R ⁶ is a hydrogen atom or an alkyl group of 1 to 3 carbons, n1 is an integer of 1 to 8.)

(Here, R ¹¹ to R ¹⁵ are each independently a hydrogen atom, R ¹⁶ OCH ₂ —, or a melamine residue represented by formula (III), and R ¹⁶ is a hydrogen atom having 1 carbon atom. to 4 alkyl groups or glycidyl groups.)

(Here, R ²¹ to R ²⁵ are each independently a hydrogen atom, R ²⁶ OCH ₂ —, or a melamine residue represented by formula (II), and R ²⁶ is a hydrogen atom having 1 carbon atom. to 4 alkyl groups or glycidyl groups.)
The melamine cross-linking agent is also represented by general formula (IV) below.

(Here, R ³¹ to R ³⁵ are a hydrogen atom, R ³⁷ —OCH ₂ —, or a melamine residue represented by formula (II) or formula (III), and R ³⁷ is a hydrogen atom, carbon 1 ~4 alkyl group or glycidyl group, ^R36 is a hydrogen atom or a C1-3 alkyl group, n2 is an integer of 1-8.)
The melamine-based cross-linking agent is also represented by general formula (V) below.

(Here, R ⁴¹ to R ⁴⁵ and R ⁵¹ to R ⁵⁴ are a hydrogen atom, R ⁴⁷ —OCH ₂ —, or a melamine residue represented by formula (II) or formula (III), and R ⁴⁷ is , a hydrogen atom, an alkyl group of 1 to 4 carbons, or a glycidyl group, R ⁵⁵ is a hydrogen atom or an alkyl group of 1 to 3 carbons, n3 and n4 are integers, and n3+n4 is 2 to 8 .)
Among the compounds represented by the general formulas (I) to (V), the melamine-based cross-linking agents are preferably Nikalac (registered trademark) MS-11 and MS-001 (both manufactured by Nippon Carbide Industry Co., Ltd.), and , Mycoat 715 (manufactured by Nippon Cytec Industries Co., Ltd.), and the like.

The amount of the melamine cross-linking agent to be added is preferably such that the methylol group is in the range of 0.3 to 3.3 equivalents to the hydroxyl groups of the polyol resin, particularly 0.4. Addition of the melamine-based cross-linking agent in the range of up to 2.3 equivalents improves the abrasion resistance of the coating formed from the resin composition.

[Benzoguanamine-based cross-linking agent]
In the resin composition according to the present invention, a benzoguanamine-based cross-linking agent may be used together with the isocyanate-based cross-linking agent. The benzoguanamine-based cross-linking agent includes, for example, benzoguanamine, a methylolated benzoguanamine derivative obtained by condensing benzoguanamine and formaldehyde, a compound obtained by reacting methylolated benzoguanamine with a lower alcohol to partially or completely etherify, or a mixture thereof. etc. can be used. The benzoguanamine-based cross-linking agent may be either a monomer or a condensate of a dimer or higher polymer, or a mixture thereof. More specific examples include butylated benzoguanamine resins, methylolated benzoguanamine resins, and the like.

[Urea-based cross-linking agent]
A urea-based cross-linking agent may be used in combination with the isocyanate-based cross-linking agent in the resin composition according to the present invention. Examples of urea-based cross-linking agents include methylolated urea derivatives obtained by condensing urea and formaldehyde, compounds obtained by reacting methylolated urea with a lower alcohol to partially or completely etherify, or mixtures thereof. can be used. The urea-based cross-linking agent may be either a monomer or a condensate composed of a dimer or higher polymer, or a mixture thereof. More specific examples include butylated urea resins and methylolated urea resins.

[Organosilane-based cross-linking agent]
In the resin composition according to the present invention, an organosilane-based cross-linking agent may be used together with the isocyanate-based cross-linking agent. The organosilane-based cross-linking agent includes, for example, an organosilane having an alkoxy group, a halogen such as chlorine, a hydrolyzable group such as hydrogen, and a substituent such as an alkyl group and a phenyl group. Organosilane cross-linking agents include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, methylhydrogen Examples include organosilanes such as siloxane, alkoxy oligomers of these organosilanes, silazanes such as hexamethyldisilazane, and silicone quaternary ammonium salts. The organosilane-based cross-linking agents include alkoxy groups, halogens such as chlorine, hydrolyzable groups such as hydrogen, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, styryl groups, amino groups, ureido groups, mercapto So-called silane coupling agents can be used, both with groups, sulfides, and functional groups such as isocyanate groups. Such an organosilane-based cross-linking agent is available from Shin-Etsu Chemical Co., Ltd., for example.

[Metal chelate-based cross-linking agent]
In the resin composition according to the present invention, a metal chelate cross-linking agent may be used together with the isocyanate cross-linking agent. Examples of metal chelate-based cross-linking agents include aluminum chelate-based cross-linking agents, zirconium chelate-based cross-linking agents, titanium chelate-based cross-linking agents, chromium chelate-based cross-linking agents, cobalt chelate-based cross-linking agents, copper chelate-based cross-linking agents, and iron chelate-based cross-linking agents. agent, nickel chelate cross-linking agent, vanadium chelate cross-linking agent, zinc chelate cross-linking agent, indium chelate cross-linking agent, calcium chelate cross-linking agent, magnesium chelate cross-linking agent, manganese chelate cross-linking agent, yttrium chelate cross-linking agent, A cerium chelate-based cross-linking agent, a strontium chelate-based cross-linking agent, a barium chelate-based cross-linking agent, a molybdenum chelate-based cross-linking agent, a lanthanum chelate-based cross-linking agent, a suzuki rate-based cross-linking agent, etc. can be used, preferably an aluminum chelate-based cross-linking agent, A zirconium chelate cross-linking agent and a titanium chelate cross-linking agent. Aluminum chelate cross-linking agents are more preferred. These metal chelate-based cross-linking agents can also act as curing accelerators for isocyanate-based cross-linking agents and organosilane-based cross-linking agents.

[Epoxy cross-linking agent]
An epoxy-based cross-linking agent may be used in combination with the isocyanate-based cross-linking agent in the resin composition according to the present invention. Examples of epoxy-based cross-linking agents include phenols such as triglycidyl isocyanurate and phenol novolac type epoxy resins, phenols such as cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and/or α-naphthol and β-naphthol. Epoxy resins obtained by epoxidizing novolak resins obtained by condensing or co-condensing naphthols such as dihydroxynaphthalene with compounds having aldehyde groups such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. in the presence of acidic catalysts, bisphenols A, diglycidyl ethers such as bisphenol F, bisphenol S, bisphenol A/D, biphenyl-type epoxy resins that are glycidyl ethers of alkyl-substituted or unsubstituted biphenols, phenols and/or naphthols and dimethoxyparaxylene or bis(methoxy epoxidized products such as phenol-aralkyl resins, naphthol-aralkyl resins, and biphenyl-aralkyl resins synthesized from methyl)biphenyl, stilbene-type epoxy resins, hydroquinone-type epoxy resins, polybasic acids such as phthalic acid and dimer acid, and epichloro Glycidyl ester type epoxy resin obtained by reaction with hydrin, dicyclopentadiene type epoxy resin, epoxy resin having a naphthalene ring, triphenylmethane type epoxy resin, trimethylolpropane type epoxy resin, terpene modified epoxy resin, sulfur atom containing epoxy resins, aliphatic epoxy resins obtained by oxidizing olefin bonds with peroxides, alicyclic epoxy resins, or modifying these epoxy resins with silicone, acrylonitrile, butadiene, isoprene rubber, polyamide resins, etc. Epoxy resin and the like.

[Acid anhydride-based cross-linking agent]
In the resin composition according to the present invention, an acid anhydride cross-linking agent may be used together with the isocyanate cross-linking agent. Acid anhydride cross-linking agents include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Examples include tetrahydrophthalic anhydride, nadic anhydride, and methyl nadic anhydride.

(Curing accelerator)
If necessary, a curing accelerator (catalyst) may be added to the resin composition. The curing accelerator may be appropriately selected according to the type of the cross-linking agent. For isocyanate-based cross-linking agents, Lewis acids are preferred, and metal alkoxides and metal salts are particularly preferred. Specific examples include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, titanium tetraisopropoxide, titanium acetylacetonate, zirconium tetraisopropoxide and zirconium acetylacetonate. Examples of melamine-based cross-linking agents include imidazoles, quaternary ammonium salts, phosphorus compounds, amines, phosphines, phosphonium salts, bicyclic amidines, and salts thereof. Polyphosphate esters are preferably used as compounds. Among these curing accelerators, phosphorus compounds can be used to reduce yellowing caused by heat and light. In particular, since polyphosphate esters retain acid, condensation can be accelerated more than other phosphorus compounds. These curing accelerators may be used in combination of two or more. In addition, for organosilane-based cross-linking agents and epoxy-based cross-linking agents, for example, the aforementioned Lewis acids, acids, and alkalis such as amines are used as curing accelerators.

(solvent)
More preferably, the resin composition contains a solvent that dissolves the materials including the polyvinylpyrrolidone, the polyol resin and the cross-linking agent. The solvent is not particularly limited as long as it can dissolve these materials, and is more preferably a solvent used for general coating agents. Solvents include, for example, alcohol solvents, ether solvents, ester solvents, ketone solvents, and the like. Examples of alcohol solvents include monoalkyl alcohols such as methanol, ethanol, 1-propanol, 2-propanol (IPA), 1-butanol, 2-butanol, and 1-amyl alcohol. Ether solvents include, for example, diethyl ether, dibutyl ether, tetrahydrofuran (THF), 1,4-dioxane and the like. Examples of ester solvents include acetic esters such as methyl acetate, ethyl acetate, 1-propyl acetate, 2-propyl acetate, butyl acetate, and amyl acetate, cyclic polyesters such as γ-butyrolactone, and ethylene. Examples thereof include monoalkyl esters of monomers or dimers of divalent alkyl alcohols such as glycol and propylene glycol, or alkyl esters of monoalkyl ethers of monomers or dimers of divalent alkyl alcohols. Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Other solvents include N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), aprotic polar solvents such as propylene carbonate, chlorinated solvents, aliphatic hydrocarbons such as hexane and cyclohexane, and toluene and xylene. Examples include aromatic hydrocarbons and petroleum hydrocarbons. These solvents may be used in combination of two or more.

The content of the solvent contained in the resin composition may be appropriately adjusted according to the film thickness of the film formed by the resin composition and the coating workability of the resin composition. It is preferable to use so that the content is within the range of 10 to 60% by weight.

(Other compositions)
The resin composition may contain additives such as antioxidants, ultraviolet absorbers, antifoaming agents, leveling agents, antistatic agents, and viscosity modifiers, as well as colorants, organic pigments, inorganic pigments, and the like. .

<Anti-fog film>
An antifogging film according to one aspect of the present invention comprises a film and an antifogging layer formed on the film, and the antifogging layer is formed from the resin composition according to one aspect of the present invention. . Further, an adhesive layer for attaching the antifogging film to the substrate may be formed on the back surface of the antifogging film on which the antifogging layer is formed.

(Anti-fogging layer)
An anti-fogging layer is formed on the surface of the film. The anti-fogging layer is composed of a cross-linking reaction product of the aforementioned resin composition. The cross-linking reaction product has a three-dimensional network molecular structure due to chemical bonding between the cross-linking agent and the polyol. The anti-fogging layer can be produced by forming a coating film from the aforementioned resin composition by a known method. The thickness of the antifogging layer is preferably in the range of 2 to 60 μm, more preferably in the range of 10 to 50 μm. The thickness of the anti-fogging layer is within the range of 2 to 60 μm. In particular, when the thickness is within the range of 10 to 50 μm, an antifogging layer having high antifogging properties and high transparency can be formed.

Moreover, the antifogging film may be provided with a protective film that protects the surface of the antifogging layer and the surface of the adhesive layer. The protective film preferably has removability, and for example, a polyolefin film such as polyethylene or polypropylene may be used.

(the film)
Examples of films that can be used include, but are not limited to, PET (polyethylene terephthalate) film, polyethylene naphthalate (PEN) film, acrylic film, vinyl chloride film, polycarbonate film, and urethane film. In order to increase the wettability of the resin composition for forming the antifogging layer and the adhesive composition for forming the adhesive layer, the surface of these films is coated with, for example, corona discharge or a primer layer. It is preferable that an easy-adhesion treatment such as coating is applied.

(adhesive layer)
The adhesive layer is a layer for attaching the anti-fogging film to the substrate, and is formed on the surface of the film by coating an adhesive composition or laminating an adhesive layer.

As the adhesive composition for forming the adhesive layer, known adhesive compositions such as acrylic adhesives, synthetic rubber adhesives, silicone adhesives, and olefin adhesives are used.

The present invention is not limited to each embodiment or each example, and various modifications are possible within the scope indicated in the claims.

An embodiment of the invention is described below.
[Preparation of resin composition]
The resin composition of Example 1 was prepared as follows. First, Pitzcol (registered trademark) K-30 (manufactured by Daiichi Kogyo Co., Ltd., polyvinylpyrrolidone (PVP)) was dissolved in isopropyl alcohol (IPA) so that the concentration of PVP was 33% by weight, thereby forming a PVP solution. Obtained. Next, PLAXEL (registered trademark) 205 (manufactured by Daicel Co., Ltd., polycaprolactone diol) is dissolved in 50 parts by mass of PVP contained in the PVP solution, and tetrahydrofuran (THF) is added. By doing so, the solid content concentration was adjusted to 30% by weight. Subsequently, 40.19 parts by mass of Takenate (registered trademark) D-120N (manufactured by Mitsui Chemicals, Inc., TMP adduct of hydrogenated XDI) as a cross-linking agent was dissolved in 50 parts by mass of Praxel 205. A coating agent (resin composition) of Example 1 was obtained.

Resin compositions of Examples 2 to 20 and resin compositions of Comparative Examples 1 and 2 were prepared in the same procedure as the resin composition of Example 1.

[Preparation of anti-fogging film test piece]
The resin composition was applied using an applicator onto a double-sided easy-adhesion treated PET film (manufactured by Toyobo Co., Ltd., trade name "Cosmoshine A4300") as a base material so that the film thickness of the antifogging layer was 22 μm. . After that, heat drying is performed for 3 minutes in an environment of 150 ° C. using a hot air dryer, and a protective film (manufactured by Futamura Chemical Co., Ltd., trade name “Taiko Polypropylene FSM-020B”) is applied to the coating film in an environment of 25 ° C.). was laminated. Next, the laminated film was aged for 3 days in a 60° C. environment using a hot air dryer.

After that, 90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid were solution-polymerized, and 100 parts by mass of an acrylic resin having a weight average molecular weight of 650,000 was added to an aluminum chelate cross-linking agent (manufactured by Kawaken Fine Chemicals Co., Ltd., trade name "Aluminum Chelate A ”) is added to 0.36 parts by mass, and the adhesive composition is applied to the separator using an applicator and dried to form an adhesive layer on the separator. An antifogging film was obtained by laminating so that the adhesive layer was in contact with the side opposite to the side on which the antifogging layer was provided.

[Measurement of film thickness]
The film thickness of the antifogging layer in the antifogging film was measured with a dial gauge (manufactured by Teclock Co., Ltd., PG-02).

[Measurement of total light transmittance]
The total light transmittance (%) was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) with the anti-fog film attached to a glass plate having a thickness of 3 mm and the protective film removed. .

[Measurement of haze]
The measurement of haze is the same as the measurement of total light transmittance (%), with the anti-fog film attached to a glass plate with a thickness of 3 mm and the protective film removed, a haze meter (Nippon Denshoku Kogyo Co., Ltd., NDH -2000).

[Evaluation of low-temperature anti-fogging property]
An anti-fog film test piece cut to 25 mm x 25 mm was pasted on both sides of a 3 mm thick glass plate, left in an environment of 0 ° C. for 30 minutes, and then exhaled at 23 ° C./50% RH to check whether it fogged. evaluated. Judgment of the presence or absence of fogging was performed by holding a glass plate at a position about 1 cm away from the surface of the anti-fogging film on which the air was blown and the white paper surface on which 6-point font size characters were printed in black. Those who could not read "hiragana" were evaluated as "cloudy", and those who could read "hiragana" were evaluated as "no cloudiness".

[Evaluation of high-temperature anti-fogging property]
An anti-fog film test piece cut to 25 mm x 25 mm was attached to a glass plate with a thickness of 3 mm, left in an environment of 23 ° C./50% RH for 24 hours, and then placed on the anti-fog film side in an environment of 23 ° C./50% RH. was directed to a water bath filled with hot water at 40°C, and the glass plate was held at a position where the surface of the antifogging film was separated from the water surface by about 1 cm, and the time until the antifogging film fogged with steam was measured. The time until fogging was determined by immersing a white film on which black characters with a font size of 6 points were printed in water, holding the glass plate at a position where the distance between the white film and the anti-fogging film was 7 cm, and visually observing 6 points. Hiragana" until I can't read it.

[Anti-fogging property after heat resistance test]
An anti-fog film test piece cut to 25 mm×25 mm was attached to a glass plate of 3 mm thickness, left in an environment of 100° C. for 1000 hours, and then left in an environment of 23° C./50% RH for 1 week. After that, the antifogging property was evaluated in the same manner as in the evaluation of the high-temperature antifogging property described above, and the antifogging property was evaluated after the heat resistance test.

The rate of change (%) in antifogging properties was obtained as follows.
T ₁ /T ₀ ×100 = rate of change (%)
T ₀ : Time until anti-fog film fogs with steam in high-temperature anti-fogging evaluation T ₁ : Time until anti-fogging film fogs with steam in anti-fogging evaluation after heat resistance test [Water resistance]
An anti-fogging film test piece cut to 25 mm×25 mm was attached to a glass plate of 3 mm thickness, immersed in hot water at 40° C. for 168 hours, and then allowed to stand at 23° C./50% RH for 1 week. After that, the antifogging property was evaluated in the same manner as the evaluation of the high-temperature antifogging property described above, and the antifogging property was evaluated after the water resistance test.

The rate of change (%) in antifogging properties after the water resistance test was determined as follows, similarly to the above-described antifogging properties after the heat resistance test.
T ₂ /T ₀ ×100 = rate of change (%)
T ₀ : Time until the anti-fogging film fogs with steam in the evaluation of high-temperature anti-fogging T ₂ : Time until the anti-fogging film fogs with steam in the evaluation of anti-fogging properties after the water resistance test [Evaluation of abrasion resistance ]
With the anti-fog film attached to the glass plate, the pencil hardness of the anti-fog layer was measured using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., No. 12944 series No. 553) and Mitsubishi UNI pencils 6B to 9H. Measured according to JIS K5600.

[Heat-resistant]
An anti-fogging film test piece cut to 25 mm x 25 mm was pasted on a glass plate with a thickness of 3 mm, and the color difference Δb* value before and after being left in an environment of 100 ° C. for 1000 hours was measured using a colorimeter CM-3600d manufactured by Konica Minolta. , and evaluated for heat-resistant yellowing.

The polyvinylpyrrolidone, polyol resin, and cross-linking agent used to prepare the resin compositions of Examples 1 to 20 and the resin compositions of Comparative Examples 1 and 2 are as shown below.

(polyvinylpyrrolidone)
Pitts Call (registered trademark) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Pitts Call K-30: Mw45000
Pitz Call K-50: Mw250000
PITZCOL K-90: Mw 1.2 million (polyol resin)
Plaxel (registered trademark) (manufactured by Daicel Corporation)
Plaxel 205: Polycaprolactone diol
Mn 530, Tg 10°C or less, hydroxyl value 212 KOHmg/g
Plaxel 320: polycaprolactone triol
Mn 2000, Tg 20°C or higher, hydroxyl value 85 KOHmg/g
DURANOL (registered trademark) T5650J (manufactured by Asahi Kasei Corporation):
Polycarbonate diol, Mn 500, Tm -5°C or less PTMG-1000M (manufactured by Sanyo Kasei Co., Ltd.):
Polyether diol, Tm 17°C, hydroxyl value 112 KOHmg/g
(crosslinking agent)
Duranate (registered trademark) D-201 (manufactured by Asahi Kasei Corporation):
HDI-based prepolymer, bifunctional type, NCO% 16.1%
Coronate (registered trademark) HK (manufactured by Tosoh Corporation):
HDI isocyanurate, NCO% 20.1%
Takenate (registered trademark) (manufactured by Mitsui Chemicals, Inc.)
Takenate D120N: hydrogenated XDI TMP adduct, concentration 75%, NCO% 11.0%
Takenate D127N: hydrogenated XDI isocyanurate, concentration 75%, NCO% 13.5%
Takenate D140N: IPDI isocyanurate, concentration 75%, NCO% 10.0%
Takenate D131N: XDI isocyanurate, concentration 75%, NCO% 14.0%
Table 1 shows the compositions of the resin compositions of Examples 1 to 20 and the evaluation results of the antifogging films produced using each resin composition. Table 2 shows the compositions of the resin compositions of Comparative Examples 1 and 2, and the evaluation results of the antifogging films produced using each resin composition. Table 2 also shows the evaluation results of antifogging properties and the like, depending on the film thickness, using the resin composition of Example 5.

Comparing the evaluation results of the antifogging films of Examples 2, 5, and 6, it was confirmed that the smaller the weight average molecular weight of polyvinylpyrrolidone, the higher the antifogging properties of the antifogging films at high temperatures. In addition, when the evaluation results of heat yellowing of the antifogging films of Examples 1, 2, 5 and 6 and the antifogging films of Examples 7, 9 to 11, and 13 to 17 are compared, the weight average molecular weight of polyvinylpyrrolidone It was confirmed that the larger the value, the higher the heat yellowing resistance. In addition, when comparing the evaluation results of heat yellowing of the anti-fogging film of Example 11 and the anti-fogging films of Examples 15 and 17, it was found that when the alicyclic isocyanate-based cross-linking agent was added, yellowing after the heat test was performed. was confirmed to be suppressed.

Furthermore, from the comparison of Examples 1, 2, and 4 and the comparison of Examples 10 to 13, it was found that the higher the equivalent ratio of the isocyanate group to the hydroxyl group of the polyol resin, the higher the abrasion resistance of the anti-fog film. confirmed.

Also, from a comparison between Example 11 and Example 15, it was confirmed that an anti-fog film with high anti-fogging properties and high water resistance can be obtained by using IPDI isocyanurate.

Moreover, as shown in Table 2, the anti-fogging film using the resin composition of Example 5 tended to have higher anti-fogging properties as the film thickness increased.

In addition, the anti-fogging films formed from the resin compositions of Examples 1 to 20 are excellent in anti-fogging properties, heat resistance, and water resistance by containing an isocyanate compound as a cross-linking agent. was confirmed. Further, in the evaluation of surface tack by touch at 23°C/50% RH, no substantial tack was observed.

On the other hand, the anti-fogging film formed from the resin composition of Comparative Example 2 had tack on the surface of the anti-fogging layer in the surface tack evaluation by finger touch at 23° C./50% RH after the anti-fogging evaluation. was confirmed to have occurred.

INDUSTRIAL APPLICABILITY The present invention can be used as a material for imparting antifogging properties to glass substrates such as windows of vehicles, aircraft, ships and buildings, camera lenses and the like, and plastic substrates.

Claims (10)

At least one polyol resin selected from the group consisting of polyvinylpyrrolidone, polyester polyols, and polycarbonate polyols;
A resin composition containing an isocyanate-based cross-linking agent,
The content of the polyvinylpyrrolidone in the resin composition is in the range of 15 to 80 parts by mass with respect to a total of 100 parts by mass of the polyvinylpyrrolidone and the polyol resin,
The number of equivalents of the functional group of the isocyanate-based cross-linking agent is in the range of 0.5 to 2.3 equivalents with respect to the hydroxyl groups of the polyol resin,
A resin composition containing a cross-linking agent derived from an aliphatic isocyanate and a cross-linking agent derived from an alicyclic isocyanate as the isocyanate-based cross-linking agent. The resin composition according to claim 1, wherein the polyester polyol is polycaprolactone polyol. 3. The resin composition according to claim 1, wherein the aliphatic isocyanate-derived cross-linking agent is a bifunctional cross-linking agent derived from an aliphatic isocyanate compound. The resin composition according to any one of claims 1 to 3 , wherein the equivalent number of functional groups of the isocyanate cross-linking agent to the hydroxyl groups of the polyol resin is within the range of 0.7 to 2.3 equivalents. 5. The resin composition according to any one of claims 1 to 4 , further comprising a melamine-based cross-linking agent. A film and an antifogging layer formed on the film, the antifogging layer comprising:
polyvinylpyrrolidone and
at least one polyol resin selected from the group consisting of polyester polyols and polycarbonate polyols;
A resin composition containing an isocyanate-based cross-linking agent,
The content of the polyvinylpyrrolidone in the resin composition is in the range of 15 to 80 parts by mass with respect to a total of 100 parts by mass of the polyvinylpyrrolidone and the polyol resin,
The number of equivalents of the functional group of the isocyanate-based cross-linking agent is in the range of 0.5 to 2.3 equivalents with respect to the hydroxyl groups of the polyol resin,
The isocyanate-based cross-linking agent contains a cross-linking agent derived from an aliphatic isocyanate or a cross-linking agent derived from an alicyclic isocyanate.
An anti-fogging film formed from a resin composition. 7. The antifogging film of claim 6, wherein said polyester polyol is polycaprolactone polyol. The anti-fogging film according to claim 6 or 7, wherein the aliphatic isocyanate-derived cross-linking agent is a bifunctional cross-linking agent derived from an aliphatic isocyanate compound. The antifogging film according to any one of claims 6 to 8, wherein the equivalent number of functional groups of the isocyanate cross-linking agent to the hydroxyl groups of the polyol resin is within the range of 0.7 to 2.3 equivalents. The anti-fogging film according to any one of claims 6 to 9, wherein the resin composition further contains a melamine-based cross-linking agent.