JP2007237728A - Clouding resistant article and clouding resistant agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clouding resistant article and a clouding resistant agent composition having excellent clouding resistant property and excellent durability. <P>SOLUTION: The clouding resistant article has a base body and a water absorbent crosslinking resin layer arranged on the surface of the base body, a water contact angle of the surface of the water-absorbent crosslinking resin is 30&deg; or more (here the measured value two minutes after contacting with a water drop), and the saturated water absorbent quantity of the same in 60 mg/cm<SP>3</SP>or more. The clouding resistant composition being a liquid composition for forming the clouding resistant crosslinking resin layer of the surface of the base body by coating the same on the surface of the base body, drying and reacting the same, includes a crosslinkable vinyl polymer including a monomer unit (U1) of an unsaturated carboxylate ester based monomer having a cationic group and a monomer unit (U2) of an unsaturated carboxylate ester base monomer having a hydrocarbon group and a monomer unit (U3) of an unsaturated carboxylic acid based monomer, a crosslinking agent and a solvent. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to an antifogging article and an antifogging agent composition.

Transparent substrates such as glass and plastic, when the substrate surface falls below the dew point temperature, cause fine water droplets to adhere to the surface and scatter the transmitted light, resulting in a loss of transparency and a so-called “cloudy” state. . Various proposals have been made as a means for preventing fogging.
(1) A method of reducing the surface tension by treating a surface of a substrate with a surfactant (for example, see Patent Document 1),
(2) A method of making a substrate surface hydrophilic by treating the substrate surface with a hydrophilic compound (see, for example, Patent Documents 2 and 3),
(3) A method of reducing the atmospheric humidity on the substrate surface by treating the substrate surface with a water-absorbing compound (see, for example, Patent Document 4),
(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 of treating the surface of the substrate with a water-repellent compound so that minute water droplets do not adhere to the surface of the substrate.

  Further, the effect of preventing fogging (hereinafter referred to as “anti-fogging performance”) is required to last for a long time in the use environment. Furthermore, durability such as abrasion resistance, water resistance, heat resistance, moisture resistance, and water wiping resistance is also required in order to maintain the antifogging performance for a long time under various environments.

  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), for example, a hydrophilic resin or a hydrophilic inorganic compound is used. However, in any case, it is particularly easy to adsorb and fix inorganic soil, and it is difficult to maintain hydrophilicity for a long time.

In the method (3), for example, a water absorbent resin is used. Although the water-absorbing resin is inferior in wear resistance and weather resistance compared to inorganic compounds, if the resin surface is designed to be hydrophobic, it is particularly effective in preventing inorganic stains and easily exhibits anti-fogging performance over a long period of time. Can be maintained. In the method (4), the antifogging performance can be maintained semipermanently, but it is very expensive because it always requires energy accompanying energization. In the method (5), water repellency is required in order to develop anti-fogging performance, so that water droplets with a diameter of 1 mm or less can be slid down or not adhered, but there is no such technique at present.
Therefore, the present inventors considered that the method using the water-absorbent resin (3) can easily maintain the antifogging performance at low cost. As a method using a water-absorbent resin, a coating agent and an antifogging film for forming a urethane resin in which a surfactant and trialkanolamine are fixed are disclosed in order to achieve both antifogging performance and wear resistance ( (See Patent Document 5).

JP 2003-238207 A JP 2001-356201 A JP 2000-192021 A Japanese Patent Laid-Open No. 2002-53792 JP 2004-269851 A

  However, the antifogging resin film disclosed in Patent Document 5 has a problem that it is difficult to maintain excellent antifogging performance over a long period of time.

The present invention has been made to solve the above problems, and provides the following inventions.
<1> An antifogging article having a substrate and a water-absorbing crosslinked resin layer provided on the surface of the substrate, wherein the water-absorbing crosslinked resin has a water contact angle of 30 ° or more on the surface (however, An anti-fogging article characterized by being a crosslinked resin having a saturated water absorption of 60 mg / cm ³ or more.
<2> The antifogging article according to <1>, wherein the crosslinked resin layer is a resin layer formed by reacting a crosslinkable resin and a crosslinking agent on the substrate surface.
<3> The cross-linked resin layer is a resin layer formed by applying a liquid composition containing a cross-linkable resin, a cross-linking agent, a silane coupling agent, and a solvent to a substrate surface, drying, and reacting, <1 > Or <2>.

<4> An antifogging article having a substrate and a water-absorbing crosslinked resin layer provided on the surface of the substrate, wherein the water-absorbing crosslinked resin has a cationic group and a crosslinking group. An antifogging article, which is a crosslinked resin obtained by a reaction between a polymer and a crosslinking agent.
<5> The antifogging article according to <4>, wherein the crosslinkable group is a carboxyl group.
<6> The crosslinkable vinyl polymer according to <4> or <5>, wherein the crosslinkable vinyl polymer is a crosslinkable vinyl polymer including a monomer unit having a cationic group, a monomer unit having a hydrocarbon group, and a monomer unit having a carboxyl group. Anti-fogging article.

<7> The antifogging article according to <5> or <6>, wherein the crosslinking agent is an epoxy-based crosslinking agent having two or more epoxy groups.
<8> A resin layer formed by applying a liquid composition containing a crosslinkable vinyl polymer, a crosslinking agent, a silane coupling agent, and a solvent to a substrate surface, drying, and reacting the water absorbing crosslinked resin layer. The antifogging article according to any one of <4> to <7>.

<9> An antifogging article having a base and a cross-linked resin layer provided on the surface of the base, wherein the cross-linked resin is a cross-linked resin obtained by a reaction between a cross-linkable vinyl polymer and a cross-linking agent. Of the unsaturated carboxylic acid ester monomer having a cationic group (U1), the unsaturated carboxylic acid ester monomer unit having a hydrocarbon group (U2), and the unsaturated carboxylic acid monomer An antifogging article, which is a crosslinkable vinyl polymer containing a monomer unit (U3).
<10> The crosslinkable vinyl polymer is 5 mol% or more of monomer units (U1), 10 mol% or more of monomer units (U2), and 1 to 20 mol% of monomer units (all monomer units). The antifogging article according to <9>, comprising U3).

<11> The antifogging article according to <9> or <10>, wherein the monomer unit (U1) is a monomer unit of 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)
However, the symbols in the formulas have the following meanings.
R ¹ : a hydrogen atom or a methyl group.
R ² , R ³ , R ⁴ : each independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a substituent.
X ⁻ : a monovalent anion.
m: An integer from 1 to 10.

<12> The antifogging article according to any one of <9> to <11>, wherein the crosslinking agent is an epoxy crosslinking agent having two or more epoxy groups.
<13> The cross-linked resin layer is a resin layer formed by applying a liquid composition containing a cross-linkable vinyl polymer, a cross-linking agent, a silane coupling agent, and a solvent to the substrate surface, drying, and reacting. The antifogging article according to any one of 9> to <12>.

<14> A liquid composition for forming an antifogging cross-linked resin layer on the surface of the substrate by applying to the surface of the substrate, drying and reacting, and an unsaturated carboxylic acid ester monomer having a cationic group Crosslinkable vinyl polymer comprising monomer unit (U1), monomer unit (U2) of unsaturated carboxylic acid ester monomer having hydrocarbon group and monomer unit (U3) of unsaturated carboxylic acid monomer, crosslinking agent, and solvent An antifogging agent composition comprising:
<15> The antifogging agent composition according to <14>, further comprising a silane coupling agent.
<16> The antifogging composition according to <14> or <15>, further comprising a silicone leveling agent.

  The anti-fogging article of the present invention has excellent anti-fogging performance and durability such as wear resistance, water resistance, moisture resistance, etc., and is excellent in various environments, particularly in high temperature and high humidity environments. Anti-fogging performance can be maintained for a long time.

  The antifogging article of the present invention has a substrate and a water-absorbing crosslinked resin layer 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 antifogging 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. Further, glass and metal oxide usually have a hydroxyl group on the surface.

  In addition, for the purpose of improving the adhesion between the substrate and the crosslinked resin layer, a metal oxide thin film such as silica, alumina, titania, zirconia, or an organic group-containing metal oxide thin film may be provided on the surface of the substrate. . 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-absorbing crosslinked resin layer in the present invention is made of a water-absorbing crosslinked resin provided on the substrate surface. The crosslinked resin is a resin having a water contact angle of 30 ° or more on the surface (however, the measurement value after 2 minutes of water droplet contact, the same shall apply hereinafter) and a saturated water absorption of 60 mg / cm ³ or more. is there.
The water-absorbing crosslinked resin layer in the present invention has a saturated water absorption of 60 mg / cm ³ or more, and has a sufficient water absorption capability to express anti-fogging performance in the first place. Even when the amount of water absorption increases and the crosslinked resin layer absorbs water exceeding the limit of the saturated water absorption amount, it is difficult to form a water film on the surface of the crosslinked resin layer because the water contact angle is 30 degrees or more. Good anti-fogging performance can be maintained.

Usually, when a water droplet comes into contact with the surface of the substrate, the surface gets wet as time passes, and the contact angle of the water droplet on the substrate surface tends to be small. However, since the antifogging article of the present invention can maintain a contact angle of 30 degrees or more even after 2 minutes of water droplet contact, it is difficult to form a water film. Further, when the surface water contact angle is 30 degrees or more, there is an advantage that water resistance is easily developed and it is difficult to adsorb and fix inorganic dirt.
The upper limit value of the water contact angle is not particularly limited, but is usually about 100 degrees considering the material of the crosslinked resin that can be used in the antifogging article of the present invention.

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 mg / cm ³ is particularly preferable.

When the water-absorbing crosslinked resin satisfies the conditions of the water contact angle and the saturated water absorption amount on the surface, it is possible to achieve both anti-fogging performance and durability.
The water contact angle is determined by leaving the antifogging article in an environment with a relative humidity of 50% at room temperature for 1 hour, and then placing 1 μl of water on the surface of the water-absorbing crosslinked resin layer, after 2 minutes. This is the value when measured.

The saturated water absorption was calculated according to the following procedure. The anti-fogging article is left in an environment of room temperature and relative humidity of 50% for 1 hour, and then the surface of the water-absorbing crosslinked resin layer is exposed to 40 ° C. warm water vapor to form a cloudy or water film on the surface of the crosslinked resin layer. Immediately after the occurrence of distortion due to, the moisture content (A) of the entire antifogging article is measured using a trace moisture meter. Separately, the moisture content (B) of the substrate itself on which the water-absorbing crosslinked resin layer 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 crosslinked resin. The value obtained by dividing 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 the measurement was when the amount of change in weight per minute was 0.02 mg or less.

Such a water-absorbing crosslinked resin is not particularly limited, and for example, among the resins shown below, a resin that satisfies the conditions of the water contact angle and the saturated water absorption amount on the surface can be used. In the present invention, the crosslinked resin refers to a non-linear polymer having a three-dimensional network structure, and preferably a linear polymer chain is bonded to form a three-dimensional network structure.
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;

  The water-absorbing crosslinked resin in the present invention preferably has a change in haze value of 20% or less before and after the test according to the abrasion resistance test conducted according to JIS R 3212. These water-absorbing crosslinked resins preferably have a crosslinking density that satisfies durability such as wear resistance, moisture resistance, and water resistance.

  As a method of providing a water-absorbing crosslinked resin layer on the substrate surface, (1) a method in which a crosslinkable resin and a crosslinking agent are reacted on the substrate surface, (2) a crosslinkable resin is formed into a film shape, Examples thereof include a method of bonding a film with a cross-linking agent, and (3) a method of forming a water-absorbing cross-linked resin into a film and bonding the film to a substrate. Among these methods, the methods (1) and (2) are preferable, and a good appearance can be maintained when a crosslinked resin layer is provided on the surface of a large-area substrate or during industrial mass production. The method is particularly preferred. Specifically, a composition having a crosslinkable resin and a crosslinking agent as essential components (hereinafter also referred to as a coating composition) is applied to the substrate surface, dried, and reacted to form a crosslinked resin layer on the substrate surface. It is preferable to form.

  The composition comprising a crosslinkable resin and a crosslinking agent as essential components may contain a coupling agent for improving the adhesion between the substrate surface and the crosslinked resin, and a solvent for improving the coating workability. preferable. Therefore, as a method of providing a water-absorbing cross-linked resin layer on the substrate surface, a method in which a liquid composition containing a cross-linkable resin, a cross-linking agent, a coupling agent, and a solvent is applied to the surface of the substrate, followed by drying and reacting. preferable. 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 these components in a solvent containing a crosslinking agent and a coupling agent is applied to the substrate surface, 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 2.0 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. In some cases, a crosslinking agent may impart water absorption to the crosslinked resin.

  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. .

  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 between antifogging properties and wear 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 cross-linking agent is merely a compound having a reactive group that reacts with the cross-linking group of the cross-linkable resin (may be the same reactive group as the main cross-linking agent or a different reactive group). Instead, 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. That is, the reaction between the crosslinkable resin and the crosslinking agent contained in the antifogging agent composition 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.

  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.

  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.

  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, 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 crosslinked resin having particularly good antifogging performance can be obtained, polyglycidyl ether of an aliphatic polyol having three or more hydroxyl groups such as glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. (The average number of glycidyl groups per molecule exceeds 2) is preferred.

  As the polyamine compound, an aliphatic polyamine compound and an alicyclic polyamine compound are preferable. Specifically, 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 combination of the cross-linking agent and the second cross-linking agent can be appropriately selected depending on the purpose of using the second cross-linking agent; For example, when the second cross-linking agent is used for the purpose of promoting the formation of a cross-linked resin, and the cross-linking resin having a carboxyl group and the cross-linking agent having an epoxy group are used in combination, It is preferable to use together the 2nd crosslinking agent which has 2 crosslinking agents and an acid anhydride group. In this case, the second crosslinking agent having an amino group is preferably an aliphatic polyamine compound or an alicyclic polyamine compound, and particularly preferably an alicyclic polyamine compound. Specifically, isophoronediamine is preferable. This combination is preferable because formation of a crosslinked resin is promoted and abrasion resistance and water wiping resistance are improved.

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.
When the second cross-linking agent is a compound having a reactive group that reacts with the reactive group of the main cross-linking agent, the ratio of the second cross-linking agent to the main cross-linking agent is the reactive group possessed by the main cross-linking agent. It is preferable that the number of reactive groups possessed by the second cross-linking agent is 5 to 1/5.

  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, a reactive compound having no crosslinking function used for the purpose of adjusting the function of the crosslinked resin is referred to as a modifier.
When a modifier is used in addition to the crosslinking agent, the amount of the modifier used is preferably equal to or less than that of the crosslinking agent, and is preferably 0.01 to 0.5 times the mass. Examples of the modifier include monoamines, monoisocyanates, monocarboxylic acids, monohydroxy compounds, monoepoxy compounds, and the like.

  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 function of the crosslinkable resin is adjusted in addition to the improvement of the adhesion between the crosslinkable resin and the substrate in the same manner as the modifier. It can also be used for purposes.

  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. Here, the coupling agent is preferably a compound having one or more (preferably one or two) bonds between a metal atom and a carbon atom. Taking a silane coupling agent as an example, three hydrolyzable groups and one monovalent organic group (provided that the terminal bonded to the silicon atom is a carbon atom) are bonded to the silicon atom. A compound; a compound in which two hydrolyzable groups and two monovalent organic groups (provided that the terminal bonded to the silicon atom is a carbon atom) is preferably bonded to the silicon atom. The monovalent organic group may be a hydrocarbon group such as an alkyl group, and a functional group (an epoxy group-containing group, a glycidoxy group, a methacryloyloxy group, an acryloyloxy group, an isocyanate group, an amino group). , A ureido group, a mercapto group, etc.), and at least one is preferably a group having a functional group.

  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. When used for the purpose of improving the adhesion of the cross-linked resin, the ratio of the coupling agent to the total of the cross-linkable resin, the cross-linking 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 examples thereof include alcohols, acetate esters, ethers, water, and the like. Is 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, it is also preferable that the liquid composition contains the modifying 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,
(3) A combination of a crosslinkable resin having an epoxy group as a crosslinkable group, a crosslinking agent having a carboxyl group or a hydroxyl group, and a silane coupling agent having an isocyanate group or an amino group.

In the present invention, “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 antifogging article becomes good, 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.
Further, as long as the progress of the crosslinking reaction is not hindered, “drying” and “reaction” may be performed successively under the same conditions.

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 50 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.

  In the present invention, the cross-linked resin 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. The crosslinkable vinyl polymer is preferably a linear polymer. 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 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.

  Moreover, the ratio of the cationic group in the crosslinkable vinyl polymer is 0.1 to 2.0 mmol per 1 g of the polymer, preferably 0.4 to 2.0 mmol, and particularly preferably 0.5 to 1.5 mmol. . Furthermore, the ratio of the crosslinkable group is preferably 1.0 to 3.0 mmol, and particularly preferably 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 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 Various monomers that bring other monomer units into the crosslinkable vinyl polymer can be selected and used according to the purpose. Examples thereof include olefin monomers, aromatic vinyl monomers, vinyl halide monomers, vinyl cyanide monomers, unsaturated carboxylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, and the like.

  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. In addition, the original monomer that gave the monomer unit is simply referred to as “monomer unit monomer”.

  As the crosslinkable vinyl polymer, a crosslinkable vinyl polymer having a monomer unit having a carboxyl group as a crosslinkable group together with a monomer unit having a cationic group and a monomer unit having a hydrocarbon group as another monomer unit is preferable. . That is, a crosslinkable vinyl polymer including a monomer unit having a cationic group, a monomer unit having a hydrocarbon group, and a monomer unit having a carboxyl group is preferable. Each monomer unit may contain two or more kinds, and may contain other monomer units. The monomer unit having a cationic group is preferably a monomer unit having a quaternary ammonium structure, and the monomer unit having a hydrocarbon group may be a carbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an arylalkyl group. Monomer units having a hydrogen group are preferred. Monomers having monomer units having a hydrocarbon group include monomers having a hydrocarbon ester group, monomers having a hydrocarbon ether group (such as alkyl vinyl ether), polymerizable unsaturated hydrocarbons such as propylene, butylene, butadiene, and styrene. And monomers having a hydrocarbon ester group are preferred. Examples of the monomer of the monomer unit having a carboxyl group include unsaturated carboxylic acid, unsaturated polycarboxylic acid, and acid anhydrides thereof.

  Each monomer unit may be a monomer unit derived from a monomer having the above group, but the monomer having the above group by chemical conversion after the polymer formation from the monomer unit formed from the monomer having no above group. It may be a monomer unit formed by converting into a 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).

  Furthermore, the monomer unit having a cationic group is preferably a monomer unit (U1) of an unsaturated carboxylic acid ester monomer having a cationic group. The monomer unit having a hydrocarbon group is preferably a monomer unit (U2) of an unsaturated carboxylic acid ester monomer having a hydrocarbon group. The monomer unit having a carboxylic acid group is preferably a monomer unit (U3) of an unsaturated carboxylic acid 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 2 to 5 is preferable because it is easy to achieve both anti-fogging 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 present invention also provides a liquid composition for forming an antifogging cross-linked resin layer on the surface of the substrate by coating, drying and reacting on the surface of the substrate, which is an unsaturated carboxylic ester having a cationic group. Crosslinkable vinyl polymer comprising monomer unit (U1) of monomer, monomer unit (U2) of unsaturated carboxylic acid ester monomer having hydrocarbon group, and monomer unit (U3) of unsaturated carboxylic acid monomer, and crosslinking agent And an antifogging agent composition comprising a solvent. As the crosslinkable vinyl polymer contained in the antifogging agent composition of the present invention, the monomer units (U1) to (U3) contained in the polymer, the crosslinking agent (main crosslinking agent, second crosslinking agent), the solvent, The same thing is mentioned, A preferable aspect is also the same.

  Although the ratio of the components contained in the antifogging agent composition of the present invention depends on the molecular weight of each component, it is generally preferable to set the ratio as follows. It is preferable that 2-20 mol% of a crosslinkable vinyl polymer is contained with respect to the sum total of a crosslinkable vinyl polymer, a crosslinking agent, and a 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.

When the preferable ratio is expressed by mass%, the following ratio is preferable. The crosslinkable vinyl polymer is preferably contained in an amount of 20 to 60% by mass with respect to the total of the crosslinkable vinyl polymer, the crosslinking agent, and the coupling agent. It is preferable that 40-80 mass% of a crosslinking agent is contained with respect to the sum total of a crosslinkable vinyl polymer, a crosslinking agent, and a coupling agent. It is preferable that 5-40 mass% of coupling agents are contained with respect to the sum total of a crosslinkable vinyl polymer, a crosslinking agent, and a 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.

  The antifogging composition of the present invention preferably contains a silane coupling agent as described above. By adding a silane coupling agent, the adhesion between the substrate surface and a water-absorbing crosslinked resin having anti-fogging performance, which is formed using the composition, can be enhanced.

  When the antifogging agent composition of the present invention is applied to a substrate, the thickness of the coating film may become nonuniform due to the wettability of the antifogging agent composition. If the cross-linking reaction proceeds with the coating film thickness non-uniform and a cross-linkable resin is formed, perspective distortion may occur in the antifogging article. In order to make the thickness of the coating film uniform, it is preferable to add a leveling agent to the antifogging agent composition. 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 from the viewpoint of imparting hydrophilicity to the antifogging agent composition and improving the antifogging performance. By adding 0.02 to 1% by mass of the silicone leveling agent to the antifogging agent composition, the wettability can be improved and the thickness of the coating film can be made uniform. 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 antifogging composition of the present invention preferably further contains a modifier. By including a modifier, functions and properties that cannot be imparted only with a crosslinkable resin or a crosslinking agent are imparted to the crosslinked resin, or functions or properties of a crosslinked resin that are not sufficient with only a crosslinkable resin or a crosslinking agent are improved. You can make it. The modifier is appropriately selected depending on the components such as the crosslinkable resin and the crosslinker, and the modifier added to the antifogging agent composition of the present invention is a resin having a carboxyl group and a crosslinker being an epoxy. In the case of a crosslinking agent having a group, monoamines and monocarboxylic acids are preferred.

  The antifogging composition of the present invention preferably further contains a filler. By including the filler, the mechanical strength and heat resistance of the crosslinked resin formed using the composition can be increased, and the curing shrinkage of the resin during the crosslinking reaction can be reduced. The filler is preferably a filler made of a metal oxide. Examples of the metal oxide include silica, alumina, titania, zirconia, and the like, and silica is preferable. Examples of such a filler include Snowtex IPA-ST (manufactured by Nissan Chemical Industries).

  In addition to the filler, a filler made of ITO (Indium Tin Oxide) can also be used. Since ITO has infrared absorptivity, heat ray absorptivity can be imparted to the crosslinked resin. Therefore, when a filler made of ITO is used, an antifogging effect due to heat ray absorption can be expected in addition to water absorption.

  The filler is preferably particulate, and the average particle size is 0.01 to 0.3 μm, preferably 0.01 to 0.1 μm. The amount of the filler is preferably 1 to 20% by mass with respect to the total amount of the crosslinkable vinyl polymer, the crosslinking agent, the silane coupling agent, and the modifier added as necessary. 10% by mass is particularly preferred. If it is less than 1% by mass, the effect of reducing the curing shrinkage of the crosslinked resin tends to be lowered, and if it exceeds 20% by mass, a sufficient space for water absorption cannot be secured, and the antifogging performance tends to be lowered.

The antifogging article of the present invention has good antifogging performance because the cross-linked resin provided on the substrate surface has a water contact angle of 30 ° or more and a saturated water absorption of 60 mg / cm ^3. And excellent durability. In the antifogging article of the present invention, the cross-linked resin provided on the substrate surface is 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. It has good anti-fogging performance and excellent durability. Furthermore, the crosslinkable resin constituting the antifogging article of the present invention is a crosslinkable resin that satisfies the above-mentioned conditions of water contact angle and saturated water absorption and is obtained by a reaction between a crosslinkable vinyl polymer and a crosslinking agent. Further, the antifogging performance is further improved, and the durability can be further improved.

  Examples of the antifogging article of the present invention include window glass for transportation equipment (automobiles, railways, ships, airplanes, etc.), refrigerated showcases, mirrors for vanity tables, bathroom mirrors, optical equipment, and the like. The anti-fogging agent composition of the present invention has good anti-fogging performance and is excellent in durability, and thus is useful for obtaining the anti-fogging article.

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

[Example 1]
[Example 1-1] Preparation of antifogging agent composition 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 Co., Ltd.) 9.0 g), glycerol polyglycidyl ether having an average number of epoxy functional groups of 2.3 (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX-314) (2.7 g), and isophorone diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 69 g) and stirred at 25 ° C. for 1 hour. N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM602) (0.5 g), tetraethyl silicate (manufactured by Junsei Kagaku) (0.1 g), and Ethanol (manufactured by Junsei) (5.2 g) was added and stirred at 25 ° C. for 1 hour to obtain an antifogging agent composition 1. 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.

[Example 1-2] Preparation of antifogging article The antifogging agent composition 1 was applied by spin coating to a clean glass substrate (100 mm x 100 mm x 2 mm) whose surface was polished and washed with cerium oxide and dried. The antifogging article 1 having a cross-linked resin layer having a thickness of 20 μm was obtained by firing at 0 ° C. for 1 hour.
About the obtained anti-fogging article | item 1, the following item was evaluated. The results are shown in Table 1. The water contact angle of the antifogging article was 45 °, and the saturated water absorption was 99.4 mg / cm ³ . Moreover, as a result of the evaluation test, the anti-fogging article 1 had excellent anti-fogging performance, abrasion resistance, water resistance, heat resistance, moisture resistance and water wiping resistance.

1. Water contact angle The antifogging article was allowed to stand for 1 hour in an environment with a room temperature and relative humidity of 50%, and then 1 μL of water droplets were dropped on the surface of the crosslinked resin layer, and the water contact angle after 2 minutes was measured.
2. Film thickness After the antifogging article was allowed to stand for 1 hour in an environment of room temperature and relative humidity of 50%, the film thickness difference was measured using a stylus type surface shape measuring instrument (trade name: DEKTAK3030 manufactured by ULVAC).

3. Saturated water absorption The antifogging article is allowed to stand for 1 hour in an environment with a relative humidity of 50% at room temperature, and then the surface of the water-absorbing crosslinked resin layer is exposed to 40 ° C. warm water vapor and cloudy on the surface of the crosslinked resin layer. Alternatively, immediately after the distortion caused by the water film, the moisture content (A) of the whole antifogging article is measured using a trace moisture meter. Separately, the moisture content (B) of the substrate itself on which the water-absorbing crosslinked resin layer 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 crosslinked resin. 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. The saturated water absorption was evaluated using an antifogging article (a coated area of the water-absorbing crosslinked resin layer was 33 cm ² ) prepared using a glass substrate having a size of 3.3 cm × 10 cm × 2 mm. .

4). Anti-fogging performance The surface of the cross-linkable resin layer of an anti-fogging article that has been allowed to stand for 1 hour in an environment with a relative humidity of 50% at room temperature is placed on a 40 ° C hot water bath to prevent fogging until cloudiness or distortion due to a water film is observed. Time (minutes) was measured. In addition, the normal glass produced cloudiness in 0.01 to 0.08 minutes.

5). Abrasion resistance Measured according to JIS R 3212 (inside the vehicle). A wear wheel CS-10F was used on a Taber 5130 type abrasion tester. The wear wheel was brought into contact with the surface of the crosslinked resin layer of the antifogging article, rotated 100 times with a load of 5.00 N, the change in haze value ΔH (%) was measured, and evaluated based on the following evaluation criteria.
○: ΔH was 20% or less.
X: At least one of ΔH was over 20% or peeling of the crosslinked resin layer was observed.

6). Water resistance The antifogging article was allowed to stand in a constant temperature water bath at 40 ° C. for 150 hours and then evaluated based on the following evaluation criteria.
○: No change in appearance, and anti-fogging time was 1 minute or longer.
X: At least one of whether the appearance was changed or the antifogging time was less than 1 minute occurred.

7). Heat resistance was performed in accordance with JIS R 3212 (Laminated glass). The antifogging article was held in boiling water for 2 hours and then evaluated based on the following evaluation criteria.
○: No change in appearance, and anti-fogging time was 1 minute or longer.
X: At least one of whether the appearance was changed or the antifogging time was less than 1 minute occurred.

8). Moisture resistance The antifogging article was held in a constant temperature and humidity chamber at 90 ° C. and 90% RH for 500 hours, and then evaluated based on the following evaluation criteria.
○: No change in appearance, and anti-fogging time was 1 minute or longer.
X: At least one of whether the appearance was changed or the antifogging time was less than 1 minute occurred.

9. Water resistance wipe The surface of the cross-linked resin of the anti-fogging article was reciprocated 5000 times with a load of 4.90 N / 4 cm ² using a flannel cloth (cotton No. 300) containing water (1 mL), and then the following Evaluation was performed based on the evaluation criteria.
○: No change in appearance, and anti-fogging time was 1 minute or longer.
X: At least one of whether the appearance was changed or the antifogging time was less than 1 minute occurred.

[Example 2]
[Example 2-1] Preparation of antifoggant composition Water (49 g), N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM602) in a glass container in which a stirrer and a thermometer were set. (1 g) was added and stirred at 25 ° C. for 1 hour, and then ethanol (50 g) was added to prepare coating solution B. Further, an antifogging agent composition 1 was prepared in the same manner as in Example 1.

[Example 2-2] Production of anti-fogging article Coating liquid B was applied to a clean and ground glass substrate by spin coating and baked at 100 ° C for 5 minutes to produce an undercoat having a thickness of 10 nm. . Subsequently, the antifogging agent composition 1 was applied onto the undercoat by spin coating and baked at 100 ° C. for 1 hour to obtain an antifogging article 2 having a crosslinked resin layer with a thickness of 20 μm.

The antifogging article 2 was evaluated in the same manner as in Example 1. The results are shown in Table 1.
The obtained antifogging article 2 had a water contact angle of 44 ° and a saturated water absorption of 95.8 mg / cm ³ . It had excellent anti-fogging performance and abrasion resistance, water resistance, heat resistance, moisture resistance and water wiping resistance.

[Example 3]
In addition to the antifogging agent composition 1 of Example 1, a polyoxyalkylene amino-modified dimethylpolysiloxane copolymer (manufactured by Nippon Unicar Co., Ltd., product number: FZ-3789) (0.03 g) (0.08 g relative to the antifogging agent composition) Mass%) and ethanol (18 g) were added to obtain antifogging composition 3. Using this antifogging agent composition 3, an antifogging article 3 was obtained in the same manner as in Example 1.
The obtained antifogging article 3 having a crosslinked resin layer having a thickness of 21 μm has a water contact angle of 41 ° and a saturated water absorption of 106.7 mg / cm ³ , and has excellent antifogging performance, abrasion resistance, and water resistance. , Heat resistance, moisture resistance and water wiping resistance.

[Example 4]
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (0.5 g) and tetraethyl silicate (0.1 g) contained in the antifogging composition 1 in Example 1 were combined with tetraisocyanate silane (Matsumoto Antifogging composition 4 was prepared in the same manner as in Example 1 except that the product was changed to “Product Number: SI-400” (0.1 g) manufactured by Pharmaceutical Industries, Ltd., and antifogging article 4 was obtained.
The obtained antifogging article 4 having a crosslinked resin layer with a thickness of 30 μm had a water contact angle of 32 ° and a saturated water absorption of 124.8 mg / cm ³ . Although it had excellent anti-fogging performance, ΔH was 20% or more in terms of wear resistance, and film peeling was confirmed in terms of water resistance, heat resistance, moisture resistance, and water wiping resistance.

[Example 5]
Isophoronediamine (0.69 g) contained in the anti-fogging agent composition 1 in Example 1 was replaced with N, N, N ′, N′-tetraglycidyl-m-xylylenediamine (trade name: TETRAD-, manufactured by Mitsubishi Gas Chemical Company). X) An antifogging composition 5 was prepared in the same manner as in Example 1 except that it was changed to (0.67 g). The obtained anti-fogging article 5 having a crosslinked resin layer having a thickness of 12 μm had a water contact angle of 52 ° and a saturated water absorption of 56.7 mg / cm ³ . Anti-fogging article 5 It had excellent anti-fogging performance and was excellent in water resistance, heat resistance and moisture resistance, but was found to have a wear resistance of ΔH of 20% or more and a water wiping resistance to scratches.

[Example 6]
Antifoggant composition as in Example 1 except that N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (0.5 g) is not added compared to antifoggant composition 1 of Example 1 The product 6 was prepared and the antifogging article 6 was obtained. The resulting antifogging article having a crosslinked resin layer with a film thickness of 15 μm had a water contact angle of 35 ° and a saturated water absorption of 136.1 mg / cm ³ . Although the antifogging article 6 had excellent antifogging performance, it was confirmed that the abrasion resistance was ΔH of 20% or more, the heat resistance was film peeling, and the water wiping resistance was scratched.

[Example 7]
Compared with antifogging agent composition 1 of Example 1, antifogging agent composition 7 was prepared in the same manner as in Example 1 except that isophoronediamine (0.69 g) was not added, and antifogging article 7 was obtained. . The obtained antifogging article 7 having a crosslinked resin layer having a film thickness of 19 μm had a water contact angle of 47 ° and a saturated water absorption of 49.1 mg / cm ³ . The anti-fogging article 7 was excellent in anti-fogging properties and was excellent in water resistance, heat resistance, and moisture resistance, but was found to have a wear resistance of ΔH of 20% or more and a water wiping resistance to scratches.

[Example 8]
An antifogging composition 8 was prepared in the same manner as in Example 1 except that tetraethyl silicate (0.1 g) was not added. The resulting antifogging article 8 having a crosslinked resin layer with a thickness of 21 μm had a water contact angle of 50 ° and a saturated water absorption of 98.5 mg / cm ³ . The antifogging article 8 was excellent in antifogging properties, abrasion resistance, water resistance, heat resistance, moisture resistance, and water wiping resistance.

[Example 9]
An antifogging composition in the same manner as in Example 1 except that the mixture of the crosslinkable vinyl polymer and the solvent in Example 1 (9.0 g) was changed to the following mixture of the crosslinkable vinyl polymer and the solvent (9.0 g). 9 is prepared to obtain an antifogging article 9.
The antifogging article 9 having a crosslinked resin layer with a film thickness of about 15 μm has a water contact angle of 40 ° or more and a saturated water absorption of 70 mg / cm ³ or more. The antifogging article 9 has excellent antifogging performance and abrasion resistance, water resistance, heat resistance, moisture resistance, and water wiping resistance.

<Mixture of crosslinkable vinyl polymer and solvent in Example 9>
Ethyltrimethylammonium methacrylate (1.07 g) [25 mol% as monomer unit (U1)], 2-methoxyethyl acrylate (0.80 g) [30 mol% as monomer unit (U2)], methyl methacrylate (0. 61 g) [30 mol% as monomer unit (U2)], acrylic acid (0.22 g) [15 mol% as monomer unit (U3)], a mixed solvent of isopropyl alcohol (3.15 g) and water (3.15 g) Mixture of crosslinkable vinyl polymer and solvent obtained by thermal polymerization in

[Example 10]
Compared with Example 1, the stirring time at 25 ° C. of the antifogging agent composition 1 is 3 hours or more, and a crosslinked resin 10 having a viscosity (25 ° C.) of 10 Pa · s or more is obtained. The crosslinked resin 10 is molded to obtain a film-like crosslinked resin 10 having a thickness of about 30 μm. An adhesive is applied to one surface of the crosslinked resin 10, and the surface coated with the adhesive is bonded to a clean glass surface to obtain an antifogging article 10 having a crosslinked resin layer with a thickness of 30 μm.

The antifogging article 10 has a water contact angle of 50 ° or more and a saturated water absorption of 70 mg / cm ³ or more. Although it is excellent in anti-fogging performance and abrasion resistance, film peeling is confirmed after tests of water resistance, heat resistance, moisture resistance and water wiping resistance. The peeling of the film is thought to be due to the deterioration of the adhesive.

[Example 11]
An antifogging composition in the same manner as in Example 1 except that the mixture of the crosslinkable vinyl polymer and the solvent in Example 1 (9.0 g) was changed to the following mixture of the crosslinkable vinyl polymer and the solvent (9.0 g). 11 is prepared to obtain an antifogging article 11.
The antifogging article 11 having a crosslinked resin layer with a film thickness of about 15 μm has a water contact angle of 40 ° or more and a saturated water absorption of 30 mg / cm ³ or less. As a result of evaluating the anti-fogging performance, the anti-fogging time is 1 minute or less, and film peeling is confirmed with abrasion resistance, water resistance, heat resistance, moisture resistance and water wiping resistance.

<Mixture of crosslinkable vinyl polymer and solvent in Example 11>
N, N-dimethylacrylamide (0.64 g), 2-methoxyethyl acrylate (1.01 g), methyl methacrylate (0.77 g), and acrylic acid (0.28 g) with isopropyl alcohol (3.15 g) A mixture of a crosslinkable vinyl polymer and a solvent obtained by thermal polymerization in a mixed solvent with water (3.15 g).

[Example 12]
Other than changing the mixture of crosslinkable vinyl polymer and solvent (Nippon Junyaku Co., Ltd., trade name: Julimer SPO-601) (9.0 g) to the following mixture of crosslinkable vinyl polymer and solvent (9.0 g) Prepare an antifogging composition 12 in the same manner as in Example 1 to obtain an antifogging article 12.
The thickness of the crosslinked resin layer in the antifogging article 12 is about 20 μm. The antifogging article 12 has a water contact angle of 60 ° or more and a saturated water absorption of 15 μg / cm ³ or less. The anti-fogging time of the anti-fogging article 12 is 1 minute or less, and the anti-fogging time after the water resistance, heat resistance, moisture resistance and water wiping resistance test is 1 minute or less.

<Mixture of crosslinkable vinyl polymer and solvent in Example 12>
Polyethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., trade names: FA-220M, Mw: 330) (0.31 g), 2-methoxyethyl acrylate (1.11 g), methyl methacrylate (0.94 g), and acrylic A mixture of a crosslinkable vinyl polymer and a solvent obtained by thermal polymerization of an acid (0.34 g) in a mixed solvent of isopropyl alcohol (3.15 g) and water (3.15 g).

[Example 13]
A mixture of a crosslinkable vinyl polymer and a solvent obtained by thermally polymerizing ethyl acrylate, methyl methacrylate, and acrylic acid in a solvent (9.0 g) in Example 1 An antifogging article 13 is obtained in the same manner as in Example 1 except that the product name is Jurimer AT-510) (9.0 g).
The antifogging article 13 having a crosslinked resin layer with a film thickness of about 8 μm has a water contact angle of 55 ° or more and a saturated water absorption of 10 μg / cm ³ or less. When the antifogging performance is evaluated, the antifogging time is 1 minute or less. ΔH is 20% or less in the evaluation of wear resistance, and the antifogging time is 1 minute or less in the evaluation of water resistance, heat resistance, moisture resistance and water wiping resistance.

[Example 14]
Glycerol polyglycidyl ether (2.7 g) having an average epoxy functional group number of 2.3 in Example 1 was converted to lauryl alcohol (EO) 15 glycidyl ether having an epoxy functional group number of 1 (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX-171) ( The antifogging article 14 is obtained in the same manner as in Example 1 except that 2.7 g).
The antifogging article 14 having a crosslinked resin layer having a film thickness of about 10 μm has a water contact angle of 60 ° or more and a saturated water absorption of 15 μg / cm ³ or less. When antifogging performance is evaluated, the antifogging time is 1 minute or less. Membrane peeling is confirmed after tests for wear resistance, water resistance, heat resistance, moisture resistance and water wiping resistance.

[Example 15]
In a glass container in which a stirrer and a thermometer are set, polycaprolactone diol (manufactured by Daicel Chemical Industries, trade name: Plaxel L205AL) (10 g) and polyethylene glycol (average molecular weight: 1000) (20 g) are placed at 25 ° C. For 1 hour. Next, polyisocyanate (manufactured by Sumitomo Bayer Urethane, burette type, trade name: N3200) (40 g) is added and stirred at 25 ° C. for 1 hour. Subsequently, it is diluted with diacetone alcohol to obtain an antifogging agent composition 15.
The antifogging article 15 having a crosslinked resin layer having a thickness of about 10 μm has a water contact angle of 10 ° or less and a saturated water absorption of 20 mg / cm ³ or less. The antifogging performance is 1 minute or less, and ΔH is 20% or less in the evaluation of wear resistance.

Since the anti-fogging article of the present invention has excellent anti-fogging performance and durability, window glass for transport equipment (automobile, railway, ship, airplane, etc.), refrigerated showcase, vanity table It can be used for mirrors, bathroom mirrors, optical equipment, etc. The antifogging agent composition of the present invention is useful for producing these antifogging articles.

Claims (16)

An anti-fogging article having a substrate and a water-absorbing crosslinked resin layer provided on the surface of the substrate, wherein the water-absorbing crosslinked resin has a water contact angle of 30 degrees or more on the surface (however, water droplet contact 2 And a cross-linked resin having a saturated water absorption of 60 mg / cm ³ or more.   The antifogging article according to claim 1, wherein the crosslinked resin layer is a resin layer formed by reacting a crosslinkable resin and a crosslinking agent on the surface of the substrate.   The cross-linked resin layer is a resin layer formed by applying a liquid composition containing a cross-linkable resin, a cross-linking agent, a silane coupling agent, and a solvent to a substrate surface, drying, and reacting. The antifogging article as described in 2.   An antifogging article having a substrate and a water-absorbing crosslinked resin layer provided on the surface of the substrate, wherein the water-absorbing crosslinked resin is crosslinked with a crosslinkable vinyl polymer having a cationic group and a crosslinkable group. An antifogging article, which is a cross-linked resin obtained by a reaction with an agent.   The antifogging article according to claim 4, wherein the crosslinkable group is a carboxyl group.   The antifogging article according to claim 4 or 5, wherein the crosslinkable vinyl polymer is a crosslinkable vinyl polymer including a monomer unit having a cationic group, a monomer unit having a hydrocarbon group, and a monomer unit having a carboxyl group. .   The antifogging article according to claim 5 or 6, wherein the crosslinking agent is an epoxy-based crosslinking agent having two or more epoxy groups.   The water-absorbing cross-linked resin layer is a resin layer formed by applying a liquid composition containing a cross-linkable vinyl polymer, a cross-linking agent, a silane coupling agent, and a solvent to a substrate surface, drying, and reacting. Item 8. The antifogging article according to any one of Items 4 to 7.   An antifogging article having a substrate and a crosslinked resin layer provided on the surface of the substrate, wherein the crosslinked resin is a crosslinked resin obtained by a reaction between a crosslinkable vinyl polymer and a crosslinking agent, and the crosslinkable vinyl polymer Is a monomer unit (U1) of an unsaturated carboxylic acid ester monomer having a cationic group, a monomer unit (U2) of an unsaturated carboxylic acid ester monomer having a hydrocarbon group, and a monomer unit of an unsaturated carboxylic acid monomer ( An antifogging article, which is a crosslinkable vinyl polymer containing U3).   The crosslinkable vinyl polymer contains 5 mol% or more of monomer units (U1), 10 mol% or more of monomer units (U2), and 1 to 20 mol% of monomer units (U3) based on all monomer units. The anti-fogging article according to claim 9, comprising: The antifogging article according to claim 9 or 10, wherein the monomer unit (U1) is a monomer unit of 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)
However, the symbols in the formulas have the following meanings.
R ¹ : a hydrogen atom or a methyl group.
R ² , R ³ , R ⁴ : each independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a substituent.
X ⁻ : a monovalent anion.
m: An integer from 1 to 10.   The antifogging article according to any one of claims 9 to 11, wherein the crosslinking agent is an epoxy-based crosslinking agent having two or more epoxy groups.   The cross-linked resin layer is a resin layer formed by applying a liquid composition containing a cross-linkable vinyl polymer, a cross-linking agent, a silane coupling agent, and a solvent to a substrate surface, drying, and reacting. The antifogging article according to any one of 12 above.   A liquid composition for forming an antifogging cross-linked resin layer on a substrate surface by applying to the substrate surface, drying and reacting, and a monomer unit of an unsaturated carboxylic acid ester monomer having a cationic group ( U1), a crosslinkable vinyl polymer containing a monomer unit (U2) of an unsaturated carboxylic acid ester monomer having a hydrocarbon group and a monomer unit (U3) of an unsaturated carboxylic acid monomer, a crosslinking agent, and a solvent. An antifogging composition characterized by the above.   The antifogging composition according to claim 14, further comprising a silane coupling agent. The antifogging composition according to claim 14 or 15, further comprising a silicone leveling agent.