JP2007177196A - Antifogging and stain-resistant item - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifogging and stain-resistant item which is preferable for a window for a transportation machine such as an automobile, a train, a ship, an airplane or the like and has excellent antifogging and stain-resistant performances which can prevent the view of a crew from being limited. <P>SOLUTION: This antifogging and stain-resistant item has a substrate and a water-absorbing resin film formed on the surface of the substrate. The saturating amount of absorbed water is not less than 60 mg/cm<SP>3</SP>. The contact angle of water on the surface of the water-absorbing resin film at its saturated absorption is 40-90°. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an article having antifogging and antifouling properties.

In a transparent substrate such as glass or plastic, when the difference between the temperature of the substrate surface and the ambient temperature in contact with the substrate becomes large, moisture in the atmosphere adheres to the surface of the substrate as fine water droplets and dew condensation occurs. When condensation occurs, fine water droplets scatter transmitted light, and a so-called “cloudy” state occurs.
If the substrate is a window for transportation equipment (especially a windshield or rear glass of a car), the difference between the car interior temperature and the car outside temperature tends to be large, and the car interior temperature tends to be high. On snowy days and the like, water droplets often form condensation on the inner surface of the glass car, resulting in hindering the driver's and passengers' visibility, which may hinder safety and comfort. Therefore, various means for preventing fogging have been studied. For example, the following proposals have been made.

(1) A method of applying a surfactant to the substrate surface (see, for example, Patent Document 1),
(2) A method of treating the surface of the substrate with a hydrophilic resin or a hydrophilic inorganic compound to make the surface of the substrate hydrophilic (see, for example, Patent Documents 2 and 3),
(3) A method of forming a water-absorbing film such as a film made of a water-absorbing resin or a film made of a porous inorganic material compound on the surface of the substrate and imparting water-absorbing performance to the surface of the substrate (for example, see Patent Documents 4 to 7) ,
(4) A method of maintaining the surface of the substrate above the dew point temperature by installing a heater or the like on the substrate and heating,
(5) A method in which warm air or dehumidified air of an air conditioner is blown to the surface of a substrate by a device called a defroster or defogger to evaporate condensed water,
(6) A method in which the surface of the substrate is treated with a water-repellent compound so that fine water droplets do not adhere to the surface of the substrate.

  However, in the method (1), it is difficult to fix the surfactant to the substrate surface, and it is difficult to maintain a low surface tension over a long period of time. In the method (2), it is easy to adsorb and fix inorganic dirt, and it is difficult to maintain hydrophilicity for a long time. Further, when water droplets continuously adhere to the hydrophilic surface, the thickness of the water film increases, and even if the water film increases with a uniform thickness, some distortion of the fluoroscopic image is inevitable. When the substrate is a window member for transportation equipment, the distortion of the fluoroscopic image may cause trouble or danger in driving, which is not preferable. Furthermore, since the distortion of the perspective image does not occur suddenly but progresses gradually, even if the driver recognizes the danger and activates the defroster, the water film is often already quite thick, Visibility is not immediately improved because it takes time for the water film to evaporate.

In the method (4), the antifogging performance can be maintained semipermanently, but it is very expensive because it always requires energy accompanying energization. The method (5) often uses part of the heat generated by driving the engine, and it may take time to obtain a sufficient effect, particularly when the engine is cold during the winter period. In addition, the negative effect on fuel consumption due to the use of electricity is inevitable. In the method (6), water repellency is required so that an extremely minute water droplet having a diameter of 1 nm or less can be slid down or not adhered, but there is no such technique at present.
Therefore, the method (3) can provide an excellent anti-fogging effect and can maintain the effect easily and at low cost over a long period of time.

  On the other hand, when the base is used as a window for a transport device such as an automobile, the inner surface of the base of the base is contaminated with plasticizer generated from resin used as an interior material in the vehicle or tobacco smoke sucked by the occupant. May be obstructed or the passenger may feel uncomfortable. Therefore, it is also required that the substrate has antifouling properties.

JP 2003-238207 A JP 2003-226842 A JP 2001-356201 A Japanese Patent Laying-Open No. 2005-187276 Japanese Patent Laid-Open No. 2002-53792 JP 2004-269851 A JP 11-335142 A

  In order to obtain a good antifogging effect, it is effective to impart water absorption performance to the substrate surface as described above. However, water-absorbing coatings such as coatings made of water-absorbing resins and coatings made of porous inorganic materials may easily absorb dirt, which may impede the occupant's view and cause the passengers to feel uncomfortable. was there.

The present invention has been made to solve the above-described problems, and provides the following inventions.
[1] An anti-fogging and antifouling article having a substrate and a water-absorbing resin film provided on the surface of the substrate, wherein the water-absorbing resin film has a saturated water absorption of 60 mg / cm ³ or more and is saturated An anti-fogging and antifouling article, wherein the water contact angle of the surface of the water-absorbent resin film during water absorption is 40 to 90 °.
[2] The anti-fogging and antifouling article according to [1], wherein the water-absorbing resin film is a resin film formed by reacting a film-forming material on the substrate surface.

[3] The antifogging and antifouling article according to [2], wherein the film forming material is a film forming material containing a crosslinkable resin and a crosslinking agent.
[4] The antifogging and antifouling article according to [2] or [3], wherein the film forming material further contains 1% by mass or less of silicone with respect to the total amount of the crosslinkable resin and the crosslinking agent.
[5] The antifogging and antifouling article according to any one of [1] to [4], wherein the antifogging and antifouling article is a glass plate for automobile windows.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-fogging antifouling article which expresses an antifogging effect and an antifouling effect simultaneously is obtained. By using this anti-fogging and antifouling article for a window glass for transportation equipment (particularly, a window glass for automobiles), a good field of view can be secured constantly.

  The anti-fogging effect referred to in the present invention refers to an effect that does not cause fogging at all but makes it difficult to fog, for example, delays the occurrence of fogging. In addition, the antifouling effect referred to in the present invention means an effect of reducing the amount of adhesion of dirt as compared with ordinary glass, and does not decompose attached dirt and does not cause dirt to adhere at all.

  The anti-fogging and antifouling article of the present invention has a substrate and a water-absorbing resin film provided on the surface of the substrate.

The substrate is preferably a substrate made of glass, plastic, metal, ceramics, or a combination thereof (composite material, laminated material, etc.), particularly preferably a transparent substrate made of glass or plastic.
The shape of the substrate may be a flat plate or may have a curvature on the entire surface or a part thereof. The thickness of the substrate is appropriately selected depending on the use of the anti-fogging and antifouling article, and generally 1 to 10 mm is preferable.

  The substrate preferably has a reactive group on the surface. The reactive group is preferably a hydrophilic group, and the hydrophilic group is preferably a hydroxyl group. In addition, even if the surface is made hydrophilic by subjecting the substrate to oxygen plasma treatment, corona discharge treatment, ozone treatment, etc. to decompose and remove organic substances adhering to the surface or to form a fine uneven structure on the surface. Good. Glass and metal oxide usually have a hydroxyl group on the surface.

  Further, for the purpose of improving the adhesion between the substrate and the water-absorbent resin film, a metal oxide thin film such as silica, alumina, titania, zirconia, or an organic group-containing metal oxide thin film is provided on the surface of the substrate. Good. The metal oxide thin film can be formed by a sol-gel method using a metal compound having a hydrolyzable group. As the metal compound, tetraalkoxysilane and its oligomer, tetraisocyanate silane and its oligomer are preferable. The organic group-containing metal oxide thin film is a thin film obtained by treating the surface of a substrate with an organometallic coupling agent. As the organometallic coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, or the like can be used, and a silane coupling agent is particularly preferable.

The water absorbent resin film in the present invention is made of a water absorbent resin provided on the surface of the substrate. The water absorbent resin is a resin having a saturated water absorption of 60 mg / cm ³ or more and a water contact angle of 40 to 90 ° on the surface of the water absorbent resin film at the time of saturated water absorption. When the water-absorbent resin satisfies the conditions of the saturated water absorption amount and the water contact angle, both antifogging properties and antifouling properties can be achieved. Furthermore, the durability of the water absorbent resin film is also improved, which is preferable.

The saturated water absorption is a value calculated by the following procedure. The antifogging and antifouling article is allowed to stand in an environment of room temperature and relative humidity of 50% for 1 hour, and then the surface of the water absorbent resin film is exposed to 40 ° C. warm water vapor so that the surface of the water absorbent resin film is cloudy or water. Immediately after the film is distorted, the moisture content (A) of the entire antifogging and antifouling article is measured using a trace moisture meter. Separately, the moisture content (B) of the substrate itself on which the water absorbent resin film is not formed is measured in the same procedure, and the value obtained by subtracting the moisture content (B) from the moisture content (A) is divided by the volume of the water absorbent resin. The value obtained was taken as the saturated water absorption.
In the measurement of the amount of water with a micro moisture meter, the test sample was heated at 120 ° C., the moisture released from the sample was adsorbed on the molecular sieve in the micro moisture meter, and the weight change of the molecular sieve was used as the moisture content. The end point of measurement is when the amount of change in weight per minute becomes 0.02 mg or less.

The water contact angle at the time of saturated water absorption is a value measured by using an automatic contact angle measuring device (manufactured by CRUSS) with 2 μL of water attached to the surface of the water absorbent resin film at the time of saturated water absorption. In the present invention, “at the time of saturated water absorption” refers to the following state.
The antifogging and antifouling article is completely immersed in water (tap water, distilled water, etc.) and left for 10 minutes. Next, the antifogging and antifouling article is taken out, and the water adhering to the surface of the water absorbent resin is removed by blowing. Next, it evaluates with an anti-fogging performance evaluation apparatus, confirms that it is cloudy immediately, and makes the state into the time of saturated water absorption. In addition, evaluation of anti-fogging performance is explained in full detail in an Example.

The saturated water absorption amount is 75 to 185 mg / cm ³ from the viewpoint that both anti-fogging performance and durability (abrasion resistance, water resistance, heat resistance, moisture resistance, water wiping resistance, etc.) can be achieved. 90 to 155 μg / cm ³ is particularly preferable.

  The water contact angle at the time of saturated water absorption is 40 to 90 °, and preferably 60 to 80 °. When the water contact angle is 40 to 90 °, when the anti-fogging and antifouling article of the present invention is used for a window member for transportation equipment, there is an effect of suppressing the visibility hindrance and the occurrence of flushing due to the generation of a water film. Since the water contact angle on the surface of a general water-absorbent resin film at the time of saturated water absorption is about 110 ° at the maximum, the water droplets stay on the substrate surface at the time of saturated water absorption. Therefore, when the water contact angle is larger than 90 ° (greater than 90 ° and smaller than about 110 °), the scattered light is significantly scattered, and flashing may occur, which may reduce the visibility. Since there is no device such as a wiper for removing water droplets on the vehicle inner surface side of the base, if any flushing occurs, the visual field can be immediately affected. When the upper limit value of the water contact angle at the time of saturated water absorption is 90 °, a small amount of flushing can be sufficiently suppressed. Further, if the water contact angle at the time of saturated water absorption is less than 40 °, there is a risk of seeing distortion due to the water film being formed by the water that the resin film could not absorb.

Such a water-absorbing resin is not particularly limited, and for example, among the resins shown below, resins satisfying the above-described conditions of the saturated water absorption amount and the contact angle can be used.
Starch resins such as starch-acrylonitrile graft polymer hydrolyzate, starch-acrylic acid graft polymer composites, etc .; cellulose resins such as cellulose-acrylonitrile graft polymer, carboxymethyl cellulose cross-linked products; polyvinyl alcohol cross-linked polymers Polyvinyl alcohol resin such as polyacrylic acid sodium crosslinked product, polyacrylic acid ester crosslinked product, etc .; Polyethylene glycol diacrylate crosslinked polymer, polyether resin such as polyalkylene oxide-polycarboxylic acid crosslinked product A cross-linked polyurethane which is a reaction product of polyether polyol or polyester polyol and polyisocyanate;

  In addition, as a water absorbing resin film in this invention, it is preferable that the change of the haze value before and behind the test by the abrasion resistance test implemented according to JISR3212 is 20% or less.

  The water-absorbent resin in the present invention may be a linear polymer or a non-linear polymer having a three-dimensional network structure, and the latter is preferable because of its excellent durability. The latter is preferably one in which linear polymer chains are bonded to form a three-dimensional network structure.

  As a method of providing a water-absorbing resin film on the surface of the substrate, (1) a method of reacting a film-forming material on the surface of the substrate, (2) a water-absorbing resin is obtained using the film-forming material, and the water-absorbing resin is formed into a film And (3) a method of applying a water-absorbing resin to the surface of the substrate, and the like. Among these methods, the methods (1) and (2) are preferable, the adhesion to the substrate is excellent and the durability is good, the case where a water-absorbing resin layer is provided on the surface of a large substrate, or industrial The method (1) is particularly preferred because it can maintain a good appearance during mass production.

  Hereinafter, a method of providing a water-absorbing resin film, which is a non-linear polymer having a three-dimensional network structure, on the substrate surface by the method (1) will be described. Hereinafter, a non-linear polymer having a three-dimensional network structure is referred to as “crosslinked resin”.

  The film-forming material is a material for obtaining a water-absorbent resin film, and is a composition containing a crosslinkable resin and a crosslinking agent as essential components. The film-forming material preferably further contains a coupling agent for improving the adhesion between the substrate surface and the crosslinked resin, and a solvent for improving the coating workability. Therefore, as a method of providing a water-absorbing resin film (water-absorbing cross-linked resin layer) on the substrate surface, a liquid composition containing a cross-linkable resin, a cross-linking agent, a coupling agent and a solvent is applied to the substrate surface and dried. The reaction method is particularly preferred. In addition, after reacting a crosslinkable resin and a crosslinking agent in a solvent, a liquid composition obtained by adding a coupling agent is applied to the surface of the substrate, followed by drying and further reacting; A method in which a liquid composition obtained by reacting in a solution containing a crosslinking agent and a coupling agent is applied to the surface of the substrate, dried, and further reacted is also preferred.

  The crosslinkable resin in the present invention is not particularly limited as long as it is a polymer having a crosslinkable group and can react with a crosslinker to form a crosslinkable resin. The polymer having a crosslinkable group is preferably a linear polymer. Examples of the crosslinkable group include vinyl group, epoxy group, styryl group, acryloyloxy group, methacryloyloxy group, amino group, ureido group, chloro group, thiol group, sulfide group, hydroxyl group, carboxyl group, and acid anhydride group. A carboxyl group, an epoxy group, a hydroxyl group, and the like are preferable, and a carboxyl group is particularly preferable. The number of crosslinkable groups possessed by the crosslinkable resin may be any number as long as the antifogging performance and durability required in the present invention are satisfied, and is usually 0.1 to 3.0 mmol per 1 g of the crosslinkable resin. Preferably there is.

  As such a crosslinkable resin, a vinyl polymer having a crosslinkable group as described above (hereinafter referred to as a crosslinkable vinyl polymer) is preferable. In the present invention, the crosslinkable vinyl polymer refers to a polymer having a main chain formed by polymerization of a monomer having a polymerizable site containing a carbon-carbon double bond. The crosslinkable vinyl polymer is preferably a linear polymer. Moreover, it is preferable that the crosslinkable vinyl polymer has a hydrophilic group or a hydrophilic polymer chain in that a crosslinked resin having high water absorption can be obtained.

  The crosslinkable vinyl polymer is preferably a crosslinkable vinyl polymer having a cationic group and a crosslinkable group. Therefore, the cross-linked resin in the present invention is preferably a cross-linked resin obtained by a reaction between a cross-linkable vinyl polymer having a cationic group and a cross-linkable group and a cross-linking agent. As the cationic group, a group having a quaternary ammonium structure is preferable. The crosslinkable group is not particularly limited as long as it is a group that can react with the reactive group possessed by the crosslinker to form a three-dimensional network structure. Examples of the crosslinkable group include the crosslinkable groups described above, and a carboxyl group, an epoxy group, a hydroxyl group, and the like are preferable, and a carboxyl group is particularly preferable.

  The molecular weight of the crosslinkable vinyl polymer is not particularly limited, but the number average molecular weight is preferably 500 to 50,000, and particularly preferably 1,000 to 20,000. When the molecular weight is less than 500, the antifogging and antifouling performance may be lowered. On the other hand, if the molecular weight exceeds 50000, the adhesion between the substrate and the crosslinked resin may be reduced.

  The proportion of the cationic group in the crosslinkable vinyl polymer is preferably 0.4 to 2.0 mmol, and particularly preferably 0.5 to 1.5 mmol, per 1 g of the polymer. Furthermore, the ratio of the crosslinkable group is preferably from 0.1 to 3.0 mmol, particularly preferably from 1.0 to 3.0 mmol, particularly preferably from 1.5 to 2.5 mmol per 1 g of the polymer.

  The crosslinkable vinyl polymer includes a monomer unit having a cationic group and a monomer unit having a crosslinkable group. Further, it usually further contains other monomer units other than these monomer units. Other monomer units are used to control the amount of cationic groups and crosslinkable groups in the crosslinkable vinyl polymer and to adjust the physical and chemical properties of the crosslinkable vinyl polymer and the crosslinkable resin it crosslinks. The

  The monomer unit having a cationic group is preferably a monomer unit having a quaternary ammonium structure as a cationic group, and particularly preferably an unsaturated carboxylic acid ester monomer unit (U1) having a quaternary ammonium structure. .

  The other monomer unit is preferably a monomer unit having a hydrocarbon group, and particularly preferably a monomer unit (U2) of an unsaturated carboxylic acid ester monomer having a hydrocarbon group.

  The monomer unit having a crosslinkable group is preferably a monomer unit having a carboxyl group as a crosslinkable group, and particularly preferably a monomer unit (U3) of an unsaturated carboxylic acid monomer.

  The monomer unit in the crosslinkable vinyl polymer means a unit formed by polymerization of the monomer, and the specific monomer unit is expressed as “monomer unit of (monomer name)” or simply “specific monomer name” unit. ". The monomer unit means a monomer unit directly formed by polymerization of the monomer (the chemical structure other than the unsaturated double bond portion is the same as the monomer). In the present invention, the polymer is further chemically converted after polymerization. In some cases, even if the monomer unit portion is chemically changed, the unit of the monomer unit before chemical conversion is also referred to as a monomer unit. For example, after forming a polymer using an unsaturated carboxylic acid ester as a monomer, the monomer unit can be hydrolyzed to a monomer unit having a carboxyl group. Similarly, after forming a polymer using an unsaturated carboxylic acid as a monomer, the carboxyl group of the monomer unit can be alkylesterified to form a monomer unit having an alkyl group (one kind of hydrocarbon group). In addition, the original monomer that gave the monomer unit is simply referred to as “monomer unit monomer”.

  The monomers of the monomer units (U1) to (U3) are hereinafter referred to as monomers (M1) to (M3), respectively. As unsaturated carboxylic acid of a monomer (M3), unsaturated aliphatic carboxylic acid is preferable and acrylic acid and methacrylic acid are especially preferable. As unsaturated carboxylic acid ester of monomers (M1) and (M2), unsaturated aliphatic carboxylic acid ester is preferable, and acrylic acid ester and methacrylic acid ester are particularly preferable.

  The content of the monomer unit (U1) in the crosslinkable vinyl polymer is preferably 5 mol% or more, particularly preferably 15 to 50 mol%, based on all monomer units constituting the crosslinkable vinyl polymer. . The content of the monomer unit (U2) is preferably 10 mol% or more, particularly preferably 20 to 80 mol%, based on all monomer units. The content of the monomer unit (U3) is preferably 1 to 20 mol%, particularly preferably 10 to 20 mol%, based on all monomer units.

  The crosslinkable vinyl polymer can be obtained by copolymerizing monomers including monomers (M1) to (M3). The copolymer may be either a block copolymer or a random copolymer. The polymerization reaction for obtaining the crosslinkable vinyl polymer is preferably based on a thermal polymerization reaction. When performing the thermal polymerization reaction, it is preferable to use a polymerization catalyst such as azobisisobutyronitrile.

The monomer unit (U1) is preferably a monomer unit of a monomer represented by the following formula (1). That is, the monomer (M1) is preferably a monomer represented by the following formula (1).
^{_{CH 2 = CR 1 -COO- (CH}} 2) m -N + R 2 R 3 R 4 X - ··· (1)
In Formula (1), R ¹ is a hydrogen atom or a methyl group, and is preferably a methyl group because it is effective for improving the water resistance of the resulting water-absorbent crosslinked resin.
R ² , R ³ , and R ⁴ are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 9 carbon atoms. When R ² , R ³ , and R ⁴ are the latter group, it may be a linear structure or a branched structure, and is preferably a linear structure. Moreover, it is preferable that it is an unsubstituted group. When it has a substituent, the substituent is preferably an alkoxy group, an aryl group, or a halogen atom. As an alkoxy group, a methoxy group and an ethoxy group are preferable. The aryl group is preferably a phenyl group. As a halogen atom, a fluorine atom and a chlorine atom are preferable. “C1-9” means that the alkyl group part excluding the substituent part has 1-9 carbon atoms.

R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, a methyl group, or an ethyl group. These groups may be the same group or different groups. R ² , R ³ , and R ⁴ are preferably all methyl groups, and one of them is preferably a hydrogen atom, and the other two are methyl groups.

X ⁻ is a monovalent anion, and includes F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , and p-CH ₃ C ₆ H ₄ SO ₃ ^— , and retains water inside the crosslinked resin layer that governs water absorption. F ⁻ and Cl ⁻ are preferable because it is easy to secure a space to be used.
m is an integer of 1 to 10 and is preferably 2 to 5 because it is easy to achieve both anti-fogging and antifouling performance and durability.

As the monomer (M1), the following monomers are preferable.
_{CH 2 = CH-COO- (CH} 2) 2 -N + H (CH 3) 2 Cl - ··· (1A),
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -N + H (CH 3) 2 Cl - ··· (1B),
_{CH 2 = CH-COO- (CH} 2) 2 -N + (CH 3) 3 Cl - ··· (1C),
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -N + (CH 3) 3 Cl - ··· (1D).

The monomer unit (U2) is preferably a monomer unit of a monomer represented by the following formula (2). That is, as the monomer (M2), a monomer represented by the following formula (2) is preferable.
_{^{CH 2 = CR 5 -COOR 7 ···}} (2)
However, the symbols in the formulas have the following meanings.
R ⁵ : a hydrogen atom or a methyl group.
R ⁷ : an alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an aryl group, or an arylalkyl group.

R ⁵ is preferably a methyl group because it is effective for improving the water resistance of the resulting water-absorbent crosslinked resin. When R ⁷ is an alkyl group having 1 to 30 carbon atoms, it may be a linear structure or a branched structure, and is preferably a linear structure. As a C1-C30 alkyl group, a C1-C20 alkyl group is preferable, a C1-C10 alkyl group is especially preferable, and a methyl group, an ethyl group, and a propyl group are especially preferable. When R ⁷ is an alkoxyalkyl group having 2 to 8 carbon atoms, the alkyl group moiety preferably has 1 to 4 carbon atoms, and the alkoxy group moiety substituted on the alkyl group preferably has 1 to 4 carbon atoms. . When R ⁷ is an alkoxyalkyl group having 2 to 8 carbon atoms, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a methoxypropyl group can be preferably used.
When R ⁷ is an aryl group, a phenyl group and a tolyl group are preferable. When R ⁷ is an arylalkyl group, a benzyl group is preferred.

As the monomer (M2), the following monomers are preferable.
_{CH 2 = CH-COOCH 3 ···} (2A)
_{CH 2 = C (CH 3)} -COOCH 3 ··· (2B)
_{CH 2 = CH-COO- (CH} 2) 2 -OCH 3 ··· (2C)
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -OCH 3 ··· (2D).

As a monomer unit (U3), the monomer unit of the monomer represented by the following Formula (3) is mentioned.
^{_{CH 2 = CR 8 -COOH ··· (}} 3)
However, R ⁸ in the formula represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. When R ⁸ is a hydrogen atom, the polymerization reaction for obtaining a crosslinkable vinyl polymer proceeds rapidly, and the yield of the polymerization reaction is also good. This is thought to be because the steric hindrance at the site involved in the polymerization reaction is reduced.

  As the monomer (M3), an unsaturated dicarboxylic acid and an anhydride of an unsaturated dicarboxylic acid can be used in addition to the monomer represented by the formula (3). Examples of the unsaturated dicarboxylic acid include maleic acid and fumaric acid. Examples of anhydrides of unsaturated dicarboxylic acids include maleic anhydride. As the monomer (M3), a monomer represented by the formula (3) is preferable.

  The cross-linking agent in the present invention is a compound that reacts with the cross-linkable resin to form a cross-linked resin having a three-dimensional network structure, and has a reactive group that can react with the cross-linkable group of the cross-linkable resin. . By using the cross-linking agent, the reactive group possessed by the cross-linking agent reacts with the reactive group present on the substrate surface and the cross-linkable group possessed by the cross-linking resin, so that a strong cross-linked resin layer can be formed on the base surface. . In some cases, a crosslinking agent may impart water absorption to the crosslinked resin.

  The reactive group of the crosslinking agent is selected from reactive groups capable of reacting with the crosslinking group depending on the type of the crosslinking group of the crosslinking resin combined with the crosslinking agent. Examples of the reactive group include vinyl group, epoxy group, styryl group, acryloyloxy group, methacryloyloxy group, amino group, ureido group, chloropropyl group, mercapto group, sulfide group, isocyanate group, hydroxyl group, carboxyl group, and acid anhydride. Examples include physical groups. For example, when the crosslinkable group of the crosslinkable resin is a carboxyl group, an epoxy group or an amino group is preferable, and an epoxy group is particularly preferable. When the crosslinkable group is a hydroxyl group, an epoxy group or an isocyanate group is preferable. When the crosslinkable group is an epoxy group, a carboxyl group, an amino group, an acid anhydride group, or a hydroxyl group is preferable. Moreover, the number of the reactive groups which 1 molecule | numerator of a crosslinking agent has is 1.5 or more on average, and it is preferable that it is 2-8. When the number of reactive groups is within the above range, a water-absorbing crosslinked resin having an excellent balance of antifogging property, antifouling property and abrasion resistance can be obtained.

  Two or more crosslinking agents can be used in combination. For example, the second crosslinking agent can be used in combination with the main crosslinking agent. This second crosslinker is not only a reactive group that reacts with the crosslinkable group of the crosslinkable resin (may be the same reactive group as the main crosslinking agent or a different reactive group), It may be a compound having a reactive group that reacts with the reactive group of the main crosslinking agent. The second crosslinking agent that reacts with the main crosslinking agent binds to the crosslinkable resin via the main crosslinking agent. By using such a second cross-linking agent in combination, the formation of a cross-linked resin by the cross-linkable resin and the main cross-linking agent can be promoted. For example, in a combination of a crosslinkable resin having a carboxyl group and a crosslinker having an epoxy group, a second crosslinker having an amino group or a second crosslinker having an acid anhydride group may be used in combination. Resin formation is promoted. Moreover, this 2nd crosslinking agent can be functioned as a component which adjusts the physical property of crosslinked resin rather than the function which bridge | crosslinks crosslinkable resin. For example, the water absorption of the crosslinked resin can be increased by the second crosslinking agent.

  Examples of the crosslinking agent in the present invention include polyol compounds, polyamine compounds, polycarboxylic acid compounds (including polycarboxylic acid anhydrides), polyisocyanate compounds, polyepoxy compounds, and the like. These crosslinking agents are selected according to the crosslinkable group of the crosslinkable resin. As a crosslinking agent used for crosslinking of a crosslinkable resin having a carboxyl group, a polyepoxy compound is particularly preferable. It is also preferable to use a polyamine compound, a polycarboxylic acid anhydride, or the like as the second crosslinking agent together with the polyepoxy compound.

  As the polyepoxy compound, an aliphatic polyglycidyl compound is preferable. Specifically, ethylene glycol diglycidyl ether, polyethylene glycol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol polyglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol poly Examples thereof include glycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine and the like. These may use only 1 type and may use 2 or more types together. Among these, since a cross-linked resin having particularly good anti-fogging and anti-fouling performance can be obtained, a polyhydric aliphatic polyol having three or more hydroxyl groups such as glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Glycidyl ether (one having an average number of glycidyl groups exceeding 2 per molecule) is preferred.

  As the polyamine compound, hexamethylenediamine, isophoronediamine, mensendiamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and the like are preferable. As the polycarboxylic acid compound, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride and the like are preferable. As the polyol compound, polyhydric alcohol-ethylene oxide adduct, polyhydric alcohol-propylene oxide adduct, polyester polyol and the like are preferable, and as the polyisocyanate compound, hexamethylene diisocyanate, isophorone diisocyanate and the like are preferable.

  The ratio of the crosslinking agent to the crosslinkable resin is suitably a ratio in which the number of crosslinkable groups and reactive groups is substantially equal, and the equivalent ratio of reactive groups to the crosslinkable group is about 0.8 to 1.2. preferable. However, when there is a reactive compound (for example, a silane coupling agent having an amino group) coexisting with the second crosslinking agent or other crosslinking reaction system, reactive groups including these react with each other. An equivalent ratio of about 0.8 to 1.2 is appropriate. Further, as long as it is a crosslinkable group or a reactive group that may remain in the crosslinked resin, the ratio of the reactive group to the other reactive group may be further increased.

As described above, the second crosslinking agent can be used for adjusting the physical properties of the crosslinked resin in addition to the function of crosslinking the crosslinking resin. For example, by using an amine that reacts with an epoxy-based compound that is a crosslinking agent, a hydrophilic bond in which an epoxy group and an amino group are reacted can be provided to the crosslinked resin. In this case, the function is exhibited even when only one reactive group of the second crosslinking agent is reacted. Moreover, the compound which has one reactive group which can couple | bond with a crosslinkable resin or a crosslinking agent may be used, if the function of physical property adjustment of a crosslinked resin is exhibited. The compound having one reactive group is a compound having no crosslinking function. Hereinafter, the second crosslinking agent used for the purpose of adjusting the function of such a crosslinked resin or a reactive compound having no crosslinking function is referred to as a curing agent. The main crosslinking agent also affects the function of the crosslinked resin, and there is no essential distinction from the second crosslinking agent in that respect.
When using a hardening | curing agent in addition to a crosslinking agent, the usage-amount of a hardening | curing agent has preferable equal mass or less with respect to a crosslinking agent, and 0.01-0.5 times mass is preferable.

  In the present invention, when the crosslinkable resin and the crosslinking agent are reacted on the surface of the substrate, the cohesiveness between the substrate surface and the crosslinked resin can be improved by allowing the coupling agent to coexist. Also, the adhesion between the substrate surface and the crosslinked resin can be improved by treating the substrate surface with a coupling agent in advance as described above. Although it is not essential to add a coupling agent to a coating composition containing a crosslinkable resin and a crosslinking agent for forming a crosslinked resin, even if a substrate previously treated with a coupling agent is used. It is preferable that a coupling agent is present in the coating composition containing the crosslinkable resin and the crosslinking agent. When the coupling agent has a crosslinkable resin or a reactive group with the crosslinker, the purpose of adjusting the function of the crosslinkable resin in addition to improving the adhesion between the crosslinkable resin and the substrate is the same as the curing agent. Can also be used.

  Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent, and a silane coupling agent is preferable. These coupling agents preferably have a reactive group capable of reacting with the crosslinkable group of the crosslinkable resin or the reactive group of the crosslinker.

  As silane coupling agents, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltri Tokishishiran, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. Of these, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl An aminosilane-based silane coupling agent such as trimethoxysilane is preferred.

  The usage amount of the coupling agent in the coating composition containing the crosslinkable resin and the crosslinking agent is not limited because the amount of the coupling agent is not an essential component. However, in order to exhibit the effect of blending the coupling agent, the ratio of the coupling agent to the total of the crosslinkable resin, the crosslinking agent, and the coupling agent is preferably 0.1% by mass or more, and 0.5% by mass or more. More preferred. The upper limit of the amount of coupling agent used is limited by the physical properties and functions of the coupling agent. The ratio of the coupling agent to the total of the crosslinkable resin, the crosslinking agent, and the coupling agent is preferably 10% by mass or less, and more preferably 5% by mass or less. When adjusting the physical properties such as the water absorption of the crosslinked resin and the water contact angle of the surface with the coupling agent or with the crosslinking agent and the coupling agent, a relatively large amount of the coupling agent may be used. In that case, the ratio of the coupling agent to the total of the crosslinkable resin, the crosslinking agent, and the coupling agent is preferably 15% by mass or less, and more preferably 10% by mass or less. When the amount of the coupling agent used is excessive, there may be a problem that the crosslinked resin is likely to be colored due to oxidation or the like when exposed to a high temperature.

The solvent is not particularly limited as long as the solubility of components such as a crosslinkable resin and a crosslinking agent is good, and the solvent is inactive with respect to these components. Alcohols, acetates, ethers , And water, and alcohols and water are preferred. As alcohols, ethanol and isopropyl alcohol are preferable. Only 1 type may be used for a solvent and it may use 2 or more types together.
Moreover, components, such as a crosslinkable resin and a crosslinking agent, may be used as a mixture with a solvent. In this case, the solvent contained in the mixture may be used as a solvent in the liquid composition, or another solvent may be added to form a liquid composition.

  When the cross-linked resin layer is formed using a liquid composition containing a cross-linkable resin, a cross-linking agent, a silane coupling agent and a solvent, they can be appropriately selected and used. For example, combinations (solvents shown below) The description is omitted). Furthermore, the liquid composition preferably contains the curing agent as necessary.

(1) A combination of a crosslinkable resin having a carboxyl group as a crosslinkable group, a crosslinker having an epoxy group, and a silane coupling agent having an amino group,
(2) A combination of a crosslinkable resin having a carboxyl group as a crosslinkable group, a crosslinker having an amino group, and a silane coupling agent having an isocyanate group or an epoxy group.

  The film forming material in the present invention is a film forming material containing a crosslinkable resin and a crosslinking agent, and is preferably a film forming material containing a coupling agent and a solvent. The crosslinkable resin contained in the film forming material is preferably a crosslinkable vinyl polymer, the monomer unit (U1) of the unsaturated carboxylic acid ester monomer having the cationic group, and the unsaturated group having a hydrocarbon group. A cross-linkable vinyl polymer including a monomer unit (U2) of a carboxylic acid ester monomer and a monomer unit (U3) of an unsaturated carboxylic acid monomer is particularly preferable.

  In this film-forming material, the crosslinkable vinyl polymer is preferably contained in an amount of 2 to 20 mol% based on the total of the crosslinkable vinyl polymer, the crosslinker, and the coupling agent. It is preferable that 10-90 mol% of a crosslinking agent is contained with respect to the sum total of a crosslinkable vinyl polymer, a crosslinking agent, and a coupling agent. The coupling agent is preferably contained in an amount of 10 to 90 mol% with respect to the total of the crosslinkable vinyl polymer, the crosslinking agent, and the coupling agent. Moreover, it is preferable that the quantity of a solvent is 0.5-9 times amount with respect to the total amount of a crosslinkable vinyl polymer, a crosslinking agent, and a coupling.

In the present invention, the antifogging and antifouling article is obtained by applying the film-forming material to the substrate surface, drying it, and further reacting it. Here, “drying” means that the solvent in the liquid composition applied to the substrate is volatilized and removed. The drying conditions are appropriately set depending on the type of solvent contained in the liquid composition, the thickness of the coating film, and the like. For example, the substrate coated with the liquid composition is held at 20 to 100 ° C. for 1 minute to 20 hours. Can be implemented.
In addition, the “reaction” means that a crosslinked resin is formed by a reaction between a crosslinkable resin and a crosslinking agent contained in the composition. At this time, it may be accompanied by a bond formation reaction with the substrate surface, and since the durability of the anti-fogging and antifouling article is improved, it is preferably accompanied by a bond formation reaction with the substrate surface. The “reaction” can be carried out, for example, by holding the dried substrate at 80 to 200 ° C. for 1 minute to 1 hour.

Examples of the method for applying the composition to the substrate surface include spin coating, dip coating, spray coating, flow coating, and die coating, and spray coating, flow coating, and die coating are preferable.
The thickness of the composition layer obtained by applying the liquid composition to the substrate surface is preferably 10 to 80 μm, the thickness after drying is preferably 5 to 40 μm, and the crosslinked resin layer obtained after the reaction The thickness of is preferably 5 to 30 μm.

  When the film-forming material in the present invention is applied to a substrate, the thickness of the coating film becomes non-uniform due to the wettability of the film-forming material, which may cause perspective distortion. In order to make the thickness of the coating film uniform, it is preferable to add a leveling agent to the film forming material. Examples of the leveling agent include a silicone-based leveling agent, a fluorine-based leveling agent, and a surfactant, and a silicone-based leveling agent is preferable. Examples of the silicone leveling agent include amino-modified silicone, carbonyl-modified silicone, epoxy-modified silicone, polyether-modified silicone, and alkoxy-modified silicone, and amino-modified silicone and polyether-modified silicone are preferable.

  In addition, a silicone leveling agent having an oxyalkylene chain such as an oxyethylene chain or an oxypropylene chain is also preferred because it can impart hydrophilicity to the film-forming material and improve the antifogging performance.

These silicone leveling agents may or may not have reactive groups, but they can be part of the structure of the water absorbent resin film and contribute to antifogging properties. It is preferable that the silicone has a reactive group. Specifically, a reactive dimethyl silicone oil having at least one reactive group is preferable, and examples include polyoxyalkylene amino-modified dimethyl polysiloxane copolymer (manufactured by Nippon Unicar Co., Ltd., product number: FZ-3789).
Furthermore, lubricity can be given to the surface of the water-absorbent resin film by adding these silicones. As a result, an effect of reducing film deterioration caused by abrasion due to cloth or solid matter can be obtained.

  The addition amount of the silicone leveling agent can improve wettability and make the thickness of the coating film uniform by setting it to 1% by mass or less with respect to the total amount of the crosslinkable resin and the crosslinker. If the amount of the silicone leveling agent added is too large, the coating film may become cloudy, so 0.02 to 0.30 mass% is preferable, and 0.02 to 0.10 mass% is particularly preferable.

  The film forming material in the present invention preferably further contains a curing agent. By including the curing agent, the reaction between the crosslinkable resin and the crosslinking agent contained in the film forming material is promoted, and the crosslinking density of the crosslinked resin is increased. Therefore, it is preferable because durability of the crosslinked resin such as wear resistance and water resistance can be improved. Also, in order to impart functions and properties to the crosslinked resin that cannot be imparted only with the crosslinkable resin or the crosslinking agent, and to improve the functions and properties of the crosslinked resin that is not sufficient with only the crosslinkable resin or the crosslinking agent, curing is performed. Agents can also be used. The curing agent is appropriately selected depending on components such as a crosslinkable resin and a crosslinker. When the crosslinkable resin is a resin having a carboxyl group and the crosslinker is a crosslinker having an epoxy group, diamines and acid anhydrides are preferable.

In the anti-fogging and antifouling article of the present invention, the water absorbent resin film provided on the substrate surface has a saturated water absorption of 60 mg / cm ³ and a water contact angle of 40 to 90 ° during saturated water absorption. Therefore, it is possible to exhibit good antifogging performance and antifouling performance at the same time, and excellent durability. Further, the anti-fogging and antifouling article of the present invention is a crosslinked resin obtained by reacting a water-absorbing resin provided on the substrate surface with a crosslinking agent having a cationic group and a crosslinking group and a crosslinking agent. By being, it has good anti-fogging and antifouling performance and is excellent in durability. Furthermore, the water-absorbing resin constituting the anti-fogging and anti-fouling article of the present invention satisfies the water contact angle and saturated water absorption conditions, and is obtained by a reaction between a cross-linkable vinyl polymer and a cross-linking agent. When it is, antifogging performance and antifouling performance are further improved, and durability can be further improved.

  Examples of the anti-fogging and antifouling article of the present invention include window glass for transport equipment (automobiles, railways, ships, airplanes, etc.), refrigerated showcases, mirrors for bathroom vanities, mirrors for bathrooms, optical equipment and the like. Moreover, since the film forming material in the present invention has good anti-fogging and antifouling performance and excellent durability, it is useful for obtaining the above antifogging and antifouling article.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[1] Preparation of film-forming material In a glass container in which a stirrer and a thermometer are set, a mixture of a crosslinkable vinyl polymer and a solvent (trade name: Jurimer SPO-601, manufactured by Nippon Pure Chemical Industries, Ltd.) (36.0 g) Put glycerol polyglycidyl ether having an average epoxy functional group number of 2.3 (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX-314) (10.8 g), and isophoronediamine (manufactured by Tokyo Chemical Industry) (2.76 g). And stirred at 25 ° C. for 1 hour. Next, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM602) (2.0 g) was added, and the mixture was further stirred for 30 minutes. Next, tetraethyl silicate (manufactured by Junsei Chemical) (0.4 g) and ethanol (manufactured by Junsei Chemical) (92.8 g) were added, and the mixture was further stirred for 30 minutes. Next, polyoxyalkyleneamino-modified dimethylpolysiloxane copolymer (manufactured by Nippon Unicar Co., Ltd., product number: FZ-3789) (0.043 g) was added, and the mixture was further stirred for 30 minutes to obtain a film forming material. In addition, it is thought that Jurimer SPO-601 is obtained by thermally polymerizing ethyl trimethyl ammonium chloride, methoxyethyl acrylate, methyl methacrylate, and acrylic acid in a solvent.

[2] Production and Evaluation of Antifogging and Antifouling Article [2-1] Production of Antifogging and Antifouling Article Using the film forming material obtained in [1] with a nozzle flow coat, a driver seat on the inner surface of an automobile windshield It was applied to the side half surface and heated in a flat state at 110 ° C. for 60 minutes to obtain an automotive windshield having a water absorbent resin film formed on only the half surface. The windshield was attached to the car.

[2-2] Evaluation of antifouling performance The automobile described in [2-1] was used for 8 months under conditions in which a normal automobile was used. During the period of use (8 months), no measures such as wiping the inner surface of the windshield are taken. After 8 months, the degree of adhesion and white turbidity on the inner surface of the windshield was visually evaluated. The part where the water-absorbing resin film was formed was free from dirt and clouded, but the part where the water-absorbing resin film was not formed was soiled and the glass was thin and cloudy. Moreover, when the inner surface of the windshield was wiped with a clean white paper waste, there was no deposit on the paper waste in the part where the water absorbent resin film was formed, but the part where the water absorbent resin film was not formed. Then, dark gray dirt adhered.

[2-3] Evaluation of anti-fogging performance Four people got on the car described in [2-1] and ran with the air conditioner turned off in the winter at a temperature of 0 ° C., and a water-absorbing resin film was formed. The part where no water-absorbent resin film was formed was clouded until 20 minutes, whereas the part where the water-absorbent resin film was formed was clouded in about 5 minutes. Further, after the antifogging and antifouling article produced by the same method as [2-1] is left in an environment of room temperature relative humidity 50% for 1 hour, the surface of the water absorbent resin film is placed on a 40 ° C. hot water bath. On the other hand, when the antifogging time until cloudiness or distortion due to a water film was observed was measured, the antifogging time was 50 seconds (0.83 minutes). In addition, the normal glass produced cloudiness in 0.01 to 0.08 minutes.

[3] Evaluation of contact angle and saturated water absorption at the time of saturated water absorption of the anti-fogging and antifouling article [3-1] Evaluation of contact angle at the time of saturated water absorption The film-forming material obtained in [1] is obtained as flat soda lime. It was applied to glass (30 cm × 30 cm) by a flow coating method, dried and fired. A 10 cm × 10 cm sample was cut out from the center of the glass. After immersing the sample in room temperature tap water for 10 minutes, remove it from the water, blow off the water droplets remaining on the surface of the water-absorbent resin with an air gun, immediately drop 2 μL of water droplets on the surface of the water-absorbent resin, and contact the water droplets. The corner was measured. The measurement was performed at 5 points, and the average value was 87.2 °. In addition, when the contact angle is measured, “at the time of saturated water absorption”, a sample prepared separately in the same procedure is subjected to the same treatment (immersion in tap water to air blow) as shown in the following prevention. It evaluated and confirmed using the haze performance evaluation apparatus.

<Anti-fogging performance evaluation device>
FIG. 1 shows an anti-fogging performance evaluation device. This apparatus includes an anti-fogging and antifouling article 1, a high-humidity tank 2, a water bath 4 (WK-40 manufactured by Shibata Chemical Instruments Co., Ltd.), a CCD camera 6 (CV-070 manufactured by Keyence Corporation), and a display 7 ( Keyence CV-M10).

  The high-humidity tank 2 does not have an upper surface and a lower surface, has only a side surface, and is made of a polycarbonate material having a thickness of 2 mm. The size is 70 × 70 × 70 mm. The high-humidity tank 2 and the water bath 4 are partitioned by a partition 3 made of soda lime glass having a thickness of 3.5 mm and having a 20 × 20 mm hole in the center. Water vapor generated in the water bath 4 enters the high-humidity tank 2 through the holes in the partition 3. The distance from the water surface of the water bath 4 to the partition 3 was 15 mm, and the water temperature was set to 35 ° C. These conditions were determined in consideration of a phenomenon in which water vapor evaporated from an occupant, clothes, and the like riding on the vehicle is about 36 ° C., and the water vapor gradually fills the passenger compartment space. An anti-fogging and antifouling article 1 that has been immersed in tap water for 10 minutes on the high-humidity tank 2 and splashed water droplets on the surface is disposed. did.

[3-2] Evaluation of saturated water absorption The saturated water absorption measured by the following procedure was 106.7 mg / cm ³ .
<Evaluation procedure for saturated water absorption>
The antifogging and antifouling article is allowed to stand for 1 hour in an environment of room temperature and relative humidity of 50%, then the surface of the water absorbent resin film is exposed to 40 ° C. warm water vapor, and the surface of the water absorbent resin film is cloudy or water film Immediately after the occurrence of distortion due to, the moisture content (A) of the entire anti-fogging and antifouling article is measured using a trace moisture meter. Separately, the moisture content (B) of the substrate itself on which the water absorbent resin film is not formed is measured in the same procedure, and the value obtained by subtracting the moisture content (B) from the moisture content (A) is the volume of the water absorbent resin film. The value obtained by dividing was taken as the saturated water absorption. The moisture content was measured with a micro moisture meter (manufactured by Kett Science Laboratory, product number: FM-300). The test sample was heated at 120 ° C., and the moisture released from the sample was adsorbed on the molecular sieves in the trace moisture meter, and the weight change of the molecular sieves was taken as the moisture content. The end point of the measurement was when the amount of change in weight per minute was 0.02 mg or less.

  Since the anti-fogging and antifouling article of the present invention has excellent antifogging and antifouling properties and has durability, window glass for transport equipment (automobiles, railways, ships, airplanes, etc.), refrigerated showcases It can be used for vanity mirrors, bathroom mirrors, optical equipment, etc.

Schematic of an anti-fogging performance evaluation apparatus.

Explanation of symbols

1: Antifogging and antifouling article 2: High humidity tank 3: Partition 4: Water bath 5: Incident angle of CCD camera 6: CCD camera 7: Display

Claims (5)

An anti-fogging and antifouling article having a substrate and a water absorbent resin film provided on the surface of the substrate, wherein the water absorbent resin film has a saturated water absorption of 60 mg / cm ³ or more, and at the time of saturated water absorption. An antifogging and antifouling article, wherein the water contact angle of the surface of the water absorbent resin film is 40 to 90 °.   The anti-fogging and antifouling article according to claim 1, wherein the water-absorbing resin film is a resin film formed by reacting a film forming material on the surface of a substrate.   The antifogging and antifouling article according to claim 2, wherein the film forming material is a film forming material containing a crosslinkable resin and a crosslinking agent.   The anti-fogging and antifouling article according to claim 2 or 3, wherein the film-forming material further contains 1% by mass or less of silicone with respect to the total amount of the crosslinkable resin and the crosslinking agent. The anti-fogging and antifouling article according to any one of claims 1 to 4, wherein the antifogging and antifouling article is a glass plate for automobile windows.

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