JP2005153166A - Laminate having ultraviolet cutting properties - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate excellent in dispersibility, transparency and surface smoothness, having gas barrier properties or steam barrier properties as a result, capable of cutting off ultraviolet rays with a wavelength of 420 nm or below and capable of being adapted to various uses of food, cosmetics, a medicine packaging container and the like. <P>SOLUTION: This laminate having ultraviolet cutting properties has a base material and an ultraviolet cutting layer including a resin binder and a metal oxide surface-treated using a polyhydric alcohol and an organopolysiloxane or a transparent vapor deposition layer formed using a vapor deposition compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate in which a film-like, sheet-like or plate-like ultraviolet cut layer is provided and a transparent vapor deposition layer is provided thereon. More specifically, the present invention relates to a laminate that can simultaneously form a barrier layer for gas and water vapor and cut ultraviolet rays on a substrate or a substrate covered with a substrate by forming a transparent vapor deposition layer and an ultraviolet cut film on the substrate.

  It is already known that metal oxides have the ability to cut ultraviolet rays, and are put to practical use in applications such as cosmetics. However, in general, the dispersibility of the metal oxide in the resin is poor, and there is a problem in that defects such as unevenness occur in the coating or become opaque due to poor dispersibility.

Further, when the dispersibility of the metal oxide with respect to the resin is poor, the surface becomes rough. When transparent vapor deposition is performed on such a film, the transparent vapor deposition film having an uneven surface is not uniform, and as a result, the target gas barrier property and water vapor barrier property are not exhibited.
This unevenness greatly depends on the particle diameter of the metal oxide.

In order to improve the gas barrier property and the water vapor barrier property, it is necessary to reduce the surface roughness of the metal oxide. For this purpose, it is necessary to increase the dispersibility of the metal oxide or to reduce the particle diameter.
For the purpose of improving dispersibility, the shape of α-ferric oxide is controlled (Patent Document 1), and the surface of the metal oxide is made of polyhydric alcohol (Patent Document 2) or siloxane (Patent Document 3). However, further improvement in dispersibility is demanded.
JP-A-8-59398 JP 2002-173579 A JP 2002-173580 A

  An object of the present invention is to provide a laminate that is excellent in dispersibility, transparency, and surface smoothness, and as a result has good gas barrier properties and water vapor barrier properties and can shield ultraviolet rays having a wavelength of 420 nm or less.

The present invention comprises a substrate,
The present invention relates to an ultraviolet cut layer comprising a resin binder and a metal oxide surface-treated with a polyhydric alcohol or organopolysiloxane, and a laminate having an ultraviolet cut property having a transparent vapor deposited layer on which a vapor deposited compound is deposited. .

The present invention also provides a substrate,
A laminate having the above-mentioned UV-cutting properties, comprising an ultraviolet-cutting layer comprising a resin binder, a metal oxide surface-treated with a polyhydric alcohol and organopolysiloxane, and a transparent vapor-deposited layer on which a vapor-depositable compound is deposited. About.

  Moreover, this invention relates to the laminated body which has the said ultraviolet cut property whose metal oxide is (alpha) -ferric oxide, a titanium oxide, and a zinc oxide.

  Moreover, this invention relates to the said ultraviolet cut laminated body which is the non-needle shape whose aspect-ratio of a metal oxide is 0.2-1.0, and an average particle diameter is 0.01-0.06 micrometer.

  In addition, the present invention relates to the ultraviolet cut laminate, wherein the metal oxide is surface-treated with polyhydric alcohol and then surface-treated with organopolysiloxane.

  Moreover, this invention relates to the said ultraviolet cut laminated body in which a film further contains a dispersing agent.

  Moreover, this invention relates to the said ultraviolet cut laminated body whose vapor deposition compound contains 1 type, or 2 or more types of silicon oxide, aluminum oxide, magnesium oxide, and titanium oxide.

  Further, the present invention provides an ultraviolet-cutting property characterized by depositing a vapor-depositable compound on a film comprising a resin binder and a metal oxide surface-treated with a polyhydric alcohol and an organopolysiloxane. The present invention relates to a method for producing a laminate having

  According to the present invention, it is possible to provide a laminate that is excellent in dispersibility, transparency, and surface smoothness, and as a result has good gas barrier properties and water vapor barrier properties and can shield ultraviolet rays having a wavelength of 420 nm or less.

<Base material>
Base materials used in the present invention include polyethylene terephthalate film, polypropylene film, polyethylene film, vinyl chloride film, vinylidene chloride film, acrylic film, nylon film, fluorine film, polyvinylidene fluoride film, polycarbonate film, polyethylene-2. , 6-naphthalate film. Among these, a biaxially stretched polyethylene terephthalate film and a biaxially stretched nylon film are desirable. Also, a coating process such as anchor coating may be performed.

The surface of the plastic film may be subjected to surface treatment such as corona discharge treatment, flame treatment or plasma treatment, but these surface treatments are not essential.
Although it is desirable that nothing is applied to the surface of the plastic film, an organic conductive agent such as a surfactant or a polymer electrolyte, a UV absorber or a light stabilizer is applied or kneaded in advance. It doesn't matter what is being done.
The thickness of the plastic film is not particularly limited, but is preferably 6 μm to 2 mm, and particularly preferably 12 to 200 μm.

<UV cut layer>
Examples of the metal oxide used in the present invention include α-ferric oxide, titanium oxide, zinc oxide, cerium oxide and the like. Among these, α-ferric oxide, titanium oxide, and zinc oxide are preferably used from the viewpoint of easy availability and ease of handling.

  The shape of the metal oxide used in the present invention, particularly α-ferric oxide, is preferably non-acicular. Here, the term “non-needle” refers to a range in which the ratio of the minor axis to the major axis (minor axis / major axis) is 0.2 to 1.0 as observed by an electron microscope. In order to obtain a molded article having good transparency and dispersibility, a true spherical shape (minor axis / major axis = 1.0) is most preferable.

  The average particle diameter of the metal oxide used in the present invention, particularly α-ferric oxide, is 0.01 to 0.06 μm. Preferably it is 0.03-0.05 micrometer. When the average particle size is less than 0.01 μm, particle aggregation and poor dispersion occur, resulting in insufficient transparency and gas barrier properties. When it exceeds 0.06 μm, the surface roughness of the molded product becomes too large, The appearance of the molded product becomes poor due to a decrease in transparency and pigment aggregation. Here, the average particle diameter means a value indicating the maximum value of the particle size distribution with the average of the short diameter and the long diameter as the particle diameter.

In the present invention, a polyhydric alcohol or organopolysiloxane is used as a surface treatment agent capable of achieving surface treatment by coating with a metal oxide. More preferably, the polyhydric alcohol and the organopolysiloxane are treated.
Each of the surface treatment agents is preferably added in an amount corresponding to 0.01 to 10% by weight of the weight of the metal oxide. Particularly preferably, it is 0.1 to 2% by weight, respectively.

  Specific examples of the polyhydric alcohol include alkylene glycol such as ethylene glycol, propylene glycol, 1,3-butanediol, and tetramethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and the like. And polyhydric alcohols such as glycerin, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, 1,2,6-hexanetriol, inositol, and polyvinyl alcohol. Preferably, trimethylolpropane (TMP), trimethylolethane (TME), etc. are mentioned. These polyhydric alcohols can be used alone or in combination.

  The polyhydric alcohol is preferably added in an amount corresponding to 0.01 to 10% by weight of the weight of the metal oxide. If it exceeds 10% by weight, foaming or unevenness may occur in the produced coating. If it is less than 0.01% by weight, the coating amount of polyhydric alcohol on the surface of the metal oxide is not sufficient, and the dispersion of the metal oxide into the resin binder becomes poor, which may cause poor physical properties in the film.

Specific examples of organopolysiloxanes include dimethylpolysiloxane, methylhydrogen polysiloxane, methylphenyl polysiloxane, and various modified polysiloxanes such as polydimethylsiloxane, alcohol-modified polysiloxane, ether-modified polysiloxane, and fluorine-modified polysiloxane. Can be used. These organopolysiloxanes can be used alone or in combination. Methyl hydrogen polysiloxane and dimethyl polysiloxane are preferred.
The methyl hydrogen polysiloxane exemplified above is preferably represented by the following formula.

（式中ｎは正の整数を表し、１２以下であることが好ましい。）

(In the formula, n represents a positive integer and is preferably 12 or less.)

  The organopolysiloxane is preferably added in an amount corresponding to 0.01 to 10% by weight of the weight of the metal oxide. If it exceeds 10% by weight, foaming or unevenness may occur in the produced coating. If it is less than 0.01% by weight, the coating amount of the organopolysiloxane on the surface of the metal oxide is not sufficient, and the dispersion of the metal oxide into the resin binder becomes poor, which may cause poor physical properties in the film.

As a method of coating the metal oxide with the surface treatment agent, a known method such as a wet treatment method or a dry treatment method can be used.
In the wet treatment, a metal oxide and a surface treatment agent are added to a polar solvent such as alcohol, and the mixture is uniformly mixed using a high shear mixer such as a Henschel mixer or a super mixer, and then the solvent is removed. In the wet treatment, if there is a heat drying step of the metal oxide particles during or after the surface treatment, the water content due to moisture adsorption or the like is greatly reduced. The low water content metal oxide thus obtained has the advantage of improving dispersibility upon mixing into the resin binder.

  In the dry treatment, a surface treatment agent is added when the metal oxide is pulverized by a fluid energy pulverizer such as a micronizer or a jet mill. As the fluid at this time, compressed air, heated compressed air, steam or the like is usually used. Further, when the polyhydric alcohol is solid at room temperature, a polyhydric alcohol solution dissolved in a solvent may be used in the treatment step. For example, an ethanol solution of trimethylolethane can be used.

  In the present invention, the surface of the metal oxide, particularly α-ferric oxide, is subjected to one surface treatment, and at least twice, the affinity for the resin binder on the surface of the metal oxide, particularly α-ferric oxide. Can be improved effectively. Metal oxide, especially α-ferric oxide, is first treated with polyhydric alcohol, and the reaction of siloxane with the hydroxyl group derived from polyhydric alcohol, which is generated by this, leads to particularly improved affinity. It is expected that

Examples of the resin binder used in the present invention include a polymerization type thermoplastic resin and a condensation type thermoplastic resin.
Examples of the polymerization type thermoplastic resin include (meth) acrylic resin, styrene resin, polyalkylene resin and the like.
Condensation type thermoplastic resins include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, aromatic carboxylic acids such as 4,4-diphenyldicarboxylic acid, or esters thereof with ethylene glycol, propylene glycol, 1,4- Examples thereof include conventionally known polyester resins that can be obtained by condensation polymerization with aliphatic glycols such as butanediol, diethylene glycol, 1,4-cyclohexanedimethanol and the like.

  Typical examples include polyester resins such as polyethylene terephthalate and polybutylene terephthalate.

  Moreover, a microbial disintegrating resin can also be used as the condensation type thermoplastic resin used in the present invention. Examples of the microorganism-disintegrating resin include polylactic acid, polycaprolactone, or an aliphatic polyester resin obtained using aliphatic dicarboxylic acid and a polyhydric alcohol as raw materials, and a polyester resin synthesized from microorganisms or plants.

  Specifically, commercially available or experimentally manufactured polybutylene succinate, polyethylene succinate, polybutylene succinate adipate, manufactured by Showa Polymer Co., Ltd. or Nippon Shokubai Co., Ltd., Mitsui Chemicals, Cargill, Shimadzu Of polylactic acid, polycaprolactone manufactured by Daicel Chemical Industries, poly (3-hydroxybutyric acid-CO-3-hydroxyvaleric acid) (P (3HB-3HV)) and poly (3-hydroxybutyric acid-CO-4) manufactured by Monsanto -Hydroxybutyric acid) (P (3HB-4HB)) and poly (3-hydroxybutyric acid-CO-3-hydroxypropionate) (P (3HB-3HP)).

The dispersant that can be used in combination with the resin binder in the present invention can be used to further improve the compatibility between the surface-treated α-ferric oxide and the resin binder. The kind and amount are appropriately selected and used according to the resin binder to be used.
As such a dispersant, a metal soap, that is, a metal salt of a higher fatty acid or a metal salt of oxycarboxylic acid can be used.

  For example, calcium stearate, magnesium stearate, barium stearate, zinc stearate, aluminum stearate, lithium stearate, calcium laurate, zinc laurate, magnesium laurate, α-hydroxymyristic acid as metal oxycarboxylate, α- Hydroxypalmitic acid, α-hydroxystearic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaicosanoic acid, α- Gold such as hydroxytriacontanoic acid, β-hydroxymyristic acid, 10-hydroxydecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxystearic acid, ricinoleic acid Salt and the like.

  Additives such as pigments or dyes can be used in combination with the resin binder used in the present invention. Examples of the pigment or dye include organic pigments such as azo, anthraquinone, perylene, perinone, quinacridone, phthalocyanine, isoindolinone, dioxazine, indanthrene, and quinophthalone, zinc oxide, and titanium oxide. Colored inorganic pigments such as ultramarine, cobalt blue, carbon black, titanium yellow, extender pigments such as barium sulfate, kaolin, talc, anthraquinone, perylene, perinone, monoazo, methine, heterocyclic, lactone Oil-soluble dyes such as phthalocyanine and disperse dyes can be used.

  Furthermore, additives such as antioxidants, UV absorbers other than iron oxide, light stabilizers, metal deactivators, etc. that are usually used in combination with resin binders can be blended. As the antioxidant, phenol-based, phosphite-based and the like can be used. Examples of phenolic compounds include diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate and the like. Examples of the phosphite system include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, and the like. be able to.

  Benzotriazole-based, triazine-based and the like can be used as the ultraviolet ray preventing agent. Examples of the benzotriazole series include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2- (2H- Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- ( tert-butyl) phenol and the like. Examples of the triazine series include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  As the light stabilizer, a hindered amine or the like can be used. Examples of hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [[6- (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]] Dibutylamine, 1,3,5-triazine, N, N-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine, N- (2,2,6, 6-tetramethyl-4-piperidyl) butylamine polycondensate, etc. Examples of the metal deactivator include 2,3-bis [[3- [3,5-di-tert-butyl-4. -Hydroxyphenyl] propionyl]] propionohydrazide and the like.

  The surface-treated metal oxide used in the present invention is mixed with a resin binder by a known technique. Usually, a resin binder is used as a solution, and the metal oxide is mixed while stirring the solution using a stirrer. The dispersant and other additives that may be added at the time of stirring are added and stirred before and after the addition of the metal oxide, if necessary.

A resin binder solution containing a resin binder and a metal oxide is applied to a substrate with a known coating machine to form a film on the substrate. The thickness of the coating is usually 1 μm to 100 μm (dry). There is no particular limitation on the solvent at this time, aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and acetone, petroleum mixed solvents such as Solvesso, dimethylformamide and the like Examples include polar solvents such as N-methylpyrrolidone.
Moreover, you may perform solvent mixing for adjusting a viscosity for improving coating property, and addition of a viscosity modifier.

<Transparent deposition layer>
In the present invention, a transparent vapor deposition layer is provided on an ultraviolet cut layer.
The transparent vapor deposition layer is obtained by vapor-depositing a vapor-depositable compound, and the composition of the vapor-depositable compound may be any of an inorganic compound such as a metal oxide, a metal, and an organometallic compound, or an organic compound alone or a mixture. Particularly preferably, it contains one or more of silicon oxide, aluminum oxide, magnesium oxide, and titanium oxide.

Silicon oxide constituting the transparent deposition layer is a compound represented by SiOx (x = 0.5 to 2), specifically SiO (silicon monoxide) and SiO ₂ (silicon dioxide), Si ₂ O ₃ etc. are mentioned. The transparent vapor-deposited layer made of silicon oxide alone becomes colorless and transparent as x of SiOx is closer to 2, and on the contrary, the smaller the value of x, the more brown-yellow color is exhibited. When forming a transparent vapor deposition layer using a vacuum thin film forming technique, it is quite difficult to completely set x of SiOx to 2, and when the transparent vapor deposition layer is made of silicon oxide alone, it is at least slightly colored. .
The aluminum oxide constituting the transparent vapor deposition layer may not be a complete oxide such as Al ₂ O ₃ (aluminum oxide), and is somewhat oxygen deficient such as Al ₂ Ox (x = 1.5-3). It doesn't matter if it is in the state. When forming a transparent vapor deposition layer by vacuum vapor deposition among vacuum thin film formation techniques, this oxygen deficiency is likely to occur.

  Examples of the titanium oxide include titanium monoxide, titanium sesquioxide, and titanium dioxide. As titanium dioxide, either anatase / rutile may be used.

  In the composition of the transparent vapor deposition layer, when other oxides are mixed with silicon oxide or aluminum oxide, the ratio is not particularly limited.

Examples of the silicon oxide used as the raw material include a mixture of silicon and silicon dioxide, silicon monoxide alone, and a mixture of silicon, silicon dioxide, and silicon monoxide. When a mixture of silicon (Si) and silicon dioxide (SiO ₂ ) is used as the silicon oxide, the composition ratio is basically preferably equimolar, but Si: SiO ₂ = 40 to 60 mol%: 60 to 40 mol. % Is acceptable. When the silicon oxide used as a raw material is a mixture of Si, SiO, and SiO ₂ , Si: SiO ₂ may be approximately equimolar, and the ratio of (Si + SiO ₂ ): SiO is not particularly limited.

  Examples of the aluminum oxide used as a raw material include aluminum oxide, metallic aluminum, and an organoaluminum compound. The aluminum oxide may be formed in the state of a transparent vapor deposition layer.

At the same time, another raw material may be vapor-deposited from another evaporation source.
A transparent vapor deposition layer can be formed on a base material with a vacuum thin film formation technique. Examples of the vacuum thin film forming technique include physical vapor deposition (PVD) such as vacuum deposition, ion plating, and sputtering, and chemical vapor deposition (CVD) using plasma or the like. Among these, vacuum deposition is particularly desirable from the viewpoint of deposition speed.

  There is no restriction | limiting in particular as a heating method of vacuum evaporation, Well-known heating methods, such as high frequency induction heating, resistance heating, and electron beam heating, can be used. A general crucible method may be used as an evaporation source for vacuum deposition.

When a transparent vapor deposition layer is formed on a substrate or a substrate having an ultraviolet cut layer, the raw material composition may be directly reflected in the composition of the transparent vapor deposition layer by a vacuum vapor deposition method. It is good also as a composition of a transparent vapor deposition layer, reacting these raw materials.
As a method of laminating a transparent vapor deposition layer by reactive vapor deposition, there is a method of vacuum vapor deposition while oxidizing a compound containing a metal such as a metal or an organometallic oxide. The oxidation treatment method is not particularly limited as long as the treatment is performed within the usable temperature range of the base material, and examples thereof include an oxygen gas introduction method, a discharge treatment method, an oxygen plasma method, and a thermal oxidation method during vapor deposition.

  The film thickness of the transparent vapor deposition layer is generally preferably 1 to 100 nm from the viewpoint of developing barrier properties. Furthermore, 5 to 30 nm is desirable, and 5 to 10 nm is particularly desirable. Good. When the film thickness of the transparent vapor deposition layer exceeds 30 nm, the internal stress of the transparent vapor deposition layer gradually begins to exist, and when the film thickness exceeds 100 nm, the internal stress of the transparent vapor deposition layer becomes completely large, which causes the peeling of the substrate and the transparent vapor deposition layer. Related to.

  The transparent vapor deposition layer may be a two-layer stack or a multiple stack as long as the necessary function of the finally obtained layer is obtained. That is, lamination may be performed in two or more times, and at that time, different types of metal fluorides, magnesium oxides, and titanium oxides may be laminated. Moreover, when laminating | stacking two or more layers, you may put layers, such as resin of an organic substance, between transparent vapor deposition layers.

  The present invention has a substrate, a resin binder, an ultraviolet cut layer formed by forming a film comprising a metal oxide surface-treated with a polyhydric alcohol and an organopolysiloxane, and a transparent vapor deposition layer. It is a laminate. There are no particular restrictions on the order in which the UV-cutting layer and transparent deposition layer are formed.

In the laminate of the present invention, the base material, the ultraviolet cut layer, and the transparent vapor deposition layer coexist, but the formation order of the ultraviolet cut layer and the transparent vapor deposition layer is not particularly a problem. Moreover, it is also possible to form a primer layer on the application | coating surface of an ultraviolet cut layer, and the vapor deposition surface of a transparent vapor deposition layer as needed. The transparent vapor deposition layer is preferably the outermost surface. Although it is preferable to form an ultraviolet cut layer before forming the transparent vapor deposition layer, it is not limited thereto.
Further, the ultraviolet cut layer and the gas barrier layer do not need to be the same surface of the substrate, and may be separately formed on both surfaces of the substrate. Further, the ultraviolet cut layer and the gas barrier layer are not necessarily required to be only one layer in the laminate.

  When forming a transparent vapor deposition layer on this ultraviolet cut layer, the ultraviolet cut layer which is the deposition surface must be fairly flat. This flatness greatly depends on the average particle diameter of the metal oxide. The average particle diameter of α-ferric oxide used in the present invention is 0.01 to 0.06 μm. Preferably it is 0.03-0.05 micrometer. When the average particle size is less than 0.01 μm, particle aggregation and poor dispersion occur, resulting in insufficient transparency and gas barrier properties. When it exceeds 0.06 μm, the surface roughness of the molded product becomes too large, The barrier performance is not fully exhibited after the transparent vapor deposition layer is laminated. Here, the average particle diameter means a value indicating the maximum value of the particle size distribution with the average of the short diameter and the long diameter as the particle diameter.

  EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Hereinafter, “wt%” is simply “%”, and “part by weight” is simply “part”.

[Surface treatment of α-ferric oxide]
As shown in Table 1, a surface treatment agent was added while pulverizing metal oxide with a jet mill (working fluid: compressed air) to obtain a surface-treated metal oxide. Each surface treatment agent was adjusted by changing the treatment weight of the metal oxide and the supply concentration or supply flow rate of the treatment agent by a known method so as to obtain a predetermined coating amount based on Table 1.
Table 1
――――――――――――――――――――――――――――――――
Example Metal oxide (particle size μm, aspect ratio) Treatment 1 Treatment 2
――――――――――――――――――――――――――――――――
Production Example 1 Iron oxide (0.03, 0.9) 0.5 0.5
Production Example 2 Titanium oxide (0.03, 0.9) 0.5 0.5
Production Example 3 Zinc oxide (0.03, 0.9) 0.5 0.5
Production Example 4 Iron oxide (0.03, 0.9) 0.5 0
Production Example 5 Iron oxide (0.03, 0.9) 0 0.5
Comparative Production Example 1 Iron oxide (0.03, 0.9) 0 0
――――――――――――――――――――――――――――――――
Treatment 1: Tetramethylolpropane treatment Treatment amount (% by weight) relative to metal oxide
Treatment 2: Methyl hydrogen polysiloxane treatment Amount of treatment for metal oxide (wt%)

[Production example of UV cut layer]
70 parts of toluene, 30 parts of polyester-based resin Byron 200 (manufactured by Toyobo Co., Ltd.), and 0.24 parts of the surface-treated metal oxide shown in Table 1 are added to the entire resin to form a coating solution. A 50 μm-thick polyethylene terephthalate film (Tetron Film HB manufactured by Teijin Ltd.) was applied to one side using a bar coater and applied to a thickness of 25 μm to prepare a sheet having an ultraviolet cut layer.

Table 2
―――――――――――――――
Example UV-cut layer ―――――――――――――――
Production Example 6 Production Example 1
Production Example 7 Production Example 2
Production Example 8 Production Example 3
Production Example 9 Production Example 1
Production Example 10 Production Example 1
Production Example 11 Production Example 1
Production Example 12 Production Example 4
Production Example 13 Production Example 5
Comparative Production Example 2 Comparative Production Example 1
―――――――――――――――

[Example 1]
A continuous-winding resistance heating type vacuum vapor deposition machine that continuously feeds and discharges evaporation materials described in JP-A-1-252786 on the surface of the UV-cutting layer of the sheet having the UV-cutting layer of Production Example 4 Using a mixture of silicon and silicon dioxide (mixing ratio 50 mol%: 50 mol%) as a raw material, vacuum evaporation was performed by heating to obtain a transparent vapor deposition layer (the thickness of the transparent vapor deposition layer was about 20 nm) to obtain a laminate.

[Examples 2 to 8, Comparative Example 1]
A transparent vapor deposition layer was obtained on the ultraviolet cut layer surface of the sheet having the ultraviolet cut layer shown in Table 3 in the same manner as in Example 1 (the thickness of the transparent vapor deposition layer was about 20 nm) to obtain a laminate.

Table 3
―――――――――――――――
Example UV-cut layer ―――――――――――――――
Example 1 Production Example 6
Example 2 Production Example 7
Example 3 Production Example 8
Example 4 Production Example 9
Example 5 Production Example 10
Example 6 Production Example 11
Example 7 Production Example 12
Example 8 Production Example 13
Comparative Example 1 Comparative Production Example 2
―――――――――――――――

[Production Example 2 of Transparent Deposition Layer: Example 9]
A mixture of silicon, silicon dioxide, and magnesium fluoride (mixing ratio: 46 mol%: 46 mol) was used on the surface of the ultraviolet cut layer of the sheet having the ultraviolet cut layer of Production Example 4 using an electron beam heating type continuous winding vacuum deposition machine. %: 8 mol%) was used as a raw material to heat and vacuum deposit to obtain a transparent deposited layer (the thickness of the transparent deposited layer was about 5 nm) to obtain a laminate.

Example 10
A continuous-winding resistance heating type vacuum vapor deposition machine that continuously feeds and discharges evaporation materials described in JP-A-1-252786 on the surface of the UV-cutting layer of the sheet having the UV-cutting layer of Production Example 4 Using a mixture of silicon, silicon dioxide, magnesium fluoride and steatite (mixing ratio 46 mol%: 46 mol%: 4 mol%: 4 mol%) as a raw material, vacuum evaporation is performed to obtain a transparent vapor deposition layer (transparent vapor deposition layer) Was about 100 nm) to obtain a laminate.

Example 11
A continuous-winding resistance heating type vacuum vapor deposition machine that continuously feeds and discharges evaporation materials described in JP-A-1-252786 on the surface of the UV-cutting layer of the sheet having the UV-cutting layer of Production Example 4 Using a mixture of silicon, silicon dioxide and magnesium oxide (mixing ratio: 46 mol%: 46 mol%: 8 mol%) as a raw material, a vacuum vapor deposition is obtained by heating and vacuum deposition (the thickness of the transparent vapor deposition layer is about 5 nm) Got the body.

Example 12
On the surface of the UV-cutting layer of the sheet having the UV-cutting layer of Production Example 4, using the electron beam heating-type continuous winding vacuum deposition machine used in Example 2, aluminum was used as a raw material while being vacuum-deposited while introducing oxygen. A transparent vapor deposition layer was obtained (the thickness of the transparent vapor deposition layer was about 5 nm) to obtain a laminate.

Example 13
Using a reactive sputtering method sputtering machine on one side of a 50 μm thick polyethylene terephthalate film (Tetron film HB made by Teijin Ltd.), oxygen was introduced using metal silicon and metal titanium as the target (molar ratio 95: 5). Then, sputtering was performed (with the inside of the sputtering machine being 5 × 10 ⁻⁴ torr) to obtain a transparent vapor deposition layer (the thickness of the transparent vapor deposition layer was about 5 nm) to obtain a laminate.

[Film evaluation method]
[Evaluation of flatness]
The surface was observed using AFM (manufactured by Seiko Instruments Inc.), the height of the protrusion was measured, and the following criteria were evaluated.
○: 1μm or more × less than 1μm

[Haze]
Measured with Gardner Hayes Guard Plus and evaluated according to the following criteria.
○: Less than 3 Δ: 3 or more and less than 5 ×: 5 or more

[UV light transmittance]
Measured with UV-265FW manufactured by Shimadzu Corporation, the shielding rate in the ultraviolet region of 420 nm or less was determined and evaluated according to the following criteria.
○: shielding rate of 95% or more Δ: shielding rate of 80% or more and less than 95% ×: shielding rate of less than 80%

[Dispersibility]
Observation was performed with an optical microscope at a magnification of 100 times, and evaluation was performed with the worst field of view based on the series of ISO-DIS11420 series.
○: Less than grade 2 △: Grade 2 or more and less than 3 ×: Grade 3 or more

[Gas permeability]
The film was measured for oxygen permeation under conditions of 25 ° C. and 80% RH using OX-TRANT100 manufactured by MODERN CONTROL, and evaluated according to the following criteria.
○: Less than 5 ml / m ² · 24 hours · atm ×: More than 5 ml / m ² · 24 hours · atm

  Table 4 shows the results.

Table 4
――――――――――――――――――――――――――――――――
Example Flatness Haze UV light transmittance Dispersibility Gas permeability ――――――――――――――――――――――――――――――――
Example 1 ○ ○ ○ ○ ○
Example 2 ○ ○ ○ ○ ○
Example 3 ○ ○ ○ ○ ○
Example 4 ○ ○ ○ ○ ○
Example 5 ○ ○ ○ ○ ○
Example 6 ○ ○ ○ ○ ○
Example 7 ○ △ △ △ ○
Example 8 ○ × △ × ○
Comparative Example 1 × × × × ×
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Example 9 ○ ○ ○ ○ ○
Example 10 ○ ○ ○ ○ ○
Example 11 ○ ○ ○ ○ ○
Example 12 ○ ○ ○ ○ ○
Example 13 ○ ○ ○ ○ ○
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  Since the molded product of the present invention has light shielding properties and gas shielding properties in the ultraviolet region, it can be applied to foods, cosmetics, medicine packaging containers and the like in place of glass bottles and aluminum vapor deposition films.

Claims (8)

Base material,
An ultraviolet cut layer comprising a resin binder and a metal oxide surface-treated with a polyhydric alcohol or organopolysiloxane, and a gas barrier layer comprising a polyalcohol polymer and a polycarboxylic acid polymer Laminate with UV-cutting properties. Base material,
The ultraviolet-cutting property of Claim 1 which has the ultraviolet-ray cut layer containing the resin binder, the metal oxide surface-treated using polyhydric alcohol and organopolysiloxane, and the transparent vapor deposition layer which vapor-deposited the vapor-depositable compound. A laminate having   The laminate having ultraviolet cut-off properties according to claim 1 or 2, wherein the metal oxide is α-ferric oxide, titanium oxide, or zinc oxide.   The metal oxide has a non-needle shape with an aspect ratio of 0.2 to 1.0, and an average particle size of 0.01 to 0.06 μm. Laminated body.   The laminate having ultraviolet cut-off properties according to any one of claims 1 to 4, wherein the metal oxide is surface-treated with polyhydric alcohol and then surface-treated with organopolysiloxane.   The laminated body which has a UV cut property in any one of Claims 1-5 in which a film further contains a dispersing agent.   The laminate having ultraviolet cut-off properties according to any one of claims 1 to 6, wherein the vapor-depositable compound contains one or more of silicon oxide, aluminum oxide, magnesium oxide, and titanium oxide. Production of a laminate having UV-cutting characteristics, wherein a vapor-depositable compound is vapor-deposited on a film comprising a resin binder and a metal oxide surface-treated with a polyhydric alcohol and organopolysiloxane Method.