JP2013244691A - Anti-fogging article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-fogging article which is excellent in anti-fogging properties, abrasion resistance, durability such as scratch resistance, and appearance.SOLUTION: An anti-fogging article has a base and an anti-fogging film on a surface of at least a part of the base. The anti-fogging film has an underlying resin layer and a water absorbing resin layer which are laminated in turn on a surface of the base. The water absorbing resin layer mainly contains a first cured epoxy resin obtained by reacting a first polyepoxide component in which a low molecular weight polyepoxide having a molecular weight of 200-500 and a high molecular weight polyepoxide having a molecular weigh of 900-1,300 are combined in a mass ratio of 30:70-70:30 with a water absorbing resin layer forming composition containing a first curing agent and fine silica particles of 10-30 mass% to the total mass of the first polyepoxide component and the first curing agent. The underlying resin layer mainly contains a second cured epoxy resin obtained by reacting an underlying resin layer forming composition containing a second polyepoxide component and a second curing agent. The water absorbing properties of the anti-fogging article are lower than those of the water absorbing resin layer.

Description

  The present invention relates to an antifogging article.

  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.

For example, a method is known in which a water-absorbing resin layer is provided on the surface of the substrate and minute water droplets formed on the surface of the substrate are absorbed and removed, and / or the atmospheric humidity on the surface of the substrate is reduced.
Since this method has no water on the surface, the appearance is not changed and the feeling of use is often well received. In addition, it can exhibit excellent antifogging properties without requiring running costs. It is considered to be a particularly excellent method as a means for preventing this.

  Specifically, as an anti-fogging technique using such a water-absorbing compound layer, an anti-fogging article including a water-absorbing crosslinked resin layer obtained from polyepoxides (see Patent Document 1), and a substrate surface with low moisture absorption An anti-fogging article having an anti-fogging film in which a water-soluble crosslinked resin layer and a highly hygroscopic crosslinked resin layer are sequentially laminated (see Patent Document 2) has been proposed.

  However, although the water-absorbing crosslinked resin layer in the antifogging article described in Patent Document 1 has excellent antifogging properties, there are problems in durability such as wear resistance, peel resistance, and scratch resistance. Although the anti-fogging film described in Patent Document 2 has excellent anti-fogging property and durability is improved to some extent, it is a problem in that the appearance is impaired when the durability is increased. Accordingly, an antifogging article having an antifogging film that has excellent antifogging properties, durability such as wear resistance, peel resistance, and scratch resistance and a good appearance has been desired.

International Publication No. 2007/052710 Pamphlet JP 2008-273067 A

  An object of the present invention is to provide an antifogging article having excellent antifogging properties, durability such as wear resistance and scratch resistance, and excellent appearance.

The present invention has been made to solve the above-described problems, and has the following configuration.
The antifogging article of the present invention is an antifogging article having a base and an antifogging film on at least a part of the surface of the base, and the antifogging film is a base layer sequentially laminated on the surface of the base. A low molecular weight polyepoxide having a molecular weight of 200 to 500 and a high molecular weight polyepoxide having a molecular weight of 900 to 1300, and the low molecular weight polyepoxide: the high molecular weight polyepoxide. Is 10 to the total mass of the first polyepoxide component having a mass ratio of 30:70 to 70:30, the first curing agent, the first polyepoxide component, and the first curing agent. A water-absorbing resin layer mainly composed of a first cured epoxy resin obtained by reacting a composition for forming a water-absorbing resin layer containing ~ 30% by mass of silica fine particles, A base resin mainly composed of a second cured epoxy resin obtained by reacting a composition for forming a base resin layer containing a polyepoxide component of 2 and a second curing agent, and having a water absorption lower than that of the water absorbent resin layer It is a layer.

  The antifogging article of the present invention is excellent in antifogging property, and is excellent in durability such as wear resistance and scratch resistance, and in appearance.

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 an antifogging film on at least a part of the surface of the base, and the antifogging film is a base layer sequentially laminated on the surface of the base. A low molecular weight polyepoxide having a molecular weight of 200 to 500 and a high molecular weight polyepoxide having a molecular weight of 900 to 1300, and the low molecular weight polyepoxide: the high molecular weight polyepoxide. Is 10 to the total mass of the first polyepoxide component having a mass ratio of 30:70 to 70:30, the first curing agent, the first polyepoxide component, and the first curing agent. A water-absorbing resin layer mainly composed of a first cured epoxy resin obtained by reacting a composition for forming a water-absorbing resin layer containing ~ 30% by mass of silica fine particles, A base resin mainly comprising a second cured epoxy resin obtained by reacting a composition for forming a base resin layer containing a polyepoxide component of 2 and a second curing agent, and having a water absorption lower than that of the water absorbent resin layer. It is a layer.

  In the antifogging article of the present invention, for the polyepoxide which is a raw material component of the cured epoxy resin mainly constituting the water-absorbing resin layer, the high molecular weight polyepoxide contributes to improvement of durability such as wear resistance, and the low Under the hypothesis that the molecular weight polyepoxide has an effect of improving the appearance of the cured epoxy resin obtained from the high molecular weight polyepoxide, the mass ratio represented by the low molecular weight polyepoxide: the high molecular weight polyepoxide is 30:70 to 70:30. Thus, it has been found that an antifogging article having excellent antifogging property, durability such as wear resistance, and excellent appearance can be obtained.

  In addition, the antifogging article of the present invention is a combination of a water-absorbing resin layer mainly composed of a cured epoxy resin and a base resin layer, the water absorption of the water-absorbing resin layer> the base resin layer. By configuring the anti-fogging film, it is possible to obtain an anti-fogging article having excellent peeling resistance as described in Patent Document 2.

That is, the water-absorbent resin layer having high water absorption accumulates interfacial stress at the adhesive interface by repeating large expansion and contraction associated with high water absorption, and various ionic components taken together with water reach the adhesive interface. Furthermore, the adhesion at the adhesion interface tends to decrease due to factors such as the elution of ionic components from the adherend layer such as the substrate to the interface due to the influence of moisture reaching the adhesion interface.
Therefore, when a base resin layer mainly having the same kind of cured epoxy resin as the water absorbent resin layer is provided between the substrate and the water absorbent resin layer, the water absorbent resin layer is provided. It is made of the same kind of resin between the base resin layer and the base resin layer, so that the base resin layer has a high degree of adhesion, and since the base resin layer has a low water absorption, the degree of expansion / contraction is small, and it accumulates at the adhesive interface with the substrate. Interfacial stress is alleviated, and it has the effect of suppressing moisture and ionic components from reaching the adhesion interface with the substrate, improving adhesion with the substrate interface and improving the overall peel resistance. It has high durability.
Furthermore, the water-absorbent resin layer-forming composition in the present invention contains fine particles of silica as a filler in a predetermined ratio, so that the formed water-absorbent resin layer has mechanical strength such as abrasion resistance and scratch resistance, heat resistance, and the like. It is possible to improve the properties and to reduce the shrinkage of the resin during the curing reaction.

[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.

  The substrate preferably has a reactive group on the surface. As the reactive group, a hydrophilic group is preferable, and as the hydrophilic group, a hydroxyl group is preferable. Glass and metal oxide usually have a hydroxyl group on the surface.

  In addition, the substrate is a metal oxide such as silica, alumina, titania, zirconia on the surface of the substrate such as glass for the purpose of improving adhesion to the base resin layer formed on the surface of the antifogging article of the present invention. A thin film or an organic group-containing metal oxide thin film may be provided.

  The metal oxide thin film can be formed by a known method such as a sol-gel method using a metal compound having a hydrolyzable group. As the metal compound, tetraalkoxysilane, tetraisocyanatesilane, oligomers thereof (that is, partially hydrolyzed condensates thereof) and the like are preferable.

  The organic group-containing metal oxide thin film can be obtained by treating the substrate surface with an organometallic coupling agent. As the organometallic coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, or the like can be used, and a silane coupling agent is preferably used. Hereinafter, a coupling agent for treating the substrate surface in advance is referred to as a “surface treatment coupling agent”.

[2] Anti-fogging film In the anti-fogging article of the present invention, the anti-fogging film formed on at least a part of the surface of the substrate is composed of a base resin layer and a water-absorbing resin layer in this order from the substrate side.

[2-1] Water-absorbing resin layer The water-absorbing resin layer constituting the antifogging film is composed of a low molecular weight polyepoxide having a molecular weight of 200 to 500 and a high molecular weight polyepoxide having a molecular weight of 900 to 1300, and the low molecular weight polyepoxide: the high molecular weight With respect to the total mass of the 1st polyepoxide component whose mass ratio shown by polyepoxide is 30: 70-70: 30, the 1st hardening agent, the 1st polyepoxide component, and the 1st hardening agent. It is a water absorbent resin layer mainly composed of a first cured epoxy resin obtained by reacting a composition for forming a water absorbent resin layer containing 10 to 30% by mass of silica fine particles.

  The water-absorbing resin layer in the anti-fogging article of the present invention also has a water-absorbing property to exhibit a sufficient anti-fogging property when used as an anti-fogging film. It is higher than the water absorption of the base resin layer provided between the two. The water absorption of the water absorbent resin and the base resin is relative, and hereinafter, the water absorbent resin mainly composed of the first cured epoxy resin constituting the water absorbent resin layer is referred to as a high water absorbent resin and a base resin. A resin mainly composed of a second cured epoxy resin described later in the layer is also referred to as a low water absorption resin. Since the water absorption of both resins is relative, “high water absorption” and “low water absorption” in these resins do not mean high or low with a threshold value.

Here, if the water absorption of the superabsorbent resin constituting the water absorbent resin layer is specifically shown, the saturated water absorption measured by the following method is preferably 200 mg / cm ³ or more, preferably 300 mg / cm 3. More preferably, it is ³ or more. When the saturated water absorption amount of the highly water-absorbent resin constituting the water-absorbent resin layer takes the above value, sufficient antifogging property can be ensured. On the other hand, from the viewpoint of preventing the durability of the antifogging film from being lowered, the saturated water absorption amount of the water absorbent resin layer is preferably 900 mg / cm ³ or less, and more preferably 500 mg / cm ³ or less.

(Measurement method of saturated water absorption)
A resin layer as a specimen is provided on a 3 cm × 4 cm × 2 mm thick soda lime glass substrate, immersed in a constant temperature water bath at 25 ° C. for 1 hour, taken out, wiped off moisture on the surface with a waste cloth, The moisture content (I) of the entire substrate with the resin layer is measured. Further, the moisture content (II) is measured for the substrate only by the same procedure. The value obtained by subtracting the water content (I) from the water content (I) by the volume of the resin layer is defined as the saturated water absorption. The moisture content is measured as follows using a trace moisture meter FM-300 (manufactured by Kett Science Laboratory Co., Ltd.). 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 end point of the measurement is the time when the mass change per 25 seconds becomes 0.05 mg or less.

Note that the saturated water absorption is an index indicating the water absorption of the resin constituting the water absorbent resin layer, but as an index indicating the water absorption of the water absorbent resin layer itself, in this specification, as necessary, The “water absorption antifogging” defined is used.
The anti-fogging property of water absorption is that the surface of the anti-fogging article of an anti-fogging article left for 1 hour in an environment of 20 ° C. and 50% relative humidity is placed on a warm water bath at 40 ° C. until the cloudiness is visually observed. Shown in cloudy time (seconds).
With respect to the water absorption of the water-absorbent resin layer provided in the anti-fogging article of the present invention, if the water-absorbing and anti-fogging property is shown as an index, the water-absorbing and anti-fogging property can be set to 30 seconds or more. For example, in a particularly preferable aspect, it can be set to 100 seconds or more.
Regarding the water absorption of the water-absorbent resin layer provided in the anti-fogging article of the present invention, the water-absorbing and anti-fogging property can be expressed by converting the water-absorbing and anti-fogging property per 20 μm. In this case, the water absorption antifogging property converted per 20 μm of the water absorbent resin layer can be 80 seconds or more, more preferably 100 seconds or more, and particularly preferably 130 seconds or more. be able to.

From the relationship between the saturated water absorption amount of the superabsorbent resin constituting the water absorbent resin layer and the water absorption and antifogging property of the water absorbent resin layer, the film thickness of the water absorbent resin layer according to the antifogging article of the present invention is 3 μm. Preferably, it is preferably 10 μm or more. Thereby, it becomes easy to ensure the saturated water absorption necessary for the entire antifogging film. On the other hand, from the viewpoint of preventing the durability of the antifogging film from being lowered, the film thickness of the water absorbent resin layer is preferably 50 μm or less, and more preferably 30 μm or less.
In addition, you may use for the performance evaluation the value which remove | divided water absorption anti-fogging property by the film thickness of the water absorbing resin layer.
Here, since the anti-fogging performance required of the anti-fogging article varies depending on the application, the design may be changed as appropriate in accordance with the required performance.

  The cured epoxy resin mainly constituting the water absorbent resin layer is a first cured epoxy resin obtained by reacting the first polyepoxide component and the first curing agent, and the water absorbent resin layer is the water absorbent resin. It is the main component for designing.

  In this specification, polyepoxide refers to a compound having two or more epoxy groups. 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. The curing agent is a compound having two or more reactive groups that react with the epoxy group of the polyepoxide, and is a polyaddition type curing agent that polyadds to the polyepoxide by reaction, and polycondenses with the polyepoxide by reaction. It is used as a term encompassing a type of condensation type curing agent and a reaction type catalyst such as a Lewis acid, which 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 is obtained by reacting the main agent and the curing agent, and a structure in which the polyepoxide is cross-linked by a polyaddition type curing agent or the like to form a three-dimensional structure, and / or the polyepoxides are linearly or three-dimensionally formed. A cured product having a polymerized structure. The water absorption of the cured epoxy resin mainly depends on the abundance of hydrophilic groups such as hydroxyl groups and hydrophilic chains (polyoxyethylene groups etc.) 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.

  Therefore, it is generally preferable to control the glass transition point of the cured epoxy resin low to increase the antifogging performance, and to control the glass transition point of the cured epoxy resin high to increase durability. Considering these, the glass transition point of the first water-absorbent resin layer that forms the water-absorbent resin layer is preferably -20 to 60 ° C., although it depends on the type of the cured epoxy resin. More preferably, it is −5 to 40 ° C.

  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 the 1st hardening | curing agent which mainly comprise a water absorbing resin layer react is demonstrated.
(First polyepoxide component)
The first polyepoxide component which is a raw material component of the first cured epoxy resin is composed of a low molecular weight polyepoxide having a molecular weight of 200 to 500 and a high molecular weight polyepoxide having a molecular weight of 900 to 1300, 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 900-1300, preferably 1000-1200. The high molecular weight polyepoxide is considered to impart durability such as high water absorption and wear resistance to the first cured epoxy resin obtained as described above. When the molecular weight of the high molecular weight polyepoxide is within the above range when used in combination with the low molecular weight polyepoxide in the ratio of the present invention, the first cured epoxy resin can ensure sufficient durability such as wear resistance. 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 500, preferably 300 to 400. 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 both polyepoxides constituting the first polyepoxide component in the above range, the first cured epoxy resin can ensure both durability such as sufficient wear resistance and a good appearance. Become.

  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 500, 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 1300 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. ., 0.0 / molecule), Denacol EX-314 (Mw: 454, average number of epoxy groups: 2.3 / molecule), and the like.

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 / molecule), polyglycerin polyglycidyl ether, Denacol EX-521 (Mw: 1294, average number of epoxy groups: 6.3 / molecule), etc. Is mentioned.
Examples of sorbitol polyglycidyl ether include Denacol EX-622 (Mw: 930, average number of epoxy groups: 4.9 / molecule).

(First curing agent)
The first cured epoxy resin mainly constituting the water-absorbing resin 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 that is the main component of the water-absorbent resin layer in the present invention is the above-described two molecular weights having no aromatic nucleus from the viewpoint of obtaining high water absorption. The polyepoxide is preferably used. 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 in the above range, a three-dimensional network structure appropriately crosslinked so as to have the above water absorption without lowering durability such as wear resistance. A cured epoxy resin having 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. It is preferable that 1.0-10 mass% is more preferable, and 1.0-5 mass% is especially preferable. If the usage-amount of the catalyst type hardening | curing agent with respect to a 1st polyepoxide component shall be 1.0 mass% or more, reaction will fully advance and sufficient water absorption and durability can be implement | achieved in the 1st hardening epoxy resin obtained. . 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).

(Silica fine particles)
The water-absorbing resin layer forming composition used in the present invention contains 10 to 30% by mass of silica fine particles as a filler with respect to the total mass of the first polyepoxide component and the first curing agent. By including silica fine particles in this proportion, the mechanical strength and heat resistance such as abrasion resistance and scratch resistance of the formed water-absorbent resin layer can be increased, and the curing shrinkage of the resin during the curing reaction is reduced. it can. If the blending amount of the silica fine particles is 10% by mass or more, the resulting water-absorbent resin layer can be sufficiently provided with wear resistance and scratch resistance, and the water-absorbent mainly composed of the first cured epoxy resin. It is easy to suppress a decrease in the effect of reducing the curing shrinkage of the resin. Moreover, if the compounding quantity of a silica fine particle shall be 30 mass% or less, the space for water absorption can fully be ensured and it is easy to make anti-fogging performance high.

  The average particle size of the silica fine particles contained in the composition for forming a water absorbent resin layer is preferably 0.01 to 0.3 μm, and more preferably 0.01 to 0.1 μm. Moreover, it is preferable that the compounding quantity of a silica particle is 10-30 mass% with respect to the total mass of a 1st polyepoxide component and a 1st hardening | curing agent, and 13-30 mass% is more preferable.

  The silica fine particles can be blended in the water absorbent resin 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. Examples of colloidal silica include silica hydrosol dispersed in water and organosilica sol in which water is replaced with an organic solvent. When used in a water-absorbing resin layer forming composition, it is preferably used in this composition. It is preferable to use an organosilica sol using an organic solvent similar to the organic solvent described later as a 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 Co., Ltd.) in which silica particles having an average primary particle size 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 by Kogyo Co., Ltd.), organosilica sol NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) in which the organic solvent of organosilica sol IPA-ST is changed from isopropanol to butyl acetate, and the organic solvent of organosilica sol IPA-ST is changed from isopropanol to methyl ethyl ketone. Examples thereof include changed organosilica sol MEK-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.). In addition, when using colloidal silica as a silica particle, the quantity of the solvent mix | blended with the composition for water absorption layer formation is adjusted suitably in consideration of the amount of solvent contained in colloidal silica.

(Composition for forming water-absorbent resin layer)
The water-absorbing resin layer in the anti-fogging film of the anti-fogging article of the present invention is obtained by reacting the water-absorbing resin layer forming composition containing the first polyepoxide component, the first curing agent, and silica fine particles. It is a water-absorbing resin layer mainly composed of the obtained first cured epoxy resin.

  About the said 1st polyepoxide component and 1st hardening | curing agent which the composition for water-absorbent resin 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 absorbent resin layer usually contains a solvent in addition to the first polyepoxide component, the first curing agent, and the silica fine particles. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed.

  Usually, the reaction of the first polyepoxide component for obtaining a water-absorbing resin mainly composed of the first cured epoxy resin and the first curing agent is applied to the coated surface as a water-absorbing resin layer-forming composition ( This is performed after coating on the base resin layer, but when the composition contains a solvent, these components are reacted in advance in the composition before coating on the coated surface, and then coated on the coated surface and dried. Further reaction may be performed later. 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 resin layer forming composition, the reaction temperature when the reaction is performed in advance is 30 ° C. or higher. This is preferable because the curing reaction surely proceeds.

  The solvent used in the water-absorbing resin layer forming composition is a solvent having good solubility with respect to the first polyepoxide component, the first curing agent, the silica fine particles, and other components including optional components, and these The solvent is not particularly limited as long as it is an inert solvent, and specific examples include alcohols, acetate esters, 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, isopropanol, n-propanol, and 1-methoxy-2-propanol. 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, a 1st hardening | curing agent, and silica fine particles, 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 the solvent in the water absorbent resin layer forming composition, and the water absorbent resin layer forming composition may be of the same type or Other solvents may be added.

The amount of the solvent in the water-absorbing resin layer forming composition is 100 parts by mass with respect to the total solid content of the first polyepoxide component, the first curing agent, the silica fine particles, and other various blended components optionally blended. It is preferable that it is 100-500 mass parts with respect to 200-350 mass parts.

  Here, the blending amount of the first polyepoxide component and the first curing agent in the water absorbent resin layer forming composition may be 15 to 30% by mass with respect to the total amount of the composition for the first polyepoxide component. Preferably, 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 resin layer forming composition is increased. On the other hand, it is preferable to mix | blend the amine compound which has active hydrogen in the ratio of 3-15 mass%, and the imidazole compound in the ratio of 0.1-1.0 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 composition for forming the water absorbent resin layer, the reactive additive includes a compound having one reactive group reactive with an epoxy group such as alkyl monoamine, an epoxy group or an amino group. A coupling agent etc. are mentioned. In the water-absorbent resin layer forming composition, the coupling agent is used for adhesion between the water-absorbent resin layer and the base resin layer, or a water-absorbent resin layer and a functional layer (described later) laminated thereon as necessary. It is a component that is blended for the purpose of improving adhesion, and is one of the components that is 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 a reactive group that the first polyepoxide component or the first curing agent has and a reactive group that remains on the surface of the base resin layer described later. In addition, it can use also for the purpose of adjusting the physical property of a water absorbing resin 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 absorbent resin layer forming composition is not an essential component, so there is no lower limit. However, in order to sufficiently exhibit the effect of the coupling agent blending, the mass ratio of the coupling agent to the total mass of the first polyepoxide component and the first curing agent in the water absorbent resin layer forming composition Is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. 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-absorbent resin 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: It is preferable that it is 40 mass% or less, and 30 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-absorbing-resin layer formation, when using a silane coupling agent, it is preferable that it is 2-10 mass%, and 3-7 mass%. It is more preferable that
In addition, regarding a particularly preferable composition in the composition for forming a water-absorbent resin layer containing a silane coupling agent, the first polyepoxide component is contained in an amount of 15 to 30% by mass and active hydrogen based on the total amount of the composition. 3-15% by mass of amine compound, 0.1-1.0% by mass of imidazole compound, 3-7% by mass of silica fine particles, 2-10% by mass of silane coupling agent, and 50-75% by mass of solvent. The composition which contains is mentioned.

  Here, when the composition for forming a water absorbent resin 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 same as that in the first curing agent. The amine active hydrogen and the amine active hydrogen possessed by the coupling agent are combined to calculate an equivalent ratio with the epoxy group of the first polyepoxide component so as to be within the preferred range.

  Similarly, when the water-absorbing resin 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 same as that of the first polyepoxide component. The epoxy group possessed by the coupling agent and the epoxy group possessed by the coupling agent are combined to calculate the equivalent ratio of amine active hydrogen in the first curing agent so as to be in the preferred range.

  A leveling agent, a defoaming agent, a viscosity modifier, a light stabilizer, etc. can be further added to the composition for forming the water absorbent resin 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 composition for forming a water absorbent resin layer is 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. be able to.

(Water absorbent resin layer)
The water-absorbent resin layer in the anti-fogging article of the present invention is a three-dimensional network obtained by reacting the first polyepoxide component contained in the water-absorbent resin layer-forming composition with the first curing agent. Due to the properties of the first cured epoxy resin described above, which is mainly composed of the first cured epoxy resin having a structure and the silica fine particles are uniformly dispersed and included in the three-dimensional network structure, high water absorption is achieved. It is a resin layer having both a durability such as abrasion resistance and scratch resistance due to the properties of silica fine particles and a good appearance. The reaction conditions will be described in the production method described later.

  Further, an optional reactive additive such as a silane coupling agent is present in the water-absorbent resin layer in a form bonded to a part of the three-dimensional network structure of the first cured epoxy resin. In addition to the silica fine particles, the non-reactive additive that is optionally added is present in the water-absorbent resin layer by being uniformly dispersed and included in the three-dimensional network structure of the first cured epoxy resin. is there.

[2-2] Underlying resin layer In the antifogging article of the present invention, the underlying resin layer constituting the antifogging film formed on at least a part of the surface of the substrate together with the water absorbent resin layer is composed of the substrate and the water absorbent material. A layer formed between the resin layers, mainly composed of a second cured epoxy resin obtained by reacting a composition for forming a base resin layer containing a second polyepoxide component and a second curing agent, It is a layer having a lower water absorption than the water absorbent resin layer. Hereinafter, the resin mainly composed of the second cured epoxy resin in the base resin layer is also referred to as a low water absorption resin.

  Here, as described in the water-absorbing resin layer, in this specification, the water-absorbing property of the water-absorbing resin (high water-absorbing resin) and the base resin (low water-absorbing resin) is relative. “High water absorption” and “low water absorption” do not mean high or low with a threshold value.

If the water absorption of the low water absorption resin which comprises the base resin layer provided in the anti-fogging article of this invention is shown concretely, the saturated water absorption measured by the method demonstrated by the said water absorbent resin layer will be 20 mg / preferably cm ³ or less, more preferably 10 mg / cm ³ or less. By setting the saturated water absorption amount of the low water-absorbent resin to 20 mg / cm ³ or less, as described above, there is a difference in the degree of expansion / contraction at the bonding interface between the substrate and the antifogging film, actually between the substrate and the base resin layer. It becomes small and it becomes possible to prevent that an anti-fogging film | membrane peels from a base | 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 / contraction between the base resin layer and the water absorbent resin layer in the antifogging film, the saturated water absorption amount of the low water absorbent resin constituting the base resin layer is 1 mg / cm ³ or more. It is preferable that it is 3 mg / cm ³ or more.

  As for the water absorption of the base resin layer provided in the antifogging article of the present invention, if the water absorption antifogging property described in the water absorbent resin layer is used as an index, the water absorption antifogging property can be 10 seconds or less. 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 amount, the water absorption and antifogging property is preferably 1 second or more from the viewpoint of reducing the difference in expansion and contraction between the base resin layer and the water absorbent resin layer in the antifogging film. More preferably, it is 2 seconds or more.

From the relationship between the saturated water absorption amount of the low water absorption resin constituting the base resin layer and the water absorption and antifogging property of the base resin layer, the film thickness of the base resin layer according to the antifogging article of the present invention is 1 μm or more. More preferably, it is 3 μm or more, more preferably 5 μm or more. If the film thickness of the base resin layer is 1 μm or more, it is 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. Also, for the reason that the stress generated at the interface due to expansion / contraction of the water-absorbent resin layer is relaxed, the film thickness of the base resin layer is more preferably 3 μm or more, and further preferably 5 μm or more. Particularly preferred. In addition, the film thickness of the base resin layer 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 base resin 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 base resin layer is a second cured epoxy resin obtained by reacting the second polyepoxide component and the second curing agent, and the base resin layer is designed to absorb water. For the main component.

  As described above, it is generally preferable to control the glass transition point of the cured epoxy resin low to increase the antifogging performance, and to control the glass transition point of the cured epoxy resin high to increase durability. 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 glass transition point of the highly water-absorbing first cured epoxy resin that mainly constitutes the water-absorbing resin layer is within the above range (-20 to 60 ° C, preferably -5 to 40 ° C), and further the underlying resin layer is mainly constituted. If the glass transition point of the second cured epoxy resin having low water absorption is in the above range and higher than the glass transition point of the first cured epoxy resin, the antifogging performance and durability are high. It is easy to make it compatible. The difference in glass transition point between the second cured epoxy resin in the base resin layer 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 resin 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 at the time of solution coating and unevenness of the coating film, about 300 to 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 mainly constituting the base resin layer is a second cured epoxy resin obtained by reacting the second polyepoxide component with the 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 base resin layer, if a compound having an aromatic nucleus is used in at least one of the second polyepoxide component and the second curing agent, the obtained second cured epoxy resin The water absorption 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.
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.

(Base resin layer forming composition)
The base resin layer in the antifogging film of the antifogging article of the present invention is a second cured epoxy obtained by reacting a composition for forming a base resin layer containing the second polyepoxide component and a second curing agent. This is a base resin layer mainly composed of resin.

  About the said 2nd polyepoxide component and 2nd hardening | curing agent which the composition for base resin 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 the base resin layer 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 forming the base resin layer is the same as the composition for forming the water-absorbent resin layer in the composition before the application to the application surface as the composition containing the solvent, and the second polyepoxide component and the second composition. The curing agent may be reacted to some extent in advance, then applied to the application surface, and further reacted after drying. The conditions for the reaction in advance can be the same as in the case of the water-absorbing resin layer forming composition.

  The solvent used in the composition for forming the base resin layer is a solvent having good solubility for the blending component including the second polyepoxide component, the second curing agent, and other optional components. If it is an inert solvent with respect to it, it will not specifically limit, Specifically, the solvent similar to the said composition for water-absorbing-resin-layer formation is mentioned. The preferred embodiment of the solvent is the same as that of the composition for forming a water absorbent resin layer.

  Moreover, the quantity of the solvent in the composition for base resin 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. It is preferable that it is -950 mass parts, and 400-950 mass parts is more preferable.

  Here, it is preferable that the compounding quantity of the 2nd polyepoxide component and 2nd hardening | curing agent in the composition for base resin layer formation is 4-10 mass% with respect to the composition whole quantity about a 2nd polyepoxide component. The second curing agent is preferably 0.1 to 4.0% by mass with respect to the total amount of the composition. 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 base resin layer forming composition include the same additives as the reactive additive optionally contained in the water absorbent resin layer forming composition. Among the reactive additives, the coupling agent is blended in the composition for forming the base resin layer for the purpose of improving the adhesiveness between the base resin layer and the substrate and the adhesiveness between the base resin layer and the water absorbent resin layer. It is a component and is one of the components that are preferably blended.

About the coupling agent arbitrarily mix | blended with the composition for base resin layer formation, it can be made to be the same as that of the coupling agent used for the said water absorbent resin layer formation composition including the compound used and a preferable aspect. .
Moreover, about the quantity of the coupling agent mix | blended with the composition for base resin 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. % Is preferable, and 10 to 40% by 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 base resin layer 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. It is preferable that it is mass% or less, and 40 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 resin layer formation, when using a silane coupling agent, it is preferable that it is 0.1-3.0 mass%, for example, It is more preferable that it is 2 mass%.
Here, regarding a particularly preferable composition in the composition for forming a base resin layer containing a silane coupling agent, the second polyepoxide component is contained in an amount of 4 to 10% by mass and active hydrogen based on the total amount of the composition. Examples include a composition containing 0.1 to 4.0% by mass of an amine 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 the base resin layer contains a coupling agent having an amino group or a coupling agent having an epoxy group as a coupling agent, the equivalent ratio of amine active hydrogen to the epoxy group is as follows: It is preferable to adjust the blending amount of each component so that this is within the above range.

  Further, for the base resin layer forming composition, if necessary, the same filler as the fine silica particles, leveling agent, antifoaming agent, viscosity, etc. A similar amount of regulator, light stabilizer, etc. can be added.

(Base resin layer)
The base resin layer in the antifogging article of the present invention has a three-dimensional network structure obtained by reacting the second polyepoxide component and the second curing agent contained in the base resin layer forming composition. 2 having the water-absorbing resin layer lower than the water-absorbing resin layer and the adhesion to the substrate and the water-absorbing resin layer due to the properties of the second cured epoxy resin described above. Is a resin layer that is sufficiently secured and excellent in peel resistance. The reaction conditions will be described in the production method described later.

  Further, a reactive additive such as a silane coupling agent that is optionally added is present in the base resin layer in a form that is bonded to a part of the three-dimensional network structure of the second cured epoxy resin, and in addition, The non-reactive additive that is optionally added to the water-absorbing resin layer is uniformly dispersed and included in the three-dimensional network structure of the second cured epoxy resin.

(Anti-fogging film)
The antifogging film in the antifogging article of the present invention has a configuration in which the base resin layer and the water-absorbing resin layer are laminated in order from the substrate side. The anti-fogging film formed on the substrate by having the above-described structure is excellent in appearance in addition to excellent anti-fogging property and durability such as abrasion resistance, peeling resistance and scratch resistance.
If the water absorption of the antifogging film in the antifogging article of the present invention is specifically shown, the saturated water absorption measured by the method described for the water absorbent resin layer can be 200 mg / cm ³ or more, and In a preferred embodiment, it can be 300 mg / cm ³ or more.

Further, regarding the water absorption of the anti-fogging film in the anti-fogging article of the present invention, the anti-fogging film surface of the anti-fogging article left for 1 hour in an environment of 20 ° C. and 50% relative humidity is heated in a warm water bath at 40 ° C. The time when measuring the antifogging time (seconds) until fogging is observed, that is, the water absorption antifogging property, can be 30 seconds or more, and in a more preferred embodiment, it is 50 seconds or more. In a particularly preferred embodiment, it can be set to 100 seconds or longer. Moreover, when converted per 20 μm of the water-absorbent resin layer, it can be 80 seconds or longer, more preferably 100 seconds or longer, and particularly preferred mode 130 seconds or longer. . Here, since the anti-fogging performance required of the anti-fogging article varies depending on the application, the design may be changed as appropriate in accordance with the required performance.
In addition, the soda-lime glass which has not performed the anti-fogging process usually fogs in about 1 to 3 seconds in the above test.

  Further, the antifogging film in the antifogging article of the present invention has various functions as long as it does not impair the effects of the present invention on the base resin layer and the water absorbent resin layer laminated from the substrate side. You may have a film. Specific examples of such a functional film include an antifouling layer that imparts antifouling properties to the antifogging film, an ultraviolet shielding layer, and an infrared absorbing layer.

<Method for producing antifogging article>
The anti-fogging film of the anti-fogging article of the present invention has a configuration in which a base resin layer and a water-absorbing resin layer are sequentially laminated from the substrate side. Such an antifogging film can be specifically formed by the following method (1) or (2).

(1) A base resin layer-forming composition is applied to the substrate surface and reacted to form a base resin layer, and then the water-absorbent resin layer-forming composition is applied to the surface of the base resin layer and reacted to cause a water-absorbing resin. Method of forming an antifogging film by forming a layer (2) When the water-absorbent resin 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-absorbent resin layer. And the film (water-absorbent resin layer) are bonded together by forming a base resin layer that is an adhesive layer between them using the base resin layer forming composition as an adhesive, and from the substrate surface side. Method for obtaining an antifogging film in which a base resin layer and a water absorbent resin layer are laminated

  In the method (2), a film-like water-absorbing resin (water-absorbing resin layer) is formed on a releasable support, which is separated from the support to form a base resin layer on the substrate surface. Although it is possible to bond the composition using the adhesive as an adhesive, a film-like water-absorbing resin (water-absorbing resin layer) is used together with this support on the substrate surface using the base resin layer forming composition as an adhesive. A method of attaching is preferable. 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, a good appearance can be maintained when a base resin layer or a water-absorbing resin layer is provided on the surface of a large-area substrate or during industrial mass production (1). The method is more preferable.
Hereinafter, a method for producing the antifogging article of the present invention by the method (1) will be described.

  As a method for producing the antifogging article of the present invention, (A) a base resin layer-forming composition containing a second polyepoxide component and a second curing agent is applied to a substrate surface and reacted. A step of forming a base resin layer mainly comprising a cured epoxy resin of 2, and (B) the surface of the base resin layer is composed of a low molecular weight polyepoxide having a molecular weight of 200 to 500 and a high molecular weight polyepoxide having a molecular weight of 900 to 1300, A first polyepoxide component having a mass ratio of low molecular weight polyepoxide: high molecular weight polyepoxide of 30:70 to 70:30, a first curing agent, the first polyepoxide component, and the first curing agent. By applying and reacting a water-absorbent resin layer-forming composition containing 10 to 30% by mass of silica fine particles with respect to the total mass, the first cured epoxy resin is reacted Forming a water-absorbent resin layer to the body, the method having the preferred.

The components contained in the base resin layer-forming composition and the water-absorbent resin layer-forming composition are as described above, and the above-mentioned two types of compositions can be obtained by mixing these components in the usual manner. .
In the above step (A), in order to form the base resin layer on the substrate, the method for applying the base resin layer forming composition obtained above to the coated surface of the substrate is not particularly limited. Examples include known methods such as a method, 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. The coating thickness of the composition for forming the base resin layer is set such that the thickness of the base resin layer finally obtained by reaction of the reaction components in the composition falls within the above range.

After applying the composition for forming the base resin layer on the substrate, the solvent is removed by drying as necessary, and the base is mainly composed of the second cured epoxy resin by performing a curing treatment according to the conditions suitable for the reaction components used. Let it be a resin layer. 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 base resin layer, that is, as a reaction condition of the second polyepoxide component and the second curing agent, specifically, a heat treatment at 70 to 150 ° C. for about 1 to 60 minutes is performed. Can be mentioned. 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.

  As a method of applying the water-absorbing resin layer forming composition in the step (B) to the surface of the base resin layer formed on the substrate in the step (A), the method for applying the base resin layer forming composition is as follows. You can do the same. The coating thickness of the water-absorbing resin layer forming composition is set such that the thickness of the water-absorbing resin layer finally obtained by reaction of the reaction components in the composition falls within the above range.

After applying the water-absorbing resin layer forming composition on the base resin layer, if necessary, the solvent is removed by drying, and a curing treatment is performed under conditions suitable for the reaction components to be used. It is set as the water-absorbing resin layer. Specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. Moreover, as reaction conditions in the composition for water-absorbing resin layer formation, ie, the said 1st polyepoxide component, and a 1st hardening | curing agent, specifically, 50-120 degreeC and about 10 to 60 minutes. Heat treatment. 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.
Thus, the anti-fogging article of the present invention in which the anti-fogging film is formed on the substrate is obtained through the steps (A) and (B).

  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 3 are examples, and examples 4 to 6 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 jER828 used as the second polyepoxide component (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 thicknesses of the base resin layer and the water absorbent resin layer were measured.

[Evaluation of water absorption and antifogging properties]
The anti-fogging film surface of the anti-fogging article left in an environment of 20 ° C. and 50% relative humidity for 1 hour was placed on a 40 ° C. hot water bath, and the anti-fogging time (seconds) until cloudiness was observed was measured. . In each of the examples described later, the water-absorbing resin layer is at least twice as thick as the base resin layer, and it is considered that the water-absorbing speed of the water-absorbing resin layer dominates the water-absorbing antifogging property. The water absorption anti-fogging property on the surface of the cloudy film and the water absorption anti-fogging property of the water-absorbent resin layer are almost the same. Therefore, after the antifogging time (seconds) measured above was divided by the film thickness of the water absorbent resin layer, it was converted to 20 μm of the water absorbent resin layer to evaluate the water absorption antifogging property.
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 example, water absorption and anti-fogging properties of 30 seconds or more are necessary for practical use, preferably 50 seconds or more, and more preferably 100 seconds or more. Further, when converted to about 20 μm of the water-absorbent resin layer, the water-absorbing and anti-fogging property of 80 seconds or more is necessary, preferably 100 seconds or more, and more preferably 130 seconds or more.

[Evaluation of appearance]
The appearance of the antifogging film was evaluated based on the following evaluation criteria.
○: Insufficient wetting and spreading of the coating solution, unevenness of the coating film, wrinkling of the coating film, and any appearance defects are not observed.
X: Insufficient wetting and spreading of the coating liquid, unevenness of the coating film, generation of wrinkles in the coating film, and at least any appearance defect were observed.

[Evaluation of wear resistance]
This was performed in accordance with JIS R 3212 (inside the vehicle). A wear wheel CS-10F was used on a Taber 5130 type abrasion tester. A wear ring was brought into contact with the surface of the antifogging film of the antifogging article, rotated 100 times with a load of 4.90 N, measured for change in haze value ΔH (%), and evaluated based on the following evaluation criteria.
A: ΔH was 5% or less.
X: At least one of ΔH exceeding 5% or partial peeling of the antifogging film occurred.

[Evaluation of scratch resistance]
The scratch resistance of the antifogging film was evaluated by the following scratch test.
A ball pencil (manufactured by Mitsubishi Pencil Co., Ltd.) was pressed against the surface of the anti-fogging film by hand and scratched for 2 cm, and then the presence or absence of a scar on the film surface was visually observed to make a scratch test.
○: The film cannot be observed with the naked eye.
X: The film can be observed with the naked eye.

<1> Preparation of composition for forming base resin layer [Production Example A]
In a glass container in which a stirrer and a thermometer are set, 1-methoxy-2-propanol (8.07 g, manufactured by Daishin Chemical Co., Ltd.), bisphenol A diglycidyl ether (5.00 g, jER828, manufactured by Mitsubishi Chemical Corporation), Polyoxyalkylene triamine (2.06 g, Jeffamine T403, manufactured by Huntsman) and aminosilane (1.01 g, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred at 25 ° C. for 30 minutes. Subsequently, it diluted 5 times with 1-methoxy-2-propanol (made by Daishin Chemical Co., Ltd.), and obtained the composition (A) for base resin layer formation.

  Table 1 shows the composition of the obtained composition A for forming the base resin layer. In Table 1, the blending amount of the second polyepoxide component and the second curing agent (amine compound) indicates the blending amount (mass%) of each component with respect to the total amount of the base resin layer forming composition, and silane coupling. The compounding quantity of an agent shows the mass percentage (%) with respect to the total mass of the 2nd polyepoxide component and 2nd hardening | curing agent (amine compound) which the composition for base resin layer formation contains.

<2> Preparation of water-absorbing resin 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), 33.55 g, PIP, manufactured by Daishin Chemical Co., Ltd.), fat Group polyglycidyl ether (10.95 g, Denacol EX-1610, manufactured by Nagase ChemteX), glycerin polyglycidyl ether (9.10 g, Denacol EX-313, manufactured by Nagase ChemteX), 2-methylimidazole (0.47 g) , Shikoku Kasei Co., Ltd.), polyoxyalkylenetriamine (3.97 g, Jeffamine T403, manufactured by Huntsman), aminosilane (4.09 g, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and added at 25 ° C. Stir for 1 hour. Subsequently, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 17.24 g, PIP, manufactured by Daishin Chemical Co., Ltd.), organosilica sol (10.58 g, MEK-ST, Nissan) Chemical Industry Co., Ltd., SiO ₂ content 30% by mass) and leveling agent (0.04 g, BYK307, manufactured by Big Chemie) were added with stirring to obtain a water-absorbent resin layer forming composition (B-1). .

[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), 31.38 g, PIP, manufactured by Daishin Chemical Co., Ltd.), fat Group polyglycidyl ether (10.24 g, Denacol EX-1610, manufactured by Nagase ChemteX), glycerin polyglycidyl ether (8.51 g, Denacol EX-313, manufactured by Nagase ChemteX), 2-methylimidazole (0.44 g) Shikoku Kasei Co., Ltd.), polyoxyalkylene triamine (3.72 g, Jeffamine T403, manufactured by Huntsman), aminosilane (3.83 g, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and added at 25 ° C. Stir for 1 hour. Subsequently, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 16.13 g, PIP, manufactured by Daishin Chemical Co., Ltd.), organosilica sol (15.72 g, MEK-ST, Nissan) Chemical Industry Co., Ltd., SiO ₂ content 30% by mass) and leveling agent (0.04 g, BYK307, manufactured by Big Chemie) were added with stirring to obtain a water-absorbent resin layer forming composition (B-2). .

[Production Example B-3]
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), 29.24 g, PIP, manufactured by Daishin Chemical Co., Ltd.), fat Group polyglycidyl ether (9.54 g, Denacol EX-1610, manufactured by Nagase ChemteX Corp.), glycerin polyglycidyl ether (7.93 g, Denacol EX-313, manufactured by Nagase ChemteX Corp.), 2-methylimidazole (0.41 g) Shikoku Kasei Co., Ltd.), polyoxyalkylene triamine (3.46 g, Jeffamine T403, manufactured by Huntsman), aminosilane (3.57 g, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and added at 25 ° C. Stir for 1 hour. Next, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 15.03 g, PIP, manufactured by Daishin Chemical Co., Ltd.), organosilica sol (20.77 g, MEK-ST, Nissan) Chemical Industry Co., Ltd., SiO ₂ content 30% by mass) and leveling agent (0.04 g, BYK307, manufactured by Big Chemie) were added with stirring to obtain a water-absorbent resin layer forming composition (B-3). .

[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), 27.77 g, PIP, manufactured by Daishin Chemical Co., Ltd.), fat Polyglycidyl ether (11.77 g, Denacol EX-1610, manufactured by Nagase ChemteX Corporation), glycerin polyglycidyl ether (9.78 g, Denacol EX-313, manufactured by Nagase ChemteX Corporation), organosilica sol (1.42 g, NBAC) -ST, manufactured by Nissan Chemical Industries, SiO ₂ content 30% by mass), 2-methylimidazole (0.50 g, manufactured by Shikoku Kasei Co., Ltd.), polyoxyalkylenetriamine (4.27 g, Jeffamine T403, manufactured by Huntsman) , Aminosilane (4.40 g, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) It added, stirring, and stirred at 25 degreeC for 1 hour. Next, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 30.08 g, PIP, manufactured by Daishin Chemical Co., Ltd.), leveling agent (0.05 g, BYK307, manufactured by Big Chemie) ) Was added with stirring to obtain a water-absorbent resin layer forming composition (B-4).

[Production Example B-5]
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), 35.76 g, PIP, manufactured by Daishin Chemical Co., Ltd.), fat Group polyglycidyl ether (11.67 g, Denacol EX-1610, manufactured by Nagase ChemteX Corporation), glycerin polyglycidyl ether (9.70 g, Denacol EX-313, manufactured by Nagase ChemteX Corporation), 2-methylimidazole (0.50 g) , Shikoku Kasei Co., Ltd.), polyoxyalkylene triamine (4.24 g, Jeffamine T403, manufactured by Huntsman), aminosilane (4.36 g, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and added at 25 ° C. Stir for 1 hour. Subsequently, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 18.38 g, PIP, manufactured by Daishin Chemical Co., Ltd.), organosilica sol (5.34 g, MEK-ST, Nissan) Chemical Industry Co., Ltd., SiO ₂ content 30% by mass) and a leveling agent (0.04 g, BYK307, manufactured by Big Chemie) were added with stirring to obtain a water absorbent resin layer forming composition (B-5). .

[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), 23.76 g, PIP, manufactured by Daishin Chemical Co., Ltd.), fat Group polyglycidyl ether (7.75 g, Denacol EX-1610, manufactured by Nagase ChemteX Corporation), glycerin polyglycidyl ether (6.44 g, Denacol EX-313, manufactured by Nagase ChemteX Corporation), 2-methylimidazole (0.33 g) Shikoku Kasei Co., Ltd.), polyoxyalkylene triamine (2.81 g, Jeffamine T403, manufactured by Huntsman), aminosilane (2.90 g, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and added at 25 ° C. Stir for 1 hour. Next, mixed alcohol (ethanol: isopropyl alcohol: n-propyl alcohol = 88: 4: 8 (mass ratio), 9.62 g, PIP, manufactured by Daishin Chemical Co., Ltd.), organosilica sol (36.33 g, MEK-ST, Nissan) Chemical Industry Co., Ltd., SiO ₂ content 30% by mass) and a leveling agent (0.04 g, BYK307, manufactured by Big Chemie) were added with stirring to obtain a water absorbent resin layer forming composition (B-6). .

  Table 2 shows compositions of the water-absorbent resin layer-forming compositions B-1 to B-6 obtained above. In Table 2, the blending amount of the first polyepoxide component and the first curing agent (amine compound) indicates the blending amount (% by mass) of each component with respect to the total amount of the water-absorbent resin layer forming composition, and the silica fine particles, The compounding quantity of a silane coupling agent shows the mass percentage (%) with respect to the total mass of the 1st polyepoxide component and 1st hardening | curing agent (Amine compound and imidazole compound) which the composition for water-absorbent resin layer formation contains. Moreover, the compounding quantity of a 1st hardening | curing agent (imidazole compound) shows the mass percentage (%) with respect to the total mass of a 1st polyepoxide component.

<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. The obtained results are shown in Table 3.

[Examples 1 to 6]
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. As shown in Table 3, the surface of the glass substrate was used. The base resin layer-forming composition obtained in Production Example A was applied by flow coating, and held in an electric furnace at 100 ° C. for 30 minutes to form a base resin layer. Subsequently, as shown in Table 3, the water-absorbing resin layer forming composition obtained in Production Example B (B-1 to B-6) was applied to the surface of the formed base resin layer by flow coating, and the electric power at 100 ° C. Holding for 30 minutes in a furnace, a water-absorbing resin layer was formed, and an antifogging article having an antifogging film consisting of two layers was obtained. The evaluation results are shown in Table 3.

From the evaluation results shown in Table 3, the antifogging articles obtained in Examples 1 to 3, which are examples, have excellent antifogging properties and appearance / abrasion resistance / scratch resistance. It can be seen that the antifogging articles obtained in Comparative Examples 4 to 6 do not have sufficient scratch resistance.
The evaluation of the water absorption antifogging property is performed on the surface of the base resin layer when the base resin layer is formed, and further, the water absorbent resin layer is formed on the surface of the base resin layer to form an antifogging article. The test was performed on the surface of the antifogging film, that is, the surface of the water absorbent resin layer in which the water absorbent resin layer was laminated on the base resin layer. Here, although the evaluation result of the water absorption antifogging property of only the water absorbent resin layer has not been obtained, as described above, the water absorption antifogging property on the surface of the antifogging film and the water absorption antifogging property of the water absorbent resin layer are substantially equivalent. May be considered.

  The anti-fogging article of the present invention is useful as an anti-fogging glass for automobiles and buildings because it has excellent anti-fogging properties, abrasion resistance, durability such as peeling resistance and scratch resistance, and also excellent appearance. is there.

Claims (7)

An antifogging article having a base and an antifogging film on at least a part of the surface of the base,
The antifogging film has a base resin layer and a water absorbent resin layer sequentially laminated on the surface of the base,
The water absorbent resin layer is composed of a low molecular weight polyepoxide having a molecular weight of 200 to 500 and a high molecular weight polyepoxide having a molecular weight of 900 to 1300, and a mass ratio represented by the low molecular weight polyepoxide: the high molecular weight polyepoxide is 30:70 to 70:30. A water-absorbent resin layer comprising a first polyepoxide component, a first curing agent, and 10 to 30% by mass of silica fine particles based on a total mass of the first polyepoxide component and the first curing agent. A water-absorbent resin layer mainly composed of a first cured epoxy resin obtained by reacting a forming composition;
The base resin layer is mainly composed of a second cured epoxy resin obtained by reacting a composition for forming a base resin layer containing a second polyepoxide component and a second curing agent. An antifogging article which is a base resin layer having low water absorption.   The antifogging article according to claim 1, wherein the low molecular weight polyepoxide has a molecular weight of 300 to 400, and the high molecular weight polyepoxide has a molecular weight of 1000 to 1200.   The antifogging article according to claim 1 or 2, wherein each of the high molecular weight polyepoxide and the low molecular weight polyepoxide is a glycidyl ether-based polyepoxide.   The water absorbent resin layer forming composition contains the first polyepoxide component in an amount of 15 to 30% by mass and the first curing agent in a proportion of 3 to 20% by mass with respect to the total amount of the composition, The composition for forming a base resin layer contains 4 to 10% by mass of the second polyepoxide component and 0.1 to 4.0% by mass of the second curing agent with respect to the total amount of the composition. The antifogging article according to any one of claims 1 to 3.   The antifogging article according to any one of claims 1 to 4, wherein the first curing agent and the second curing agent both contain an amine compound having active hydrogen.   The antifogging article according to claim 5, wherein the first curing agent further contains an imidazole compound.   The antifogging article according to any one of claims 1 to 6, wherein the second polyepoxide component is a polyepoxide having an aromatic nucleus.