TW202313926A - Antifogging layer and use of same - Google Patents

Abstract

The present invention provides an antifogging layer which is able to be produced with use of an aqueous solvent, and which is suppressed in change of gloss value in cases where the antifogging layer is exposed to high temperatures. This antifogging layer contains organic fine particles (A); and the change ratio between the gloss value (at 60 DEG) of this antifogging layer before being left at rest in a heating environment at 80 DEG C and the gloss value (at 60 DEG) of this antifogging layer after being left at rest in the heating environment for 240 hours and subsequently left at rest in an environment at 23 DEG C and 50% RH for one hour is -5% to +5%.

Description

Anti-fog layer and its application

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

Patent Document 1 describes an anti-fogging film formed from a solution dispersed with metal alkoxides, oxide particles with low saturated vapor pressure, and titanium dioxide particles in the form of photocatalyst active anatase crystals.

Patent Document 2 describes a water-absorptive anti-fog member whose surface has a fine uneven structure smaller than the wavelength λ of transmitted light.

Patent Document 3 describes a composition for forming an anti-fog layer, which contains a copolymer containing a specific structural unit and a hydrolyzate.

Patent Document 4 describes a coating film containing metal oxide and polymer particles and having a ten-point average roughness 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

[Problem to be solved by the invention] The production of VOC (Volatile Organic Compound) is one of the causes of air pollution. Therefore, in 2004, Japan promulgated an amendment to the Air Pollution Prevention and Control Law in order to reduce the amount of VOC produced. In order to reduce the viscosity during coating operations, the paint and ink industry uses a large amount of organic solvents. In addition, the paint industry accounts for about 40% of the 700,000 tons of VOC production in Japan, and the ink industry accounts for about 5%. Therefore, the measures against VOC become the subject of the paint and ink industry.

In the coating operation of paint, various measures will be taken to reduce the use of organic solvents, such as switching from organic solvent-based paints to water-based paints.

As for anti-fog coatings suitable for headlights, solvent-based coatings are mostly used at present, but in order to reduce the amount of organic solvents used, it is necessary to switch to water-based coatings. However, anti-fog coatings suitable for headlights need to be heat-resistant, and so far, there is no water-based anti-fog coating that can meet the standard of heat resistance.

In addition, as disclosed in Patent Document 1, in the method of forming an anti-fog film by forming a film of a composition containing a metal alkoxide, it is necessary to bake at about 650° C. after coating on a glass substrate. Therefore, this method cannot be applied to plastics.

Patent Document 2 describes an anti-fog member having a fine uneven structure on the surface as described above, but it is actually difficult to produce an uneven structure on the surface of a water-absorbing anti-fog film.

The composition for forming an anti-fog layer described in Patent Document 3 is difficult to maintain its anti-fog property after the heat resistance test. In addition, the manufacture of the copolymer in the anti-fog layer requires organic solvents, so it is difficult to use water-based paints without organic solvents.

In the coating film described in Patent Document 4, it is difficult to maintain the anti-fog property after the heat resistance test.

In addition, after the anti-fog layer is formed on the substrate, it may be exposed to heat generated by direct sunlight or a light source. However, Patent Documents 1 to 4 do not disclose any knowledge that the gloss of the anti-fog layer can be prevented from being lowered by heat. One aspect of the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an anti-fog layer that can be formed using an aqueous solvent and has less change in gloss when exposed to high temperatures.

[Technical means to solve the problem] In order to solve the above problems, the anti-fog layer of an aspect of the present invention contains organic particles (A), and the glossiness (60°) of the anti-fog layer before standing in a heated environment of 80°C is the same as that in the aforementioned heated environment. After standing for 240 hours, the change rate of gloss (60°) after standing for 1 hour at 23°C and 50%RH is -5% or more +5% or less.

[Efficacy of Invention] According to one aspect of the present invention, it is possible to provide an anti-fog layer prepared by using a water-based solvent and having less change in gloss when exposed to high temperature.

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

In this specification, "(meth)acrylic acid" means one or both of "acrylic acid" and "methacrylic acid", and "(meth)acrylate copolymer" means "containing (meth)acrylic acid and its derivatives as the main structural unit of the resin". Here, "(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) ) acrylates (esters of (meth)acrylic acid) and (meth)acrylamide.

＜Anti-fog layer＞ The anti-fog layer according to one embodiment of the present invention contains organic fine particles (A). The glossiness (60°) of the anti-fog layer before standing in a heating environment of 80°C is the same as that of the anti-fog layer in the heating environment. After standing still for 240 hours, the rate of change in glossiness (60°) after standing still at 23° C. and 50% RH for 1 hour is more than -5% and less than 5%.

Since the change rate of the glossiness (60°) of the anti-fog layer before and after standing in a heated environment at 80°C for 240 hours can be within the range of -5% to +5%, it can prevent exposure to direct sunlight or The appearance of the anti-fog layer changes due to heat generated by light sources, etc. In addition, since the surface roughness Ra of the organic fine particles (A) contained in the anti-fog layer can be prevented from changing, the anti-fog performance of the anti-fog layer can be maintained.

In addition, the glossiness of the anti-fog layer before standing in a heated environment of 80° C. is preferably in the range of 150 or more and 200 or less. The anti-fog layer not only has high anti-fog performance, but also has a glossy appearance.

For the glossiness of the test piece before heating, it was measured after standing in a constant temperature library under air-conditioning conditions of 23° C. and 50% RH for 1 hour. The heating of the test piece is carried out with a hot air dryer. Immediately move the test piece after being heated by the dryer for 240 hours to a constant temperature room with the air conditioner adjusted to 23°C and a humidity of 50%, and evaluate its glossiness after standing for 1 hour.

Gloss is measured using a three-angle surface gloss meter under the condition of an incident angle of 60°. Gloss evaluation was prepared by preparing a 2 mm thick polycarbonate test piece with a 1 µm thick anti-fog layer. After overlapping 10 sheets of A4 photocopy paper (whiteness 92%), the polycarbonate test piece with an anti-fog layer was prepared. Test strips are placed on it for evaluation. The rate of change in the glossiness of the anti-fogging layer is calculated as a percentage of the difference between the glossiness before heating and the glossiness after heating relative to the glossiness before heating.

(Glass transition temperature of anti-fog layer) The anti-fog layer according to one aspect of the present invention has a glass transition temperature of 60°C or higher, preferably 80°C or higher, more preferably 90°C or higher, more preferably 100°C or higher, and further preferably 110°C or higher. More preferably, above 120°C is the best. Thereby, the heat resistance of an anti-fog layer can be improved. In addition, it is also possible to appropriately prevent the glossiness of the anti-fog layer from changing due to heat.

In order to increase the glass transition temperature (Tg) of the anti-fog layer, to select the organic fine particles (A) described later, and to contain more organic fine particles ( A) is better. The evaluation method of the glass transition temperature of the anti-fog layer is evaluated by differential scanning calorimetry (DSC analysis method), and the measurement method of the glass transition temperature of the organic particles (A) described later shall prevail.

(Contact angle to water) The water contact angle of the anti-fog layer according to one aspect of the present invention is preferably not more than 10°, more preferably not more than 5°. The water contact angle of the anti-fog layer is 10° or less, and the anti-fog layer can have high anti-fog properties. The water contact angle of the anti-fog layer can be evaluated using a test piece left to stand in an environment with a room temperature of 23°C and a relative humidity of 50%.

(surface roughness Ra) The anti-fog layer according to one aspect of the present invention has a surface roughness Ra in the range of 5 nm to 200 nm. The anti-fog layer contains organic fine particles (A), preferably a curing agent (B) and a resin (C), and may also contain other components. According to an aspect of the present invention, water can be used to prepare an anti-fog layer having excellent anti-fog properties, so the amount of organic solvent used can be reduced. As a result, the cause of air pollution and the generation of VOC can be suppressed. Therefore, by means of one aspect of the present invention, the adverse impact on the atmospheric environment can be reduced, thereby contributing to goal 11 of the Sustainable Development Goals (SDGs) led by the United Nations, "building a long-lived and safe community overall construction".

The surface roughness Ra of the anti-fog layer is not less than 5 nm, preferably not less than 10 nm. When the surface roughness Ra of the anti-fog layer is thicker than 5 nm, the specific surface area of the surface of the anti-fog layer can be increased, thereby improving the anti-fog property of the anti-fog layer. In other words, when the surface roughness Ra of the anti-fog layer is less than 5nm, the unevenness formed on the surface of the anti-fog layer becomes smaller, and as a result, the surface area due to the fine unevenness becomes smaller, so that less water penetrates into the anti-fog layer . Therefore, the anti-fog property of the anti-fog layer is lowered. In addition, the surface roughness Ra of the anti-fog layer may be less than 200nm, preferably less than 150nm, more preferably less than 100nm, more preferably less than 70nm, most preferably less than 50nm. When the surface roughness Ra of the anti-fog layer is as small as 200 nm or less, it is possible to prevent the decrease in light transmittance of the anti-fog layer due to scattering of visible light in the unevenness existing on the surface of the anti-fog layer. Therefore, the light transmittance of the anti-fog layer can be improved. In addition, the anti-fog layer can have high glossiness since it is possible to prevent reduction in light transmittance. That is, when the surface roughness Ra of the anti-fog layer is not less than 5 nm and not more than 200 nm, the anti-fog layer can have high anti-fog properties, high light transmittance, and high gloss.

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 instrument [manufactured by Kosaka Laboratories Co., Ltd., model name: Surfcorer SE500], the surface roughness Ra was determined under conditions of a scanning range of 4 mm and a scanning speed of 0.2 mm/s.

The main component of the anti-fog layer is a solid content composed of materials contained in the composition used to manufacture the anti-fog layer and their reactants. "Solid content" contains organic fine particles (A), curing agent (B), and preferably resin (C). In the anti-fog layer, the solid content of organic particles (A) and resin (C) can react with the hardener (B) to generate reactants in the anti-fog layer. In addition, the solid content of the anti-fog layer may contain inorganic particles, absorbents, and other components described later, in addition to organic fine particles (A), curing agent (B), and resin (C), within the range that does not impair the efficacy of the present invention. .

(Organic particles (A)) The organic particle (A) is a resin particle with a polar group, and its glass transition temperature is above 60°C, preferably above 80°C, preferably above 90°C, more preferably above 100°C, and above 110°C. Further more preferably, it is most preferably above 120°C. The organic fine particles (A) are contained in the anti-fog layer while maintaining the particle shape. Since the glass transition temperature is 60°C or higher, the anti-fog layer can be absorbed while maintaining the particle shape even when heated. Anti-fog layer included. Thus, for example, the anti-fogging layer can maintain the desired surface roughness Ra even if it is exposed to heat of 80° C. for a long time. The resin constituting the organic fine particles (A) is not limited as long as its glass transition temperature is 250°C or lower. The total solid content in the anti-fog layer is 100% by mass, and the content of the organic particles (A) in the anti-fog layer can be more than 58% by mass, preferably more than 65% by mass, preferably more than 75% by mass, and preferably more than 75% by mass. More than 80% by mass is more preferable. When the content of the organic fine particles (A) in the anti-fog layer is in the range of 58 to 99% by mass, the surface roughness of the anti-fog layer can be increased, thereby improving the anti-fog property. In addition, when the organic fine particles (A) with a glass transition temperature of 60°C or higher are contained in a high content in the range of 58 to 99% by mass, the heat resistance of the anti-fog layer can be further improved, and the glossiness of the anti-fog layer can be prevented from being affected by heat. And change. In addition, when the content of the organic fine particles (A) in the anti-fog layer is less than 99% by mass, the coating strength of the anti-fog layer can be further improved. Therefore, if the content is less than 99% by mass, the organic microparticles (A) can increase the number of components bonded to each other, making it suitable for forming an anti-fog layer. In addition, the content of the organic fine particles (A) in the anti-fog layer means the content of the solid content that does not substantially contain the dispersion medium.

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

The glass transition temperature of the organic fine particles (A) can be obtained from the DSC curve judged in accordance with JIS-K-7122:2012 by differential scanning calorimetry (DSC) analysis. The evaluation conditions for obtaining the DSC curve, such as the temperature scanning range and temperature scanning speed, etc., are described in detail in the examples, please refer to them.

In addition, the glass transition temperature of the organic microparticles (A) can be roughly calculated as the average value of the glass transition temperatures of the homopolymers of the monomers contained in the organic microparticles (A) as structural units. The glass transition temperature of organic particles (A) is estimated as the sum of the values obtained by multiplying the glass transition temperature of the homopolymer of each monomer by the mass ratio (mass %) of each monomer as a structural unit in the resin . Here, the glass transition temperature of the homopolymer can refer to the value calculated by the Fox formula recorded in the polymer handbook [Polymer Hand Book (J. Brandrup, Interscience 1989)]. For example, the above-mentioned organic The glass transition temperature of the microparticles (A) is measured in the same way as JIS-K-7122:2012, and the glass transition temperature of homopolymers with a number average molecular weight of about 5,000 to 100,000 is obtained from the DSC curve. By making the organic microparticles (A) contain more monomers with higher glass transition temperatures of homopolymers as structural units, the glass transition temperature of the organic microparticles (A) can be increased, thereby improving the anti-fog layer. heat resistance. From the point of view of increasing the glass transition temperature of the organic microparticles (A), as a structural unit, the glass transition temperature of the homopolymer of the monomers contained in the organic microparticles (A) can be above 60°C, and 80°C The above is preferable, more preferably 90°C or higher, more preferably 100°C or higher, still more preferably 110°C or higher, most preferably 120°C or higher. Moreover, although not limited, the glass transition temperature of the homopolymer of the monomer contained in organic microparticles (A) as a structural unit may be 250 degreeC or less. (Meth)acrylamide-based monomers having a high glass transition temperature of homopolymers, such as acrylamide (Tg of homopolymer: 153°C) and acrylmorpholine (Tg of homopolymer: 145°C) ℃), etc. From the viewpoint of increasing the glass transition temperature of the organic microparticles (A), in the organic microparticles (A), assuming that the copolymer constituting the organic microparticles (A) is 100% by mass, it is derived from homopolymers having a glass transition temperature of 60°C or higher. The content of the structural unit of the monomer of the polymer is preferably at least 60% by mass, more preferably at least 80% by mass. In addition, although not limited, in the organic microparticles (A), the content of structural units derived from a monomer having a relatively high glass transition temperature of 80° C. or higher in the homopolymer is 60% by mass or more, and the organic The copolymer of the microparticles (A) is 100% by mass, and the content of the structural unit derived from a monomer whose glass transition temperature is lower than 80°C of the homopolymer can be set to 40% by mass or less to increase the organic microparticles (A) ) glass transition temperature. For example, from the standpoint of improving the dispersion stability of the organic microparticles (A) itself in an aqueous system, the organic microparticles (A) may be derived from poly(ethylene glycol) methacrylates having methoxy polyethylene glycol methacrylate or the like. The structural unit of the monomer of the ethylene glycol chain is preferable. However, structural units derived from monomers such as methoxypolyethylene glycol methacrylate, etc., have lower glass transition temperatures for homopolymers. Therefore, the heat resistance of the organic fine particles (A) also decreases, and as a result, the anti-fog property tends to decrease after heating. From the viewpoint of preventing the anti-fogging properties from being reduced by heat, in the organic fine particles (A), if the total amount of the structural units contained in the organic fine particles (A) is 100% by mass, the glass transition of the homopolymer The low-temperature structural unit is preferably 40% by mass or less. For structural units of homopolymers with a relatively low glass transition temperature, the glass transition temperature may be lower than -40°C, preferably lower than 0°C, more preferably lower than 40°C, most preferably lower than 80°C.

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

The particle diameter D50 of the organic fine particles (A) is preferably in the range of 5 nm to 200 nm, preferably in the range of 10 nm to 150 nm, more preferably in the range of 15 nm to 100 nm . The surface roughness Ra of the anti-fog layer can be increased by the irregularities caused by the larger organic particles (A) with a particle diameter D50 in the range of 5 nm to 200 nm. That is, the organic fine particles (A) can make the surface roughness Ra of the anti-fog layer within the range of 5 nm to 200 nm. That is, the organic fine particles (A) can provide the anti-fog layer with a surface roughness Ra of 5 nm or more and 200 nm or less. Therefore, the anti-fog property of the anti-fog layer can be improved. Moreover, the light transmittance of an anti-fog layer can be further improved by using the organic fine particle (A) whose particle diameter D50 is in the range of 5 nm or more and 200 nm or less.

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熱(cal/mol)，Σ _iΔvi為單體的莫耳體積(cm ³/mol)。又，由上列數式(1)求得之溶解度參數的單位為(cal/cm ³) ^1/2，本說明書中，令2.0455×(cal/cm ³) ^1/2=(J/cm ³) ^1/2=MPa ^1/2，採用MPa ^1/2作為SP值的單位。有機微粒(A)所具有的親水性，可以以有機微粒(A)中作為結構單元所內含之單體之SP值之平均值為指標來確認。 (SP value) The average value of the SP value of the monomer contained in the resin constituting the organic particle (A) as a structural unit is the SP value of each monomer multiplied by each monomer as a structural unit in the resin The sum of the values obtained from the mass proportions (mass%). The SP value of each monomer can be obtained from the following formula (1) according to the Fedors calculation method (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 heat of vaporization (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 from the above formula (1) is (cal/cm ³ ) ^1/2 , in this specification, let 2.0455×(cal/cm ³ ) ^1/2 =(J/cm ³ ) ^1/2 = MPa ^1/2 , using MPa ^1/2 as the unit of SP value. The hydrophilicity of the organic microparticles (A) can be confirmed by using the average value of SP values of the monomers contained in the organic microparticles (A) as structural units as an index.

The average value of the SP value of each monomer contained as a structural unit in the organic particle (A) may be 21MPa ^1/2 or more, preferably 24MPa ^1/2 or more, and more preferably 26MPa ^{1/2 or} more, More than 27MPa ^1/2 is better. In addition, the SP value of the organic fine particles (A) may be 32 MPa ^1/2 or less. In order to improve the hydrophilicity of the organic particles (A), from the viewpoint of being closer to the SP value (47.9) of water, the average value of the SP value of the monomer (or called the SP average value) is 21MPa ^1/2 as the lower limit value, the higher the value, the better. In addition, 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 (47.9MPa ^1/2 ), but may be 32MPa ^1/2 or less.

The monomer contained in the resin as a structural unit can be a (meth)acrylic monomer, and the (meth)acrylic monomer can be exemplified by (meth)acrylamide monomer, (meth)acrylate monomers and (meth)acrylic monomers, and other monomers described later may also be included. (Meth)acrylic monomers represented by (meth)acrylamide monomers, (meth)acrylate monomers, etc., may have crosslinkable functional groups, and the crosslinkable functional groups mean In addition to vinyl groups, (meth)acryloyl groups, etc., crosslinkable functional groups other than unsaturated double bond groups contributing to monomers contained in the resin constituting the organic fine particles (A) as structural units.

As a monomer having a high SP value, a (meth)acrylamide-based monomer is a preferable monomer. That is, by including a structural unit derived from a (meth)acrylamide-based monomer in the (meth)acrylate copolymer, the SP value of the resin can be increased, and the hydrophilicity of the organic microparticles (A) can be improved. sex. (Meth)acrylamide-based monomers include dialkyl (meth)acrylamides such as acrylamide, acrylmorpholine, methacrylamide, and dimethylacrylamide, and isopropyl Monoalkyl(meth)acrylamides such as methacrylamide and the like. From the viewpoint of improving the hydrophilicity of the organic fine particles (A), assuming that the total of the structural units derived from the monomers contained in the (meth)acrylate copolymer is 100% by mass, the units derived from (meth)acrylamide The content of the monomer-like structural unit is 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.

(Meth)acrylamide-based monomers have cross-linking functional groups such as N-methylol, N-alkoxymethylol, N-methylol ether groups, etc. The (meth)acrylamide-based monomer of the crosslinkable functional group may, for example, be N-methylolacrylamide or N-methylolmethacrylamide.

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. (Meth)acrylate monomers without crosslinkable functional groups, such as alkyl (meth)acrylates such as butyl methacrylate and ethyl methacrylate; dimethylaminoethyl acrylate, etc. (meth)acrylic acid esters with dialkylamino groups; (meth)acrylic acid esters having a structure derived from (poly)alkylene glycol, such as methoxyethyl acrylate, methoxydiethylene glycol acrylate, etc. ester monomers. Structural units derived from (meth)acrylate-based monomers that do not have a crosslinkable functional group in the particulate resin, for example, as long as the average value of the SP value of the above-mentioned monomers is 21 MPa ^1/2 or more within.

The cross-linking functional groups possessed by (meth)acrylate monomers include, for example, cross-linking functional groups such as hydroxyl, carboxyl, mercapto, phenol, amino, silanol, and alkoxysilyl, As a (meth)acrylate monomer which has such a crosslinkable functional group, 2-hydroxyethyl (meth)acrylate etc. are mentioned, for example.

When (meth)acrylic ester monomers having cross-linkable functional groups other than unsaturated double bond groups such as vinyl groups and (meth)acryl groups are contained in (meth)acrylic acid as structural units In the case of an ester copolymer, the crosslinkable functional group may react with, for example, a curing agent (B) or inorganic particles described later. In addition, because the structural units derived from (meth)acrylamide monomers with N-methylol, N-alkoxymethylol, and N-methylol ether groups undergo dehydration condensation reaction, dealcohol condensation The reaction crosslinks the organic fine particles (A), stabilizes the shape of the organic fine particles (A), and is expected to be easy 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 its content is 100% by mass of the total structural units derived from monomers contained in the (meth)acrylate copolymer. It is preferably 1 to 100% by mass, more preferably 5 to 90% by mass.

The (meth)acrylic acid-based monomer may, for example, be acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, or maleic acid. The (meth)acrylic monomer is preferably acrylic acid or methacrylic acid. Since these (meth)acrylic monomers have a carboxyl group as a crosslinkable functional group, they may react with the hardening|curing agent (B) etc. mentioned later, for example.

Other monomers include monomers such as acrylonitrile and methacrylonitrile, and vinyl monomers such as vinyl acetate, styrene, N-vinylpyrrolidone, and vinylmethyloxazolidone. For example, vinylmethyloxazolidinone may be a monomer having an oxazolidinone group as a crosslinkable functional group.

Organic microparticles (A) typically may contain structural units derived from (meth)acrylamide monomers, (meth)acrylate monomers, and (meth)acrylic monomers as described above. Microparticles of (meth)acrylate copolymer as the main structural unit. Since the (meth)acrylate copolymer contains the structural unit derived from the monomer which has a high SP value, hydrophilicity can be imparted suitably to an organic fine particle (A).

Organic microparticles (A) can be obtained from Takamatsu Yushi Co., Ltd. in the form of powder or dispersion liquid.

In Table 1 below, typical monomers that can be contained in the resin of the organic fine particles (A) as structural units, and glass transition temperatures and SP values of homopolymers thereof are shown. From the glass transition temperatures and SP values of homopolymers of the monomers listed in Table 1, it can be confirmed that (meth)acrylamide-based monomers are preferable because they have high glass transition temperatures and high SP values.

[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, an antifogging layer in which individual particles constituting the organic fine particles (A) are fixed to each other in the layer through the curing agent (B) can be obtained. The curing agent (B) may contain a compound having at least one crosslinkable functional group. The anti-fogging layer may be a layer formed of a crosslinking reaction product of the compound having a crosslinkable functional group contained in the curing agent (B) and the organic fine particles (A). Although the hardener (B) itself can also be a compound that can undergo a crosslinking polymerization reaction, the hardener (B) is preferably a compound with a functional group that can be combined with ( The crosslinking functional group contained in the meth)acrylate monomer undergoes a crosslinking reaction. The compound contained in the curing agent (B) preferably has at least one, preferably two or more, crosslinkable functional groups in its chemical structure. As long as the curing agent (B) has at least one crosslinkable functional group, the 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 not less than 1% by mass and not more than 30% by mass in terms of solid content. Within this range, the higher the content of the curing agent (B), the higher the coating strength of the anti-fog layer can be. Moreover, in the range of 1 mass % or more and 30 mass % or less, the less the content is, the higher the antifog property can be provided to an antifog layer.

The compound contained in the curing agent (B) capable of cross-linking with the cross-linkable functional group of the above-mentioned organic particles (A) has a functional group that is capable of cross-linking each other, Therefore, it is synonymous with the crosslinking functional group. The cross-linkable functional groups of the hardener (B) include, for example, carbodiimide groups, epoxy groups, isocyanate groups, blocked isocyanate groups, oxazoline groups, hydrazine groups, and aziridine groups, etc. . These crosslinkable functional groups can be combined with the N-methylol, N-alkoxymethylol, N-methylol ether, and hydroxyl groups that may be present in the above-mentioned (meth)acrylate monomers. , silanol group, alkoxysilyl group, carboxyl group, mercapto group, phenol group and amine group and other cross-linking functional groups have a good reaction.

The compound having such a cross-linkable functional group is not limited, but is preferably a water-soluble compound that can be dissolved in an aqueous system or a water-dispersible compound that can be dispersed in an aqueous system. That is, the curing agent (B) can be obtained in the form of an aqueous solution, aqueous dispersion or emulsion, and contained in the composition for forming the anti-fog layer. The curing agent (B) may contain an organic solvent as long as the effect of the present invention is not impaired.

The curing agent (B) includes, for example, a curing agent having a carbodiimide group, such as CARBODILITE(®) (manufactured by Nisshinbo Chemical Co., Ltd.), Carbosista(®) (manufactured by Teijin Corporation), N, N '-Dicyclohexylcarbodiimide (available from Tokyo Chemical Industry Co., Ltd.), N, N'-diisopropylcarbodiimide (available from Fujifilm Wako Pure Chemical Industries, Ltd.), 1-[3-( Dimethylamino)propyl]-3-ethylcarbodiimide (available from Fujifilm Wako Pure Chemical Industries, Ltd.), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Hydrochloride (available from Fujifilm Wako Pure Chemical Industries, Ltd.), bis(2,6-diisopropylphenyl)carbodiimide (available from Kawaguchi Chemical Industry Co., Ltd.), and the like. Examples of hardeners having epoxy groups include DENACOL(®) (manufactured by Nagase ChemteX Co., Ltd.), water-based epoxy resin jER(®) series (manufactured by Mitsubishi Chemical Corporation), ADEKA RESIN(®) EM series (manufactured by ADEKA Co., Ltd.), etc. Examples of the curing agent having a blocked isocyanate group include DURANATE (®) (manufactured by Asahi Kasei Co., Ltd.), Coronate (®) series (manufactured by Tosoh Corporation), and the like. In terms of hardeners having an oxazoline group, for example, EPOCROS (®) (manufactured by Nippon Shokubai Co., Ltd.), poly(2-ethyl-2-oxazoline) (available from Fujifilm Wako Pure Chemical Industries, Ltd. acquired by the club), etc. In addition, examples of curing agents having a hydrazine group include dihydrazide adipate (available from Tokyo Chemical Industry Co., Ltd.), dihydrazide sebacate, dodecanedihydrazide, isophthalic acid dihydrazine, Formic acid dihydrazide, salicylic acid hydrazide (both available from Otsuka Chemical Co., Ltd.), and the like. Examples of hardeners having an aziridine group include CHEMITITE(®) (manufactured by Nippon Shokubai Co., Ltd.), trimethylolpropane tris[3-(2-methylaziridine-1-yl ) propionate] (available from Japan Daqing Energy Co., Ltd.), etc.

(Resin (C)) The anti-fog layer preferably contains resin (C) in addition to the organic fine particles (A) and curing agent (B) described above. By containing the resin (C), the anti-fog layer can react the resin (C) and the curing agent (B) to form a tougher coating. Moreover, the adhesiveness of an anti-fog layer and a board|substrate can be improved by containing resin (C).

That is, the resin (C) should at least be able to react with the curing agent (B), and preferably has a crosslinkable functional group. Among them, from the viewpoint of improving the water solubility or water dispersibility of the resin (C) itself, the crosslinkable functional group is preferably an acid group such as a carboxyl group, a hydroxyl group, a phenol group, an amino group, or the like. Resin (C) can for example be polyester resin, polycarbonate urethane resin, epoxy ester resin, alkyd resin, water-soluble phenolic resin etc., 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, more preferably 2 to 60 mgKOH/g. Therefore, within this acid value range, 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 improved. In addition, the higher the acid value, the more it is possible to make the composition described later into a water vehicle 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, more preferably 2 to 120 mgKOH/g. Therefore, within this hydroxyl value range, the higher the hydroxyl value, the more the water solubility of the resin (C) can be improved, and the heat resistance of the anti-fog layer can be improved. In addition, the higher the hydroxyl value, the more it is possible to make the composition described later into a water vehicle composition. In addition, the lower the hydroxyl value, the more water resistance of the anti-fog layer containing the resin (C) can be improved.

In addition, when the resin (C) is a resin having a phenolic group or an amino group, in the same manner as the resin (C) having a carboxyl group and a hydroxyl group, consider the water solubility of the resin (C) and the heat resistance of the anti-fog layer produced. And the water resistance of the anti-fog layer can be designed according to the amount of phenolic group or amine group.

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

The mixing ratio of curing agent (B) and resin (C) can be determined according to the types of curing agent (B) and resin (C), for example, according to the acid value and/or hydroxyl value, so as to improve the curing agent ( B) and the glass transition temperature of the cured product of resin (C).

When the total amount of hardener (B) and resin (C) contained in the anti-fog layer is converted into the solid content contained in the anti-fog layer, the anti-fog layer preferably contains 2% by mass or more and 43% by mass or less . Within this range, the less the content is, the more the heat resistance of the anti-fog layer can be improved. In addition, the total content of the hardener (B) and the resin (C) in the anti-fog layer is preferably not more than 43% by mass, more preferably not more than 20% by mass, in terms of solid content. Moreover, when the total content 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), for example, can be obtained in the form of an aqueous solution, an aqueous dispersion, or an emulsion and contained in a composition described later.

As for the resin (C), polyester resins include, for example, Pes resin series (manufactured by Takamatsu Yushi Co., Ltd.) and Aron melt (®) PES-1000, 2000 series (manufactured by Toagosei Co., Ltd.). Moreover, as a water-soluble phenolic resin, PHENOLITE (®) TD-4304 (made by DIC Corporation) etc. are mentioned. The polycarbonate-based urethane resin may, for example, be HYDRAN(®) (manufactured by DIC Corporation), epoxy ester resin, or WATERSOL(®) (manufactured by DIC Corporation) which is an alkyd resin.

(inorganic particles) The anti-fog layer may contain inorganic particles as another component. The inorganic particles contained in the anti-fog layer are preferably alumina, silica, zirconia, titania, zinc oxide, other metal oxide particles, carbon, etc., and alumina sol, silicic acid gel, and silica sol can be used. , zirconia sol, titania sol, sol of other metal oxide particles and other colloidal particles. Colloidal particles can be acidic sol, basic sol or neutral stable sol. The inorganic particles may be cross-linked with the curing agent (B) and/or the resin (C), and the inorganic particles may be cross-linked with each other.

The volume-based particle diameter D50 of the inorganic particles may be greater than 2 nm, preferably greater than 3 nm. Thereby, the surface roughness of the anti-fog layer can be prevented from being damaged. In addition, from the viewpoint of imparting high light transmittance to the anti-fog layer, the particle diameter D50 of the inorganic particles is preferably 200 nm or less.

The total solid content contained in the anti-fog layer is 100% by mass, and the content of inorganic particles is preferably in the 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 reduction of the anti-fog property due to the inorganic particles. In addition, when the content of the inorganic particles is at least 0.1% by mass, there is an effect of providing the anti-fog layer with heat resistance as high light transmittance.

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 impair the effects of the present invention. Such inorganic particles include, for example, Alumina sol 10A (manufactured by Kawaken Fine Chemicals Co., Ltd.), SNOWTEX(®) series of colloidal silica (manufactured by Nissan Chemical Co., Ltd.), and the like.

(other ingredients) The anti-fog layer may contain absorbents, coalescents, antifreezes as other components.

The absorbent is exemplified by mixed layer clay. The mixed layer clay is preferably industrially synthesized synthetic clay, such as smectite, bentonite, montmorillonite, and the like. Through the addition of absorbent, the anti-fog layer can also increase the function of water absorption and water retention, which can improve the anti-fog performance. 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 of 200 nm or less on the major axis. The content of the clay in the mixed layer can be appropriately designed within the range that does not impair the effect of the present invention, for example, in the range of 0.1 mass % to 5.0 mass % in the total solid content of the anti-fog layer contained in 100 mass % Inside is better.

The mixed layer clay mineral may, for example, be Smecton(®) or Kunipia(®) of smectite (both manufactured by Kunimine Industry Co., Ltd.).

Film-forming aids can be exemplified by boiling point higher than water and water-soluble organic solvents, such as butyl cellosolve (ethylene glycol-monobutyl ether), texanol (2,2,4-trimethylpentane-1,3 - organic solvents such as diol monoisobutyrate). In addition, the antifreeze is typically ethylene glycol. The water-soluble organic solvent refers to an organic solvent that can be dissolved 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 may be less than 4.0% by mass, preferably less than 2.0% by mass, more preferably less than 0.5% by mass, and preferably less than 0.1% by mass. The following is better. Moreover, if it is 4.0 mass % or less, it can prevent the heat resistance of an anti-fog layer from being impaired, and can reduce the change rate of glossiness. By making it less than 4.0% by mass, the problem that the organic fine particles (A) themselves are easily dissolved by the organic solvent can be prevented, and the surface roughness Ra of the anti-fog layer can be maintained. Thereby, it can be expected to prevent the reduction of the anti-fog property due to the surface roughness.

Other components of the anti-fog layer, including surfactants, such as leveling agents, defoamers, dispersants and emulsifiers, etc., and additives, such as viscosity modifiers, antioxidants, ultraviolet absorbers, plasticizers, preservatives, Antifungal agent and anti-water agent, etc. Some of these surfactants and additives can be contained in the composition used to manufacture the anti-fog layer in the form of solids. The anti-fog layer may contain colorants such as coloring pigments and dyes to improve the appearance of the substrate within the range that does not impair the effects of the present invention. The anti-fog layer may contain, for example, a pH adjuster, a pH buffer, etc. derived from the composition used to prepare 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 of one aspect of the above-mentioned present invention. The description of the anti-fog layer (b) is based on 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. The substrate layer (a) may, for example, be glass, resin material, metal, ceramic, etc., or may be a composite material thereof. Among them, plastics with light transmission are preferred. Plastics with light transmission can, for example, be polycarbonate resins for molding, acrylic resins, polyester resins, polystyrene resins, ABS resins, polyvinyl chloride resins, polyamide resins, polymethyl methacrylate (PMMA) ), polyethylene terephthalate (PET), poly(cyclohexanedimethylene terephthalate) copolyester resin (Tritan(®): manufactured by Eastman Chemical Company), and the like.

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 of one aspect of the present invention may be formed into a desired shape according to the application. The substrate can be a light-transmitting substrate constituting a part of lighting devices such as headlights and taillights of vehicles such as passenger cars, ships, aircrafts, etc., and spectacle lenses.

The method of arranging the anti-fogging layer (b) on the substrate layer (a) is not particularly limited. For example, what is necessary is just to harden this composition after apply|coating the composition for manufacturing an anti-fog layer (b) on a board|substrate layer (a). The method of curing the composition can be appropriately selected according to the components of the composition, for example, it can be cured by drying by heating or the like.

For example, in the substrate layer (a), the surface on which the anti-fog layer (b) is formed may be subjected to surface treatment such as improving the wettability and/or adhesion of the anti-fog layer (b). The surface treatment may, for example, be surface treatment such as corona discharge treatment, chemical conversion treatment, plasma treatment, acid or alkali solution treatment. In addition, surface treatment agents such as primers and coupling agents can also be coated on the surface of the substrate layer (a) on which the anti-fog layer (b) is formed.

The coating method of the composition of one aspect of the present invention can be a known method, for example, the coating method can include spray coating method, dip coating method, roll coating method, bar coating method and the like.

In addition, after coating the composition of one aspect of the present invention, its drying and curing can be appropriately designed according to the type of hardener (B) or resin (C), and there is no special limitation, but it is preferably at 60°C or higher , preferably above 100°C. One of the advantages of the composition of one aspect of the present invention is that the glass transition temperature of the organic fine particles (A) contained in the composition is high, so that the aqueous solvent can be sufficiently dried, and the curing agent (B) can be sufficiently accelerated. Cross-linking reaction while preventing reduction of anti-fog properties due to heating of the anti-fog layer.

In the preparation 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 several times to obtain a desired film thickness. In addition, the anti-fog layer can also be prepared by repeating the application of the composition of one aspect of the present invention, drying, and heating again several times.

The film thickness of the composition of one aspect of the present invention after coating and drying, that is, the film thickness of the anti-fog layer, is preferably, for example, 20 nm to 10000 nm on the surface of the substrate. When the film thickness of the anti-fog layer is 20 nm or more, suitable anti-fog properties can be imparted to the substrate coated with the anti-fog layer. In addition, when the film thickness of the anti-fog layer is 10000 nm or less, high light transmittance can be imparted to the anti-fog layer.

[composition] The composition for producing the anti-fog layer of one aspect of the present invention (hereinafter, simply referred to as "the composition of one aspect of the present invention") contains organic fine particles (A) and water, and the organic fine particles (A) The glass transition temperature is preferably above 60°C. That is, the organic fine particles (A) of the composition may be an aqueous composition. The description of the composition of the composition of one aspect of the present invention (including the description of the components described later) is based on the description of the anti-fog layer of one aspect of the present invention, and the same description will not be repeated. The anti-fog layer of one aspect of the present invention can be suitably prepared by using the composition of one aspect of the present invention.

The composition of one aspect of the present invention preferably contains a curing agent (B). In addition, the content of the curing agent (B) is preferably not less than 1% by mass and not more than 30% by mass in terms of solid content. When the content of the curing agent (B) is 1% by mass or more, an anti-fog layer with good heat resistance can be obtained, and when the content of the hardener (B) is 30% by mass or less, an anti-fog layer with sufficient strength can be obtained.

The composition of one aspect of the present invention preferably further contains a curing agent (B) and a resin (C). In addition, the total amount of the curing agent (B) and the resin (C) is preferably 2% by mass or more and 43% by mass or less in terms of solid content. If the total amount of hardening agent (B) and resin (C) is more than 2% by mass, the anti-fog layer can obtain adhesion with the substrate. If the total amount of hardening agent (B) and resin (C) is 43% by mass or less, the anti-fog layer can obtain the surface roughness for improving the anti-fog property.

In addition, in the composition of one aspect of the present invention, the content of the organic fine particles (A) is preferably 58% by mass or more and 99% by mass or less in terms of solid content. This is for suitably preparing the anti-fog layer of one aspect of the present invention.

In addition, in the composition of one aspect of the present invention, the content of the organic solvent is preferably less than 4% by mass relative to the solid content. According to the composition of one aspect of the present invention, since water can be used to produce an anti-fog layer excellent in anti-fog properties, the amount of organic solvent used can be reduced. In addition, the organic solvent may, for example, be used as the above-mentioned film-forming aid or refrigerant, and a water-soluble organic solvent having a higher boiling point than water.

The composition of one aspect of the present invention is a composition for producing an anti-fog layer, preferably containing 30 to 50,000 parts by mass of water as a solvent when the total amount of solid content is 100 parts by mass. Thereby, a composition (coating agent) for producing an anti-fog layer capable of appropriately expressing anti-fog properties by the organic fine particles (A) can be obtained. Water as a solvent may be, for example, deionized water, distilled water, tap water, or industrial water. In addition, the "solid content" in this specification is as long as it can be distinguished from water and volatile solvents evaporated from the composition, and it is used as the composition of the anti-fog layer produced using the composition of one aspect of the present invention. The contained ingredients are sufficient, and do not have to be "solid".

In addition, production of an anti-fog layer containing organic fine particles (A) and having a surface roughness Ra of 5 nm or more and 200 nm or less by applying and curing the composition of an aspect of the present invention methods are also within the scope of the present invention. In this way, the anti-fog layer of one aspect of the present invention can be suitably produced by using the composition of one aspect of the present invention. In addition, the substrate to be coated with the composition can be appropriately selected according to the purpose of the anti-fog layer.

[Summarize] The anti-fog layer of aspect 1 of the present invention contains organic particles (A), and the glossiness (60°) of the aforementioned anti-fog layer before standing in a heating environment of 80°C is the same as that after standing in a heating environment of 240°C. After one hour, the rate of change between the glossiness (60°) after standing still in an environment of 23° C. and 50% RH for 1 hour is -5% or more and +5% or less.

The anti-fogging layer of aspect 2 of the present invention is in aspect 1, and its surface roughness Ra is preferably not less than 5 nm and not more than 200 nm. .

The anti-fog layer according to aspect 3 of the present invention, in aspect 1 or 2, preferably has a glossiness (60°) of not less than 150 and not more than 200 before standing in the heated environment.

In the anti-fog layer of aspect 4 of the present invention, in any aspect of aspects 1 to 3, the particle diameter D50 of the aforementioned organic particles (A) is preferably not less than 5 nm and not more than 200 nm.

In the anti-fog layer of aspect 5 of the present invention, in any aspect of aspects 1 to 4, the glass transition temperature (Tg) of the aforementioned organic particles (A) is preferably 60° C. or higher.

The anti-fog layer of aspect 6 of the present invention is based on the fact that in any aspect of aspects 1 to 5, the content of the aforementioned organic fine particles (A) is 58% by mass or more and 99% by mass or less in terms of solid content. good.

The anti-fog layer of aspect 7 of the present invention is based on any aspect of aspects 1 to 6, converted to solid content, the aforementioned organic particles (A) are particles of acrylate copolymers, derived from homopolymerization The content of the structural unit of the monomer having a glass transition temperature of -40°C or lower is preferably 40% by mass or less relative to 100% by mass of the acrylate copolymer.

The substrate of Aspect 8 of the present invention is provided with a substrate layer (a) and an anti-fog layer (b); the aforementioned anti-fog layer (b) is the anti-fog layer described in any one of Aspects 1 to 7, which and disposed on the aforementioned substrate layer (a).

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.

[Example] The following describes an embodiment of the present invention.

The coating agents of Examples 1-37 and Comparative Examples 1-3 were prepared, and the anti-fog layers prepared by these coating agents were evaluated.

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

[Material] (organic particles) It was obtained as an aqueous dispersion (manufactured by Takamatsu Yushi Co., Ltd.) of 20% by mass of (meth)acrylate copolymer fine particles. The respective monomers constituting the (meth)acrylate copolymers used in Examples and Comparative Examples are shown in Table 2 and Table 3 below.

(inorganic particles) Alumina sol: Alumina sol 10A (solid content 10% by mass, manufactured by Kawaken Fine Chemicals Co., Ltd.) Colloidal silica: SNOWTEX(®) OXS (solid content 10% by mass, manufactured by Nissan Chemical Co., Ltd.) (Organic particles: resin (C)) polyester resin: Pes resin A-640; Takamatsu Yushi Co., Ltd., 25% solid content product Pes resin A-645GH; manufactured by Takamatsu Yushi Co., Ltd., solid content 30% product Polycarbonate urethane resin: HYDRAN(®)WLS-210; manufactured by DIC Corporation, 35% solids Epoxy ester resin: WATERSOL(®)EFD-5560; manufactured by DIC Corporation, 40% solids Alkyd resin: WATERSOL(®)BCD-3100; manufactured by DIC Corporation, 43% solids Water-soluble phenolic resin: Water-soluble resol PE-602; DIC Co., Ltd., solid content 42% product (absorbent) Synthetic smectite: Smecton(®) SA (Kunimine Industry Co., Ltd.) (hardener) Carbodiimide: CARBODILITE(®) E-02 (manufactured by Nisshinbo Chemical Co., Ltd.) Aziridine: CHEMITITE(®) DZ-22E (Nippon Shokubai Co., Ltd.) Dihydrazine adipate (manufactured by Tokyo Chemical Industry Co., Ltd.) Epoxy compound: DENACOL(®) EX-810 (manufactured by Nagase ChemteX Co., Ltd.) Blocked isocyanate: DURANATE(®) WM44-L70G (manufactured by Asahi Kasei Co., Ltd.) Oxazoline compound: EPOCROS(®)WS-700 (manufactured by Nippon Shokubai Co., Ltd.) (film forming aids) Butyl cellosolve: (manufactured by Tokyo Chemical Industry Co., Ltd.)

[preparation] The coating agent of Example 1 was prepared in the following order. First, 500 g of an aqueous dispersion of (meth)acrylate copolymer fine particles was prepared, and 20 g of an aqueous dispersion of polyester resin was added to this aqueous dispersion. Next, to the aqueous dispersion of the (meth)acrylate copolymer fine particles, 10 g of an aqueous dispersion of alumina sol and, as a curing agent, 10 g of carbodiimide in terms of solid content were added. Then, the aqueous dispersion was stirred, and ammonia water (1 mol/L) was added to adjust the pH to 8.0 to obtain the coating agent of Example 1. According to the compositions shown in Table 2 and Table 3 below, the coating agents of Examples 2 to 37 and Comparative Examples 1 to 3 were prepared in the same procedure as that of the coating agent of Example 1.

[Preparation of anti-fog layer] The coating agent of Example 1 was coated on a polycarbonate test piece (thickness 2 mm) using a bar coater #2. Then, 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. Thus, a test piece having an anti-fog layer having a film thickness of about 1 μm was prepared. According to the same procedure of manufacturing the anti-fog layer with the coating agent of Example 1, the test pieces with the anti-fog layer of Examples 2-37 and Comparative Examples 1-3 were prepared.

[Each evaluation] Using the test pieces provided with the anti-fog layer of Examples 1 to 37 and Comparative Examples 1 to 3, the following evaluations were performed. 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 50% of the cumulative 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 Microtrac-Bell). Nanotrac is a registered trademark of the company.

(Glass transition temperature (Tg) of organic particles) The glass transition temperature (Tg) of the organic fine particles 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 follows JIS-K-7122:2012, measures a DSC curve, and obtain|requires it from this DSC curve. The sample mass for DSC measurement was 5 mg. The first scan ramps the temperature range from -10°C to 300°C at a rate of 20°C/min, and after cooling the sample with liquid nitrogen, the second scan ramps the temperature range at a rate of 20°C/min From -10°C to 300°C, the glass transition temperature of the organic particles was derived from the DSC curve obtained from the second scan.

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

(Atomic force microscope observation) The anti-fog layer formed from the coating agent of Example 37 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 Figure 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 mass of the anti-fog layer sample is 5mg. Since the temperature range, heating rate, and number of scans used to obtain the DSC curve are the same as the conditions for obtaining the DSC curve of the glass transition temperature (Tg) of organic fine particles, description thereof will be omitted.

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

(transparency of coating film) Use a haze meter ("HAZE METER NDH5000", (manufactured by Nippon Denshoku Industries Co., Ltd.) to measure the transparency (transparency) of the coating film of the test piece with the anti-fog layer. The HAZE value follows JIS-K7361-1:1997, Measured under the condition that the light source is a white LED and the luminous flux is 14mm. In the standard shown below, it is evaluated as no problem if it is above △, and it is better if it is ○. The polycarbonate test piece itself with a thickness of 2mm The HAZE value is 0.30. ○: The 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. ╳: HAZE value is 0.50 or more.

(anti-fog) In an air-conditioned room with a temperature of 23°C and a humidity of 50%, blow air on the anti-fog layer prepared on the test piece for 5 seconds, and evaluate the anti-fog performance according to the standards shown below. ○: There is no fog at all. Δ: Slightly fogged, but recovered quickly. ╳: Fog.

(heat resistance) Each test piece was placed under the temperature conditions of 80°C, 100°C, and 110°C for 240 hours, and then left to stand for 1 hour in an air-conditioned constant temperature library with a temperature of 23°C and a humidity of 50%. Afterwards, its anti-fogging properties and light transmittance were evaluated.

(Gloss) Using a three-angle surface gloss meter (device name: micro-TRI-gloss, manufactured by BYK Corporation), gloss was measured under the condition of an incident angle of 60°. Glossiness was measured by stacking 10 sheets of A4 photocopy paper (manufactured by Itochu Pulp Co., Ltd., whiteness 92%), and setting the test pieces prepared with the anti-fog layers of each embodiment and comparative example on it. . [Table 2] Homopolymer 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-Methylolacrylamide 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 particles (resin (C)) Polyester resin (Pes resin 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 (Pes resin A-645GH: Takamatsu grease) 30% product Polycarbonate urethane resin (HYDRAN WLS-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 resol PE-602: DIC) 42% product Inorganic particles Alumina sol 10A (Chuanyan 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 Smectite (Smecton SA Kunimine Industries) hardener Carbodiimide (CARBODILITE E-02: Nisshinbo) 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) Oxazoline (EPOCROS WS-700: Nippon Shokubai) Coalescent Butyl cellosolve pH regulator 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 25 27 29 30 31 29 29 28.8 28.8 26.7 28 28.4 29.2 28.2 29.6 29.5 28.2 28.8 [table 3] 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 Acrylamide 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 10 Acrylmorpholine 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20 Dimethacrylamide Isopropylacrylamide Diethylacrylamide acrylic acid 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 N-Methylolacrylamide 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Methoxypolyethylene glycol methacrylate 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 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 Organic particles (resin (C)) Polyester resin (Pes resin A-640: Takamatsu oil) 25% product 20 20 20 20 20 240 120 4 80 20 20 20 400 280 20 Polyester resin (Pes resin A-645GH: Takamatsu grease) 30% product 17 Polycarbonate urethane resin (HYDRAN WLS-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 resol PE-602: DIC) 42% product 12 Inorganic particles Alumina sol 10A (Chuanyan Fine Chemicals) 10% product 10 10 10 10 10 10 10 10 10 10 10 10 10 Colloidal silicon dioxide (SNOWTEX OXS) 10% product 10 absorbent Synthetic Smectite (Smecton SA Kunimine Industries) 2 hardener Carbodiimide (CARBODILITE E-02: Nisshinbo) 10 10 10 2 40 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 Oxazoline (EPOCROS WS-700: Nippon Shokubai) 10 Coalescent Butyl cellosolve 4 pH regulator ammonia 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 28.8 28.8 26.4 [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 particulate content (converted solid content%) 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 Hardener content (converted to solid content%) 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Resin + hardener content (converted solids %) 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 Solvent content (converted to solid content%) 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 50 50 50 50 50 50 50 50 50 Organic particle 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 ○ ○ ○ ○ ○ ○ ○ ○ ○ △ △ ○ ○ ○ ○ ○ ○ ○ ○ ○ Anti-fog ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 80℃ heat resistance test Gloss before test 172 172 171 172 172 172 172 172 172 162 166 172 169 172 172 171 172 171 172 172 Gloss before test 172 171 172 172 171 172 172 172 171 162 165 164 167 171 172 171 172 171 171 172 Change rate (%) 0.0 -0.6 0.6 0.0 -0.6 0.0 0.0 0.0 -0.6 0.0 -0.6 -4.7 -1.2 -0.6 0.0 0.0 0.0 0.0 -0.6 0.0 Film transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Anti-fog ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 100℃ heat resistance test Film transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Anti-fog ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ○ ○ ○ ○ ○ ○ ○ ○ 110℃ heat resistance test Film transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Anti-fog ╳ ╳ ╳ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ╳ ○ ○ ○ ○ ○ ○ [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 hardening temperature 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 Organic particulate content (converted solid content%) 86 86 86 86 86 58 71 96 62 86 85 87 87 87 87 87 87 47 55 86 Hardener content (converted to solid content%) 9 9 9 9 9 6 7 2 25 9 8 9 9 9 9 9 9 5 6 9 Resin + hardener content (converted solids %) 13 13 13 13 13 41 28 3 37 13 13 9 9 9 9 9 13 52 44 13 Solvent content (converted to solid content%) 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 0 Organic particle size (nm) D50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Organic particle Tg 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 53 Coating surface roughness Ra 53 48 47 50 50 30 38 37 38 101 51 48 50 47 48 47 48 2.0 2.0 49 Anti-fog layer Tg 115 115 115 115 115 110 112 116 113 115 115 113 109 111 111 111 115 108 109 55 Contact angle 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ 5＜ Film transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Anti-fog ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ○ 80℃ heat resistance test Gloss before test 171 172 172 172 172 171 172 172 172 172 171 171 171 170 171 171 170 171 172 172 Gloss before test 170 172 172 172 172 171 172 172 171 169 171 172 170 170 172 171 170 102 105 132 Change rate (%) -0.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 -0.6 -1.7 0.0 0.6 -0.6 0.0 0.6 0.0 0.0 -40.4 -39.0 -23.3 Film transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ╳ Anti-fog ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ╳ 100℃ heat resistance test Film transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ╳ Anti-fog ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ╳ 110℃ heat resistance test Film transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ╳ Anti-fog ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ╳ ╳

As shown in Table 4 and Table 5, the anti-fog layer according to one aspect of the present invention shows that since the Tg of the anti-fog layer is 60° C. or higher, the change rate of the gloss before and after the heat resistance test is very small, which is in the within the range of ±5%.

none

[ Fig. 1 ] is an AFM (Atomic force microscopy: atomic force microscope) image of the anti-fog layer of Example 37.

none.

Claims (8)

An anti-fog layer containing organic particles (A); The glossiness (60°) of the aforementioned anti-fog layer before standing in a heated environment at 80°C is the same as that after standing in a heated environment for 240 hours, and then at 23°C, 50%RH for 1 hour The change rate between the glossiness (60°) is -5% or more +5% or less. 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. The anti-fog layer according to claim 1, wherein the glossiness (60°) of the anti-fog layer before standing under the heating environment is 150 or more and 200 or less. The anti-fog layer according to claim 1, wherein the particle diameter D50 of the organic fine particles (A) is not less than 5 nm and not more than 200 nm. The anti-fog layer according to claim 1, wherein the glass transition temperature (Tg) of the organic fine particles (A) is 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 organic microparticles (A) are particles of an acrylate copolymer derived from a homopolymer monomer having a glass transition temperature of -40°C or lower in terms of solid content. The content of the structural unit is 40 mass % or less with respect to 100 mass % of the said acrylate copolymer. A substrate comprising a substrate layer (a) and an anti-fog layer (b); The aforementioned anti-fog layer (b) is the anti-fog layer described in any one of claims 1 to 7, and is arranged on the aforementioned substrate layer (a).

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