JP2016017013A - Antifogging glass article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifogging glass article having a high anti-fogging performance which is suitable for the applications requiring high antifogging properties of a cold insulation showcase or the like.SOLUTION: There is provided an antifogging glass article which mainly comprises a multiple glass in which a plurality of glass plates arranged to face each other are sealed via a spacer in a peripheral part thereof and an intermediate layer is formed between the glass plates facing each other and a first curable epoxy resin disposed on at least one principal surface of the multiple glass and has an anti-fogging film having a water-absorbing layer having an antifogging time (T) in a steam test at 45°C of 40 seconds or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an anti-fogging glass article, and more particularly to an anti-fogging glass article having a highly water-absorbing anti-fogging film on the surface of a multilayer glass suitable for a cold showcase door.

  Glass is excellent in transparency, so it is used in various windows for buildings, vehicles, showcases, etc., but when the glass surface falls below the dew point in the glass window, fine water droplets adhere to the surface. As a result, the transmitted light is scattered, so that the transparency is impaired and a so-called “cloudy” state is obtained.

  For example, in a cold showcase such as a refrigerator or a freezer having a glass window, such fogging may occur when one side of the glass window is exposed to a cold environment. When the cold / warm environment is below freezing, the cloudiness may appear as frozen, making it difficult to ensure the visibility of the glass window.

  A glass window having a multiple glass structure in which a plurality of glass plates such as a double-glazed glass are opposed to each other has better heat insulation than a single glass window, and is effective in suppressing the occurrence of fogging. Therefore, in an environment where one side of the glass window is in a cold / warm environment, a glass window having a multiple glass structure is widely adopted as the glass window. In particular, the frequency of use as a window in a cold showcase is particularly noteworthy.

  However, these glass windows are used in many cases by being incorporated in movable devices such as doors, lids, doors and the like. In such a case, when the glass window is opened, the surface of the glass plate that has been in contact with the cold environment of the cold insulation showcase is brought to the warm environment in a cooled state, and the surface is cloudy. It tends to occur. This results in hindering visual recognition after the glass window is sealed.

  In order to solve this problem, for example, Patent Document 1 describes a technique in which a water-absorbing film made of a specific urethane resin is provided on a glass plate surface that is exposed to a cold environment when the glass window of a cold-insulated showcase is closed. . According to Patent Document 1, the water-absorbing coating absorbs moisture that causes fogging when the glass window is opened, and releases water absorbed in the coating when the glass window is closed. Designed. However, the method described in Patent Document 1 cannot be said to have sufficient antifogging properties.

JP 2009-242219 A

  The present invention has been made from the above viewpoint, and an object of the present invention is to provide an antifogging glass article having high antifogging performance, which is suitable for applications requiring high antifogging properties such as a cold showcase.

The present invention provides an antifogging glass article having the following configuration.
[1] Double-glazed glass in which a plurality of glass plates opposed to each other are sealed with a spacer at the periphery and an intermediate layer is formed between the opposed glass plates, and at least one main surface of the double-glazed glass An anti-fogging film having a water-absorbing layer mainly composed of the first cured epoxy resin and having an anti-fogging time (T ₄₅ ) in a 45 ° C. steam test measured by the following method of 40 seconds or more,
Antifogging glass article having
(Measurement method of anti-fogging time (T ₄₅ ))
A water-absorbing layer as a specimen is provided on one main surface of the soda lime glass substrate, and left for 1 hour in an environment of 23 ° C. and 50% RH. Next, a 70 mm × 70 mm square area on the surface of the water absorption layer is placed on a 45 ° C. hot water bath, and the antifogging time (T [second]) until fogging is visually observed after starting to wrinkle is measured.
[2] The water absorbing layer is a layer obtained by reacting a water absorbing layer forming composition containing a first polyepoxide component and a first polyaddition type curing agent, and the first polyepoxide component contains chlorine. The antifogging glass article according to [1], wherein the polyepoxide (A) having an amount of 2% by mass or less and a water content of 90% or more is contained by 90% by mass or more based on the total amount of the polyepoxide component.
[3] The antifogging glass article according to [2], wherein the first polyaddition type curing agent contains a polyamine compound having amine active hydrogen.
[4] The antifogging according to [3], wherein an equivalent ratio of amine active hydrogen contained in the first polyaddition type curing agent to an epoxy group contained in the first polyepoxide component is 0.6 to 2.0. Glass articles.
[5] The antifogging is antifogging according to any one of further the double glazing side of the water-absorbing layer, the saturation water absorption has a 10 mg / cm ³ or less of the underlying layer [1] to [4] Glass articles.
[6] The underlayer mainly comprises a second cured epoxy resin obtained by reacting a composition for forming an underlayer containing a second polyepoxide component and a second polyaddition type curing agent. [5] An antifogging glass article as described in 1.
[7] The antifogging glass article according to any one of [1] to [6], which is used for a cold storage showcase door.

  According to the present invention, it is possible to provide an antifogging glass article having high antifogging performance, which is suitable for applications requiring high antifogging properties such as a cold showcase.

It is sectional drawing of an example of the anti-fogging glass article of embodiment of this invention. It is an expanded sectional view of the glass plate which has an anti-fogging film | membrane in the anti-fogging glass article shown in FIG. It is sectional drawing of another example of the anti-fogging glass article of embodiment of this invention.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, this invention is limited to the following description and is not interpreted.

  FIG. 1 shows a cross-sectional view of an example of an antifogging glass article according to an embodiment of the present invention, and FIG. 2 is an enlarged cross-sectional view of a glass plate having an antifogging film in the antifogging glass article shown in FIG. . The antifogging glass article shown in FIG. 1 and FIG. 2 is used, for example, for a door of a cold storage showcase.

  An anti-fogging glass article 10A shown in FIG. 1 seals two glass plates 11 and 12 arranged opposite to each other and peripheral portions of the two glass plates 11 and 12, and the two glass plates A multilayer glass 20A having a spacer 21 arranged so as to form an intermediate layer 31 between the plates 11 and 12, and an intermediate layer 31 of the glass plate 11 on one main surface 11a of the multilayer glass 20A. And an anti-fogging film 41 disposed on the main surface 11a on the side not facing the surface.

As shown in FIG. 2, the antifogging film 41 has a water absorption layer 41a mainly composed of a first cured epoxy resin, and an antifogging time (T ₄₅₎ in a 45 ° C. steam test measured by the above method of the water absorption layer 41a. ) Is 40 seconds or longer. The antifogging time (T ₄₅ ) in the 45 ° C. steam test measured by the above method is hereinafter simply referred to as antifogging time (T ₄₅ ). The anti-fogging film 41 shown in FIG. 2 further has a low water absorption base layer 41b with a saturated water absorption of 10 mg / cm ³ or less on the multilayer glass 20A side of the water absorption layer 41a, that is, the main surface 11a side of the glass plate 11. Have. In the antifogging glass article 10A, the antifogging film 41 is composed of the base layer 41b and the water absorption layer 41a. However, in the antifogging glass article of the embodiment of the present invention, the base layer is not an essential layer, A cloudy film may be comprised only by a water absorption layer.

Moreover, in this specification, saturated water absorption means the saturated water absorption mass [mg / cm < ³ >] per unit volume measured with the following method.

  A layer (hereinafter referred to as “specimen layer”) serving as a specimen is provided on a soda lime glass substrate having a size suitable for measurement, for example, 3 cm × 4 cm × thickness 2 mm, and this is maintained at a constant temperature and constant temperature of 10 ° C. and 95 to 99% RH. After leaving for 2 hours in a wet tank and taking out, the moisture content (I) of the whole substrate with the specimen layer is measured using a trace moisture meter. Further, the moisture content (II) is measured for the substrate only by the same procedure. A value obtained by dividing a value obtained by subtracting the water content (II) from the water content (I) by the volume of the specimen layer is defined as a saturated water absorption amount. The moisture content is measured as follows using a trace moisture meter FM-300 (trade name, 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.

Here, the anti-fogging time (T ₄₅ ) of the water absorption layer of the anti-fogging film in the embodiment of the present invention is 40 seconds or more. The saturated water absorption of such a water absorption layer is approximately 150 mg / cm ³ or more, and the underlayer having a saturation water absorption of 10 mg / cm ³ or less is a layer having lower water absorption performance than the water absorption layer.

The low water-absorbing base layer has a low degree of expansion / contraction compared to a high water absorption layer that expands / contracts to some extent due to water absorption / discharge. Has the effect of improving. Note that the antifogging film does not need to have a base layer as long as it has a water absorption layer mainly composed of the first cured epoxy resin and having an antifogging time (T ₄₅ ) of 40 seconds or more. However, it is preferable to have an underlayer from the viewpoint of the adhesion between the antifogging film and the multilayer glass. The underlayer also has an action of suppressing water and various ion components taken together with water from reaching the main surface of the double-glazed glass on which the antifogging film is disposed.

  In the multi-layer glass 20A, the two glass plates 11 and 12 are spaced apart by the spacers 21 disposed on the peripheral edge thereof, so that an intermediate layer 31 is formed between the glass plates 11 and 12. ing. In the multilayer glass 20A, the two main surfaces are in contact with the main surface 11a that is not in contact with the intermediate layer 31 of one of the two glass plates and the intermediate layer 31 of the other glass plate 12. This corresponds to the main surface 12a not being provided.

  The antifogging glass article of the present invention has a multi-layer glass and an antifogging film disposed on at least one main surface thereof. The antifogging glass article 10A shown in FIG. 1 has a configuration in which an antifogging film 41 is provided on one main surface 11a of the multilayer glass 20A and no antifogging film is provided on the other main surface 12a.

  When such an antifogging glass article 10A is used for, for example, a door of a cold insulation showcase, the antifogging film 41 is located inside the door where a temperature difference occurs due to opening and closing of the door and fogging is likely to occur, that is, inside the warehouse. Used as follows. In this case, the anti-fogging film 41 arranged on the inner side of the cabinet absorbs moisture that causes fogging when the door is opened, and releases water absorbed in the anti-fogging film 41 when the door is closed. By doing so, generation | occurrence | production of cloudiness can be suppressed.

In order to effectively suppress the occurrence of fogging in such applications, a highly water-absorbing antifogging film is required. The anti-fogging film of the anti-fogging glass article of the embodiment of the present invention includes a water-absorbing layer having a high anti-fogging property with an anti-fogging time (T ₄₅ ) of 40 seconds or more. It is also possible to cope with.

  The antifogging glass article 10A is an aspect of the antifogging glass article of the present invention having the antifogging film 41 on one main surface of the multilayer glass 20A, but the antifogging glass article of the embodiment of the present invention. The aspect which has an anti-fogging film | membrane on both main surfaces of a multilayer glass may be sufficient. When an antifogging glass article having an antifogging film on both main surfaces of the double-glazed glass is used, for example, in a cold showcase door, the antifogging film on the inside of the cabinet is protected when the door is opened and closed as described above. Demonstrates fogging function. On the other hand, the anti-fogging film on the outside of the warehouse functions to suppress the occurrence of fogging on the outside of the warehouse when the temperature of the outside of the warehouse rises in a state where the door is closed and the interior is sufficiently cooled.

Hereinafter, each element of the antifogging glass article 10A will be described.
[Multilayer glass]
The multi-layer glass 20A included in the antifogging glass article 10A seals the two glass plates 11 and 12 disposed opposite to each other, and the peripheral portions of the two glass plates 11 and 12, and A spacer 21 is disposed between the two glass plates 11 and 12 so as to form an intermediate layer 31. As the multi-layer glass, multi-layer glass usually used for various applications can be used without particular limitation, and specific examples include multi-layer glass having the following constitution.

(Glass plate)
Examples of the glass constituting the two glass plates 11 and 12 include ordinary soda lime glass, aluminosilicate glass, borosilicate glass, non-alkali glass, and quartz glass. Among these, soda lime glass is particularly preferable. . It can be used regardless of the production method such as float method, duplex method, roll-out method and the like. It is also possible to use ultraviolet shielding glass, infrared shielding glass, or electromagnetic wave shielding glass. Glass that can be used for fireproof glass such as netted glass, low expansion glass, and zero expansion glass, air-cooled tempered glass, chemically tempered glass, and laminated glass can be used.

  The plate thickness of the two glass plates 11 and 12 is not particularly limited, but is preferably 0.1 to 10 mm, and particularly preferably 0.2 to 5.0 mm. The two glass plates 11 and 12 have the same size, but the glass materials constituting them may not necessarily be the same. Similarly, the two glass plates 11 and 12 may not be the same in thickness.

(Spacer)
The spacer 21 is provided to seal the peripheral portions of the two opposing glass plates 11 and 12 to form an intermediate layer 31 as a sealed space surrounded by the spacer 21 and the two glass plates 11 and 12. It is done. By having the intermediate layer 31, the double-glazed glass 20 </ b> A has higher heat insulation performance than the single-layer glass.

  The spacer 21 may be any material that can be formed on the peripheral edge of the two glass plates 11 and 12 and can be sandwiched between the two glass plates 11 and 12 to form the intermediate layer 31 as a sealed space. There is no limitation, and specifically, general-purpose resins such as vinyl chloride resin, polyethylene resin, polystyrene resin, ABS resin, and acrylic resin, engineering plastics, metals, and the like can be used. For adhesion between the glass plates 11 and 12 and the spacer 21, a commonly used adhesive or the like can be used as appropriate.

  The thickness of the spacer 21 is set to be equal to the thickness of the intermediate layer 31 to be obtained. Although it depends on the application, the spacer 21 has a thickness of about 3 to 30 mm when used for a door of a cold storage showcase.

(Intermediate layer 31)
The intermediate layer 31 is generally configured to be filled with dry air or nitrogen gas. The thermal insulation performance can be improved by encapsulating the intermediate layer 31 with an insulating gas having a thermal conductivity smaller than that of air, for example, an inert gas such as helium, neon, argon, krypton, or xenon.

  The multi-layer glass 20A can be prepared by preparing two glass plates 11 and 12 and spacers 21 provided in a frame shape on the peripheral portions of the glass plates 11 and 12, and bonding them by a normal method. The inert gas can be sealed in the intermediate layer 31 by a conventional method. Here, the antifogging film 41 disposed on the main surface 11a on the side not facing the intermediate layer 31 of the glass plate 11 of the multi-layer glass 20A is the main layer of the glass plate 11 after the multi-layer glass 20A is assembled. Although it may be formed on the surface 11a, it is usually formed on the main surface 11a of the glass plate 11 before the multilayer glass 20A is assembled.

[Anti-fogging film]
The anti-fogging film 41 has an anti-fogging film 41 on the main surface 11a on the side of the double-glazed glass 20A that does not face the intermediate layer 31 of the glass plate 11, and a water-absorbing layer 41a mainly composed of a first cured epoxy resin. The anti-fogging time (T ₄₅ ) of the water absorption layer 41a is 40 seconds or longer. In the antifogging glass article 10A, the antifogging film 41 further includes a base layer 41b having a saturated water absorption of 10 mg / cm ³ or less between the glass plate 11 and the water absorbing layer 41a.

(Water absorption layer)
The water absorption layer 41a of the antifogging film 41 is a layer mainly composed of the first cured epoxy resin. As described above, the water absorption layer has an anti-fogging time (T ₄₅ ) of 40 seconds or more and a saturated water absorption amount of about 150 mg / cm ³ or more. The anti-fogging time (T ₄₅ ) of the water absorbing layer is preferably 50 seconds or longer, and more preferably 60 seconds or longer. The saturated water absorption is preferably 250 mg / cm ³ or more, more preferably 300 mg / cm ³ or more. On the other hand, from the viewpoint of preventing the durability of the antifogging decreases, the saturated water absorption of the water-absorbing layer is preferably 800 mg / cm ³ or less, 600 mg / cm ³ or less is more preferable.

  The film thickness of the water-absorbing layer according to the antifogging glass article of the embodiment of the present invention is preferably 3 to 50 μm in consideration of both antifogging properties and durability. The film thickness of the water absorbing layer is more preferably 5 μm or more, and particularly preferably 10 μm or more. The film thickness of the water absorbing layer is more preferably 40 μm or less, and particularly preferably 30 μm or less.

  In addition, when the antifogging film has a base layer, the thickness of the water absorbing layer is 2 to 12 times the thickness of the base layer from the viewpoint of preventing the anti-fogging film from having low peel resistance, durability and the like. preferable. If the thickness of the water-absorbing layer is more than twice the thickness of the base layer, the anti-fogging performance of the anti-fogging film can sufficiently eliminate the influence of the base layer, and the anti-fogging performance of the water-absorbing layer and the anti-fogging performance of the anti-fogging film are almost It can be said that they are equal. If the thickness of the water absorbing layer is 12 times or less than the thickness of the underlayer, the antifogging film can obtain sufficient durability and peeling resistance.

The water absorption layer according to the present invention is not particularly limited as long as it is mainly composed of the first cured epoxy resin and the anti-fogging time (T ₄₅ ) is 40 seconds or longer. Specifically, the water-absorbing layer mainly composed of the first cured epoxy resin and satisfying the anti-fogging time (T ₄₅ ) is a polyepoxide (A) having a chlorine content of 2% by mass or less and a water content of 90% or more. The layer obtained by making the composition for water absorption layer formation containing the 1st polyepoxide component and 1st polyaddition type hardening | curing agent which contain 90 mass% or more with respect to the polyepoxide component whole quantity include is mentioned. In addition, that the water absorption layer is mainly composed of the first cured epoxy resin means that the proportion of the first cured epoxy resin in the entire water absorption layer is 80% by mass or more.

  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 only of a polyepoxide composed of at least one polyepoxide, and may be hereinafter referred to as a main agent as necessary.

  Among the curing agents, the “polyaddition type curing agent” is a compound having two or more reactive groups that react with the epoxy group of the polyepoxide and is polyadded to the polyepoxide by reaction. Say. The “catalytic curing agent” is a reaction catalyst such as a Lewis acid, and refers to a curing agent that catalyzes a polymerization reaction between polyepoxides and / or a polyaddition reaction between a polyepoxide and a polyaddition curing agent. The catalyst type curing agent includes a thermosetting type and a photocuring type, both of which are treated as a catalyst type curing agent.

  Furthermore, the “cured epoxy resin” means a structure obtained by reacting the above main agent with a polyaddition type curing agent, a polyepoxide crosslinked with a polyaddition type curing agent to form a three-dimensional structure, and / or a catalyst type curing agent. A cured product having a structure in which polyepoxides are linearly or three-dimensionally polymerized by function.

  The cured epoxy resin has a three-dimensional structure so that it has a water retention space inside the resin, thereby exhibiting water absorption. The abundance of hydrophilic groups and hydrophilic chains (polyoxyethylene groups, etc.) of the cured epoxy resin also contributes to water absorption. Here, the larger the water retention space that the cured epoxy resin has, the higher the water absorption, but if the water retention space becomes larger than necessary, the durability is lowered. Therefore, the three-dimensional structure of the cured epoxy resin is adjusted as appropriate according to the application. The water retention space also depends on the molecular structure of the polyepoxide used as the main agent.

Hereinafter, a description will be given of a first cured epoxy resin mainly constituting the superabsorbent water-absorbing layer of the anti-fogging time antifogging film according to the present invention has (T ₄₅₎ is more than 40 seconds.

<First cured epoxy resin>
The first cured epoxy resin is a cured epoxy resin obtained by reacting the first polyepoxide component and the first polyaddition type curing agent.
The first polyepoxide component is not particularly limited as long as the obtained water-absorbing layer mainly composed of the first cured epoxy resin can achieve an anti-fogging time (T ₄₅ ) of 40 seconds or more. Specifically, as the first polyepoxide component, a polyepoxide (A) having a chlorine content of 2% by mass or less and a water content of 90% or more is 90% by mass or more based on the total amount of the first polyepoxide component. The polyepoxide component contained in a ratio is mentioned.

  The polyepoxide (A) having a chlorine content of 2% by mass or less and a water content of 90% or more is a linear polyepoxide. In a polyepoxide, usually, a chlorine atom is present at the molecular end, and a low chlorine content means that there are few branches. A polyepoxide having a chlorine content of 2% by mass or less is regarded as a linear polyepoxide.

Further, the water solubility means the solubility in water and can be measured by the following method.
A resin as a specimen is added to water so that the ratio of the resin to water is 10% by mass to prepare a mixture of resin and water, and stirring and mixing are performed for 1 to 5 hours. Thereafter, the mixture is allowed to stand for 24 hours, and then the insoluble resin is sucked off. Mass is measured about the insoluble resin part sucked up, and water-soluble rate (%) is computed by a following formula.
Water content (%) = (input resin amount (g) −insoluble resin amount (g)) / input resin amount (g) × 100
When the water percentage of the polyepoxide is 90% or more, the affinity of the antifogging film with water is increased, and the water absorption performance is further improved.

If the content of the polyepoxide (A) in the first polyepoxide component is 90% by mass or more, it has sufficient water retention space to obtain a water-absorbing layer having an antifogging time (T ₄₅ ) of 40 seconds or more and sufficient. A first cured epoxy resin having durability is obtained. The content of the polyepoxide (A) in the first polyepoxide component is preferably 95% by mass or more and more preferably 100% by mass from the viewpoint of imparting high antifogging properties to the water absorbing layer.

  As the polyepoxide (A), other molecular structures are not particularly limited as long as the chlorine content is 2% by mass or less and the water content is 90% or more. The polyepoxide (A) may be any of an aliphatic polyepoxide, an alicyclic polyepoxide, and an aromatic polyepoxide. When aliphatic polyepoxide is used, the resulting three-dimensional structure of the first cured epoxy resin has a moderately large space and flexibility, so that both high water absorption and durability can be achieved at a higher level. Conceivable and preferred.

  The molecular weight of the polyepoxide (A) is preferably 600 to 3000, more preferably 800 to 2000, considering the high water absorption and durability of the first cured epoxy resin obtained. 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).

  The number of epoxy groups per molecule of polyepoxide in polyepoxide (A) is not particularly limited as long as it is 2 or more on average, but is preferably 2 to 10, more preferably 3 to 8, and 3 ~ 7 are more preferred. The epoxy equivalent of the polyepoxide (A) (gram number of resin containing 1 gram equivalent of epoxy group [g / eq], hereinafter the unit is omitted) is preferably 140 to 250, and 150 to 220. More preferably.

  As the polyepoxide (A), among polyepoxides such as glycidyl ether polyepoxide, glycidyl ester polyepoxide, glycidylamine polyepoxide and the like used as raw material components of ordinary cured epoxy resins, those having a chlorine content and a water content within the above range Can be used. A polyepoxide (A) may be used individually by 1 type, and may use 2 or more types together.

  Hereinafter, although it mentions only about the kind of compound, a thing with a chlorine content and a water-soluble rate of the said range is used as a polyepoxide (A) among these compounds.

  The glycidyl ether-based polyepoxide is a polyepoxide (or an oligomer of the polyepoxide) having a structure in which a hydroxyl group of a polyol having two or more hydroxyl groups is substituted with a glycidyloxy group. 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.

  As the polyepoxide (A), aliphatic glycidyl ether-based polyepoxides derived from aliphatic polyols are preferable. Specific examples of aliphatic glycidyl ether-based polyepoxides derived from aliphatic polyols include polyethylene glycol polyglycidyl ether, polyethylene glycol sorbitol polyglycidyl ether, polyoxypropylene diol polyglycidyl ether, polyoxypropylene triol polyglycidyl ether, poly ( And oxypropylene / oxyethylene) triol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polysorbitol polyglycidyl ether, and the like.

  Among these aliphatic polyepoxides, as the polyepoxide (A), among the polyglycerol polyglycidyl ether, polyethylene glycol polyglycidyl ether, sorbitol polyglycidyl ether, and polysorbitol polyglycidyl ether, the chlorine content and water solubility are within the above ranges. Those are preferred.

  In addition, as a polyepoxide (A), it is possible to use a commercial item. As such a commercially available product, specifically, Denacol EX-1610 (chlorine content: 0.5 mass%, water solubility: all manufactured by Nagase ChemteX Corporation, which is an aliphatic polyglycidyl ether, is a trade name. 100%, Mw; 1130, epoxy equivalent; 170), Denacol EX-1410 (chlorine content; 0.5% by mass, water solubility: 100%, Mw; 988, epoxy equivalent; 160), Denacol EX-610U (chlorine) Content: 0.5% by mass, water solubility: 100%, Mw: 1408, epoxy equivalent; 210) and the like.

  As a polyepoxide other than the polyepoxide (A) contained in the first polyepoxide component (hereinafter also referred to as polyepoxide (B)), a glycidyl ether polyepoxide or a glycidyl ester polyepoxide used as a raw material component of a normal cured epoxy resin. Of the polyepoxides such as glycidylamine-based polyepoxide, those not in the category of polyepoxide (A) can be used without particular limitation.

  As the polyepoxide (B), an aliphatic polyepoxide is preferable like the polyepoxide (A), and an aliphatic glycidyl ether-based polyepoxide derived from aliphatic polyols is particularly preferable.

<First polyaddition type curing agent>
The first polyaddition type curing agent is a compound having two or more reactive groups that react with the epoxy group of the first polyepoxide component and is a type of curing agent that polyadds to the polyepoxide by reaction. There is no particular limitation.

  Examples of the reactive group that reacts with the epoxy group in the first polyaddition type curing agent include an amino group having active hydrogen, a carboxyl group, and a thiol group. That is, the first polyaddition type curing agent is preferably a 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, and more preferably. A compound having two or more amino groups having active hydrogen is used.

The amino group having active hydrogen specifically refers to a primary amino group represented by —NH ₂ or a secondary amino group represented by> NH. In this specification, the active hydrogen bonded to the amino group is referred to as “amine active hydrogen”. A compound having an amino group having active hydrogen is referred to as an amine compound having active hydrogen, and a compound having two or more amino groups having active hydrogen is referred to as a polyamine compound having active hydrogen. Here, the secondary amino group having a terminal primary amino group such as an N-aminoalkyl-substituted amino group or a hydrazinyl group is counted as one amino group having active hydrogen. Further, in this specification, unless otherwise specified, “polyamine compound” refers to a polyamine compound having active hydrogen.

  Specific examples of the compound having two or more reactive groups that react with the epoxy group include polyamine compounds, polycarboxylic acid anhydrides, polyamide compounds, and polythiol compounds. In the present invention, polyamine compounds and polycarboxylic acid anhydrides are preferably used. As a 1st polyaddition type hardening | curing agent, these 1 type may be used independently and 2 or more types may be used together.

  The first polyaddition type curing agent may be an aliphatic compound, an alicyclic compound, or an aromatic compound. From the viewpoint of obtaining a water absorbing layer having high water absorption, the first polyaddition type curing agent is preferably a compound having no aromatic ring. As described above, the first cured epoxy resin is a compound in which the first polyepoxide component mainly containing the linear polyepoxide (A) is an aliphatic compound and the first polyaddition type curing agent does not have an aromatic ring. It is preferable that That is, the first cured epoxy resin preferably has no aromatic ring in the molecular structure from the viewpoint of achieving both high water absorption and durability.

  The first polyaddition type curing agent is preferably a polyamine compound having no aromatic ring, a polythiol, or a polycarboxylic acid anhydride, and particularly preferably a polyamine compound having no aromatic ring. As the polyamine compound, a polyamine compound having 2 to 4 amino groups having active hydrogen is preferable. As the polythiol compound, polyether polythiol is preferable. As the polycarboxylic acid anhydride, dicarboxylic acid anhydride, tricarboxylic acid anhydride and tetracarboxylic acid anhydride are preferable.

  Examples of the polyamine compound having no aromatic ring include aliphatic polyamine compounds and alicyclic polyamine compounds. Specific examples of these polyamine compounds 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 ring include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like.

  A commercial item can also be used for the first polyaddition type curing agent. As such a commercial product, specifically, as polyoxyalkylenetriamine, Jeffamine T403 (trade name, manufactured by Huntsman, Mw: 390) and the like, as polyether polythiol, polythiol QE-340M (trade name, Toray Industries, Inc.) Fine chemicals).

  The mixing 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 polyaddition type curing agent is such that the reactive group of the first polyaddition type curing agent is an epoxy. In the case of a group that reacts with the group in a ratio of 1: 1, the equivalent ratio of the reactive group of the first polyaddition type curing agent to the epoxy group derived from the first polyepoxide component is 0.6 to 2.0. The ratio is preferably 0.8 to 1.5. When the first polyaddition type curing agent having a reactive group that reacts 1: 1 with the epoxy group is used, the equivalent of the reactive group of the first polyaddition type curing agent to the epoxy group derived from the first polyepoxide component When the ratio is within 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 lowering durability such as wear resistance and moisture resistance can be obtained.

  In the present invention, when a polyamine compound having active hydrogen is used as the first polyaddition type curing agent, the equivalent ratio of amine active hydrogen to epoxy group derived from the first polyepoxide component is 0.6 to 2.0. It is preferable to use so that it may become a ratio, and 0.8-1.5 are more preferable. Similarly to the above, if the equivalent ratio of amine active hydrogen to epoxy group is in the above range, it does not cause yellowing, and it is appropriate to have the above-mentioned water absorption without decreasing durability such as wear resistance and moisture resistance. Thus, a cured epoxy resin having a three-dimensional network structure cross-linked to the resin is obtained.

  Even when the water-absorbing layer-forming composition contains a compound having an epoxy group and / or a compound having amine active hydrogen in addition to the first polyepoxide component and the first polyaddition type curing agent, When a polyamine compound having active hydrogen is used as the addition type curing agent, for the same reason as described above, the equivalent ratio of the amine active hydrogen possessed by the first polyaddition type curing agent to the epoxy group derived from the first polyepoxide component is It is preferable to use so that it may become a ratio which will be 0.6-2.0.

  In addition, when the first cured epoxy resin is obtained by a polyaddition reaction between the first polyepoxide component and the first polyaddition type curing agent, the polyaddition reaction is performed according to the first catalyst type curing as necessary. It is also possible to carry out in the presence of an agent.

  The first catalyst-type curing agent is a reaction catalyst such as a Lewis acid and is a catalyst-type curing agent that catalyzes a polymerization reaction between polyepoxides and / or a polyaddition reaction between a polyepoxide and a polyaddition-type curing agent. Can be used without any particular restrictions.

  By using the first catalyst type curing agent, the effect of accelerating the crosslinking rate by the polyaddition reaction between the first polyepoxide component and the first polyaddition type curing agent, and the first polyepoxide component and the first weight The effect which reduces the malfunction which generate | occur | produces in the bridge | crosslinking site | part formed with an addition type hardening | curing agent is acquired.

  Specific examples of the first catalyst-type curing agent include curing catalysts such as tertiary amines, imidazoles, Lewis acids, onium salts, and phosphines. More specifically, 2-methylimidazole, 2-ethyl-4-methylimidazole, tris (dimethylaminomethyl) phenol, boron trifluoride-amine complex, methyl p-toluenesulfonate, diphenyliodonium hexafluorophosphate, tri Examples thereof include phenylsulfonium hexafluorophosphate. As a 1st catalyst type hardening | curing agent, these 1 type may be used independently and 2 or more types may be used together.

  The onium salts exemplified above, such as diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate, are catalytic curing agents that generate a Lewis acid catalyst by being decomposed by light such as ultraviolet rays, and are usually photocured. It is used as a catalyst-type curing agent that gives a cured epoxy resin.

  Of these, imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole are preferable as the first catalyst-type curing agent used in the present invention.

  A commercial item can also be used for the 1st catalyst type hardening agent. Examples of such commercially available products include Adekaoptomer SP152 (trade name, manufactured by ADEKA) as a triarylsulfonium salt that is a photocurable catalyst-type curing agent.

  6 mass% or less is preferable with respect to 100 mass% of 1st polyepoxide components, and, as for the usage-amount of a 1st catalyst type hardening | curing agent, 4 mass% or less is more preferable. If the usage-amount of the 1st catalyst type hardening | curing agent with respect to 100 mass% of 1st polyepoxide components is 6 mass% or less, the residue of a 1st catalyst type hardening | curing agent exists in the obtained 1st hardening epoxy resin. It is easy to suppress the appearance problems such as yellowing of the cured epoxy resin. In addition, since the 1st catalyst type hardening | curing agent is an arbitrary component, the minimum of the usage-amount is not specifically limited. However, from the viewpoint of promoting the curing reaction, it is preferable to use the first catalytic curing agent with a lower limit of about 0.5% by mass with respect to 100% by mass of the first polyepoxide component.

<Water absorbing layer forming composition>
The water absorption layer in the antifogging film of the antifogging glass article of the embodiment of the present invention is obtained by reacting the water absorbing layer forming composition containing the first polyepoxide component and the first polyaddition type curing agent. A water absorption layer mainly composed of a first cured epoxy resin.

  About the 1st polyepoxide component and 1st polyaddition type hardening agent which the composition for water absorption layer formation contains, and the 1st catalyst type hardening agent containing arbitrarily, the compound used, the ratio at the time of combining, etc. As described above, including preferred embodiments. The water-absorbing layer forming composition usually contains a solvent in addition to the first polyepoxide component, the first polyaddition type curing agent, and the first catalyst type curing agent optionally contained. In addition to these, reactive additives such as coupling agents, fillers, antioxidants, ultraviolet absorbers, infrared absorbers, light stabilizers and other non-reactive additives are contained as necessary. In addition, the said reactive additive is handled as a part of raw material component of a 1st hardening epoxy resin.

  Usually, the reaction between the first polyepoxide component and the first polyaddition-type curing agent in the water-absorbing layer-forming composition for obtaining the water-absorbing layer, and the reaction between these and the optional reactive additive, It is carried out after being applied as a water-absorbing layer-forming composition on the application surface (on the main surface of the multilayer glass or on the underlayer). When the water-absorbing layer-forming composition contains a solvent, these components may be reacted to some extent in the composition before being applied to the coated surface, then coated on the coated surface, dried, and further reacted. As described above, when the reactive component such as the first polyepoxide component and the first polyaddition type curing agent is reacted to some extent in the solvent as the water absorbing layer forming composition, the reaction temperature when the reaction is performed in advance is If it is set to 30 ° C. or higher, the curing reaction proceeds reliably, which is preferable.

(solvent)
The solvent used in the water-absorbing layer forming composition is a solvent having good solubility with respect to the first polyepoxide component, the first polyaddition type curing agent, and other components including optional components, and these The solvent is not particularly limited as long as it is an inert solvent with respect to the blending components, and specific examples thereof 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, isopropyl alcohol, and n-propyl alcohol. 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 polyaddition type hardening | curing agent, a 1st catalyst type hardening | curing agent, may be prepared as a mixture with a solvent. In such a case, the solvent contained in the mixture may be used as it is as a solvent in the water-absorbing layer-forming composition, and the water-absorbing layer-forming composition may contain the same or other solvents. May be added.

  The amount of the solvent in the water-absorbing layer-forming composition is 100% by mass with respect to the total mass of the total solid content in the first polyepoxide component, the first polyaddition type curing agent, and other various blended components. It is preferable that it is 40-500 mass%, and 80-300 mass% is more preferable.

  Here, the blending amounts of the first polyepoxide component, the first polyaddition type curing agent, and the first catalytic curing agent in the water absorbing layer forming composition are based on the total amount of the composition for the first polyepoxide component. 15-60 mass% is preferable and 18-50 mass% is more preferable. The blending amounts of the first polyaddition type curing agent and the first catalyst type curing agent are as described above.

  Among the additives optionally contained in the water-absorbing layer forming composition, the reactive additive includes a compound having one reactive group reactive with the first polyepoxide component such as alkyl monoamine, an epoxy group, an amino group, etc. And a coupling agent having a reactive group reactive with the first polyepoxide component and the first polyaddition type curing agent.

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

  The blending amount of the coupling agent in the water-absorbing layer-forming composition is such that the first polyepoxide component and the first polyaddition-type curing agent in the water-absorbing layer-forming composition are used in order to sufficiently exhibit the effect of the coupling agent blending. And it is preferable that it is 5-40 mass% with respect to 100 mass% of total mass of a 1st catalyst type hardening | curing agent, and 10-30 mass% is more preferable.

  For example, in the case of using a coupling agent having an epoxy group or an active amino group in a coupling agent such as a silane coupling agent, the first polyaddition type curing agent for the epoxy group derived from the first polyepoxide component The amount of the epoxy group and amine active hydrogen contained in these components is adjusted so that the equivalent ratio of the amine active hydrogen is 0.6 to 2.0. It is preferable to use the total amount added to the amount of the epoxy group and amine active hydrogen in the addition type curing agent in the calculation of the equivalent ratio of the amine active hydrogen to the epoxy group in the same range as the above equivalent ratio.

  As the filler, a filler made of a metal oxide is preferable. Examples of the metal oxide include silica, alumina, titania, and zirconia. Among these, silica is preferable. As the shape of the filler, a particle shape having an average primary particle diameter of 300 nm or less is preferable. The average primary particle size is more preferably 100 nm or less, and particularly preferably 50 nm or less. When the average primary particle diameter is 300 nm or less, the tendency of aggregation of particles in a composition containing the average particle diameter does not increase, and sedimentation of particles can be avoided. Moreover, when forming a water absorption layer with the composition containing this, generation | occurrence | production of the cloudiness (cloudiness value, haze) by scattering can be suppressed, and it is preferable to set it as the said particle diameter from the point of transparency maintenance. The lower limit of the average primary particle diameter is not particularly limited, but particles of about 2 nm that can be produced by the current technology can also be used. Here, the average primary particle diameter of the particles refers to that measured from an observation image with a transmission electron microscope.

  Moreover, the compounding quantity of a filler shall be 0.5-30 mass% with respect to 100 mass% of total mass of a 1st polyepoxide component, a 1st polyaddition type hardening | curing agent, and a 1st catalyst type hardening | curing agent. Preferably, 1-25 mass% is more preferable.

  As infrared absorbers, Re, Hf, Nb, Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, It consists of infrared absorbers or organic dyes composed of particles of metals such as Mo, oxides, nitrides, sulfides, silicon compounds of these metals, or inorganic compounds doped with dopants such as Sb, F, Sn or Sb. An infrared absorber etc. are mentioned. The average primary particle diameter in the inorganic compound particles used as the infrared absorber can be the same as the average primary particle diameter of the filler, including a suitable particle diameter.

  The blending amount of the infrared absorbent in the water-absorbing layer-forming composition is the first polyepoxide because the water-absorbing layer formed using the composition has a heat insulating effect by sufficient infrared shielding without impairing the effects of the present invention. 0.5-15 mass% is preferable with respect to 100 mass% of total mass of a component, a 1st polyaddition type hardening | curing agent, and a 1st catalyst type hardening | curing agent, and 10-15 mass% is more preferable. When blending inorganic compound particles as an infrared absorber, the inorganic compound particles also fulfill the function as the filler. Therefore, in that case, it is possible to reduce the blending amount of the filler by the blending amount of the inorganic compound particles.

  Antioxidants include phenolic antioxidants that suppress the oxidation of resins by capturing and decomposing peroxy radicals, and phosphorus antioxidants that suppress the oxidation of resins by decomposing peroxides. In the present invention, a phenolic antioxidant is preferably used.

  Examples of the ultraviolet absorber include conventionally known ultraviolet absorbers, specifically, benzophenone compounds, triazine compounds, benzotriazole compounds, and the like. The maximum absorption wavelength of light of the ultraviolet absorber is in the range of 325 to 425 nm, and preferably approximately in the range of 325 to 390 nm. Thus, the ultraviolet absorber which has an absorptivity with respect to the ultraviolet of a comparatively long wavelength is used preferably from the characteristic.

  Examples of the light stabilizer include hindered amines; nickel complexes such as nickel bis (octylphenyl) sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, and the like. .

  In the composition for forming the water absorbing layer, the blending amount of the antioxidant, the ultraviolet absorber, and the light stabilizer is sufficient so that the water absorbing layer formed using these does not impair the effects of the present invention and functions by each additive. From the point which can be exhibited to 0.5 to 5 mass for every additive with respect to the total mass of 100 mass% of a 1st polyepoxide component, a 1st polyaddition type hardening | curing agent, and a 1st catalyst type hardening | curing agent. % Is preferable, and 0.5 to 1% by mass is more preferable.

  A leveling agent, an antifoaming agent, a viscosity adjusting agent, etc. can be further added to the composition for forming a water absorbing layer as necessary from the viewpoint of improving the film formability.

  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, and viscosity modifiers include acrylic copolymers, polycarboxylic acid amides, modified urea compounds and the like. Each component may be used alone or in combination of two or more of the exemplified compounds. In addition, a hydrolyzable silane compound having a hydrophobic group, for example, a polyfluoroalkyl group or a long-chain alkyl group having 6 to 22 carbon atoms, may be added to the water absorbing layer forming composition. The blending amount of various components in the water-absorbing layer-forming composition is 100% by mass with respect to the total mass of the first polyepoxide component, the first polyaddition type curing agent and the first catalytic curing agent for each component. And 0.001 to 10% by mass.

<Water absorption layer>
The water absorption layer in the antifogging glass article of the embodiment of the present invention is a three-dimensional product obtained by reacting the first polyepoxide component and the first polyaddition curing agent contained in the water absorption layer forming composition. It is composed mainly of the first cured epoxy resin having a network structure. Due to the properties of the first cured epoxy resin described above, the antifogging time (T ₄₅ ) has a high water absorption of 40 seconds or more and wear resistance. It is a layer having both durability such as moisture resistance.

  When the water absorbing layer forming composition contains the first catalyst type curing agent, the reaction between the first polyepoxide component and the first polyaddition type curing agent is performed in the presence of the first catalyst type curing agent. To be done. 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-absorbing layer in a form bonded to a part of the three-dimensional network structure of the first cured epoxy resin. The optional non-reactive additive is one that is uniformly dispersed and included in the three-dimensional network structure of the first cured epoxy resin and exists in the water absorption layer.

(Underlayer)
In the antifogging glass article 10A, the antifogging film 41 further includes a base layer 41b having a saturated water absorption of 10 mg / cm ³ or less between the glass plate 11 and the water absorbing layer 41a. The underlayer is an optional layer in the antifogging film according to the antifogging glass article of the embodiment of the present invention.

The saturated water absorption amount of the underlayer is 10 mg / cm ³ or less, and the water absorption is set lower than that of the water absorption layer. The saturated water absorption amount of the underlayer is more preferably 8 mg / cm ³ or less. By setting the saturated water absorption amount of the underlayer to 10 mg / cm ³ or less, as explained above, the difference in the degree of expansion / contraction at the bonding interface between the double-layer glass and the underlayer, in practice, as described above. Becomes smaller, and the antifogging film can be prevented from being peeled off from the multilayer glass. On the other hand, from the viewpoint of reducing the degree difference of the expansion and contraction of the base layer and the water-absorbing layer in the antifogging film, the saturated water absorption of the underlayer, 1 mg / cm ³ or more preferably, 3 mg / cm ³ or more and more preferably .

  The thickness of the underlayer is preferably 2 μm or more, more preferably 3 μm or more. If the film thickness of the underlayer is 2 μm or more, it is possible to prevent the antifogging film from peeling from the substrate. The film thickness of the underlayer is preferably 8 μm or less, more preferably 6 μm or less, from the viewpoint of reducing material costs and improving the yield rate. In addition, since peeling resistance calculated | required by a base layer in an anti-fogging glass article changes with uses, what is necessary is just to change the design of a base layer suitably according to the performance calculated | required.

The underlayer is not particularly limited as long as it has water absorption performance as described above, but a layer mainly composed of the same material as that of the water absorption layer is preferable from the viewpoint of improving the adhesion with the water absorption layer. That is, the underlayer is a layer mainly composed of the second cured epoxy resin obtained by reacting the underlayer-forming composition containing the second polyepoxide component and the second polyaddition type curing agent. preferable. That the base layer is mainly composed of the second cured epoxy resin means that the ratio of the second cured epoxy resin in the entire base layer is 80% by mass or more as in the case of the water absorbing layer.
Hereinafter, the second cured epoxy resin obtained by reacting the second polyepoxide component mainly constituting the base layer with the second polyaddition type 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, a glycidyl ether-based polyepoxide or a glycidyl ester-based polyepoxide usually used as a raw material component of the cured epoxy resin so that the water absorption is in the above preferred range. Polyepoxides appropriately selected from glycidylamine-based polyepoxides and the like can be used.

  The molecular weight of the polyepoxide used as the second polyepoxide component is not particularly limited, but the coating liquid is insufficiently spread when the liquid composition (coating liquid) containing the polyepoxide is applied onto the substrate, and the coating film is uneven. From the viewpoint of avoiding poor appearance such as crystallization, a polyepoxide having a molecular weight of about 200 to 1000 is preferred. 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.

  The second polyepoxide component may be any of an aliphatic polyepoxide, an alicyclic polyepoxide, and an aromatic polyepoxide. For example, a three-dimensional network structure of a cured epoxy resin obtained by selecting an aromatic polyepoxide. It is possible to reduce the water absorption by making the space hard and reducing the space.

  The aromatic polyepoxide 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. Among these aromatic polyepoxides, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether are preferably used as the second polyepoxide component.

  Even in the alicyclic polyepoxide, although depending on the type and number of the ring structure, the space of the three-dimensional network structure can be reduced by the presence of the ring structure, and the water absorption of the cured epoxy resin can be lowered. An alicyclic 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. Examples thereof include epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.

  Further, even if an aliphatic polyepoxide having no ring structure is used, if the number of cross-linking points is increased, the resulting cured epoxy resin has a dense three-dimensional network structure, and a space for water retention is reduced, resulting in low water absorption. It is considered to be. As the aliphatic polyepoxide used for the second polyepoxide component, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc., classified into aliphatic glycidyl ether-based polyepoxides derived from aliphatic polyols are preferable. .

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, for example, the second polyepoxide component is an aliphatic derived from aliphatic polyols. In the case of a glycidyl ether polyepoxide, the epoxy equivalent is preferably 100 to 200, more preferably 100 to 150.
A 2nd polyepoxide component may be comprised from 1 type of these polyepoxides, and may be comprised from 2 or more types.

  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 product described in the first polyepoxide component, a commercial product of an aliphatic polyepoxide having a lower molecular weight than these, bisphenol A diglycidyl ether, jER828 (trade name, manufactured by Mitsubishi Chemical Corporation) Examples of bisphenol F diglycidyl ether include Adeka Resin EP4901 (trade name, manufactured by ADEKA).

<Second polyaddition type curing agent>
The second cured epoxy resin that mainly constitutes the foundation layer is a second cured epoxy resin obtained by reacting the second polyepoxide component with the second polyaddition type curing agent.

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

  As the second polyaddition type curing agent, for example, by selecting a polyaddition type curing agent having an aromatic ring that is not selected as a preferred polyaddition type curing agent in the first polyaddition type curing agent. The water absorption of the resulting cured epoxy resin can be lowered. Depending on the degree of water absorption required for the underlayer, a second cured epoxy obtained by using a compound having an aromatic ring in at least one of the second polyepoxide component and the second polyaddition type curing agent is used. The water absorption of the resin can be set in the desired range.

  Further, even when a polyepoxide having no aromatic ring is used as the second polyepoxide component and a polyaddition type curing agent having no aromatic ring is used as the second polyaddition type curing agent, crosslinking is performed as described above. The water absorption of the obtained 2nd cured epoxy resin can be made into the said desired range by combining so that a point may increase. Furthermore, the second cured epoxy resin having no aromatic ring thus obtained is superior in terms of weather resistance compared to the second cured epoxy resin having an aromatic ring.

As the polyaddition type curing agent having no aromatic ring, the same curing agent as the polyaddition type curing agent having no aromatic ring described in the first polyaddition type curing agent can be used. Examples of the polyaddition type curing agent having an aromatic ring include polyamine compounds having an aromatic ring and aromatic polycarboxylic acid anhydrides. Specific examples of the polyamine compound having an aromatic ring include phenylenediamine, xylylenediamine, diaminodiphenylmethane, and the like, and examples of the aromatic polycarboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, and anhydrous anhydride. Examples include pyromellitic acid.
As a 2nd polyaddition type hardening | curing agent, these 1 type may be used independently and 2 or more types may be used together.

  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 polyaddition type curing agent is such that the reactive group of the second polyaddition type curing agent is an epoxy. In the case of a group that reacts with the group at a ratio of 1: 1, the equivalent ratio of the reactive group of the second polyaddition type curing agent to the epoxy group derived from the second polyepoxide component is 0.8 to 1.5. The ratio is preferably 0.9 to 1.2. When using a second polyaddition type curing agent having a reactive group that reacts 1: 1 with an epoxy group, the equivalent weight of the reactive group of the second polyaddition type curing agent to the epoxy group derived from the second polyepoxide component If the ratio is within the above range, the first cured epoxy having a dense three-dimensional network structure by crosslinking at a sufficiently large number of crosslinking points at room temperature without increasing the reaction temperature and accelerating the polyaddition reaction. A second cured epoxy resin having lower water absorption than the resin is obtained.

  When using a polyamine compound having active hydrogen as the second polyaddition type curing agent, the ratio in which the equivalent ratio of amine active hydrogen to the epoxy group derived from the second polyepoxide component is 0.8 to 1.5; It is preferable to use so that it may become a ratio which becomes 0.9-1.2. 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 lower water absorption than the first cured epoxy resin is obtained. In addition, it is preferable that the equivalent ratio of the amine active hydrogen with respect to an epoxy group is the same range as the above also, when calculating about the total solid content which the composition for base layer formation contains. Moreover, about the calculation method of the equivalent ratio of the amine active hydrogen with respect to an epoxy group in this case, it can carry out similarly to the case of the composition for water absorption layer formation.

  In addition, if the mass ratio of the second polyaddition type curing agent to the second polyepoxide component is too large, the physical properties of the second cured epoxy resin obtained may be insufficient. The ratio of the second polyaddition type curing agent with respect to 100% by mass is preferably 60% by mass or less.

  In addition, when obtaining the 2nd hardening epoxy resin used for this invention by the polyaddition reaction of a 2nd polyepoxide component and a 2nd polyaddition type hardening | curing agent, this polyaddition reaction is made into 2nd as needed. It is also possible to carry out in the presence of a catalytic curing agent. As the second catalyst-type curing agent used for the second cured epoxy resin as necessary, the same curing agent as the first catalyst-type curing agent described in the first cured epoxy resin can be used. The blending amount of the second catalytic curing agent in the second cured epoxy resin can be the same as the blending amount of the first catalytic curing agent in the first curing epoxy resin.

Hereinafter, the underlayer-forming composition used for forming the underlayer mainly composed of the second cured epoxy resin will be described.
(Underlayer forming composition)
The underlayer-forming composition usually contains a solvent in addition to the second polyepoxide component, the second polyaddition-type curing agent, and the second catalyst-type curing agent blended as necessary. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed. Regarding the second polyepoxide component, the second polyaddition type curing agent, and the second catalyst type curing agent blended as required, contained in the composition for forming the underlayer, the compound used and the combination It is as above-mentioned including preferable aspects, such as a ratio.

  Here, the composition for forming the underlayer is the second polyepoxide component and the second polyaddition type in the composition before being applied to the coating surface as a composition containing a solvent, like the composition for forming the water absorption layer. The curing agent may be allowed to react to some extent in the presence of the second catalyst-type curing agent that is blended as necessary, then applied to the coated surface, dried, and further reacted. The conditions for the reaction in advance can be the same as those in the case of the water absorbing layer forming composition.

  The solvent used in the composition for forming the underlayer includes a second polyepoxide component, a second polyaddition type curing agent, a second catalyst type curing agent blended as necessary, and other optional components. The solvent is not particularly limited as long as it is a solvent having good solubility with respect to the components and is inactive with respect to these blended components, and specifically, the same solvents as the water-absorbing layer-forming composition are mentioned. It is done. The preferred embodiment of the solvent is the same as that of the water absorbing layer forming composition.

  Further, the amount of the solvent in the composition for forming the underlayer is blended with the second polyepoxide component, the second polyaddition type curing agent, the second catalytic curing agent blended as necessary, and other arbitrarily. It is preferable that it is 200-950 mass% with respect to 100 mass% of total mass of the total solid in various compounding components, and 400-950 mass% is more preferable.

  Here, the blending amount of the second polyepoxide component, the second polyaddition type curing agent, and the second catalytic curing agent blended as necessary in the composition for forming the underlayer is about the second polyepoxide component. Is preferably 4 to 10% by mass with respect to the total amount of the composition. The total amount of the second polyaddition type curing agent and the second catalytic curing agent blended as necessary is the composition. It is preferable that it is 0.1-5.0 mass% with respect to the whole quantity.

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

About the coupling agent arbitrarily mix | blended with the composition for base layer formation, it can be made to be the same as that of the coupling agent used for the said composition for water absorption layer formation including the compound used and a preferable aspect.
Moreover, about the quantity of the coupling agent mix | blended with the composition for base layer formation, it is the 2nd polyepoxide component, the 2nd polyaddition type hardening | curing agent, and the 2nd catalyst type hardening | curing agent mix | blended as needed. It is preferable that the mass ratio of a coupling agent is 5-50 mass% with respect to 100 mass% of total mass, and 10-40 mass% is more preferable.

  The upper limit of the amount of coupling agent is limited by the physical properties and functions of the coupling agent. When used for the purpose of improving the adhesion of the base layer mainly composed of the second cured epoxy resin, the second polyepoxide component, the second polyaddition type curing agent, and the second blended as necessary. The mass ratio of the coupling agent to the total mass of the catalyst-type curing agent is preferably 50% by mass or less, and more preferably 40% by mass or less.

  On the other hand, when adjusting the physical properties such as water absorption of the base material mainly composed of the second cured epoxy resin by the coupling agent or by the second polyaddition type curing agent and the coupling agent, the second polyepoxide is used. The mass ratio of the coupling agent to the total mass of 100% by mass of the component, the second polyaddition type curing agent and the second catalytic curing agent blended as necessary is preferably 40% by mass or less, and 20% by mass. The following is more preferable. If the amount of the coupling agent used is not excessive, it is possible to prevent the base material mainly composed of the second cured epoxy resin from being colored due to oxidation or the like when exposed to a high temperature.

In addition, as a compounding quantity of the coupling agent with respect to the composition for base layer formation, for example, when a silane coupling agent is used, it is preferable that it is 0.1-3.0 mass%, 0.5 More preferably, it is -2 mass%.
Here, regarding a particularly preferable composition in the composition for forming an underlayer containing the silane coupling agent, the polyamine having 4 to 10% by mass of the second polyepoxide component and active hydrogen with respect to the total amount of the composition. Examples include a composition containing 0.1 to 4.0% by mass of a compound, 0.1 to 3.0% by mass of a silane coupling agent, and 70 to 95% by mass of a solvent.

  In addition, when the composition for forming an underlayer contains a coupling agent having an amino group having active hydrogen or a coupling agent having an epoxy group as a coupling agent, the equivalent ratio of amine active hydrogen to the epoxy group The equivalent ratio of the active hydrogen possessed by the reactive group (other than the amino group having active hydrogen) possessed by the second polyaddition-type curing agent with respect to the epoxy group is calculated using this, and this is within the above range. It is preferable to adjust the blending amount of each component so that

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

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

  Regarding the amount of tetraalkoxysilane and / or oligomer thereof blended in the underlayer-forming composition, the second polyepoxide component, the second polyaddition type curing agent, and the second catalyst type blended as necessary 10-40 mass% is preferable in conversion of an oxide with respect to 100 mass% of total mass of a hardening | curing agent, and 10-30 mass% is more preferable.

It is preferable that the composition for forming the underlayer further contains an antioxidant as an optional component in order to improve the weather resistance of the obtained underlayer, for the same reason as the composition for forming the water absorbing layer.
About the antioxidant arbitrarily mix | blended with the composition for base layer formation, it can be made to be the same as that of the antioxidant used for the said composition for water absorption layer formation including the compound used and a preferable aspect.

  Moreover, about the quantity of antioxidant mix | blended with the composition for base layer formation, it is 2nd polyepoxide component, 2nd polyaddition type hardening | curing agent, and 2nd catalyst type hardening | curing agent mix | blended as needed. It is preferable that it is 0.5-3 mass% with respect to 100 mass% of total mass, and 0.5-1 mass% is more preferable.

  Further, for the underlayer-forming composition, if necessary, the same filler, ultraviolet absorber, infrared absorber, light stabilizer, leveling agent as those contained in the water-absorbing layer-forming composition, Arbitrary components, such as an antifoamer and a viscosity modifier, can be added in the same amount.

If an underlayer is formed using such an underlayer-forming composition, the second polyepoxide component and the second polyaddition type curing agent contained in the composition are blended as necessary. Underlayer 2 having a saturated water absorption of 10 mg / cm ³ or less mainly composed of the second cured epoxy resin having a three-dimensional network structure obtained by reaction in the presence of the catalyst type curing agent 2 is obtained. The reaction conditions will be described in the production method described later.

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

As described above, in the present invention, the base layer arbitrarily provided between the double-glazed glass and the water-absorbing layer has been described as an example in which the second cured epoxy resin is mainly used, but the base layer has a saturated water absorption of 10 mg / It should just be cm < ³ > or less, and is not limited to this.

(Anti-fogging film)
In the antifogging glass article 10A, the antifogging film 41 is formed on one main surface 11a of the multilayer glass 20A. As described above, when the antifogging glass article 10A is used for, for example, a door of a cold insulation showcase, the antifogging glass article 10A is disposed so that the antifogging film 41 is located inside the warehouse. . The anti-fogging film 41 arranged on the inner side has a water-absorbing layer having a high anti-fogging property with an anti-fogging time (T ₄₅ ) of 40 seconds or more. It can be effectively suppressed.

The anti-fogging film 41 has an anti-fogging time (T ₄₅ ) of 40 seconds or more due to the high water absorption of the water absorption layer 41a. The antifogging time (T ₄₅ ) of the antifogging film in the antifogging glass article of the embodiment of the present invention is preferably 50 seconds or longer, and more preferably 60 seconds or longer. In addition, since the anti-fogging performance requested | required of an anti-fogging glass article changes with uses, what is necessary is just to change the design of an anti-fogging film | membrane suitably according to the calculated | required performance.
In addition, the soda-lime glass which has not performed the anti-fogging process usually fogs in approximately 0 to 1 second in the above test.

<Formation method of anti-fogging film>
The antifogging film 41 may be formed on the main surface 11a of the glass plate 11 after assembling the multi-layer glass 20A, but normally, on the main surface 11a of the glass plate 11 before assembling the multi-layer glass 20A. It is formed. Specifically, the antifogging film 41 can be formed by the following method (1) or (2). The following method is a method for manufacturing the antifogging film 41 having the base layer 41b and the water absorption layer 41a. However, in the case of the antifogging film consisting of only the water absorption layer, the base layer is not formed by the following method. Similarly, a water absorption layer may be directly formed on the surface of the antifogging film.

  In the following description, a glass plate that forms an antifogging film is also referred to as a substrate. The main surface on which the antifogging film of the glass plate (substrate) is formed is also referred to as a surface to be formed.

(1) A base layer forming composition is applied to the surface on which the substrate is formed and reacted to form a base layer, and then the water absorbing layer forming composition is applied to the surface of the base layer and reacted to form a water absorbing layer. To obtain an antifogging film.
(2) When the water-absorbing layer forming composition is reacted to obtain the water-absorbing layer, it is formed into a film, and the surface to be formed of the substrate and the film (water-absorbing layer) are used as the base layer-forming composition as an adhesive. And a method of obtaining an antifogging film in which a base layer and a water absorbing layer are laminated from the surface to be formed by bonding by forming a base layer as an adhesive layer between them.

  In the method (2), a film-like water-absorbing layer is formed on a releasable support, and this is separated from the support, and the composition for forming the underlayer is adhered to the surface on which the substrate is formed. It is also possible to use a film-like water-absorbing material (water-absorbing layer) together with this support, and a method of adhering to the surface on which the substrate is formed using the underlayer-forming composition as an adhesive. . The support to be used is not particularly limited as long as it does not impair the effects of the present invention, but an acrylic resin film such as polymethyl methacrylate is preferably used.

  In the present invention, among these methods for forming an antifogging film, the method (1) can maintain a good appearance when a base layer or a water absorption layer is provided on a large-area surface to be formed or during industrial mass production. Is more preferable. The underlayer-forming composition also comprises an underlayer-forming composition comprising a second polyepoxide component and a second polyaddition curing agent for forming an underlayer mainly composed of the second cured epoxy resin. It is preferable to use a product. Hereinafter, the formation method of the anti-fogging film | membrane by the method of said (1) using such a composition for base layer formation is demonstrated.

  The antifogging film is formed by, for example, applying a composition for forming an underlayer containing (A) the second polyepoxide component and the second polyaddition type curing agent to the surface on which the substrate is formed and reacting the second anti-fogging film. A step of forming a base layer mainly composed of a cured epoxy resin; and (B) a polyepoxide component total amount of polyepoxide (A) having a chlorine content of 2% by mass or less and a water content of 90% or more on the surface of the base layer. Water absorption mainly composed of the first cured epoxy resin by applying and reacting a water-absorbing layer-forming composition containing the first polyepoxide component containing 90% by mass or more with the first polyaddition curing agent And a step of forming a layer.

The components contained in the underlayer-forming composition and the water-absorbing-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 step (A), in order to form an underlayer on the surface of the substrate, the method for applying the underlayer-forming composition obtained above to the surface of the substrate is not particularly limited. And known methods such as flow coating, dip coating, spin coating, spray coating, flexographic printing, screen printing, gravure printing, roll coating, meniscus coating, die coating, and wiping. . The coating thickness of the composition for forming the underlayer is set such that the thickness of the underlayer finally obtained by reaction of the reaction components in the composition falls within the above range.

After coating the base layer forming composition on the substrate, the base layer mainly composed of the second cured epoxy resin is subjected to curing treatment under conditions suitable for the reaction components used by removing the solvent by drying if necessary. And Specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. Moreover, the reaction component in the composition for forming the underlayer, that is, the second polyepoxide component and the second polyaddition type curing agent in the presence of the second catalytic curing agent blended as necessary. Specific examples of the reaction conditions include heat treatment at 70 to 150 ° C. for about 1 to 60 minutes. 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 layer forming composition in the step (B) to the surface of the base layer formed on the surface on which the substrate is formed in the step (A), the method for applying the base layer-forming composition is described. You can do the same. The coating thickness of the water-absorbing layer forming composition is set such that the thickness of the water-absorbing layer finally obtained by reaction of the reaction components in the composition falls within the above range.

After applying the water-absorbing layer-forming composition on the underlayer, the solvent is removed by drying as necessary, and a curing treatment is performed under conditions suitable for the reaction components to be used. Layer. Specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. Further, the reaction component in the water-absorbing layer forming composition, that is, the first polyepoxide component and the first polyaddition type curing agent, in the presence of the first catalytic curing agent blended as necessary. Specific examples of reaction conditions include heat treatment at 50 to 120 ° C. for about 10 to 60 minutes. 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.
In this way, the antifogging film is formed on the surface to be formed of the substrate through the steps (A) and (B).

  The antifogging glass article 10A having the antifogging film 41 on one main surface 11a of the multilayer glass 20A shown in FIG. 1 has been described above. The antifogging glass article of the embodiment of the present invention may also be provided with an antifogging film having a water absorbing layer having the predetermined antifogging performance on both main surfaces of the multilayer glass. FIG. 3 shows a cross-sectional view of an example of such an antifogging glass article provided with the predetermined antifogging film on both main surfaces of the multilayer glass.

  The antifogging glass article 10B shown in FIG. 3 has antifogging films 41 and 42 on both main surfaces 11a and 13a of the multilayer glass 20B. The multi-layer glass 20B includes three glass plates 11, 12, and 13 arranged to face each other in that order, and a spacer 21 and a glass plate arranged so as to seal the peripheral portions of the glass plate 11 and the glass plate 12. 12 and a spacer 22 arranged to seal the peripheral edge of the glass plate 13. The multilayer glass 20B has an intermediate layer 31 and an intermediate layer 32 between the glass plate 11 and the glass plate 12, and between the glass plate 12 and the glass plate 13, which are disposed to face each other.

  The multi-layer glass 20B of the anti-fogging glass article 10B has three glass plates 11 and 12 separated by spacers 21 while the multi-layer glass 20A of the anti-fogging glass article 10A separates the two glass plates 11 and 12 by a spacer 21. Although the glass plates 11, 12, and 13 are separated from each other by the spacers 21 and 22, the respective constituent elements can be the same.

  Specifically, the three glass plates 11, 12, and 13 in the multilayer glass 20B can be made in the same manner as the glass plates in the multilayer glass 20A, respectively. The three glass plates may be the same or different in thickness, material, and the like. The spacers 21 and 22 in the multilayer glass 20B can be made in the same manner as the spacers in the multilayer glass 20A. The thickness and material of the spacer 21 and the spacer 22 may be the same or different.

  Regarding the intermediate layer 31 as a sealed space surrounded by the spacer 21 and the glass plates 11 and 12 and the intermediate layer 32 as a sealed space surrounded by the spacer 22 and the glass plates 12 and 13, the gas to be sealed is also a multilayer. This can be done in the same manner as for the glass 20A.

  Although it depends on the thickness of the glass plate and spacer, the type of gas sealed in the intermediate layer, etc., the double-layer glass with three glass plates such as the double-layer glass 20B is usually more like the double-layer glass 20A. High heat insulation can be expected as compared with double-layer glass made of two glass plates.

In the multilayer glass 20B, the two main surfaces correspond to the main surface 11a and the main surface 13a that are not in contact with the intermediate layers 31 and 32.
The multilayer glass 20B can be produced by a normal method, similarly to the multilayer glass 20A. The anti-fogging films 41 and 42 disposed on the principal surfaces 11a and 13a on the side of the glass plates 11 and 13 of the multilayer glass 20B that do not face the intermediate layers 31 and 32, respectively, assembled the multilayer glass 20B. Later, it may be formed on the main surfaces 11a and 13a of the glass plates 11 and 13, respectively, but usually on the main surface 11a of the glass plate 11 and on the main surface 13a of the glass plate 13 before assembling the multilayer glass 20B. Formed.

  When the antifogging glass article 10B is used for, for example, a door of a cold insulation showcase, the antifogging film 41 inside the warehouse exhibits an antifogging function when the door is opened and closed as described above. On the other hand, the antifogging film 42 on the outside of the warehouse functions to suppress the occurrence of fogging on the outside of the warehouse when the temperature of the outside of the warehouse rises with the door closed and the inside of the warehouse sufficiently cooled.

The antifogging films 41 and 42 that the antifogging glass article 10B has on both main surfaces of the multilayer glass 20B can be formed in the same manner as the antifogging film 41 in the antifogging glass article 10A. Similarly to the above, the antifogging films 41 and 42 may be composed of a single water-absorbing layer whose antifogging time (T ₄₅ ) mainly composed of the first cured epoxy resin is 40 seconds or more. A structure in which a base layer having a saturated water absorption amount of 10 mg / cm ³ or less and the water absorption layer are laminated in that order from the main surface side of the glass 20B may be employed.

  The anti-fogging films 41 and 42 disposed on both main surfaces of the multilayer glass 20B may be the same or different as long as the above characteristics are maintained.

As mentioned above, although embodiment of this invention was described exemplifying the antifogging glass articles 10A and 10B shown in FIGS. 1 to 3, the antifogging glass article of the present invention is not limited to these. As long as it does not contradict the spirit of the present invention, the configuration can be changed as necessary.
For example, the anti-fogging film in the anti-fogging glass article of the embodiment of the present invention has various functions within or below the water absorption layer formed on the substrate, as long as the effects of the present invention are not impaired as necessary. 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.

  Furthermore, the glass plate constituting the multilayer glass in the antifogging glass article of the embodiment of the present invention has functional layers such as an ultraviolet shielding layer and an infrared absorption layer on the main surface facing the intermediate layer. Also good. For example, in the antifogging glass article 10A shown in FIG. 1 and the antifogging glass article 10B shown in FIG. 3, the main surface 11b facing the intermediate layer of the glass plate 11 and the intermediate layer of the glass plate 13 are faced. A Low-E film or the like having a configuration in which Ag or the like is sandwiched between dielectric films may be disposed on the main surface 13b or the like on the side. Further, when the antifogging glass article of the embodiment of the present invention has an antifogging film only on one main surface of the multilayer glass, functional layers such as an ultraviolet shielding layer and an infrared absorption layer are provided on the other main surface. It is good also as a structure to have.

  The antifogging glass article of the embodiment of the present invention is suitably used as a door for a cold display case. Other uses include building windows, vanity mirrors, vehicle windows, and the like.

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 15 are examples, and examples 16 to 21 are comparative examples.
The abbreviations and physical properties of the compounds used in Examples and Comparative Examples are summarized below. Denacol is a trade name of Nagase ChemteX Corporation.

(1) Polyepoxide polyepoxide (A)
EX1610: Denacol EX-1610 (aliphatic polyglycidyl ether; chlorine content; 0.5 mass%, water content: 100%, Mw: 1130, epoxy equivalent: 170)
Polyepoxide (B)
EX521: Denacol EX-521 (polyglycerol polyglycidyl ether; chlorine content; 6.4% by mass, water solubility: 100%, Mw: 1294, epoxy equivalent: 179)
jER828 (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A diglycidyl ether; chlorine content: 0.1% by mass, water content: insoluble, Mw: 340, epoxy equivalent: 190)

(2) Polyaddition type curing agent T403: Jeffamine T403 (trade name, manufactured by Huntsman, Mw: 390, amine active hydrogen equivalent: 78), polyoxyalkylene triamine (3) catalyst type curing agent 2MZ: 2-methylimidazole (Made by Shikoku Chemicals)
(4) Various additives KBM903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.): 3-aminopropyltrimethoxysilane BYK307 (trade name, manufactured by Big Chemie): polyether-modified polydimethylsiloxane

[Examples 1 to 21]
On the soda lime glass substrate, the underlayer forming composition is prepared by the following method to form the underlayer, and then the water absorbing layer forming composition is prepared thereon to form the water absorbing layer, with an antifogging film. A glass plate was produced. Using this glass plate with an antifogging film as a sample, the antifogging film on the glass substrate was evaluated. The performance of the antifogging film in the glass plate with the antifogging film can be said to be the same even when the glass plate is changed to a double-layer glass.

<Underlayer forming composition>
In a glass container in which a stirrer and a thermometer are set, 1-methoxy-2-propanol (6.00 g, manufactured by Daishin Chemical Co., Ltd.), bisphenol A diglycidyl ether (5.51 g, jER828), polyoxyalkylenetriamine ( 1.59 g, Jeffamine T403,) and aminosilane (0.78 g, KBM903) were added and stirred at 35 ° C. for 120 minutes. Subsequently, 1-methoxy-2-propanol (66.14 g, manufactured by Daishin Chemical Co., Ltd.) was added to obtain an underlayer-forming composition P-1.

<Preparation of water-absorbing layer forming composition>
In a glass container in which a stirrer and a thermometer are set, 4.71 g (manufactured by Daishin Chemical Co., Ltd.) of methyl ethyl ketone and aliphatic polyglycidyl ether (Denacol EX-1610) in the amounts shown in Tables 1 to 3 in each example. Polyglycerin polyglycidyl ether (Denacol EX-521) was added and dissolved, and then polyoxyalkylene triamine (Jefamine T403), aminosilane (KBM903) and 2-methylimidazole were added with stirring, and the mixture was added at 120 ° C. at 120 ° C. Stir for minutes. Next, 4.28 g (manufactured by Daishin Chemical Co., Ltd.) of methyl ethyl ketone and a leveling agent (0.01 g, BYK307, manufactured by Big Chemie) were added with stirring to obtain a water-absorbing layer forming composition.

<Manufacture of glass plate with antifogging film>
Using the various compositions obtained with the water absorbing layer forming composition obtained above, an antifogging film is formed on a soda lime glass substrate as follows, and as an antifogging test sample in each example, antifogging is performed. A glass plate with a film was produced. In each example, all the underlayers were produced under the same conditions using the underlayer-forming composition P-1.

As the substrate, a clean soda lime glass substrate (water contact angle 3 degrees, 100 mm × 100 mm × thickness 4 mm), which was polished and cleaned with cerium oxide, was obtained on the surface of the glass substrate as described above. The underlayer-forming composition P-1 was applied by spin coating (conditions: 100 rpm, 30 seconds) and held in an electric furnace at 100 ° C. for 30 minutes to form an underlayer. The undercoat layer had a thickness of 3.5 μm, and the saturated water absorption was 3.2 mg / cm ³ . This value is common to all examples.

  Next, the water-absorbing layer-forming composition obtained in each of the above examples was applied to the surface of the formed underlayer by spin coating (conditions: 50 rpm, 30 seconds) and held in an electric furnace at 100 ° C. for 30 minutes to form a water-absorbing layer. A glass plate with an antifogging film having an antifogging film consisting of two layers was obtained.

Evaluation of the glass plate with an antifogging film in each example was performed as follows. A result is shown in Table 1-Table 3 with the component composition in the composition for water absorption layer formation used for each example.
[Measurement of film thickness]
A cross-sectional image of the glass plate with the antifogging film was taken with a scanning electron microscope (manufactured by Hitachi, Ltd., S4300), and the film thicknesses of the underlayer and the water absorption layer were measured.

[Evaluation of anti-fogging property]
With respect to the antifogging film, the antifogging time (T ₄₅ ) in the 45 ° C. steam test was measured by the above method. In the present invention, the antifogging time (T ₄₅ ) of the antifogging film is 40 seconds or more, preferably 50 seconds or more, and more preferably 60 seconds or more. Here, antifogging time antifogging film _{(T 45)} corresponds to the anti-fogging time of the water-absorbing layer _{(T 45).}

[Evaluation as a cold insulation showcase door (RID evaluation)]
Evaluation in the case of using an antifogging glass article as a door for a cold insulation showcase was performed as follows.
After the glass plate with the antifogging film obtained in each example was attached to the inside of the reach door using adhesive double-sided tape so that the antifogging film was inside, the door was closed and cooled to -25 ° C. Left for 1 hour. Then, after confirming that the antifogging film surface of the glass plate with an antifogging film was cooled to −15 ° C., the reach door was opened and the time until clouding was measured. External environmental conditions are 25 ° C. and 75% RH. As the anti-fogging property of the reach indoor, it takes 30 seconds or more until fogging in the above test, and preferably 60 seconds or more. In the evaluation of each example, the case where no fogging occurred for 60 seconds or more was evaluated as “no fogging”.

[Evaluation of initial yellowing]
In the antifogging film of the glass plate with the antifogging film obtained in each example, the YI value, which is an index of yellowness, was measured using a Spectrophotometer SD6000 manufactured by Nippon Denshoku Industries Co., Ltd. A larger YI value indicates stronger yellowness. In addition, YI (C light source 2 degree | times) of the soda-lime glass which is not normally antifogging processed is -0.46.

[Evaluation of wear resistance]
Using a reciprocating traverse tester (wear: felt) manufactured by KT Corporation, the antifogging film surface of the glass sheet with antifogging film obtained in each example was subjected to 50 reciprocating abrasions at a load of 4.0 N, before and after the abrasion test. The haze value change ΔH (%) was measured. ΔH is preferably 0.5% or less, and more preferably 0.1% or less.

  The antifogging glass article of the present invention has high antifogging performance suitable for applications requiring high antifogging properties such as a cold insulation showcase. It is suitable for doors of cold storage showcases, and is also useful for windows for transportation equipment such as automobiles and for building materials attached to buildings such as houses and buildings.

10A, 10B ... Antifogging glass article, 11, 12, 13 ... Glass plate, 21, 22 ... Spacer, 31, 32 ... Intermediate layer, 41, 42 ... Antifogging film, 41a ... Water absorption layer, 41b ... Underlayer

Claims (7)

A plurality of glass plates opposed to each other and sealed with a spacer at the periphery thereof, and a multilayer glass in which an intermediate layer is formed between the opposing glass plates; and
An anti-fogging time (T ₄₅ ) in a 45 ° C. steam test measured by the following method is mainly 40 seconds or more, mainly composed of the first cured epoxy resin disposed on at least one main surface of the multilayer glass. An anti-fogging film having a certain water absorption layer;
Antifogging glass article having
(Measurement method of anti-fogging time (T ₄₅ ))
A water-absorbing layer as a specimen is provided on one main surface of the soda lime glass substrate, and left for 1 hour in an environment of 23 ° C. and 50% RH. Next, a 70 mm × 70 mm square area on the surface of the water absorption layer is placed on a 45 ° C. hot water bath, and the antifogging time (T [second]) until fogging is visually observed after starting to wrinkle is measured.   The water-absorbing layer is a layer obtained by reacting a water-absorbing layer-forming composition containing a first polyepoxide component and a first polyaddition type curing agent, and the first polyepoxide component has a chlorine content of 2 The anti-fogging glass article according to claim 1, comprising 90% by mass or more of polyepoxide (A) having a water content of 90% or less by mass based on the total amount of the polyepoxide component.   The antifogging glass article according to claim 2, wherein the first polyaddition type curing agent contains a polyamine compound having amine active hydrogen.   The antifogging glass article according to claim 3, wherein an equivalent ratio of amine active hydrogen contained in the first polyaddition type curing agent to an epoxy group contained in the first polyepoxide component is 0.6 to 2.0. . The antifogging film is further antifogging according to any one of claims 1 to 4, saturated water absorption has a 10 mg / cm ³ or less of the underlying layer between the double glazing and the water absorbing layer Glass article.   The said base layer consists mainly of the 2nd cured epoxy resin obtained by making the composition for base layer formation containing the 2nd polyepoxide component and the 2nd polyaddition type hardening | curing agent react. Antifogging glass article.   The antifogging glass article according to any one of claims 1 to 6, wherein the antifogging glass article is used for a cold insulation showcase door.

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