TW202313175A - Anti-fog layer and use thereof - Google Patents

Abstract

Provided is an anti-fog layer that uses a water-based solvent and has superior heat resistance. This anti-fog layer includes organic fine particles (A) and has a glass transition temperature of 60 DEG C or greater.

Description

Anti-fog layer and its application

The present invention relates to the anti-fog layer and its utilization.

Patent Document 1 describes an anti-fogging film formed by dispersing a solution of a metal alkoxide compound, oxide particles with a low equilibrium water vapor pressure, and photocatalytically active anatase crystal-form titanium oxide particles.

Patent Document 2 discloses a water-absorptive anti-fog member having a surface having a fine concavo-convex structure smaller than the wavelength λ of light to be transmitted.

Patent Document 3 discloses a composition for forming an anti-fog layer, which includes a copolymer and a hydrolyzate, wherein the copolymer includes a specific structural unit.

Patent Document 4 discloses a coating film containing metal oxides and polymer particles, and having a ten-point average thickness of 5 nm to 300 nm.

[Prior Art Literature] [Patent Document] [Patent Document 1] Japanese Patent Application Laid-Open No. 10-101374 [Patent Document 2] Japanese Patent Laid-Open No. 2004-45671 [Patent Document 3] Japanese Patent Laid-Open No. 2018-2865 [Patent Document 4] Specification of Japanese Patent No. 6483822

[Problems to be Solved by the Invention] The generation of VOC becomes a cause of air pollution. Therefore, in 2004, Japan promulgated the revised Air Pollution Prevention Law, requiring the reduction of VOC production. In the paint and printing ink industry, a large amount of organic solvents are used for the purpose of reducing the viscosity during coating operations. In addition, among the 700,000 tons of VOC production in Japan, the coating industry accounts for about 40%, and the printing ink industry accounts for about 5% of the VOC production. In this way, VOC countermeasures are a problem in the paint industry and the printing ink industry.

Various measures have been taken to reduce the amount of organic solvents used in the application of paint. For example, switching from an organic solvent-based paint to a water-based paint.

With regard to anti-fog paints for headlamps, solvent-based paints are currently used. However, in order to reduce the amount of organic solvents used, it was necessary to switch to water-based paints. However, heat resistance is required for anti-fog paints for headlamps. So far, no water-based anti-fog coating can exceed the standard of heat resistance.

Also, as in Patent Document 1, in the method of forming an anti-fogging film from a composition containing a metal alkoxide-based compound, it is necessary to bake at about 650° C. after coating on a glass substrate. Therefore, this method cannot be used for plastic applications.

An anti-fog member having a fine uneven structure on the surface is described in the aforementioned Patent Document 2, but it is actually difficult to form an uneven structure on the surface using a water-absorbent anti-fog film.

The composition for forming an anti-fog layer described in Patent Document 3 has difficulty in maintaining anti-fog properties after a heat resistance test. In addition, organic solvents are necessary for the production of polymers in the anti-fog layer, so it is also difficult to use water-based coatings without using organic solvents.

The coating film described in Patent Document 4 has difficulty maintaining anti-fogging properties after the heat resistance test.

One aspect of the present invention was made in view of such circumstances, and an object of the present invention is to provide an anti-fog layer that can be produced using an aqueous solvent and is excellent in heat resistance.

[Means to solve the problem] In order to solve the said subject, the antifogging layer concerning one aspect of this invention contains organic fine particle (A), and has a glass transition temperature of 60 degreeC or more.

[Effect of Invention] According to one aspect of the present invention, it is possible to provide an anti-fog layer that uses an aqueous solvent and is excellent in heat resistance.

Hereinafter, one embodiment of the present invention will be described in detail.

In this specification, "(meth)acrylic acid" means either or both of "acrylic acid" and "methacrylic acid", and "(meth)acrylate copolymer" means "containing (meth)acrylic acid , and its derivatives as the main constituent units of the resin". Among them, "(meth)acrylic acid" and "(meth)acrylic acid derivatives" are collectively referred to as "(meth)acrylic monomers", and "(meth)acrylic acid derivatives" can be exemplified by (meth) Acrylate ((meth)acrylate/(meth)acrylic acid ester) and (meth)acrylamide.

＜Anti-fog layer＞ The anti-fog layer according to one embodiment of the present invention contains organic fine particles (A) and has a glass transition temperature of 60° C. or higher. In addition, the anti-fog layer contains organic fine particles (A), preferably contains a curing agent (B) and a resin (C), and may contain other components.

The heat resistance of the anti-fog layer was evaluated by the change in the anti-fog property of the anti-fog layer caused by exposure to heat, and the less the decrease in the anti-fog property, the higher the heat resistance was evaluated. The anti-fog layer contains organic fine particles (A), and is an anti-fog layer with little decrease in anti-fog properties due to exposure to heat. For the evaluation method of the heat resistance of the anti-fog layer, please refer to the description in the examples.

(Glass transition temperature of anti-fog layer) The glass transition temperature (Tg) of the anti-fog layer system in one aspect of the present invention is 60°C or higher, preferably 80°C or higher, preferably 90°C or higher, more preferably 100°C or higher, and still more preferably 110°C above, preferably above 120°C. Thereby, the heat resistance of the anti-fog layer can be improved.

In order to increase the glass transition temperature (Tg) of the anti-fog layer, it is preferable to select the organic microparticles (A) described later, so that the anti-fog layer contains more organic microparticles ( A). The evaluation method of the glass transition temperature of the anti-fog layer is evaluated by differential scanning calorimetry (DSC) analysis method, and follows the method of measuring the glass transition temperature of organic microparticles (A) described later.

(Contact angle to water) The water contact angle of the anti-fog layer according to one aspect of the present invention is preferably 10° or less, more preferably 5° or less. Since the water contact angle of the anti-fog layer is 10° or less, the anti-fog layer can have high anti-fog properties. The water contact angle of the anti-fog layer can be evaluated by using a test piece left at room temperature of 23°C and a relative humidity of 50%.

(surface roughness Ra) The anti-fogging layer in one aspect of the present invention preferably has a surface roughness Ra of 5 nm or more and 200 nm or less. According to one aspect of the present invention, water can be used to produce an anti-fog layer excellent in anti-fog properties, so that the amount of organic solvents used can be reduced. As a result, the cause of air pollution and the generation of VOC can be suppressed. Accordingly, according to one aspect of the present invention, the adverse impact on the atmospheric environment can be reduced, and thus it may contribute to goal 11 "sustainable urban construction" of the Sustainable Development Goals (SDGs) led by the United Nations.

The surface roughness Ra of the anti-fog layer is at least 5 nm, more preferably at least 10 nm. The surface roughness Ra of the anti-fog layer can increase the specific surface area of the surface of the anti-fog layer, thereby improving the anti-fog performance of the anti-fog layer. In other words, when the surface roughness Ra of the anti-fog layer is less than 5 nm, the shape of the unevenness formed on the surface of the anti-fog layer becomes smaller. The amount of moisture decreases. Therefore, the anti-fog property of the anti-fog layer decreases. In addition, the surface roughness Ra of the anti-fog layer is 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less, further preferably 70 nm or less, most preferably 50 nm or less. With the preferred fineness of the surface roughness Ra of the anti-fog layer below 200 nm, the light transmittance of the anti-fog layer can be prevented from being reduced due to the scattering of visible light caused by the unevenness existing on the surface of the anti-fog layer. Therefore, the light transmittance of the anti-fog layer can be improved. That is, when the surface roughness Ra is not less than 5 nm and not more than 200 nm, the anti-fog layer can have both high anti-fog properties and high light transmittance.

The "surface roughness Ra" of the anti-fog layer adopts the "arithmetic mean roughness Ra" defined in JIS-B-0601:2013. Using a surface roughness measuring device [manufactured by Kosaka Laboratory Co., Ltd., model Surfcorer SE500], the surface roughness Ra was obtained under the conditions of a scanning range of 4 mm and a scanning speed of 0.2 mm/s.

The anti-fog layer has, as a main component, a solid component including materials contained in the composition for producing the anti-fog layer and their reactants. "Solid content" contains organic microparticles (A), hardener (B), preferably resin (C). The organic fine particles (A) and resin (C) which are solid components in the anti-fog layer and the curing agent (B) react with each other, and reactants can be generated in the anti-fog layer. In addition, the anti-fog layer may contain inorganic particles, absorbents, and other substances described later in the range that does not impair the effect of the present invention, in addition to organic fine particles (A), curing agent (B), and resin (C) as solid components. Element.

(Organic Microparticles (A)) Organic microparticles (A) are microparticles of resin with polar groups, and the glass transition temperature may be 60°C or higher, preferably 80°C or higher, more preferably 90°C or higher, more preferably 100°C or higher, even more preferably 110°C above, preferably above 120°C. Organic microparticles (A) are contained in the anti-fog layer while maintaining the particle shape, and the glass transition temperature is 60° C. or higher. Even when the anti-fog layer is heated, the particle shape can be contained in the state. Anti-fog layer. Thereby, for example, even if exposed to heat of 80° C. for a long time, the desired surface roughness Ra possessed by the anti-fogging layer can be maintained. The resin constituting the organic fine particles (A) is not limited, as long as the glass transition temperature is 250° C. or lower. Assuming that the total amount of solids contained in the anti-fog layer is 100% by mass, the content of the organic microparticles (A) in the anti-fog layer may be at least 58% by mass, preferably at least 65% by mass, and more preferably at least 65% by mass. More than 75% by mass, preferably more than 80% by mass. By increasing the content of the organic fine particles (A) in the anti-fog layer in the range of 58 to 99% by mass, the surface roughness Ra of the anti-fog layer can be increased, thereby improving the anti-fog performance. Moreover, the heat resistance of an anti-fog layer can be improved more by containing many organic microparticles (A) whose glass transition temperature is 60 degreeC or more in the range of 58-99 mass %. In addition, since the content of the organic fine particles (A) in the anti-fog layer decreases within the range of 99% by mass, the film strength of the anti-fog layer can be further increased. According to this, by making it 99 mass % or less, the component which organic fine particle (A) mutually bonds can increase, and can form an anti-fog layer suitably. Moreover, content of the organic fine particle (A) in an anti-fog layer means content of the solid content which does not contain a dispersion medium substantially.

The organic fine particle (A) can be selected based on the glass transition temperature (Tg), its particle diameter D50, and the average value of the SP value of the monomer contained as a constituent unit in the resin of the organic fine particle (A).

The glass transition temperature of the organic fine particle (A) can be calculated|required from the DSC curve evaluated based on JIS-K-7122:2012 by differential scanning calorimetry (DSC) analysis. For evaluation conditions such as the scanning range of temperature used to obtain the DSC curve, and the scanning speed of temperature, please refer to the details described in the examples.

In addition, the glass transition temperature of the organic fine particle (A) can be roughly calculated as the average value of the glass transition temperature of the homopolymer of each monomer contained in the organic fine particle (A) as a constituent unit. The glass transition temperature of organic microparticles (A) is the value obtained by multiplying the glass transition temperature of the homopolymer of the monomer and the mass ratio (mass %) of each monomer contained in the resin as a constituent unit for each monomer Summed up roughly. Here, the glass transition temperature of the homopolymer can refer to the value calculated by Fox's formula described in the polymer handbook [Polymer Hand Book (J. Brandrup, Interscience 1989)]. The glass transition temperature of the polymer can be obtained from the DSC curve in accordance with JIS-K-7122:2012 in the same way as the glass transition temperature of the above-mentioned organic microparticles (A). The organic microparticles (A) can increase the glass transition temperature of the organic microparticles (A) by containing a large amount of monomers with a high glass transition temperature of the homopolymer as constituent units, thereby improving the heat resistance of the anti-fog layer . From the viewpoint of increasing the glass transition temperature of the organic fine particle (A), the glass transition temperature of the homopolymer of the monomer contained as a constituent unit in the organic fine particle (A) may be 60° C. or higher, preferably 80° C. or higher. Preferably it is 90°C or higher, more preferably 100°C or higher, further preferably 110°C or higher, most preferably 120°C or higher. Moreover, although it is not limited, the glass transition temperature in the homopolymer of the monomer contained as a structural unit in an organic fine particle (A) may be 250 degreeC or less. For (meth)acrylamide-based monomers with a high glass transition temperature of the homopolymer, acrylamide (Tg of the homopolymer: 153°C), acrylmorpholine (Tg of the homopolymer: 145°C), etc. From the viewpoint of raising the glass transition temperature of the organic fine particles (A), the copolymer constituting the organic fine particles (A) is set to 100% by mass, and the organic fine particles (A) preferably contain 60% by mass or more of It is more preferable to contain 80 mass % or more of the structural unit of the monomer whose glass transition temperature is 60 degreeC or more in a homopolymer. Also, although not limited, assuming that the copolymer constituting the organic fine particle (A) is 100% by mass, the organic fine particle (A) contains 60% by mass or more, and the glass transition temperature derived from the homopolymer is high and 80°C or higher. The glass transition temperature of the organic fine particle (A) can be raised by setting the structural unit derived from the monomer whose glass transition temperature is lower than 80 degreeC in a homopolymer to 40 mass % or less of the structural unit of the monomer. For example, from the viewpoint of improving the dispersion stability of the organic fine particle (A) itself in an aqueous system, the organic fine particle (A) preferably contains poly Monomers of ethylene glycol chains serve as constituent units. Among these, the glass transition temperature of the homopolymer which is a structural unit derived from a monomer, such as methoxypolyethylene glycol methacrylate, is low. Therefore, it also contributes to lowering the heat resistance of the organic fine particle (A), and as a result, the antifogging property after being exposed to heat tends to decrease. From the viewpoint of prevention of heat-induced reduction in anti-fogging properties, the organic fine particle (A) is preferably a homopolymer with the total amount of constituent units contained in the organic fine particle (A) being 100% by mass. The structural unit with a low glass transition temperature is 40 mass % or less. The glass transition temperature of the constituent units of the homopolymer having a low glass transition temperature may be -40°C or lower, preferably 0°C or lower, further preferably 40°C or lower, most preferably lower than 80°C.

(Particle size (D50)) The organic microparticles (A) can adjust the surface roughness Ra of the anti-fog layer according to the particle diameter. Among them, the particle diameter D50 of the organic fine particle (A) is a particle diameter corresponding to the cumulative 50% on a volume basis, and the particle diameter D50 may also be called a median particle diameter or a median particle diameter. The volume-based particle size D50 can be obtained by a laser diffraction method using a dynamic light scattering type particle size distribution measuring device or the like.

The particle diameter D50 of the organic microparticles (A) is preferably in the range of 5 nm to 200 nm, more preferably in the range of 10 nm to 150 nm, further preferably in the range of 15 nm to 100 nm. The surface roughness Ra of the anti-fog layer can be further increased by the unevenness caused by the larger organic microparticles (A) with a particle diameter D50 in the range of 5nm to 200nm. That is, with the organic fine particles (A), the surface roughness Ra of the anti-fog layer can be set within a range of 5 nm to 200 nm. That is, the surface roughness Ra of 5 nm or more and 200 nm or less can be provided to the anti-fog layer by the organic fine particle (A). Accordingly, the anti-fog property of the anti-fog layer can be improved. In addition, the permeability of the anti-fog layer can be further improved by using organic microparticles (A) having a particle diameter D50 as small as 5 nm to 200 nm.

數式(1)中，δ為溶解度參數(SP值)，Σ _iΔei為單體所具有的莫耳蒸發能(cal/mol)，Σ _iΔvi為單體之莫耳體積(cm ³/mol)。又，由上述數式(1)所求得的溶解度參數之單位為(cal/cm ³) ^1/2，於本說明書中，設為2.0455×(cal/cm ³) ^1/2＝(J/cm ³) ^1/2＝MPa ^1/2，於SP值之單位採用MPa ^1/2。有機微粒子(A)所具有的親水性可將有機微粒子(A)中作為構成單元而含有的單體之SP值的平均值作為指標而確認。 (SP value) The average value of the SP value of the monomer contained as a constituent unit in the resin constituting the organic microparticle (A) is the SP value of each monomer multiplied by the mass ratio of each monomer contained in the resin as a constituent unit (mass %) and obtain the sum of the values obtained. The SP value of each monomer can be obtained by the following formula (1) based on the calculation method of Fedors (refer to "Polymer Engineering and Science", Vol. 14, No. 2 (1974), pp. 148-154). 【Number 1】

In formula (1), δ is the solubility parameter (SP value), Σ _i Δei is the molar evaporation energy (cal/mol) of the monomer, and Σ _i Δvi is the molar volume of the monomer (cm ³ /mol ). Also, the unit of the solubility parameter obtained by the above formula (1) is (cal/cm ³ ) ^1/2 , and in this specification, it is 2.0455×(cal/cm 3 ) ^1/2 =(J/cm ³ ) 1/2 cm ³ ) ^1/2 = MPa ^1/2 , MPa ^1/2 is used as the unit of SP value. The hydrophilicity of the organic fine particle (A) can be confirmed by using the average value of the SP value of the monomer contained as a structural unit in the organic fine particle (A) as an index.

The average value of the SP value of each monomer contained as a constituent unit in the organic microparticle (A) may be 21 MPa ^1/2 or more, preferably 24 MPa ^1/2 or more, preferably 26 MPa ^1/2 or more, more preferably 27MPa ^1/2 or more. Also, the organic fine particles (A) preferably have an SP value of 32 MPa ^1/2 or less. From the point of view of improving the hydrophilicity of the organic microparticles (A) and making them closer to the SP value (47.9) of water, the average value of the SP value of the monomer is preferably higher than 21MPa ^1/2 as the lower limit By. Also, the SP value of the monomer obtained from the formula (1) is not limited as long as it is close to the SP value of water (47.9 MPa ^1/2 ), but may be 32 MPa ^1/2 or less.

The monomer contained in the resin as a constituent unit may be a (meth)acrylic monomer, and the (meth)acrylic monomer includes, for example, a (meth)acrylamide monomer, (meth) Acrylic monomers and (meth)acrylic monomers may contain other monomers described later. (Meth)acryl-based monomers such as (meth)acrylamide-based monomers and (meth)acrylate-based monomers may have crosslinkable functional groups, which means Crosslinkable functional groups other than unsaturated double bond groups such as vinyl groups and (meth)acryl groups contained in monomers as constituent units of the resin constituting the organic microparticles (A).

(Meth)acrylamide-based monomers are preferred monomers for monomers with high SP values. That is, when the (meth)acrylate copolymer contains a structural unit derived from a (meth)acrylamide-based monomer, the SP value of the resin can be increased, and the hydrophilicity of the organic microparticles (A) can be improved. Examples of (meth)acrylamide-based monomers include dialkyl (meth)acrylamides such as acrylamide, acrylmorpholine, methacrylamide, and dimethylacrylamide. , and monoalkyl (meth)acrylamide such as isopropyl acrylamide, etc. The structural unit derived from a (meth)acrylamide-based monomer is derived from a monomer contained in a (meth)acrylate copolymer from the viewpoint of improving the hydrophilicity of the organic fine particle (A). The total of the constituent units is 100% by mass, preferably 5 to 100% by mass, more preferably 50 to 95% by mass. The (meth)acrylamide-based monomer may have a crosslinkable functional group similarly to the (meth)acrylate-based monomer described later.

The cross-linkable functional groups possessed by (meth)acrylamide-based monomers include, for example, N-methylol, N-alkoxymethylol, N-methylol ether groups, etc. The (meth)acrylamide-based monomer having a crosslinkable functional group includes, for example, N-methylolacrylamide, N-methylolmethacrylamide, and the like.

As a (meth)acrylate monomer, the (meth)acrylate monomer which does not have a crosslinkable functional group, and the (meth)acrylate monomer which has a crosslinkable functional group are mentioned. Examples of (meth)acrylate-based monomers that do not have a crosslinkable functional group include alkyl (meth)acrylates such as butyl methacrylate and ethyl methacrylate; (meth)acrylates with dialkylamine groups such as ethoxylate acrylates; methoxyethylacrylates, methoxydiethylene glycol acrylates, etc. structure of (meth)acrylate monomers. The structural unit derived from the (meth)acrylate monomer which does not have a crosslinkable functional group in the resin of the fine particles, for example, is within the range where the average value of the SP value of the above-mentioned monomer is 21 MPa ^1/2 or more. Can.

Among the cross-linkable functional groups possessed by (meth)acrylate monomers, for example, cross-linkable functional groups such as hydroxyl, carboxyl, mercapto, phenol, amine, silanol, and alkoxysilyl groups are listed. As a functional group, 2-hydroxyethyl (meth)acrylate etc. are mentioned as a (meth)acrylate type monomer which has such a crosslinkable functional group.

(Meth)acrylate-based monomers having cross-linkable functional groups other than unsaturated double bond groups such as vinyl groups and (meth)acryl groups are used as constituents in (meth)acrylate copolymers. When contained as a unit, the crosslinkable functional group can react with, for example, a curing agent (B) or inorganic particles described later. In addition, for constituent units derived from (meth)acrylamide-based monomers having N-methylol, N-alkoxymethylol, and N-methylol ether groups, dehydration condensation reaction, dehydration Alcohol condensation reaction leads to crosslinking in the organic microparticles (A), which stabilizes the shape of the organic microparticles (A), and is presumably easier to maintain the surface roughness Ra of the anti-fogging layer, so it is preferable. The (meth)acrylic monomer having a crosslinkable functional group is not limited, but the total of the constituent units derived from the monomers contained in the (meth)acrylate copolymer is 100% by mass, preferably It is 1-100 mass %, and it is more preferable to contain 5-90 mass %.

Examples of (meth)acrylic acid-based monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid. The (meth)acrylic monomer is preferably acrylic acid or methacrylic acid. These (meth)acrylic monomers which have a carboxyl group as a point of a crosslinkable functional group may react with the hardening|curing agent (B) etc. which are mentioned later, etc., for example.

Other monomers include monomers such as acrylonitrile and methacrylonitrile, and vinyl-based monomers such as vinyl acetate, styrene, N-vinylpyrrolidone, and vinylmethylxazolidone. As a monomer, for example, vinylmethyl oxazolidone may be a monomer having a oxazolidone group as a crosslinkable functional group.

Organic microparticles (A) typically include (meth)acrylamide-based monomers, (meth)acrylate-based monomers, and (meth)acrylic-based monomers as the main constituent units. Microparticles of (meth)acrylate copolymers constituting the unit. The (meth)acrylate copolymer can provide suitable hydrophilicity to an organic microparticle (A) by containing the structural unit derived from the monomer which has a high SP value.

Organic microparticles (A), for example, may be in the form of powder or dispersion, and are available from Takamatsu Yushi Co., Ltd.

In Table 1 below, typical monomers that can be contained in the resin that can be included in the organic fine particle (A) as a constituent unit, the glass transition temperature of its homopolymer, and the SP value are exemplified. From the glass transition temperatures and SP values of the homopolymers of the monomers listed in Table 1, it can be confirmed that the (meth)acrylamide-based monomers are preferable at the point of having a high glass transition temperature and a high SP value.

[Table 1] monomer Homopolymer Tg/℃ SP value: MPa ^1/2 Acrylamide 153 30.9 Acrylmorpholine 145 28.4 Dimethacrylamide 119 21.7 Hydroxyethylacrylamide 98 29.5 Isopropylacrylamide 134 21.7 Diethylacrylamide 81 20.5 diacetone acrylamide 77 22.3 Methacrylamide 77 27.4 Dimethylaminopropylmethacrylamide 96 21.1 N-butylacrylamide 46 23.3 acrylic acid 106 24.6 Methacrylate 130 22.9 Acrylonitrile 100 22.7 vinyl acetate 30 18.4 Butyl methacrylate 20 16.8 n-butyl acrylate -54 18.0 Methyl methacrylate 105 18.0 Ethyl methacrylate 65 17.0 Styrene 100 19.0 N-Methylolacrylamide 150 31.5 2-Hydroxyethyl methacrylate 55 24.7 2-Hydroxyethyl Acrylate -15 25.4 2-Hydroxypropyl methacrylate 26 23.5 Acrylonitrile 97 27.3 Methoxypolyethylene glycol methacrylate -60 22.5 Methoxypolyethylene glycol acrylate -65 18.7

(Hardener (B)) The anti-fog layer preferably contains a curing agent (B). Thereby, the antifogging layer in which each particle which comprises organic fine particle (A) is mutually fixed by hardening agent (B) in a layer can be obtained. The curing agent (B) preferably contains a compound having at least one crosslinkable functional group. The antifogging layer may be a layer formed of a crosslinking reaction product of a compound having a crosslinkable functional group contained in the curing agent (B) and an organic fine particle (A). The curing agent (B) may be a compound that undergoes a cross-linking polymerization reaction itself, but preferably has a cross-linking functional group that can carry out cross-linking with the (meth)acrylate-based monomer that is a constituent unit of the organic microparticle (A). Compounds with functional groups for crosslinking reactions. The compound contained in the curing agent (B) preferably has at least one, preferably two or more, crosslinkable functional groups in its chemical structure. The curing agent (B) only needs to have at least one crosslinkable functional group, and its compound may be any of monomeric compounds, oligomers, and polymers.

The total solid content of the anti-fog layer is 100% by mass, and the content of the curing agent (B) is preferably in the range of 1% by mass to 30% by mass in terms of solid content. Within this range, the more the content of the curing agent (B) is, the more the film strength of the anti-fog layer can be improved. Moreover, in the range of 1 mass % or more and 30 mass % or less, the smaller the amount, the higher the anti-fog property can be imparted to the anti-fog layer.

The compound contained in the curing agent (B) has a functional group capable of crosslinking with the crosslinkable functional group of the above-mentioned organic fine particle (A) is a functional group that crosslinks with each other, so it has nothing to do with the crosslinkability. Functional groups have the same meaning. The cross-linkable functional group contained in the curing agent (B) includes, for example, carbodiimide group, epoxy group, isocyanate group, blocked isocyanate group, oxazoline group, hydrazine group, and aziridine group. Base etc. These crosslinkable functional groups can be suitably combined with the N-methylol group, N-alkoxymethylol group, N-methylol ether group, and hydroxyl group that the above-mentioned (meth)acrylate monomers can have. , Silanol group, alkoxysilyl group, carboxyl group, mercapto group, phenol group, amine group and other cross-linking functional group reactions.

The compound having such a crosslinkable functional group is not limited, but is preferably a water-soluble compound dissolved in a water system, or a water-dispersible compound dispersed in a water system. That is, the curing agent (B) can be obtained in the form of an aqueous solution, an aqueous dispersion, or an emulsion, and can be contained in a composition for forming an anti-fog layer. The hardening agent (B) may contain an organic solvent within the range which does not impair the effect of this invention.

As the curing agent (B), for example, as a curing agent having a carbodiimide group, CARBODILITE (registered trademark) (manufactured by Nisshinbo Chemical Co., Ltd.), Carbosista (registered trademark) (manufactured by Teijin Co., Ltd.) , N,N'-dicyclohexylcarbodiimide (available from Tokyo Chemical Industry Co., Ltd.), N,N'-diisopropylcarbodiimide (available from FUJIFILM Wako Pure Chemical Co., Ltd.), 1 -[3-(Dimethylamino)propyl]-3-ethylcarbodiimide (available from FUJIFILM Wako Pure Chemical Co., Ltd.), 1-ethyl-3-(3-dimethylamine hydrochloride propyl)carbodiimide (available from FUJIFILM Wako Pure Chemical Co., Ltd.), bis(2,6-diisopropylphenyl)carbodiimide (available from Kawaguchi Chemical Industry Co., Ltd.), and the like. The curing agent having an epoxy group includes, for example, DENACOL (registered trademark) (manufactured by Nagase ChemteX Co., Ltd.), water-based epoxy resin jER (registered trademark) series (manufactured by Mitsubishi Chemical Co., Ltd.), ADEKA RESIN (registered trademark) Trademark) EM series (manufactured by ADEKA Co., Ltd.), etc. Examples of the curing agent having a blocked isocyanate group include DURANATE (registered trademark) (manufactured by Asahi Kasei Co., Ltd.), Coronate (registered trademark) series (manufactured by Tosoh Co., Ltd.), and the like. The curing agent having an oxazoline group includes, for example, EPOCROS (registered trademark) (manufactured by Nippon Shokubai Co., Ltd.), poly(2-ethyl-2-oxazoline) (available from FUJIFILM Wako Pure Chemical Co., Ltd. acquired by the company), etc. Moreover, examples of the curing agent having a hydrazine group include dihydrazide adipate (available from Tokyo Chemical Industry Co., Ltd.), dihydrazide sebacate, dodecanediohydrazide, isohydrazide, Dihydrazine phthalate, hydrazine salicylate (both available from Otsuka Chemical Co., Ltd.), and the like. Examples of curing agents having an aziridine group include CHEMITITE (registered trademark) (manufactured by Nippon Shokubai Co., Ltd.), trimethylolpropane ginseng[3-(2-methylaziridine-1-yl)propane acid ester] (available from Nihon Daikei Energy Co., Ltd.) and the like.

(Resin (C)) The anti-fog layer preferably contains resin (C) in addition to the above-mentioned organic fine particles (A) and curing agent (B). The anti-fog layer can form a stronger film by containing the resin (C) and reacting the resin (C) with the curing agent (B). Moreover, the adhesiveness to a board|substrate can be improved by containing resin (C).

That is, the resin (C) preferably has a crosslinkable functional group in order to react with at least the curing agent (B). Especially, from the viewpoint of improving the water solubility or water dispersibility of the resin (C) itself, the crosslinkable functional group is more preferably an acid group such as a carboxyl group, a hydroxyl group, a phenol group, an amino group, or the like. For the resin (C), for example, polyester resin, polycarbonate urethane resin, epoxy ester resin, alkyd resin, water-soluble phenol resin, etc., the resin (C) can be water-soluble resin, water-dispersible Resin, or resin emulsion. The anti-fog layer can be suitably prepared as a water-based coating agent by containing the resin (C).

When the resin (C) has an acid group such as a carboxyl group, the acid value of the resin (C) is preferably in the range of 1 to 200 mgKOH/g, preferably 2 to 60 mgKOH/g. Thereby, within the range of the acid value, the higher the acid value, the more the water solubility of the resin (C) can be improved, and the heat resistance of the anti-fog layer can be further improved. Also, the higher the acid value, the more it is possible to use the composition described later as an aqueous solvent-based composition. Moreover, the lower the acid value, the more water resistance of the anti-fog layer containing the resin (C) can be improved.

When the resin (C) has a hydroxyl group, the hydroxyl value of the resin (C) is preferably in the range of 1 to 200 mgKOH/g, preferably 2 to 120 mgKOH/g. Thereby, in the range of this hydroxyl value, the water solubility of resin (C) can be improved more so that a hydroxyl value is high, and the heat resistance of an antifog layer can be improved more. In addition, the higher the hydroxyl value, the more it is possible to use the composition described later as an aqueous solvent-based composition. Moreover, the water resistance of the anti-fog layer which consists of resin (C) can be improved more, so that a hydroxyl value is low.

In addition, when the resin (C) is a resin having a phenol group or an amino group, it is the same as the resin (C) having a carboxyl group and a hydroxyl group, considering the water solubility of the resin (C), the heat resistance of the anti-fog layer produced, and The water resistance of the anti-fog layer can be determined by the amount of phenolic groups or amine groups in the resin (C).

The resin (C)-based glass transition temperature is preferably at least 20°C, more preferably at least 50°C. Thereby, the heat resistance of an anti-fog layer can be further improved.

The blending ratio of the hardener (B) and the resin (C) is such that the glass transition temperature of the hardened product of the hardener (B) and the resin (C) is increased, depending on the ratio of the hardener (B) and the resin (C). As for the species, for example, an appropriate blending ratio may be determined by the acid value and/or the hydroxyl value.

The anti-fog layer is preferably contained in the anti-fog layer so that the total amount of the hardener (B) and the resin (C) is 2% by mass or more and 43% by mass or less in terms of the solid content contained in the anti-fog layer , less in this range can improve the heat resistance of the anti-fog layer. In addition, the total content of the curing agent (B) and the resin (C) in the anti-fog layer is preferably at most 43% by mass, more preferably at most 20% by mass, in terms of solid content. Moreover, when the content of the total amount of the hardener (B) and resin (C) in an antifog layer is 2 mass % or more, the film strength of an antifog layer can be improved.

The resin (C) is obtained, for example, in the form of an aqueous solution, an aqueous dispersion, or an emulsion, and can be contained in a composition described later.

Resin (C) includes, for example, Pesresin series (manufactured by Takamatsu Yushi Co., Ltd.) and ARON MELT (registered trademark) PES-1000, 2000 series (manufactured by Toagosei Co., Ltd.), which are polyester resins. Moreover, as a water-based phenol resin, PHENOLITE (registered trademark) TD-4304 (made by DIC Corporation) etc. are mentioned. Examples of polycarbonate-based urethane resins include HYDRAN (registered trademark) (manufactured by DIC Corporation), epoxy ester resins, and alkyd resins such as WATERSOL (registered trademark) (manufactured by DIC Corporation). .

(inorganic particles) The anti-fog layer may contain inorganic particles as other components. Inorganic particles contained in the anti-fog layer, such as alumina, silica, zirconia, titanium oxide, zinc oxide, other metal oxide particles, carbon, etc., are preferred, and can be in the form of alumina sol, colloidal silica , silica sol, zirconia sol, titania sol, and other colloidal particles of metal oxide particles. The colloidal particles may be acidic sols, basic sols, or sols stabilized in neutral regions. The inorganic particles can be cross-linked with the above-mentioned curing agent (B) and/or resin (C), and the inorganic particles can also be cross-linked with each other.

The particle size D50 of the inorganic particles based on the volume may be 2 nm or more, preferably 3 nm or more. Thereby, the surface roughness of the anti-fog layer can be prevented from being damaged. Moreover, it is preferable that the particle diameter D50 of an inorganic particle system is 200 nm or less from a viewpoint of imparting high translucency to an anti-fog layer.

The content of the inorganic particles is, for example, based on 100% by mass of the total amount of solids contained in the anti-fog layer, preferably within a range of 0.1% by mass to 10.0% by mass. When the content of the inorganic particles is 10.0% by mass or less, it is possible to appropriately prevent the decrease in the anti-fog property due to the inorganic particles. Moreover, when content of an inorganic particle is made into 0.1 mass % or more, there exists the effect which can provide heat resistance as high translucency by an anti-fog layer.

The inorganic particles can be obtained in the form of powder, dispersion, or sol, and may contain organic solvents such as alcohol within the range that does not inhibit the effect of the present invention. Such inorganic particles include, for example, alumina sol 10A (manufactured by Kawaken Fine Chemicals), SNOWTEX (registered trademark) series (manufactured by Nissan Chemical Co., Ltd.), which is colloidal silica, and the like.

(other ingredients) The anti-fog layer may contain absorbents, film-forming aids, and antifreezing agents as other components.

The absorbent includes, for example, mixed layer clay and the like. The mixed layer clay is preferably a synthetic clay that can be synthesized industrially, and examples thereof include bentonite, bentonite, and montmorillonite. By adding an absorbent, the function of absorbing and retaining water can be added to the anti-fog layer, and the anti-fog performance can be improved. These mixed-layer clays may be included in the composition described later as an anti-sedimentation agent and/or a viscosity modifier in addition to an absorbent.

Although the mixed layer clay is not limited, it is preferable to use, for example, a particle diameter D50 in a long diameter of 200 nm or less. The content of the mixed layer clay may be appropriately designed within the range that does not inhibit the effect of the present invention. For example, the total solid content contained in the anti-fog layer is set to 100% by mass, preferably 0.1% by mass to 5.0% by mass within the following range.

Examples of the mixed layer viscosity minerals include Sumecton (registered trademark) and Kunipia (registered trademark) (both manufactured by Kunimine Industries Co., Ltd.) as bentonite.

The film-forming aids include water-soluble organic solvents with a higher boiling point than water, for example, butyl celuso (ethylene glycol-monobutyl ether), texanol (2,2,4-trimethyl Pentane-1,3-diol monoisobutyrate) and other organic solvents. Also, the antifreeze agent is typically ethylene glycol. The water-soluble organic solvent refers to an organic solvent that dissolves in water at room temperature (23° C.) at a concentration of at least 4.0% by mass. The film-forming aid and antifreeze are also organic solvents, and the content of the film-forming aid in the anti-fog layer is preferably at most 4.0% by mass, preferably at most 2% by mass, preferably at most 0.5% by mass, and even more preferably 0.1% by mass or less. Moreover, by setting it as 4.0 mass % or less, it can prevent that the heat resistance of an anti-fog layer is impaired, in other words, it can prevent that anti-fog property fall by exposure to heat. Moreover, by making it 4.0 mass % or less, organic fine particle (A) itself can be prevented from being dissolved by an organic solvent, and the surface roughness Ra of an antifogging layer can be maintained. Thereby, it is presumed that the anti-fogging property fall by surface roughness can be prevented.

The anti-fog layer may contain surfactants such as leveling agents, defoamers, dispersants, and emulsifiers as other components, as well as viscosity modifiers, antioxidants, ultraviolet absorbers, plasticizers, preservatives, and anti-fogging agents. Examples of additives such as fungicides and water repellents. These, surfactants, and additives may be partly contained in the composition for producing the anti-fog layer as solid components. The anti-fog layer may contain coloring agents such as coloring pigments and dyes in order to impart a beautiful appearance to the substrate within the range that does not inhibit the effect of the present invention. The anti-fog layer may contain, for example, a pH adjuster, a pH buffer, and the like derived from the composition used to produce the anti-fog layer.

〔Substrate〕 A substrate according to an aspect of the present invention includes a substrate layer (a) and an anti-fog layer (b), and the anti-fog layer (b) is disposed on the substrate layer (a). The anti-fog layer (b) is the anti-fog layer related to one aspect of the above-mentioned present invention. The description of the anti-fog layer (b) follows the description of the anti-fog layer in one aspect of the present invention, and the same description will not be repeated.

The substrate layer (a) is a layer for disposing the anti-fogging layer (b) thereon. The material of the substrate layer (a) can be appropriately selected according to the use of the substrate and the like. For example, glass, resin material, metal, ceramics, etc. are mentioned as a board|substrate layer (a), and these composite materials may be used. Among them, plastics with light transmission are more preferable. In terms of plastics having light transmission, for example, polycarbonate resins, acrylic resins, polyester resins, polystyrene resins, ABS resins, polyvinyl chloride resins, polyamide resins, polymethyl Methyl acrylate (PMMA), polyethylene terephthalate (PET), polycyclohexylenedimethylene terephthalate copolyester resin (Tritan (registered trademark): Eastman Chemical Company) etc.

The shape of the substrate layer (a) is not limited as long as the substrate according to one aspect of the present invention includes the anti-fog layer (b). That is, the substrate according to one aspect of the present invention can be molded into a desired shape depending on the application. The substrate may be, for example, a light-transmitting substrate constituting a part of lighting devices such as headlights and taillights of vehicles such as passenger cars, ships, and airplanes, and spectacle lenses.

The method of disposing the anti-fog layer (b) on the substrate layer (a) is not particularly limited. For example, what is necessary is just to harden the composition after apply|coating the composition for making an anti-fog layer (b) on a board|substrate layer (a). The method of hardening the composition may be appropriately selected depending on the components of the composition, for example, drying may be performed by heating or the like to harden.

For example, in order to improve the wettability and/or adhesion of the anti-fog layer (b), surface treatment may be performed on the surface of the substrate layer (a) on which the anti-fog layer (b) is formed. The surface treatment includes, for example, surface treatments such as corona discharge treatment, conversion treatment, plasma treatment, acid or alkali treatment, and the like. In addition, on the surface of the substrate layer (a) on which the anti-fogging layer (b) is formed, a surface treatment agent such as a primer and a coupling agent may be coated. Known methods can be used for the coating method of the composition of one aspect of the present invention, and examples of coating methods include spray coating, dip coating, roll coating, and bar coating.

In addition, drying and curing after coating the composition according to one aspect of the present invention may be appropriately designed according to the type of curing agent (B) or resin (C), and are not limited, and may be 60°C or higher. Yes, preferably above 100°C. The composition of one aspect of the present invention can sufficiently dry the water solvent and fully promote the crosslinking reaction of the curing agent (B) by virtue of the high glass transition temperature of the organic microparticles (A) contained in the composition, At the same time, it is also one of the advantages that the reduction of the anti-fog property can be prevented by heating the anti-fog layer.

In the production of the anti-fog layer, the coating, drying, and heating of the composition of one aspect of the present invention may be performed once or may be repeated multiple times to obtain a desired film thickness. In addition, the coating and drying of the composition related to one aspect of the present invention may be repeated multiple times, and the anti-fog layer may be produced by heating once.

The film thickness after coating and drying of the composition of one aspect of the present invention, that is, the film thickness of the anti-fogging layer depends on the surface of the substrate, for example, preferably 20 nm to 10000 nm. When the film thickness of the anti-fog layer is 20 nm or more, suitable anti-fog properties can be imparted to the substrate covered with the anti-fog layer. Moreover, when the film thickness of an anti-fog layer is 10000 nm or less, high translucency can be provided to an anti-fog layer.

[composition] The composition for making the anti-fog layer according to one aspect of the present invention (hereinafter, simply referred to as "the composition according to one aspect of the present invention") includes organic fine particles (A) and water, preferably the aforementioned organic The glass transition temperature of the fine particles (A) is 60° C. or higher. That is, the composition, the organic microparticles (A) may be a water-based composition. The description of the composition of the composition of one aspect of the present invention (including the description of the components described later) follows the description of the anti-fog layer of one aspect of the present invention, and the same description will not be repeated. When the composition related to the aspect of the present invention is used, the antifogging layer relating to the aspect of the present invention can be produced appropriately.

The composition according to one aspect of the present invention further preferably contains a curing agent (B). Also, the content of the curing agent (B) is more preferably at least 1% by mass and at most 30% by mass in terms of solid content. By setting the content of the hardener (B) to 1% by mass or more, an anti-fog layer with excellent heat resistance can be obtained, and by making the content of the hardener (B) to 30% by mass or less, an anti-fog layer with sufficient strength can be obtained. fog layer.

It is preferable that the composition concerning one aspect of this invention further contains a hardening|curing agent (B) and resin (C). Moreover, the total amount of the curing agent (B) and the resin (C) is more preferably 2% by mass or more and 43% by mass or less in terms of solid content. By setting the total amount of the hardener (B) and the resin (C) to 2% by mass or more, the adhesion of the anti-fog layer to the substrate is obtained, and by making the total amount of the hardener (B) and the resin (C) When the content is 43 mass % or less, the surface roughness for improving the anti-fog property in the anti-fog layer can be obtained.

Moreover, in the composition concerning one aspect of this invention, it is more preferable that content of an organic fine particle (A) is 58 mass % or more and 99 mass % or less in conversion of a solid content. It is used for suitably producing the antifogging layer concerning one aspect of this invention.

Moreover, in the composition concerning one aspect of this invention, it is more preferable that content of an organic solvent is less than 4.0 mass % with respect to solid content. According to the composition according to one aspect of the present invention, since water can be used to form an anti-fog layer having excellent anti-fog properties, the amount of organic solvent used can be reduced. Moreover, examples of the organic solvent include water-soluble organic solvents having a higher boiling point than water, which are used as the above-mentioned film-forming aids or freezing agents.

Regarding the composition of one aspect of the present invention, the composition for producing the anti-fog layer preferably contains 30 to 50,000 parts by mass of water as a solvent, with the total amount of solid content being 100 parts by mass. Thereby, the composition (coating agent) for producing the anti-fog layer which suitably expresses the anti-fog property by an organic fine particle (A) can be obtained. Water as a solvent may be, for example, deionized water, distilled water, tap water, or industrial water. In addition, in this specification, "solid content" is as long as it can be distinguished from water and volatile solvents evaporated from the composition, and is included as a composition in the anti-fog layer produced using the composition according to one aspect of the present invention. The composition is enough, it does not have to be "solid".

Also, by coating and curing the composition according to one aspect of the present invention, an anti-fog layer comprising organic fine particles (A) and having an anti-fog layer having a surface roughness Ra of 5 nm or more and 200 nm or less is produced. Methods are also within the scope of the present invention. In this way, if the composition related to the aspect of the present invention is used, the antifogging layer relating to the aspect of the present invention can be produced suitably. In addition, the substrate to which the composition is applied may be appropriately selected according to the purpose of the anti-fog layer.

The present invention is not limited to the above-mentioned embodiments, and various changes can be made within the scope indicated in the claims. Embodiments obtained by appropriately combining the technical means disclosed in the embodiments are also included in the technical scope of the present invention.

〔Summarize〕 The anti-fog layer according to aspect 1 of the present invention contains organic fine particles (A), and has a glass transition temperature (Tg) of 60° C. or higher.

Regarding the anti-fog layer of the second aspect of the present invention, it is related to the aspect 1, and the content of the aforementioned organic fine particles (A) is preferably 58% by mass or more and 99% by mass or less in terms of solid content.

Regarding the anti-fog layer of aspect 3 of the present invention, which is related to aspect 1 or 2, the contact angle to water is preferably less than 10°.

Regarding the anti-fog layer of aspect 4 of the present invention, it is any one of aspects 1 to 3, and the glass transition temperature of the aforementioned organic fine particles (A) is preferably 60° C. or higher.

Regarding the anti-fog layer of aspect 5 of the present invention, it is any one of aspects 1 to 4, and the surface roughness Ra is preferably not less than 5 nm and not more than 200 nm.

The substrate of aspect 6 of the present invention is provided with a substrate layer (a) and an anti-fog layer (b), and the anti-fog layer (b) is the anti-fog layer described in any one of aspects 1 to 5, and is arranged on On the aforementioned substrate layer (a).

Regarding the substrate of Aspect 7 of the present invention, it is in Aspect 6, and the above-mentioned substrate layer (a) is preferably a light-transmitting plastic.

The composition of aspect 8 of the present invention is a composition for producing the anti-fog layer described in any one of aspects 1 to 5, and contains organic fine particles (A) and water.

Regarding the composition of aspect 9 of the present invention, which is based on aspect 8, the content of the organic solvent is preferably less than 4.0% by mass relative to the solid content of the anti-fog layer.

Regarding the composition of Aspect 10 of the present invention is in Aspect 8 or 9, it is preferable that the aforementioned organic microparticle (A) is a (meth)acrylate copolymer, and the aforementioned (meth)acrylate copolymer is A copolymer made by polymerizing a mixture of monomers.

The composition of aspect 11 of the present invention is any one of aspects 8 to 10, further comprising a resin (C), and the aforementioned resin (C) is preferably selected from water-soluble resins, water-dispersible resins, and resin emulsion.

[Example] One embodiment of the present invention will be described below.

The coating agents of Examples 1 to 37 and the coating agents of Comparative Examples 1 to 4 were prepared, and the anti-fog layers prepared from these coating agents were evaluated.

The materials used to prepare each coating agent are as follows.

〔Material〕 (organic microparticles) It was obtained as an aqueous dispersion of 20% by mass (meth)acrylate copolymer fine particles (manufactured by Takamatsu Yushi Co., Ltd.). In the following Table 2 and Table 3, each monomer which comprises the (meth)acrylate copolymer used in the Example and the comparative example is shown.

(inorganic particles) Alumina sol: Alumina sol 10A (solid content 10% by mass, manufactured by Kawaken Fine Chemicals Co., Ltd.) Colloidal silica: SNOWTEX (registered trademark) OXS (solid content 10% by mass, manufactured by Nissan Chemical Co., Ltd.) (Organic microparticles: resin (C)) polyester resin: Pesresin A-640; manufactured by Takamatsu Oil & Fat Co., Ltd., a product with a solid content of 25% Pesresin A-645GH; manufactured by Takamatsu Oil & Fat Co., Ltd., a product with a solid content of 30% Polycarbonate-based urethane resin: HYDRAN (registered trademark) WLS-210; manufactured by DIC Co., Ltd., a product with a solid content of 35% Epoxy ester resin: WATERSOL (registered trademark) EFD-5560; manufactured by DIC Co., Ltd., 40% solid content product Alkyd resin: WATERSOL (registered trademark) BCD-3100; manufactured by DIC Co., Ltd., solid content 43% product Water-soluble phenolic resin: Water-soluble phenolic resin PE-602, manufactured by DIC Co., Ltd., a product with a solid content of 42% (absorbent) Synthetic bentonite: Sumecton (registered trademark) SA (KUNIMINE INDUSTRIES Co., Ltd.) (hardener) Carbodiimide: CARBODILITE (registered trademark) E-02 (manufactured by Nisshinbo Chemical Co., Ltd.) Aziridine: CHEMITITE (registered trademark) DZ-22E (Nippon Shokubai Co., Ltd.) Dihydrazine adipate (manufactured by Tokyo Chemical Industry Co., Ltd.) Epoxy compound: DENACOL (registered trademark) EX-810 (manufactured by Nagase ChemteX Co., Ltd.) Blocked isocyanate: DURANATE (registered trademark) WM44-L70G (Asahi Kasei Co., Ltd.) Oxazoline compound: EPOCROS (registered trademark) WS-700 (manufactured by Nippon Shokubai Co., Ltd.) (Membrane Auxiliary) Butyl Cyrus: (manufactured by Tokyo Chemical Industry Co., Ltd.)

〔modulation〕 The coating agent of Example 1 was prepared in the following order. First, the aqueous dispersion of 500 g of (meth)acrylate copolymer microparticles|fine-particles was prepared, and the aqueous dispersion of 20 g of polyester resins was added to this aqueous dispersion. Next, 10 g of an aqueous dispersion of alumina sol and 10 g of carbodiimide in terms of solid content as a curing agent were added to the aqueous dispersion of (meth)acrylate copolymer fine particles. Thereafter, the aqueous dispersion was stirred, and adjusted to pH 8.0 by adding ammonia water (1 mol/L), thereby obtaining the coating agent of Example 1. According to the composition shown in the following Table 2 and Table 3, the coating agent of Examples 2-37 and Comparative Examples 1-4 were prepared in the same procedure as the coating agent of Example 1.

〔Production of anti-fog layer〕 The coating agent of Example 1 was coated on the polycarbonate test piece (thickness 2mm) using the bar coater #2. Next, the test piece coated with the coating agent was heated at a temperature of 90° C. for 20 minutes to dry and harden the coating agent. Thereby, the test piece provided with the antifogging layer which has a film thickness of about 1 micrometer was produced. The test pieces provided with the antifog layer of Examples 2-37 and Comparative Examples 1-4 were produced in the same procedure as the preparation of the antifog layer using the coating agent of Example 1.

[Each evaluation] The following evaluation was performed using the test piece provided with the anti-fog layer of Examples 1-37 and Comparative Examples 1-4. The evaluation results are shown in Table 4 and Table 5.

(particle size) The particle size (unit: nm) of the organic fine particles was evaluated as a particle size corresponding to cumulative 50% on a volume basis. The particle size of the organic fine particles was measured with a dynamic light scattering particle size distribution measuring device (device name: Nanotrac Wave II UT151, manufactured by MicrotracBEL). Nanotrac is a registered trademark of the same company.

(Glass transition temperature (Tg) of organic microparticles) The glass transition temperature (Tg) of the organic microparticles was measured using DSC (differential scanning calorimetry, device name: EXSTAR DSC6200, manufactured by Seiko Instruments). The glass transition temperature (Tg) of organic microparticles|fine-particles was calculated|required from the DSC curve measured according to JIS-K-7122:2012. The mass of the sample used in the DSC measurement was 5 mg. In the first scan, the temperature range is from -10°C to 300°C at a rate of 20°C/min, and then the sample is cooled with liquid nitrogen, and in the second scan, from -10°C to 300°C From the temperature range up to the present, the temperature was raised at a rate of 20°C/min, and the glass transition temperature of the organic microparticles was derived from the DSC curve obtained in the second scan.

(surface roughness Ra) According to JIS-B-0601-2013, the surface roughness of the anti-fog layer was obtained using a surface roughness tester [manufactured by Kosaka Laboratories Co., Ltd., model Surfcorer SE500] with a scanning range of 4 mm and a scanning speed of 0.2 mm/s. Degree Ra.

(Observation by atomic force microscope) The anti-fog layer produced from the coating agent of Example 32 was observed with an atomic force microscope using an AFM (atomic force microscope, device name: Dimension 3100, manufactured by Veeco). The results are shown in Fig. 1 .

(Glass transition temperature (Tg) of anti-fog layer) The glass transition temperature Tg of the anti-fog layer was measured by DSC (differential scanning calorimetry, device name: EXSTAR DSC6200, manufactured by Seiko Instruments). The sample mass of the anti-fog layer is 5 mg. The temperature range, heating rate, and number of scans used to obtain the DSC curve are the same as those used to obtain the glass transition temperature (Tg) of organic particles, so the description is omitted.

(Contact angle to water) The water contact angle of the anti-fog layer was measured using a contact angle meter (device name: CV-DT・A type, manufactured by Kyowa Interface Science Co., Ltd.).

(transparency of coating film) The transparency (light transmittance) of the coating film of the test piece provided with the anti-fog layer was measured using a haze meter ("HAZE METER NDH5000", manufactured by Nippon Denshoku Kogyo Co., Ltd.). The HAZE value was measured in accordance with JIS-K7361-1:1997 under the condition that the light source is a white LED and the light beam is 14mm. According to the criteria shown below, if it is △ or more, it is evaluated as no problem, and if it is 0, it is evaluated as better. good. Moreover, the HAZE value of the polycarbonate test piece itself with a thickness of 2 mm was 0.30. 〇: HAZE value is 0.30 or more and less than 0.40. Δ: HAZE value is 0.40 or more and less than 0.50. x: HAZE value is 0.50 or more.

(anti-fog) In a room air-conditioned at a temperature of 23°C and a humidity of 50%, the anti-fog layer of the prepared test piece was blown out for 5 seconds, and the anti-fog performance was evaluated according to the following criteria. 〇: No fogging at all. Δ: Fogging was slight but recovered quickly. ×: Fogging.

(heat resistance) After each test piece was left to stand for 240 hours at individual temperature conditions of 80°C, 100°C, and 110°C, it was left to stand for 1 hour in a constant temperature room air-conditioned to a temperature of 23°C and a humidity of 50%. Thereafter, anti-fog properties and light transmittance were evaluated.

(Glossy Value) The glossy value was measured under the condition of an incident angle of 60° using a 3-angle surface gloss meter (apparatus name: micro-TRI-gloss, manufactured by BYK Corporation). The gloss value was measured by stacking 10 sheets of A4 copy paper (manufactured by ITOCHU PULP & PAPER, whiteness: 92%), and setting the test piece on which the anti-fog layer of each Example and Comparative Example was prepared. [Table 2] monomer Polymer Tg SP value MPa 1/2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Acrylamide 153 30.9 5 20 35 10 5 35 35 35 35 10 25 30 40 45 35 35 Acrylmorpholine 145 28.4 5 10 20 25 20 5 25 25 25 25 25 25 25 25 65 20 25 25 25 Dimethacrylamide 119 21.7 25 10 Isopropylacrylamide 134 21.7 35 40 20 10 Diethylacrylamide 81 20.5 20 25 25 acrylic acid 106 24.6 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 n-butyl acrylate -54 18.0 N-Hydroxymethylacrylamide 150 31.5 5 10 20 20 20 60 85 20 20 20 20 20 20 20 20 20 65 20 20 20 Methoxypolyethylene glycol methacrylate -60 22.5 15 15 15 15 15 5 5 15 15 15 15 40 25 20 10 10 10 10 15 Methoxypolyethylene glycol acrylate -65 18.7 15 water 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 Organic fine particles (resin (C)) Polyester resin (Pesresin Ａ-640: Takamatsu oil:) 25% product 64 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Polyester resin (Pesresin A-645GH: Takamatsu grease) 30% product Polycarbonate-based urethane resin (HYDRAN WLWLS-210: DIC) 35% product Epoxy ester resin (WATERSOL EFD-5560: DIC) 40% product Alkyd resin (WATERSOL BCD-3100: DIC) 43% product Water-soluble phenolic resin (water-soluble phenolic resin PE-602: DIC) 42% product Inorganic particles Alumina sol 10A (Kawaken Fine Chemicals) 10% product 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Colloidal silicon dioxide (SNOWTEX OXS) 10% product absorbent Synthetic bentonite (Sumecton SA, KUNIMINE INDUSTRIES) hardener CARBODILITE (CARBODILITE E-02: Nisshinbo Chemical) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Aziridine (CHEMITITE DZ-22E: Nippon Shokubai) 10 Dihydrazine adipate (Tokyo Chemical Industry) Epoxy compound (DENACOL EX-810: Nagase ChemteX Blocked isocyanate (DURANATE WM44-L70G: Asahi Kasei) Ozoline (EPOCROS WS-700: Nippon Shokubai) Membrane Auxiliary Ding Kelusu pH adjuster ammonia 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 SP average twenty two twenty three 24.7 27.1 28.8 30 30.9 28.8 28.8 28.8 28.8 26.7 28 28.4 29.2 28.2 29.6 29.5 28.2 28.8 [table 3] monomer Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Acrylamide 35 3 35 3 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 10 10 10 5 Acrylmorpholine 25 2 25 2 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20 10 10 10 Dimethacrylamide Isopropylacrylamide 15 5 Diethylacrylamide 5 15 25 2 acrylic acid 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 n-butyl acrylate N-Methylolacrylamide 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 10 10 10 Methoxypolyethylene glycol methacrylate 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 45 45 45 45 Methoxypolyethylene glycol acrylate water 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 Organic fine particles (resin (C)) Polyester resin (Pesresin Ａ-640: Takamatsu oil:) 25% product 20 20 20 20 20 240 120 4 80 20 20 20 20 20 20 20 Polyester resin (Pesresin A-645GH: Takamatsu grease) 30% product 17 Polycarbonate-based urethane resin (HYDRAN WLWLS-210: DIC) 35% product 14 Epoxy ester resin (WATERSOL EFD-5560: DIC) 40% product 13 Alkyd resin (WATERSOL BCD-3100: DIC) 43% product 12 Water-soluble phenolic resin (water-soluble phenolic resin PE-602: DIC) 42% product 12 Inorganic particles Alumina sol 10A (Kawaken Fine Chemicals) 10% product 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Colloidal silicon dioxide (SNOWTEX OXS) 10% product 10 absorbent Synthetic bentonite (Sumecton SA, KUNIMINE INDUSTRIES) 2 hardener CARBODILITE (CARBODILITE E-02: Nisshinbo Chemical) 10 10 10 2 40 10 10 10 10 10 10 10 10 10 10 10 10 Aziridine (CHEMITITE DZ-22E: Nippon Shokubai) Dihydrazine adipate (Tokyo Chemical Industry) 10 Epoxy compound (DENACOL EX-810: Nagase ChemteX 10 Blocked isocyanate (DURANATE WM44-L70G: Asahi Kasei) 10 Ozoline (EPOCROS WS-700: Nippon Shokubai) 10 Membrane Auxiliary Ding Kelusu 4 pH adjuster ammonia 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 SP average 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 28.8 26.4 24.7 24.6 twenty four [Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 hardening temperature 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 Organic fine particle content (solid content conversion %) 86 8 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 Hardener content (solid content conversion %) 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Resin + hardener content (solid content conversion %) 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 Solvent content (solid content conversion %) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Organic particle size (nm) D50 50 50 50 50 50 50 50 30 100 150 200 2 50 50 50 50 50 50 50 50 50 Organic fine particles Tg 91 92 96 111 116 137 139 116 116 116 116 63 95 105 127 124 126 129 115 116 Coating surface roughness Ra 48 48 48 48 48 48 48 28 101 147 191 49 52 46 46 49 49 48 47 51 Anti-fog layer Tg 92 93 96 111 115 135 138 115 115 115 115 65 95 105 125 122 125 128 115 115 Contact angle 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ △ 〇 〇 〇 〇 〇 〇 〇 〇 〇 Anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 80℃ heat resistance test Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 100℃ heat resistance test Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 〇 〇 〇 〇 〇 〇 〇 110℃ heat resistance test Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Anti-fog △ △ △ 〇 〇 〇 〇 〇 〇 〇 〇 x △ △ 〇 〇 〇 〇 〇 〇 [table 5] Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 hardening temperature 90 90 90 90 90 9 90 90 90 9 90 90 90 9 90 90 90 90 90 90 90 90 90 90 Organic fine particle content (solid content conversion %) 86 8 86 86 86 86 58 71 96 62 86 85 87 87 87 87 87 87 86 86 86 86 Hardener content (solid content conversion %) 9 9 9 9 9 6 7 2 25 2 9 8 9 9 9 9 9 9 9 9 9 9 Resin + hardener content (solid content conversion %) 13 13 13 13 13 41 28 2 3 37 3 13 13 13 9 9 9 9 9 13 13 13 13 Solvent content (solid content conversion %) 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 0 0 Organic particle size (nm) D50 50 50 50 50 50 5 50 50 50 5 50 50 50 50 50 50 50 50 50 50 50 50 50 Organic fine particles Tg 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 53 5 47 42 36 3 Coating surface roughness Ra 53 5 48 47 50 5 50 30 38 3 37 3 38 3 101 51 48 48 50 47 48 47 40 28 2 22 2 18 Anti-fog layer Tg 115 115 115 115 115 110 112 116 113 115 115 115 113 109 111 111 111 55 5 50 45 39 3 Contact angle 5＜ 5＜ 5＜ 5＜ ＜ 5 5＜ 5＜ ＜ 5 5＜ 5＜ ＜ 5 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 80℃ heat resistance test Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x 〇 〇 〇 Anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x x x x 100℃ heat resistance test Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x 〇 〇 〇 Anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x x x x 110℃ heat resistance test Film transparency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x 〇 〇 〇 Anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x x x x

As shown in Table 4 and Table 5, according to the anti-fog layer according to one aspect of the present invention, the Tg passing through the anti-fog layer is 60°C or higher, more preferably 110°C or higher, and after the heat resistance test, it also shows anti-fog excellent.

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FIG. 1 is an AFM (Atomic Force Microscopy: atomic force microscope) image of the anti-fog layer of Example 32.

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Claims (11)

An anti-fog layer comprising organic fine particles (A) and having a glass transition temperature (Tg) of 60°C or higher. The anti-fog layer according to claim 1, wherein the content of the organic fine particles (A) is 58% by mass or more and 99% by mass or less in terms of solid content. The anti-fog layer according to Claim 1, wherein the contact angle to water is less than 10°. The anti-fog layer according to claim 1, wherein the glass transition temperature of the organic fine particles (A) is 60°C or higher. The anti-fog layer according to claim 1, wherein the surface roughness Ra is not less than 5 nm and not more than 200 nm. A substrate comprising a substrate layer (a) and an anti-fog layer (b), Wherein the aforementioned anti-fog layer (b) is the anti-fog layer as described in any one of Claims 1 to 5, and is disposed on the aforementioned substrate layer (a). The substrate according to claim 6, wherein the substrate layer (a) is made of light-transmitting plastic. A composition for making the anti-fog layer according to any one of claims 1 to 5, comprising organic microparticles (A) and water. The composition according to claim 8, wherein the content of the organic solvent is less than 4.0% by mass relative to the solid content of the anti-fog layer. The composition as described in Claim 8, wherein the aforementioned organic microparticles (A) are (meth)acrylate copolymers, The aforementioned (meth)acrylate copolymer is a copolymer obtained by polymerizing a mixture of monomers. The composition as described in Claim 8, which further comprises resin (C), The aforementioned resin (C) is selected from water-soluble resins, water-dispersible resins, and resin emulsions.

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