WO2016006624A1 - Antifogging film and door for refrigerated showcase - Google Patents

Abstract

　Provided is an antifogging film with which antifogging properties can be imparted to various articles, wherein the antifogging film has exceptional water absorbency, as well as exceptional resistance to peeling. This antifogging film is provided with a resin film, and a water absorbent layer arranged on one principal surface of the resin film, the water absorbent layer having an antifogging duration (T₃₅) of at least 200 seconds in a steam test measured at 35°C by the following method. (Antifogging duration (T₃₅) measurement method) A polyethylene terephthalate (PET) film 100 μm thick composed of a PET film having a water absorbent layer on one principal surface is adhered to one principal surface of a soda lime glass base, so that the water absorbent layer is exposed at the surface, and left to stand for one hour at 23°C, 50% RH. Next, an area 70 mm × 70 mm square on the surface of the water absorbent layer is placed in a sealed state above a hot water bath having a temperature of 35°C, at a distance of 85 mm from the hot water surface, and the antifogging duration (T₃₅) [sec] from the time of initial placement until fogging or distortion due to a water film was visually observed is measured.

Description

Antifogging film and door for cold storage showcase

The present invention relates to an antifogging film and a door for a cold insulation showcase, and relates to an antifogging film having a water absorption layer having excellent water absorption on the main surface of a resin film and a door for a cold insulation showcase.

Transparent substrates such as glass and plastic have a so-called “cloudy” state when the substrate surface falls below the dew point temperature because fine water droplets adhere to the surface and scatter transmitted light. . As a means for preventing such fogging, a method of lowering the surface tension of water droplets attached by treating the surface of the substrate with a surfactant, a method of making the substrate surface hydrophilic using a hydrophilic resin, etc. A method of removing a water droplet by providing a water-absorbent resin film is known.

Also, instead of directly treating the surface of the substrate, the antifogging film in which the hydrophilic resin or the water-absorbing resin film is formed on the surface of the resin film is attached to the surface of the substrate to impart antifogging properties. This is also widely done.

For example, Patent Document 1 describes a technique of an antifogging sheet in which a water-absorbing resin layer such as polyvinyl alcohol or polyacrylic acid is formed on one side of a resin film and an adhesive layer is provided on the opposite side. ing. However, conventionally known anti-fogging films and anti-fogging sheets are not sufficiently water-absorbing, and therefore are not sufficiently anti-fogging. In addition, there was a problem that peeling occurred when water was absorbed.

In order to achieve both anti-fogging performance and peel resistance, it has been proposed to provide an underlayer between the water-absorbent resin layer and the substrate for the purpose of relaxing stress during water absorption and enhancing peel resistance (for example, patents). Reference 2). However, when the substrate is a film, it takes time to wind up each time a protective film is provided to form each layer for manufacturing in a roll shape, or the film deteriorates because the film is heated each time a layer is formed. There is a concern. Therefore, in the case of a film, an antifogging film without a base layer is required.

JP 2011-025692 A JP 2008-273067 A

The present invention has been made from the above viewpoint, and in an antifogging film capable of imparting antifogging properties to various articles, the antifogging film has excellent water absorption, antifogging performance and excellent peeling resistance. The purpose is to provide doors for cold showcases.

The present invention provides, as one aspect, an antifogging film and a cold showcase door having the following configurations.
An antifogging film comprising: a resin film; and a water-absorbing layer having an antifogging time (T ₃₅ ) in a 35 ° C. steam test measured by the following method of 200 seconds or more on one main surface of the resin film.
(Measurement method of anti-fogging time (T ₃₅ ))
A polyethylene terephthalate film having the water-absorbing layer on one main surface of a polyethylene terephthalate film having a thickness of 100 μm is pasted on one main surface of the soda lime glass substrate so that the water-absorbing layer is exposed. Leave in a% RH environment for 1 hour. Next, a 70 mm × 70 mm square area on the surface of the water absorption layer is placed in a sealed state on a 35 ° C. hot water bath so that the distance from the hot water surface is 85 mm, and after the start of installation, cloudy or water is visually observed. The anti-fogging time (T ₃₅ ) [seconds] until distortion due to the film is recognized is measured.

An antifogging film comprising: a resin film; and a water-absorbing layer having an antifogging time (T ₄₅ ) in a 45 ° C. steam test measured by the following method of 35 seconds or more on one main surface of the resin film.
(Measurement method of anti-fogging time (T ₄₅ ))
A polyethylene terephthalate film having the water-absorbing layer on one main surface of a polyethylene terephthalate film having a thickness of 100 μm is pasted on one main surface of the soda lime glass substrate so that the water-absorbing layer is exposed. Leave in a% RH environment for 1 hour. 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 in a sealed state so that the distance from the hot water surface is 85 mm. The anti-fogging time (T ₄₅ ) [seconds] until distortion is recognized is measured.

Water absorption comprising a resin film and a cured epoxy resin provided directly on one main surface of the resin film, containing nitrogen, having a chlorine content of 2% by mass or less and a silicon content of 2.5% by mass or less An antifogging film comprising a layer.

A plurality of plate glasses provided with a predetermined interval, an intermediate layer provided between each of the plurality of plate glasses, and the outermost main surface of the plurality of plate glasses, by the following method And a water absorption layer having an anti-fogging time (T ₄₅ ) of 35 seconds or more in a 45 ° C. steam test to be measured.
(Measurement method of anti-fogging time (T ₄₅ ))
A polyethylene terephthalate film having the water-absorbing layer on one main surface of a polyethylene terephthalate film having a thickness of 100 μm is pasted on one main surface of the soda lime glass substrate so that the water-absorbing layer is exposed. Leave in a% RH environment for 1 hour. 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 in a sealed state so that the distance from the hot water surface is 85 mm. The anti-fogging time (T ₄₅ ) [seconds] until distortion is recognized is measured.

According to the present invention, an antifogging film that can impart antifogging properties to various articles can be provided with an antifogging film excellent in water absorption and peeling resistance and a door for a cold showcase.

Fogging time _{(T 35),} it is a schematic diagram showing an example of a measurement method for anti-fogging time _{(T 45).} It is a perspective view which shows an example of the door for cold storage showcases. It is sectional drawing which shows an example of the door for cold storage showcases.

Embodiments of the present invention will be described below.
The antifogging film of the present invention is used for the purpose of imparting antifogging properties to various articles. In order to affix to various articles | goods, the structure which has an adhesion layer on the main surface on the opposite side to the main surface which has the said water absorption layer of the said resin film may be sufficient, for example.
Hereinafter, the elements constituting the antifogging film will be described in order.

(Resin film)
The resin film used for the antifogging film of the present invention is not particularly limited as long as it is a resinous film. The resin film may have a single layer structure or a multilayer structure in which a plurality of films are laminated.

Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyolefins such as polyethylene (PE) and polypropylene (PP); polyacrylates such as polymethyl methacrylate (PMMA); Polycarbonate (PC); polystyrene (PS); acetates such as triacetyl cellulose (TAC); polyvinyl alcohol (PVA); polyvinyl chloride (PVC); polyvinylidene chloride (PVDC); ethylene-vinyl acetate copolymer (EVA); Polyvinyl butyral (PVB); Polyurethanes; Films made of any of cellophane, norbornene compounds, and the like.

For example, in the case of a PET film, oligomers are deposited on the film surface every time heat treatment for layer formation is performed. If it does so, the adhesiveness of the film surface and the adhesion layer will fall, or the haze of film itself will raise and the problem that visibility will fall will arise.

As the resin film, a PET film that has been stretched, particularly biaxially stretched, is preferably used because of its excellent mechanical strength and dimensional stability. The thickness of the resin film is not particularly limited. For example, considering the use by attaching to various articles, the thickness of the resin film is preferably 10 to 250 μm.

The resin film used in the present invention may have one or both main surfaces subjected to easy adhesion treatment. By using a resin film that has been subjected to an easy-adhesion treatment on the main surface, it is possible to improve the adhesion with a water-absorbing layer or a pressure-sensitive adhesive layer, which will be described later, as compared with a film that is not subjected to this. Examples of the easy adhesion treatment include various surface treatments such as plasma treatment, corona treatment, chemical activation treatment, oxidation flame treatment, deep ultraviolet irradiation treatment, and formation of an easy adhesion layer.

The easy adhesion layer is mainly composed of a binder component. The binder component of the easy adhesion layer includes acrylic resin, polyester resin, silicone resin, urethane resin, styrene resin, cellulose resin, vinyl resin, epoxy resin, butyral resin, amino resin, and rubber. Based resins and the like. Among these, polyester resins are particularly preferably used from the viewpoints of adhesion to a resin film and a water absorption layer and workability.

The easy adhesion layer is a layer having a thickness of 0.01 to 1.50 μm from the viewpoint of achieving both workability and adhesion. The thickness of the easy adhesion layer is preferably 0.02 to 1.00 μm, more preferably 0.05 to 0.80 μm. If the thickness of the easy adhesion layer is less than 0.01 μm, the adhesion may be insufficient, and if it exceeds 1.50 μm, blocking may occur.

In addition, in this specification, the water absorption layer shall be directly provided on the resin film. Since the easy adhesion layer is a layer having a thickness of 1.50 μm or less, it does not function as a base layer for stress relaxation. Therefore, the easy-adhesion layer can be considered as a part of the resin film and is essentially different from the base layer. Therefore, in this specification, “directly” means easy between the resin film and the water absorption layer. When the adhesive layer is provided, it may be interpreted as being provided “directly”.

Also, the resin film used in the present invention may be one in which one or both main surfaces are subjected to a hard coat treatment. By using a resin film that has been subjected to a hard coat treatment and forming a water absorbing layer on the hard coat layer, the hardness of the surface of the water absorbing layer can be improved as compared with a case in which this is not performed.

The main component curable resin used for forming the hard coat layer is preferably an actinic ray curable resin or a thermosetting resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. In particular, an ultraviolet curable resin that is cured by ultraviolet irradiation is preferable.

Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

The thickness of the hard coat layer is preferably 0.05 to 10 μm, more preferably 0.5 to 5 μm, from the viewpoints of adhesion to a resin film or a water absorption layer and workability. In this specification, the water absorption layer is directly provided on the resin film. Since the hard coat layer is a film having a pencil hardness evaluated according to JIS K5600-5-4 of H or higher, it does not function as a base layer for stress relaxation. For this reason, the hard coat layer can be considered as a part of the resin film and is essentially different from the base layer. Therefore, in this specification, “directly” means a hard film between the resin film and the water absorption layer. When the coating layer is provided, it may be interpreted that it is provided “directly”.

In the antifogging film of the present invention, the region where the water absorption layer on the resin film main surface is provided is usually the entire region on one main surface, but may be selectively provided on a predetermined region depending on the application. I do not care.

[Water absorption layer]
The water absorption layer is a layer having an antifogging time (T ₃₅ ) of 200 seconds or more. Although depending on the application of the article in which the antifogging film is used, the antifogging time (T ₃₅ ) of the water absorbing layer is preferably 225 seconds or more, and more preferably 250 seconds or more.
Applications where the anti-fogging film has a large temperature difference between the film surface temperature and steam, such as doors for cold showcases (reach-in doors) and vanity mirrors, and is exposed to a large amount of steam in a short time. In the case where the water absorption layer is used, the anti-fogging time (T ₄₅ ) in the 45 ° C. steam test in which the temperature of the hot water bath in the 35 ° C. steam test is changed from 35 ° C. to 45 ° C. is 35 seconds or more. Used. In that case, the anti-fogging time (T ₄₅ ) is preferably 40 seconds or longer, and more preferably 50 seconds or longer.

Incidentally, antifogging time of the water-absorbing layer _{(T 35)} and anti-fogging time _{(T 45),} for example, be measured by the method shown a schematic diagram in Figure 1. FIG. 1 shows a PET film having a thickness of 100 μm (hereinafter referred to as a PET film with a water absorbing layer) 10 provided with a water absorbing layer as a sample in the anti-fogging time measuring device 1, and the water absorbing layer is exposed on one main surface. The soda glass base | substrate G stuck so that it has shown the mode that it installed. The anti-fogging time measuring device 1 is a hot water bath filled with warm water set to 35 ° C. when measuring the anti-fogging time (T ₃₅ ) and 45 ° C. when measuring the anti-fogging time (T ₄₅ ). 2 and a hot water bath lid 3 having a square through hole of 70 mm × 70 mm in the approximate center and completely closing the opening of the hot water bath 2 except for the through hole portion. Further, a transparent frame 4 having a rectangular inner circumference of 70 mm × 70 mm provided so as to face the through-hole and having a height (85 mm—the thickness of the hot water bath lid 3) is disposed on the hot water bath lid 3. It is installed. That is, the transparent frame 4 is disposed on the hot water bath lid 3 so that the lower opening thereof coincides with the through hole of the hot water bath lid 3, and hot water at 35 ° C. or 45 ° C. from the upper opening of the transparent frame 4. The distance to the surface is 85 mm.

For example, when measuring the anti-fogging time (T ₃₅ ), the soda glass substrate G affixed so that the water absorbing layer is exposed on the one main surface of the soda glass substrate G is 23 ° C., After being left in an environment of 50% RH for 1 hour, as shown in FIG. 1, a soda-lime glass substrate G to which a water-absorbing layer-attached PET film 10 is applied is placed with the water-absorbing layer side facing down and an anti-fogging time measuring device. It installs so that the upper opening part of 1 transparent frame 4 may be plugged up. As a result, a 70 mm × 70 mm square area of the water absorption layer is used as the measurement area S, and the water is absorbed in a sealed state so that the distance from the hot water surface is 85 mm. When the soda lime glass substrate G with the water absorbing layer-attached PET film 10 attached to the antifogging time measuring device 1 is set to 0 [seconds], the measurement region S of the water absorbing layer is visually clouded or watered through the soda glass substrate G. Observe until distortion by the film is observed, and measure the antifogging time (T ₃₅ ) [seconds]. The antifogging time (T ₄₅ ) can be measured in the same manner as the antifogging time (T ₃₅ ) except that the hot water bath 2 is filled with warm water set at 45 ° C.

Here, the schematic diagram shown in FIG. 1 is an example showing a method for measuring the antifogging time (T ₃₅ ) and the antifogging time (T ₄₅ ), and the antifogging time (T ₃₅ ) and antifogging time ( The measuring method of T ₄₅ ) is not limited to this. In addition, in this specification, “cloudiness is recognized” means that after a cloudiness of 3 cm in diameter is visually confirmed, a sample is taken from the evaluation device, and a haze meter (Hazeguard Plus, Gardner Company) is taken within 2 seconds. Haze measured by (manufactured) is 10 or more. Further, in the present specification, “a strain due to a water film is recognized” means that the maximum value of the perspective strain in the perspective strain test based on JIS R 3212 exceeds 2 (minutes).

The film thickness of the water-absorbing layer is preferably 3 to 50 μm considering both anti-fogging 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 35 μm or less.

The resin applied to the water-absorbing layer is not particularly limited. For example, among the resins shown below, in the water-absorbing layer obtained by using the resin, the anti-fogging time (T ₃₅ ) in the 35 ° C. steam is 45 ° C. Resins satisfying the physical property conditions according to anti-fogging time (T ₄₅ ), abrasion resistance test described later, and scratch resistance test can be used.

Starch resin such as starch-acrylonitrile graft polymer hydrolyzate, starch-acrylic acid graft polymer complex, etc .; Cellulose-acrylonitrile graft polymer, cellulose resin such as carboxymethylcellulose cross-linked product; polyvinyl alcohol cross-linked polymer Polyvinyl alcohol resins such as polyacrylic acid sodium cross-linked products and polyacrylic acid ester cross-linked products, etc .; Polyethylene glycol diacrylate cross-linked polymers, polyether resins such as polyalkylene oxide-polycarboxylic acid cross-linked products A cross-linked polyurethane which is a reaction product of polyether polyol or polyester polyol and polyisocyanate;

The water absorbing layer is preferably a material containing nitrogen. By containing nitrogen, the adhesiveness with the resin film is improved, so that improvement in durability can be expected. For example, the water absorption layer can contain nitrogen by using a nitrogen-containing curing agent.

A more preferred water-absorbing layer includes a water-absorbing resin layer mainly composed of a cured epoxy resin. It mainly comprises a cured epoxy resin, and satisfies the conditions of physical properties by the anti-fogging time (T ₃₅ ) in the ₃₅ ° C. steam, the anti-fogging time (T ₄₅ ) in the 45 ° C. steam, and the abrasion resistance test and scratch resistance test described later. Specifically as a water absorption layer, the polyepoxide component and polyaddition type hardening | curing agent which contain 60 mass% or more of polyepoxide (A) whose chlorine content is 2 mass% or less and whose water content rate is 90% or more with respect to the total amount of polyepoxide components And a layer obtained by reacting a composition for forming a water-absorbing layer. The phrase “the water-absorbing layer is mainly composed of a cured epoxy resin” means that the ratio of the cured epoxy resin in the entire water-absorbing layer is 80% by mass or more. In the case of a cured epoxy resin, it is preferable to use an amine-based curing agent because a film having both antifogging properties and durability can be easily prepared.

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, “polyaddition type curing agent” is a compound having two or more reactive groups that react with the epoxy group of the polyepoxide, and is a type of curing agent that polyadds 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 expressing 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, the cured epoxy resin mainly constituting the highly water-absorbing water-absorbing layer having an anti-fogging time (T ₃₅ ) according to the present invention of 200 seconds or more will be described.

<Hardened epoxy resin>
The cured epoxy resin is a cured epoxy resin obtained by reacting a polyepoxide component and a polyaddition type curing agent.
The polyepoxide component is not particularly limited as long as the water-absorbing layer mainly composed of the obtained cured epoxy resin can achieve the anti-fogging time (T ₃₅ ) of 200 seconds or more. Specifically, as the polyepoxide component, a polyepoxide component containing a polyepoxide (A) having a chlorine content of 2% by mass or less and a water content of 90% or more in a proportion of 60% by mass or more based on the total amount of the polyepoxide component. 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 solubility (%) = (input resin amount (g) −insoluble resin amount (g)) / input resin amount (g) × 100
When the water content of the polyepoxide is 90% or more, the affinity of the water absorption layer with water is increased, and the water absorption performance is further improved.

If the content of the polyepoxide (A) in the polyepoxide component is 60% by mass or more, the anti-fogging time (T ₃₅ ) has a sufficient water retention space to obtain a water absorbing layer of 200 seconds or more and sufficient durability. A cured epoxy resin is obtained. In order to make the antifogging time (T ₃₅ ) longer, the content of the polyepoxide (A) in the polyepoxide component is preferably 70% by mass or more.

It should be noted that, for example, an anti-fogging film suitable for applications in which the temperature difference between the surface of the film such as a door for a cold insulation showcase or a vanity mirror is large and the temperature of the steam is exposed to a large amount of steam in a short time. Therefore, in order to obtain a water absorption layer having an antifogging time (T ₄₅ ) of 35 seconds or more, the content of the polyepoxide (A) in the polyepoxide component is 85% by mass or more. In order to further increase the antifogging time (T ₄₅ ) from the viewpoint of imparting higher antifogging properties, the content of the polyepoxide (A) in the polyepoxide component is preferably 95% by mass or more, and 100% by mass. More preferred.

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 three-dimensional structure of the resulting cured epoxy resin is considered to be capable of achieving both high water absorption and durability at a higher level because it has a moderately sized space and flexibility. preferable.

The molecular weight of the polyepoxide (A) is preferably 600 to 3000, and more preferably 800 to 2000, considering the high water absorption and durability of the resulting cured epoxy resin. 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 the polyepoxide in the 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, more preferably 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, 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, only the types of compounds will be referred to, but among these compounds, those having a chlorine content and a water content within the above ranges are used as the polyepoxide (A).

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.

The polyepoxide (A) is preferably an aliphatic glycidyl ether-based polyepoxide derived from aliphatic polyols. 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.

A commercially available product can be used as the polyepoxide (A). As such a commercial product, specifically, Denacole 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; 165), Denacol EX-1410 (chlorine content; 0.5% by weight, water content: 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 the polyepoxide other than the polyepoxide (A) contained in the polyepoxide component (hereinafter also referred to as polyepoxide (B)), glycidyl ether polyepoxide, glycidyl ester polyepoxide, glycidylamine used as a raw material component of a normal cured epoxy resin. Of the polyepoxides such as polyepoxides, those not in the category of the 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 polyepoxide derived from aliphatic polyols is particularly preferable.

As a constituent component of the cured epoxy resin obtained by reacting the polyepoxide component and the polyaddition type curing agent, specifically, as described above, the chlorine content is 2% by mass or less and the water content is 90% or more. Since it is preferable to use a polyepoxide component containing 60% by mass or more of the polyepoxide (A) with respect to the total amount of the polyepoxide component, the chlorine content is preferably 2% by mass or less based on the entire resin. When the chlorine content with respect to the entire resin is 2% by mass or more, a sufficient water retention space cannot be secured, and the antifogging time may be reduced.

<Polyaddition type curing agent>
The polyaddition type curing agent is a compound having two or more reactive groups that react with the epoxy group of the polyepoxide component, and is not particularly limited as long as it is a type of curing agent that is polyadded to the polyepoxide by reaction.

Examples of the reactive group that reacts with the epoxy group in the polyaddition type curing agent include an amino group having active hydrogen, a carboxyl group, and a thiol group. That is, the polyaddition type curing agent is preferably 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 active hydrogen. A compound having two or more amino groups having the formula 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, a secondary amino group having a primary amino group at the terminal, 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 polyaddition type curing agent, one of these may be used alone, or two or more may be used in combination.

The 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 polyaddition type curing agent is preferably a compound having no aromatic ring. Thus, the cured epoxy resin is preferably a compound in which the polyepoxide component mainly containing the linear polyepoxide (A) is an aliphatic compound and the polyaddition type curing agent does not have an aromatic ring. That is, it is preferable that the cured epoxy resin does not have an aromatic ring in the molecular structure from the viewpoint of achieving both high water absorption and durability.

The polyaddition type curing agent is preferably a polyamine compound having no aromatic ring, polythiols, or polycarboxylic acid anhydride, and particularly preferably a polyamine compound having no aromatic ring. The polyamine compound is preferably a polyamine compound having 2 to 4 amino groups having active hydrogen. 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 polyamine compounds 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. Examples thereof include 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 commercially available product can be used as the polyaddition type curing agent. As such commercially available products, specifically, as polyoxyalkylene triamine, 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 blending ratio of the polyepoxide component, which is a raw material component of the cured epoxy resin used in the present invention, and the polyaddition type curing agent is such that the reactive group of the polyaddition type curing agent reacts with the epoxy group in a ratio of 1: 1. In this case, it is preferable that the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group derived from the polyepoxide component is a ratio of 0.6 to 2.0, more preferably 0.8 to 1.5. . When a polyaddition type curing agent having a reactive group that reacts 1: 1 with an epoxy group is used, if the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group derived from the polyepoxide component is in the above range, A cured epoxy resin having a three-dimensional network structure that is appropriately cross-linked so as to have the above-mentioned water absorption without lowering the durability such as wear and moisture resistance can be obtained.

When a polyamine compound having active hydrogen is used as a polyaddition type curing agent in the present invention, it is used so that the equivalent ratio of amine active hydrogen to the epoxy group derived from the polyepoxide component is 0.4 to 3.0. It is 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 above can be obtained.

Therefore, it is more preferable that the cured epoxy resin constituting the water-absorbing layer having a sufficient anti-fogging time contains nitrogen and contains an amine material.

Here, the water absorption layer used in the present invention is practically required to have both water absorption and durability according to various applications.
For example, in an automobile application, specifically, the water absorption layer has an anti-fogging time (T ₃₅ ) of 200 seconds or longer and ΔH ₁ in the following wear resistance test (1) is 4.0% or lower. Is preferable, and 2.5% or less is more preferable.

(Abrasion resistance test (1))
The abrasion resistance test (1) is a Taber 5130 type abrasion tester in accordance with JIS R 3212 (vehicle interior) (2008), using the abrasion wheel CS-10F, and contacting the abrasion wheel to the surface of the water absorption layer. And a wear resistance test in which a load of 4.90 N is applied and rotated 100 times. The evaluation of abrasion resistance is performed by measuring the haze value (%) before and after the wear resistance test (1), and the increase in haze indicated by haze value after the test (Ha)-haze value before the test (Hb) This is done by calculating ΔH ₁ (%).

Also, for example, in applications where the temperature difference between the surface of the film and the temperature of the film such as a door for a cold storage showcase such as a refrigerator or freezer or a vanity mirror is large, and it is exposed to a large amount of steam in a short time. Specifically, the water absorption layer preferably has an anti-fogging time (T ₄₅ ) of 35 seconds or more and ΔH ₂ in the following abrasion resistance test (2) is 0.5% or less, 0.1% or less is more preferable.

(Abrasion resistance test (2))
The wear resistance test (2) is a wear resistance test in which a reciprocating traverse tester (wear: felt) is used and the felt is brought into contact with the surface of the water absorption layer and reciprocated 50 times with a load of 4.0 N. is there. The evaluation of abrasion resistance is performed by measuring the haze (%) before and after the wear resistance test (2), and the increase in haze indicated by haze after the test (Ha) minus haze before the test (Hb). This is done by calculating ΔH ₂ (%).

Further, in any of the above applications, the water absorption layer preferably has the hardness of the hardest pencil that is not damaged in the scratch resistance test (pencil hardness test) evaluated by the following method being H or more. 2H or more is more preferable.
(Scratch resistance: evaluation method for pencil hardness)
The pencil hardness is evaluated according to JIS K5600-5-4 (1999). A pencil having various hardnesses is applied to the surface of the water absorption layer at an angle of 45 °, and a scratch test is performed with a load of 750 g. The hardness of the hardest pencil that is not damaged is defined as pencil hardness.

In the case where such extremely high water absorption is required, 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 polyepoxide component and the polyaddition type curing agent. Then, water absorption may be impaired. In particular, when a compound having an amine active hydrogen, such as a coupling agent having an amine active hydrogen described later, is used, the equivalent ratio of the amine active hydrogen of the polyaddition type curing agent to the epoxy group derived from the polyepoxide component is 0.4 to Even if it is 3.0, the antifogging time (T ₃₅ ) of 200 seconds or longer and the antifogging time (T ₄₅ ) of 35 seconds or longer may not be achieved. Therefore, when high water absorption is required, it is preferable that the water-absorbing layer forming composition does not contain a compound having an epoxy group and / or a compound having amine active hydrogen in addition to the polyepoxide component and the polyaddition type curing agent. .

Further, when the cured epoxy resin is obtained by a polyaddition reaction between a polyepoxide component and a polyaddition type curing agent, the polyaddition reaction can be performed in the presence of a catalytic curing agent, if necessary.

The catalyst-type curing agent is not particularly limited as long as it is a reaction catalyst such as a Lewis acid and catalyzes a polymerization reaction between polyepoxides and / or a polyaddition reaction between a polyepoxide and a polyaddition-type curing agent. Can be used.

By using a catalyst-type curing agent, the effect of accelerating the crosslinking speed by polyaddition reaction between the polyepoxide component and the polyaddition type curing agent, and problems that occur in the crosslinking site formed by the polyepoxide component and the polyaddition type curing agent The effect of reducing is obtained.

Specific examples of catalytic curing agents 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 the catalyst type curing agent, one of these may be used alone, or two or more may be used in combination.

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 catalyst-type curing agent used in the present invention.

Commercially available products can be used as the catalyst type curing 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.

The amount of the catalyst-type curing agent used is preferably 4% by mass or less, more preferably 2% by mass or less with respect to 100% by mass of the polyepoxide component. If the use amount of the catalyst type curing agent with respect to 100% by mass of the polyepoxide component is 4% by mass or less, there is a catalyst type curing agent residue in the obtained cured epoxy resin and the cured epoxy resin is yellowed. It is easy to suppress the occurrence of problems. In addition, since a catalyst type hardening | curing agent is an arbitrary component, the minimum of the usage-amount is not specifically limited. However, from the viewpoint of accelerating the curing reaction, it is preferable to use a catalyst type curing agent with a lower limit of about 0.5% by mass with respect to 100% by mass of the polyepoxide component.

Further, the water absorption layer may contain a filler made of a metal oxide. 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.

The blending amount of the filler is preferably 0.5 to 30% by mass and more preferably 1 to 25% by mass with respect to 100% by mass of the total mass of the polyepoxide component, polyaddition type curing agent and catalyst type curing agent. preferable.

The water absorbing layer may contain an infrared absorber. 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.

<Water absorbing layer forming composition>
The water absorption layer of the antifogging film of the embodiment of the present invention is, for example, a water absorption layer mainly composed of a cured epoxy resin obtained by reacting the above-described polyepoxide component and a composition for forming a water absorption layer containing a polyaddition type curing agent. It is.

The polyepoxide component and polyaddition type curing agent contained in the water-absorbing layer-forming composition, and the optional catalyst-type curing agent contained are as described above, including preferred embodiments such as the compound used and the ratio in combination. It is. The water-absorbing layer-forming composition usually contains a solvent in addition to the polyepoxide component, the polyaddition type curing agent, and an optional catalyst-type curing agent. 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. The reactive additive is treated as a part of the raw material component of the cured epoxy resin.

Usually, the reaction between the polyepoxide component and the 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 are the compositions for forming the water-absorbing layer. It is carried out after being applied as an object on the application surface (on the main surface of the resin film 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 polyepoxide component and the 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 30 ° C. or more. It is preferable because the curing reaction proceeds reliably.

(solvent)
Solvents used in the water-absorbing layer-forming composition are solvents that have good solubility with respect to compounding components including polyepoxide components, polyaddition-type curing agents, and other optional components, and are incompatible with these compounding components. It is not particularly limited as long as it is an active solvent, and specific examples include alcohols, acetate esters, ethers, ketones, water and the like.

In addition, when a protic solvent is used as the solvent, depending on the type of the polyepoxide component, the solvent and the epoxy group may react to make it difficult to form a cured epoxy resin. Therefore, when a protic solvent is used, it is preferable to select a solvent that does not easily react with the 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. In addition, blending components such as a polyepoxide component, a polyaddition type curing agent, and a catalyst type 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 the solvent in the water-absorbing layer-forming composition, and the water-absorbing layer-forming composition is otherwise the same or different from these. Additional solvent may be added.

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

Here, the blending amount of the polyepoxide component, the polyaddition type curing agent and the catalyst type curing agent in the water absorbing layer forming composition is preferably 15 to 60% by mass, and preferably 18 to 50% by mass with respect to the total amount of the polyepoxide component. % Is more preferable. The compounding amounts of the polyaddition type curing agent and the 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 a polyepoxide component such as an alkyl monoamine, and a polyepoxide component such as an epoxy group or an amino group. And a coupling agent having a reactive group reactive with the polyaddition type curing agent.

As the 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 preferably have a reactive group capable of reacting with a reactive group possessed by a polyepoxide component or a polyaddition type curing agent. The purpose of adding the coupling agent is to improve the hardness of the water absorption layer, and is used particularly when a higher level of pencil hardness is required. The introduction of the coupling agent is not only for improving the hardness but also reducing the water retention space due to the increase in density, resulting in a reduction in the anti-fogging time. Therefore, as will be described later, there is an optimum value for the introduction amount.

The amount of the coupling agent in the water-absorbing layer forming composition is such that the polyepoxide component in the water-absorbing layer forming composition is used so as not to impair the antifogging effect while fully exhibiting the effect of the coupling agent. The total mass of the polyaddition type curing agent and the catalyst type curing agent is preferably 19% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. In addition, as a hardening epoxy resin, it is preferable that the silicon content with respect to the whole resin is 2.5 mass% or less, 2.0 mass% or less is more preferable, 1.5 mass% or less is further more preferable.

As described above, in applications where the temperature difference between the film surface and the steam is large and the film is exposed to a large amount of steam in a short time, the water-absorbing layer forming composition is a reactive additive containing a coupling agent. It is preferable not to contain an agent. For example, when a coupling agent is contained, it does not depend on the range of the above content, and does not affect particularly high water absorption, for example, antifogging time (T ₄₅ ) of 35 seconds or more, for example, 7 mass % Or less. In addition, as a hardening epoxy resin, the silicon content with respect to the whole resin shall be 1.0 mass% or less.

The blending amount of the infrared absorber in the water-absorbing layer-forming composition is such that the water-absorbing layer formed using the composition has a heat insulating effect due to sufficient infrared shielding without impairing the effects of the present invention. 0.5 to 15% by mass is preferable and 10 to 15% by mass is more preferable with respect to 100% by mass as a total mass of the addition type curing agent and the catalyst type curing agent. 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. And sulfur-based antioxidants. In the present invention, it is preferable to use a phenolic antioxidant.

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 usually in the range of 325 to 425 nm, and preferably 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 light stabilizers 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. In terms of the total weight of the polyepoxide component, the polyaddition type curing agent and the catalyst type curing agent, which is 100 to 5% by mass, preferably 0.5 to 5% by mass for each additive. The mass% is more preferable.

A leveling agent, an antifoaming agent, a viscosity modifier, etc. can be further added to the water absorbing layer forming composition as needed from the viewpoint of improving the film-forming property.

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

(Adhesive layer)
In the antifogging film of the present invention, the adhesive layer that may be provided on the main surface opposite to the main surface having the water absorbing layer of the resin film will be described.

Examples of the material constituting the adhesive layer include acrylic adhesives, silicone adhesives, butadiene adhesives, polyurethane adhesives, and the like. Among these, an acrylic pressure-sensitive adhesive is preferable from the viewpoint of handleability.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be appropriately selected according to the material of the base material. Specifically, the thickness is preferably 0.5 μm to 50 μm, preferably 5 to 30 μm. .

(Door for cold showcase)
FIG. 2 is a perspective view showing a cold showcase door according to an embodiment of the present invention. The cold insulation showcase door 20 is installed in a convenience store, a supermarket, or the like. The multi-layer glass structure is composed of a plurality of plate glasses provided at a predetermined interval, and a sash attached to the peripheral edge of the multi-layer glass structure, and a handle is attached to the front surface of the sash. ing. When the customer opens and closes the handle, the door is opened and closed back and forth.

FIG. 3 is a cross-sectional view taken along the line AA in FIG. In FIG. 3, a multi-layer glass structure using three plate glasses 21, 23 and 25 is used, but a multi-layer glass structure using two plate glasses may of course be used. Intermediate layers 22 and 24 are provided between the plate glasses 21 and 23 and the plate glasses 23 and 25, respectively. The intermediate layers 22 and 24 can be appropriately changed to an inert gas such as dry air, sulfur hexafluoride gas, argon gas, or krypton gas, vacuum, or the like in consideration of heat insulation performance.

In addition, the thickness of each intermediate layer, that is, the interval between the plate glasses can be appropriately changed. In the case of a multilayer glass structure made of three plate glasses, the thickness of the two intermediate layers may be different. The cold insulation showcase door is provided on at least one main surface of the outermost surfaces of the plurality of plate glasses, that is, on at least one of the outer main surfaces of the two outermost glass plates. The anti-fogging film which concerns on is attached. The antifogging film may be affixed to one of the main surfaces, or may be affixed to both the main surfaces. However, the surface to which the antifogging film is attached is a surface that is usually disposed as the inside of the cold storage.

In the cold showcase door 20, the two outermost glass plates among the three glass plates 21, 23, 25 are the glass plate 21 and the glass plate 25. The glass plate 21 is disposed on the inside of the cool box, and the glass plate 25 is disposed on the outside of the cool box. The cold insulation showcase door 20 has an antifogging film 28 on the main surface outside the glass plate 21. That is, the anti-fogging film 28 is affixed to the surface arrange | positioned as a cold storage interior side. In addition, spacers 26 are provided on the peripheral surfaces of the main surfaces of the respective plate glasses 21, 23, 25 that face each other, and the peripheral portions of the multilayer glass structure are covered with a sash 27.

As described above, in FIG. 3, an example in which the antifogging film 28 is attached to the entire main surface outside the plate glass 21 on the inner side of the cool box (main surface on the inner side of the cool box) is shown as an example. The antifogging film 28 may not be attached to the portion covered with the sash 27.

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 13 and 16 to 18 are examples, and examples 14, 15 and 19 to 23 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% by mass, water content: 100%, Mw: 1130, epoxy equivalent: 165)
Polyepoxide (B)
EX521: Denacol EX-521 (polyglycerol polyglycidyl ether; chlorine content; 6.4% by mass, water solubility: 100%, Mw: 1294, epoxy equivalent: 179)

(2) Polyaddition type curing agent T403: Jeffamine T403 (trade name, manufactured by Huntsman, Mw: 390, amine active hydrogen equivalent: 78), polyoxyalkylene triamine (3) Various additives KBM903 (trade name, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd.): 3-aminopropyltrimethoxysilane BYK307 (trade name, manufactured by BYK Chemie): polyether-modified polydimethylsiloxane

[Examples 1 to 23]
On one main surface of the resin film, a water-absorbing layer was formed using a water-absorbing layer-forming composition prepared by the following method to produce an antifogging film.

<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 (MEK) is charged with aliphatic polyglycidyl ether (Denacol EX) in the amounts shown in Tables 1 to 3 in each example. -1610) and polyglycerin polyglycidyl ether (Denacol EX-521) are dissolved, and then polyoxyalkylene triamine (Jephamine T403) and aminosilane (KBM903) are added with stirring and stirred at 35 ° C. for 120 minutes. did. 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 anti-fogging film>
A PET film (100 mm × 100 mm × thickness 100 μm) was used as a substrate, and the water-absorbing layer forming composition obtained in each of the above examples was applied onto one main surface of the PET film with an applicator (8MIL). The film was kept in an electric furnace at 100 ° C. for 30 minutes to form a water absorption layer, and an antifogging film was obtained.

Adhesive layer is affixed to the main surface of the resulting anti-fogging film where the water absorption layer is not formed, and is laminated on a soda lime glass substrate (4 mm thick), or in the reach indoors. The following evaluations were made. In the following tests, evaluation was performed using a glass substrate with an antifogging film except for RID evaluation. The results are shown in Tables 1 to 3 together with the component compositions in the water absorbing layer forming composition used in each example.

[Measurement of film thickness]
A cross-sectional image of the antifogging film was taken with a scanning electron microscope (S4300, manufactured by Hitachi, Ltd.), and the film thickness of the water absorption layer was measured.

[Evaluation of anti-fogging property]
For the water absorption layer, the antifogging time (T ₃₅ ) in the 35 ° C. steam test and the antifogging time (T ₄₅ ) in the 45 ° C. steam test are the same as those shown in FIG. The temperature of the hot water bath was set to 35 ° C., and in the 45 ° C. steam test, the temperature of the hot water bath was set to 45 ° C., and the above methods were used for measurement.
With respect to the antifogging time (T ₃₅ ), a normal PET film not subjected to the antifogging process was fogged in 0 to 10 seconds. The required anti-fogging performance varies depending on the application. In the examples, the antifogging time (T ₃₅ ) is 200 seconds or longer, preferably 225 seconds or longer, and more preferably 250 seconds or longer. In Tables 1 to 3, the case where no clouding occurred for 360 seconds or more was indicated as “360 or more”.

With respect to the antifogging time (T ₄₅ ), the usual PET film not subjected to the antifogging process was fogged in 0 to 1 second. The anti-fogging time (T ₄₅ ) of the water absorbing layer is preferably 35 seconds or more, more preferably 40 seconds or more, and particularly preferably 50 seconds or more.

[Evaluation as a cold insulation showcase door (RID evaluation)]
Evaluation in the case of applying an antifogging film to a door for a cold showcase was performed as follows.
The antifogging film obtained in each example was attached to the inner side of the reach door with an adhesive layer so that the water absorption layer was on the inner side, then the door was closed, cooled to −25 ° C., and left for 1 hour. did. Thereafter, after confirming that the surface of the water-absorbing layer of the 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 water absorption layer of the glass substrate with an antifogging film obtained in each example, the YI value, which is a yellowness index, was measured using a Spectrophotometer SD6000 manufactured by Nippon Denshoku Industries Co., Ltd. A larger YI value indicates stronger yellowness. In addition, the YI (C light source 2 degrees) of soda lime glass that is not subjected to normal antifogging is −0.46.

[Evaluation of wear resistance]
As wear resistance test (1), in accordance with JIS R 3212 (vehicle interior) (2008), wear wheel CS-10F is used with Taber 5130 type wear tester, and the wear wheel is brought into contact with the surface of the water absorption layer. Then, a wear resistance test was performed in which a load of 4.90 N was applied and rotated 100 times. The evaluation of abrasion resistance is performed by measuring the haze value (%) before and after the wear resistance test (1), and the increase in haze indicated by haze value after the test (Ha)-haze value before the test (Hb) (Change) ΔH ₁ (%) was calculated. ΔH ₁ is preferably 4.0% or less.

As a wear resistance test (2), using a reciprocating traverse tester (manufactured by KT Corporation, wearer: felt), the felt is brought into contact with the surface of the water absorption layer and reciprocated 50 times with a load of 4.0 N. An abrasion test was performed. The evaluation of abrasion resistance is performed by measuring the haze (%) before and after the wear resistance test (2), and the increase in haze indicated by haze after the test (Ha) minus haze before the test (Hb). (Change) ΔH ₂ (%) was calculated. ΔH ₂ is preferably 0.5% or less, and more preferably 0.1% or less.

[Scratch resistance: evaluation of pencil hardness]
The pencil hardness was evaluated according to JIS K5600-5-4 (1999). A pencil having various hardnesses was applied to the surface of the water absorption layer at an angle of 45 °, and a scratch test was performed with a load of 750 g. The hardness of the hardest pencil that was not damaged was defined as the pencil hardness. H or higher is preferable, and 2H or higher is more preferable.

[Use determination]
About the anti-fogging film obtained in each example, it determined by the following references | standards about the application use.
(1) Cold showcase door (reach-in door)
○: Anti-fogging time (T ₄₅ ) is 35 seconds or more, and abrasion resistance test (2) is 0.5% or less.
Δ: Anti-fogging time (T ₄₅ ) is 35 seconds or more, and wear resistance test (2) exceeds 0.5%.
X: Anti-fogging time (T ₄₅ ) is less than 35 seconds.
(2) Washing vanity mirror ○: The anti-fogging time (T ₄₅ ) is 35 seconds or more, and the wear resistance test (2) is 0.5% or less.
Δ: Anti-fogging time (T ₄₅ ) is 35 seconds or more, and wear resistance test (2) exceeds 0.5%.
X: Anti-fogging time (T ₄₅ ) is less than 35 seconds.

(3) Residential window ○: The anti-fogging time (T ₃₅ ) is 200 seconds or more, and the scratch resistance is H or more.
Δ: Anti-fogging time (T ₃₅ ) is 200 seconds or more, and scratch resistance is less than H.
×: antifogging time _{(T 35)} is less than 200 seconds.
(4) Automobile window ○: The anti-fogging time (T ₃₅ ) is 200 seconds or more, and the abrasion resistance test (1) is 4.0% or less.
△: antifogging time _{(T 35)} is not less than 200 seconds, a wear resistance test (1) exceeds 4.0%, or peeling.
×: antifogging time _{(T 35)} is less than 200 seconds.

The anti-fogging film of the present invention is an anti-fogging film capable of imparting anti-fogging properties to various articles, and has excellent water absorption and peel resistance. Articles to which the antifogging film is applied include articles for transportation equipment that require excellent antifogging properties and high wear resistance, such as bodies in trains, automobiles, ships, aircrafts, window glass (front glass, Side glass, rear glass), mirrors and the like are preferable. In addition, it is also suitably used for articles requiring particularly high antifogging properties, such as doors for cold showcases such as refrigerators and freezers, and vanity mirrors. Furthermore, it is also useful for building windows, glasses, goggles, helmet visors, and the like.

DESCRIPTION OF SYMBOLS 1 ... Anti-fogging time measuring apparatus, 2 ... Warm water bath, 3 ... Warm water bath lid, 4 ... Transparent frame, 10 ... PET film with a water absorption layer, G ... Soda glass base | substrate, S ... Measurement area | region, 20 ... For cold storage showcase Door, 21, 23, 25 ... glass plate, 22, 24 ... intermediate layer, 26 ... spacer, 27 ... sash, 28 ... anti-fogging film.

Claims (11)

A resin film;
On one main surface of the resin film, a water absorption layer having an antifogging time (T ₃₅ ) in a 35 ° C. steam test measured by the following method of 200 seconds or more,
Antifogging film comprising
(Measurement method of anti-fogging time (T ₃₅ ))
A polyethylene terephthalate film having the water-absorbing layer on one main surface of a polyethylene terephthalate film having a thickness of 100 μm is pasted on one main surface of the soda lime glass substrate so that the water-absorbing layer is exposed. Leave in a% RH environment for 1 hour. Next, a 70 mm × 70 mm square area on the surface of the water absorption layer is placed in a sealed state on a 35 ° C. hot water bath so that the distance from the hot water surface is 85 mm, and after the start of installation, cloudy or water is visually observed. The anti-fogging time (T ₃₅ ) [seconds] until distortion due to the film is recognized is measured. The anti-fogging film according to claim 1, wherein the change in haze ΔH (%) before and after the test in the abrasion resistance test evaluated by the following method is 4.0% or less.
(Evaluation method for wear resistance test)
In accordance with JIS R 3212 (vehicle interior) (2008), a wearer wheel CS-10F is used with a Taber 5130 type wear tester, and the wear wheel is brought into contact with the surface of the water absorption layer, and a load of 4.90 N is applied. A wear resistance test is performed by rotating 100 times. For the evaluation of wear resistance, the haze value (%) before and after the wear resistance test is measured, and the haze increase ΔH (%) expressed by haze value after test (Ha) − haze value before test (Hb) ) Is calculated. A resin film;
On one main surface of the resin film, a water absorption layer having a defogging time (T ₄₅ ) in a 45 ° C. steam test measured by the following method of 35 seconds or more,
Antifogging film comprising
(Measurement method of anti-fogging time (T ₄₅ ))
A polyethylene terephthalate film having the water-absorbing layer on one main surface of a polyethylene terephthalate film having a thickness of 100 μm is pasted on one main surface of the soda lime glass substrate so that the water-absorbing layer is exposed. Leave in a% RH environment for 1 hour. 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 in a sealed state so that the distance from the hot water surface is 85 mm. The anti-fogging time (T ₄₅ ) [seconds] until distortion is recognized is measured. The anti-fogging film according to claim 3, wherein the change in haze ΔH (%) before and after the test in the abrasion resistance test evaluated by the following method is 0.5% or less.
(Evaluation method for wear resistance test)
Using a reciprocating traverse tester (manufactured by KT Corporation, wearer: felt), the felt is brought into contact with the surface of the water absorption layer and subjected to a wear resistance test by reciprocating 50 times under a load of 4.0 N. To do. The evaluation of wear resistance is carried out by measuring the haze value (%) before and after the wear resistance test, and the change in haze value ΔH (% expressed by haze value after test (Ha) − haze value before test (Hb) ) Is calculated. The antifogging film according to claim 2 or 4, wherein the hardness of the hardest pencil that is not scratched is H or more in a scratch resistance test (pencil hardness test) evaluated by the following method.
(Scratch resistance: evaluation method for pencil hardness)
The pencil hardness is evaluated according to JIS K5600-5-4 (1999). A pencil having various hardnesses is applied to the surface of the water absorption layer at an angle of 45 °, and a scratch test is performed with a load of 750 g. The hardness of the hardest pencil that is not damaged is defined as pencil hardness. The antifogging film according to any one of claims 1 to 5, wherein the water absorbing layer is a layer containing a cured epoxy resin. The anti-fogging film according to claim 6, wherein the cured epoxy resin contains nitrogen, has a chlorine content of 2% by mass or less, and a silicon content of 2.5% by mass or less. A resin film;
A water-absorbing layer provided directly on one main surface of the resin film, containing nitrogen, containing a cured epoxy resin having a chlorine content of 2% by mass or less and a silicon content of 2.5% by mass or less;
Antifogging film comprising The anti-fogging film according to claim 8, wherein the water absorption layer contains an amine-based material. A plurality of plate glasses provided with a predetermined interval;
An intermediate layer provided between each of the plurality of plate glasses;
A water-absorbing layer having an anti-fogging time (T ₄₅ ) in a 45 ° C. steam test measured by the following method on the outermost main surface of any one of the plurality of plate glasses is 35 seconds or more;
A door for a cold showcase.
(Measurement method of anti-fogging time (T ₄₅ ))
A polyethylene terephthalate film having the water-absorbing layer on one main surface of a polyethylene terephthalate film having a thickness of 100 μm is pasted on one main surface of the soda lime glass substrate so that the water-absorbing layer is exposed. Leave in a% RH environment for 1 hour. 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 in a sealed state so that the distance from the hot water surface is 85 mm. The anti-fogging time (T ₄₅ ) [seconds] until distortion is recognized is measured. The door for a cold-insulated showcase according to claim 10, wherein a change amount HH (%) of the haze before and after the test in an abrasion resistance test evaluated by the following method is 0.5% or less.
(Evaluation method for wear resistance test)
Using a reciprocating traverse tester (manufactured by KT Corporation, wearer: felt), the felt is brought into contact with the surface of the water absorption layer and subjected to a wear resistance test by reciprocating 50 times under a load of 4.0 N. To do. The evaluation of wear resistance is carried out by measuring the haze value (%) before and after the wear resistance test, and the change in haze value ΔH (% expressed by haze value after test (Ha) − haze value before test (Hb) ) Is calculated.

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