JP2000153578A - Window applying laminated film having photocatalytic function and laminate consisting of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a window applying laminated film having photocatalytic function good in execution properties at the time of application, having a self-adhesive layer not generating size residue at the time of peeling, excellent in weatherability and developing anti-fogging and antistaining effect by photocatalytic function, and a lami nate using the same. SOLUTION: A window applying laminated film having photocatalytic function is formed by laminating a photocatalytical function layer B consisting of a compsn. containing titanium oxide with a mean particle size of 0.001-0.5 μm and a hydrolysate of a hydrolyzable silicon compd. represented by formula (wherein n is an integer of 0-8, X1-X4 are each a halogen atom or a 1-8C alkoxy group), a base material film layer A and a self-adhesive layer C in this order and has characteristics showing conditions such that dry self-adhesive strength is 300 g/cm or more, holding force is 3 mm or less after 1 hr, self-adhesive strength after water spraying is 20% or more of dry self-adhesive strength and self-adhesive residue of a 1 mm2 size or more bonded to a glass plate at the time of peeling is 1/100 cm2 or less when the surface of the self-adhesive layer of the laminated film is applied to a glass plate and a laminate is constituted by laminating release paper to the self-adhesive layer of the laminated film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film for window application provided with a titanium oxide-containing layer used as a photo-oxidation catalyst, and a laminate comprising the same. It has good workability when attaching and has an adhesive layer that does not leave adhesive residue when it needs to be peeled off, and has excellent weather resistance, is useful for long-term outdoor exposure applications, and is highly transparent The present invention also relates to a photocatalytic functional window-attached laminated film excellent in scattering prevention performance and a laminated body comprising the same.

[0002]

2. Description of the Related Art Titanium oxide is itself an optical semiconductor, and has light having an energy greater than its band gap.
For example, when irradiated with ultraviolet rays, electrons are excited in the conduction band, and holes are generated in the valence band. A photocatalytic activity of decomposing nearby substances by an oxidation-reduction action based on electron transfer generated by the excited electrons and holes is known. Further, as disclosed in Japanese Patent No. 2756474, a large number of hydroxyl groups, which are said to be derived from water adsorbed and bonded to the surface of the excited titanium oxide, are generated.
The phenomenon of so-called “superhydrophilization” is also known. Various attempts have been made to utilize these photocatalytic activities in industry.

[0003] As disclosed in Japanese Patent No. 2756474, the effects obtained by these photocatalytic activities include an antifogging effect on a substrate surface by superhydrophilicity, prevention of adhesion of oily stains by superhydrophilicity, and an aqueous solution. There are so-called "self-cleaning effects" such as easy cleaning of dirt and photocatalytic decomposition of dirt remaining after cleaning. Use of these effects in industries, such as protection of agricultural houses, tents, and windows, has been a challenge. Examples of applications that are required to maintain transparency by fogging and antifouling can be given.

On the other hand, a laminated film for window application generally has a structure in which a transparent film is used as a base material and an adhesive is provided on one side of the film. This laminated film is used for automobiles,
It is pasted on glass such as lenses for spectacles and the like as windows other than windows for vehicles such as buses, trains, aircrafts and ships, windows for buildings such as houses and buildings, and other uses.
The target to be pasted is not limited to glass,
As long as it has transparency, such as a polyethylene plate, a polypropylene plate, or a polycarbonate plate, it may be a plastic plate used for a showcase, for example.

The effect of attaching the laminated film to glass or plastic is, for example, prevention of scattering. More specifically, an adhesive is applied to a transparent film and applied to the entire inner or outer surface of the window glass to provide the effect of reducing the scattering of broken pieces even if the glass is broken by a disaster or the like. It is.

In this case, if the adhesive strength of the applied pressure-sensitive adhesive is too low, or if the film thickness of the base material is too thin, the strain applied to the glass cannot be sufficiently relaxed, and the laminated film is easily peeled off from the glass to easily form the glass. There is a risk that the fragments are scattered and the fragments are scattered, or the film is easily broken and the glass is scattered.

Further, when a laminated film is pasted on a glass plate having a large area, especially when the laminated film has a shape conforming to the glass plate, if the laminating position is deviated during the laminating operation, it is necessary to peel off and relaminate. . In that case, a mark such as zipping may be formed on the pressure-sensitive adhesive, or a curl may be formed on the film, which is not preferable in appearance, and also reduces workability. In order to solve this problem, a method of wetting a glass plate with water before laminating a laminated film is generally performed. This method has an advantage that even if the bonding position is shifted, the adhesive force is low due to water, and the bonding is easy.
Ideally, it is preferable that the water evaporates with time after the lamination, and that the adhesive strength required for the scattering prevention effect is exhibited by maintaining the water as it is. However, the conventional laminated film has a problem in that the pressure-sensitive adhesive does not have affinity for water in many cases, and the adhesive strength is insufficient and the film is peeled off. Also, when peeling, the adhesive force between the adhesive and the base film is too low,
If the cohesive force of the pressure-sensitive adhesive is too small, the pressure-sensitive adhesive peels off from the base film and remains on the glass plate.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve such a problem, to provide good workability when affixing it to a window glass of an automobile or a building, and to leave glue residue when it needs to be peeled off. It has no pressure-sensitive adhesive layer, and has excellent weather resistance, is useful for applications that are exposed outdoors for long periods, and is highly transparent.
It is another object of the present invention to provide a photocatalytic functional window-attached laminated film which is excellent in anti-scattering performance and has excellent properties such as anti-fogging and transparency retention by anti-fouling because of its photocatalytic action.

[0009]

An object of the present invention is to provide a base film layer (A), a titanium oxide having an average particle size of 0.001 to 0.5 μm, and a hydrolyzable silicon represented by the following formula (1). A laminated film comprising a photocatalytic functional layer (B) and a pressure-sensitive adhesive layer (C) at least as layer components, which are composed of a composition containing a hydrolyzate of a compound, and are laminated in the order of B layer, A layer, and C layer. A photocatalytic function characterized in that the properties when the pressure-sensitive adhesive layer side surface of the laminated film is bonded to a glass plate satisfy all of the following conditions (a) to (d): This is achieved by a laminated film for attaching windows. (B) The normal state adhesive strength is 300 g / cm or more. (B) When the holding force was measured under the conditions of a load of 1 kg and a temperature of 80 ° C., the deviation was 3 mm or less after 1 hour. (C) The adhesive strength after maintaining for 6 hours after bonding to the glass plate after water spraying is 20% or more of the normal adhesive strength. (D) After adhering to a glass plate and maintaining it at a temperature of 70 ° C. for one week, it adheres to the glass plate when peeled off.
Adhesive residue of mm square size or more 1 per 100cm ²
Or less.

[0010]

Embedded image

(In the formula (1), n is an integer of 0 to 8, X ¹ ,
X ² , X ³ and X ⁴ each represent a halogen atom or an alkoxy group having 1 to 8 carbon atoms. Where X ¹ , X ² , X
³ and X ⁴ may be the same or different from each other. Hereinafter, the present invention will be described in detail.

[Base Film Layer (A)] The base film layer (A) of the present invention may be made of various known materials, for example, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate. ,
Polyolefins such as polyethylene and polypropylene,
Aliphatic / semi-aromatic / wholly aromatic polyamide, polyimide,
Polycarbonate, polyphenylene sulfide, polysulfone, a polymer such as a fluororesin such as polytetrafluoroethylene or ethylene-tetrafluoroethylene copolymer, a film obtained by biaxial stretching or uniaxial stretching, or a film obtained without stretching. No. Among these, the biaxially stretched polyester film has excellent mechanical properties, heat resistance, chemical resistance, etc., magnetic tape,
In addition to being used as photographic film, electrical insulating material, metallized film, packaging film, etc., it is also widely used for long-term outdoor applications such as agricultural houses, tents, window surface protective films, etc. Is preferred.

The above-mentioned polyester is a crystalline linear saturated polyester produced from an aromatic dibasic acid or its ester-forming derivative and a diol or its ester-forming derivative, and specifically, polyethylene terephthalate, Polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate,
Poly (1,4-cyclohexylene dimethylene terephthalate) and the like are preferably exemplified, and polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferably exemplified.

Further, a copolymer in which a part of an acid component and / or a diol component is substituted with another component, or a mixture with a polyalkylene glycol or another resin can also be used.

Further, various additives can be blended with the polyester. For example, sodium dodecylbenzenesulfonate or the like can be contained as an antistatic agent.

As the biaxially oriented polyester film in the present invention, a polyester film having good transparency is preferably used for applications requiring transparency, and a transparent biaxially oriented polyester film is particularly preferred. For applications requiring light-shielding properties, it is preferable to use a polyester film containing a pigment, and a white biaxially oriented polyester film containing a pigment such as TiO ₂ or SiO ₂ is particularly preferable.

The biaxially oriented polyester film of the present invention can be produced by a conventionally known method. For example, the above polyester is dried and then melted, extruded from a die (for example, T die, I die, etc.) onto a cooling drum and cooled to form an unstretched film. Can be manufactured by The thickness of the film is not particularly limited.
μm is preferred. As the polyester film, a film containing no lubricant is preferable from the viewpoint of surface flatness, but a lubricant is used for controlling surface roughness, for example, inorganic fine particles such as calcium carbonate, kaolin, silica, etc., precipitated fine particles of catalyst residue and / or silicone, It may be a film containing organic fine particles such as a crosslinked polystyrene. In addition, additives such as a stabilizer, a dye, and a flame retardant can be optionally contained in the polyester film of the present invention.

The base film layer (A) in the present invention comprises:
It preferably has weather resistance. As a method for imparting weather resistance, a known method can be used, and for example, a method of including an ultraviolet absorbing compound is exemplified. The ultraviolet absorbing compound will be described later.

In the present invention, as another method for imparting weather resistance to the base film layer (A), the base film layer (A) may be formed of a biaxially oriented polyester film layer (A1) and a weather resistant resin layer (A). A method of forming a layer composed of A2) is also preferable. In this case, as the layer constitution in the laminated film for photocatalytic functional window application of the present invention, a B layer, an A2 layer,
It is preferable that the layers A1 and C are stacked in this order.

As the resin constituting the weather-resistant resin layer (A2), a thermoplastic resin or a thermosetting resin having excellent weather resistance can be used, and a resin conventionally used as a weather-resistant coating film can also be used. Can be. As the thermoplastic resin or thermosetting resin having excellent weather resistance, acrylic resin,
It is preferably at least one resin selected from polyvinyl alcohol resin, epoxy resin, unsaturated polyester resin, urethane resin, melamine resin, silicone resin and acrylic silicone resin.
It is particularly preferable that an acrylic resin having good weather resistance alone is used as at least one of its constituent components.

It is more preferable that the weatherable resin layer (A2) contains an ultraviolet absorbing compound. Of course, the biaxially oriented polyester film layer (A
It is more preferable that the compound (1) contains an ultraviolet absorbing compound. The ultraviolet absorbing compound will be described later.

The method for forming the weather-resistant resin layer (A2) in the present invention is not particularly limited. For example, a solution or an aqueous dispersion of the weather-resistant resin is applied, if necessary, to a primer layer (P _A12 ) described later. A method of applying to the surface of the biaxially stretched polyester base material layer (A1) and drying it. To apply this solution or aqueous dispersion,
Various known methods can be applied, for example, application such as doctor blade coating, gravure roll coating, air knife coating, reverse roll coating, dip coating, curtain roll coating, spray coating, and rod coating. A method can be used.

The coating amount of the solution or the aqueous dispersion of the weather-resistant resin is 0.5 to 15 g / m ² (solid content), especially 1.
The range of 0 to 10 g / m ² (solid content) is preferable, and the thickness of the weather-resistant resin layer is 0.5 to 15 μm,
In particular, it can be 1.0 to 10 μm. If the coating amount is less than the above range, the weather resistance may be insufficient,
If the amount is more than the above range, there is a possibility that defects such as peeling of the weather-resistant resin layer may occur.

[Ultraviolet Absorbing Compound] Examples of the ultraviolet absorbing agent in the present invention include conventionally known ones such as salicylic acid compounds, benzophenone compounds and benzotriazole compounds. Among these, 2,4-dihydroxybenzophenone, 2,2′-
Dihydroxy-4-methoxybenzophenone, 2-
(2′-Hydroxy-5′-t-butylphenyl) benzotriazole or a benzophenone derivative represented by the formula (2) or (3) is particularly preferred.

[0025]

Embedded image

(In the formula (2), R ¹ and R ² each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, or a hydroxyl group. However, R ¹ and R ² are the same or different from each other. R ^{3 to} R ¹⁰ each represent a hydrogen atom or a hydrocarbon group, provided that R ^{3 to} R ¹⁰
May be the same or different from each other. )

[0027]

Embedded image

(In the formula (3), R ¹ and R ² each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, or a hydroxyl group. However, R ¹ and R ² are the same or different from each other. May be.)

The method of adding the above-mentioned ultraviolet absorbing compound to the polyester when it is present in, for example, a biaxially stretched polyester film is not particularly limited, but may be added to the resin in a polyester polymerization step or a melting step before film formation. Kneading, impregnation into a biaxially stretched film, and the like can be mentioned. In particular, kneading into a resin in a melting step before film formation is preferable from the viewpoint of preventing a decrease in the degree of polyester polymerization. At that time, the kneading of the ultraviolet absorbing compound can be performed by a direct addition method of the compound powder, a master batch method or the like. Further, the method of adding the ultraviolet absorbing compound to the weather-resistant resin is not particularly limited, but it can be carried out by dissolving or uniformly dispersing the compound in a solution or an aqueous dispersion of the weather-resistant resin.

The content of the ultraviolet absorbing compound in the polyester is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight. It is preferable to prevent mechanical properties from being deteriorated due to a decrease in the degree of polymerization of the polyester due to an excessive amount of the ultraviolet absorbing compound. In addition, the content of the UV-absorbing compound in the weatherable resin is 10 to 10% with respect to the total amount of the resin constituting the weatherable resin layer, in order to prevent insufficient or insufficient bleeding when the amount is too small. Preferably it is 25% by weight.

The ultraviolet absorbing compound may be contained in a layer other than the substrate film layer (A) as long as the object of the present invention is not hindered.

As described above, the substrate film layer (A) having weather resistance is used, and a glass plate is bonded to the surface of the laminated film of the present invention on the side of the pressure-sensitive adhesive layer (C). 100 rays with weather meter
When the haze change after irradiation for 0 hour is less than 5%, it becomes more preferable as a laminated film for photocatalytic functional window application. The film in which the haze change is 5% or more is used for crazing of a photocatalytic functional layer film described later,
Alternatively, the deterioration of the base film is considered to be a cause, which impairs the transparency of the laminated film and the mechanical strength of the coating and / or the base film, and may not be usable as a laminated film for window application. There is. The above haze value is measured according to JIS-K-6783b.

As a method for producing a laminated film having a haze change of less than 5%, for example, after forming the photocatalytic functional layer, a temperature of room temperature or more and less than 250 ° C. for 10 minutes or more
It is preferable to pass through a process in which the treatment is performed for less than a time. By this heat treatment, the polycondensation reaction of the binder film of the photocatalytic function layer is completed, and a strong and highly transparent film is generated. If this treatment is not performed, the residual reaction of the binder film of the photocatalytic functional layer that has not been completed by the polycondensation reaction is accelerated by a severe environment such as outdoor use, and the transparency of the film decreases due to cracking (crazing) due to shrinkage of the film. And the curl of the laminated film may be caused by the shrinkage of the coating film, and the laminated film for window application may not be usable.

The above-mentioned treatment temperature is preferably not lower than room temperature and lower than the glass transition temperature of the substrate, particularly for maintaining the flatness of the laminated film and preventing the transparency of the laminated film from lowering due to precipitation of low molecular weight substances in the substrate film. preferable. Further, the processing time is more preferably 1 hour or more and less than 100 hours.

In the present invention, during the total processing time,
The time during which the processing temperature is within the above-mentioned range is defined as the processing time of the heat treatment, and does not include a time outside the above-mentioned range, for example, a time corresponding to a temperature rise or a temperature drop.

The method of performing the above heat treatment is not particularly limited, but it is also possible to adopt a method in which after forming the photocatalytic functional layer by a method such as coating, the material once wound in a roll shape is heated again in the roll shape. Alternatively, a method in which the film is guided to a heating device while the film is running during the process to perform the treatment may be employed. Further, after the laminated film is cut into a desired size, a heat treatment may be performed on each sheet.

Further, the heating method is not limited either, and a known hot-air circulating thermostatic bath may be used, or electromagnetic waves such as ultraviolet light, visible light, infrared light, microwave, or ultrasonic waves may be used. Alternatively, a method of raising the temperature of the film and / or the coating layer may be adopted.

[Primer Layer (P _AB , P _AC , P _A12 )] In the present invention, the base film layer (A) or the weather-resistant resin layer (A2) is combined with the photocatalytic functional layer (B) or the hydrolyzable silicon compound. Between the hydrolyzate layer (S),
Between the base film layer (A) or the biaxially oriented polyester film layer (A1) and the pressure-sensitive adhesive layer (C), and / or between the biaxially oriented polyester film layer (A1) and the weather resistant resin layer (A2) It is preferable to provide a primer layer (P _AB , P _AC , P _A12 ) between the layers because the adhesion between the layers is improved. Here, P _AB ... between the A or A2 layer and the B or S layer, P _AC ... between the A or A1 layer and the C layer, P _A12 ... between the A1 layer and the A2 layer, It is. Examples of the layer configuration in these cases are shown in FIGS.

Of these primer layers, no primer layer (P _AB ) was present, and B
When the layer or the S layer is directly provided, the adhesiveness between the obtained film and the adjacent layer is low, and the film may fall off and the photocatalytic function may be impaired during subsequent processing and further when used as a product. is there.

These primer layers (P _AB , P _AC , P
_A12 ) is composed of a polyurethane resin, a polyester resin, an acrylic resin, at least one resin selected from an acrylic resin and a vinyl resin-modified polyester resin, or a composition mainly containing a silane coupling agent. More preferably, it is a layer.

The primer layers (P _AB ,
P _AC and P _A12 ) are preferably layers obtained by applying and drying a coating solution containing a composition for forming a primer layer. These primer layers (P _AB , P _AC , P _A12 )
May be the same or different.

Further, the base film layer (A) is a biaxially oriented polyester film, or the biaxially oriented polyester film layer (A1) and the weather resistant resin layer (A2)
In the case of a laminated film consisting of, for the primer layer, among those applied on the A layer or the A2 layer,
It is more preferable to apply the composition mainly composed of the aqueous solution or the aqueous dispersion of the resin to the surface of the polyester film before the completion of the orientation crystallization, and then perform drying, stretching and heat fixing.

The application of the primer layer is preferably carried out in a polyester film production process in a clean atmosphere. In particular, it is preferable to apply an aqueous coating solution to one or both surfaces of the polyester film before the crystal orientation is completed in this step. If performed in a step of separating and applying the film, it is not preferable because, unless the step is made to have a particularly clean atmosphere, trash, dust and the like are easily involved, and the performance of the product may be impaired. .

Here, the polyester film before the completion of the crystal orientation means an unstretched film obtained by heat-melting and rapidly solidifying the polyester to form a film, or an unstretched film in the longitudinal direction (longitudinal direction) or the transverse direction. Uniaxially stretched film oriented in one of two directions (width direction), and further stretched and oriented at a low magnification in two directions of longitudinal and transverse directions (finally oriented by re-stretching in the longitudinal or transverse direction) Biaxially stretched film before crystallization is completed).

The solid content of the coating solution is not particularly limited, but is usually 30% by weight or less, more preferably 10% by weight or less. The coating amount is 0.5 to ²⁰ g, preferably 1 to 10 g, per m ² of the running film.

As a coating method, any known coating method can be applied. For example, kiss coat method, berth coat method,
A die coating method, a reverse coating method, an offset gravure coating method, a myrbar coating method, a gravure coating method, a roll brushing method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, or the like may be used alone or in combination.

For the purpose of improving the wettability of the coating liquid to the polyester film before the completion of the crystal orientation, the surface of the polyester film may be activated by a known method such as corona discharge treatment.

The polyester film to which the coating liquid has been applied and before the completion of the crystal orientation is dried and led to steps such as stretching and heat setting. For example, a vertically uniaxially stretched polyester film to which an aqueous liquid has been applied is guided to a stenter and is horizontally stretched and thermally fixed. During this time, the coating liquid is dried and, if necessary, thermally crosslinked.

The orientation and crystallization conditions of the polyester film,
For example, stretching, heat setting, and the like can be performed under conditions conventionally accumulated in the art.

Examples of the polyurethane resin constituting the primer layer include the following polyvalent hydroxy compounds, polyvalent isocyanate compounds, chain extenders, crosslinking agents, and the like as components constituting the primer layer.

Examples of the polyvalent hydroxy compound include polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol, polyethylene adipate, polyethylene
Polyesters such as butylene adipate and polycaprolactone, polycarbonates, acrylic polyols, castor oil and the like can be used.

Examples of the polyvalent isocyanate compound include tolylene diisocyanate, phenylene diisocyanate,
4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like can be used.

Examples of the chain extender or the crosslinking agent include:
Ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, hydrazine,
Ethylenediamine, diethylenetriamine, ethylenediamine-sodium acrylate adduct, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, water and the like can be used.

Of these compounds, one
One or more are selected and a polyurethane resin is synthesized by a conventional polycondensation-crosslinking reaction.

As the polyester resin constituting the primer layer, the following polyvalent carboxylic acids and polyvalent hydroxy compounds can be exemplified as the components constituting the polyester resin.

As the polyvalent carboxylic acid, terephthalic acid,
Isophthalic acid, orthophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,
6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-
Sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, trimellitic acid mono Potassium salts and their ester-forming derivatives can be used.

As the polyhydroxy compound, ethylene glycol, 1,2-propylene glycol, 1,3-
Propylene glycol, 1,4-butanediol, 1,
6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, bisphenol A-1,2-propylene Glycol adducts, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethyl sulfonate, potassium dimethylolpropionate Etc. can be used.

Of these compounds, one is appropriately
One or more polyester resins are synthesized by a conventional polycondensation reaction.

As the acrylic resin constituting the primer layer, a resin containing alkyl acrylate or alkyl methacrylate as a main component is preferable. The component is 30 to 90 mol%, and a copolymerizable vinyl monomer having a functional group is used. It is a water-soluble or water-dispersible resin containing 70 to 10 mol% of a monomer component.

Examples of the alkyl group of the alkyl acrylate and the alkyl methacrylate include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, t-butyl group, 2-ethylhexyl group,
Lauryl, stearyl, cyclohexyl and the like can be mentioned.

The vinyl monomer copolymerizable with the alkyl acrylate or the alkyl methacrylate and having a functional group has a functional group such as a reactive functional group, a self-crosslinkable functional group, and a hydrophilic group. A carboxyl group or a salt thereof, an acid anhydride group, a sulfonic acid group or a salt thereof, an amide group or an alkylolated amide group, an amino group (including a substituted amino group) or an alkylolated amino group, or a group thereof; Having a salt, a hydroxyl group, an epoxy group and the like. Of these, particularly preferred are vinyl monomers having a carboxyl group or a salt thereof, an acid anhydride group, or an epoxy group. Two or more functional groups may be present in the acrylic resin.

The following are examples of specific compounds.
Examples of the compound having a carboxyl group or a salt thereof, an acid anhydride group include acrylic acid, methacrylic acid, itaconic acid,
Maleic acid, metal salts of these carboxylic acids with sodium and the like, ammonium salts, maleic anhydride and the like can be mentioned.

Examples of the compound having a sulfonic acid group or a salt thereof include vinyl sulfonic acid, styrene sulfonic acid, metal salts of these sulfonic acids with sodium and the like, and ammonium salts.

Compounds having an amide group or an alkylolated amide group include acrylamide, methacrylamide, N-methylmethacrylamide, methylolated acrylamide, methylolated methacrylamide,
Examples include ureido vinyl ether, β-ureido isobutyl vinyl ether, and ureido ethyl acrylate.

Compounds having an amino group or an alkylolated amino group or a salt thereof include diethylaminoethyl vinyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether,
Examples thereof include 2-aminobutyl vinyl ether, dimethylaminoethyl methacrylate, dimethylaminoethyl vinyl ether, those in which the amino group is converted into methylol, those quaternized with alkyl halide, dimethyl sulfate, sultone, and the like.

Examples of the compound having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate,
-Hydroxypropyl methacrylate, β-hydroxyethyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate and the like.

Examples of the compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate. Other compounds having a functional group include vinyl isocyanate and allyl isocyanate.

Further, olefins such as ethylene, propylene, methylpentene, butadiene, styrene, α-methylstyrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl chloride , Vinylidene fluoride, ethylene tetrafluoride, vinyl acetate, and the like are also examples of the vinyl monomer compound.

The acrylic resin and the vinyl resin-modified polyester resin constituting the primer layer are water-soluble or water-dispersible resins, and the acrylic resin and the vinyl resin are polymerized in the water-soluble or water-dispersible polyester resin. Can be synthesized by Examples of the components constituting the polyester include the same polyvalent carboxylic acids and polyvalent hydroxy compounds as described above, and ester-forming derivatives of these compounds. From these compounds, one or more may be appropriately selected. A polyester resin is synthesized by a conventional polycondensation reaction. As the components constituting the acrylic resin and the vinyl resin, one or more of the same alkyl acrylate or alkyl methacrylate as described above and a vinyl monomer compound having a functional group can be appropriately used. The acrylic resin and the vinyl resin-modified polyester resin of the present invention include those having a molecular structure such as so-called acrylic graft polyester described in JP-A-1-165633.

The silane coupling agent constituting the primer layer is a compound represented by the general formula YRSIX ₃ . Here, Y is an organic functional group such as a vinyl group, an epoxy group, an amino group, and a mercapto group; R is an alkylene group such as methylene, ethylene, and propylene; X is a hydrolytic group such as a methoxy group and an ethoxy group; It is an alkyl group. Specific compounds include, for example, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl)
-Γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. Preferred silane coupling agents are water-soluble or water-dispersible silane coupling agents. Of these compounds, one
One or more are selected and used.In particular, it is necessary to use an appropriate amount of a combination in which the functional groups can react with each other such as an epoxy group-containing silane coupling agent and an amino group-containing silane coupling agent. This is one of the preferred modes of use in terms of improving strength.

It is also one of the preferred modes of use to form a crosslinked primer layer by using alkaline inorganic fine particles together with the silane coupling agent. Examples of the alkaline inorganic fine particles to be used include iron oxide sol, alumina sol, tin oxide sol, zirconium oxide sol, silica sol and the like, and alumina sol and silica sol are particularly preferable. In particular, from the point of promoting the initial reactivity (dimerization, trimerization, etc.) of the silane coupling agent,
Silica sol is preferred.

The alkaline inorganic fine particles preferably have a small particle diameter having a large surface area, and preferably have an average particle diameter of 1 to 150 nm, more preferably 2 to 100 nm, and particularly preferably 3 to 50 nm. If the average particle size is larger than 150 nm, the surface area becomes too small, the reaction promoting action of the silane coupling agent is reduced, and the surface of the crosslinked primer layer is unfavorably roughened. On the other hand, when the average particle size is smaller than 1 nm, the surface area is too large, and it may be difficult to control the reaction of the silane coupling agent.

The amount of the alkaline inorganic fine particles is 1 to 50% by weight, and more preferably 2 to 50% by weight, based on the amount of the silane coupling agent.
Preferably, it is about 20% by weight. This amount is 1% by weight
If it is less than 50% by weight, the crosslinking reaction does not proceed. On the other hand, if it exceeds 50% by weight, the stability of the coating solution is lacking. For example, precipitation may occur in the coating solution in a short time after the addition of the inorganic fine particles.

A primer coating solution containing a silane coupling agent and alkaline inorganic fine particles, particularly an aqueous coating solution, has a pH of 4.0 to 7.0, preferably 5.0 to 7.0.
Adjust to 6.7. If this p is less than 4.0, the catalytic activity of the inorganic fine particles is lost, while if it exceeds 7.0, the coating liquid becomes unstable and precipitation may occur.

As the acid for adjusting the pH, inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as oxalic acid, formic acid, citric acid and acetic acid are used, and organic acids are particularly preferable.

A necessary amount of a surfactant such as an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be added to such a primer coating liquid, particularly an aqueous liquid.

As such a surfactant, the surface tension of the coating solution is 50 dyne / cm or less, preferably 40 dyne / cm.
/ Cm or less, and promotes wetting to the polyester film. For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-fatty acid ester sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap , Alkyl sulfates, alkyl sulfonates, alkyl sulfosuccinates, quaternary ammonium chloride salts, alkylamine hydrochlorides and the like. Further, other additives such as an antistatic agent, an ultraviolet absorber, a pigment, an organic or inorganic filler, a lubricant, and an anti-blocking agent can be mixed as long as the effects of the present invention are not lost.

[Photocatalytic Functional Layer (B)] The titanium oxide constituting the photocatalytic functional layer (B) in the present invention has a catalytic action on the oxidation-reduction of organic substances by irradiation with light having a specific energy. Yes, in addition to pure titanium oxide, includes those called hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, and titanium hydroxide. Titanium dioxide or those in a lower oxidation state than this are particularly preferably used. The crystal form of titanium dioxide may be any of anatase type, rutile type and flukite type, and may be a mixture thereof, but anatase type is particularly preferable.

These titanium oxides are in the form of fine powder,
The particle size is 0.001 to 0.
It needs to be 5 μm. This fine powder may be used as a dry powder, but it is desirable to prepare a dispersion in advance for uniform dispersion with a silica binder derived from a hydrolyzable silicon compound described later. Whether or not titanium oxide is well dispersed in the composition of the present invention greatly affects the photocatalytic function when a coating film is formed.

[0080] Titanium oxide is produced by various known methods. For example, A. A method of hydrolyzing a titanium compound such as titanyl sulfate, titanium chloride, and an organic titanium compound in the presence of a nucleating species, if necessary; B. a method in which an alkali is added to a titanium compound such as titanyl sulfate, titanium chloride, or an organic titanium compound, if necessary, in the presence of a nucleation seed to neutralize the compound; A method of vapor-phase oxidation of titanium chloride, an organic titanium compound, or the like; A method of firing the titanium oxide obtained by the methods A and B described above, and the like. In particular, A,
The titanium oxide obtained by the method B is preferable because of its high photocatalytic function. In order to further improve the photocatalytic function, the surface of the titanium oxide may be coated with a metal such as platinum, gold, silver, copper, palladium, rhodium, ruthenium, or a metal oxide such as ruthenium oxide or nickel oxide.

These titanium oxides are used after being highly dispersed in a solvent such as water. In order to uniformly disperse the ultrafine titanium oxide in a solvent such as water without secondary aggregation, it is preferable to store the titanium oxide as acidic or alkaline. PH 0.5 when placed under acidic conditions
To 4, particularly preferably 1 to 3.5. As a dispersion medium, a mixture of water and an alcohol may be used in addition to water.

The hydrolyzable silicon compound represented by the above formula (1) used in the present invention includes alkyl silicates, silicon halides and partially hydrolyzed products thereof. As the alkyl silicate, methyl, ethyl, isopropyl silicate and the like are used. Each of these silicates is used in the form of a monomer or an oligomer formed by partial hydrolysis. As the oligomer, a compound represented by the general formula Si _n O _n-1 (OR) _{2n + 2} (where n is 2 to 6,
R is an alkyl silicate condensate represented by an alkyl group having 1 to 4 carbon atoms). These oligomers can also be used in a mixture.

As a catalyst for the partial hydrolysis, an acid,
Any of the alkalis can be used. When the titanium oxide dispersion is acidic, an alkyl silicate hydrolyzed with an acid is preferred. The dispersion solvent of the hydrolysis solution is water or one having 1 carbon atom.
~ 4 alcohols are used. Esters such as ethyl acetate are not preferred because they make the composition liquid unstable.
The hydrolyzable silicon compound and its partial hydrolyzate used in the present invention are used for the purpose of binding titanium oxide, and are hereinafter referred to as silica binder.

The mixing of the titanium oxide and the silica binder can be appropriately performed. For example, a predetermined amount of an aqueous dispersion of titanium dioxide under an acidic condition is maintained at a liquid temperature of 10 to 50 ° C. and weighed. The alkyl silicate or partial hydrolyzate thus obtained is added dropwise over a period of time. After dropping,
The composition is reacted for 1 to 5 hours under stirring to prepare a composition liquid. When the alkyl silicate or the partial hydrolyzate is added, the hydrolysis catalyst may be added at the same time, or the hydrolysis may be promoted by utilizing the acid component present in the titanium dioxide dispersion. When an alcohol-based medium is used as the dispersion medium, a water / alcohol mixed medium dispersion of titanium dioxide and a liquid obtained by hydrolyzing 50 to 1500% of an alkyl silicate or a partial hydrolyzate in an alcohol medium are mixed with stirring. To obtain the present composition.

In the present invention, the hydrolysis rate is calculated based on the amount of water used assuming that the rate of hydrolysis is 100% when 2 moles of water is used per mole of alkyl silicate. When a partial hydrolyzate in the form of the general formula Si _n O _n-1 (OR) _{2n + 2} is used, a hydrolysis rate of 100% is obtained when 1 mol of this condensate is used and n + 1 mol of water is used.
Calculate as%.

In the present invention, the ratio of titanium and silica binder in the composition constituting the layer B is determined by the weight ratio (TiO ₂ / Si ₂ ) in terms of titanium dioxide and silicon dioxide, respectively.
O ₂ ) is preferably 96/4 to 30/70.
If the proportion of silica exceeds 70%, the photocatalytic function of the titanium oxide becomes small, and the practicality becomes poor. This is presumably because the proportion of silica covering the surface of the titanium oxide particles is increased, which hinders contact between the titanium oxide and the substance to be oxidatively decomposed. On the other hand, if the mixing ratio of the silica binder is 4% or less, the adhesive strength between the base material and the titanium oxide is not sufficient, and easily falls off by finger touch or vibration, which makes it difficult to industrially use as a coating film. become. A more preferable ratio of the silica binder is 10 to
50%.

The layer B in the present invention can be formed by applying a coating solution containing the above composition. The solid content concentration of the composition in the coating liquid is 30% or less by weight. Here, the solid content refers to the total amount of titanium oxide and silica binder in the entire composition, titanium oxide being titanium dioxide, silica binder being alkyl silicate in the composition or silicon (Si) content in an oligomer thereof. Is converted to SiO ₂ . Other components are mainly composed of water and / or an organic solvent, and should be substantially removed by drying after applying the composition on the surface of the substrate. The preferred solid content concentration is 5 to 20%, and when it is 5% or less, the adhesion to the substrate becomes strong, but the thickness of the coating film, that is, the amount of titanium dioxide is insufficient, and the coating film can sufficiently exhibit the photocatalytic function. Cannot be formed. It is possible to increase the thickness of the coating film by two-layer coating or three-layer coating, but usually, there is no merit of taking a troublesome two-layer coating by lowering the solid content concentration. However, it can be used for special applications such as when a strong thin coating is required even if the photocatalytic function is sacrificed.

On the other hand, if the solids content exceeds 30%, the dispersibility of the solids in the composition becomes poor, the storage stability of the composition is remarkably reduced, and gelation easily occurs in a few days.
Further, when the concentration is high, the film forming property is poor, and the adhesion of the formed film to the substrate is greatly reduced, and the film is peeled off when rubbed with a finger, which is not preferable.

A small amount of titanium alkoxide or titanium tetrachloride may be added to the composition of the present invention. Further, titanium or a silane coupling agent may be added. Further, various surfactants may be added to ensure the stability of the composition and improve the wetting characteristics. Also, a small amount of alkoxysilane or hydrosilane containing two or more alkoxy groups may be added, but these titanium and silane compounds are to be added in terms of silica when calculating the solid content.

When the base film layer of the laminated film of the present invention is a single layer, such a composition is applied to the layer A or the surface on which the primer layer (P _AB ) is provided. When there are two or more layers (A1, A2 layers and other layers), they are applied to the surface of the weather-resistant resin layer (A2 layer) or the primer layer (P _AB layer) thereon. As a lamination method, a method of applying a coating liquid containing such a composition is preferable in any case. Further, a method in which the above composition is applied, dried, and optionally baked at a low temperature to form a coating film is preferable. As an application method, spin coating, spray coating, bar coating, dipping, or the like is appropriately used depending on the shape of the substrate to be applied. The thickness of the coating film is from 0.001 to 3
μm, particularly 0.03 to 2 μm, is suitable. The photocatalytic activity of titanium oxide is related to the amount of titanium oxide that can be exposed to the surface and contacted with the compound to be oxidatively decomposed. In addition, the dispersion of particles does not always achieve the ideal uniformity.If the thickness is too small, the amount of titanium oxide on the surface of the coating film is small and the photocatalytic activity is not sufficient. preferable. When the thickness is within this range, the coating film can be made transparent, and a photoactive coating film can be formed on the surface of the substrate without impairing the transparency and color of the substrate.

The coating film provided by the above method is 100 to 1
By drying at 80 ° C., a strong film that does not easily peel off even when rubbed with a nail can be formed.

Further, in the present invention, a layer (S layer) composed of a hydrolyzable silicon compound hydrolyzate represented by the above formula (1) is provided between the layer provided with the photofunctional catalyst and the photofunctional catalyst layer. Provision of such a layer is preferable because oxidative decomposition of the layer adjacent to the photofunctional catalyst layer can be completely prevented by photocatalysis, and the long-term durability of the laminated film is improved.

The hydrolyzable silicon compound is the same or the same type as the hydrolyzable silicon compound constituting the photocatalytic functional layer, and the layer can be formed by the same method.

The provision of a layer made of a hydrolyzate of the hydrolyzable silicon compound has the effect of further improving the adhesiveness between the layer adjacent to the photofunctional catalyst layer and the photocatalytic functional layer.

[Adhesive layer (C)] In order to fix the photocatalytic functional window-attached laminated film of the present invention to a window glass, an adhesive layer (C) is formed on at least one surface of the base film layer (A).
Are laminated. Therefore, the essential layers in the photocatalytic functional window-attached laminated film of the present invention, that is, the base film layer (A), the photocatalytic functional layer (B), and the pressure-sensitive adhesive layer (C) are
The layers are stacked in the order of layer, layer A, and layer C.

Since this pressure-sensitive adhesive is required to withstand various light rays from the outside, particularly with respect to ultraviolet rays, an acrylic or silicone-based pressure-sensitive adhesive is preferable. Also,
Considering the cost and the case where the laminated film needs to be peeled off, an acrylic pressure-sensitive adhesive is particularly preferable.

Since the laminated film is not easily peeled off after being attached to the window glass, it needs to have a normal adhesion to glass of 300 g / cm or more. When the normal adhesive strength is less than 300 g / cm, the edge is rolled up, or the window glass is easily broken without being able to absorb the stress applied to the window glass at the time of a disaster or the window glass is broken. It is not preferable because the glass pieces cannot be sufficiently held and the glass is scattered.

Further, at the time of applying the laminated film to the window glass, the adhesive strength to the glass 6 hours after spraying water and applying the laminated film to the glass must be 20% or more of the normal adhesive strength. is there. If it is less than 20%,
Swelling of the pressure-sensitive adhesive layer due to water, curling of the laminated film,
Further, it is not preferable because air enters from the edge and further when it is stuck up and down on the window glass, it is peeled off from above by its own weight.

Further, in order to prevent the laminated film from being displaced with the lapse of time after pasting the laminated film on the window glass, the deviation after 1 hour under a load of 1 kg and a temperature of 80 ° C. in the holding force measurement was 3 mm or less. It is necessary to be. Preferably it is 1 mm or less. If the deviation is larger than 3 mm, the laminated film is easily displaced with time after being attached to the window glass, which is not preferable in appearance.

After the laminated film is pasted on the window glass, the film surface becomes dirty or scratched for some reason, making the appearance unsightly. When replacing the laminated film, the laminated film is peeled off. There is a need.
At that time, if the pressure-sensitive adhesive remains without being peeled, it will be a defect in appearance when pasting later. Therefore, after laminating the laminated film on glass and maintaining at 70 ° C. for one week, the adhesive residue of 1 mm square size or more adhered on the glass plate when peeled off may be one or less per 100 cm ^2. is necessary. Further, it is preferable that the pressure-sensitive adhesive residue is zero, that is, it is not present. If the number of adhesive residue is two or more, the appearance is unsightly, and it takes time and effort to clean the window glass with a solvent or the like, which is not preferable.

The above four characteristics are measured and evaluated by the following methods. (A) Adhesive force in normal state The laminated film is directly stuck on a washed glass plate, cut into a strip having a width of 25 mm, and evaluated by measuring the peeling force with a tensile tester. (B) Holding force (displacement) The laminated film was cut into a 20 mm width x 100 mm length, stuck on a washed glass plate, cut so that the stuck area became 20 mm x 20 mm, and automatically detected and held. The displacement after one hour is measured with a force tester under the conditions of a load of 1 kg and a temperature of 80 ° C. (C) Adhesion after water spraying 2 m on a washed glass plate of 10 cm x 20 cm
of water, spray the laminated film immediately, and measure the adhesion after 6 hours. (D) Adhesive Residue A sample prepared in the same manner as in the measurement of normal adhesive strength was subjected to a temperature of 70
After maintaining at ℃ for one week, the laminated film was peeled off at a speed of 10 m / min, and the remaining condition of the pressure-sensitive adhesive on the glass plate was observed.

The pressure-sensitive adhesive to be used is not particularly limited as long as it satisfies all of the above four conditions. However, in order to obtain the necessary adhesive force immediately after the application using water, In order to maintain the adhesive strength of the adhesive and to prevent the adhesive from remaining on the window glass when the laminated film is peeled off the window glass, for example, an adhesive described below is preferable.

The acrylic pressure-sensitive adhesive includes a solvent-based pressure-sensitive adhesive and an emulsion-based pressure-sensitive adhesive, but a solvent-based pressure-sensitive adhesive is particularly preferable for easily obtaining the above-mentioned pressure-sensitive adhesive properties.

As the acrylic solvent-based pressure-sensitive adhesive, those obtained by solution polymerization are used to satisfy various properties.
As a raw material, a known material for solution polymerization of an acrylic pressure-sensitive adhesive can be used. For example, as a main monomer as a skeleton, ethyl acrylate, butyl acrylate, 2-acrylate
Ethyl hexyl acrylate, acrylates such as acrylyl acrylate, as comonomers for improving cohesion, vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc., further promote crosslinking,
Functional group-containing monomers such as methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, glycidyl methacrylate, etc., for imparting a stable adhesive force and maintaining a certain adhesive force even in the presence of water. In the pressure-sensitive adhesive layer of the laminated film, a material having a low glass transition temperature (Tg), such as butyl acrylate, is particularly useful because a particularly high tackiness is required as a main polymer.

In the synthesis of the pressure-sensitive adhesive, a known method can be used. For example, in the presence of an organic solvent such as ethyl acetate or toluene, the necessary raw materials are charged into a reaction furnace, and heated using a peroxide system such as benzoyl peroxide or an azobis system such as azobisisobutyronitrile as a catalyst. It can be polymerized below. To increase the molecular weight, for example,
Ethyl acetate is preferably used in the method of batch-injecting monomers at the beginning and in the kind of organic solvent used, because toluene has a large chain transfer coefficient and suppresses polymer growth. At this time, the weight average molecular weight (Mw) is preferably 400,000 or more, more preferably 500,000 or more. If the molecular weight is less than 400,000, even if cross-linked with an isocyanate curing agent, sufficient cohesive strength cannot be obtained. When peeled off after a lapse of time, the adhesive may remain on the glass plate.

In order to improve the molecular weight, control at the polymerization stage is important. However, since a solvent system generally does not increase the molecular weight even if a sufficient adhesive strength is obtained, the molecular weight is controlled by the amount of the curing agent added during use. It is necessary to improve the ratio or the crosslinking ratio.

As the curing agent for the pressure-sensitive adhesive, a general isocyanate-based curing agent or an epoxy-based curing agent can be used particularly in the case of an acrylic solvent system. Is required, an isocyanate-based curing agent is preferred.

The adhesive may contain additives such as a stabilizer, an ultraviolet absorber, a flame retardant, and an antistatic agent. Especially when used for window application, in order to suppress the deterioration of the laminated film due to ultraviolet rays,
The addition of an ultraviolet absorber is effective.

The application of the pressure-sensitive adhesive solution to the base film layer (A) can be performed at any stage. When applying, if necessary, as a preliminary treatment for improving adhesion and coatability, the surface of the base film layer (A) may be subjected to physical treatment such as flame treatment, corona discharge treatment, plasma discharge treatment, or the like. Surface treatment or the primer layer (P
By providing _AC ), the adhesiveness between the pressure-sensitive adhesive and the base film layer (A) can be strengthened.

The pressure-sensitive adhesive layer (C) has a thickness of 1 to 50.
The range is preferably 0 μm, more preferably 5 to 50 μm. Since the adhesive strength depends on the thickness of the adhesive, the thickness of the adhesive layer is required to some extent, and if it is less than 1 μm,
In combination with the unevenness of the thickness of the plastic film, for example, the contact with the window glass becomes insufficient partially, and it is difficult to obtain the necessary adhesive strength. In addition, the thickness of the adhesive is 500 μm
If it is larger than the cost, the cost will be high, and sufficient hardening will not be performed in the processing, and cohesive failure will occur between the adhesive layers when the adhesive is peeled off after attaching to the window glass, and the adhesive will remain.

As the method of applying the pressure-sensitive adhesive, any known method can be used, and for example, a die coater method, a gravure roll coater method, a blade coater method, a spray coater method, an air knife coat method, a dip coat method and the like are preferable. And can be used alone or in combination.

The pressure-sensitive adhesive may be applied to the base film layer (A) by directly applying it to the film by the above-mentioned coating method. Alternatively, after once applying to the release paper and drying, The adhesive may be transferred by bonding a plastic film. The drying temperature at this time is preferably such that the residual solvent is as small as possible. For this purpose, the drying temperature and the time are not specified.
It is preferable to provide a drying time of 0 seconds to 5 minutes.

Since the pressure-sensitive adhesive has fluidity, the reaction has not yet been completed immediately after heating and drying, and curing is necessary to complete the reaction and obtain a stable pressure-sensitive adhesive strength. Generally, when heated at room temperature for about one week or more, for example, 50
When the temperature is about ° C, 3 days or more are preferable. In the case of heating, if the temperature is too high, the flatness of the plastic film may be deteriorated.

The laminated film of the present invention obtained by the above method is preferably transparent depending on its use, and specifically, the visible light transmittance is preferably 50% or more, more preferably 65% or more. The visible light transmittance is 45.
The transmittance is measured at a wavelength of 0 to 700 nm, and 50 n
The product of the solar energy intensity and the transmittance is calculated for each m, and the sum is divided by the total of the solar energy intensity at 450 to 700 nm to obtain a normalized value.

The laminated film of the present invention comprises a pressure-sensitive adhesive layer (C)
It is preferable to store in the form of a laminate in which a release paper is laminated on the layer C in order to protect the layer C. Such a release paper is a laminate in which a release layer is provided on at least one side of the paper, and the release layer is obtained by applying a wax, or by applying a curable silicone resin, drying and curing. Known ones such as those that can be used can be used.

[0116]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” means “parts by weight”. The properties of the laminated film were measured and evaluated by the following methods.

(1) Adhesive force in normal state A laminated film is stuck directly on a washed glass plate with a rubber roller (light load), and reciprocated once from above with a 2 kg rubber roller to make close contact. Temperature 23 as it is
It is left for 1 day under the conditions of ° C. and humidity 55 ± 5% RH, and then cut into strips having a width of 25 mm. This was attached to a tensile tester (Strograph manufactured by Toyo Seiki Co., Ltd.), and the glass plate was fixed. The laminated film was rotated 180 ° at 300 mm / min.
And its strength is defined as the normal adhesive strength.

(2) Holding force The laminated film is cut into a size of 20 mm width × 100 mm length, and is stuck on a washed glass plate in the same manner as in the normal adhesion measurement method. At this time, the bonding area between the laminated film and the glass plate is set to 20 mm × 20 mm. The glass plate is fixed and attached to an automatic detection holding force tester (made by Uni Kogyo Co., Ltd.). At this time, the ambient temperature is set to 8
The temperature was set to 0 ° C., a weight of 1 kg was hung toward the laminated film, and the shift after one hour was read to determine the holding force.

(3) Glass adhesive strength after spraying with water 2 m on a washed glass plate of 10 cm × 20 cm
Spray 1 l of water. Immediately thereafter, the laminated film is laminated, and excess water is swept away from the center with a squeegee to remove the water. Then, the adhesive strength after maintaining for 6 hours is measured by the same method as the normal adhesive strength.

(4) Evaluation of Adhesive Remaining A sample prepared in the same manner as in the measurement of normal adhesive strength is left at 70 ° C. for one week after application. After that, 10m /
The laminated film is peeled off at a speed of minutes, the remaining condition of the adhesive on the glass plate is observed, and the evaluation is made according to the following criteria. ：: No adhesive residue at all Δ: One adhesive residue having a size of 1 mm square or more / 100 cm ² ×: Residual adhesive. 1 mm square or larger
More than pieces / 100cm ²

(5) Visible light transmittance Visible light transmittance at a wavelength of 450 to 700 nm
The transmittance is measured (Shimadzu Corporation, UV-310PC type). Calculate the product of solar energy intensity and transmittance every 50 nm. The sum is normalized and calculated by dividing the sum by the sum of the solar energy intensity at 450 to 700 nm. The evaluation is made according to the following criteria. ：: visible light transmittance of 65% or more △: visible light transmittance of 50% or more ×: visible light transmittance of less than 50%

(6) Anti-scattering property A laminated film is stuck on a glass plate of 30 cm × 30 cm and 3 mm in thickness in the same manner as in the preparation of the sample when measuring the adhesive strength after spraying with water. The center of the glass plate is hit with a metal hammer from the side where the film is not attached, and the state of scattering of the glass is checked. ：: The total amount of scattered glass is 70 g or less and the mass of one piece is 30 g or less Δ: The total amount of scattered glass is 100 g or less and the mass of one piece is 50 g or less, other than the evaluation of ○ above X: The total amount of scattered glass Is heavier than 100g, or one piece weighs more than 50g

(7) Outdoor exposure promotion test Sunshine weather meter (Suga Test Instruments Co., Ltd.
WEL-SUN-HCL type) and JIS-K-6
The outdoor exposure acceleration test is performed by irradiating the film for 1000 hours (corresponding to one year of outdoor exposure) according to 783b.

(8) Weather resistance-1 (change in haze) A haze meter (POIC Co., SEP-HS-D1 type) was used for the samples before and after the outdoor exposure promotion test.
And the haze change before and after the test is used to evaluate the weather resistance according to the following criteria. ：: Haze change is less than 5% Δ: Haze change is 5% or more and less than 15% ×: Haze change is 15% or more

(9) Weather resistance-2 (elongation retention) Tensile rupture elongation of each sample before and after the outdoor exposure promotion test was measured using a tensile tester (Orientec Co., Ltd., UCT-100 type). The weather resistance is evaluated according to the following criteria using the elongation retention obtained by the following formula. Elongation retention (%) = (S / S ₀ ) × 100 In the above formula, S indicates the tensile elongation at break after the test is performed, and S ₀ indicates the tensile elongation at break before the test is performed. ：: Elongation retention is 85% or more Δ: Elongation retention is 50% or more and less than 85% ×: Elongation retention is less than 50%

(10) Degradability of aldehyde The sample is placed in a 0.8-liter glass container, and a quantity of acetaldehyde, which is a malodorous component, having a concentration of 100 ppm is introduced into the glass container and sealed. Next, after maintaining for 30 minutes without irradiating ultraviolet rays for 30 minutes, an amount of ultraviolet light on the sample surface to be 1 mW / cm ² was irradiated with black light for 60 minutes, and then the concentration of acetaldehyde in the glass container was measured. Evaluate according to the following criteria. ：: less than 50 ppm Δ: 50 ppm or more and less than 75 ppm ×: 75 ppm or more

(11) Anti-fogging property 100 ml of water was placed in a 500 ml beaker, and 30 ° C.
Then, the sample film is covered with a beaker so that the photocatalytic function layer is on the inside, the room temperature is kept at 8 ° C. or lower, observed for 7 days, and evaluated according to the following criteria. ：: There was no fogging on the film surface. X: Fogging occurred on the film surface.

Example 1 At the end of the polymerization step, the following formula
1 part by weight of the compound shown in (4) was added to 99 parts by weight of the resin, and polyethylene terephthalate having an intrinsic viscosity of 0.65 measured in o-chlorophenol at 35 ° C. (lubricant 50)
0 ppm).

[0129]

Embedded image

The polyethylene terephthalate was melt-extruded on a rotary cooling drum maintained at 20 ° C. to a thickness of 480 μm.
m, and then stretched 3.5-fold in the machine axis direction. Then, an aqueous acrylic resin dispersion (methyl methacrylate component (65 mol%), ethyl acrylate component (28 Mol%), a copolymer of a 2-hydroxyethyl methacrylate component (2 mol%) and an N-methylolacrylamide component (5 mol%), and a glass transition temperature of 45 ° C) as a solid content of 40%.
Parts by weight, polyester resin aqueous dispersion (Takamatsu Oil & Fat Co., Ltd.)
50 parts by weight as solids, and a mean particle size of 0.03
An aqueous coating liquid having a solid content of 2.7% by weight was prepared by diluting a composition consisting of 10 parts by weight of an aqueous dispersion of fine particles of a crosslinked acrylic resin fine particle having a solid content of 2.7% by weight with a kiss coat method. 1 m ² per coating solution about 3 as the weight
g. Subsequently, the film was stretched 3.9 times in the transverse direction while drying at 105 ° C., and further heat-treated at 210 ° C. to obtain a primer-coated polyester film having a thickness of 50 μm.

A coating solution obtained by partially hydrolyzing ethyl silicate as a hydrolyzate of a hydrolyzable silicon compound (Colcoat 103X, manufactured by Colcoat Co., Ltd.) was applied on the primer layer of the film to give a coating solution of 5 g / m ² . Coated with the coating amount and dried at 150 ° C. for 1 minute. Further, a composition of anatase-type titanium dioxide having an average particle size of 0.07 to 0.1 μm and ethyl silicate was further added to the composition.
A coating solution (ST-K03, manufactured by Colcoat Co., Ltd.) was prepared by dissolving a composition in a ratio of 50 parts / 50 parts in terms of iO ₂ / SiO ₂ into a solution having a solid content of 10%. And coated at an application amount of 5 g / m ² ,
C. for 2 minutes to obtain a laminated film provided with a photocatalytic functional layer.

On the other hand, butyl acrylate as a main monomer and methyl acrylate as a comonomer in a ratio of 3: 1 as an acrylic pressure-sensitive adhesive were subjected to solution polymerization using azobisisobutyronitrile as a reaction catalyst in a solvent of ethyl acetate. A polymer for a pressure-sensitive adhesive having a weight average molecular weight of about 650,000 was prepared, and an ultraviolet absorber (Tinuvin 328 (manufactured by Ciba Geigy)) was further added.

An isocyanate-based cross-linking agent was added to the pressure-sensitive adhesive polymer, the surface of the laminated film opposite to the photocatalytic functional layer was subjected to corona treatment, and the dried film had a thickness of 2%.
It was applied so as to have a thickness of 0 μm. Tables 1 and 2 show the properties of this laminated film.

Example 2 A primer-coated polyester film was obtained in the same manner as in Example 1. On the primer layer of this film, 98 parts by weight of an acrylic resin paint (BR-60, manufactured by Mitsubishi Rayon Co., Ltd.), 2 parts by weight of an ultraviolet absorber (2,4-dihydroxybenzophenone) and 500 parts by weight of methyl ethyl ketone (solid content) Concentration of 20% by weight) is continuously applied by a roll coating method,
It was kept at 100 ° C. for 1 minute in a drying oven to dilute the solvent and at the same time heat-treat to obtain a weather-resistant resin-coated polyester film provided with a 2.8 μm-thick weather-resistant resin layer. On the weather-resistant resin layer of this film, a layer made of a hydrolyzable silicon compound hydrolyzate and a photocatalytic functional layer were provided in the same manner as in Example 1, and an adhesive layer was further provided in the same manner as in Example 1. Thus, a laminated film was obtained. Tables 1 and 2 show the properties of this laminated film.

Example 3 A laminated film was obtained in the same manner as in Example 1, except that no ultraviolet absorbing compound was added to polyethylene terephthalate and the polymer for the pressure-sensitive adhesive. Tables 1 and 2 show the properties of this laminated film. This laminated film is slightly inferior to the weather resistance of the substrate,
It is not suitable for outdoor use for a long time, but because it satisfies the above-mentioned properties as an adhesive layer, it has good workability at the time of application as a film for window application and when it is necessary to peel it off Has an adhesive layer in which no adhesive residue remains, is highly transparent, and has excellent scattering prevention performance.

[Comparative Example 1] A solution using butyl acrylate alone as a main monomer as an acrylic pressure-sensitive adhesive and azobisisobutyronitrile as a reaction catalyst in a solvent of ethyl acetate / toluene (mixing ratio 1/1). A laminated film was obtained in the same manner as in Example 1, except that a polymer having a weight average molecular weight of about 350,000 was prepared and used. Table 1 shows the properties of the laminated film. This laminated film does not satisfy the above-mentioned various properties as the pressure-sensitive adhesive layer and is not suitable for use as a film for window application.

[Comparative Example 2] The same method as in Example 1 except that a layer made of a composition of anatase type titanium dioxide and ethyl silicate was not provided on the hydrolyzate layer of the hydrolyzable silicon compound. Produced a laminated film. Tables 1 and 2 show the properties of this laminated film. Since there is no photocatalytic functional layer of anatase type titanium dioxide, various properties such as antifouling and antifogging cannot be expected.

[0138]

[Table 1] ---------------------------------------------- -------------------- Glass holding power Floating film after spraying Adhesive Normal adhesive strength Glass adhesive strength ・ Hagare Remaining (g / cm) (mm) (g / cm) ------------------------------------------------ ------------------ Example 1 550 0 150 None ○ Example 2 550 0 150 None ○ Example 3 550 0 150 None ○ Comparative Example 1 400 5 65 Initially Peeling ○ Comparative Example 2 550 0 150 None ○ ---------------------------------------- --------------------------

[0139]

[Table 2] ---------------------------------------------- ----------------------- Visible light scattering prevention Weather resistance Photocatalytic activity Transmittance performance Haze change Elongation retention Artificial human degradability Antifogging property ----- -------------------------------------------------- -------------- Example 1 ○ ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ ○ Example 3 ○ ○ × × ○ ○ Comparative Example 1 △ △ ○ ○ ○ ○ Comparative Example 2 ○ ○ ○ − × × --------
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[0140]

According to the present invention, it has good workability when affixed to a window glass of a car or a building, has an adhesive layer which does not leave an adhesive residue when it needs to be peeled off, and has a weather resistance. It is excellent in properties, useful for applications exposed outdoors for a long period of time, and is also highly transparent, excellent in scattering prevention performance, and excellent in properties such as anti-fog, retention of transparency by anti-fouling due to its photocatalytic action And a laminated film for photocatalytic functional window application.

[Brief description of the drawings]

FIG. 1 shows a laminated film of the present invention in which a primer layer (P _AB ) is interposed between a base film layer (A) and a photocatalytic functional layer (B), and a base film layer (A) and an adhesive layer (C). )
FIG. 3 is a diagram showing a layer configuration in a case where a primer layer (P _AC ) is provided between the first and second layers.

FIG. 2 shows a laminated film according to the present invention, in which a primer layer (P _AB ) is provided between a base film layer (A) and a layer (S) composed of a hydrolyzable silicon compound hydrolyzate. FIG. 2 is a diagram showing a layer configuration in a case where a primer layer (P _AC ) is provided between a film layer (A) and an adhesive layer (C).

FIG. 3 In the laminated film of the present invention, the base film layer (A) is a biaxially oriented polyester film layer (A1) and a weather resistant resin layer (A2), and a primer layer (P
_A12 ) and a biaxially oriented polyester film layer (A1) comprising a primer layer (P _AB ) between the weather-resistant resin layer (A2) and the photocatalytic functional layer (B).
FIG. 3 is a diagram showing a layer configuration in a case where a primer layer (P _AC ) is provided between the adhesive layer and a pressure-sensitive adhesive layer (C).

FIG. 4 In the laminated film of the present invention, the base film layer (A) has a biaxially oriented polyester film layer (A1) and a weather resistant resin layer (A2), and a primer layer (P
_A12 ) and a primer layer (P _AB ) between the weather-resistant resin layer (A2) and the layer (S) composed of a hydrolyzable silicon compound hydrolyzate;
FIG. 3 is a diagram illustrating a layer configuration when a primer layer ( _PAC ) is provided between a biaxially oriented polyester film layer (A1) and an adhesive layer (C).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (Reference) C03C 17/23 C03C 17/23 F term (Reference) 4F100 AA20B AA21B AH03A AH03E AH03H AH03K AH06B AH06K AK21D AK21E AK25E AK25E AK25E AK25E AK41A AK41D AK41K AK44E AK51D AK51E AK52D AK52E AK53E AR00A AR00B AR00C AR00D AR00E AT00A BA03 BA04 BA05 BA07 BA10B BA10C CA07A CA07E DE01B EH46 EJ37 EJ38A EJ42 EJ65D EJ67D GB07 GB32 JB07 JK06 JL00 JL08B JL09 JL09A JL09E JL13C JN01 JN08 YY00 YY00B 4G059 AA01 AC21 AC22 EA04 EA05 EB09 FA11 FA14 FA18 FA19 GA02 GA16

Claims (18)

[Claims] 1. A substrate film layer (A) having an average particle size of 0.0
A photocatalytic functional layer (B) and a pressure-sensitive adhesive layer (C) each comprising at least a layer containing a composition containing a titanium oxide of 01 to 0.5 μm and a hydrolyzate of a hydrolyzable silicon compound represented by the following formula (1): A laminated film as a constituent component, characterized by being laminated in the order of layer B, layer A, and layer C, and characteristics when the surface of the laminated film on the side of the pressure-sensitive adhesive layer is bonded to a glass plate. Satisfies all of the following conditions (a) to (d): (B) The normal state adhesive strength is 300 g / cm or more. (B) When the holding force was measured under the conditions of a load of 1 kg and a temperature of 80 ° C., the deviation was 3 mm or less after 1 hour. (C) The adhesive strength after maintaining for 6 hours after bonding to the glass plate after water spraying is 20% or more of the normal adhesive strength. (D) After adhering to a glass plate and maintaining it at a temperature of 70 ° C. for one week, it adheres to the glass plate when peeled off.
Adhesive residue of mm square size or more 1 per 100cm ²
Or less. Embedded image (In the formula (1), n is an integer of 0 to 8, X ¹ , X ² , X ³ , X ⁴
Represents a halogen atom or an alkoxy group having 1 to 8 carbon atoms, respectively. However, X ¹ , X ² , X ³ and X ⁴ may be the same or different from each other. ) 2. A layer (S) comprising a hydrolyzable silicon compound represented by the formula (1) is provided between the base film layer (A) and the photocatalytic functional layer (B). 1
The photocatalytic functional laminated film for window application according to the above. 3. The photocatalytic functional windowing laminated film according to claim 1, wherein the substrate film layer (A) has weather resistance. 4. The laminated film for photocatalytic functional window application according to claim 1, wherein the base film layer (A) is a biaxially oriented polyester film. 5. The laminated film for photocatalytic functional window application according to claim 3, wherein the base film layer (A) contains an ultraviolet absorbing compound. 6. The base film layer (A) comprises a biaxially oriented polyester film layer (A1) and a weather-resistant resin layer (A).
2) a laminated film layer comprising: B layer, A2 layer,
The photocatalytic functional windowing laminated film according to claim 3, wherein the A1 layer and the C layer are laminated in this order. 7. The resin constituting the weather-resistant resin layer (A2) is at least one selected from acrylic resin, polyvinyl alcohol resin, epoxy resin, unsaturated polyester resin, urethane resin, melamine resin, silicone resin and acrylic silicone resin. The laminated film for photocatalytic functional window sticking according to claim 6, which is a resin of the above. 8. The photocatalytic functional windowing laminated film according to claim 7, wherein the weatherable resin layer (A2) comprises an acrylic resin as at least one of its constituent components. 9. The laminated film for photocatalytic functional windowing according to claim 6, wherein the weatherable resin layer (A2) contains an ultraviolet absorbing compound. 10. A biaxially oriented polyester film layer (A
1) wherein 1) contains an ultraviolet absorbing compound.
10. The laminated film for applying a photocatalytic function to a window according to any one of items 9. 11. The photocatalytic functional windowing laminated film according to claim 5, wherein the ultraviolet absorbing compound is a benzophenone derivative represented by the following formula (2) or (3). Embedded image (In the formula (2), R ¹ and R ² each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group or a hydroxyl group. However, R ¹ and R ² may be the same or different from each other. R ^{3 to} R ¹⁰ each represent a hydrogen atom or a hydrocarbon group, provided that R ^{3 to} R ¹⁰ may be the same or different from each other. (In the formula (3), R ¹ and R ² each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, or a hydroxyl group. However, even if R ¹ and R ² are the same or different from each other, Good.) 12. The photocatalytic functional window sticker according to claim 4, wherein the biaxially oriented polyester film is a biaxially oriented polyethylene terephthalate film or a biaxially oriented polyethylene-2,6-naphthalate film. For laminated film. 13. A haze change after laminating a glass plate on the surface of the laminated film on the side of the pressure-sensitive adhesive layer (C) and irradiating the photocatalytic functional layer surface with light rays for 1000 hours with a sunshine weather meter is less than 5%. The photocatalytic functional laminated film according to any one of claims 3 to 12. 14. The photocatalytic functional windowing laminated film according to claim 1, wherein at least one primer layer selected from the following primer layers is provided. (1) Primer layer (P _AB ): A layer or A2 layer and B
Between layer and S layer (2) Primer layer ( _PAC ): A
Layer or between A1 layer and C layer (3) Primer layer (P _A12 ): between A1 layer and A2 layer 15. The primer layers (P _AB , P _AC and P
_A12 ) at least one of which is composed mainly of a polyurethane resin, a polyester resin, an acrylic resin, and at least one resin selected from an acrylic resin and a vinyl resin-modified polyester resin, or a silane coupling agent; 15. A layer made of an object.
The laminated film for sticking a photocatalyst window according to the above item. 16. The base film layer (A) is a biaxially oriented polyester film or a laminated film comprising a biaxially oriented polyester film layer (A1) and a weather resistant resin layer (A2), and a primer layer ( P _AB ,
_PAC and / or P _A12 ) is a primer layer formed by applying a coating solution containing the composition constituting the primer layer to the surface of the layer A or A1 layer, and the primer layer constitutes the primer layer After applying a coating solution composed of an aqueous solution or aqueous dispersion containing the composition to at least one surface of the polyester film before completion of the orientation crystallization,
The photocatalytic functional windowing laminated film according to any one of claims 14 to 15, which is a layer formed by performing drying, stretching, and heat setting. 17. The photocatalytic functional windowing laminated film according to claim 1, which has a visible light transmittance of 50% or more. 18. A laminate obtained by laminating a release paper on the pressure-sensitive adhesive layer (C) of the laminated film for photocatalytic functional window according to any one of claims 1 to 17.