JP2014148042A - Antifogging article and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifogging article excellent in antifogging property, excoriation resistance such as scratch resistance, and low in an initial haze value, and to provide its manufacturing method.SOLUTION: There is provided an antifogging article having a base material and a water-absorbing layer which contains a crosslinked resin arranged on the base material, with the water-absorbing layer containing metal oxide particles of 20 to 60 mass% based on the total amount, and having a haze value of 1% or less. There is also provided a method of manufacturing the antifogging article having the base material and the water-absorbing layer containing the crosslinked resin arranged on the base material and the metal oxide particles of 20 to 60 mass% based on the total amount, the method including formation of the water-absorbing layer by proceeding a crosslinking action by adding a part of content of the metal oxide particles to a liquid composition containing a raw material composition of the crosslinked resin, then processing further the crosslinking action by adding further remaining metal oxide particles, and further crosslinking it by applying the liquid composition on a surface of the base material.

Description

  The present invention relates to an antifogging article and a method for producing the same.

Transparent substrates such as glass and plastic have a so-called “cloudy” state when the substrate surface falls below the dew point temperature because fine water droplets adhere to the surface and scatter transmitted light. . Various proposals have been made as a means for preventing fogging.
Specifically, a method of providing a water-absorbing resin layer on the substrate surface and absorbing and removing minute water droplets formed on the substrate surface, or reducing the atmospheric humidity on the substrate surface, and the like are known.

As an anti-fogging technique using such a water-absorbing compound layer, specifically, an anti-fogging article (see Patent Document 1) including a water-absorbing crosslinked resin layer obtained from polyepoxides has been proposed. .
However, even when the water-absorbent resin layer as described above is used, there is a problem in scratch resistance such as scratch resistance although it is excellent in antifogging property.

International Publication No. 2007/052710 Pamphlet

  An object of the present invention is to provide an anti-fogging article having excellent anti-fogging property, scratch resistance such as scratch resistance and low initial fog value, and a method for producing the same.

The present invention provides an antifogging article having the following configurations [1] to [7].
[1] An antifogging article having a substrate and a water absorbing layer containing a crosslinked resin disposed on the surface of the substrate, wherein the water absorbing layer contains metal oxide fine particles in a proportion of 20 to 60% by mass. An anti-fogging article characterized by containing a haze value of 1% or less.
[2] On the surface of the water absorption layer, the Martens hardness measured at measurement conditions: loading speed / unloading speed F = 0.05 mN / 5 s and creep C = 5 s is 20 N / mm ² or more. The antifogging article as described.
[3] The test is performed on the surface of the water-absorbing layer. When the specimen is left in an environment of 20 ° C. and a relative humidity of 50% for 1 hour, the specimen surface is clouded or placed on a hot water bath at 40 ° C. The antifogging article according to [1] or [2], wherein an antifogging time is 90 seconds or more in an antifogging test in which a time until a perspective image distortion due to a water film is recognized is measured as an antifogging time.

[4] The antifogging article according to any one of [1] to [3], wherein the material constituting the water absorption layer has a saturated water absorption of 50 mg / cm ³ or more.
[5] The antifogging article according to any one of [1] to [4], wherein the water absorption layer has a thickness of 7 μm to 30 μm.
[6] The antifogging article according to any one of [1] to [5], wherein the metal oxide fine particles have an average primary particle diameter of 10 to 50 nm.
[7] The antifogging article according to any one of [1] to [6], wherein the metal oxide fine particles are silica fine particles.
[8] Any of [1] to [7], wherein the crosslinked resin is a cured epoxy resin obtained by a reaction between a polyepoxide and a curing agent, or a urethane resin obtained by a reaction between a polyisocyanate and a polyol. Antifogging article according to crab.

The present invention also provides a method for producing an antifogging article having the following configurations [9] to [13].
[9] A method for producing an antifogging article comprising a substrate and a water-absorbing layer containing a crosslinked resin and metal oxide fine particles provided on the surface of the substrate, the liquid composition comprising a raw material component of the crosslinked resin The step (1) of adding a part of the content of the metal oxide fine particles to the step, the step (2) of proceeding the crosslinking reaction of the liquid composition obtained by the step (1), and the step (2) The step (3) of adding the remainder of the content of the metal oxide fine particles to the obtained liquid composition, and the liquid composition obtained by the step (3) is applied to the surface of the substrate and further subjected to a crosslinking reaction. And a step (4) of forming a water-absorbing layer, wherein the water-absorbing layer contains the metal oxide fine particles in a proportion of 20 to 60% by mass.

[10] The antifogging article according to [9], wherein the addition amount of the metal oxide fine particles in the step (1) is 5 to 50% by mass of the content of the metal oxide fine particles in the water absorption layer. Manufacturing method.
[11] The method for producing an antifogging article according to [9] or [10], wherein the metal oxide fine particles have an average primary particle diameter of 10 to 50 nm.
[12] The method for producing an antifogging article according to any one of [9] to [11], wherein the metal oxide fine particles are silica fine particles.
[13] The antifogging article according to any one of [9] to [12], wherein the raw material component of the crosslinked resin is a combination of a polyepoxide and a curing agent, or a combination of a polyisocyanate and a polyol. Manufacturing method.

  The antifogging article of the present invention is excellent in antifogging property, excellent in scratch resistance such as scratch resistance, and has a low initial fog value. Moreover, according to the production method of the present invention, an antifogging article having excellent antifogging properties and scratch resistance and having a sufficiently low initial haze value can be obtained.

Embodiments of the present invention will be described below. In addition, this invention is limited to the following description and is not interpreted.
<Anti-fogging article>
The antifogging article of the present invention is an antifogging article having a base and a water absorbing layer containing a crosslinked resin disposed on the surface of the base, wherein the water absorbing layer contains 20 to 20 metal oxide fine particles. It is contained at a ratio of 60% by mass, and the haze value is 1% or less. Here, when the water absorption layer contains moisture, the content of the metal oxide fine particles is defined as the amount with respect to the solid content excluding moisture.
In the present specification, the haze [%] refers to the haze [%] measured using a haze meter in accordance with the standard of JIS K-7361 unless otherwise specified.

In the anti-fogging article having a base and a water-absorbing layer containing a crosslinked resin disposed on the surface of the base of the present invention, the water-absorbing layer contains a metal oxide fine particle as high as 20 to 60% by mass. Present in proportion. In the antifogging article of the present invention, the metal oxide fine particles present at a high content ratio in the water absorption layer have a low haze value of 1% or less by being uniformly dispersed throughout the water absorption layer. It becomes possible.
Thus, the water absorption layer containing the crosslinked resin disposed on the surface of the substrate contains the metal oxide fine particles uniformly at the high content, so that the antifogging article of the present invention is as described below. It has excellent antifogging properties and scratch resistance such as scratch resistance.

In the antifogging article of the present invention, the specimen is placed on the surface of the water-absorbing layer and left for 1 hour in an environment of 20 ° C. and 50% relative humidity, and then the specimen surface is placed in a 40 ° C. hot water bath. It is preferable that the anti-fogging time is 90 seconds or more in an anti-fogging test in which the time until fogging or distortion of a fluoroscopic image due to a water film is observed as the anti-fogging time is measured.
In the antifogging article of the present invention, the material constituting the water absorbing layer preferably has a saturated water absorption amount of 50 mg / cm ³ or more. Moreover, it is preferable that the film thickness of the said water absorption layer is 7 micrometers-30 micrometers.

(Measurement method of anti-fogging time and saturated water absorption)
A water-absorbing layer as a specimen is provided on a soda-lime glass substrate having a size of 3.3 cm × 10 cm × 2 mm, and this is left for 1 hour in an environment of 20 ° C. and a relative humidity of 50%. The time until exposure to warm water vapor causes clouding or distortion of a fluoroscopic image due to a water film on the surface is measured, and this time is defined as antifogging time. Note that the determination of the occurrence of perspective image distortion due to cloudiness or a water film is made visually.

  On the other hand, the saturated water absorption amount is a 3 cm × 4 cm × 2 mm thick soda lime glass substrate provided with a water absorption layer as a specimen, which is immersed in distilled water at 25 ° C. for 10 minutes, so that excessive water cannot be discriminated visually. Wipe off with a Kim towel and measure the water content (I) of the entire substrate with the water-absorbing layer using a trace moisture meter. Further, the moisture content (II) is measured for the substrate only by the same procedure. The value obtained by subtracting the amount of water (II) from the amount of water (I) divided by the volume of the water-absorbing layer is the saturated water-absorbing amount of the material constituting the water-absorbing layer. The moisture content is measured as follows using a trace moisture meter FM-300 (manufactured by Kett Science Laboratory). The measurement sample is heated at 120 ° C., the moisture released from the sample is adsorbed to the molecular sieve in the micro moisture meter, and the mass change of the molecular sieve is measured as the moisture content. The measurement is performed for the same time as the blank measurement, and the maximum value during that time is adopted as the moisture content.

  The anti-fogging time is an index indicating the anti-fogging property of the water-absorbing layer itself depending on the material constituting the water-absorbing layer and the layer thickness, but the saturated water absorption is an index indicating the anti-fogging property of the material constituting the water-absorbing layer. The antifogging property of the water absorbing layer is evaluated together with the thickness of the layer.

  If the anti-fogging time in the water-absorbing layer of the anti-fogging article of the present invention is 90 seconds or more, the anti-fogging property of the water-absorbing layer can be said to be sufficient, but the anti-fogging time of the water-absorbing layer is preferably 100 seconds or more. . Although the upper limit of the antifogging time is not particularly set, in a water absorbing layer having an antifogging time exceeding 200 seconds, there is a possibility that the mechanical strength is not sufficient at the time of water absorption due to containing a large amount of water.

The material constituting the water absorption layer, that is, the saturated water absorption amount of the composite containing the crosslinked resin and the metal oxide fine particles is 50 mg / cm ³ or more, and if the water absorption layer has a film thickness of 7 μm to 30 μm, the water absorption layer is sufficient. Although it can be said that it has a good anti-fogging property, it is preferable that the saturated water absorption is 60 mg / cm ³ or more under the same film thickness conditions. The upper limit of the saturated water absorption amount is not particularly set as in the anti-fogging time. However, in the water absorption layer containing a crosslinked resin having a saturated water absorption amount exceeding 150 mg / cm ³ , the machine absorbs a large amount of water. Strength may be insufficient.
In addition, it is preferable that the range of the film thickness of a water absorption layer is 7-25 micrometers from a viewpoint of ensuring adhesiveness further, and 7-20 micrometers is more preferable.

  The antifogging article of the present invention may be evaluated by any antifogging index of antifogging time or a combination of saturated water absorption and film thickness. The use of antifogging articles is diverse, and the antifogging performance required varies depending on the use, but within the range of antifogging properties of the antifogging article of the present invention, it is required for antifogging articles for each use. The design can be changed as appropriate according to the performance.

In the antifogging article of the present invention, in addition to the above water absorption and antifogging properties, the water absorbing layer containing a crosslinked resin disposed on the surface of the substrate has surface mechanical strength, in particular, scratch resistance. Measurement conditions: It is preferable that the Martens hardness measured by loading speed / unloading speed F = 0.05 mN / 5 s and creep C = 5 s is 20 N / mm ² or more.

  Here, when determining the “hardness” of a thin film such as a water-absorbing layer containing a cross-linked resin disposed on the substrate surface of the anti-fogging article of the present invention, that is, when determining the mechanical strength such as scratch resistance, Specifically, a micro hardness measurement test or the like that measures the Martens hardness corresponding to the scratch resistance and calculates the hardness from the penetration depth of the indenter under a constant load condition on the measurement surface is used.

As for the Martens hardness in the water absorption layer of the antifogging article of the present invention, if the value in the above measurement condition is 20 N / mm ² or more, it can be said that the scratch resistance of the water absorption layer is sufficient, but the water absorption layer in the same measurement condition. The Martens hardness is preferably 30 N / mm ² or more. The upper limit of the Martens hardness is not particularly set, but in a water absorbing layer having a Martens hardness exceeding 200 N / mm ² or more, there is a risk of deterioration in appearance such as cracking or whitening. In addition, in this specification, Martens hardness means the Martens hardness in the said measurement conditions unless there is particular notice.

  The antifogging article of the present invention has the above excellent antifogging property and scratch resistance in a water absorbing layer containing a crosslinked resin disposed on the surface of a substrate. Furthermore, the antifogging article of the present invention is left for 1 hour in an environment of 20 ° C. and 50% relative humidity, which is an index indicating hydrophobicity, on the surface of the water-absorbing layer containing the crosslinked resin disposed on the substrate surface. After that, the water contact angle immediately after dropping 2 μL of water droplets is preferably 40 to 100 °, and within this range, it is advantageous in terms of the recovery speed of visibility. In addition, the water absorption layer of the antifogging article of the present invention is measured in the DFM mode using a scanning probe microscope (SPM, SPA-400, SII Nanotechnology) showing surface flatness. A smaller surface roughness (Ra) is preferable in terms of ensuring transparency.

  In the anti-fogging article according to the present invention, the water absorption layer has a specific configuration, specifically, the water absorption layer includes metal oxide fine particles together with a crosslinked resin, and the metal oxide fine particles in the water absorption layer By making content into the ratio of 20-60 mass%, it became possible for the water absorption layer to have the said characteristic. Hereinafter, members constituting the antifogging article of the present invention will be described.

[1] Substrate The substrate used in the antifogging article of the present invention is not particularly limited as long as it is a substrate made of a material that is generally required to be imparted with antifogging properties, but is preferably glass, plastic, or metal. , Ceramics, or a substrate made of a combination thereof (composite material, laminated material, etc.), and more preferably a transparent substrate made of glass or plastic, a mirror, and the like. Examples of the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Among these, soda lime glass is particularly preferable. Examples of the plastic include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET). Among these, polyethylene terephthalate (PET) ) And polyphenylene carbonate are preferred.

  The shape of the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature. Although the thickness of a base | substrate can be suitably selected according to the use of an anti-fogging article, generally it is preferable that it is 1-10 mm.

[2] Water-absorbing layer In the anti-fogging article of the present invention, the water-absorbing layer formed on at least a part of the surface of the base contains metal oxide fine particles together with the crosslinked resin. Content is the ratio of 20-60 mass% of the whole water absorption layer.
The cross-linked resin contained in the water-absorbing layer is a water-absorbing cross-linked resin, and the water-absorbing layer obtained in combination with the metal oxide fine particles blended in the above proportion together with the water-absorbing layer is the anti-fogging article of the present invention. There is no particular limitation as long as it has both haze and scratch resistance.

(1) Crosslinked resin Specific examples of the crosslinked resin contained in the water absorbing layer include a cured epoxy resin obtained by a reaction between a polyepoxide and a curing agent, and a urethane resin obtained by a reaction between a polyisocyanate and a polyol.

In this specification, polyepoxide refers to a compound having two or more epoxy groups in one molecule. Polyepoxide includes low molecular weight compounds, oligomers, and polymers. The polyepoxide component is a component composed of at least one polyepoxide, and may be hereinafter referred to as a main agent as necessary.
Further, the curing agent is a compound having two or more reactive groups in one molecule that react with the epoxy group of the polyepoxide, and is a polyaddition type curing agent that polyadds to the polyepoxide by reaction, and the polyepoxide by reaction. It is used as a term encompassing a condensation type curing agent that is polycondensed with a catalyst and a reaction type catalyst such as a Lewis acid that catalyzes a polymerization reaction between polyepoxides. The catalyst-type curing agent includes a thermosetting type and a photo-curing type, and these are collectively referred to as a catalyst-type curing agent.
Further, the cured epoxy resin refers to a cured product obtained by a crosslinking reaction between the main agent and the curing agent. The cured epoxy resin has a structure in which polyepoxide is cross-linked by a polyaddition type curing agent or the like to form a three-dimensional structure and / or a structure in which polyepoxides are linearly or three-dimensionally polymerized.

  In this specification, polyisocyanate refers to a compound having two or more isocyanate groups in one molecule. Polyisocyanates include low molecular compounds, oligomers and polymers. Polyol refers to a polymer compound having an active hydrogen group such as two or more alcoholic hydroxyl groups in one molecule and a molecular weight of approximately 200 or more. The urethane resin refers to a cured product obtained by crosslinking reaction of the polyisocyanate and the polyol. The urethane resin has a structure in which a polyol is cross-linked with a polyisocyanate to form a three-dimensional structure.

(1-1) Cured Epoxy Resin When a cured epoxy resin is used as the cross-linked resin contained in the water absorbing layer, the present invention is obtained when the cured epoxy resin and metal oxide fine particles described later are combined in the above ratio to form a water absorbing layer. The cured epoxy resin is not particularly limited as long as the antifogging property and scratch resistance can be obtained. Here, the antifogging property of the water absorption layer according to the present invention is substantially determined by the water absorption performance of the cured epoxy resin used. Therefore, the cured epoxy resin used for the water absorption layer is selected to have a water absorption performance that is high enough to achieve the antifogging property.
Specifically, the water absorption performance of the cured epoxy resin is preferably such that the saturated water absorption measured by the above method is 120 mg / cm ³ or more, and more preferably 150 mg / cm ³ or more. When the saturated water absorption amount of the cured epoxy resin takes the above value, the antifogging article of the present invention can ensure sufficient antifogging properties in the water absorbing layer. On the other hand, from the viewpoint of preventing the durability of the water absorbing layer from being lowered, the saturated water absorption amount of the cured epoxy resin is preferably 900 mg / cm ³ or less, and more preferably 500 mg / cm ³ or less.

  Specifically, the cured epoxy resin having such a high water absorption performance is composed of a low molecular weight polyepoxide having a molecular weight of 200 to 800 and a high molecular weight polyepoxide having a molecular weight of 900 to 2000, and the mass ratio shown by the low molecular weight polyepoxide: the high molecular weight polyepoxide. The 1st hardening epoxy resin obtained by making the composition for water absorption layer formation containing the 1st polyepoxide component which is 30: 70-70: 30 and the 1st hardening | curing agent react is mentioned.

  In addition, the water absorption evaluated by, for example, the saturated water absorption of the cured epoxy resin mainly depends on the abundance of hydrophilic groups such as hydroxyl groups and hydrophilic chains (polyoxyethylene groups and the like) derived from the main agent. The water absorption also depends on the degree of crosslinking in the cured epoxy resin. If the number of cross-linking points contained in the cured epoxy resin per unit amount is large, the cured epoxy resin has a dense three-dimensional network structure, and it is considered that the water absorption becomes low because the space for water retention becomes small. On the other hand, if the number of cross-linking points contained per unit amount is small, it is considered that the space for water retention becomes large and the water absorption becomes high. The glass transition point of the cured epoxy resin is closely related to the number of crosslinking points in the cured epoxy resin. In general, a resin having a high glass transition point is considered to have a large number of crosslinking points per unit amount.

  Accordingly, it is generally preferable to control the glass transition point of the cured epoxy resin low to increase the water absorption, and to control the glass transition point of the cured epoxy resin high to increase the scratch resistance. In consideration of these, the glass transition point of the first water-absorbing layer-containing first cured epoxy resin is preferably −20 to 60 ° C., although it depends on the type of the cured epoxy resin. More preferably, it is 40 degreeC.

  The glass transition point is a value measured according to JIS K 7121. Specifically, it is a value measured using a differential scanning calorimeter after providing a resin layer as a specimen on a substrate and leaving it in an environment of 20 ° C. and 50% relative humidity for 1 hour. However, the heating rate at the time of measurement shall be 10 degrees C / min.

Hereinafter, the 1st hardening epoxy resin obtained by making the said 1st polyepoxide component and 1st hardening | curing agent which mainly comprise a water absorption layer react will be demonstrated.
The first polyepoxide component, which is a raw material component of the first cured epoxy resin, comprises a low molecular weight polyepoxide having a molecular weight of 200 to 800 and a high molecular weight polyepoxide having a molecular weight of 900 to 2000, and a mass ratio represented by low molecular weight polyepoxide: high molecular weight polyepoxide. Is 30: 70-70: 30.

  The molecular weight of the high molecular weight polyepoxide used in the present invention is 900 to 2000, preferably 900 to 1500, and more preferably 900 to 1450. The high molecular weight polyepoxide is considered to impart high water absorption and abrasion resistance such as abrasion resistance to the first cured epoxy resin obtained as described above. When the low molecular weight polyepoxide is used in combination with the low molecular weight polyepoxide in the present invention, the first cured epoxy resin can ensure sufficient abrasion resistance such as wear resistance by setting the molecular weight of the high molecular weight polyepoxide within the above range. . In this invention, high molecular weight polyepoxide may be used individually by 1 type, or may use 2 or more types together.

  The molecular weight of the low molecular weight polyepoxide used in the present invention is 200 to 800, preferably 300 to 700, more preferably 300 to 650. As described above, the low molecular weight polyepoxide has a role of favorably maintaining the appearance of the first cured epoxy resin obtained by using in combination with the high molecular weight polyepoxide. When the molecular weight of the low molecular weight polyepoxide is within the above range when used in combination with the high molecular weight polyepoxide in the proportion of the present invention, the first cured epoxy resin has insufficient wetting and spreading of the coating liquid during solution coating. A good appearance can be ensured without causing unevenness of the coating film. In this invention, low molecular weight polyepoxide may be used individually by 1 type, or may use 2 or more types together.

  In the present specification, molecular weight refers to mass average molecular weight (Mw) unless otherwise specified. Moreover, the mass average molecular weight (Mw) in this specification means the mass average molecular weight which uses polystyrene as a standard measured by gel permeation chromatography (GPC).

  For the high molecular weight polyepoxide and the low molecular weight polyepoxide constituting the first polyepoxide component, compounds of the same class can be used except for the difference in molecular weight. Hereinafter, specific compounds used as the high molecular weight polyepoxide and the low molecular weight polyepoxide will be described.

  As the polyepoxide constituting the first polyepoxide component, the glycidyl ether polyepoxide, glycidyl ester polyepoxide, glycidylamine polyepoxide, cycloaliphatic polyepoxide, etc., which are used as raw material components of ordinary cured epoxy resins, have the molecular weight described above. It can adjust and use so that it may become a range. Further, the number of epoxy groups per molecule of polyepoxide in the first polyepoxide component is not particularly limited as long as it is 2 or more on average, but is preferably 2 to 10, in high molecular weight polyepoxide, 3-8 are more preferable, 3-7 are more preferable, 2-8 are more preferable in a low molecular weight polyepoxide, and 2-5 are more preferable.

  The glycidyl ether-based polyepoxide is a polyepoxide having a structure in which a glycidyloxy group is substituted for a phenolic hydroxyl group of a polyphenol having two or more phenolic hydroxyl groups or an alcoholic hydroxyl group of a polyol having two or more alcoholic hydroxyl groups. Polyepoxide oligomer). The glycidyl ester polyepoxide has a structure in which the carboxyl group of a polycarboxylic acid having two or more carboxyl groups is substituted with a glycidyloxycarbonyl group, and the glycidylamine polyepoxide has two or more hydrogen atoms bonded to a nitrogen atom. It is a polyepoxide having a structure in which a hydrogen atom bonded to a nitrogen atom of an amine is substituted with a glycidyl group. The cycloaliphatic polyepoxide is a polyepoxide having an alicyclic hydrocarbon group (such as a 2,3-epoxycyclohexyl group) in which an oxygen atom is bonded between adjacent carbon atoms of the ring.

  Among such various polyepoxides, as the polyepoxide constituting the first polyepoxide component, a polyepoxide having no aromatic nucleus is preferable from the viewpoint of obtaining high water absorption in the obtained cured epoxy resin. A cured epoxy resin obtained using a polyepoxide having an aromatic nucleus, for example, a glycidyl ether-based polyepoxide derived from polyphenols, is difficult to incorporate moisture into the three-dimensional network structure due to the hard aromatic nucleus, It is thought that water absorption is low.

  Specific examples of the polyepoxide having no aromatic nucleus include glycidyl ether polyepoxides derived from polyols, glycidyl ester polyepoxides, glycidylamine polyepoxides, and polyepoxides having no aromatic nucleus among cyclic aliphatic polyepoxides. Of these, glycidyl ether polyepoxides derived from polyols having no aromatic nucleus are particularly preferred in the invention.

  As a raw material polyol of glycidyl ether-based polyepoxide derived from polyols having no aromatic nucleus, there are polyols having no aromatic nucleus such as aliphatic polyols and alicyclic polyols, and the number of hydroxyl groups per molecule is 2 to 10 The number of hydroxyl groups is more preferable, and the more preferable number of hydroxyl groups is the number listed as the number of preferable epoxy groups in the high molecular weight polyepoxide and the low molecular weight polyepoxide. Hereinafter, such a polyol having no aromatic nucleus is referred to as an aliphatic / alicyclic polyol. Examples of the aliphatic / alicyclic polyol include alkane polyol, etheric oxygen atom-containing polyol, sugar alcohol, polyoxyalkylene polyol, and polyester polyol. The polyoxyalkylene polyol is obtained by ring-opening addition polymerization of a monoepoxide such as propylene oxide or ethylene oxide to a relatively low molecular weight polyol such as an alkane polyol, an etheric oxygen atom-containing polyol or a sugar alcohol. The polyester polyol includes a compound having a structure in which an aliphatic diol and an aliphatic dicarboxylic acid are condensed, a compound having a structure in which a cyclic ester is ring-opening polymerized, and the like.

  Specific examples of the glycidyl ether-based polyepoxide derived from aliphatic / alicyclic polyols preferably used in the present invention include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol. Diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol poly Glycidyl ether, polyethylene glycol diglycidyl ether, polyoxypropylene diol diglycidyl ether, Polyoxypropylene triol triglycidyl ether, poly (oxypropylene-oxyethylene) triol triglycidyl ether and the like.

  Among these, the glycidyl ether-based polyepoxide derived from aliphatic / alicyclic polyols which are preferably used further preferably has an average number of glycidyloxy groups of 2 to 10 per molecule, more preferably the above-mentioned high In the molecular weight polyepoxide and the low molecular weight polyepoxide, the number of polyepoxides listed as the preferred number of epoxy groups.

  Such polyepoxides include, for example, triol triglycidyl ether, tetraol tetraglycidyl ether, a mixture of triol triglycidyl ether and the same triol diglycidyl ether, tetraol tetraglycidyl ether, triglycidyl ether and diol. Examples thereof include a mixture of glycidyl ether, a mixture of triglycidyl ether of triol and diglycidyl ether of diol, and the like. More specifically, the average number of glycidyloxy groups per molecule is preferably 2 to 10, more preferably the number of epoxy groups preferred for the high molecular weight polyepoxide and the low molecular weight polyepoxide. Glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, and the like.

  In addition, as a polyepoxide having no aromatic nucleus other than the glycidyl ether-based polyepoxide derived from the above aliphatic / alicyclic polyols, 3,4-epoxycyclohexylmethyl-3 ′, 4′-, which is a cyclic aliphatic polyepoxide, is used. Examples thereof include epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.

  Among these, as the low molecular weight polyepoxide, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether and the like, which are glycidyl ether-based polyepoxides derived from aliphatic / alicyclic polyols, are particularly preferable in the present invention. Used. Furthermore, the average number of glycidyloxy groups per molecule in the low molecular weight polyepoxide is preferably 2 to 8, and more preferably 2 to 4. The epoxy equivalent of the low molecular weight polyepoxide showing the relationship between the preferred molecular weight as the low molecular weight polyepoxide and the average number of epoxy groups per molecule (grams of resin containing 1 gram equivalent of epoxy groups [g / eq]) It is preferably 120 to 200 g / eq, and more preferably 120 to 180 g / eq.

  Further, as the high molecular weight polyepoxide, polyethylene glycol polyglycidyl ether, polyglycerin polyglycidyl ether, polyethylene glycol sorbitol polyglycidyl ether and the like, which are glycidyl ether polyepoxides derived from aliphatic / alicyclic polyols, are particularly preferably used in the present invention. It is done. Furthermore, the average number of glycidyloxy groups per molecule in the high molecular weight polyepoxide is preferably 3 to 8, and more preferably 3 to 6. Moreover, as an epoxy equivalent of the high molecular weight polyepoxide calculated similarly to the said low molecular weight polyepoxide, it is preferable that it is 140-200 g / eq, and it is more preferable that it is 150-190 g / eq.

  The first polyepoxide component, which is a raw material component of the first cured epoxy resin used in the present invention, is composed of at least one of the high molecular weight polyepoxides and at least one of the low molecular weight polyepoxides. The mass ratio of low molecular weight polyepoxide: high molecular weight polyepoxide in the first polyepoxide component is 30:70 to 70:30, preferably 40:60 to 70:30, more preferably 40:60 to 60. : 40. By setting the mass ratio of the two polyepoxides constituting the first polyepoxide component within the above range, the first cured epoxy resin can ensure both abrasion resistance such as sufficient abrasion resistance and a good appearance. It becomes.

  Here, as a preferable combination of the low molecular weight polyepoxide and the high molecular weight polyepoxide constituting the first polyepoxide component used in the present invention, specifically, the low molecular weight polyepoxide has a molecular weight of 200 to 800, and an average epoxy per molecule. The number of groups is 2 to 4, and an epoxy equivalent of 120 to 180 g / eq of glycerin polyglycidyl ether, polyglycerin polyglycidyl ether and sorbitol polyglycidyl ether, and a high molecular weight polyepoxide having a molecular weight of 900 to 2000 Yes, the average number of epoxy groups per molecule is 3-6, polyethylene glycol polyglycidyl ether, polyglycerin polyglycidyl ether having an epoxy equivalent of 150-190 g / eq, and polyethylene glycol A combination of at least one selected from Lumpur sorbitol polyglycidyl ether, low molecular weight polyepoxides weight ratio of high molecular weight polyepoxides 40: 60 to 60: and a combination of 40.

  Commercially available products can be used for both the low molecular weight polyepoxide and the high molecular weight polyepoxide constituting the first polyepoxide component. As such a commercially available product, specifically, any product manufactured by Nagase ChemteX Corporation is a trade name, and as a low molecular weight polyepoxide, Denacol EX-313 (Mw: 383, average number of epoxy groups: 2) which is glycerin polyglycidyl ether. , Denacol EX-314 (Mw: 454, average number of epoxy groups: 2.3 per molecule), polyglycerin polyglycidyl ether, Denacol EX-512 (Mw: 630, average number of epoxy groups: 4) .1 piece / molecule).

Similarly, Denasel EX-1410 (Mw: 988, average number of epoxy groups: 3.5 / molecule), which is an aliphatic polyglycidyl ether as a high molecular weight polyepoxide, is a product name manufactured by Nagase ChemteX Corporation. Denacol EX-1610 (Mw: 1130, average number of epoxy groups: 4.5 per molecule), Denacol EX-610U (Mw: 1408, average number of epoxy groups: 4.5 per molecule), polyglycerin polyglycidyl ether, Denacol EX-521 (Mw: 1294, average number of epoxy groups: 6.3 / molecule) and the like.
Examples of sorbitol polyglycidyl ether include Denacol EX-622 (Mw: 930, average number of epoxy groups: 4.9 / molecule).

The first cured epoxy resin contained in the water absorbing layer is a first cured epoxy resin obtained by reacting the first polyepoxide component with a first curing agent.
As a 1st hardening | curing agent, it is a compound which has two or more reactive groups which react with the epoxy group which polyepoxide has, Comprising: It is preferable to use the polyaddition type hardening | curing agent of the type which carries out polyaddition to polyepoxide by reaction. In addition to the polyaddition type curing agent, it is more preferable to use a catalyst type curing agent that is a reaction catalyst such as a Lewis acid and catalyzes a polymerization reaction between polyepoxides.
Some catalyst-type curing agents have the effect of accelerating the crosslinking progress of polyaddition-type curing agents, and are expected to reduce defects at the cross-linking sites formed by some polyaddition-type curing agents. It is to be done. An example of a defect is color change of a cured epoxy resin due to alteration of a cross-linked site due to heat load.

  Examples of the reactive group that reacts with the epoxy group in the polyaddition type curing agent include an amino group having active hydrogen, a carboxyl group, and a thiol group. That is, the polyaddition type curing agent is preferably an amino compound having two or more amino groups having active hydrogen, a compound having two or more carboxyl groups, or a compound having two or more thiol groups, more preferably The amino compound having the active hydrogen is used. Specific examples of such a compound having two or more reactive groups include polyamines, polycarboxylic acid anhydrides, polyamides, polythiols and the like. In the present invention, polyamines and polycarboxylic acid anhydrides are exemplified. The product is preferably used.

  As described above, the first polyepoxide component used in the first cured epoxy resin contained in the water-absorbing layer in the present invention is the above-mentioned two kinds of molecular weight polyepoxides having no aromatic nucleus from the viewpoint of obtaining high water absorption. It is preferable to become. For the same reason, it is preferable that the polyaddition type curing agent which is one of the reactive raw materials of the first cured epoxy resin is also a compound having no aromatic nucleus. That is, even if the first polyepoxide component is composed of a compound having no aromatic nucleus, if the polyaddition curing agent used has an aromatic nucleus, the first curing comprising the polyaddition curing agent is used. The cured epoxy resin obtained from the combination with the agent becomes a cured epoxy resin having a relatively large number of aromatic nuclei, which may result in insufficient water absorption.

  Therefore, the polyaddition type curing agent used as the first curing agent is preferably a polyamine or polycarboxylic acid anhydride having no aromatic nucleus, and particularly preferably a polyamine having no aromatic nucleus. Polyamines having 2 to 4 amino groups having active hydrogen are preferable as polyamines, and dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and tetracarboxylic acid anhydrides are preferable as polycarboxylic acid anhydrides.

  Examples of polyamines having no aromatic nucleus include aliphatic polyamine compounds and alicyclic polyamine compounds. Specific examples of these polyamines include ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylenepolyamine, isophoronediamine, mensendiamine, 3,9-bis (3-amino Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and the like.

The polyoxyalkylene polyamine is a polyamine having a structure in which the hydroxyl group of the polyoxyalkylene polyol is substituted with an amino group. For example, the hydroxyl group of the polyoxypropylene polyol having 2 to 4 hydroxyl groups is converted to an amino group having active hydrogen. There are compounds having 2 to 4 amino groups having a structure substituted on the group. The molecular weight per amino group is preferably 1000 or less, and particularly preferably 500 or less.
Examples of the polycarboxylic acid anhydride having no aromatic nucleus include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like.

  In addition, as the catalyst-type curing agent that is preferably used together with the polyaddition-type curing agent in the first curing agent, tertiary amines, imidazoles, Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, phosphine And other curing catalysts. Specific examples of such a catalyst-type curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, tris (dimethylaminomethyl) phenol, boron trifluoride-amine complex, dicyandiamide, diphenyliodonium hexafluoro. Examples include phosphate, triphenylsulfonium hexafluorophosphate, and the like.

  Here, as described below, the catalyst-type curing agent contained in the first curing agent is a cured epoxy obtained even if it is a compound having an aromatic nucleus due to a small amount of use relative to the first polyepoxide component. Since there is almost no influence on the water absorption of the resin, a compound having an aromatic nucleus may be used. In addition, onium salts such as diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate exemplified as the catalyst-type curing agent are catalyst-type curing agents that decompose with light such as ultraviolet rays to generate a Lewis acid catalyst. Usually, it is used as a catalyst-type curing agent that gives a photocurable cured epoxy resin.

  Among these, as the catalyst type curing agent used together with the polyaddition type curing agent, preferably polyamines having no aromatic nucleus in the present invention, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole are used. Compounds are preferred.

  The blending ratio of the first polyepoxide component, which is a raw material component of the first cured epoxy resin used in the present invention, and the first curing agent is as follows when a polyaddition type curing agent is used as the first curing agent. The equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group derived from the polyepoxide component is preferably about 0.8 to 1.2, more preferably about 1.0 to 1.1. If the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group is within the above range, a three-dimensional network that is appropriately crosslinked so as to have the above water absorption without decreasing the abrasion resistance such as abrasion resistance. A cured epoxy resin having a structure is obtained.

  In the present invention, when an amino compound having active hydrogen which is a polyaddition type curing agent is used as the first curing agent, the equivalent ratio of amine active hydrogen to epoxy group derived from the first polyepoxide component is 0.00. It is preferable to use it so that it may become a ratio which becomes 5-1.5, and it is more preferable to use it so that it may become a ratio which becomes 0.6-0.8. Similarly to the above, when the equivalent ratio of the amine active hydrogen to the epoxy group is in the above range, a cured epoxy resin having a three-dimensional network structure that is appropriately cross-linked so as to have the above-mentioned water absorption without significant yellowing can be obtained.

  Here, there is a possibility that the physical properties of the first cured epoxy resin obtained when the mass ratio of the polyaddition type curing agent used as the first curing agent with respect to the first polyepoxide component is too large may be insufficient. The ratio of the polyaddition type curing agent to the first polyepoxide component is preferably 40% by mass or less.

  In the case of using a catalyst type curing agent such as an imidazole compound in addition to the polyaddition type curing agent as the first curing agent, the amount of the catalyst type curing agent used is 1.0 to 20% by mass with respect to the first polyepoxide component. 1 to 10% by mass is more preferable, and 1 to 5% by mass is particularly preferable. If the amount of the catalyst-type curing agent used for the first polyepoxide component is 1.0% by mass or more, the reaction proceeds sufficiently, and sufficient water absorption and scratch resistance are realized in the obtained first cured epoxy resin. it can. Moreover, if the usage-amount of the catalyst-type hardening | curing agent with respect to a 1st polyepoxide component is 20 mass% or less, the residue of a catalyst-type hardening | curing agent exists in the obtained 1st hardening epoxy resin, and a hardening epoxy resin turns yellow. It is easy to suppress the appearance problems such as.

  In addition, when using a catalyst type hardening | curing agent in addition to a polyaddition type hardening | curing agent as a 1st hardening | curing agent, the use ratio with respect to the 1st polyepoxide component of a polyaddition type hardening | curing agent is the above-mentioned ratio of a catalyst type hardening | curing agent. In this case, the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group may be reduced by about 10 to 50% from the above 0.5 to 1.0.

  A commercial item can also be used for the first curing agent as described above. As a commercial product of the first curing agent, specifically, as a polyoxyalkylene triamine which is a polyaddition type curing agent, Jeffamine T403 (trade name, manufactured by Huntsman) and the like can be mentioned. Examples of the triarylsulfonium salt that is a photocurable catalyst-type curing agent include Adekaoptomer SP152 (trade name, manufactured by Adeka).

(1-2) Urethane resin When a urethane resin is used as the cross-linked resin contained in the water-absorbing layer, the anti-fogging of the present invention is obtained when the urethane resin and metal oxide fine particles described later are combined in the above ratio to form a water-absorbing layer. The urethane resin is not particularly limited as long as it can provide good properties and scratch resistance. Here, the antifogging property of the water absorption layer according to the present invention is substantially determined by the water absorption performance of the urethane resin used. Therefore, the urethane resin used for the water absorption layer is selected to have a water absorption performance that is high enough to achieve the antifogging property.

Specifically, the water absorption performance of the urethane resin is such that the saturated water absorption measured by the above method is preferably 120 mg / cm ³ or more, and more preferably 150 mg / cm ³ or more. When the saturated water absorption amount of the urethane resin takes the above value, the antifogging article of the present invention can ensure sufficient antifogging properties in the water absorbing layer. On the other hand, from the viewpoint of preventing the durability of the water absorbing layer from being lowered, the saturated water absorption amount of the urethane resin is preferably 900 mg / cm ³ or less, and more preferably 500 mg / cm ³ or less.

Specifically, the urethane resin having such a high water absorption performance is obtained by reacting a polyisocyanate with a polyol containing an acrylic polyol having an average molecular weight of 1000 to 4000 and a polyoxyalkylene polyol having an average molecular weight of 400 to 5000. A urethane resin is mentioned.
By using a combination of an acrylic polyol having an average molecular weight of 1000 to 4000 and a polyoxyalkylene polyol having an average molecular weight of 400 to 5000 as a polyol for producing a urethane resin, water in which the chain in the urethane resin is absorbed by the water absorbing layer is used. This is thought to contribute to increasing the speed of dehydration.

  The polyoxyalkylene-based polyol is used as a polyol for causing the water absorption layer to exhibit an antifogging function. As the polyoxyalkylene polyol, a polyol having an oxyethylene chain, an oxypropylene chain, or the like can be used. In particular, the oxyethylene chain is excellent in the function of absorbing water as bound water, and thus is advantageous for forming a water-absorbing layer having reversible absorption and dehydration that has a high dehydration rate during dehydration. Therefore, it is preferable to use a polyol having an oxyethylene chain in consideration of the antifogging property in a low temperature environment such as winter when the ambient temperature is 5 ° C. or lower.

  The average molecular weight of the polyoxyalkylene polyol is 400 to 5000. When the average molecular weight is less than 400, the ability to absorb water as bound water is low, and when the average molecular weight exceeds 5000, Problems such as a decrease in film strength are likely to occur. Considering the water absorption and mechanical strength of the water absorbing layer, the average molecular weight is more preferably 400 to 4500. In the present specification, the material used for the urethane resin and the average molecular weight of the obtained urethane resin refer to the number average molecular weight (Mn). The number average molecular weight (Mn) refers to the number average molecular weight based on polystyrene measured by gel permeation chromatography (GPC).

  In particular, when the polyoxyalkylene-based polyol is polyethylene glycol, the average molecular weight is preferably set to 400 to 2000 in consideration of the ability to absorb water, poor curing and mechanical strength of the water absorption layer. In the case of an oxyethylene / oxypropylene copolymer polyol, the average molecular weight is preferably 1500 to 5000.

  A plurality of types of polyols may be used as the polyoxyalkylene-based polyol. In this case, the polyol to be used includes polyethylene glycol having an average molecular weight of 400 to 2000 that is particularly excellent in the ability to absorb water as bound water. It is preferable. Since polyethylene glycol is particularly excellent in the ability to absorb water as bound water, all polyoxyalkylene polyols may be polyethylene glycol.

  The acrylic polyol mainly exerts an effect of lowering the wear resistance, water resistance, and surface friction coefficient on the water absorption layer, that is, exhibits the slip property on the surface of the water absorption layer. In addition to this, this acrylic polyol has the effect of shortening the leveling step of uniforming the film thickness deviation when the water-absorbing layer-forming composition for forming the water-absorbing layer is applied to the substrate.

  The acrylic polyol has an average molecular weight of 1000 to 4000. If it is less than 1000, the wear resistance of the water-absorbing layer tends to decrease, and if it exceeds 4000, the applicability of the water-absorbing layer-forming composition at the time of forming the water-absorbing layer tends to be poor, and the water-absorbing layer formation tends to be difficult. . In consideration of the density and hardness of the water-absorbing layer to be obtained, the number of hydroxyl groups of the acrylic polyol is preferably 3 or 4.

  In the present invention, the chain in the urethane resin obtained by reacting the polyoxyalkylene polyol and the polyol containing the acrylic polyol with the polyisocyanate has the effect of increasing the dehydration rate of the water absorbed in the water absorption layer. It has gained. Since this effect tends to improve as the molecular weight of the acrylic polyol increases, the average molecular weight of the acrylic polyol is preferably 2000 or more.

  The acrylic polyol contributes to improving the durability of the water absorption layer and increasing the water dehydration rate as described above. Considering only the improvement of the durability of the water absorbing layer, a hydrophobic polyol other than the above acrylic polyol can be used, but it does not contribute to increasing the water dehydration rate. Therefore, although it is preferable that an acrylic polyol is included as a polyol for obtaining a urethane resin, it may not be an essential component depending on the design of the antifogging article.

The polyisocyanate for forming a urethane resin by crosslinking reaction with the polyol is an organic polyisocyanate such as an organic diisocyanate, preferably a trifunctional having a biuret and / or isocyanurate structure starting from hexamethylene diisocyanate. The polyisocyanate can be used.
Such polyisocyanates have weather resistance, chemical resistance, and heat resistance, and are particularly effective for weather resistance. Further, as polyisocyanate, diisophorone diisocyanate, diphenylmethane diisocyanate, bis (methylcyclohexyl) diisocyanate, toluene diisocyanate and the like can be used in addition to the above.

  As a blending ratio of the polyisocyanate and the polyol, the number of isocyanate groups as the whole polyisocyanate is 1 to 2 times, more preferably 1.4 times to 1 with respect to the number of hydroxyl groups as the whole polyol. It is preferable to adjust so that it may become 8 times amount. When the amount is less than 1 times, the curability deteriorates and the formed water-absorbing layer is soft, and durability such as weather resistance, solvent resistance, and chemical resistance may be lowered. On the other hand, when the amount exceeds 2 times, the antifogging property is deteriorated because the water absorption and dehydration is inhibited by excessive curing.

  The ratio between the polyoxyalkylene polyol and the acrylic polyol is adjusted so that the water absorption performance of the resulting urethane resin becomes the saturated water absorption. For example, in the case of polyethylene glycol and acrylic polyol, the component ratio is preferably “polyethylene glycol: acryl polyol = 50: 50 to 70:30” by weight.

(Metal oxide fine particles)
The water absorption layer contains metal oxide fine particles. By including the metal oxide fine particles, the mechanical strength such as abrasion resistance and scratch resistance and heat resistance of the formed water absorption layer can be increased, and the curing shrinkage of the resin during the curing reaction can be reduced. Examples of the metal oxide of such metal oxide fine particles include silica, alumina, titania, and zirconia, and silica is particularly preferable.

  Moreover, ITO (Indium Tin Oxide) fine particles can also be used as the metal oxide fine particles. Since ITO has infrared absorptivity, heat absorption can be imparted to the water-absorbing crosslinked resin. Therefore, if ITO fine particles are used, in addition to water absorption, an antifogging effect by heat ray absorption can be expected.

The metal oxide fine particles contained in the water absorption layer preferably have an average primary particle size of 10 to 50 nm, more preferably 10 to 30 nm. If the average primary particle diameter of the metal oxide fine particles is within this range, it is advantageous for ensuring transparency. In the present specification, the average primary particle diameter refers to that measured by the BET method.
The content of the metal oxide fine particles in the water absorption layer is a ratio of 20 to 60% by mass with respect to the total amount of the water absorption layer, and a ratio of 30 to 50% by mass is preferable. By setting the content of the metal oxide fine particles in the water absorption layer to 20% by mass or more, the scratch resistance of the water absorption layer can be within the range of the present invention. Moreover, by setting it as 60 mass% or less, anti-fogging property can fully be ensured, maintaining a haze value low.

  Silica fine particles, which are preferably used as the metal oxide fine particles, are incorporated into the water-absorbing layer forming composition as colloidal silica dispersed in water or an organic solvent such as methanol, ethanol, isobutanol, propylene glycol monomethyl ether, butyl acetate or the like. can do. A method of blending the metal oxide fine particles into the water absorbing layer forming composition will be described later. Examples of colloidal silica include silica hydrosol dispersed in water and organosilica sol in which water is replaced with an organic solvent. When blended in a water-absorbing layer forming composition, the organic solvent preferably used for this composition It is preferable to use an organosilica sol using the same organic solvent as the dispersion medium.

As such an organosilica sol, a commercially available product can be used. Examples of commercially available products include organosilica sol IPA-ST (trade name, Nissan Chemical Industries, Ltd.) in which silica fine particles having a particle diameter of 10 to 20 nm are dispersed in isopropanol at a ratio of 30% by mass as SiO ₂ content with respect to the total amount of organosilica sol. Manufactured), organosilica sol NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), particles in which silica fine particles having a particle diameter of 10 to 20 nm are dispersed in butyl acetate in a proportion of 30% by mass as SiO ₂ content with respect to the total amount of organosilica sol, particles Organosilica sol MEK-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) in which silica fine particles having a diameter of 10 to 20 nm are dispersed in methyl ethyl ketone in a proportion of 30% by mass as SiO ₂ content with respect to the total amount of organosilica sol, silica fine particles in MEK-ST Particle diameter of 40-50 nm Outside is the same organo-silica sol and MEK-ST MEK-ST-L (trade name, manufactured by Nissan Chemical Industries, Ltd.), and the like can be given.

  When colloidal silica is used as the silica fine particles, the amount of the solvent to be blended in the water absorbing layer forming composition is appropriately adjusted in consideration of the amount of solvent contained in the colloidal silica.

(Water absorbing layer forming composition)
The water absorption layer in the antifogging article of the present invention is mainly composed of a crosslinked resin and metal oxide fine particles. The content of the metal oxide fine particles in the water absorption layer is a ratio in which the metal oxide fine particles are 20 to 60% by mass, preferably 30 to 50% by mass with respect to the total amount of the water absorption layer. On the other hand, the content of the cross-linked resin element in the water-absorbing layer is a ratio such that the cross-linked resin element is 40 to 80% by mass, preferably 50 to 70% by mass, with respect to the total amount of the water-absorbing layer. For example, in the case of a cured epoxy resin, the crosslinked resin is obtained by reacting a water-absorbing layer-forming composition containing the first polyepoxide component and the first curing agent.

  About the said 1st polyepoxide component and 1st hardening | curing agent which the composition for water absorption layer formation contains, it is as above including preferable aspects, such as a compound used and the ratio at the time of combining. The composition for forming a water absorption layer usually contains a solvent in addition to the first polyepoxide component and the first curing agent. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed.

Usually, the reaction of the first polyepoxide component and the first curing agent for obtaining the first cured epoxy resin is carried out after application on the coated surface as a water-absorbing layer forming composition. In the composition before being applied to the coated surface, these components may be reacted to some extent in advance, then coated on the coated surface, dried, and further reacted. In the present invention, in order to make a large amount of the metal oxide fine particles as described above uniformly exist in the crosslinked resin of the water absorption layer, the above-described method of reacting to some extent is taken, and the metal oxide fine particles are put before and after this reaction. A method of separately charging the water absorbing layer forming composition is employed.
As described above, when the first polyepoxide component and the first curing agent are reacted in advance to some extent in the solvent as the water absorbing layer forming composition, the reaction temperature when the reaction is performed in advance should be 30 ° C. or higher. This is preferable because the curing reaction proceeds reliably.

  The solvent used in the water-absorbing layer forming composition is a solvent having good solubility with respect to the blending component including the first polyepoxide component, the first curing agent, and other optional components, and with respect to these blending components. The solvent is not particularly limited as long as it is an inert solvent, and specific examples include alcohols, acetates, ethers, ketones, and water.

  If a protic solvent is used as the solvent, depending on the type of the first polyepoxide component, the solvent and the epoxy group may react to make it difficult to form a cured epoxy resin. Accordingly, when a protic solvent is used, it is preferable to select a solvent that does not easily react with the first polyepoxide component. Examples of protic solvents that can be used include ethanol and isopropanol. As other solvents, acetone, methyl ethyl ketone, butyl acetate, propylene carbonate, diethylene glycol dimethyl ether, diacetone alcohol, propylene glycol monomethyl ether and the like are preferable.

  These solvents may be used alone or in combination of two or more. Moreover, compounding components, such as a 1st polyepoxide component and a 1st hardening | curing agent, may be prepared as a mixture with a solvent. In such a case, the solvent contained in the mixture may be used as it is as a solvent in the water-absorbing layer-forming composition, and the water-absorbing layer-forming composition may contain the same or other solvents. May be added.

  Moreover, the quantity of the solvent in the composition for water absorption layer formation is 100- with respect to the total mass of 100 mass parts of the total solid in a 1st polyepoxide component, a 1st hardening | curing agent, and the other various mixing components mix | blended arbitrarily. The amount is preferably 500 parts by mass, and more preferably 200 to 350 parts by mass.

  Here, the blending amount of the first polyepoxide component and the first curing agent in the water-absorbing layer forming composition is preferably 15 to 30% by mass with respect to the total amount of the composition for the first polyepoxide component, About 1st hardening | curing agent, it is preferable that it is 3-20 mass% with respect to the composition whole quantity. In addition, when using a polyaddition type hardening | curing agent and a catalyst type hardening | curing agent as a 1st hardening | curing agent, it is preferable that the total amount is 3-16 mass% with respect to the composition whole quantity.

  The blending ratio of the polyaddition type curing agent and the catalyst type curing agent in the first curing agent depends on the type of curing agent used. For example, when an amine compound having active hydrogen (polyaddition type curing agent) and an imidazole compound (catalytic type curing agent) are used in combination as the first curing agent, the total amount of the water absorbing layer forming composition The amine compound having active hydrogen is preferably blended at a ratio of 3 to 15% by mass and the imidazole compound at a ratio of 0.1 to 1.0% by mass. By setting it as such a mixture ratio, both the advantages which the said polyaddition type hardening | curing agent and a catalyst type hardening | curing agent have can be exhibited effectively.

  Among the additives optionally contained in the water-absorbing layer forming composition, the reactive additive includes a compound having one reactive group reactive with an epoxy group such as alkyl monoamine, a coupling having an epoxy group or an amino group Agents and the like. In the composition for forming a water-absorbing layer, the coupling agent is used for the purpose of improving the adhesion between the water-absorbing layer and the base layer, or the adhesion between the water-absorbing layer and a functional layer described later on the water-absorbing layer as necessary. It is a component to be blended, and is one of the components that are preferably blended.

  As the coupling agent to be used, an organometallic coupling agent or a polyfunctional organic compound is preferable. Examples of organometallic coupling agents include silane coupling agents (hereinafter referred to as silane coupling agents), titanium coupling agents, and aluminum coupling agents, with silane coupling agents being preferred. These coupling agents preferably have a reactive group that can react with the reactive group that the first polyepoxide component or the first curing agent has and the reactive group that remains on the surface of the underlayer described later. In addition, it can use also for the purpose of adjusting the physical property of a water absorption layer besides the objective of improving the adhesiveness between each layer by having such a reactive group. 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. As the organometallic coupling agent, a silane coupling agent is particularly preferable.

  A silane coupling agent is a compound in which one or more hydrolyzable groups and one or more monovalent organic groups (however, the terminal bonded to the silicon atom is a carbon atom) are bonded to the silicon atom. One of the monovalent organic groups is a functional organic group (an organic group having a reactive group or an organic group exhibiting characteristics such as hydrophobicity). As the organic group other than the functional organic group, an alkyl group having 4 or less carbon atoms is preferable. The number of hydrolyzable groups bonded to the silicon atom is preferably 2 or 3. The silane coupling agent is preferably a compound represented by the following formula (1).

R ³ R ⁴ _c SiX ² _3-c (1)
In the above formula (1), R ³ represents a monovalent functional organic group, R ⁴ represents an alkyl group having 4 or less carbon atoms, and c represents an integer of 0 or 1. R ⁴ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. X ² is a hydrolyzable group such as a chlorine atom, an alkoxy group, an acyl group, or an amino group, and an alkoxy group having 4 or less carbon atoms is particularly preferable.

  The functional organic group may be a hydrophobic organic group such as a polyfluoroalkyl group or a long-chain alkyl group having 6 to 22 carbon atoms. Preferably, it is an alkenyl group having an addition polymerizable unsaturated group or an alkyl group having a reactive group. The alkyl group having a reactive group may be an alkyl group substituted with an organic group having a reactive group. As for carbon number of such an alkyl group, 1-4 are preferable. Examples of the reactive group include an epoxy group, amino group, mercapto group, ureido group, hydroxyl group, carboxyl group, acryloyloxy group, methacryloyloxy group, and isocyanate group. Examples of the organic group having such a reactive group include a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted amino group. Among these, a silane coupling agent whose reactive group is an epoxy group, an amino group, a mercapto group, or a ureido group is preferable.

  Examples of such silane coupling agents include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycol. Sidoxypropylmethyldiethoxysilane, 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- Mino propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Among these, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane and the like are preferable.

  In the present invention, among these, in particular, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino) A silane coupling agent having an amino group such as ethyl) -3-aminopropyltrimethoxysilane is preferably used.

  The blending amount of the coupling agent in the water absorbing layer forming composition is not an essential component, so there is no lower limit. However, in order to fully exhibit the effect of the coupling agent blending, the mass ratio of the coupling agent is 5 with respect to the total mass of the first polyepoxide component and the first curing agent in the water absorbing layer forming composition. It is preferable that it is -40 mass%, and 10-30 mass% is more preferable. The upper limit of the amount of coupling agent is limited by the physical properties and functions of the coupling agent. When used for the purpose of improving the adhesion of the water-absorbing layer mainly composed of the first cured epoxy resin, the mass ratio of the coupling agent to the total mass of the first polyepoxide component and the first curing agent is 40 mass. % Or less is preferable, and 30% by mass or less is more preferable. If the amount of the coupling agent used is not excessive, it is possible to prevent the water-absorbing resin mainly composed of the first cured epoxy resin from being colored due to oxidation or the like when exposed to a high temperature.

In addition, as a compounding quantity of the coupling agent with respect to the composition for water absorption layer formation, when using a silane coupling agent, it is preferable that it is 2-10 mass%, and is 3-7 mass%. It is more preferable.
In addition, regarding a particularly preferable composition in the water-absorbing layer-forming composition containing a silane coupling agent, an amine compound having 15 to 30% by mass of the first polyepoxide component and active hydrogen relative to the total amount of the composition 3 to 15% by mass, imidazole compound 0.1 to 1.0% by mass, silane coupling agent 2 to 10% by mass, and solvent 50 to 75% by mass.

  Here, when the composition for forming a water absorbing layer contains a coupling agent having an amino group as a coupling agent, the equivalent ratio of amine active hydrogen to the epoxy group is the amine activity in the first curing agent. By combining hydrogen and the amine active hydrogen of the coupling agent, the equivalent ratio with the epoxy group of the first polyepoxide component is calculated so as to be within the preferred range.

  Similarly, when the water-absorbing layer-forming composition contains a coupling agent having an epoxy group as a coupling agent, the equivalent ratio of amine active hydrogen to the epoxy group is the epoxy contained in the first polyepoxide component. By combining the group and the epoxy group of the coupling agent, the equivalent ratio of amine active hydrogen in the first curing agent is calculated so as to be in the preferred range.

The water-absorbing layer-forming composition preferably further contains an antioxidant as an optional component in order to improve the weather resistance of the water-absorbing layer obtained. When the second cured epoxy resin that mainly constitutes the water absorption layer when exposed to heat or light is oxidized and deteriorated, stress accumulation is likely to occur in the water absorption layer, thereby easily peeling off the antifogging film. By adding an antioxidant, such a phenomenon can be suppressed.
Antioxidants include phenolic antioxidants that suppress the oxidation of resins by capturing and decomposing peroxy radicals, and phosphorus antioxidants that suppress the oxidation of resins by decomposing peroxides. In the present invention, a phenolic antioxidant is preferably used.

  As a phenolic antioxidant, the following phenolic antioxidants usually blended in a cured epoxy resin can be used without particular limitation. One of these may be used alone, or two of them may be used in combination.

  Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitile -2,4,6-triyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (Octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-di-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [[3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-4-butyl-4-hydroxybenzyl) -1,3,5-triazine-2 , 4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1, , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl- 4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Examples of commercially available phenolic antioxidants include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 (trade name, manufactured by Ciba Japan), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90 (trade name, manufactured by ADEKA), Sumilizer GA-80, Sumizer MDP-S, Sumizer BBM-S, Sumizer GM, Sumizer GS (F), Sumitomo G Etc.).

  Moreover, about the quantity of antioxidant mix | blended with the composition for water absorption layer formation, 0.5-2 mass% is preferable with respect to the total mass of a 1st polyepoxide component and a 1st hardening | curing agent, 2 mass% is more preferable.

A leveling agent, an antifoamer, a viscosity modifier, a light stabilizer, etc. can be further added to the composition for forming a water absorbing layer as necessary.
Examples of the leveling agent include polydimethylsiloxane-based surface conditioners, acrylic copolymer surface conditioners, fluorine-modified polymer-based surface conditioners, and antifoaming agents include silicone-based antifoaming agents, surfactants, Organic antifoaming agents such as ethers and higher alcohols, viscosity modifiers include acrylic copolymers, polycarboxylic acid amides, modified urea compounds, etc., and light stabilizers include hindered amines; nickel bis (octylphenyl) Examples include nickel complexes such as sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate. Each component may be used in combination of two or more of the exemplified compounds. The content of various components in the water-absorbing layer-forming composition may be 0.001 to 10% by mass with respect to the total mass of the first polyepoxide component and the first curing agent for each component. it can.

  When the crosslinked resin used in the water-absorbing layer in the antifogging article of the present invention is, for example, a urethane resin, the crosslinked resin is obtained by reacting the water-absorbing layer-forming composition containing the polyol and the polyisocyanate. .

  About the said polyol and said polyisocyanate which the composition for water absorption layer formation contains, it is as above including preferable aspects, such as a compound used and the ratio at the time of combining. The composition for forming a water absorption layer usually contains a solvent in addition to the polyol and the polyisocyanate. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed.

  Usually, the reaction between the polyol and the polyisocyanate for obtaining the urethane resin is carried out after application on the coated surface as a water-absorbing layer forming composition, but when the composition contains a solvent, it is coated on the coated surface. These components may be allowed to react to some extent in the composition before being applied, then applied to the coated surface, dried, and further reacted. In the present invention, in order to make a large amount of the metal oxide fine particles as described above uniformly exist in the crosslinked resin of the water absorption layer, the above-described method of reacting to some extent is taken, and the metal oxide fine particles are put before and after this reaction. A method of separately charging the water absorbing layer forming composition is employed.

  Thus, when the polyol and the polyisocyanate are reacted in advance to some extent in the solvent as the water-absorbing layer forming composition, the curing reaction can be ensured by setting the reaction temperature to 30 ° C. or higher in advance. This is preferable because it proceeds.

  The solvent used in the water-absorbing layer-forming composition is a solvent having good solubility with respect to the above-mentioned polyol, polyisocyanate, and other optional ingredients, and an inert solvent for these ingredients. If it is, it will not specifically limit, Specifically, it is preferable to use an acetate ester solvent, ketones, and diacetone alcohol.

  These solvents may be used alone or in combination of two or more. Moreover, compounding components, such as the said polyol and the said polyisocyanate, may be prepared as a mixture with a solvent. In such a case, the solvent contained in the mixture may be used as it is as a solvent in the water-absorbing layer-forming composition, and the water-absorbing layer-forming composition may contain the same or other solvents. May be added.

  Moreover, the quantity of the solvent in the composition for water absorption layer formation is 100-500 mass parts with respect to the total mass of 100 mass parts of the total solid in the said polyol, said polyisocyanate, and the other various mixing components mix | blended arbitrarily. It is preferably 200 to 350 parts by mass.

In the composition for forming a water absorption layer when the crosslinked resin is a urethane resin, an organic tin compound that is a curing catalyst may be added as another component in order to increase the curing rate of the polyol and the polyisocyanate. . Examples of the compound include dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin markabutide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin makercarboxylate, dioctyltin thiocarboxylate Etc. can be used.
As a compounding quantity, 0.1-5 mass parts is preferable with respect to 100 mass parts of the total amount of the said polyol and polyisocyanate.

  As other components that can be blended in the water-absorbing layer-forming composition when the crosslinked resin is a urethane resin, other components similar to those when the crosslinked resin is the first cured epoxy resin, specifically, organic A coupling agent comprising a metal-based coupling agent or a polyfunctional organic compound, an antioxidant, a leveling agent, an antifoaming agent, a viscosity adjusting agent, a light stabilizer and the like can be added.

(Water absorption layer)
The water absorbing layer in the antifogging article of the present invention is obtained by reacting the first polyepoxide component and the first curing agent contained in the water absorbing layer forming composition or the polyol and polyisocyanate. The first cured epoxy resin or urethane resin having a three-dimensional network structure and the predetermined amount of the metal oxide fine particles are uniformly dispersed and included in the three-dimensional network structure of the crosslinked resin. Thus, it is a resin layer having both excellent anti-fogging properties and abrasion resistance such as abrasion resistance and scratch resistance. The reaction conditions will be described in the production method described later.

  In addition, a reactive additive such as a silane coupling agent that is optionally added is present in the water absorption layer in a form that is bonded to a part of the three-dimensional network structure of the crosslinked resin, and is optionally added in addition to that. The non-reactive additive is, as in the case of the metal oxide fine particles, present in the water-absorbing layer by being uniformly dispersed and included in the three-dimensional network structure of the crosslinked resin.

  Here, in the antifogging article of the present invention, a functional layer may be provided between the substrate and the water absorbing layer as long as the effects of the present invention are not impaired. For example, when the crosslinked resin contained in the water absorbing layer is the first cured epoxy resin, the antifogging index is more antifogging than the water absorbing layer in order to prevent peeling of the substrate and the water absorbing layer. You may have a low base layer. Since antifogging properties are relative, “high antifogging properties” and “low antifogging properties” do not mean high or low with a threshold.

[3] Underlayer The underlayer is a layer formed between the substrate and the water absorbing layer, and is obtained by reacting a composition for forming an underlayer containing a second polyepoxide component and a second curing agent. It is a layer having lower water absorption than the water absorption layer mainly composed of the second cured epoxy resin. Hereinafter, the resin mainly composed of the second cured epoxy resin in the underlayer is also referred to as a low water absorption resin.

If the water absorption of the low water absorption resin which comprises the foundation | substrate layer provided in the anti-fogging article | item of this invention is shown concretely, the saturated water absorption measured by the method demonstrated with the said water absorption layer is 30 mg / cm < ³ > or less. And is more preferably 20 mg / cm ³ or less. By setting the saturated water absorption amount of the low water-absorbent resin to 30 mg / cm ³ or less, as described above, the difference in expansion and contraction is small at the bonding interface between the substrate and the antifogging film, actually between the substrate and the underlayer. Thus, it is possible to prevent the antifogging film from peeling off from the substrate. As a result, an antifogging article excellent in acid resistance and alkali resistance is obtained. On the other hand, from the viewpoint of reducing the degree of expansion / shrinkage between the underlayer and the water absorption layer in the antifogging film, the saturated water absorption amount of the low water absorbent resin constituting the underlayer is 1 mg / cm ³ or more. It is preferably 3 mg / cm ³ or more.

  With respect to the water absorption of the base layer provided in the antifogging article of the present invention, if the antifogging property described in the water absorbing layer is shown as an index, the antifogging property can be 10 seconds or less, and in a more preferred embodiment It can be 7 seconds or less, and in a particularly preferred embodiment, it can be 3 seconds or less. As with the saturated water absorption, the antifogging property is preferably 1 second or more from the viewpoint of reducing the degree of expansion / contraction between the base layer and the water absorption layer in the antifogging film, preferably 2 seconds or more. More preferably.

From the relationship between the saturated water absorption amount of the low water-absorbing resin constituting the foundation layer and the antifogging property of the foundation layer, the film thickness of the foundation layer according to the antifogging article of the present invention is preferably 1 μm or more, More preferably, it is 3 μm or more, and further preferably 5 μm or more. If the film thickness of the underlayer is 1 μm or more, it becomes possible to prevent the antifogging film from peeling from the substrate, and as a result, an antifogging article having excellent acid resistance and alkali resistance is obtained. Further, the thickness of the underlayer is more preferably 3 μm or more, and even more preferably 5 μm or more, for the reason of relieving the stress generated at the interface due to the expansion / contraction of the water absorption layer. The thickness of the underlayer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less, from the viewpoint of reducing material costs and improving the yield rate.
Here, in the antifogging article, the peel resistance required for the undercoat layer varies depending on the use, and therefore the design may be appropriately changed in accordance with the required performance.

  The cured epoxy resin mainly constituting the foundation layer is a second cured epoxy resin obtained by reacting the second polyepoxide component and the second curing agent, and is used for designing the foundation layer to have the above water absorption. The main component.

  As described above, generally, in order to increase the antifogging performance, it is preferable to control the glass transition point of the cured epoxy resin low, and to increase the scratch resistance, it is preferable to control the glass transition point of the cured epoxy resin high. . Considering these, the glass transition point of the second cured epoxy resin mainly constituting the low water-absorbent resin is preferably 40 to 150 ° C., although it depends on the type of the cured epoxy resin, and is 40 to 120 ° C. More preferably.

  The first water-absorbing layer mainly constituting the water-absorbing layer has a glass transition point in the above range (-20 to 60 ° C., preferably -5 to 40 ° C.), and further has a low water absorption mainly constituting the underlayer. If the glass transition point of the second cured epoxy resin is within the above range and higher than the glass transition point of the first cured epoxy resin, the antifogging performance and the scratch resistance are compatible at a high level. Easy to do. The difference in glass transition point between the second cured epoxy resin in the underlayer and the first cured epoxy resin in the water-absorbent resin is preferably 10 ° C. or higher, and more preferably 20 ° C. or higher.

Hereinafter, the second cured epoxy resin obtained by reacting the second polyepoxide component mainly constituting the base layer with the second curing agent will be described.
(Second polyepoxide component)
As the second polyepoxide component which is a raw material component of the second cured epoxy resin, the first polyepoxide component which is usually used as the raw material component of the cured epoxy resin has been described so that the water absorption is in the preferred range. A polyepoxide appropriately selected from glycidyl ether polyepoxide, glycidyl ester polyepoxide, glycidylamine polyepoxide, cyclic aliphatic polyepoxide, and the like can be used. The molecular weight of the polyepoxide used as the second polyepoxide component is not particularly limited, but from the viewpoint of avoiding poor appearance such as insufficient wetting and spreading of the coating liquid during coating and unevenness of the coating film, about 500 to about 1000 Polyepoxides with a molecular weight of Further, the number of epoxy groups per molecule of polyepoxide in the second polyepoxide component is not particularly limited as long as it is 2 or more on average, but is preferably 2 to 10, more preferably 2 to 8 2 to 4 are more preferable.

  As the second polyepoxide component, for example, by selecting a polyepoxide having an aromatic nucleus that is not selected as a preferred polyepoxide in the first polyepoxide component, the water absorption of the resulting cured epoxy resin can be lowered. Is possible.

  The polyepoxide having an aromatic nucleus that can be used as the second polyepoxide component is preferably a polyepoxide having a structure in which a phenolic hydroxyl group is substituted with a glycidyloxy group. Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol type diglycidyl ethers such as bis (4-glycidyloxyphenyl), phenol novolac type diglycidyl ethers, cresol novolac type diglycidyl ethers, And aromatic polycarboxylic acid polyglycidyl esters such as diglycidyl phthalate. Of these polyepoxides having aromatic nuclei, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether are preferably used as the second polyepoxide component.

  Further, even if the polyepoxide does not have an aromatic nucleus, if the number of cross-linking points is increased, the resulting cured epoxy resin has a dense three-dimensional network structure, and the space for water retention is reduced, resulting in a decrease in water absorption. It is done.

Therefore, by appropriately selecting the type and blending amount of the second curing agent, it is possible to use the polyepoxide having no aromatic nucleus exemplified in the first polyepoxide component as the second polyepoxide component as it is, A polyepoxide preferable as the first polyepoxide component is also preferably used as the second polyepoxide component.
Particularly preferred polyepoxides as the second polyepoxide component are sorbitol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers and the like classified into glycidyl ether-based polyepoxides derived from aliphatic / alicyclic polyols. It is.

  In the second polyepoxide component, in order to increase the number of crosslinking points of the obtained second cured epoxy resin and control the water absorption low, for example, the second polyepoxide component is aliphatic / alicyclic. In the case of a glycidyl ether-based polyepoxide derived from polyols, the epoxy equivalent is preferably 100 to 200 g / eq, and more preferably 100 to 150 g / eq.

  In addition, also about the polyepoxide which comprises the said 2nd polyepoxide component, it is possible to use a commercial item similarly to the polyepoxide which comprises the said 1st polyepoxide component. As such a commercial product, in addition to the commercial products described in the first polyepoxide component, jER828 (trade name, manufactured by Mitsubishi Chemical Corporation) as bisphenol A diglycidyl ether, Adeka Resin EP4901 (product) Name, manufactured by Adeka).

(Second curing agent)
The second cured epoxy resin that mainly constitutes the underlayer is a second cured epoxy resin obtained by reacting the second polyepoxide component with a second curing agent.
As a 2nd hardening | curing agent, it is preferable to use a polyaddition type hardening | curing agent similarly to the said 1st hardening | curing agent. It is also possible to use a catalyst type curing agent in combination with this polyaddition type curing agent.

  The kind of polyaddition type curing agent that can be used is the same as that of the first curing agent. That is, the polyaddition type curing agent is preferably an amino compound having two or more amino groups having active hydrogen, a compound having two or more carboxyl groups, or a compound having two or more thiol groups, more preferably The amino compound having the active hydrogen is used.

  Here, as the second curing agent, for example, a cured epoxy resin obtained by selecting a polyaddition curing agent having an aromatic nucleus that is not selected as a preferable curing agent in the first curing agent. It is possible to reduce the water absorption. Depending on the degree of water absorption required for the underlayer, if a compound having an aromatic nucleus is used in at least one of the second polyepoxide component and the second curing agent, the water absorption of the second cured epoxy resin obtained is obtained. The property can be in the desired range.

  Even when a polyepoxide having no aromatic nucleus is used as the second polyepoxide component and a polyaddition type curing agent having no aromatic nucleus is used as the second curing agent, the number of crosslinking points increases as described above. Thus, the water absorption of the obtained 2nd cured epoxy resin can be made into the said desired range by combining. Furthermore, the second cured epoxy resin having no aromatic nuclei thus obtained is superior in terms of weather resistance compared to the second cured epoxy resin having aromatic nuclei.

As the polyaddition type curing agent having no aromatic nucleus, the same curing agent as the polyaddition type curing agent having no aromatic nucleus described in the first curing agent can be used. Examples of the polyaddition type curing agent having an aromatic nucleus include polyamines having an aromatic nucleus and aromatic polycarboxylic acid anhydrides. Specific examples of the polyamine having an aromatic nucleus include phenylenediamine, xylylenediamine, diaminodiphenylmethane, and the like, and examples of the aromatic polycarboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, and pyrophilic anhydride. And merit acid.
As for the catalyst-type curing agent that can be used as necessary in the second curing agent, the same curing agent as the catalyst-type curing agent described in the first curing agent can be used.

  The blending ratio of the second polyepoxide component, which is a raw material component of the second cured epoxy resin used in the present invention, and the second curing agent is the second when a polyaddition curing agent is used as the second curing agent. The equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group derived from the polyepoxide component is preferably about 0.8 to 1.5, more preferably about 1.0 to 1.5. If the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group is in the above range, the reaction temperature is raised and the polyaddition reaction is accelerated to crosslink at a sufficient number of crosslinking points at room temperature. Thus, a second cured epoxy resin having a low water absorption as compared with the first cured epoxy resin having a three-dimensional network structure is obtained.

  In the present invention, when an amino compound having active hydrogen which is a polyaddition type curing agent is used as the second curing agent, the equivalent ratio of amine active hydrogen to epoxy group derived from the second polyepoxide component is 0.00. It is preferable to use it so that it may become a ratio which becomes 5-1.5, and it is more preferable to use it so that it may become a ratio which becomes 1.2-1.5. Similarly to the above, if the equivalent ratio of amine active hydrogen to epoxy group is in the above range, a dense three-dimensional network structure can be formed by crosslinking at a sufficient number of crosslinking points without increasing the reaction temperature and accelerating the polyaddition reaction. A second cured epoxy resin having a low water absorption as compared with the first cured epoxy resin having the above is obtained.

  Further, if the mass ratio of the polyaddition type curing agent used as the second curing agent with respect to the second polyepoxide component is too large, the physical properties of the obtained second cured epoxy resin may be insufficient. The ratio of the polyaddition type curing agent to the polyepoxide component is preferably 40% by mass or less.

(Underlayer forming composition)
The underlayer in the antifogging film of the antifogging article of the present invention comprises a second cured epoxy resin obtained by reacting the underlayer forming composition containing the second polyepoxide component and the second curing agent. This is the underlying layer.

  About the said 2nd polyepoxide component and 2nd hardening | curing agent which the composition for base layer formation contains, it is as above including preferable aspects, such as a compound used and the ratio at the time of combining. The underlayer-forming composition usually contains a solvent in addition to the second polyepoxide component and the second curing agent. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed.

  Here, the composition for base layer formation is the same as the composition for water absorption layer formation in that the second polyepoxide component and the second curing agent are contained in the composition before being applied to the coating surface as a composition containing a solvent. You may make it react to some extent previously, it may apply | coat to an application surface after that, and may make it react further after drying. The conditions for the reaction in advance can be the same as those in the case of the water absorbing layer forming composition.

  The solvent used in the composition for forming the underlayer is a solvent having good solubility with respect to the blending component including the second polyepoxide component, the second curing agent, and other optional components, and with respect to these blending components. The solvent is not particularly limited as long as it is an inert solvent, and specific examples thereof include the same solvents as the water absorbing layer forming composition. The preferred embodiment of the solvent is the same as that of the water absorbing layer forming composition.

  Moreover, the quantity of the solvent in the composition for base layer formation is 200- with respect to 100 mass parts of total mass of the total solid in a 2nd polyepoxide component, a 2nd hardening | curing agent, and the other various mixing components mix | blended arbitrarily. The amount is preferably 950 parts by mass, and more preferably 400 to 950 parts by mass.

  Here, it is preferable that the compounding quantity of the 2nd polyepoxide component and 2nd hardening | curing agent in a composition for base layer formation is 4-10 mass% with respect to the composition whole quantity about a 2nd polyepoxide component, About the 2nd hardening | curing agent, it is preferable that it is 0.1-4.0 mass% with respect to the composition whole quantity. In addition, when using a polyaddition type hardening | curing agent and a catalyst type hardening | curing agent as a 2nd hardening | curing agent, it is preferable that the total amount is 0.1-4.0 mass% with respect to the composition whole quantity.

  Examples of the reactive additive optionally contained in the underlayer-forming composition include the same additives as the reactive additive optionally contained in the water-absorbing layer-forming composition. Among the reactive additives, the coupling agent is a component that is blended for the purpose of improving the adhesion between the foundation layer and the substrate and the adhesion between the foundation layer and the water absorbing layer in the composition for forming the foundation layer. It is one of the preferred components.

About the coupling agent arbitrarily mix | blended with the composition for base layer formation, it can be made to be the same as that of the coupling agent used for the said composition for water absorption layer formation including the compound used and a preferable aspect.
Moreover, about the quantity of the coupling agent mix | blended with the composition for base layer formation, the mass ratio of a coupling agent is 5-50 mass% with respect to the total mass of a 2nd polyepoxide component and a 2nd hardening | curing agent. It is preferable that 10-40 mass% is more preferable.

The upper limit of the amount of coupling agent is limited by the physical properties and functions of the coupling agent. When used for the purpose of improving the adhesion of the underlayer mainly composed of the second cured epoxy resin, the mass ratio of the coupling agent to the total mass of the second polyepoxide component and the second curing agent is 50 mass. % Or less is preferable, and 40% by mass or less is more preferable.
On the other hand, when adjusting physical properties such as water absorption of the base resin mainly composed of the second cured epoxy resin by the coupling agent or by the second curing agent and the coupling agent, the second polyepoxide component and the second 40 mass% or less is preferable and, as for the mass ratio of the coupling agent with respect to the total mass of 2 hardening | curing agents, 20 mass% or less is more preferable. If the amount of the coupling agent used is not excessive, it is possible to prevent the base resin mainly composed of the second cured epoxy resin from being colored due to oxidation or the like when exposed to a high temperature.

In addition, as a compounding quantity of the coupling agent with respect to the composition for base layer formation, for example, when a silane coupling agent is used, it is preferable that it is 0.1-3.0 mass%, and 1-2. More preferably, it is mass%.
Here, regarding a particularly preferable composition in the composition for forming an underlayer containing the silane coupling agent, the amine having 4 to 10% by mass of the second polyepoxide component and active hydrogen with respect to the total amount of the composition. Examples include a composition containing 0.1 to 4.0% by mass of a compound, 0.1 to 4.0% by mass of a silane coupling agent, and 70 to 95% by mass of a solvent.

  Further, when the composition for forming an underlayer contains a coupling agent having an amino group or a coupling agent having an epoxy group as a coupling agent, the equivalent ratio of the amine active hydrogen to the epoxy group is determined as follows. It is preferable to adjust the blending amount of each component so that this is within the above range.

  The underlayer forming composition preferably further contains tetraalkoxysilane and / or an oligomer thereof (that is, a partially hydrolyzed condensate thereof) as an optional component. By blending tetraalkoxysilane and / or an oligomer thereof (hereinafter referred to as a tetraalkoxysilane compound), the viscosity of the underlayer-forming composition is lowered, and a crosslinking reaction between the second polyepoxide component and the second curing agent. Is performed uniformly. Moreover, the reaction point with a base | substrate and a water absorption layer increases, and adhesiveness improves further. Thereby, the weather resistance of the base layer obtained can be improved.

  Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, and tetra n-butoxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferable. One of these may be used alone, or two of them may be used in combination. Further, the above tetraalkoxysilane may be blended into the underlayer forming composition as an oligomer obtained by partial hydrolysis (co) condensation of about 2 to 3 of the tetraalkoxysilane, and as a mixture of the tetraalkoxysilane and its oligomer. You may mix | blend with the composition for formation.

  The amount of tetraalkoxysilane and / or oligomer thereof blended in the underlayer-forming composition is preferably 10 to 40% by mass with respect to the total mass of the second polyepoxide component and the second curing agent, 25 -35 mass% is more preferable.

It is preferable that the composition for forming the underlayer further contains an antioxidant as an optional component in order to improve the weather resistance of the obtained underlayer, for the same reason as the composition for forming the water absorbing layer.
About the antioxidant arbitrarily mix | blended with the composition for base layer formation, it can be made to be the same as that of the antioxidant used for the said composition for water absorption layer formation including the compound used and a preferable aspect.
Moreover, it is preferable that it is 0.5-3 mass% about the quantity of the antioxidant mix | blended with the composition for base layer formation with respect to the total mass of a 2nd polyepoxide component and a 2nd hardening | curing agent. 1 to 2% by mass is more preferable.

  In addition, for the underlayer forming composition, if necessary, the same leveling agent, antifoaming agent, viscosity adjusting agent, light stabilizer, etc. as those contained in the water absorbing layer forming composition are contained. Can be added. Moreover, although metal oxide fine particles may be added, the blending amount is preferably 0.5 to 5% by mass with respect to the total mass of the second polyepoxide component and the second curing agent, and 1 to 3 The mass% is more preferable.

  The underlayer in the antifogging article of the present invention is a second layer having a three-dimensional network structure obtained by reacting the second polyepoxide component and the second curing agent contained in the underlayer forming composition. Consisting of a cured epoxy resin, due to the properties of the second cured epoxy resin described above, it has a lower water absorption than the water absorption layer and sufficiently secures adhesion to the substrate and adhesion to the water absorption layer. It is a resin layer with excellent properties. The reaction conditions will be described in the production method described later.

<Method for producing antifogging article>
The antifogging article of the present invention has a configuration in which a water absorbing layer is disposed on a substrate. Furthermore, when it has a base layer as needed, it has the structure by which the base layer and the water absorption layer were laminated | stacked in order from the base | substrate side. Such an antifogging article can be specifically manufactured by the following method (A) or (B), taking as an example the case of having a foundation layer. When the base layer is not provided, the method is limited to the method (A). By eliminating the step of forming the base layer by the method (A), an antifogging article having a water absorption layer directly formed on the substrate surface is obtained.

(A) A method for forming a water-absorbing layer by applying and reacting a composition for forming a base layer on the surface of the substrate to form a base layer, and then applying and reacting the composition for forming a water-absorbing layer on the surface of the base layer (B) ) When the water-absorbing layer-forming composition is reacted to form a water-absorbent resin, it is formed into a film, that is, in the form of a water-absorbing layer, and the substrate surface and the film (water-absorbing layer) are combined with the underlayer-forming composition. A method for obtaining an antifogging article in which a base layer and a water absorbing layer are laminated from the substrate surface side by using as an adhesive and bonding them by forming a base layer as an adhesive layer between them

  In the method (B), a film-like water-absorbing resin (water-absorbing layer) is formed on a releasable support, and this is separated from the support and the underlayer-forming composition is formed on the substrate surface. Although it is possible to use and bond together as an adhesive, a method in which a film-like water-absorbing resin (water-absorbing layer) is attached to the substrate surface together with this support using the underlayer-forming composition as an adhesive is preferred. The support to be used is not particularly limited as long as it does not impair the effects of the present invention, but an acrylic resin film such as polymethyl methacrylate is preferably used.

In the present invention, among these methods for forming an antifogging film, the method (A) is capable of maintaining a good appearance when a base layer or a water absorption layer is provided on the surface of a large-area substrate or during industrial mass production. More preferred.
Hereinafter, a method for producing the antifogging article of the present invention by the method (A) will be described.

  In the method for producing an antifogging article according to the present invention, when the antifogging article has an underlayer, (a) a composition for forming an underlayer containing a second polyepoxide component and a second curing agent. A step of forming a base layer mainly composed of the second cured epoxy resin by applying to the surface of the substrate and reacting; and (b) a water-absorbing layer forming composition prepared by the following method on the surface of the base layer. And a step of forming a water absorbing layer by applying and reacting. When the antifogging article does not have a base layer, the same operation may be performed with the “surface of the base layer” in the step (b) as the “substrate surface”.

  In the present invention, the step (b) is specifically performed with respect to the content of the metal oxide fine particles in the liquid composition containing the raw material component of the crosslinked resin, that is, the total amount of the water-absorbing layer to be obtained. Step (1) for adding a part of the metal oxide fine particles in a content of 20 to 60% by mass, Step (2) for proceeding the crosslinking reaction of the liquid composition obtained by Step (1), Step ( Step (3) of adding the remainder of the content of the metal oxide fine particles to the liquid composition obtained in 2), and the liquid composition obtained in Step (3) on the surface of the underlayer or the surface of the substrate It can be performed by a method including the step (4) of forming a water-absorbing layer by applying to the resin and further causing a crosslinking reaction.

  Each step of the above method is classified into a step for preparing a water-absorbing layer-forming composition and a step for forming a water-absorbing layer from the obtained composition. In other words, in the present invention, as a method for preparing the water absorbing layer forming composition, a method including the above step (1), step (2), and step (3) can be used. Moreover, as a method of forming a water absorption layer from the composition for water absorption layer formation, the method containing the said process (4) can be used.

In the production method of the present invention, the content of the metal oxide fine particles in the water absorbing layer can have both excellent antifogging properties and abrasion resistance, scratch resistance, and other scratch resistance in the resulting water absorbing layer. Therefore, the content of the metal oxide fine particles is 20 to 60% by mass with respect to the total amount of the water absorption layer, and the content is more preferably 30 to 50% by mass.
In the production method of the present invention, the addition amount of the metal oxide fine particles in the step (1) is a metal content relative to the content of the metal oxide fine particles in the water absorption layer, that is, the total amount of the water absorption layer to be obtained. It is preferable that it is 5-50 mass% of content used as oxide fine particles 20-60 mass%, and it is more preferable that it is 5-40 mass%.

  In the above step (2), the degree of the cross-linking reaction of the liquid composition is such that the cross-linking reaction when the water-absorbing layer is finally formed is 100% cross-linking, and the cross-linking is about 50-70%. It is preferable to advance, and it is more preferable to advance crosslinking to about 50 to 60%.

  Next, in the step (3), the amount added in the step (1) is subtracted from the content of the metal oxide fine particles in the water absorption layer to the liquid composition in which the crosslinking reaction has progressed to the above degree in the step (2). Add the remainder. The amount of the metal oxide fine particles to be added in the step (3) is converted from the amount to be added in the step (1), the content of the metal oxide fine particles in the water absorption layer, that is, the total amount of the water absorption layer to be obtained. It is preferable that it is 50-95 mass% of content with which metal oxide microparticles | fine-particles will be 20-60 mass%, and it is more preferable that it is 60-95 mass%.

  As described above, the metal oxide fine particles are divided into two stages and blended into the water-absorbing layer forming composition, whereby the resulting water-absorbing layer is crosslinked with the first cured epoxy resin or urethane resin having a three-dimensional network structure. The resin and the cross-linked resin have a structure in which the predetermined amount of the metal oxide fine particles are uniformly dispersed and included in the three-dimensional network structure of the cross-linked resin, thereby providing excellent antifogging properties. And scratch resistance such as scratch resistance, and a water-absorbing layer with a low initial haze value.

The components contained in the underlayer-forming composition and the water-absorbing-layer-forming composition are as described above, and the underlayer-forming composition is prepared by mixing these components in a normal manner. .
In the step (a), in order to form an underlayer on the substrate, the method for applying the underlayer-forming composition obtained above to the application surface of the substrate is not particularly limited. Known methods such as a dip coating method, a spin coating method, a spray coating method, a flexographic printing method, a screen printing method, a gravure printing method, a roll coating method, a meniscus coating method, a die coating method, and a wiping method may be mentioned. The coating thickness of the composition for forming the underlayer is set such that the thickness of the underlayer finally obtained by reaction of the reaction components in the composition falls within the above range.

After the base layer forming composition is applied on the substrate, the solvent is removed by drying as necessary, and a curing treatment is performed under conditions suitable for the reaction components used, and the base layer mainly composed of the second cured epoxy resin. And Specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. The reaction component in the underlayer forming composition, that is, the reaction condition of the second polyepoxide component and the second curing agent, specifically, heat treatment at 70 to 150 ° C. for about 1 to 60 minutes is mentioned. It is done. Moreover, when UV curable photocurable resin is used, the process of performing 100 to 500 mJ / cm < ² > UV irradiation for 1 to 5 seconds with a UV curing apparatus etc. is mentioned.

  Here, in the manufacturing method of this invention, it is preferable to perform reaction of the said composition for base layer formation on fixed humidification conditions. By performing the above reaction under humidified conditions, the reaction time can be shortened in the reaction performed under the same temperature conditions as compared with the case where no humidification is performed. Moreover, if the reaction time is the same, the reaction can be sufficiently performed even if the reaction temperature is set low by humidification. In any case, it is economically advantageous to perform the above reaction under humidified conditions. Furthermore, by performing the above reaction under humidified conditions, the reaction can be performed uniformly throughout the entire layer, and quality variations in the underlayer can be suppressed.

  Specific examples of the humidification condition include 40 to 80% RH, but a condition of 50 to 80% RH is more preferable. If more preferable reaction conditions are shown together with temperature conditions, reaction conditions of about 50 to 80% RH, 70 to 100 ° C., and about 5 to 30 minutes may be mentioned. More preferable conditions include reaction conditions of 50 to 80% RH, 80 to 100 ° C., and about 10 to 30 minutes.

  In step (4) of step (b) including steps (1) to (4), a water-absorbing layer-forming composition is applied to the surface of the base layer formed on the substrate in step (a). The method can be the same as the coating method of the underlayer forming composition. The coating thickness of the water-absorbing layer forming composition is set such that the thickness of the water-absorbing layer finally obtained by reaction of the reaction components in the composition falls within the above range.

After applying the water-absorbing layer-forming composition on the underlayer, subsequently, in step (4), if necessary, the solvent is removed by drying, and a curing treatment is performed under conditions suitable for the reaction components to be used. A water-absorbing layer containing oxide fine particles in the above proportion is used.
When the first cured epoxy resin is used as the cross-linked resin, specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. Moreover, as a reaction component in the composition for forming a water absorption layer, that is, a reaction condition of the first polyepoxide component and the first curing agent, specifically, heat treatment at 50 to 120 ° C. for about 10 to 60 minutes can be mentioned. It is done. Moreover, when UV curable photocurable resin is used, the process of performing UV irradiation of 50-1000 mJ / cm < ² > for 5 to 10 seconds with a UV curing apparatus etc. is mentioned.

  When a urethane resin is used as the cross-linked resin, specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. Moreover, as a reaction component in the composition for water absorption layer formation, ie, the reaction conditions of the said polyol and polyisocyanate, the heat processing for 50 to 200 degreeC and about 1 to 60 minutes are specifically mentioned.

  Here, in the production method of the present invention, when the first cured epoxy resin is used as the cross-linked resin contained in the water absorbing layer forming composition, the reaction is performed in the case of the base layer forming composition. Similarly to the above, it is preferable to perform the treatment under a constant humidification condition in that the scratch resistance such as scratch resistance can be drastically improved. Specific examples of the humidification condition include 40 to 80% RH, but a condition of 50 to 80% RH is more preferable. If more preferable reaction conditions are shown together with temperature conditions, reaction conditions of about 50 to 80% RH, 70 to 100 ° C., and about 5 to 30 minutes may be mentioned. More preferable conditions include reaction conditions of 50 to 80% RH, 80 to 100 ° C., and about 10 to 30 minutes.

  Thus, the antifogging article of the present invention in which the antifogging film is formed on the substrate is obtained through the steps (a) and (b). In the production method of the present invention, when the first cured epoxy resin is used as the crosslinked resin contained in the water absorbing layer forming composition, after the step (b), (c) the obtained underlayer It is preferable to further include a step of immersing the substrate with the water absorbing layer in warm water. As conditions for the immersion, it is preferable to immerse in a sufficient amount of warm water of 40 to 90 ° C. for 1 to 20 minutes with respect to the substrate with the base layer and the water absorption layer, and in warm water of 50 to 70 ° C., 3 to It is more preferable to immerse for about 5 minutes.

  By this hot water immersion treatment, it becomes possible to remove excess reactive components remaining in the underlayer and the water absorption layer, and problems such as anti-fogging reduction caused by these remaining, and whitening due to bleeding out Problems such as surface unevenness can be solved.

  The base layer and the water absorbing layer are preferably formed on the interior substrate surface when applied to a building window glass, and formed on the interior substrate surface when applied to a vehicle window glass. preferable.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 7 are examples, and examples 8 and 9 are comparative examples.

The physical properties of the polyepoxide used in the production examples are summarized below. Denacol is a trade name of Nagase ChemteX Corporation.
(1) Low molecular weight polyepoxide Glycerin polyglycidyl ether: Denacol EX-313 (Mw: 383, average number of epoxy groups: 2.0 / molecule),

(2) High molecular weight polyepoxide Aliphatic polyglycidyl ether: Denacol EX-1610 (Mw: 1130, average number of epoxy groups: 4.5 / molecule),
(3) Polyepoxide bisphenol A diglycidyl ether used as the second polyepoxide component: jER828 (trade name, manufactured by Mitsubishi Chemical Corporation, Mw: 340, average number of epoxy groups: about 2 / molecule),

Evaluation of the anti-fogging article in each example was performed as follows.
[Measurement of film thickness]
A cross-sectional image of the antifogging article was taken with a scanning electron microscope (manufactured by Hitachi, Ltd., S4300), and the film thickness of the water absorption layer was measured.
[Measurement of haze value]
In accordance with the standard of JIS K-7361, the haze value [%] of the anti-fogging article (indicated by “Haze” in Table 1 described later) is measured using a haze meter (Haze Guard Plus, manufactured by Gardner). did.

[Measurement of water contact angle]
After the anti-fogging article was left in an environment of 20 ° C. and 50% relative humidity for 1 hour, the water contact angle [°] immediately after dropping 2 μL of water droplets was measured with CA-X150 (manufactured by Kyowa Interface Science Co., Ltd.). did.
[Measurement of surface roughness (Ra)]
With respect to the surface of the antifogging article, the surface roughness (Ra) at a measurement area of 4 μm was measured in the DFM mode using a scanning probe microscope (SPM, SPA-400, SII Nanotechnology Inc.). In the present embodiment, a surface roughness (Ra) of 8.0 or less is preferable for practical use.

[Evaluation of anti-fogging property]
(Anti-fogging time)
The surface of the water-absorbing layer of the anti-fogging article left for 1 hour in an environment of 20 ° C. and 50% relative humidity was placed on a 40 ° C. hot water bath, and the anti-fogging time (seconds) until cloudiness was observed was measured. A normal soda lime glass not subjected to anti-fogging processing was fogged in 1 to 2 seconds. The required anti-fogging performance varies depending on the application. In this embodiment, antifogging properties of 90 seconds or more are necessary for practical use, and 100 seconds or more are preferable.

(Saturated water absorption)
A 3cm x 4cm x 2mm thick soda lime glass is provided with a water-absorbing layer, immersed in distilled water at 25 ° C for 10 minutes, and excess water is wiped off with a kim towel to the extent that it cannot be discerned visually. The moisture content (I) of the whole substrate with a water absorbing layer was measured. Furthermore, the moisture content (II) was measured for the glass alone by the same procedure. A value obtained by dividing the value obtained by subtracting the amount of moisture (II) from the amount of moisture (I) by the volume of the water-absorbing layer was defined as the saturated water absorption amount of the material constituting the water-absorbing layer.

The moisture content was measured with a trace moisture meter FM-300 (manufactured by Kett Science Laboratory) as follows. The measurement sample was heated at 120 ° C. for the same time as the blank measurement, the amount of water released from the sample was measured, and the maximum value during that time was adopted as the amount of water.
The water content (II) of soda lime glass not subjected to normal antifogging processing was 0.11 mg.

[Evaluation of scratch resistance]
Martens hardness was measured under the measurement conditions: loading speed / unloading speed F = 0.05 mN / 5 s and creep C = 5 s using a picodenter (Fischer).

<1> Preparation of Composition for Forming Underlayer / Composition for Forming Adhesion Layer [Production Example A-1]
In a glass container in which a stirrer and a thermometer are set, propylene glycol monomethyl ether (7.21 g, manufactured by Daishin Chemical Co., Ltd.), bisphenol A diglycidyl ether (5.00 g, jER828, manufactured by Mitsubishi Chemical Corporation), polyoxyalkylene Triamine (1.03 g, Jeffamine T403 (trade name), manufactured by Huntsman) and aminosilane (1.18 g, KBM903 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred at 25 ° C. for 30 minutes. Next, it is diluted 5 times with propylene glycol monomethyl ether (manufactured by Daishin Chemical Co., Ltd.), a leveling agent (0.04 g, BYK307 (trade name), manufactured by BYK Chemie) is added, and an underlayer forming composition ( A-1) was obtained.

[Production Example A-2]
In a glass container in which a stirrer and a thermometer are set, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 99.00 g, neoethanol PIP (trade name), Dainobu Chemical), 3-aminopropyltriethoxysilane (1.00 g, KBE903 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.), stirred at 25 ° C. for 30 minutes to form an adhesive layer forming composition (A-2). Obtained.

<2> Preparation of water-absorbing layer-forming composition [Production Example B-1]
In a glass container in which a stirrer and a thermometer are set, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 6.00 g, neoethanol PIP (trade name), Dainobu Chemical), aliphatic polyglycidyl ether (3.44 g, Denacol EX-1610, manufactured by Nagase ChemteX), glycerin polyglycidyl ether (2.86 g, Denacol EX-313, manufactured by Nagase ChemteX), organosilica sol ( 5.39 g, MEK-ST (trade name), average primary particle size: 10-20 nm, manufactured by Nissan Chemical Industries, SiO ₂ content 30% by mass, 2-methylimidazole (0.15 g, manufactured by Shikoku Chemicals) , Aminosilane (1.29 g, KBM903 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyalkylene Triamine (1.25 g, Jeffamine T403, manufactured by Huntsman) was added with stirring and stirred at 25 ° C. for 1 hour. Next, organosilica sol (10.81 g, MEK-ST (trade name)), mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 8.81 g, neoethanol PIP (product) Name), manufactured by Daishin Chemical Co., Ltd.) and a leveling agent (0.02 g, BYK307 (trade name), manufactured by Big Chemie) were added with stirring to obtain a water-absorbing layer-forming composition (B-1).

  In addition, in the said manufacture example B-1, in the process (1) in the manufacturing method of this invention, the quantity of 33 mass% (1/3) of the total amount of the silica contained in a water absorption layer is added, In process (3) The amount of 67% by mass (2/3) of the total amount of silica contained in the water absorption layer was added. In Table 1, the case where it added by said each addition amount in process (1) and process (3) is shown as "A1B2" in the column of the addition method.

[Production Example B-2]
In a glass container in which a stirrer and a thermometer are set, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 3.25 g, neoethanol PIP (trade name), Dainobu Chemical), aliphatic polyglycidyl ether (2.68 g, Denacol EX-1610, manufactured by Nagase ChemteX), glycerin polyglycidyl ether (2.23 g, Denacol EX-313, manufactured by Nagase ChemteX), organosilica sol ( 7.59 g, MEK-ST), 2-methylimidazole (0.11 g, manufactured by Shikoku Chemicals), aminosilane (1.00 g, KBM903 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyalkylenetriamine (0. 97 g, Jeffermin T403 (trade name, manufactured by Huntsman) It was added, and stirred for 1 hour at 25 ° C.. Next, organosilica sol (15.26 g, MEK-ST (trade name)), mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 6.91 g, neoethanol PIP (product) Name), manufactured by Daishin Chemical Co., Ltd.) and a leveling agent (0.02 g, BYK307 (trade name), manufactured by Big Chemie) were added with stirring to obtain a water-absorbing layer-forming composition (B-2).

  Also in the said manufacture example B-2, the amount of 33 mass% (1/3) of the silica total amount contained in a water absorption layer at a process (1) is added similarly to the said manufacture example B-1, and a process (3) The amount of 67% by mass (2/3) of the total amount of silica contained in the water absorption layer was added. The addition method is “A1B2”.

[Production Example B-3]
As an organosilica sol, MEK-ST-L (trade name) (average primary particle size: 40-50 nm, manufactured by Nissan Chemical Industries, Ltd., SiO, instead of MEK-ST (trade name, average primary particle size: 10-20 nm) ₂ content 30 mass%) Except having used, it prepared similarly to manufacture example B-2, and obtained the composition (B-3) for water absorption layer formation.

[Production Example B-4]
In a glass container in which a stirrer and a thermometer are set, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 5.48 g, neoethanol PIP (trade name), Dainobu Chemical), aliphatic polyglycidyl ether (2.66 g, Denacol EX-1610, manufactured by Nagase ChemteX), glycerin polyglycidyl ether (2.21 g, Denacol EX-313, manufactured by Nagase ChemteX), organosilica sol ( 1.93 g, MEK-ST (trade name), manufactured by Nissan Chemical Industries, SiO ₂ content 30% by mass, 2-methylimidazole (0.11 g, manufactured by Shikoku Chemicals), aminosilane (0.99 g, KBM903 ( Product name), manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyalkylene triamine (0.97 g, Jeffer) -Min T403 (trade name, manufactured by Huntsman) was added with stirring and stirred at 25 ° C. for 1 hour. Then, organosilica sol (5.78 g, MEK-ST (trade name)), mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 6.61 g, PIP, neoethanol PIP (Trade name, manufactured by Daishin Kagaku) and leveling agent (0.02 g, BYK307 (trade name), manufactured by Big Chemie) were added with stirring to obtain a water-absorbing layer-forming composition (B-4).

  In addition, in the said manufacture example B-4, in process (1) in the manufacturing method of this invention, the quantity of 25 mass% (1/4) of the total amount of the silica contained in a water absorption layer is added, In process (3) The amount of 75% by mass (3/4) of the total amount of silica contained in the water absorption layer was added. In Table 1, the case where it added by said each addition amount in process (1) and process (3) is shown as "A1B3" in the column of the addition method.

[Production Example B-5]
An acrylic polyol solution (40.00 g, hydroxyl value: 4 mg KOH / g, 50% solution, Desmophen A450MPA / X (trade name), manufactured by Bayer AG), polyethylene in a glass container in which a stirrer and a thermometer are set. Glycol (60.00 g, average hydroxyl value: 113 mg KOH / g, average molecular weight 1000, manufactured by Lion) hexamethylene diisocyanate type polyisocyanate (36.00 g, NCO%: 23%, Desmodur N3200 (trade name), Bayer AG Co., Ltd.), organosilica sol (52.27 g, MEK-ST-L (trade name), manufactured by Nissan Chemical Industries, Ltd., SiO ₂ content 30% by mass) were added with stirring, and the mixture was stirred at 25 ° C. for 1 hour. . Next, organosilica sol (156.82 g, MEK-ST-L (trade name)), isobutyl acetate (165.53 g, manufactured by Junsei Co., Ltd.), leveling agent (0.05 g, BYK307 (trade name), manufactured by BYK Chemie) Was added with stirring to obtain a water-absorbing layer-forming composition (B-5).

  Also in the said manufacture example B-5, the amount of 25 mass% (1/4) of the silica total amount contained in a water absorption layer at a process (1) is added similarly to the said manufacture example B-4, and a process (3) The amount of 75% by mass (3/4) of the total amount of silica contained in the water absorption layer was added. The addition method is “A1B3”.

[Production Example B-6]
In a glass container in which a stirrer and a thermometer are set, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 18.51 g, neoethanol PIP (trade name), Dainobu Chemical), aliphatic polyglycidyl ether (7.85 g, Denacol EX-1610, manufactured by Nagase ChemteX), glycerin polyglycidyl ether (6.52 g, Denacol EX-313, manufactured by Nagase ChemteX), organosilica sol ( 0.94 g, NBAC-ST (trade name), average primary particle size: 10-20 nm, manufactured by Nissan Chemical Industries, SiO ₂ content 30% by mass, 2-methylimidazole (0.34 g, manufactured by Shikoku Chemicals) , Polyoxyalkylenetriamine (2.85 g, Jeffamine T403 (trade name), Huntsma And Silane (2.93 g, KBM903 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) were added with stirring, and the mixture was stirred at 25 ° C. for 1 hour. Subsequently, methyl ethyl ketone (20.06 g, manufactured by Daishin Chemical Co., Ltd.) and a leveling agent (0.03 g, BYK307 (trade name), manufactured by Big Chemie) were added with stirring to form a water absorbing layer forming composition (B-6). Got. In addition, in the said manufacture example B-6, the whole quantity of the silica contained in a water absorption layer in the step corresponded to the process (1) in the manufacturing method of this invention was added. In Table 1, this addition method is indicated as “A”.

[Production Example B-7]
In a glass container in which a stirrer and a thermometer are set, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 1.47 g, neoethanol PIP (trade name), Dainobu Chemical), aliphatic polyglycidyl ether (3.44 g, Denacol EX-1610, manufactured by Nagase ChemteX), glycerin polyglycidyl ether (2.86 g, Denacol EX-313, manufactured by Nagase ChemteX), organosilica sol ( 16.20 g, MEK-ST (trade name), manufactured by Nissan Chemical Industries, SiO ₂ content 30 mass%, 2-methylimidazole (0.15 g, manufactured by Shikoku Kasei Co., Ltd.), aminosilane (1.29 g, KBM903 ( Product name), manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyalkylene triamine (1.25 g, Jeff) Armin T403 (trade name, manufactured by Huntsman) was added with stirring, and the mixture was stirred at 25 ° C. for 1 hour. Subsequently, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 13.35 g, PIP, neoethanol PIP (trade name), manufactured by Daishin Chemical), leveling agent (0. 02 g, BYK307 (trade name), manufactured by Big Chemie) was added with stirring to obtain a water-absorbing layer-forming composition (B-7). In Production Example B-7, the total amount of silica contained in the water absorption layer was added in the same manner as in Production Example B-6. The addition method is “A”.

<3> Manufacture and Evaluation of Antifogging Articles Using the various compositions obtained in the above production examples, antifogging films were formed on various substrates as follows, and evaluation was performed by the above evaluation method. Table 1 shows the materials and production conditions used for production, and the evaluation results obtained.

[Examples 1-3]
As a substrate, a clean soda lime glass substrate (water contact angle 3 °, 200 mm × 200 mm × thickness 2 mm), which was polished and cleaned with cerium oxide, was used, and the surface of the glass substrate was obtained in Production Example A. The underlayer-forming composition (A-1) was applied by flow coating, held in an electric furnace at 90 ° C. for 10 minutes, and then held in a constant temperature and humidity chamber at 90 ° C. and 70% RH for 20 minutes. Formed. Next, as shown in Table 1 for each example, the water-absorbing layer-forming composition B-1 to B-3 obtained in Production Example B was applied to the formed base layer surface by flow coating, and 90 It was kept for 10 minutes in an electric furnace at 90 ° C., and then kept in a constant temperature and humidity chamber at 90 ° C. and 70% RH for 20 minutes to form a water absorption layer to obtain an antifogging article having a two-layer antifogging film.

[Example 4, Examples 6-9]
As a substrate, a clean soda lime glass substrate (water contact angle 3 °, 200 mm × 200 mm × thickness 2 mm), which was polished and cleaned with cerium oxide, was used, and the surface of the glass substrate was shown for each example. As shown in 1, either the underlayer-forming composition A-1 or the adhesion-layer-forming composition A-2 obtained in Production Example A was applied by flow coating and held in an electric furnace at 100 ° C. for 30 minutes. Then, an underlayer or an adhesion layer was formed. Next, on the surface of the formed underlayer or adhesion layer, as shown in Table 1 for each example, any one of the water-absorbing layer forming compositions B-1 and B-4 to B-6 obtained in Production Example B is used. The film was applied by flow coating and held in an electric furnace at 100 ° C. for 30 minutes to form a water absorption layer, and an antifogging article having an antifogging film composed of two layers was obtained.

[Example 5]
As a substrate, a clean soda lime glass substrate (water contact angle 3 °, 200 mm × 200 mm × thickness 2 mm), which was polished and cleaned with cerium oxide, was obtained on the surface of the glass substrate in Production Example B. The water-absorbing layer-forming composition (B-1) was applied by flow coating and held in an electric furnace at 100 ° C. for 30 minutes to form a water-absorbing layer and to have an anti-fogging film consisting of one layer. Got.

In Table 1, the symbols shown in the column of the method for adding metal oxide fine particles indicate the addition time and amount of the metal oxide fine particles when preparing the water absorbing layer forming composition. “A1B2” indicates that 33% of the total amount of fine particles is added in the step (1) and the remaining 67% is added in the step (3). “A1B3” represents that 25% of the total amount of fine particles is added in the step (1) and the remaining 75% is added in the step (3). “A” indicates that the total amount of fine particles is added in the step (1).
Further, the content of metal fine particles indicates the content of metal fine particles in the obtained absorption layer in mass%.

  From the evaluation results shown in Table 1, the antifogging articles obtained in Examples 1 to 7 which are Examples have excellent antifogging properties and scratch resistance, and the haze value is sufficiently low. It can be seen that the antifogging articles obtained in Comparative Examples 8 and 9 are not sufficiently antifogging, scratch resistant or low in haze value.

  The antifogging article of the present invention is useful as an antifogging glass for automobiles and buildings because it has excellent antifogging properties and scratch resistance such as scratch resistance.

Claims (13)

An antifogging article having a base and a water absorbing layer containing a crosslinked resin disposed on the surface of the base,
The water absorption layer contains metal oxide fine particles in a proportion of 20 to 60% by mass,
An antifogging article having a haze value of 1% or less. ^2. The prevention according to claim 1, wherein the Martens hardness measured at measurement conditions: loading speed / unloading speed F = 0.05 mN / 5 s and creep C = 5 s on the surface of the water absorption layer is 20 N / mm ² or more. Cloudy article.   When the specimen is left in an environment of 20 ° C. and a relative humidity of 50% for 1 hour, and then the specimen surface is placed on a 40 ° C. hot water bath, it is carried out on the surface of the water-absorbing layer. The antifogging article according to claim 1 or 2, wherein an antifogging time is 90 seconds or more in an antifogging test in which a time until a distortion of a fluoroscopic image is recognized is measured as an antifogging time. The antifogging article according to any one of claims 1 to 3, wherein a saturated water absorption amount of a material constituting the water absorption layer is 50 mg / cm ³ or more.   The antifogging article according to any one of claims 1 to 4, wherein the water absorption layer has a thickness of 7 µm to 30 µm.   The antifogging article according to any one of claims 1 to 5, wherein an average primary particle diameter of the metal oxide fine particles is 10 to 50 nm.   The antifogging article according to any one of claims 1 to 6, wherein the metal oxide fine particles are silica fine particles.   The cross-linked resin is a cured epoxy resin obtained by a reaction between a polyepoxide and a curing agent, or a urethane resin obtained by a reaction between a polyisocyanate and a polyol. Anti-fogging article. A method for producing an antifogging article comprising a substrate and a water-absorbing layer containing a crosslinked resin and metal oxide fine particles provided on the surface of the substrate,
Adding a part of the content of the metal oxide fine particles to the liquid composition containing the raw material component of the crosslinked resin (1),
A step (2) of proceeding a crosslinking reaction of the liquid composition obtained by the step (1);
Adding the remainder of the content of the metal oxide fine particles to the liquid composition obtained by the step (2) (3); and
A step (4) of applying the liquid composition obtained in the step (3) to the surface of the substrate and further causing a crosslinking reaction to form a water absorbing layer;
The method for producing an antifogging article, wherein the water absorption layer contains the metal oxide fine particles in a proportion of 20 to 60% by mass.   The method for producing an antifogging article according to claim 9, wherein the addition amount of the metal oxide fine particles in the step (1) is 5 to 50% by mass of the content of the metal oxide fine particles in the water absorption layer. .   The method for producing an antifogging article according to claim 9 or 10, wherein the metal oxide fine particles have an average primary particle diameter of 10 to 50 nm.   The method for producing an antifogging article according to any one of claims 9 to 11, wherein the metal oxide fine particles are silica fine particles.   The method for producing an antifogging article according to any one of claims 9 to 12, wherein the raw material component of the crosslinked resin is a combination of a polyepoxide and a curing agent, or a combination of a polyisocyanate and a polyol. .