JP2015101007A - Laminate, composition for forming light transmission layer and method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simultaneously realize improvement of hardness (curl suppression), improvement of blocking resistance (prevention of light transmittance deterioration), and improvement of adhesion between a support layer and a hard coat layer.SOLUTION: A laminate 1 is obtained by laminating: a light transmission layer 20 having a binder and a string-like aluminum silicate; and a support layer 10 that supports the light transmission layer 20. In the laminate 1, the content of the binder is 70-99 mass% based on the light transmission layer 20. The content of the string-like aluminum silicate is 1-30 mass% based on the light transmission layer 20. The film thickness of the light transmission layer 20 is 0.5-100 μm.

Description

  The present invention relates to a laminate in which a light transmission layer and a support layer are laminated, a composition for forming a light transmission layer, and a method for producing the laminate.

Conventionally, the surface of a touch panel display or the surface of a vehicle body body is coated with a hard hard resin layer for the purpose of preventing scratches. Such a hard coat layer expresses better scratch resistance as the hardness increases, and is usually used in a state of being laminated on a film-like support layer.
In recent years, from the viewpoints of durability, visibility, and productivity, the hardness is high and curling (a phenomenon in which the hard coat layer turns off from the support layer and peels off) does not occur, and blocking between films (roll There is a demand for a film that does not generate a phenomenon in which films are stuck to each other when the film is wound by a to-roll method.

In Patent Document 1, as a method for increasing the hardness of the hard coat layer, a method for increasing the degree of crosslinking of a resin or the like serving as a binder material is reported.
However, in the technique of Patent Document 1, there is a problem that curl is generated due to a decrease in the volume of the resin due to the condensation reaction because the hard coat layer is made to exhibit sufficient hardness by a method of increasing the degree of crosslinking.

On the other hand, as a method for increasing the hardness of the hard coat layer and suppressing curling, a method of laminating the hard coat layer on both sides of the support layer to balance the stress has been reported (Patent Document 2).
However, in the technique of Patent Document 2, the provision of hard coat layers on both sides of the support layer itself is a direct factor that increases the number of manufacturing steps and layers, leading to an increase in cost and thickness.

On the other hand, inorganic fine particles such as silica are added to the hard coat layer for the purpose of suppressing the blocking phenomenon between the films while increasing the hardness of the hard coat layer and further improving the adhesion between the hard coat layer and the support layer. A method of forming an uneven shape on the surface of the hard coat layer and imparting an anchor effect at the interface with the support layer has also been reported (Patent Document 3).
However, as in the technique of Patent Document 3, when sufficient inorganic fine particles are added to suppress blocking, the incident light is scattered due to the unevenness of the surface of the hard coat layer and the refractive index difference between the binder and the inorganic fine particles. There exists a subject that the transmittance | permeability of this falls. The film containing the hard coat layer may be stretched, but at that time, voids (voids) are generated at the interface between the binder and the inorganic fine particles, and in this case also incident light is scattered and light is transmitted. The rate will drop.
In addition, the anchor effect by the inorganic fine particles is obtained when the relationship between the unevenness of the surface of the support layer and the particle size of the inorganic fine particles becomes appropriate, that is, when a part of the inorganic fine particles are fitted to the unevenness of the support layer. It is difficult to find a hard coat layer with good adhesion to any type of support layer, especially for support layers with small irregularities. It has been difficult to improve the adhesion of the layers.

JP 2003-80644 A JP 2013-132785 A JP2013-95108A

Thus, at present, even if any of the techniques disclosed in Patent Documents 1-3 is used, improvement in hardness (inhibition of curling), improvement in blocking resistance (prevention of reduction in light transmittance), support layer and hard The problem of improving the adhesion with the coat layer has not been realized at the same time.
Accordingly, a main object of the present invention is to provide a laminate capable of simultaneously improving hardness, blocking resistance and adhesion, and another object of the present invention is to produce the laminate. Another object of the present invention is to provide a composition for forming a light transmitting layer and a method for producing a laminate.

  Based on the above-mentioned problems, as a result of intensive studies by the present inventors, it has been difficult to achieve a balance by adding a certain amount of aluminum silicate to the binder, improving hardness (suppressing curl) and improving blocking resistance. (Preventing a decrease in light transmittance) and improving the adhesion between the support layer and the hard coat layer were successfully achieved at the same time.

That is, according to the present invention,
A laminate in which a light transmission layer having a binder and a string-like aluminum silicate and a support layer supporting the light transmission layer are laminated,
The content of the binder in the light transmission layer is 70 to 99% by mass, and the content of the string-like aluminum silicate in the light transmission layer is 1 to 30% by mass,
A layered product in which the layer thickness of the light transmission layer is 0.5 μm or more and 100 μm or less is provided.

  According to the present invention, improvement in hardness, blocking resistance and adhesion can be realized at the same time.

It is sectional drawing which shows schematic structure of a laminated body. It is an X-ray diffraction pattern of a string-like aluminum silicate. It is a scanning electron micrograph of a string-like aluminum silicate.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.
Below, the example which applied the light transmissive layer concerning this invention to the hard-coat layer is demonstrated. Here, the “hard coat layer” means a layer having a pencil hardness of 1 H or more (for the pencil hardness, see Experimental Example 1 described later; evaluation items of samples).

[Laminate (1)]
As shown in FIG. 1, the laminated body 1 concerning preferable embodiment of this invention has the support body layer 10 and the hard-coat layer 20, and the structure by which the hard-coat layer 20 was laminated | stacked on the support body layer 10 have.
The hard coat layer 20 has a pencil hardness of 1H or more.
Specifically, the hard coat layer 20 has a binder 22 and a string-like aluminum silicate 24. The content of the binder 22 in the hard coat layer 20 is 70 to 99% by mass (70% by mass or more and 99% by mass or less), and the content of the string-like aluminum silicate 24 in the hard coat layer 20 is It is 1-30 mass% (1 mass% or more and 30 mass% or less).
The layer thickness of the hard coat layer 20 is 0.5 to 100 μm (0.5 μm or more and 100 μm or less).

[Support layer (10)]
The support layer 10 is preferably a resin film, and may be a resin molded product having a shape such as a resin bumper for automobiles.

(1) Resin film As a resin film, conventionally well-known various resin films can be used.
For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films.

Among these, a polycarbonate film, a polyester film, an acrylic film, and a cellulose ester film are preferable.
In particular, it is preferable to use a polyester film or a cellulose ester film, and it may be a film manufactured by melt casting or a film manufactured by solution casting.

  The thickness of the resin film is preferably set to an appropriate thickness according to the type and purpose of the resin. For example, it is generally in the range of 10 to 300 μm. Preferably it is 20-200 micrometers, More preferably, it is 30-100 micrometers.

(2) Resin-molded product Various known resin-molded products can be used as the resin-molded product.
Examples thereof include resin parts that are generally used in the fields of electrical / electronic / OA equipment, optical parts, precision machines, automobiles, security / medicine, building materials, general merchandise, and the like.
In addition, as the resin molded product, a conventionally known thermoplastic resin may be formed into a target shape by a general molding technique such as injection molding, in-mold molding, blow molding or the like.
As the thermoplastic resin, various conventionally known thermoplastic resins can be used.
For example, polyester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyethersulfone) resins, polyethylene terephthalate resins, polyester resins such as polyethylene naphthalate, polyethylene resins, polypropylene resins, cellophane, cellulose diacetate Resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, syndiotactic polystyrene, polycarbonate resin, norbornene resin, polymethylpentene resin , Polyether ketone resin, polyether ketone imide film, polyamide film, fluororesin film, nano Ron resin, polymethyl methacrylate resin, and acrylic resin.
Moreover, the thermoplastic resin can contain conventionally well-known various additives in the range which does not impair said transparency.
Examples of such additives include heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, colorants, mold release agents, sliding agents, infrared absorbers, light diffusing agents, fluorescent whitening agents, and antistatic agents. Examples include agents, flame retardants, flame retardant aids, plasticizers, reinforcing fillers, impact modifiers, photocatalytic antifouling agents, and photochromic agents.
The heat stabilizer, the antioxidant, the ultraviolet absorber, the light stabilizer, the colorant, the release agent, and the like can be blended with known appropriate amounts in the above thermoplastic resins.

[Hard coat layer (20)]
As described above, the hard coat layer 20 has the binder 22 and the string-like aluminum silicate 24.

(1) Binder As the binder 22, a thermosetting resin or a photocurable resin (UV curable resin) can be used.
For example, an organic silicate compound, acrylic resin, urethane resin, melamine resin, epoxy resin, organic silicate compound, silicone resin, urethane acrylate resin, or the like can be used.

(1.1) Thermosetting resin Thermosetting resins include polysiloxane compounds or silicone-modified resins, acrylic resins, phenolic resins, epoxy resins, polyester resins, polyurethane resins, melamine resins, Although a urea-based resin can be used, in the present invention, a siloxane-based compound is preferably used, and a polysiloxane-based compound is preferably used from the viewpoint of light resistance.

Precursor constituting the polysiloxane compound has the general formula _R m Si (OR _') are those represented by _n, R and R' represents an alkyl group having 1 to 10 carbon atoms, m and n are, It is an integer that satisfies the relationship m + n = 4.
Specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-polopoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, terapentaethoxy Silane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxy Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, dimethyl Dimethoxysilane, dimethyl diethoxy silane, hexyl trimethoxy silane and the like. In addition, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β- ( N-aminobenzylaminoethyl) -γ-aminopropylmethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloro Silanes such as propyltrilimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane, dimethyldichlorosilane Coupling agent can be used.

An ionizing radiation-curable siloxane compound can also be used as the polysiloxane compound.
Specific examples of the ionizing radiation curable siloxane compound include organic silicon compounds having a molecular weight of 5000 or less and having a plurality of functional groups that react and crosslink by irradiation with ionizing radiation, for example, a polymerizable double bond group. Specifically, one-end vinyl functional polysiloxane, both-end vinyl functional polysiloxane, or vinyl functional polysiloxane obtained by reacting these compounds may be used. This composition is three-dimensionally cross-linked by dehydration condensation of silanol groups to obtain a high hardness coating.

The polysiloxane compound is a reaction product obtained by hydrolyzing at least one selected from silane compounds represented by the following general formula (0), and siloxane bonds are three-dimensionally formed. Polymer. Preferably, it is a polymer having a mass average molecular weight of 1000 to 3000.
R _4-n Si (OR ′) _n (0)
In general formula (0), R represents a hydrogen atom, an alkyl group or a phenyl group, R ′ represents an alkyl group or a phenyl group, and n represents an integer of 2 to 4.

  The silicone-modified resin is a graft copolymer having silicone in the side chain. An acrylic graft copolymer having silicone as a side chain is preferred. As a silicone-based graft copolymer obtained by radical polymerization of an acrylic-modified silicone polymer monomer and a radical polymerizable monomer, the acrylic-modified silicone is represented by the following general formula (1) and the following general formula (2): And a product obtained by condensation with an acrylic compound represented by

In general formula (1), R ₆ and R ₇ represent a monovalent aliphatic hydrocarbon group, a phenyl group or a monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms, and q is a positive number of 1 or more. is there.

In the general formula (2), R ₈ represents a hydrogen atom or a methyl group, R ₉ represents a methyl group, an ethyl or a phenyl group, two R _{9 s} may be the same or different from each other, and Z represents a chlorine atom Represents a methoxy group or an ethoxy group.

The silicone or polysiloxane compound represented by the general formula (1) can be obtained as a commercial product, and those suitable for the purpose can be used.
R ₆ and R ₇ in the general formula (1) are a monovalent aliphatic hydrocarbon group, phenyl group or monovalent halogenated hydrocarbon having 1 to 10 carbon atoms, Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, and an acyl group. Examples of the monovalent halogenated hydrocarbon include a 3,3,3-trifluoropropyl group, 4,4,4- Examples thereof include a trifluoro-3,3-difluorobutyl group and a 2-chloroethyl group. Particularly preferred as R ₆ and R ₇ is a methyl group.

  In the general formula (1), q is a positive number of 1 or more, but from the combination of an acrylic-modified silicone derived from a high molecular weight silicone having a number of q of 100 or more and a radical polymerizable monomer. From the copolymerization of an acrylic-modified silicone derived from a low molecular weight silicone having a q number of 100 or less and a radical polymerizable monomer, an oil-like one tends to be obtained, depending on the type of monomer used, Various types such as jelly and solid can be obtained.

  Next, examples of the acrylsilane compound represented by the general formula (2) include γ-methacryloxypropyldimethylchlorosilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldiphenylchlorosilane, and γ-acryloxypropyldimethylchlorosilane. , Γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, and the like. These acrylic silane compounds can be easily obtained by reacting a silicon compound and a compound having an aliphatic multiple bond in the presence of chloroplatinic acid according to the method of JP-B-33-9969.

Moreover, as a polysiloxane type compound, a conventionally well-known method can be used and it can superpose | polymerize by a heat polymerization method etc. At this time, a polymer in which a siloxane bond is three-dimensionally formed using a reactive group such as a silanol group of polysiloxane as a crosslinking point.
In addition, radical copolymerization of an acrylic-modified silicone and a radical polymerizable monomer can be performed by a conventionally known method, such as a radiation irradiation method or a method using a radical polymerization initiator. Furthermore, when copolymerizing by the ultraviolet irradiation method, a known sensitizer is used as a radical polymerization initiator, and when copolymerizing by electron beam irradiation, it is not necessary to use a radical polymerization initiator. The silicone copolymer thus obtained is a comb-shaped graft copolymer having a radical polymerizable monomer as a trunk and silicone as a branch.

Examples of the polysiloxane compound include Sircoat NP730 and Sircoat NP720 (manufactured by Koken Co., Ltd.).
Examples of commercially available silicone copolymers include Cymac US-150, US-270, US-350, US-450, Reseda GP-700 (manufactured by Toagosei Co., Ltd.), and the like.

(1.2) UV curable resin Examples of the UV curable resin include trimethylolpropane tri (meth) acrylate, trimethylolpropane tris (hydroxyethyl (meth) acrylate), and tris (2-hydroxyethyl) isocyanurate tris. (Meth) acrylate resins based on (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyfunctional urethanized (meth) acrylate, etc. Etc. are exemplified.
Here, the polyfunctional urethanized (meth) acrylate is, for example, a polyisocyanate having at least two isocyanato groups (—NCO) in the molecule, such as isophorone diisocyanate or hexamethylene diisocyanate, and trimethylolpropane di ( A urethane bond and at least two compounds obtained by addition reaction of a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule, such as (meth) acrylate and pentaerythritol tri (meth) acrylate It is a compound having a (meth) acryloyl group. These ultraviolet curable resins can be used alone or in admixture of two or more. Moreover, it is also possible to combine and use the polyfunctional (meth) acrylate which does not have a urethane bond as mentioned above in polyfunctional urethanized (meth) acrylate.

A commercially available UV curable resin can be suitably used.
Specific examples of commercially available UV curable resins include Kayrad DPHA (manufactured by Nippon Kayaku Co., Ltd.), Kayarad DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), Kayrad DPCA-30 (Nippon Kayaku ( Kayarad DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad D-310 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad D- 330 (Nippon Kayaku Co., Ltd.), Kayalad PET-30 (Nippon Kayaku Co., Ltd.), Kayalad GPO-303 (Nippon Kayaku Co., Ltd.), Kayarad TMPTA (Nippon Kayaku Co., Ltd.) Kayrad THE-330 (Nippon Kayaku Co., Ltd.), Kayarad TPA-330 (Nippon Kayaku Co., Ltd.), Aronix M-305 (Toagosei Co., Ltd.), Aronix M-315 (Toagosei Co., Ltd.) stock Ltd.), Ltd. Aronix M-325 (Toagosei Co.), manufactured by Aronix M-403 (Toagosei Co.), and the like.

The UV curable resin as described above is usually used by mixing with a photopolymerization initiator.
Commercially available products such as Irgacure 907 (manufactured by Ciba Japan), Irgacure 184 (manufactured by Ciba Japan), and Lucirin TPO (manufactured by BASF) can be suitably used as the photopolymerization initiator.

(2) Stringed aluminum silicate (2.1) Characteristics and physical properties "Aluminum silicate" means that the main constituent elements are silicon (Si), aluminum (Al), oxygen (O) and hydrogen ( H), and a hydrated aluminum silicate composed of a number of ≡Si—O—Al≡ bonds, typically having a composition formula of SiO ₂ .Al ₂ O ₃ .2H ₂ O or (OH) ₃ Al It is a compound represented by ₂ O ₃ SiOH.
As an example of such an aluminum silicate, a string-like (tubular) aluminum silicate called imogolite is known.
“Imogolite” is a kind of natural clay component that appears in soils based on falling volcanic ejecta such as volcanic ash and pumice, and is a nano-sized string-like amorphous aluminum silicate.
Such imogolite has a nanotube-like structure having an outer diameter of 2.0 to 3.0 nm, an inner diameter of 0.5 to 1.5 nm, and a length of several tens of nm to several μm.
In addition, imogolite has a unique shape such as a string in nano size and a high specific surface area. Therefore, it has excellent affinity with water, ion exchange capacity, and substance adsorption capacity, and is a natural gas fuel storage medium and catalyst carrier. It is expected to be used in various industrial applications such as humidity control materials and heat pump system heat exchangers that produce refrigerants using low-temperature heat sources.

(2.2) Manufacturing method The manufacturing method of a string-like aluminum silicate (imogolite) treats an inorganic silicon compound solution with an ion exchanger, so that the electric conductivity is 5 to 500 μS / cm, and the pH is 3.5 to 7. A first step of preparing an orthosilicic acid solution of No. 5, and a second step of mixing the orthosilicic acid solution, the inorganic aluminum compound solution and urea or ammonia, adjusting the pH to 2.8 to 7.5, and then heating. .

(2.2.1) First Step In the first step, an orthosilicate having an electric conductivity of 5 to 500 μS / cm and a pH of 3.5 to 7.5 is obtained by subjecting the inorganic silicon compound solution to an ion exchange treatment with an ion exchanger. Prepare an acid solution.
In order to synthesize a string-like aluminum silicate, orthosilicic acid is required as a raw material, but orthosilicic acid is not generally distributed and is difficult to obtain. Here, orthosilicate is prepared by subjecting an inorganic silicon compound solution to an ion exchange treatment with an ion exchanger.

(Inorganic silicon compound solution)
The silicon source constituting the inorganic silicon compound solution is not particularly limited as long as silicate ions are generated when solvated. Examples of such a silicon source include sodium orthosilicate, sodium metasilicate, potassium metasilicate, and water glass.

  As the solvent, a solvent that can easily be solvated with the raw material silicic acid source can be appropriately selected and used. Specifically, water, alcohols, etc. can be used, for example. From the viewpoint of salt solubility and ease of handling during heating, water is preferably used.

  Further, from the viewpoint of suppressing generation of polysilicic acid from silicic acid during ion exchange, the silicon concentration of the inorganic silicon compound solution during ion exchange is preferably 20 mM or less.

(Ion exchanger)
As the ion exchanger used for the ion exchange treatment of the inorganic silicon compound solution, an anion exchanger or a cation exchanger is used. Examples of the anion exchanger include an anion exchange membrane and the like, and examples of the cation exchanger include a cation exchange resin and a cation exchange membrane. It is preferable to use a cation exchange resin because it is high and silicon concentration control is easy. Specifically, any conventionally known ion exchanger can be used as long as the orthosilicate solution obtained after the treatment has an electric conductivity of 5 to 500 μS / cm and a pH of 3.5 to 7.5. May be used.

  As the cation exchange resin, either a strong acid cation exchange resin or a weak acid cation exchange resin may be used, or a plurality of cation exchange resins may be used in combination.

  Examples of the strongly acidic cation exchange resin include Amberlite IR120B (manufactured by Organo), Amberlite IR124 (manufactured by Organo), Amberlite 200CT (manufactured by Organo), Amberlite 252 (manufactured by Organo), Diaion SK104. (Mitsubishi Chemical Corporation), Diaion SK110 (Mitsubishi Chemical Corporation), Diaion SK112 (Mitsubishi Chemical Corporation), Diaion PK212 (Mitsubishi Chemical Corporation), Diaion PK216 (Mitsubishi Chemical Corporation), Diaion PK228 (Mitsubishi Chemical), Diaion UBK08 (Mitsubishi Chemical), Diaion UBK10 (Mitsubishi Chemical), Diaion UBK12 (Mitsubishi Chemical), Diaion UBK510L (Mitsubishi Chemical), Diaion UBK530 (Mitsubishi Chemical Corporation), Diaion U K550 (manufactured by Mitsubishi Chemical Corporation) and the like, but not limited thereto.

  Examples of the weak acid cation exchange resin include Amberlite FPC3500 (manufactured by Organo), Amberlite IRC76 (manufactured by Organo), Diaion WK10 (manufactured by Mitsubishi Chemical), Diaion WK11 (manufactured by Mitsubishi Chemical), Dia Examples include, but are not limited to, ion WK100 (manufactured by Mitsubishi Chemical Corporation) and diamond ion WK40L (manufactured by Mitsubishi Chemical Corporation).

  When ion exchange resin is used, as a method of ion exchange treatment of the inorganic silicon compound solution, for example, a batch method or a column method is used.

  In the case of the batch method, a conditioned ion exchange resin is put into a container, an inorganic silicon compound solution whose concentration is adjusted is added thereto, and the reaction is performed for about 2 hours while stirring or shaking at a strength that allows the ion exchange resin to float. Thereafter, the ion exchange resin is filtered off, and the filtrate is recovered to obtain an orthosilicate solution. If a magnetic stirrer is used, depending on the type of ion exchange resin, the ion exchange resin may be destroyed. Therefore, it is desirable to perform shaking during mixing. Here, conditioning means returning the ion exchange resin to a state where the ion exchange ability can be exhibited.

  In the case of the column method, an ion-exchange resin that has been conditioned is packed into a column, an inorganic silicon compound solution whose concentration is adjusted is flowed into the column at a constant flow rate, and the solution that flows out of the column is recovered to obtain an orthosilicate solution. obtain.

In the case of the batch method, the electric conductivity of the resulting orthosilicate solution can be adjusted by the degree of stirring or shaking, the reaction time, etc. In the case of the column method, the flow rate of the sample flowing in the column, the volume of the column ( Radius, length, etc.), the amount of ion-exchange resin filling, and the like. That is, the electrical conductivity of the orthosilicate solution can be adjusted by appropriately changing the contact time and the contact area between the inorganic silicon compound solution and the ion exchanger.
The pH of the resulting orthosilicate solution can be adjusted by the type of ion exchange resin used, the contact time between the ion exchange resin and the inorganic silicon compound solution, and the like. Specifically, when a cation exchange resin is used, the pH of the orthosilicate solution obtained becomes lower as the ion exchange proceeds. Therefore, when a strongly acidic cation exchange resin having a high ion exchange rate is used, the pH of the orthosilicate solution is increased. The pH of the orthosilicic acid solution remains high when a weakly acidic cation exchange resin with a lower ion exchange rate is used.

As described above, an ion exchange membrane may be used as the ion exchanger. The ion exchange membrane is an ion filtration membrane formed by molding an ion exchange resin into a film shape, and has a property of blocking the passage of ions having different signs and allowing only ions having the same sign to pass.
When an ion exchange membrane is used, it is preferable to use an anion exchange membrane and a cation exchange membrane together, but each may be used alone by combining with other methods.
The anion exchange membrane is positively charged because the cation group is fixed to the membrane, and only the anion is allowed to pass through without repelling the cation. Such anion exchange membranes are used, for example, for seawater concentration salt production, concentration / removal of metal ions, removal of radioactive ions / substances, and the like. By using such an anion exchange membrane, only the anion in the inorganic silicon compound solution can be permeated to prepare a target orthosilicate solution.
The cation exchange membrane is negatively charged because the anion group is fixed to the membrane, and only the cation is allowed to pass without repelling the anion.

(PH of orthosilicate solution)
The treatment conditions with the ion exchanger are set so that the pH of the orthosilicic acid solution prepared by the treatment with the ion exchanger is 3.5 to 7.5. When the pH is 7.5 or less, it is possible to suppress the formation of polysilicic acid by polymerization of orthosilicic acid in the solution, and when the pH is 3.5 or more, the pH adjustment in the second step The amount of alkali added in can be reduced.

  The pH can be measured by a pH meter using a general glass electrode. Specifically, for example, MODEL (F-71S) (Horiba, Ltd.) can be used. The pH of the orthosilicate solution is as follows: phthalate pH standard solution (pH: 4.01), neutral phosphate pH standard solution (pH: 6.86), and borate pH standard solution (pH: 9.01). 18) is used as a pH standard solution, the pH meter is calibrated at three points, the electrode of the pH meter is placed in an orthosilicic acid solution, and the value after 5 minutes has elapsed and is read is read. At this time, the liquid temperature of the pH standard solution and the orthosilicate solution can be set to 25 ° C., for example.

(Electric conductivity σ of orthosilicate solution)
The treatment conditions with the ion exchanger are set so that the electrical conductivity of the orthosilicic acid solution prepared by the treatment with the ion exchanger is 5 to 500 μS / cm. In particular, when ion exchange treatment is performed by a column method using a cation exchange resin, it is possible to adjust the electrical conductivity by adjusting the flow rate of the column. The electric conductivity of the orthosilicate solution is preferably 5 to 100 μS / cm, more preferably 5 to 15 μS / cm.
When the orthosilicate solution has an electric conductivity of 500 μS / cm or less, the mixing of the salt into the mixed solution prepared in the second step is suppressed, and a string-like aluminum silicate can be produced in a high yield. . Moreover, the treatment time by an ion exchanger can be shortened and productivity can be improved as the electrical conductivity of an orthosilicic acid solution is 5 microsiemens / cm or more.

  Since the electrical conductivity of theoretical pure water is an insulator of about 0.055 μS / cm, it can be said that the electrical conductivity is an index indicating the total amount of ions in the solution, particularly when the solvent of the orthosilicate solution is water.

  The electrical conductivity of the orthosilicic acid solution can be measured with a general electrical conductivity meter, and specifically, for example, it is measured at room temperature (25 ° C.) using ES-51 (Horiba, Ltd.).

(2.2.2) Second Step In the second step, an orthosilicic acid solution, an inorganic aluminum compound solution and urea or ammonium are mixed, adjusted to pH 2.8 to 7.5, and then heated.
In the second step, the element molar ratio Si / Al of the mixed solution obtained by mixing the orthosilicate solution and the inorganic aluminum compound solution is preferably 0.3 to 1.0. Thus, in the second step, the composition ratio of the string-like aluminum silicate to be produced can be changed by adjusting the element molar ratio Si / Al of the mixed solution. By setting the element molar ratio Si / Al within this range, the target string-like aluminum silicate can be obtained with high purity, and the production of by-products such as boehmite, gibbsite, amorphous silica, and allophane is suppressed. be able to.

(Inorganic aluminum compound solution)
The aluminum source constituting the inorganic aluminum compound solution is not particularly limited as long as aluminum ions are generated when solvated. Examples of such an aluminum source include aluminum chloride, aluminum perchlorate, aluminum nitrate, and aluminum sec-butoxide.

  As the solvent, a solvent that can easily be solvated with the aluminum source as a raw material can be appropriately selected and used. Specifically, water, alcohols, etc. can be used, for example. From the viewpoint of salt solubility and ease of handling during heating, water is preferably used.

(Urea or ammonia)
Either urea or ammonia may be used, and it is preferable from the viewpoint of handleability to add as a solution adjusted to a predetermined concentration.

(Adjusting the pH of the mixture)
In the second step, the mixed liquid obtained by mixing the orthosilicic acid solution, the inorganic aluminum compound solution, and urea or ammonia is adjusted to pH 2.8 to 7.5. In order to adjust the pH to the range, for example, a method of adding a basic solution such as an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide, a method of adding an acidic solution such as hydrochloric acid, acetic acid, or nitric acid, etc. Can be mentioned.

(Heat treatment)
In a 2nd process, the process which heats the liquid mixture after pH adjustment is performed. Although the heating temperature at this time is not specifically limited, It is preferable that it is 80-120 degreeC from a viewpoint of obtaining higher purity string-like aluminum silicate.
There exists a tendency which can suppress precipitation of the boehmite (monohydric aluminum oxide) which is a by-product as heating temperature is 120 degrees C or less. When urea is used, if the heating temperature is too high, rapid thermal decomposition may occur at the beginning of heating, and the ammonia concentration in the mixed solution may rise rapidly, causing the pH to approximate the alkaline side. It is considered to be unsuitable for the production of a string-like aluminum silicate formed with a low acidity.
Further, when the heating temperature is 80 ° C. or higher, the thermal decomposition of urea and the subsequent synthesis rate of the string-like aluminum silicate can be improved, and the productivity can be improved.

  The heating time is not particularly limited, but is preferably 12 hours or more and 100 hours or less from the viewpoint of efficiently obtaining a string-like aluminum silicate.

(2.2.3) Other steps In the method for producing a string-like aluminum silicate, in addition to the first step and the second step, the product obtained in the second step is recovered by solid separation and desalting. It is preferable to further include a step. In the recovery step, the desalting method is not particularly limited. For example, desalting can be performed by a dialysis membrane or ultrafiltration.
In addition, in the manufacturing method of string-like aluminum silicate, you may have another processes, such as solvent substitution and powder drying, as needed.

(2.2.4) Solvent substitution method of string-like aluminum silicate The string-like aluminum silicate obtained after the heating step in the second step is in the form of a gel. Since such a gel is an aqueous dispersion of string-like aluminum silicate, it is preferable to replace it with an organic solvent such as alcohol in consideration of compatibility with the binder.
When replacing the solvent, an organic solvent is added to the obtained gel, and the mixture is stirred and centrifuged. After removing the supernatant, the organic solvent is added again, stirred and dispersed, and then centrifuged. By performing the above operation an appropriate number of times, the aqueous phase of the gel can be replaced with an organic solvent phase. In addition, it can replace with this method and can also carry out solvent substitution using a semipermeable membrane, a membrane filter, etc.
Preferable examples of the organic solvent used for solvent substitution include alcohols such as methanol, ethanol, propanol, and butanol, organic solvents such as acetone, methyl ethyl ketone, and acetonitrile, or carbon dioxide.

(2.2.5) Confirmation of formation of string-like aluminum silicate Measurement by X-ray diffraction and measurement by a scanning electron microscope (SEM), and whether the desired string-like aluminum silicate is obtained Can be confirmed. An example of an X-ray diffraction diagram and a scanning electron micrograph (SEM image) of a string-like aluminum silicate produced by the above production method is shown in FIGS. 2 and 3, respectively.
As shown in FIG. 2, a peak value peculiar to the string-like aluminum silicate is obtained in the vicinity of 2θ = 4, 10, and 14, thereby confirming the formation of the target string-like aluminum silicate.
As shown in FIG. 3, a thread-like structure peculiar to the string-like aluminum silicate can be confirmed on the SEM image, whereby the formation of the target string-like aluminum silicate can be confirmed.

[Manufacturing method of laminate]
The manufacturing method of the laminated body 1 is basically:
(1) preparing a laminate-forming composition;
(2) A step of forming the light transmissive layer 20 by applying the composition for forming a laminate on the support layer 10 by a solvent casting method and curing the composition.
It has.

(1) Preparation process In a preparation process, the precursor (monomer or oligomer) of the binder 22, the string-like aluminum silicate 24, and a certain solvent are mixed as a laminated body formation composition, and a coating liquid is produced.
Preferably, the precursor (monomer or oligomer) of the binder 22 is mixed with a dispersion obtained by dispersing the string-like aluminum silicate 24 in a certain solvent to prepare a coating solution.

In such a case, the content of the precursor of the binder 22 in the coating solution is adjusted to 0.5 to 70% by mass, preferably 20 to 30% by mass.
The content of the string-like aluminum silicate 24 in the coating solution is 0.1 to 20% by mass, preferably 0.3 to 9% by mass.
The content of the solvent in the coating solution is 10 to 99.4% by mass, preferably 60 to 80% by mass.

(1.1) Solvent When the binder 22 is a resin such as an acrylic resin, any one of ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be used as the solvent. These solvents may be used alone or in combination of two or more.
On the other hand, when the binder 22 is a polysiloxane compound, any one of common alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and water can be used as a solvent. These solvents may be used alone or in combination of two or more.
When an ionizing radiation curable resin is used as the binder 22, the precursor is diluted so that the composition ratio of the precursor is 0.5 to 70% by mass. Here, when the composition ratio of the precursor of the ionizing radiation curable resin in the coating liquid is 0.5% by mass or more, the solvent concentration is appropriate when the coating liquid is applied onto the support layer 10 and 0. When the composition ratio of the ionizing radiation curable resin precursor in the coating solution is 70% by mass or less, the viscosity of the coating solution is appropriate. In addition, it is possible to avoid a situation in which unevenness occurs in the coating film and the flatness is impaired.

(1.2) Leveling agent A leveling agent can be added to the coating solution in order to ensure the surface smoothness of the hard coat layer 20. A leveling agent is an agent which has the effect of reducing the surface tension of the coating liquid and improving the surface smoothness of the coating film when added to the coating liquid.

  Substances commonly used as leveling agents include polyacrylate polymers such as polyalkyl acrylates; polyvinyl ether polymers such as polyalkyl vinyl ethers; dimethylpolysiloxanes, methylphenylpolysiloxanes, as well as polyethers, polyesters, and aralkyls. Examples thereof include silicone-based polymers such as organically modified polysiloxanes, and the like. Leveling agents that can be used in the present invention include fluorine atoms in these polymers. A leveling agent having a fluorine atom can be obtained, for example, by copolymerizing a monomer having a fluorine-containing group.

  Specific products include, for example, Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, “SC-104” (all manufactured by Asahi Glass Co., Ltd.) ), FLORAD “FC-430”, “FC-431”, “FC-173” (all made by Fluorochemicals-Sumitomo 3M), F-top “EF352”, “EF301”, “EF303” (all Shin-Akita Kasei) Co., Ltd.), Schwego Fureer "8035", "8036" (both made by Schwegman), "BM1000", "BM1100" (both made by BM Himmy), MegaFuck "F-171", " F-470 "," RS-75 "," RS-72-K "(all manufactured by Dainippon Ink & Chemicals, Inc.), BYK340 (manufactured by Big Chemie Japan), ZX-049 "," ZX-001 ", mention may be made of the" ZX-017 "(manufactured by both Fuji Chemical Industry Co., Ltd.), and the like.

In the present invention, a leveling agent having a fluorine atom is preferably contained in the hard coat layer 20.
When the leveling agent is 0.1% by mass or more of the solid content of the composition in the curable composition, the water repellency of the hard coat layer 20 is sufficient and the antifouling property is improved. Moreover, when a leveling agent is less than 10 mass% of solid content of curable composition in curable resin composition, sufficient hardness can be obtained and it is appropriate.
The leveling agent is preferably contained in the hard coat layer 20 at a ratio of 0.5% by mass or more and 5% by mass or less of the solid content of the composition in the hard coat layer 20. The property is further improved.

(1.3) UV absorber In order to improve the weather resistance of the hard coat layer 20, the coating solution may contain a UV absorber made of an inorganic compound, a UV absorber made of an organic compound, or both. . As the UV absorber made of an organic compound, a triazine UV absorber is preferably used.
Preferred UV absorbers are listed below.

(1.3.1) Inorganic UV absorber The inorganic UV absorber is mainly a metal oxide pigment, and is dispersed in the hard coat layer 20 at a concentration of 20% by mass or more to form a 6 μm thick film. And a compound having a function of reducing the light transmittance in the UV-B region (290-320 nm) to 10% or less. The inorganic UV absorber applicable to the present invention is particularly preferably selected from titanium oxide, zinc oxide, iron oxide, cerium oxide or a mixture thereof.

  In addition, from the viewpoint of improving the transparency of the inorganic UV absorber-containing layer, those having an average basic particle diameter of between 5 nm and 500 nm are preferable, and an average base between 10 nm and 100 nm is particularly preferable. It is a metal oxide particle having a particle size and a maximum particle size distribution of 150 nm or less. Such coated or uncoated metal oxide pigments are described in more detail in patent application EP-A-0 518 773.

Further, in the present invention, from the viewpoint of suppressing the oxidative degradation effect of the adjacent resin due to the photocatalytic ability of the inorganic oxide, the inorganic UV absorber fine particles having an average particle diameter of 10 nm or more and 100 nm or less coated on the surface of the inorganic UV absorber. It may be. Moreover, since surface coating also has the effect of improving the dispersibility of inorganic UV absorber particles, it is still preferable.
The surface-coated inorganic UV absorbers herein include amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium salts, potassium salts, zinc salts, iron salts or aluminum salts of fatty acids, metal alkoxides. Chemical, electronic, mechanochemical or mechanical, with compounds such as titanium (aluminum), polyethylene, silicone, protein (collagen, elastin), alkanolamine, silicon oxide, metal oxide or sodium hexametaphosphate An inorganic UV absorber that has undergone surface treatment by one or more means of special nature.

  The amount of the inorganic UV absorber used alone is 1 to 30% by mass, preferably 5 to 25% by mass, and more preferably 15 to 20% by mass with respect to the total mass of the UV absorbing layer. When it is within 30% by mass, the adhesion is good, and when it is 1% by mass or more, the weather resistance improving effect is large.

  When the inorganic UV absorber is used in combination with the organic UV absorber described later, the amount of the inorganic UV absorber used is 3 to 20% by mass, preferably 5 to 10% by mass with respect to the total mass of the UV absorbing layer. The amount of the organic UV absorber used is 0.1 to 10% by mass, preferably 0.5 to 5% by mass. When an inorganic UV absorber and an organic UV absorber are used in combination within the above-mentioned range of use, the transparency of the UV absorbing layer is high and the weather resistance is also good.

(1.3.2) Low molecular triazine UV absorber The low molecular triazine UV absorber is represented by the following general formula (I).
Q ¹ -Q ² -OH (I)
In the general formula (I), ^{Q 1} represents a 1,3,5-triazine ring, ^{Q 2} represents an aromatic ring.

  More preferred as the general formula (I) is a compound represented by the following general formula (IA).

In general formula (IA), R ¹ is an alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenyl group, a hydroxy group Group, an alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group having 5 to 12 carbon atoms, an alkenyloxy group having 3 to 18 carbon atoms, a halogen atom, —COOH, —COOR ⁴ , —O—CO—R ⁵ , —O—CO—O—R ⁶ , —CO—NH ₂ , —CO—NHR ⁷ , —CO—N (R ⁷ ) (R ⁸ ), CN, NH ₂ , NHR ⁷ , —N (R ^{7 ) (R 8), - NH} -CO-R 5, a phenoxy group, a phenoxy group substituted with an alkyl group having 1 to 18 carbon atoms, phenyl - alkoxy group having 1 to 4 carbon atoms, 6 carbon atoms 15 bicycloalkoxy groups, carbon atoms An alkyl group having 1 to 18 carbon atoms substituted with a bicycloalkylalkoxy group having 6 to 15 children, a bicycloalkenylalkoxy group having 6 to 15 carbon atoms, or a tricycloalkoxy group having 6 to 15 carbon atoms; Group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms substituted with —O—CO—R ⁵ ; a glycidyl group; —CO— R ⁹ or —SO ₂ —R ¹⁰ ; or R ¹ is carbon interrupted with one or more oxygen atoms and / or substituted with a hydroxy group, a phenoxy group or an alkylphenoxy group having 7 to 18 carbon atoms or an alkyl group of atoms 3-50; or ^{R 1} is ^{_{-A; -CH 2 -CH (XA)}} -CH 2 -O-R 12; -CR 13 R '13 ^{_{(CH 2) m -X-A}} ; -CH 2 -CH (OA) -R 14; -CH 2 -CH (OH) -CH 2 -XA;

_{^{-CR 15 R'15-C (= CH}} 2) -R "15; -CR 13 R '13 - (CH 2) m -CO-X-A; -CR 13 R' 13 - (CH 2) m - CO—O—CR ¹⁵ R ′ ¹⁵ —C (═CH ₂ ) —R ″ ¹⁵ or —CO—O—CR ¹⁵ R ′ ¹⁵ —C (═CH ₂ ) —R ″ ¹⁵ (wherein A represents —CO represents a ^{-CR 16 = CH-R 17.} ) represents one of definitions represented by.

R ² is independently of each other an alkyl group having 6 to 18 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; COOR ⁴ ; CN; —CO—R ⁵ ; a halogen atom; a trifluoromethyl group; —O—R ³ is represented.

R ³ represents the definition given for R ¹ ; R ⁴ is an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; phenylalkyl having 7 to 11 carbon atoms A cycloalkyl group having 5 to 12 carbon atoms; or R ⁴ interrupted by one or more —O—, —NH—, —NR ⁷ —, —S— and OH, phenoxy group or carbon Represents an alkyl group having 3 to 50 carbon atoms which may be substituted with an alkylphenoxy group having 7 to 18 atoms; R ⁵ represents H; an alkyl group having 1 to 18 carbon atoms; 2 to 18 carbon atoms A cycloalkyl group having 5 to 12 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkenyl group having 6 to 15 carbon atoms ; Charcoal Represents a tricycloalkyl group having 6 to 15 carbon atoms; R ⁶ represents H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; phenyl having 7 to 11 carbon atoms An alkyl group; a cycloalkyl group having 5 to 12 carbon atoms; R ⁷ and R ⁸ are independently of each other an alkyl group having 1 to 12 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; Represents a 4 to 16 dialkylaminoalkyl group; or represents a cycloalkyl group having 5 to 12 carbon atoms; or R ⁷ and R ⁸ together represent an alkylene group having 3 to 9 carbon atoms, the number of carbon atoms represents 3-9 oxaalkylene group or azaalkylene group having a carbon number of 3 to 9; ^{R 9} is an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 2 to 18 carbon atoms; a phenyl group; charcoal A cycloalkyl group having 5 to 12 atoms; a phenylalkyl group having 7 to 11 carbon atoms; a bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkylalkyl group having 6 to 15 carbon atoms, and 6 to 15 carbon atoms. Or a tricycloalkyl group having 6 to 15 carbon atoms; R ¹⁰ is an alkyl group having 1 to 12 carbon atoms; a phenyl group; a naphthyl group; or an alkylphenyl group having 7 to 14 carbon atoms R ¹¹ is independently of each other H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 6 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a halogen atom; represents an atomic number 1 to 18 alkoxy ^{group; R 12} is an alkyl group having 1 to 18 carbon atoms; a phenyl group; an alkenyl group having 3 to 18 carbon atoms TansoHara Represents a phenyl group substituted 1 to 3 times with an alkyl group having 1 to 8 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an alkenoxy group with 3 to 8 carbon atoms, a halogen atom or a trifluoromethyl group; or A phenylalkyl group having 7 to 11 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; a tricycloalkyl group having 6 to 15 carbon atoms; a bicycloalkyl group having 6 to 15 carbon atoms; 15 bicycloalkylalkyl groups; bicycloalkenylalkyl groups having 6 to 15 carbon atoms; —CO—R ⁵ ; or R ¹² represents one or more —O—, —NH—, —NR ⁷ —, —S—. in interrupted and OH, optionally substituted phenoxy group or an alkylphenoxy group having a carbon number of 7 to 18, an alkyl group having a carbon number of 3 to 50; R ¹³ and ^'13 independently of one another are H; represents a phenyl ^{group;; R 14} is an alkyl group having 1 to 18 carbon atoms; a phenyl group; an alkoxyalkyl group having 3 to 12 carbon atoms an alkyl group having 1 to 18 carbon atoms Phenyl represents an alkyl group having 1 to 4 carbon atoms; R ¹⁵ , R ′ ¹⁵ and R ″ ¹⁵ each independently represents H or CH ₃ ; R ¹⁶ represents H; —CH ₂ —COO—R ⁴ ; An alkyl group having 1 to 4 carbon atoms; or CN; R ¹⁷ represents H; —COOR ⁴ ; an alkyl group having 1 to 17 carbon atoms; or a phenyl group; X represents —NH—; —NR ⁷ ; _{-; - O -; - NH-} (CH 2) p -NH-; or _{-O- (CH} 2) q -NH- and represents; and index m is a number 0 to 19; n is a number from 1 to 8 P represents the number 0 to 4; q represents the number 2 to 4; In general formula ^(I-A), including at least one 2 or more carbon atoms of R 1, ^{R 2} and ^{R 11,} is.

(1.3.3) Low Molecular Benzophenone UV Absorber Benzophenone ultraviolet is represented by the following general formula (II).

In general formula (II), Q ¹ and Q ² each independently represent an aromatic ring. X represents a substituent, and Y represents an oxygen atom, a sulfur atom or a nitrogen atom. XY may be a hydrogen atom.

  Examples of benzophenone UV absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4' -Tetrahydroxy-benzophenone and the like.

(1.3.4) Low Molecular Benztriazole UV Absorber Benztriazole ultraviolet rays are represented by the following general formula (III).

In general formula (III), R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a monovalent organic group, and at least one of R ¹ , R ² and R ³ has a total carbon number of 10 Represents -20 unsubstituted branched or straight chain alkyl groups.

  Examples of the benztriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benztriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benztriazole. 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benztriazole, 2- (2'-hydroxy-5'-methylphenyl) benztriazole, 2- (2'-hydroxy- 3 ', 5'-di-tert-butylphenyl) benztriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benztriazole, 2- (2'-hydroxy-3' , 5'-di-tert-butylphenyl) -5-chlorobenztriazole, 2- (2'-hydroxy-3 '-(3 ", 4", 5 " 6 "-tetrahydrophthalimidomethyl) -5'-methylphenyl) benztriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benztriazol-2-yl) ) Phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenztriazole, 2 (2'-hydroxy-3 ', 5'-di-tert-butyl) Phenyl) -5-chlorobenztriazole, (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenztriazole, 2 (2'-hydroxy-3', 5'-) Di-tert-butylphenyl) -5-chlorobenztriazole, (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl)- - chloro benzotriazole, and the like.

(1.3.5) Polymer UV Absorber The polymer UV absorber used in the present invention refers to a compound having a weight average molecular weight of 500 or more. The weight average molecular weight can be measured with a gel permeation chromatography (GPC) apparatus.

  The polymer UV absorber used in the present invention is preferably a compound represented by the following general formula (3), and more preferably a benztriazole polymer UV absorber having a benztriazole group.

In General Formula (3), R ₁₁ represents a hydrogen atom or a methyl group, R ₁₂ and R ₁₃ represent a hydrogen atom, an alkyl group, or an aryl group, and R ₃ represents a benzophenone group or a benztriazole group. l, m, and n represent an integer of 1 or more.

Examples of the alkyl group represented by R ₁₂ and R ₁₃ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and 1-methylbutyl. Group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, heptyl group, octyl group, A linear, branched or cyclic alkyl group such as a cycloalkyl group, a decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. It is done.

Examples of the aryl group represented by R ₁ and R ₂ include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a benzyl group, and a phenethyl group.

  Examples of other polymer UV absorbers include compounds described in JP-A-2004-42614. Specifically, [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2 -Hydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4 -(Methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy- 4- (Metak Royloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy-4- (Methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2-dihydroxy-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2,2 ′, 4-tri Hydroxy-4 ′-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2 ′, 4-trihydroxy-4 ′-(methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [ 2,2 ', 4-trihydroxy- '-(Methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2,2', 4-trihydroxy-4 '-(methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2 , 2 ′, 4-Trihydroxy-4 ′-(methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 ′-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer [4-hydroxy-4 ′-(methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 ′-(methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [4 -Hydroxy-4 '-(methacryl (Royloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 ′-(methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4′-methyl-4 -(Methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4 ' -Methyl-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [ 2-hydroxy-4'-me 4- (methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2- (2′-hydroxy-4′-methacryloyloxyethoxy) benzotriazole] -methyl methacrylate copolymer, [2- (2′-hydroxy-4′-methacryloyloxyethoxy) -5-chlorobenzotriazole] -methyl methacrylate copolymer and the like. Furthermore, polymer UV absorption having a molecular weight of 500 or more such as 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol]. Agents are also suitable.

(1.4) Antioxidant The hard coat layer 20 in the present invention may contain an antioxidant.
Weather resistance can be improved by using an antioxidant.

  Those applicable to the present invention can be selected from the group of antioxidants of hindered phenol compounds, hindered amine compounds, and phosphorus compounds.

  Specific examples of the hindered phenol compound include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate and n-octadecyl 3- (3,5-di-t-butyl. -4-hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3 , 5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl β (3,5-di-t-butyl -4-hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, Utadecyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n -Octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenylacetate, 2- (n- Octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (2- Hydroxyethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di-t-butyl) 4-hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 2- (2-stearoyloxyethylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5-tert-butyl) -4-hydroxyphenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5-di-tert-butyl-4-hydro Cyphenyl) propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentyl glycol bis- [3- (3,5-di-t-butyl-) 4-hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin-1-n-octadecanoate-2,3-bis- (3 5-di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol tetrakis- [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis- {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl Ruethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,1-trimethylolethane-tris- [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], sorbitol hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl 7- (3-methyl-5-tbutyl-4-hydroxyphenyl) ) Propionate, 2-stearoyloxyethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ', 5'-di-t- Butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxyhydrocinname) Included). The phenol compound of the above type is commercially available from Ciba Japan Co., Ltd. under the trade names “IRGANOX1076” and “IRGANOX1010”.

  Specific examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2) , 6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6- Tramethyl-4-piperidyl) 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [ 2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2, 6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, and the like.

  Further, it may be a polymer type compound. As specific examples, N, N ′, N ″, N ″ ′-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino] -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine-N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, di Polycondensate of butylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3 -Tetramethylbutyl) amino-1,3,5-tri Gin-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], Between 1,6-hexanediamine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine Polycondensate, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6 , 6-tetramethyl-4-piperidyl) imino]], etc., high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton; dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl- 1-piperidine ester Polymer with diol, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl) (Ethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like, and the like are exemplified by compounds in which a piperidine ring is bonded through an ester bond, but the present invention is not limited thereto. It is not a thing.

  Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, etc. Those having a molecular weight (Mn) of 2,000 to 5,000 are preferred.

  The hindered amine compounds of the above type are commercially available from Ciba Japan Co., Ltd. under the trade names of “TUNUVIN 144” and “TUNUVIN 770” and ADEKA Co., Ltd. as “ADK STAB LA-52”.

  Specific examples of phosphorus compounds include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-). t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- [ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine Monophosphite compounds such as pin and tridecyl phosphite; 4,4'-butylidene-bis (3-methyl-6-t-butyl) Diphosphite compounds such as phenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite); triphenylphosphonite, tetrakis (2,4- Di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) [1,1-biphenyl]- Phosphonite compounds such as 4,4'-diylbisphosphonite; phosphinite compounds such as triphenylphosphinite and 2,6-dimethylphenyldiphenylphosphinite; triphenylphosphine and tris (2,6-dimethoxyphenyl) Phosphine compounds such as phosphine; and the like.

  Phosphorus compounds of the above type are, for example, from Sumitomo Chemical Co., Ltd. “Sumilizer GP”, from ADEKA Co., Ltd. “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, Ciba Japan Co., Ltd. It is commercially available under the trade name “IRGAFOS P-EPQ” from the company and “GSY-P101” from Sakai Chemical Industry Co., Ltd.

(2) Coating / curing step In the coating / curing step, the coating solution is coated on the support layer 10 by a solvent casting method.
As the “solvent casting method”, conventionally known solvent casting methods such as a gravure coating method, a reverse coating method, and a die coating method can be applied.
Thereafter, the coating liquid is cured (cross-linked) by a method including a heating step or a UV curing step according to the type of the binder 22 (thermosetting resin or photocurable resin).
A heating process means processing and hardening the coating liquid after application | coating in 40 degreeC or more atmosphere for 1 minute or more. In the heating step, a treatment of 1 minute to several days is required in an atmosphere of 40 to 150 ° C. in order to obtain a sufficient crosslinking density of the thermosetting resin. In order to develop sufficient hardness, it is preferable to stand for 30 minutes to 2 days in an atmosphere of 60 ° C to 100 ° C.
The coating solution may contain a photoinitiator, a photosensitizer, a thermal polymerization initiator, a surface modifier that imparts antifouling properties, or the like as necessary.

(2.1) About degree of crosslinking The ratio of the crosslinking component and the hardness and curl of the hard coat layer 20 are correlated with each other. The influence of the ratio of the crosslinking component on the hardness and curl differs depending on the type of the binder 22 such as a polysiloxane compound or an acrylic resin.

  For example, when the binder 22 is a polysiloxane compound, the binder is a polymer obtained by polymerizing a bifunctional siloxane compound, a trifunctional siloxane compound, and a tetrafunctional siloxane compound at a predetermined ratio. The hard coating layer 20 has a high degree of crosslinking and a high degree of condensation, and has high hardness but strong curl. On the other hand, the smaller the proportion of the tetrafunctional siloxane compound, the lower the hardness but the hard coat layer 20 without curling.

Here, the hard coat layer 20 has a pencil hardness of 1H or more as described above.
Usually, when the molar ratio of the tetrafunctional siloxane compound constituting the polysiloxane compound is 50 mol% or more, the hard coat layer 20 can be a high-hardness film having a pencil hardness of 1H or more. It will come out.
In this respect, in the present embodiment, a predetermined amount of a string-like aluminum silicate which is a tough inorganic nanofiber is added to the hard coat layer 20, so that the molar ratio of the tetrafunctional siloxane compound constituting the polysiloxane compound is determined. Even if it is less than 50 mol%, it is possible to develop the physical property that the pencil hardness is high as 1H or more and no curling occurs.

  Further, for example, when the binder 22 is an acrylic resin, the binder is a polymer in which a bifunctional acrylate compound, a trifunctional acrylate compound, and a tetrafunctional or higher functional acrylate compound are polymerized at a predetermined ratio. The larger the ratio of the functional acrylate compound, the higher the degree of crosslinking and the higher the degree of condensation. The hard coat layer 20 has a high hardness but a strong curl. On the other hand, the smaller the ratio of the tetrafunctional or higher functional acrylate compound, the lower the hardness but the hard coat layer 20 without curling.

Usually, if the molar ratio of the tetrafunctional or higher functional acrylate compound constituting the acrylic resin is 70 mol% or higher, the hard coat layer 20 can be a high hardness film having a pencil hardness of 1H or higher. Will come out strongly.
In this regard, in the present embodiment, a predetermined amount of a laced aluminum silicate, which is a tough inorganic nanofiber, is added to the hard coat layer 20, so the mole of the tetrafunctional or higher functional acrylate compound that constitutes the acrylic resin. Even if the ratio is less than 70 mol%, it is possible to develop the physical properties that the pencil hardness is as high as 1 H or more and no curling occurs.

(2.2) Stretching Step The resin film to be the support layer 10 or the laminate 1 of the support layer 10 and the hard coat layer 20 may be stretched.
In the stretching step, the film can be sequentially or simultaneously stretched in the longitudinal direction (MD direction) and the width direction (TD direction) of the film. The draw ratios in the biaxial directions perpendicular to each other are preferably 1.0 to 2.0 times in the MD direction and 1.05 to 2.0 times in the TD direction, respectively. It is preferably performed in a range of 1.0 to 1.5 times and 1.05 to 2.0 times in the TD direction.
For example, a method in which peripheral speed differences are applied to a plurality of rolls and a roll peripheral speed difference is used to stretch in the MD direction, both ends of the web are fixed with clips and pins, and the distance between the clips and pins is increased in the traveling direction. A method of stretching in the MD direction, a method of stretching in the transverse direction and stretching in the TD direction, a method of stretching in the MD / TD direction simultaneously and stretching in both the MD / TD directions, and the like.
These width maintenance or width direction stretching in the film forming process is preferably performed by a tenter, and may be a pin tenter or a clip tenter.
The film transport tension in the film forming process such as in the tenter depends on the temperature, but is preferably 120 to 200 N / m, more preferably 140 to 200 N / m, and most preferably 140 to 160 N / m.
The stretching temperature is (Tg-30) to (Tg + 100) ° C, more preferably (Tg-20) to (Tg + 80) ° C, where Tg is the glass transition temperature of the support layer 10 (resin film) or the hard coat layer 20. More preferably, it is (Tg-5) to (Tg + 20) ° C.

According to the above embodiment, since the hard coat layer 20 contains the string-like aluminum silicate, the inorganic and tough string-like aluminum silicate is entangled with each other in the hard coat layer 20 (FIG. 1). 3), the hardness of the hard coat layer 20 can be dramatically improved (increased), and curling and cracking can be suppressed.
Therefore, there is no need for measures for curling suppression such as forming the hard coat layer 20 on both sides of the support layer 10 and improving the hardness by extremely increasing the degree of crosslinking of the binder, as was done in the prior art. Thus, cost reduction can be realized.

  Further, instead of inorganic fine particles such as silica conventionally used as a measure for suppressing blocking, the hard coat layer 20 contains a string-like aluminum silicate 24 having a unique shape called a string, Incident light is difficult to scatter, and even if the laminate 1 is stretched, voids are unlikely to occur, and a reduction in transmittance due to light scattering can be prevented.

  Furthermore, since the aluminum silicate 24 has a nano-sized string shape, the anchor effect is likely to work effectively regardless of the size of the unevenness of the support layer 10 and improves the adhesion to the support layer 10. be able to. That is, as shown in the lower enlarged view of FIG. 1, the string-like aluminum silicate 24 is caught by a small concave portion existing in the concave portion for a large (deep) concave portion, and remains as it is for a small (shallow) concave portion. It is thought that it is caught and adhesion is improved.

  Furthermore, since the string-like aluminum silicate 24 has a characteristic that it has a large surface area and is adsorbable, it can adsorb deteriorated gas molecules, and when a metal layer is provided under the support layer 10, Corrosion can be prevented (anticorrosive action can be exhibited).

[Experimental Example 1]
(1) Production of imogolite First, sodium orthosilicate was dissolved in ion-exchanged water to prepare 10 L of a 3.0 mM sodium orthosilicate aqueous solution. The prepared sodium orthosilicate aqueous solution was poured into a cation exchange resin packed in a column to obtain a 3.0 mM orthosilicate aqueous solution. The flow rate of the column was set so that the electric conductivity of the resulting orthosilicate aqueous solution was 10 μS / cm. In addition, the electrical conductivity of the orthosilicate aqueous solution was measured at 25 ° C. using an electrical conductivity meter ES-51 (manufactured by Horiba, Ltd.).

  Next, 5 L of the obtained 3.0 mM orthosilicic acid aqueous solution, 1 L of 30 mM aluminum nitrate aqueous solution, 1 L of 28 mM urea aqueous solution, 1 L of 3.8 mM NaOH aqueous solution, and 2 L of ion-exchanged water were mixed together. A mixture was prepared so that the molar concentration of Al and Al was 1: 2. After sufficiently stirring the prepared mixed solution, the mixed solution was heated at 100 ° C. for 80 hours in an autoclave.

  After the mixture returned to room temperature, a 1M volume of 5M NaCl aqueous solution was added to the mixture to cause gelation, followed by centrifugation to obtain a transparent string-like aluminum silicate gel. NaCl, which is a salt contained in the obtained gel, was removed using a dialysis membrane to obtain an aqueous dispersion of string-like aluminum silicate.

Isopropyl alcohol (IPA) was added to the obtained gel, stirred and centrifuged, and after removing the supernatant, IPA was added again and dispersed, followed by centrifugation. The above operation was repeated an appropriate number of times to replace the aqueous phase of the gel with the IPA phase to obtain an IPA dispersion of string-like aluminum silicate.
In a similar manner, methyl ethyl ketone (MEK) was used as a solvent to obtain a MEK dispersion of string aluminum silicate.

  The obtained string-like aluminum silicate solvent dispersion was concentrated by a rotary evaporator to obtain a string-like aluminum silicate solvent dispersion having a solid content of 20% by mass.

(2) Preparation of sample <Example 1>
A biaxially stretched acrylic film (thickness: 100 μm) was prepared as a support layer.
Subsequently, a hard coat layer forming composition (coating solution) was prepared. Specifically, acrylic UV-curable resin Rioduras LCH (manufactured by Toyo Ink Co., Ltd.) is prepared as a binder (precursor), and the above imogolite MEK dispersion is prepared as an additive and a solvent, respectively, and the precursor of the binder is dispersed in imogolite MEK. Mixed with liquid.
Subsequently, such a coating solution is applied onto the support layer with a wet film thickness of 40 μm by an applicator, irradiated with UV light having a wavelength of 350 nm for 30 seconds, and the proportion of the polyfunctional acrylate compound having a functionality of 4 or more is 60 mol%. A hard coat layer having a thickness of 5 μm was formed, and this was designated as “sample (laminate) of Example 1”.
Regarding the preparation of the sample of Example 1, the constituent material (type) of the hard coat layer, the content of each constituent material in the coating liquid, the content of each constituent material in the solid content, etc. (The other samples are also as shown in Table 1 and Table 3.)

<Example 2-3>
In preparation of the sample of Example 1, the content of each constituent material in the coating liquid of the hard coat layer and the content of each constituent material in the solid content were prepared and changed as shown in Table 1.

<Example 4>
A biaxially stretched acrylic film (thickness: 100 μm) was prepared as a support layer.
Subsequently, a hard coat layer forming composition (coating solution) was prepared. Specifically, a polysiloxane-based surcoat NP720 (manufactured by Kinken Co., Ltd.) is prepared as a binder (precursor), and the above imogolite IPA dispersion is prepared as an additive and a solvent. The binder precursor is an imogolite IPA dispersion. Mixed with.
Subsequently, such a coating solution is applied onto the support layer with a wet film thickness of 40 μm by gravure coating, and heat-treated at 80 ° C. for 2 hours, and the ratio of the tetrafunctional siloxane compound is 40 mol% and the thickness is 5 μm. A hard coat layer was formed, and this was designated as “Sample of Example 4”.

<Example 5-6>
In the preparation of the sample of Example 4, the content of each constituent material in the coating liquid for the hard coat layer and the content of each constituent material in the solid content were prepared and changed as shown in Table 1.

<Comparative Example 1>
In the preparation of the sample of Example 1, a hard coat layer having a ratio of the tetrafunctional or higher polyfunctional acrylate compound of 60 mol% and a thickness of 5 μm was formed without adding imogolite. Sample ".

<Comparative Example 2>
In the preparation of the sample of Example 1, polyfunctional acrylate compound Aronix M-403 (manufactured by Toagosei Co., Ltd.) is used as a binder (precursor), and polyfunctionality of 4 or more functions is added without adding imogolite. A hard coat layer having a proportion of acrylate compound of 80 mol% and a thickness of 5 μm was formed, and this was designated as “Sample of Comparative Example 2”.

<Comparative Example 3-4>
In preparation of the sample of Example 1, the content of each constituent material in the coating liquid of the hard coat layer and the content of each constituent material in the solid content were prepared and changed as shown in Table 1.

<Comparative Example 5>
In the preparation of the sample of Example 1, silica fine particles (TECNAPOW-SIO ₂ , manufactured by TECNAN) were added instead of imogolite, the ratio of the tetrafunctional or higher polyfunctional acrylate compound was 60 mol%, and the thickness was 5 μm. A hard coat layer was formed, and this was designated as “Sample of Comparative Example 5”.

<Comparative Example 6>
In the preparation of the sample of Example 4, a hard coat layer having a proportion of the tetrafunctional siloxane compound of 40 mol% and a thickness of 5 μm was formed without adding imogolite, and this was designated as “Sample of Comparative Example 6”. .

<Comparative Example 7>
In the preparation of the sample of Example 4, tetramethoxysilane, which is a tetrafunctional siloxane compound, is used as a binder (precursor), and without adding imogolite, the proportion of the tetrafunctional siloxane compound is 60 mol% and the thickness is 5 μm. A hard coat layer was formed, and this was designated as “Sample of Comparative Example 7”.

<Comparative Example 8-9>
In the preparation of the sample of Example 4, the content of each constituent material in the coating liquid for the hard coat layer and the content of each constituent material in the solid content were prepared and changed as shown in Table 1.

<Comparative Example 10>
In the preparation of the sample of Example 4, silica fine particles (TECNAPOW-SIO ₂ , manufactured by TECNAN) were added instead of imogolite, and a hard coat having a tetrafunctional siloxane compound ratio of 40 mol% and a thickness of 5.0 μm. A layer was formed, and this was designated as “Sample of Comparative Example 10”.

(3) Sample evaluation <Pencil hardness evaluation>
Pencil hardness was measured on the surface of the hard coat layer.
Specifically, using a test pencil specified by JIS-S6006, according to the pencil hardness evaluation method specified by JIS-K5400, a predetermined surface is repeatedly scratched 5 times with a pencil of each hardness using a weight of 500 g, and scratches are 1 The hardness until the book was completed was measured and evaluated according to the following criteria.
◎: Pencil hardness 3H or more ○: Pencil hardness 2H
Δ: Pencil hardness 1H
X: Pencil hardness less than 1H

<Curl evaluation>
Each sample was cut into a size of 10 cm in length and 10 cm in width, and the rising of the edge portion of the section was measured and evaluated according to the following criteria.
○: Lift of the edge portion is 2 cm or less Δ: Lift of the edge portion is more than 2 cm and 4 cm or less ×: The section is cylindrical

<Crack resistance evaluation>
Each sample was cut into a 5 cm × 10 cm square and wound around a round bar having a diameter of 10 mm so that the hard coat layer was on the outside. Then, the crack was observed with the microscope (50 times) from the hard-coat layer surface.
The observation results were evaluated according to the following criteria.
◎: There is no crack even if the rod winding process is performed 10 times or more. ○: There is no crack even if the rod winding process is performed 9 times. Cracks are confirmed when 10 times are performed. Δ: 7 times the rod winding process is performed. The crack was confirmed when it was carried out 9 times from No .: The crack was confirmed when the rod winding process was 6 times or less.

<Blocking resistance evaluation>
A large number of 5 cm × 5 cm test pieces were cut out from each sample, 10 sheets were stacked so that the support layer and the hard coat layer were in contact with each other, and 9.8 × 10 ³ Pa (100 g / 100 μm) in the thickness direction. In a state where a load of cm ² ) was applied, the state after being left for 96 hours in an environment of 40 ° C. and 80% was visually observed and evaluated according to the following criteria.
○: Blocking was not confirmed when the affixed area was 0% Δ: Blocking was confirmed slightly when the affixed area was less than 2% ×: Blocking was confirmed when the affixed area was 2% or more

<Transmittance evaluation>
During the preparation of each sample, before and after laminating the hard coat layer on the support layer, the transmittance with respect to light having a wavelength of 400 to 800 nm is measured, and the degree to which the transmittance is reduced by laminating the hard coat layer is calculated. The evaluation was based on the following criteria.
○: Decrease in average transmittance at wavelength 400-800nm is less than 0% △: Decrease in average reflectance at wavelength 400-800nm is 0% or more and less than 5% ×: Decrease in average reflectance at wavelength 400-800nm is 5% that's all

<Adhesion evaluation>
The test was conducted according to the standard of JIS D 0202-1988.
Specifically, cellophane tape (manufactured by Nichiban Co., Ltd.) was adhered to the hard coat layer of each sample with the belly of the finger by a cross-cut tape peeling test, and then peeled.
Judgment was the number of squares that did not peel out of 100 squares, and was evaluated according to the following criteria.
○: Separation number 0 square △: Separation number 1 square or more and less than 10 squares ×: Stripping number 10 square or more

<Evaluation of corrosion resistance (corrosion resistance)>
Each sample and a copper plate silver-plated on the surface were bonded together with an adhesive film (TL-410S-02, manufactured by Lintec Corporation), and the end (exposed interface) was sealed with a copper foil tape. About each sealing body, the deterioration process was implemented for 5 hours in 10 ppm hydrogen sulfide gas atmosphere, the reflectance with respect to the light of wavelength 400-800 nm before and behind the process was measured, and the following reference | standard evaluated.
○: Decrease in average reflectance at wavelength 400-800 nm is less than 10% Δ: Decrease in average reflectance at wavelength 400-800 nm is 10% or more and less than 20% ×: Decrease in average reflectance at wavelength 400-800 nm is 20% that's all

<Light resistance evaluation>
Each sample was irradiated with ultraviolet rays for 96 hours in an environment of 63 ° C. using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., then a load of 1 kg / cm ² was applied to # 0000 (extra fine) steel wool, The surface of the hard coat layer was rubbed back and forth 10 times at a stroke of 100 mm and a speed of 30 mm / sec, and the scratch resistance (light resistance) after UV degradation treatment was evaluated according to the following criteria.
◎: Number of scratches 0: Number of scratches 1 to 5 △: Number of scratches 6 to 10 ×: Number of scratches is more than 10

(4) Summary As shown in Table 2, Comparative Examples 1-2 and 6-7 in which imogolite was not added, Comparative Examples 2 and 7 in which the degree of crosslinking of the binder was increased, and silica particles were added instead of imogolite. In both samples of Comparative Examples 5 and 10 and Comparative Examples 3-4 and 8-9 where the amount of imogolite added is outside the range of 1 to 30% by mass, both improvement in pencil hardness and curl suppression are realized. Was not.

On the other hand, in Example 1 to Example 6 in which the amount of imogolite which is a string-like aluminum silicate is in the range of 1 to 30% by mass and the thickness of the hard coat layer is 0.5 to 100 μm It can be seen that the pencil hardness, curl suppression and crack resistance are compatible (particularly, in Examples 2 and 5 where the amount of imogolite added is 15% by mass, the pencil hardness and the crack resistance were the best). .)
This is because when a string-like aluminum silicate is added to the hard coat layer, inorganic and tough string-like aluminum silicates are entangled with each other in the hard coat layer, which is extremely hard, curling is suppressed, and stress is applied. This is considered to be because the hard coat layer is less prone to cracking. For this reason, the measures to improve the degree of cross-linking of the binder, which was necessary for achieving high hardness in the prior art, are no longer necessary, and it has become possible to produce a hard coat layer that has high hardness and can suppress curling. It is done.
Further, in Example 1-6, as compared with Comparative Examples 5 and 10 in which silica particles were added, blocking was suppressed without causing a decrease in transmittance due to light scattering due to the addition of string-like aluminum silicate, Further, it is considered that the anchor effect works effectively and the adhesion is improved regardless of the type of support layer (size of irregularities).
From the above, in order to improve hardness (suppression of curling), improvement of blocking resistance (prevention of decrease in light transmittance), and improvement of the adhesion between the support layer and the hard coat layer, the cord-like aluminum silicic acid is used. It can be seen that it is useful to control the salt content to 1 to 30% by mass, the binder content to 70 to 99% by mass, and the hard coat layer thickness to be 0.5 to 100 μm.

Furthermore, in Example 1-6, anticorrosion property is improving. This is because the anticorrosive action is manifested when a deteriorated gas molecule is adsorbed and a metal exists under the support layer due to the properties of the string-like aluminum silicate, that is, the surface area has a large adsorptivity. Conceivable.
Furthermore, when Example 1-3 and Example 4-6 are compared, it is better to use a polysiloxane compound having less organic components than the acrylic resin as the binder, and thus the light resistance is improved and the light resistance is improved. It can be seen that it is useful to use a polysiloxane compound as a binder.

[Experiment 2]
(1) Preparation of sample <Example 7-8>
In the sample of Example 2 according to Experimental Example 1, the layer thickness of the hard coat layer was set to 0.5 μm and 100 μm, respectively. Other than that was produced similarly to the sample of Example 2.
<Example 9-10>
In the sample of Example 5 according to Experimental Example 1, the layer thickness of the hard coat layer was set to 0.5 μm and 100 μm, respectively. Other than that was produced similarly to the sample of Example 5.

<Comparative Example 11-12>
In the sample of Example 2 according to Experimental Example 1, the layer thickness of the hard coat layer was 0.2 μm and 150 μm, respectively. Other than that was produced similarly to the sample of Example 2.
<Comparative Example 13-14>
In the sample of Example 5 according to Experimental Example 1, the layer thickness of the hard coat layer was 0.2 μm and 150 μm, respectively. Other than that was produced similarly to the sample of Example 5.

(2) Evaluation of sample Pencil hardness and crack resistance were evaluated by the same method and standard as in Experimental Example 1.

(3) Summary As shown in Table 4, in Comparative Example 11-14 in which the layer thickness of the hard coat layer is out of the range of 0.5 to 100 μm, both improvement in pencil hardness and curl suppression have not been realized. On the other hand, these results were good in Examples 7-10 in which the layer thickness of the hard coat layer was in the range of 0.5 to 100 μm.
From this, the improvement of hardness (suppression of curling), the improvement of blocking resistance (prevention of decrease in light transmittance), and the improvement of the adhesion between the support layer and the hard coat layer, which were clarified in Experimental Example 1, are maintained. In doing so, it can be seen that it is useful to set the thickness of the hard coat layer to 0.5 to 100 μm.

DESCRIPTION OF SYMBOLS 1 Laminated body 10 Support body layer 20 Hard-coat layer 22 Binder 24 String-like aluminum silicate

Claims (6)

A laminate in which a light transmission layer having a binder and a string-like aluminum silicate and a support layer supporting the light transmission layer are laminated,
The content of the binder in the light transmission layer is 70 to 99% by mass, and the content of the string-like aluminum silicate in the light transmission layer is 1 to 30% by mass,
A laminate having a thickness of the light transmission layer of 0.5 μm or more and 100 μm or less. In the laminate according to claim 1,
A laminate characterized in that the string-like aluminum silicate is imogolite. In the laminate according to claim 1 or 2,
The laminated body, wherein the support layer is a resin film. A composition for forming a light transmissive layer for forming a light transmissive layer having a binder and a string-like aluminum silicate,
Containing the binder precursor, the string-like aluminum silicate and a solvent;
The content of the binder precursor in the composition is 0.5 to 70% by mass,
The content of the cord-like aluminum silicate in the composition is 0.1 to 20% by mass,
The composition for forming a light transmission layer, wherein the content of the solvent in the composition is 10 to 99.4% by mass. The composition for forming a light transmission layer according to claim 4,
The composition for forming a light transmission layer, wherein the binder is a polysiloxane compound. In the manufacturing method of the laminated body for manufacturing the laminated body as described in any one of Claims 1-3,
Preparing the light-transmitting layer-forming composition according to claim 4 or 5,
Applying and curing the laminate-forming composition on the support layer by a solvent casting method;
The manufacturing method of the laminated body characterized by comprising.