JP2008273067A - Anti-fogging article and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-fogging article which has both excellent anti-fogging performance and durability, and can maintain excellent anti-fogging performance under various environments for a long time, and a method of manufacturing the anti-fogging article. <P>SOLUTION: The anti-fogging article 1 has a base substance 2 and an anti-fogging film 5 on the surface of the base substance 2. The anti-fogging film 5 has a low hygroscopic cross-linked resin layer 3 and a high hygroscopic cross-linked resin layer 4 which are sequentially laminated on the surface of the base substance 2. The low hygroscopic cross-linked resin layer 3 has a film thickness of 1.0 μm or more, a saturated moisture absorption amount of 10 mg/cm<SP>3</SP>or less, and the anti-fogging film 5 has a saturated moisture absorption amount of 20 mg/cm<SP>3</SP>or more. The method of manufacturing the anti-fogging article 1 comprises the steps of coating a liquid composition containing a crosslinking component and a curing agent on the surface of the base substance, causing reaction to form the low hygroscopic cross-linked resin layer, coating the liquid composition containing the crosslinking component and the curing agent on the surface of the low hygroscopic cross-linked resin layer, and causing reaction to form the high hygroscopic cross-linked resin layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antifogging article and a method for producing the antifogging article, for example, to prevent fine water droplets from adhering to a transparent substrate such as glass or plastic to impair the transparency.

  For example, a transparent substrate such as glass or plastic has a so-called transparency, because when the surface of the substrate falls below the dew point temperature, fine water droplets adhere to the surface and transmitted light is scattered by the water droplets. It becomes “cloudy”. Various proposals have been made as means for preventing fogging.

Patent Document 1 discloses a method for preventing fogging of the substrate surface by treating the substrate surface with a surfactant to lower the surface tension. However, in this method, it is difficult to fix the surfactant to the substrate surface, and it is difficult to maintain the surface tension over a long period of time.
In addition, a method for preventing fogging by performing treatment for imparting a hydrophilic group to the surface of the substrate and making the surface of the substrate hydrophilic is disclosed (Patent Documents 2 and 3). In this method, for example, a hydrophilic resin or a hydrophilic inorganic compound containing metal oxide particles is used. In any case, particularly, inorganic dirt is easily adsorbed and fixed, and the hydrophilic property can be maintained for a long time. Have difficulty.

There is also a method of preventing the fogging by installing a heater or the like on the substrate and heating the substrate to maintain the surface of the substrate above the dew point temperature. However, with this technology, although the anti-fogging performance can be maintained semipermanently, the energy associated with energization is always required, so that the cost becomes very high.
In addition, there is a method of treating the surface of the substrate with a water-repellent compound to prevent fine water droplets from adhering to the surface of the substrate. However, in order to obtain sufficient anti-fogging performance, even a very small water droplet having a diameter of 1 mm or less needs to have such a high water repellency that it can slide down or prevent adhesion. Not achieved.

Patent Document 4 discloses a method of preventing fogging of the substrate surface by providing a hygroscopic compound layer on the substrate surface and reducing the atmospheric humidity on the substrate surface. In this method, for example, a hygroscopic resin is used. However, while the hygroscopic resin is excellent in anti-fogging performance, there is a problem that the abrasion resistance and weather resistance are inferior. However, if the resin surface is designed to be hydrophobic, it is particularly effective in preventing inorganic stains, and it is easy to maintain antifogging performance for a long period of time.
From the above, it is considered that a hygroscopic resin is useful for realizing anti-fogging performance at low cost and maintaining it easily.

As a method using a hygroscopic resin, a coating agent for forming a urethane resin having a surfactant and a trialkanolamine, which has both antifogging performance and wear resistance, and an antifogging film by the coating agent are shown. (Patent Document 5).
Further, as a method having both antifogging performance and alkali resistance, a hygroscopic and / or hydrophilic resin is formed on a primer layer comprising a hydrolyzable silane having an alkylene group and hydrolyzable zirconium or hydrolyzable titanium. A method of applying a film is shown (see Patent Document 6).
JP 2003-238207 A JP 2001-356201 A JP 2000-192021 A Japanese Patent Laid-Open No. 2002-53792 JP 2004-269851 A WO05 / 056488 pamphlet

However, in the technique of Patent Document 5, it is difficult to fix the surfactant to the substrate, and it may be difficult to sufficiently maintain the antifogging performance for a long period of time. Moreover, in the technique of patent document 6, the moisture resistance, acid resistance, and alkali resistance of the formed two-layer film were not sufficient. Therefore, an antifogging article having excellent antifogging performance and further having various durability is desired.
Therefore, the present invention has excellent anti-fogging performance for a long period of time in various environments, in addition to excellent anti-fogging performance, as well as durability such as abrasion resistance, adhesion, stain resistance, acid resistance, and alkali resistance. A sustainable antifogging article and a method for producing the antifogging article are provided.

In the present invention, an antifogging article having a substrate and an antifogging film on the surface of the substrate, the antifogging film comprising: a low hygroscopic crosslinked resin layer sequentially laminated on the substrate surface; A high hygroscopic crosslinked resin layer having a higher saturated moisture absorption than the resin layer, and the low hygroscopic crosslinked resin layer has a film thickness of 1.0 μm or more and a saturated moisture absorption of 10 mg / cm ³ or less, And the saturated moisture absorption amount of an antifogging film | membrane is 20 mg / cm < ³ > or more, The antifogging article | item characterized by the above-mentioned is provided.

In the antifogging article of the present invention, the substrate is preferably soda lime glass. Both the low hygroscopic crosslinked resin layer and the high hygroscopic crosslinked resin layer are preferably crosslinkable resins formed by reaction of polyepoxides and a curing agent.
In addition, the method for producing an antifogging article according to the present invention comprises forming a low-hygroscopic crosslinked resin layer comprising a crosslinkable resin by reacting a liquid composition containing a crosslinkable component and a curing agent after being applied to the substrate surface. Then, a liquid composition containing a crosslinkable component and a curing agent is applied to the surface of the low hygroscopic crosslinkable resin layer formed on the surface of the substrate, and then reacted to thereby cause a high hygroscopicity composed of a crosslinkable resin. A crosslinkable resin layer is formed.

  The antifogging article of the present invention exhibits excellent antifogging performance and has durability such as abrasion resistance, adhesion, stain resistance, acid resistance, and alkali resistance, and exhibits antifogging performance under various environments. Can last for a long time. Moreover, according to the manufacturing method of the present invention, the antifogging article can be manufactured.

As shown in FIG. 1, the antifogging article 1 of the present invention is provided with an antifogging film 5 on the surface of a substrate 2. The antifogging film 5 is composed of a low hygroscopic crosslinked resin layer 3 and a high hygroscopic crosslinked resin layer 4.
[Substrate 2]
The substrate 2 is preferably a substrate made of glass, plastic, metal, ceramics, or a combination thereof (composite material, laminated material, etc.), and is preferably a transparent substrate made of glass or plastic, or a mirror. More preferred. As the glass, soda lime glass is particularly preferable.
The shape of the substrate 2 may be a flat plate, or the entire surface or a part thereof may have a curvature. The thickness of the substrate 2 can be appropriately selected depending on the use of the antifogging article, but generally it is preferably 1 to 10 mm.

  The substrate 2 preferably has a reactive group on the surface. As the reactive group, a hydrophilic group is preferable, and as the hydrophilic group, a hydroxyl group is preferable. Also, the surface of the substrate can be 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.

The substrate 2 is provided with a metal oxide thin film such as silica, alumina, titania or zirconia or an organic group-containing metal oxide thin film on the surface of glass or the like for the purpose of improving the adhesion with the low hygroscopic crosslinked resin layer 3. It could be
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, tetraisocyanatesilane, oligomers thereof and the like are preferable.
The organic group-containing metal oxide thin film can be obtained by treating the substrate surface 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 preferably used. Hereinafter, a coupling agent for treating the substrate surface in advance is referred to as a “surface treatment coupling agent”.

[Anti-fogging film 5]
The saturated moisture absorption amount of the antifogging film 5 is 20 mg / cm ³ or more. The saturation moisture absorption amount of the antifogging film 5 is preferably from 45~150mg / cm ^3, and even more preferably 60 to 100 mg / cm ^3. High anti-fogging performance is obtained when the saturated moisture absorption amount is not less than the lower limit. On the other hand, when the saturated moisture absorption amount is not more than the upper limit value, it is easy to prevent the durability and adhesion during moisture absorption from being lowered.

  The low hygroscopic crosslinked resin layer 3 is composed of a low hygroscopic crosslinkable resin. The crosslinkable resin is a non-linear polymer having a three-dimensional network structure, and a three-dimensional network structure is formed by crosslinking crosslinkable components such as monomers, oligomers and polymers having two or more crosslinkable groups. It is preferable that

Examples of the crosslinkable resin that forms the low hygroscopic crosslinkable resin layer 3 include starch resins, cellulose resins, polyvinyl alcohol resins, acrylic resins, polyether resins, and crosslinked polyurethanes.
Examples of the starch-based resin include composites such as starch-acrylonitrile graft polymer hydrolyzate and starch-acrylic acid graft polymer.
Examples of the cellulose resin include a cellulose-acrylonitrile graft polymer and a crosslinked carboxymethyl cellulose.
As a polyvinyl alcohol-type resin, a polyvinyl alcohol crosslinked polymer is mentioned, for example.
Examples of the acrylic resin include a sodium polyacrylate cross-linked body and a polyacrylic acid ester cross-linked body.
Examples of the polyether-based resin include a polyethylene glycol / diacrylate crosslinked polymer and a crosslinked polyalkylene oxide-polycarboxylic acid.
Examples of the crosslinked polyurethane include a reaction product of polyether polyol or polyester polyol and polyisocyanate.
The crosslinkable resin forming the low hygroscopic crosslinked resin layer 3 is preferably the same type as the high hygroscopic crosslinked resin layer 4 as an upper layer from the viewpoint of adhesiveness.

  The high hygroscopic cross-linked resin layer 4 is made of a hygroscopic cross-linkable resin like the low hygroscopic cross-linked resin layer 3, but the saturated hygroscopic amount (saturated hygroscopic amount per unit volume) of the high hygroscopic cross-linked resin layer 4 is as follows. It is larger than the low hygroscopic crosslinked resin layer 3. Although it does not specifically limit as crosslinkable resin which forms the highly hygroscopic crosslinked resin layer 4, The same thing as the low hygroscopic crosslinked resin layer 3 is mentioned. Moreover, it is preferable that the highly hygroscopic crosslinked resin layer 4 has a change in haze value before and after the test by an abrasion resistance test performed in accordance with JIS R 3212 of 20% or less.

The saturated moisture absorption amount of the low hygroscopic crosslinked resin layer 3 is 10 mg / cm ³ or less. The saturated moisture absorption amount of the low hygroscopic crosslinked resin layer 3 is preferably 5 mg / cm ³ or less, and more preferably 1 mg / cm ³ or less. If the saturated hygroscopic amount of the low hygroscopic crosslinked resin layer 3 is 10 mg / cm ³ or less, the antifogging film 5 can be prevented from peeling off from the substrate 2, and as a result, the acid resistance and alkali resistance are excellent.
The saturated moisture absorption amount of the high hygroscopic crosslinked resin layer 4 is larger than that of the low hygroscopic crosslinked resin layer 3. The saturated moisture absorption amount of the highly hygroscopic crosslinked resin layer 4 is preferably 20 mg / cm ³ or more, and more preferably 45 mg / cm ³ or more. Thereby, it becomes easy to ensure a necessary saturated moisture absorption amount for the entire antifogging film 5. On the other hand, from the viewpoint of preventing the durability of the antifogging film 5 from being lowered, the saturated moisture absorption amount of the highly hygroscopic crosslinked resin layer 4 is preferably 150 mg / cm ³ or less, and preferably 100 mg / cm ³ or less. Is more preferable.

The film thickness of the low hygroscopic crosslinked resin layer 3 is 1.0 μm or more, preferably 5 μm or more, and more preferably 10 μm or more. If the film thickness of the low hygroscopic crosslinked resin layer 3 is 1.0 μm or more, the antifogging film 5 can be prevented from peeling off from the substrate 2, and as a result, the acid resistance and alkali resistance are excellent. In addition, the film thickness of the low hygroscopic crosslinked resin layer 3 is preferably 5 μm or more from the reason that the stress generated at the interface due to the expansion / contraction of the highly hygroscopic crosslinked resin layer 4 is relieved. More preferably, it is 10 μm or more.
The film thickness of the highly hygroscopic crosslinked resin layer 4 is preferably 3 μm or more, and more preferably 10 μm or more. Thereby, it becomes easy to ensure a necessary saturated moisture absorption amount for the entire antifogging film 5. On the other hand, from the viewpoint of preventing the durability of the antifogging film 5 from being lowered, the thickness of the highly hygroscopic crosslinked resin layer 4 is preferably 50 μm or less, and more preferably 30 μm or less.
High antifogging performance when the film thickness of the low hygroscopic crosslinked resin layer 3 is 1.0 μm or more, the saturated moisture absorption is 10 mg / cm ³ or less, and the saturated moisture absorption of the antifogging film 5 is 20 mg / cm ³ or more. And durability.

  Since the saturated moisture absorption amount of the crosslinkable resin is proportional to the amount of hydrophilic groups in the crosslinkable resin, it can be controlled by adjusting the amount of hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonyl group, an amide group, an amino group, a quaternary ammonium base, and an oxyalkylene group. The amount of the hydrophilic group in the crosslinkable resin can be controlled by adjusting the amount of the hydrophilic group (for example, hydroxyl value) contained in the crosslinkable component and the curing agent. When a hydrophilic group is formed by a crosslinking reaction, the saturated moisture absorption can be controlled by adjusting the number of functional groups and the degree of crosslinking of the crosslinking component and the curing agent.

  The saturated moisture absorption amount also depends on the degree of crosslinking in the crosslinkable resin. If the number of crosslinking points contained in a crosslinkable resin per unit amount is large, the crosslinkable resin has a dense three-dimensional network structure, and the space for water retention is reduced, so that the hygroscopicity is lowered. On the other hand, if there are few crosslinking points contained per unit amount, the space for water retention will become large and it will be thought that moisture absorption becomes high. The glass transition point of the crosslinkable resin is closely related to the number of crosslink points in the crosslinkable resin. In general, a resin having a high glass transition point is considered to have a large number of crosslink points per unit amount.

Therefore, in order to increase the antifogging performance, it is preferable to lower the glass transition point of the crosslinkable resin, and in order to increase the durability, it is preferable to increase the glass transition point of the crosslinkable resin.
From the above, the glass transition point of the crosslinkable resin forming the low hygroscopic crosslinkable resin layer 3 depends on the type of the crosslinkable resin, but is preferably 10 to 200 ° C, and preferably 30 to 150 ° C. Is more preferable. Moreover, although the glass transition point of the crosslinkable resin which forms the highly hygroscopic crosslinked resin layer 4 is based also on the kind of crosslinkable resin, it is preferable that it is 50-200 degreeC, and it is 90-150 degreeC more. preferable. If the glass transition point of the crosslinkable resin forming the low hygroscopic crosslinkable resin layer 3 and the high hygroscopic crosslinkable resin layer 4 is within this range, it is easy to achieve both antifogging performance and durability at a high level.

  The glass transition point is a value measured according to JIS K7121. Specifically, the low hygroscopic crosslinked resin layer 3 or the highly hygroscopic crosslinked resin layer 4 is provided on the substrate, and this is left in an environment of 20 ° C. and 50% relative humidity for 1 hour, and then a differential scanning calorimeter is used. It is the value measured using. However, the heating rate at the time of measurement shall be 10 degrees C / min.

The reason why the antifogging article 1 of the present invention has antifogging performance and durability is considered as follows.
In general, when a hygroscopic cross-linked resin layer is formed on the surface of a substrate, the antifogging performance that is manifested by moisture absorption correlates with the hygroscopicity of the formed hygroscopic cross-linked resin layer. The higher the hygroscopicity of the hygroscopic crosslinked resin layer, the longer the effect of reducing the atmospheric humidity on the surface of the hygroscopic crosslinked resin layer formed on the surface of the substrate, and the higher the antifogging performance. The hygroscopic crosslinked resin layer expands when absorbing moisture and contracts when releasing moisture. Therefore, the hygroscopic crosslinked resin layer having high anti-fogging performance repeats large expansion and contraction, and interface stress accumulates at the bonding interface between the substrate and the hygroscopic crosslinked resin layer, and the adhesiveness tends to decrease. In some cases, the hygroscopic crosslinked resin layer may peel off.
Further, the hygroscopic crosslinked resin layer takes in alkali ions and acidic ions derived from a cleaning agent and drinking water together with water when absorbing moisture. When alkali ions or acidic ions move to the adhesive interface between the substrate and the hygroscopic crosslinked resin layer, the bond between the reactive group on the substrate surface and the crosslinkable resin is broken, and the hygroscopic crosslinked resin layer is peeled off or decomposed. There is a case. Further, when the substrate is soda lime glass, when the hygroscopic crosslinked resin layer takes in water and the water moves to the adhesion interface, an alkaline component comes out from the substrate, which causes the same problem.

On the other hand, the low hygroscopic crosslinked resin layer 3 of the present invention has a low saturated moisture absorption amount and a small degree of expansion / contraction, and therefore has high adhesion to the substrate 2. Further, since the low hygroscopic crosslinked resin layer 3 is made of the same crosslinkable resin as the high hygroscopic crosslinked resin layer 4, the adhesiveness to the high hygroscopic crosslinked resin layer 4 is high, and the high hygroscopic crosslinked resin layer 4 is expanded.・ Follow contraction. Further, since the low hygroscopic crosslinked resin layer 3 has a constant film thickness, accumulation of large interfacial stress between the substrate 2 and the highly hygroscopic crosslinked resin layer 4 can be alleviated. Can be prevented from peeling off.
Further, in the antifogging article 1 of the present invention, since the low hygroscopic crosslinked resin layer 3 having a small saturated moisture absorption amount and a large film thickness is provided, alkali ions and acidic ions taken together with water by the highly hygroscopic crosslinked resin layer 4 are provided. Etc. can be prevented from coming between the low-hygroscopic crosslinked resin layer 3 and the substrate 2, and the bond between the substrate 2 and the antifogging film 5 is hardly broken. Therefore, it is possible to prevent the antifogging film 5 from being peeled off from the base 2. Similarly, since it is possible to prevent water from transferring between the low hygroscopic crosslinked resin layer 3 and the base 2, even if the base 2 is glass, the antifogging film 5 is peeled off from the base by an alkali component. Problems rarely occur.

[Method of forming antifogging film 5]
As a method for forming the low hygroscopic crosslinked resin layer 3, (1) a method in which a crosslinkable component and a curing agent are reacted on the surface of the substrate 2, (2) the crosslinkable component is formed into a film shape, Examples thereof include a method of bonding a film with a curing agent, and (3) a method of forming a crosslinkable resin forming the low hygroscopic crosslinkable resin layer 3 into a film and bonding the film to the substrate 2.
As a method for forming the highly hygroscopic crosslinked resin layer 4, as in the method for forming the low hygroscopic crosslinked resin layer 3, (1) a method in which a crosslinkable component and a curing agent are reacted on the surface of the low hygroscopic crosslinked resin layer 3. (2) A method in which the crosslinkable component is formed into a film and the surface of the low hygroscopic crosslinked resin layer 3 and the film are bonded using a curing agent, and (3) the high hygroscopic crosslinked resin layer 4 is formed. Examples thereof include a method in which a crosslinkable resin is formed into a film and the film is bonded to the low hygroscopic crosslinked resin layer 3.
Among these, the method (1) or (2) is preferable, and a good appearance is obtained when the low-hygroscopic cross-linked resin layer 3 and the high hygroscopic cross-linked resin layer 4 are provided on the surface of a large-sized substrate or in industrial mass production. The method (1) is more preferable because it can be maintained.

  Hereinafter, the method (1) will be described in detail. First, a composition (hereinafter referred to as a liquid composition A) for the low hygroscopic crosslinked resin layer 3 having a crosslinkable component and a curing agent as essential components is applied to the surface of the substrate 2, dried, and reacted. Thus, the low hygroscopic crosslinked resin layer 3 is formed. Thereafter, a composition (hereinafter, referred to as liquid composition B) having a crosslinkable component and a curing agent as essential components for the highly hygroscopic crosslinked resin layer 4 is applied to the surface of the low hygroscopic crosslinked resin layer 3, Drying and reaction are performed to form the highly hygroscopic crosslinked resin layer 4.

  The liquid composition A and the liquid composition B preferably contain a solvent in order to improve the coating workability. Therefore, it is preferable to prepare a liquid composition A and a liquid composition B containing a solvent, apply them to the surface of the substrate 2 or the surface of the low-hygroscopic cross-linked resin layer 3, dry them, and react. Further, a liquid composition A and a liquid composition B, in which a crosslinkable component and a curing agent are reacted to some extent in a solvent, are applied to the surface of the substrate 2 or the surface of the low hygroscopic crosslinked resin layer 3 and dried. Further reaction may be performed. In the case where the crosslinkable component and the curing agent are reacted to some extent in a solvent, it is preferable that the reaction temperature when the reaction is performed in advance is 40 ° C. or higher because the crosslinking reaction proceeds reliably.

  The crosslinkable component is not particularly limited as long as it is a monomer, oligomer or polymer having a crosslinkable group and reacts in the presence of a curing agent described later to become a crosslinkable resin. 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, carboxy group, and acid anhydride group. Is mentioned. Among these, a carboxy group, an epoxy group, and a hydroxyl group are preferable, and an epoxy group is more preferable. The number of crosslinkable groups possessed by the crosslinkable component may be any number as long as the antifogging performance and durability required in the present invention are satisfied. Moreover, only 1 type may be used for a crosslinkable component and it may use 2 or more types together.

  When the crosslinkable component is a monomer or oligomer having a crosslinkable group, the number of crosslinkable groups contained in one molecule is preferably 2 or more, and more preferably 2 to 10. In some cases, a component having only one crosslinkable group may be included, but in that case, the average number of crosslinkable groups per molecule in the crosslinkable component is 1.5 or more. It is preferable to do this.

  When the crosslinkable component is a monomer or oligomer, the crosslinkable component is preferably a polyepoxide. Polyepoxides are components that have an epoxy group as a crosslinkable group and become a crosslinkable resin by reaction with a curing agent. The average number of epoxy groups of the polyepoxides is 2 or more, and preferably 2 to 10.

  Examples of polyepoxides include glycidyl compounds such as glycidyl ether compounds, glycidyl ester compounds, and glycidyl amine compounds. Of these, glycidyl ether compounds are preferable, and aliphatic glycidyl ether compounds are more preferable. As the glycidyl ether compound, a glycidyl ether of a bifunctional or higher alcohol is preferable, and a glycidyl ether of a trifunctional or higher alcohol is more preferable because durability and antifogging performance are improved. Further, these alcohols are preferably aliphatic alcohols, alicyclic alcohols, or sugar alcohols.

  Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, poly Specific examples include glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. Here, “poly” means that the average value is more than 2. These may be used alone or in combination of two or more.

As the low hygroscopic cross-linked resin layer 3 in the present invention, since a cross-linkable resin particularly excellent in cross-link density can be obtained, polyglycidyl ether of an aliphatic polyol having 6 or more hydroxyl groups (average glycidyl group per molecule) Is more than 5). Specific examples include sorbitol polyglycidyl ether.
As the highly hygroscopic cross-linked resin layer 4 in the present invention, a cross-linkable resin having particularly good anti-fogging performance can be obtained. Therefore, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether Polyglycidyl ethers of aliphatic polyols having 3 or more hydroxyl groups such as those having an average glycidyl group of more than 2 per molecule are preferred.
As described above, in the antifogging article 1 of the present invention, it is preferable that both the low hygroscopic crosslinked resin layer 3 and the high hygroscopic crosslinked resin layer 4 are polyepoxides.

  When the crosslinkable component is a polymer having a crosslinkable group, there is no particular limitation as long as it becomes a crosslinkable resin by reacting with a curing agent described later. The polymer having a crosslinkable group is preferably a linear polymer. Examples of the crosslinkable group include the same as those in the case where the crosslinkable component is a monomer or an oligomer, and a carboxy group, an epoxy group, and a hydroxyl group are preferable. The number of crosslinkable groups possessed by the polymer which is a crosslinkable component is not particularly limited as long as the antifogging performance and durability required in the present invention are satisfied. 1 to 20 is preferable. Moreover, it is preferable that the molecular weight of a polymer is 500-50000 in a number average molecular weight.

  The crosslinking reaction of the crosslinking component in the present invention is not limited as long as a crosslinking resin having a three-dimensional network structure can be formed, and examples thereof include radical polymerization, ionic polymerization, polycondensation reaction, and polyaddition reaction. When polyepoxides are used as the crosslinkable component, ionic polymerization or polyaddition reaction is preferred. By using a curing agent suitable for each reaction, a strong low-hygroscopic crosslinked resin layer 3 and a highly hygroscopic crosslinked resin layer 4 can be formed on the surface of the substrate 2.

The curing agent preferably used in the present invention is any of the following. The curing agent (α) is suitable for polyaddition reaction, and the curing agent (β) is suitable for ionic polymerization.
Curing agent (α): A compound having a reactive group capable of reacting with the crosslinkable group of the crosslinkable component and reacting with the crosslinkable component to form a crosslinkable resin having a three-dimensional network structure.
Curing agent (β): A compound that promotes the formation of a crosslinkable resin having a three-dimensional network structure by catalyzing the crosslinking reaction of the crosslinkable component.

  The reactive group of the curing agent (α) is selected from reactive groups capable of reacting with the crosslinkable group according to the type of the crosslinkable group of the crosslinkable component combined with the curing agent (α). As the reactive group of the curing agent (α), for example, vinyl group, epoxy group, styryl group, acryloyloxy group, methacryloyloxy group, amino group, ureido group, chloropropyl group, mercapto group, sulfide group, isocyanate group, Examples thereof include a hydroxyl group, a carboxy group, and an acid anhydride group. When the crosslinkable group of the crosslinkable component is a carboxy group, the reactive group of the curing agent (α) is preferably an amino group, and more preferably an epoxy group. When the crosslinkable group of the crosslinkable component is a hydroxyl group, the reactive group of the curing agent (α) is preferably an epoxy group or an isocyanate group. When the crosslinkable group of the crosslinkable component is an epoxy group, the reactive group of the curing agent (α) is preferably a carboxy group, an amino group, an acid anhydride group, or a hydroxyl group. Moreover, the number of the reactive groups which 1 molecule | numerator of hardening | curing agent ((alpha)) has is 1.5 or more on the average, and it is preferable that it is 2-8 for formation of the highly hygroscopic crosslinked resin layer 4. FIG. When the number of reactive groups in the curing agent (α) is within this range, a hygroscopic crosslinked resin having an excellent balance between antifogging performance and wear resistance can be obtained.

  Two or more curing agents (α) can be used in combination. For example, when the second curing agent (α) is used in combination with the main first curing agent (α), the reactive group of the second curing agent (α) reacts with the crosslinking group of the crosslinking component. In addition, it may react with the reactive group of the first curing agent (α). The second curing agent (α) that reacts with the first curing agent (α) is bonded to the crosslinkable component via the first curing agent (α). By using such a second curing agent (α) in combination, the formation of a crosslinkable resin by the crosslinkable component and the main first curing agent (α) can be promoted. At this time, the reactive group of the second curing agent (α) may be the same as or different from the reactive group of the first curing agent (α). For example, a combination of a crosslinkable component having an epoxy group and a first curing agent (α) having an amino group, a second curing agent (α) having a hydroxyl group or a second curing having an acid anhydride group. By using the agent (α) in combination, the formation of the crosslinkable resin is promoted. Moreover, this 2nd hardening | curing agent ((alpha)) can be used also in order to adjust the physical property of a crosslinkable resin other than accelerating | stimulating the crosslinking reaction of a crosslinkable component. For example, the hygroscopic property of the highly hygroscopic crosslinked resin layer 4 can be enhanced by the second curing agent (α).

  Examples of the curing agent (α) that can be used in the present invention include polyamine compounds, polycarboxylic acid compounds (including polycarboxylic acid anhydrides), polyol compounds, polyisocyanate compounds, and polyepoxy compounds. . These curing agents (α) are selected according to the crosslinkable group of the crosslinkable component. As the curing agent (α) used for crosslinking of the crosslinkable component having an epoxy group, a polyamine compound is preferable among the above compounds. It is also preferable to use a polyol compound, a polycarboxylic acid anhydride, or the like as the second curing agent (α) together with the first curing agent (α) of the polyamine compound.

As the polyamine compound, an aliphatic polyamine compound and an alicyclic polyamine compound are preferable. Specifically, for example, ethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, isophoronediamine, mensendiamine, metaphenylenediamine, polypropylene glycol polyamine, polyethylene glycol polyamine, 3,9-bis (3-amino Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane.
Examples of the polycarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, malic acid, citric acid, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.
Examples of polyol compounds include polyhydric alcohol-ethylene oxide adducts, polyhydric alcohol-propylene oxide adducts, and polyester polyols.
Examples of the polyisocyanate compound include hexamethylene diisocyanate and isophorone diisocyanate.
Examples of the polyepoxy compound include glycidyl compounds such as glycidyl ether compounds, glycidyl ester compounds, and glycidyl amine compounds. Of these, glycidyl ether compounds are preferable, and aliphatic glycidyl ether compounds are more preferable. As the glycidyl ether compound, a glycidyl ether of a bifunctional or higher alcohol is preferable, and a glycidyl ether of a trifunctional or higher alcohol is more preferable because durability and antifogging performance are improved. Further, these alcohols are preferably aliphatic alcohols, alicyclic alcohols, or sugar alcohols.
Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, poly Specific examples include glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. Here, “poly” means that the average value is more than 2. These may be used alone or in combination of two or more.

The ratio of the curing agent (α) to the crosslinkable component is suitably a ratio in which the number of crosslinkable groups and reactive groups is approximately equal, and the equivalent ratio of reactive groups to crosslinkable groups is 0.8 to 1.2. It is preferable that However, when there is a reactive compound coexisting in the crosslinking reaction system (for example, a silane coupling agent having an amino group) other than the second curing agent (α) or the crosslinking component or the curing agent (α). The equivalent ratio of the reactive groups including them to the crosslinkable group is suitably about 0.8 to 1.2. Further, if the crosslinkable group or reactive group that can remain in the crosslinkable resin is present, the ratio of the reactive group to other reactive groups may be further increased.
When the liquid composition A or the liquid composition B contains polyepoxides, the content of the polyepoxides contained in the liquid composition varies depending on the type of curing agent. When using a hardening | curing agent ((alpha)) as a hardening | curing agent, it is preferable that the mass ratio of polyepoxides with respect to the total mass with polyepoxides, hardening | curing agent ((alpha)), and a coupling agent is 40-80 mass%. Moreover, as for the quantity of the hardening | curing agent at this time, it is preferable that the mass ratio of the hardening | curing agent ((alpha)) with respect to the total mass of a crosslinkable component, a hardening | curing agent ((alpha)), and a coupling agent is 10-60 mass%.

  As described above, the second curing agent (α) can be used for adjusting the physical properties of the crosslinkable resin in addition to crosslinking the crosslinkable component. For example, by using an acid anhydride compound that reacts with an amine compound that is a curing agent, a hydrophilic bond obtained by reacting an amino group and an acid anhydride group can be provided to the crosslinkable resin. At this time, the function is exhibited even when only one reactive group in the second curing agent (α) is reacted. Moreover, the compound which has only one reactive group which can couple | bond with a crosslinkable component and a 1st hardening | curing agent ((alpha)) may be sufficient if the physical property of crosslinkable resin can be adjusted. In this case, the compound having only one reactive group is a compound having no crosslinking function. In the case of using a compound having one reactive group in addition to the first curing agent (α), the amount is preferably equal to or less than the first curing agent (α), 0.01 to 0 More preferably, it is 5 times mass. The first curing agent (α) also affects the function of the crosslinkable resin, and there is no essential distinction from the second curing agent (α) in that respect.

  The curing agent (β) is a substance that promotes the crosslinking reaction of the crosslinkable component, and a compound generally known as a polymerization catalyst can be used. Examples of the curing agent (β) include dicyandiamides, organic acid dihydrazides, tris (dimethylaminomethyl) phenols, dimethylbenzylamines, phosphines, imidazoles, allyldiazonium salts, and allylsulfonium salts. Of these, tris (dimethylaminomethyl) phenols, phosphines, and allylsulfonium salts are preferable.

Although the usage-amount of a hardening | curing agent ((beta)) changes also with the kind of crosslinkable component, when polyepoxides are used as a crosslinkable component, it is preferable that it is 2-20 mass% with respect to polyepoxides. When the amount of the curing agent (β) used is 2% by mass or more, the reaction proceeds sufficiently and sufficient hygroscopicity and durability can be realized. Further, when the amount of the curing agent (β) used is 20% by mass or less, it is easy to prevent the residue from remaining in the resulting crosslinkable resin and causing problems in appearance such as yellowing of the crosslinkable resin.
When the liquid composition A or the liquid composition B contains polyepoxides and a curing agent (β) is used as the curing agent, the polyepoxides with respect to the total mass of the polyepoxides, the curing agent (β), and the coupling agent It is preferable that a mass ratio is 60-95 mass%. Moreover, the quantity of the hardening | curing agent ((beta)) at this time is that the mass ratio of the hardening | curing agent ((beta)) with respect to the total mass of a crosslinkable component, a hardening | curing agent ((beta)), and a coupling agent is 1-40 mass%. preferable.

The solvent is not particularly limited as long as it is a solvent having good solubility of components such as a crosslinkable component and a curing agent and is inactive to these components. Specific examples include alcohols, acetate esters, ethers, ketones, and water.
When a polyepoxide is used as the crosslinkable component, if a protic solvent is used as the solvent, depending on the type, the solvent and the polyepoxide may react to make it difficult to form a crosslinkable resin. Therefore, when a protic solvent is used, it is preferable to select a solvent that does not easily react with polyepoxides. Examples of protic solvents that can be used include ethanol isopropyl alcohol. Moreover, as a solvent, methyl ethyl ketone, butyl acetate, propylene carbonate, and diethylene glycol dimethyl ether are preferable.

Only one solvent may be used, or two or more solvents may be used in combination. Moreover, components, such as a crosslinkable component and a hardening | curing agent, may be used as a mixture with a solvent. In this case, the solvent contained in the mixture may be the solvent in the liquid composition A or the liquid composition B, and another solvent may be added to form the liquid composition A or the liquid composition B.
Moreover, when the liquid composition A or the liquid composition B contains polyepoxides, the amount of the solvent should be 1 to 5 times the total mass of the polyepoxides, the curing agent, and the coupling agent described later. Is preferred.

In the present invention, the adhesion between the substrate 2 and the low hygroscopic crosslinked resin layer 3 can be improved by allowing a coupling agent to coexist when the liquid composition A is reacted on the substrate surface. Similarly, when the liquid composition B is reacted on the surface of the low hygroscopic crosslinked resin layer 3, the cohesive agent is allowed to coexist so that the adhesion between the low hygroscopic crosslinked resin layer 3 and the highly hygroscopic crosslinked resin layer 4 is increased. Can be improved. Further, the adhesion between the substrate 2 and the low hygroscopic crosslinked resin layer 3 can also be improved by treating the surface of the substrate 2 with a coupling agent (coupling agent for surface treatment) in advance as described above. Can do. It is not essential to add a coupling agent to the liquid composition A and the liquid composition B. However, even when the substrate 2 previously treated with the surface treatment coupling agent is used, it is preferable that the coupling agent coexists in the liquid composition A and the liquid composition B. When the coupling agent has a functional group reactive with the crosslinkable component or the curing agent, the low hygroscopic crosslinked resin layer 3 and the highly hygroscopic crosslinked resin layer 4 can be used for purposes other than improving the adhesion. It can also be used for the purpose of adjusting physical properties. Hereinafter, the coupling agent blended in the liquid composition A and the liquid composition B is simply referred to as a coupling agent.
When the liquid composition A and the liquid composition B contain polyepoxides, the liquid composition preferably contains a coupling agent, and a silane coupling agent is preferred as the coupling agent. By adding a coupling agent such as a silane coupling agent, the adhesion between the substrate 2 and the low hygroscopic crosslinked resin layer 3 and the adhesion between the low hygroscopic crosslinked resin layer 3 and the high hygroscopic crosslinked resin layer 4 Can be increased. As the silane coupling agent, the same silane coupling agent as described above can be used, and the preferred embodiment is also the same. The silane coupling agent is preferably used in the same amount as described above.

The coupling agent is preferably an organometallic coupling agent or a polyfunctional organic compound.
Examples of the organometallic 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 include a crosslinkable group of the crosslinkable component, a reactive group of the curing agent, and a reactive group capable of reacting with the reactive group remaining on the surface of the substrate 2 and the surface of the low hygroscopic crosslinked resin layer 3. It is preferable to have. 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. In the case of a silane coupling agent, a compound in which one hydrolyzable group and three monovalent organic groups (however, the terminal bonded to the silicon atom is a carbon atom) are bonded to the silicon atom. A compound in which two hydrolyzable groups and two monovalent organic groups (however, the terminal bonded to the silicon atom is a carbon atom) is bonded to the silicon atom is preferable. In addition, the monovalent organic group may be a hydrocarbon group such as an alkyl group or may have a functional group, and at least one of them preferably has a functional group.

Examples of silane coupling agents include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxy. Propylmethyldiethoxysilane, 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-aminopropyl Pills trimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.
Among them, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane and 3-acryloxypropyltrimethoxysilane are preferred.

  The polyfunctional organic compound means an organic compound having two or more functional groups. The crosslinkable group of the crosslinkable component, the reactive group of the curing agent, the surface of the substrate 2 and the low hygroscopic crosslinked resin layer 3 It has two or more reactive groups that can react with the reactive groups on the surface. Examples of the reactive group include a vinyl group, an epoxy group, a styryl group, an acryloyloxy group, a methacryloyloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a sulfide group, an isocyanate group, a hydroxyl group, and a carboxy group. And acid anhydride groups. When the crosslinkable group of the crosslinkable component is an epoxy group, the reactive group of the coupling agent is preferably an isocyanate group, an amino group, an acid anhydride group, an epoxy group, or a hydroxyl group, and more preferably an isocyanate group or an epoxy group. . Specific examples of the polyfunctional organic compound include polyisocyanate and polyepoxide.

  When the coupling agent is a polyfunctional organic compound, the substance is not distinguished from the curing agent (α). However, the role of the coupling agent and the role of the curing agent (α) are different. That is, the coupling agent plays a role of improving the adhesion between the substrate 2 and the low hygroscopic crosslinked resin layer 3 and the adhesion between the low hygroscopic crosslinked resin layer 3 and the high hygroscopic crosslinked resin layer 4. α) plays a role of reacting with the crosslinkable component to form a crosslinkable resin.

  The amount of coupling agent used in liquid composition A and liquid composition B is not an essential component, so there is no lower limit. However, the mass ratio of the coupling agent is 0.1% by mass or more with respect to the total mass of the crosslinkable component, the curing agent, and the coupling agent in order to fully exhibit the effect of the coupling agent blending. Is preferable, and 0.5 mass% or more is more preferable. 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 adhesiveness of the crosslinkable resin, the mass ratio of the coupling agent to the total mass of the crosslinkable component, the curing agent and the coupling agent is preferably 10% by mass or less, and 5% by mass or less. Is more preferable.

  When the moisture absorption amount in the antifogging article 1 exceeds the limit amount of the crosslinkable resin, a water film may be better than a cloudy state depending on the application. In that case, the amount of the coupling agent contained in the liquid composition B that forms the highly hygroscopic crosslinked resin layer 4 is preferably as small as possible, and the amount of the coupling agent relative to the total mass of the crosslinking component, the curing agent, and the coupling agent The mass ratio is preferably 5% by mass or less, and more preferably 2% by mass or less. The coupling agent generally contains propylene in order to increase the hydrophobicity, but if the content of the coupling agent is 5% or less, the hydrophilicity can be prevented from excessively decreasing. On the other hand, when adjusting physical properties such as hygroscopicity of the crosslinkable resin with a coupling agent or with a curing agent and a coupling agent, a relatively large amount of coupling agent may be used. In that case, 15 mass% or less is preferable and, as for the mass ratio of the coupling agent with respect to the total mass of a crosslinkable component, a hardening | curing agent, and a coupling agent, 10 mass% or less is more preferable. If the amount of the coupling agent used is not excessive, it is possible to prevent the crosslinked resin from being colored due to oxidation or the like when exposed to a high temperature.

When the low hygroscopic crosslinked resin layer 3 and the high hygroscopic crosslinked resin layer 4 are formed using the liquid composition A and the liquid composition B containing the crosslinkable component, the curing agent, the solvent, and the coupling agent, Can be appropriately selected and used. For example, the following combinations (the description of the solvent is omitted) can be adopted.
(1) A combination of a crosslinkable component having an epoxy group as a crosslinkable group, a curing agent (α) having an amino group, and a coupling agent having an isocyanate group, an amino group or an epoxy group.
(2) A combination of a crosslinkable component having an epoxy group as a crosslinkable group, a curing agent (β), and a coupling agent having an isocyanate group, amino group or epoxy group.
(3) A combination of a crosslinkable component having a carboxy group as a crosslinkable group, a curing agent (α) having an epoxy group, and a coupling agent having an amino group or an epoxy group.
(4) A combination of a crosslinkable component having a carboxy group as a crosslinkable group, a curing agent (α) having an amino group, and a coupling agent having an isocyanate group or an epoxy group.

It is preferable that the liquid composition A and the liquid composition B containing polyepoxide further contain a filler. By including a filler, the mechanical strength and heat resistance of the crosslinkable resin to be formed can be increased, and the curing shrinkage of the resin during the crosslinking reaction can be reduced. As the filler, a filler made of a metal oxide is preferable. Examples of the metal oxide include silica, alumina, titania, and zirconia. Among these, 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 crosslinkable resin. Therefore, if a filler made of ITO is used, in addition to hygroscopicity, an antifogging effect due to heat ray absorption can be expected.

  The filler is preferably particulate, and the average particle size is 0.01 to 0.3 μm, preferably 0.01 to 0.1 μm. Moreover, it is preferable that it is 1-20 mass% with respect to the total mass of polyepoxide and hardening | curing agent, and, as for the compounding quantity of a filler, 1-10 mass% is more preferable. If the blending amount of the filler is 1% by mass or more, it is easy to suppress a reduction in the curing shrinkage reduction effect of the crosslinkable resin. Further, if the blending amount of the filler is 20% by mass or less, a sufficient space for water absorption can be secured and the antifogging performance can be easily improved.

When the liquid composition A and the liquid composition B are applied to the surface of the substrate 2 or the surface of the low hygroscopic crosslinked resin layer 3, the thickness of the coating film is not uniform due to the wettability of the liquid composition A and the liquid composition B. May cause perspective distortion. In order to make the thickness of the coating film uniform, it is preferable to add a leveling agent. Examples of the leveling agent include a silicone leveling agent, a fluorine leveling agent, and a surfactant. Among these, a silicone 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. As the silicone leveling agent, amino-modified silicone and polyether-modified silicone are preferable.
In addition, silicone having an oxyalkylene chain such as an oxyethylene chain or an oxypropylene chain can be imparted to the liquid composition B forming the highly hygroscopic crosslinked resin layer 4 from the viewpoint of imparting hydrophilicity and improving antifogging performance. It is also preferable to add a system leveling agent.

  The amount of the silicone leveling agent added can be 0.02 to 1% by mass with respect to the liquid composition B, so that the wettability can be improved and the thickness of the coating film can be made uniform. Moreover, since the addition amount of a silicone type leveling agent is easy to prevent the cloudiness of a coating film, 0.02-0.30 mass% is preferable with respect to the mass of the liquid composition B, and 0.02-0.10 mass % Is more preferable.

As the surfactant, any of a nonionic surfactant, a cationic surfactant, a betaine surfactant, and an anionic surfactant may be used. If the surfactant is a surfactant having an oxyalkylene chain such as an oxyethylene chain or an oxypropylene chain, hydrophilicity can be imparted to the liquid composition B, and the antifogging performance is improved.
In addition, when the moisture absorption amount exceeds the limit amount of the crosslinkable resin in the antifogging article 1, it is better to become a water film than in a cloudy state depending on the use (such as when used for a bathroom vanity). There is also. In this case, the antifogging article 1 that becomes a water film when the moisture absorption amount is saturated, for example, by adding a surfactant to the liquid composition B can be obtained. The surfactant used for this purpose preferably has a reactive group. By having the reactive group, the surfactant becomes a part of the crosslinkable resin, and the effect becomes higher.

As a method for producing the antifogging article of the present invention, the liquid composition A described above is applied to the surface of the substrate 2, dried and reacted to form the low hygroscopic crosslinked resin layer 3, and then the liquid composition It is particularly preferred that the product B is applied to the surface of the low hygroscopic crosslinked resin layer 3, dried and reacted to form the highly hygroscopic crosslinked resin layer 4. This method is easier to control the polymerization reaction than the method of applying after a crosslinking reaction in advance before coating, and the crosslinking density of the resulting film is easy to adjust, so that an anti-fogging film having high durability can be obtained. It is easy to obtain. Moreover, since there is almost no fall of stability of the liquid composition A and the liquid composition B, economical efficiency is also high.
Here, examples of the “application” include the following methods.
Examples of the method of applying the liquid composition A and the liquid composition B to the surface of the substrate 2 and the surface of the low hygroscopic crosslinked resin layer 3 include spin coating, dip coating, spray coating, flow coating, and die coating. However, spray coating, flow coating, and die coating are preferred.
The thickness of the composition layer obtained by applying the liquid composition A to the surface of the substrate 2 is preferably 3 to 50 μm, the thickness after drying is preferably 2 to 40 μm, and obtained after the reaction. The thickness of the low hygroscopic crosslinked resin layer 3 is preferably 1.0 to 30 μm.
Moreover, it is preferable that the thickness of the composition layer obtained by apply | coating the liquid composition B to the surface of the low hygroscopic crosslinked resin layer 3 is 10-70 micrometers, and the film thickness after drying is 5-60 micrometers. The thickness of the highly hygroscopic crosslinked resin layer 4 obtained after the reaction is preferably 3 to 50 μm.

  “Dry” means that the solvent in the liquid composition A or the liquid composition B applied to the surface of the substrate 2 or the low-hygroscopic crosslinked resin layer 3 is volatilized and removed. The drying conditions are appropriately set depending on the type of the solvent contained in the liquid composition A or the liquid composition B, the thickness of the coating film, etc. For example, the substrate coated with the liquid composition A or the liquid composition B is 20 It can implement by hold | maintaining at -100 degreeC for 1 minute-1 hour.

Further, the “reaction” means that a crosslinkable resin is formed by a crosslinking reaction of the crosslinkable component contained in the liquid composition A or the liquid composition B. This crosslinking reaction may be accompanied by a bond-forming reaction with the surface of the substrate 2 or the surface of the low hygroscopic crosslinked resin layer 3. From the viewpoint of durability of the antifogging article 1, it is preferable that the crosslinking reaction is accompanied by a bond forming reaction with the surface of the substrate 2 or the surface of the low hygroscopic crosslinked resin layer 3. The “reaction” can be carried out, for example, by holding the dried substrate at 80 to 200 ° C. for 1 minute to 1 hour. It can also be carried out by irradiating with ultraviolet rays or visible rays using a metal halide lamp, a high-pressure mercury lamp, a halogen lamp or the like. In this case, the integrated light quantity is preferably 10 to 1000 mJ / cm ² .

In the antifogging article 1 of the present invention, a low hygroscopic crosslinked resin layer 3 is formed on the surface of a substrate 2, and a high hygroscopic crosslinked resin layer 4 is formed on the surface of the low hygroscopic crosslinked resin layer 3. The low hygroscopic crosslinked resin layer 3 has a film thickness of 1.0 μm or more, a saturated moisture absorption of 10 mg / cm ³ or less, and the anti-fogging film 5 has a saturation moisture absorption of 20 mg / cm ³ or more. Thereby, the antifogging article 1 has both good antifogging performance and high durability.
Further, in the antifogging article 1 of the present invention, the low hygroscopic crosslinked resin layer 3 and the substrate 2 are provided by providing the low hygroscopic crosslinked resin layer 3 even when the high hygroscopic crosslinked resin layer 4 takes in water. In the meantime, the taken-in water hardly moves. Therefore, even if the substrate 2 is glass, peeling of the highly hygroscopic crosslinked resin layer 4 from the substrate 2 due to an alkali component can be prevented. Therefore, even when the substrate 2 is soda lime glass, the antifogging article 1 having excellent antifogging performance and high durability can be provided.
Moreover, if the crosslinkable resin of the antifogging article 1 of the present invention satisfies the conditions of the saturated moisture absorption and film thickness and is a crosslinkable resin obtained by a reaction between a polyepoxide and a curing agent, the antifogging article 1 The fogging performance and durability are more excellent.

The antifogging article of the present invention does not necessarily have to be provided with a low hygroscopic crosslinked resin layer on the entire surface of the substrate as shown in FIG. Moreover, the high hygroscopic crosslinked resin layer does not need to be provided in the whole formed low hygroscopic crosslinked resin layer. For example, the low hygroscopic crosslinked resin layer may be formed on a part of the substrate surface, and the high hygroscopic crosslinked resin layer may be formed on a part of the surface of the low hygroscopic crosslinked resin layer.
Moreover, the low hygroscopic crosslinked resin layer and the highly hygroscopic crosslinked resin layer of the present invention are not limited to a single layer, and may be composed of a plurality of layers as long as they satisfy the conditions of the present invention. I do not care.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited by the following description.
Evaluation of the anti-fogging articles in the examples and comparative examples was performed as follows.
[Measurement of film thickness]
After leaving the antifogging article in an environment of 20 ° C. and 50% relative humidity for 1 hour, using a stylus type surface profile measuring device DEKTAK3030 (manufactured by ULVAC), the low hygroscopic crosslinked resin layer alone and the low moisture absorption The film thickness difference of the entire antifogging film composed of the water-soluble crosslinked resin layer and the highly hygroscopic crosslinked resin layer was measured. The film thickness of the highly hygroscopic crosslinked resin layer was determined by subtracting the film thickness of the low hygroscopic crosslinked resin layer alone from the film thickness of the entire antifogging film.

[Measurement of saturated moisture absorption]
The saturated moisture absorption was measured for the low hygroscopic crosslinked resin layer alone, the high hygroscopic crosslinked resin layer alone, and the entire antifogging film composed of the low hygroscopic crosslinked resin layer and the highly hygroscopic crosslinked resin layer.
First, a low hygroscopic cross-linked resin layer and / or a high hygroscopic cross-linked resin layer substrate is provided on a base, which is left to stand in an environment of 20 ° C. and a relative humidity of 50% for 1 hour, and then the surface is heated to 40 ° C. Immediately after the surface was exposed to cloudiness or water film distortion on the surface, the total water content (I) was measured using a micro moisture meter.
Separately, the moisture content (II) of the substrate itself, in which neither the low-hygroscopic crosslinked resin layer nor the high-hygroscopic crosslinked resin layer is formed, was measured in the same procedure, and the moisture content (I) to the moisture content (II). The value obtained by dividing the value obtained by subtracting the value by the volume of the crosslinkable resin was defined as the saturated moisture absorption amount.
The moisture content was measured with a trace moisture meter FM-300 (manufactured by Kett Science Laboratory Co., Ltd.). 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 the time when the amount of change in weight per minute became 0.02 mg or less. In addition, the evaluation of the saturated moisture absorption amount was a sample prepared using a soda lime glass substrate having a size of 3.3 cm × 10 cm × 2 mm (the area of the low hygroscopic crosslinked resin layer and / or the highly hygroscopic crosslinked resin layer was 33 cm ^2. )).

[Evaluation of anti-fogging performance]
The surface of the anti-fogging film of an anti-fogging article left in an environment of 20 ° C. and 50% relative humidity for 1 hour was placed on a 40 ° C. hot water bath, and the anti-fogging time (minutes) until cloudiness was observed was measured. . A normal soda lime glass not subjected to the antifogging process was fogged in 0.01 to 0.08 minutes. The required anti-fogging performance varies depending on the application. In this example, anti-fogging performance of 0.3 minutes or more is necessary for practical use, preferably 1 minute or more, and more preferably 2 minutes or more.

[Evaluation of wear resistance]
This was performed in accordance with JIS R 3212 (inside the vehicle). A wear wheel CS-10F was used on a Taber 5130 type abrasion tester. A wear ring was brought into contact with the surface of the antifogging film of the antifogging article, rotated 100 times with a load of 4.90 N, measured for change in haze value ΔH (%), and evaluated based on the following evaluation criteria.
A: ΔH was 6% or less.
○: ΔH was more than 6% and 10% or less.
X: At least one of ΔH exceeding 10% or peeling of the hygroscopic crosslinked resin layer occurred.

[Evaluation of adhesion]
The antifogging article is held in a freezer adjusted to −10 ° C. for 30 minutes, and then held in a constant temperature and humidity chamber at 90 ° C. and 90% RH for 30 minutes. After performing this as 1 cycle and performing 3 cycles, a cross-cut test (100 squares, 1 mm interval) was performed and evaluated based on the following evaluation criteria. The cross cut test was performed in accordance with 8.5 of JIS K 5400.
◎: Number of remaining cells is 100 cells ○: Number of remaining cells is 90 to 99 cells ×: Number of remaining cells is 0 to 89 cells

[Evaluation of contamination resistance]
A commercially available hair dyeing solution (0.5 mL) was dropped on the surface of the antifogging film of the antifogging article, left at room temperature for 1 hour, then measured for color difference from before contamination, and evaluated based on the following evaluation criteria. .
◎: ΔEab = less than 5 ○: ΔEab = 5 or more and less than 10 ×: ΔEab = 10 or more

[Evaluation of acid resistance]
The antifogging article was immersed in a 1N aqueous hydrochloric acid solution, washed with water, and evaluated based on the following evaluation criteria.
A: No change in appearance after 30 hours of immersion.
○: No change in appearance after 6 hours of immersion, but changes such as peeling and cloudiness of the film were observed after 30 hours of immersion.
X: Changes such as peeling and cloudiness of the film were observed in the appearance after immersion for 6 hours.

[Evaluation of alkali resistance]
The antifogging article was immersed in a 1N sodium hydroxide aqueous solution, washed with water, and evaluated based on the following evaluation criteria.
A: There was no change in the appearance after immersion for 6 hours.
○: No change in appearance after 2 hours of immersion, but changes such as peeling and cloudiness of the film were observed after 6 hours of immersion.
X: Changes such as peeling and film turbidity were observed in the appearance after immersion for 2 hours.

[Example 1]
In a glass container in which a stirrer and a thermometer are set, 6.34 g of diacetone alcohol (manufactured by Junsei Chemical), 1.26 g of 2-chloroethanol (manufactured by Junsei Chemical), sorbitol polyglycidyl ether (Denacol) as a crosslinkable component 5.94 g of EX-622 (manufactured by Nagase ChemteX Corporation) and 1.02 g of isophoronediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing agent were added and stirred at 25 ° C. for 1 hour. Next, 0.64 g of 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a coupling agent, and the mixture was stirred at 25 ° C. for 1 hour to obtain a liquid composition A. Denacol EX-622 has an average epoxy functional group number of 4.9 and a hydroxyl value of 67 mgKOH / g (1.19 meq / g).
Also, in a glass container in which a stirrer and a thermometer are set, 12.89 g of ethanol (manufactured by Junsei Chemical), 2.17 g of polyoxyalkylene triamine (Jefamine T403, manufactured by Huntsman) as a curing agent, crosslinkable component As the polyfunctional aliphatic glycidyl ether compound (Denacol EX-1610, manufactured by Nagase ChemteX Corp.) 5.32 g, and as the leveling agent 0.1 g of epoxy-modified silicone (X-22-4741, manufactured by Shin-Etsu Chemical Co., Ltd.) And stirred at 25 ° C. for 1 hour. Next, 1.00 g of 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a coupling agent, and the mixture was stirred at 25 ° C. for 1 hour to obtain a liquid composition B. Denacol EX-1610 has an average number of epoxy functional groups of 4.5.
Next, the surface is polished and washed with cerium oxide, and the liquid composition A is applied by spin coating to a clean and dry soda-lime glass substrate (100 mm × 100 mm × 2 mm) and held in an electric furnace at 180 ° C. for 4 minutes. A low-hygroscopic crosslinked resin layer having a thickness of 10.9 μm was formed. Next, the liquid composition B is applied to the surface of the formed low hygroscopic cross-linked resin layer by spin coating, and held in an electric furnace at 200 ° C. for 5 minutes to have a high hygroscopic cross-linked resin layer having a thickness of 22.3 μm. An antifogging article was obtained.
The saturated moisture absorption of the antifogging film of the obtained antifogging article was 76.4 mg / cm ³ .

[Example 2]
In a glass container in which an agitator and a thermometer are set, 4.76 g of ethylene glycol dimethyl ether (manufactured by Junsei Chemical), 1.58 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry), 2-chloroethanol (manufactured by Junsei Chemical) 1.26 g), 5.94 g of sorbitol polyglycidyl ether (Denacol EX-622, manufactured by Nagase ChemteX Corporation) as a crosslinkable component, and 1.02 g of isophorone diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing agent, 25 Stir at 1 ° C. for 1 hour. Next, 0.64 g of 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a coupling agent, and the mixture was stirred at 25 ° C. for 1 hour. The liquid composition A was obtained by diluting twice.
Liquid composition B was obtained in the same manner as in Example 1.
Next, the surface is polished and washed with cerium oxide, and the liquid composition A is applied to a dried clean soda lime glass substrate (100 mm × 100 mm × 2 mm) by spin coating, followed by an electric furnace at 180 ° C. for 4 minutes. The low-hygroscopic crosslinked resin layer having a film thickness of 1.0 μm was formed. Next, the liquid composition B is applied to the surface of the formed low hygroscopic crosslinked resin layer by spin coating, and held in an electric furnace at 200 ° C. for 5 minutes to have a highly hygroscopic crosslinked resin layer having a film thickness of 18.1 μm. An antifogging article was obtained.
The saturated moisture absorption of the antifogging film of the obtained antifogging article was 72.6 mg / cm ³ .

[Example 3]
A liquid composition A was obtained in the same manner as in Example 2 except that it was not diluted with butyl acetate.
Further, in a glass container in which a stirrer and a thermometer are set, 17.71 g of s-butanol (manufactured by Junsei Kagaku), 2.17 g of polyoxyalkylene triamine (Jefamine T403, manufactured by Huntsman) as a curing agent, cross-linked 5.32 g of a polyfunctional aliphatic glycidyl ether compound (Denacol EX-1610, manufactured by Nagase ChemteX Corp.) as an active ingredient, and 0 of an epoxy-modified silicone (X-22-4741, manufactured by Shin-Etsu Chemical Co., Ltd.) as a leveling agent 0.1 g was added, stirred at 25 ° C. for 10 minutes, then stirred at 50 ° C. for 1 hour, and diluted with butyl acetate to obtain Liquid Composition B.
Next, the surface is polished and washed with cerium oxide, and the liquid composition A is applied by spin coating to a dry and clean soda lime glass substrate (100 mm × 100 mm × 2 mm) and held in an electric furnace at 180 ° C. for 4 minutes. Then, a low hygroscopic crosslinked resin layer having a film thickness of 10.7 μm was formed. Subsequently, the liquid composition B was applied to the surface of the formed low hygroscopic crosslinked resin layer by spin coating, and held in an electric furnace at 200 ° C. for 5 minutes to form a highly hygroscopic crosslinked resin layer having a film thickness of 4.4 μm. An antifogging article having was obtained.
The saturated moisture absorption amount of the antifogging film of the obtained antifogging article was 20.7 mg / cm ³ .

[Comparative Example 1]
In a glass container in which a stirrer and a thermometer are set, 6.34 g of diacetone alcohol (manufactured by Junsei Chemical), 1.26 g of 2-chloroethanol (manufactured by Junsei Chemical), sorbitol polyglycidyl ether (Denacol) as a crosslinkable component 5.94 g of EX-622 (manufactured by Nagase ChemteX Corporation) and 1.02 g of isophoronediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing agent were added and stirred at 25 ° C. for 1 hour. Next, 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) (0.64 g) was added as a coupling agent and stirred at 25 ° C. for 1 hour, and then with butyl acetate (manufactured by Junsei Chemical). The liquid composition A was obtained by diluting 1.67 times.
Further, a liquid composition B was obtained in the same manner as in Example 1.
Next, the surface is polished and washed with cerium oxide, and the liquid composition A is applied by spin coating to a dry and clean soda lime glass substrate (100 mm × 100 mm × 2 mm) and held in an electric furnace at 180 ° C. for 4 minutes. Then, a low hygroscopic crosslinked resin layer having a film thickness of 0.7 μm was formed. Subsequently, the liquid composition B was applied to the surface of the formed low hygroscopic crosslinked resin layer by spin coating, and held in an electric furnace at 200 ° C. for 5 minutes to form a highly hygroscopic crosslinked resin layer having a thickness of 17.5 μm. An antifogging article having was obtained.
The saturated moisture absorption of the antifogging film of the obtained antifogging article was 69.7 mg / cm ³ .

[Comparative Example 2]
In a glass container in which a stirrer and a thermometer are set, 8.49 g of ethanol (manufactured by Junsei Kagaku) and 5 polyfunctional aliphatic glycidyl ether compound (Denacol EX-1610, manufactured by Nagase ChemteX Corporation) as a crosslinkable component .32 g, 2.17 g of polyoxyalkylene triamine (Jefamine T403, manufactured by Huntsman) as a curing agent was added and stirred at 25 ° C. for 1 hour. Next, 1.00 g of 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a coupling agent and stirred at 25 ° C. for 1 hour. The liquid composition A was obtained by diluting 25 times.
Moreover, the liquid composition B was obtained similarly to Example 1.
The surface was polished and washed with cerium oxide, and the liquid composition A was applied by spin coating to a clean and clean soda lime glass substrate (100 mm × 100 mm × 2 mm), and held in an electric furnace at 180 ° C. for 4 minutes. A low hygroscopic crosslinked resin layer having a thickness of 5.6 μm was formed. Next, the liquid composition B is applied to the surface of the formed low-hygroscopic crosslinked resin layer by spin coating, and held in an electric furnace at 200 ° C. for 5 minutes to have a highly hygroscopic crosslinked resin layer having a thickness of 17.4 μm. An antifogging article was obtained.
The saturated moisture absorption of the antifogging film of the obtained antifogging article was 78.5 mg / cm ³ .

[Comparative Example 3]
A liquid composition A was obtained in the same manner as in Comparative Example 2, and a liquid composition B was obtained in the same manner as in Example 1.
Next, the surface is polished and washed with cerium oxide, and the liquid composition A is applied to a dried clean soda lime glass substrate (100 mm × 100 mm × 2 mm) by spin coating, followed by an electric furnace at 180 ° C. for 4 minutes. The low-hygroscopic crosslinked resin layer having a film thickness of 1.9 μm was formed. Next, the liquid composition B is applied to the surface of the formed low hygroscopic crosslinked resin layer by spin coating, and held in an electric furnace at 200 ° C. for 5 minutes to have a highly hygroscopic crosslinked resin layer having a thickness of 17.3 μm. An antifogging article was obtained.
The saturated moisture absorption amount of the antifogging film of the obtained antifogging article was 93.0 mg / cm ³ .

[Comparative Example 4]
A liquid composition A was obtained in the same manner as in Example 1.
Also, in a glass container in which a stirrer and a thermometer are set, 8.49 g of ethanol (manufactured by Pure Chemical), 2.17 g of polyoxyalkylene triamine (Jefamine T403, manufactured by Huntsman) as a curing agent, crosslinkable component As a leveling agent, 5.18 g of sorbitol polyglycidyl ether (Denacol EX-614, manufactured by Nagase ChemteX Corp.) and 0.1 g of epoxy-modified silicone (X-22-4741, manufactured by Shin-Etsu Chemical Co., Ltd.) as a leveling agent were added at 25 ° C. For 1 hour. Next, 1.00 g of 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a coupling agent, and the mixture was stirred at 25 ° C. for 1 hour to obtain a liquid composition B.
Next, the surface is polished and washed with cerium oxide, and the liquid composition A is applied to a dried clean soda lime glass substrate (100 mm × 100 mm × 2 mm) by spin coating, followed by an electric furnace at 180 ° C. for 4 minutes. The low-hygroscopic crosslinked resin layer having a film thickness of 10.6 μm was formed. Next, the liquid composition B is applied to the surface of the formed low-hygroscopic crosslinked resin layer by spin coating, and held in an electric furnace at 200 ° C. for 5 minutes to have a highly hygroscopic crosslinked resin layer having a thickness of 20.4 μm. An antifogging article was obtained.
The saturated moisture absorption amount of the antifogging film of the obtained antifogging article was 8.7 mg / cm ³ .
Table 1 shows the evaluation of antifogging performance and various durability of Examples 1 to 3 and Comparative Examples 1 to 4.

Examples 1-3 which are anti-fogging articles of the present invention all exhibited excellent anti-fogging performance. Moreover, it had high wear resistance, adhesion, stain resistance, acid resistance, and alkali resistance.
On the other hand, Comparative Example 1 in which the film thickness of the low hygroscopic crosslinked resin layer was 0.7 μm had a very low alkali resistance although the antifogging performance was sufficient. Further, in Comparative Examples 2 and ³ where the saturated moisture absorption amount of the low-hygroscopic crosslinked resin layer is as high as 46.8 mg / cm ³ and 10.9 mg / cm ³ , although the anti-fogging performance is sufficient, Alkali resistance was very low. In Comparative Example 4 where the anti-fogging film composed of the low hygroscopic crosslinked resin layer and the highly hygroscopic crosslinked resin layer has a low saturated moisture absorption of 8.7 mg / cm ³ , various durability is high, but the antifogging performance is 0. It was very low at 2 minutes.

  The anti-fogging article of the present invention can be used for, for example, window glass for transportation equipment (cars, railways, ships, airplanes, etc.), refrigerated showcases, vanity mirrors, bathroom mirrors, optical equipment, etc. Useful for.

It is sectional drawing which showed one example of embodiment of the anti-fogging article | item of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antifogging article 2 Base 3 Low hygroscopic crosslinked resin layer 4 High hygroscopic crosslinked resin layer 5 Antifogging film

Claims (4)

An antifogging article having a base and an antifogging film on the surface of the base,
The antifogging film has a low hygroscopic crosslinked resin layer sequentially laminated on the substrate surface and a high hygroscopic crosslinked resin layer having a higher saturated moisture absorption than the low hygroscopic crosslinked resin layer. The crosslinked resin layer has a film thickness of 1.0 μm or more, a saturated moisture absorption of 10 mg / cm ³ or less, and an anti-fogging film having a saturated moisture absorption of 20 mg / cm ³ or more. .   The antifogging article according to claim 1, wherein the substrate is soda lime glass.   The anti-fogging article according to claim 1 or 2, wherein both the low hygroscopic crosslinked resin layer and the high hygroscopic crosslinked resin layer are made of a crosslinkable resin obtained by a reaction between a polyepoxide and a curing agent. It is a manufacturing method of the antifogging article according to claims 1-3,
By applying a liquid composition containing a crosslinkable component and a curing agent to the substrate surface and then reacting it, a low hygroscopic crosslinked resin layer made of a crosslinkable resin is formed,
Thereafter, a liquid composition containing a crosslinkable component and a curing agent is applied to the surface of the low hygroscopic crosslinkable resin layer formed on the surface of the substrate and then reacted to thereby cause a high hygroscopic crosslinkable resin comprising the crosslinkable resin. A method for producing an antifogging article, wherein a layer is formed.

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