JP2012097198A - Functional film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film having homogeneity without foams, flexibility and excellent light quality converting performance, and useful for a solar cell sealing material, an optical film and an interlayer of a glass laminate such as for an automobile use, etc.SOLUTION: This functional film is obtained by molding a polyolefin resin composition (Z) which is produced by blending a polyolefin resin (Y) with a wavelength converting substance (D). The polyolefin resin composition (Z) includes: the polyolefin resin (Y) that comprises a polyethylene resin (X), as a main component, which contains an ionic polymerization process polyethylene resin (A) and/or a high pressure radical process polyethylene resin (B), wherein the melt flow rate (MFR: measured at 190°C and under a load of 21.18 N) of the polyethylene resin (X) is 1.0-10 g/10 min; and 0.01-5 pts.wt. of the wavelength converting substance (D) based on 100 pts.wt. of the polyolefin resin (Y). The polyolefin resin composition (Z) is molded at a molding temperature equal to or higher than the melting point of the polyolefin resin (Y) and equal to or lower than 160°C.

Description

  The present invention relates to a functional film comprising a polyolefin-based resin containing a wavelength converting substance and a method for producing the same, and more specifically, by selecting a polyethylene-based resin having a specific property range and molding at a low temperature, there is no air bubbles. Thus, the present invention provides a functional film having flexibility and light quality conversion ability having excellent mechanical strength, and a method for producing the functional film.

  Conventionally, films using a technology that converts the wavelength distribution and intensity of light (referred to as light quality conversion technology) have been used for agricultural films, sealing sheets for solar cell modules, etc. It is effective for planning, disease improvement such as breed improvement, pest control, and fungus growth control.

  As a light quality conversion technique using sunlight as a light source, a technique for converting short wavelength light into a long wavelength using a fluorescent agent (Patent Document 1: Japanese Patent Publication No. 46-24376, Patent Document 2: Japanese Patent Application Laid-Open No. 50). -88147) has been known for a long time. Also, a method for converting visible light into long wavelength light to enable enhancement of photosynthesis (Patent Document 3: Japanese Patent Laid-Open No. 6-41524), and a method for converting light having a wavelength in the ultraviolet region into long wavelength light. (Patent Document 4: JP-A-6-46684, Patent Document 5: JP-A-6-46685, Patent Document 6: JP-A-6-36685).

Recently, a polyolefin resin composition in which these light-converting substances are blended with low-density polyethylene produced with a metallocene catalyst, and an agricultural film using the same have also been proposed (Patent Document 7: JP-A-9-249775). Issue gazette).
In this Patent Document 7, a specific ethylene homopolymer or ethylene / α-olefin copolymer and / or 100 parts by weight of another olefinic (co) polymer is added to a compound of the general formula [I] or a polymer thereof 0 A polyolefin-based resin composition having a wavelength conversion ability containing 0.05 to 18 parts by weight and hindered amine 0.05 to 2 parts by weight, a masterbatch for the composition, and an agricultural film containing the composition are described. As a substance having conversion ability, a cyanopyrazine derivative produced using 3,6-diamino-2,5-pyrazinedicarbonitrile or the like as a starting material is used.

  However, many of these light quality conversion substances (fluorescent agents) are sensitive to heat, fading when exposed to high temperatures, resulting in a decrease in conversion efficiency or difficulty in maintaining long-term light quality conversion ability, and a light quality conversion lifetime. The problem of being inferior is included. In addition, there is a problem that bubbles are generated when a polyolefin composition containing these light quality conversion substances (fluorescent agents) is formed into a film or the like when exposed to a high temperature.

Japanese Patent Publication No.46-24376 JP 50-88147 A Japanese Patent Laid-Open No. 06-41524 Japanese Patent Laid-Open No. 06-46684 Japanese Patent Laid-Open No. 06-46685 Japanese Patent Laid-Open No. 06-36685 JP 09-249775 A

  In view of the above problems, the object of the present invention is to select a polyethylene-based resin having a specific property range and mold it at a low temperature so that it has no bubbles, is homogeneous, has flexibility, and has excellent mechanical strength. It is providing the functional film which has quality conversion capability, and its manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have selected an ethylene-based resin having a specific property in a functional film made of a polyolefin-based resin containing a wavelength converting substance, and at a lower temperature than before. By molding, the generation of bubbles is suppressed, and it is possible to obtain a functional film that is homogeneous, rich in flexibility, has good piercing strength, etc., and has excellent light quality conversion ability, and solves the above problems The present invention was completed by finding out what can be done.

  According to 1st invention of this application, the function formed by shape | molding the polyolefin resin composition (Z) which contains 0.01-5 weight part of wavelength conversion substances (D) with respect to 100 weight part of polyolefin resin (Y). The melt flow rate (MFR: 190 ° C., 21.18 N load) in which the polyolefin resin (Y) is composed of a polyethylene resin (A) and / or a high-pressure radical polyethylene resin (B) by an ion polymerization method (Measured below) having a polyethylene resin (X) of 1.0 to 10 g / 10 min as a main component, and the content of the wavelength converting substance (D) is 0.1% relative to 100 parts by weight of the polyolefin resin (Y). 01 to 5 parts by weight, wherein the polyolefin resin composition (Z) is molded at a molding temperature of not less than the melting point of the polyolefin resin (Y) and not more than 160 ° C. Functional film is provided.

  In addition, according to the second invention of the present application, in the first invention, the polyethylene resin (A) obtained by an ionic polymerization method is an ethylene-α-olefin copolymer produced by a single site catalyst. A functional film is provided.

  According to the third invention of the present application, in the first or second invention, the wavelength converting substance (D) is one or more substances selected from inorganic phosphors, organometallic complexes, or organic light emitting pigments. A functional film is provided.

  According to the fourth invention of the present application, in the third invention, the organic luminescent pigment is a condensation product of barbituric acid and p- (dimethyl) aminobenzaldehyde. The functional film described in 1. is provided.

  According to the fifth invention of the present application, in any one of the first to fourth inventions, the polyethylene resin (X) is an ion polymerization polyethylene resin (A) 90 to 10% by weight and a high pressure radical polyethylene. A functional film characterized by being a mixture of 10 to 90% by weight of the resin based resin (B) is provided.

  According to the sixth invention of this application, in any one of the first to fifth inventions, the polyolefin resin (Y) further contains another polyolefin resin (C), and the content thereof is a polyethylene resin. There is provided a functional film characterized in that the content is 0 to 50% by weight based on 100 to 50% by weight of the resin (X).

According to the seventh invention of the present application, in any one of the first to sixth inventions, the number of bubbles having an average diameter of 0.5 mm or more contained in the functional film is 2 or less per 1 m ^2. The functional film characterized by these is provided.

  On the other hand, according to the eighth invention of the present application, a melt flow rate (MFR: 190 ° C., under a 21.18 N load) composed of a polyethylene resin (A) by ion polymerization and / or a high pressure radical process polyethylene resin (B). Measurement) is a polyolefin resin (Y) whose main component is a polyethylene resin (X) of 1.0 to 10 g / 10 min, and the wavelength converting substance (D) is 100 parts by weight of the polyolefin resin (Y). A method for producing a functional film, comprising extruding a polyolefin resin composition (Z) added with 0.01 to 5 parts by weight at a molding temperature of not less than the melting point of the polyolefin resin (Y) and not more than 160 ° C. Is provided.

  Furthermore, according to the ninth invention of the present application, there is provided a laminated film characterized by including at least one layer of the functional film of any one of the first to sixth inventions.

  According to the present invention, since an ethylene-based resin having a specific property that can be molded at a low temperature is selected, it contains a wavelength converting substance (hereinafter also referred to as a wavelength converting agent) that is weak against heat or hygroscopic. However, it is possible to obtain a functional film that is homogeneous, rich in flexibility, has a piercing strength, etc., and has an excellent wavelength conversion ability by molding under specific temperature conditions.

Next, the functional film, the production method thereof, and the laminate of the present invention will be described in detail.
1. [Functional film]
The functional film of the present invention is obtained by molding a polyolefin resin composition (Z) containing 0.01 to 5 parts by weight of a wavelength converting substance (D) with respect to 100 parts by weight of a polyolefin resin (Y). In the film, the polyolefin resin (Y) is composed of a polyethylene resin (A) by ion polymerization and / or a high pressure radical polyethylene resin (B). Measured at 1.0) to 10 g / 10 min of polyethylene resin (X) as the main component, and the content of the wavelength converting substance (D) is 0.01 to 100 parts by weight of the polyolefin resin (Y). The polyolefin resin composition (Z) is molded at a molding temperature of not less than the melting point of the polyolefin resin (Y) and not more than 160 ° C. That.

[Polyolefin resin composition (Z)]
In the present invention, the polyolefin resin composition (Z) is 0.1 to 5 weight percent of the wavelength converting substance (D) with respect to 100 weight parts of the polyolefin resin (Y) containing the polyethylene resin (X) as a main component. It is a polyolefin resin composition constituted by containing a part.

[Polyethylene resin (X)]
In the present invention, the polyethylene resin (X) is an ion polymerization method, that is, an ethylene-α-olefin copolymer (A) produced by an ionic catalyst and / or a low density polyethylene produced by a high pressure radical polymerization method. The ethylene copolymer (B) includes the following.

[Ethylene polymer by ion polymerization method (A)]
The ethylene polymer by the ionic polymerization method is an ethylene polymer produced by the ionic polymerization method, and is an ethylene homopolymer having a density of 0.86 to 0.97 g / cm ³ or an α having ethylene as a main component. -Includes copolymers with olefins. The density is preferably 0.86 to 0.91 g / cm ³ , an ethylene-α-olefin copolymer (hereinafter also referred to as ultra-low density polyethylene (A1) or VLDPE), 0.91 to 0.94 g / cm ³ . An ethylene-α-olefin copolymer (hereinafter also referred to as linear low-density polyethylene (A2) or LLDPE) can be given.

[Ultra low density polyethylene (A1)]
The ultra-low density polyethylene (A1) of the present invention has a density of 0.860 to less than 0.910 g / cm ³ , preferably a density of 0.870 to 0.905 g / cm ³ , and more preferably a density of 0.880 to 0.00. It is selected in the range of 900 g / cm ³ .
If it is this range, it will become possible to hold | maintain low temperature heat-sealing property, mechanical strength, etc., maintaining the softness | flexibility (flexibility) of a film.

[Linear low density polyethylene (A2)]
In the present invention, the linear low density polyethylene (A2) means a density of 0.910 to less than 0.940 g / cm ³ , preferably a density of 0.915 to 0.935 g / cm ³ , more preferably a density of 0.920 to It is selected in the range of 0.930 g / cm ³ . Within this range, mechanical strength, heat seal strength, etc. can be obtained without impairing flexibility, which is an advantage of linear low density polyethylene.

In the present invention, when the ethylene-α-olefin copolymer (A) is used alone as a polyethylene-based resin (X) which is a raw material for a functional film, a melt flow rate (MFR: 190 ° C., under a load of 21.18 N) It is important that the measurement is selected in the range of 1 to 10 g / 10 min, and the density is preferably selected in the range of 0.860 to 0.940 g / cm ³ .
When the VLDPE and LLDPE are used as a mixture with a polyethylene resin (B) produced by a high-pressure radical polymerization method, the ethylene-α-olefin copolymer (A) has an MFR of 0.5 g / 0. It is desirable to select within a range of min to 20 g / 10 min, preferably MFR 1.0 to 10 g / 10 min, and more preferably MFR 1.5 to 8 g / 10 min. If it is this range, it will become possible to shape | mold a functional film, without reducing said various performance.

In addition, the molecular weight distribution (Mw / Mn) of the ultra-low density polyethylene (VLDPE) and the linear low density polyethylene (LLDPE) is 1.5 to 5.0, preferably 2.0 to 4.5, more preferably It is selected in the range of 2.3 to 4.0. Within this range, it is possible to provide a composition that is homogeneous and has a good balance of flexibility, transparency, mechanical strength, and the like.
If it is said range, extrusion molding, such as inflation molding and T-die molding, will be easy. In addition, Mw / Mn here is a weight average molecular weight / number average molecular weight by GPC analysis.

  The α-olefin of the ethylene-α-olefin copolymer has 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms. Specifically, propylene, 1-butene, 1-hexene, 4-methyl-1- Examples include pentene, 1-octene, 1-decene and the like. The content of these α-olefins is preferably selected in the range of 3 to 40 mol%.

Ethylene polymers by ionic polymerization are manufactured using Ziegler catalysts, vanadium catalysts, Phillips catalysts, single site catalysts (including metallocene catalysts), and especially single site catalysts (including metallocene catalysts). It is desirable to be manufactured using
Examples of the ion polymerization method include a high pressure ion polymerization method, a gas phase method, a solution method, and a slurry method. In particular, an ethylene-α-olefin copolymer produced by a high pressure ion polymerization method using a metallocene catalyst is used. preferable.

The single site catalyst is not particularly limited, but preferably includes a catalyst having a metallocene compound such as a zirconium compound coordinated with a group having a cyclopentadienyl skeleton and the like, and a promoter as catalyst components. .
Commercially available ethylene-α-olefin copolymers produced with the above single-site catalyst include Harmolex (registered trademark) series, Kernel (registered trademark) series manufactured by Nippon Polyethylene, and Evolue (registered trademark) manufactured by Prime Polymer. ) Series, Exelen (registered trademark) GMH series, Exelen (registered trademark) FX series manufactured by Sumitomo Chemical Co., Ltd., and the like.

[High pressure radical polymerization polyethylene resin (B)]
High pressure radical polymerization polyethylene resin (B) is a low density polyethylene (B1), ethylene-vinyl ester copolymer (B2), copolymer of ethylene and an α, β-unsaturated carboxylic acid or derivative thereof. It includes at least one resin selected from the polymers (B3).

[Low-density polyethylene (B1) by high-pressure radical polymerization method] (hereinafter referred to as LDPE)
The low-density polyethylene (B1) produced by the high-pressure radical polymerization method has a melt flow rate (MFR: 190 ° C., measured under a 21.18N load) of 0.5 to 20 g / 10 minutes, preferably 1 to 10 g / 10 minutes. More preferably, it is 2-7 g / 10min. Within this range, the various performances of the composition can be maintained in a well-balanced manner. The density ranges from 0.905 to 0.940 g / cm ³ , preferably from 0.910 to 0.935 g / cm ³ , and more preferably from 0.912 to 0.930 g / cm ³ .
When the melt tension is in the range of 1.5 to 25 g, preferably 3 to 20 g, more preferably 3 to 15 g, the film moldability is good.

[Ethylene-vinyl ester copolymer (B2)]
The ethylene-vinyl ester copolymer (B2) is a copolymer produced by a high-pressure radical polymerization method and a vinyl ester monomer containing ethylene as a main component. Examples of the vinyl ester monomer include vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, and other copolymerization. Unsaturated monomers can be used.
Among these vinyl ester monomers, vinyl acetate is particularly preferable. That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomers is preferable. The vinyl ester content is 3 to 50% by weight, preferably 5 to 30% by weight. The MFR of these copolymers is in the range of 0.5 to 20 g / 10 minutes, preferably 1 to 15 g / 10 minutes, more preferably 1.5 to 10 g / 10 minutes.

[Copolymer of ethylene and α, β-unsaturated carboxylic acid or derivative thereof (B3)]
The copolymer of ethylene and α, β-unsaturated carboxylic acid or a derivative thereof (B3) is a copolymer of ethylene and α, β-unsaturated carboxylic acid, or a derivative thereof, and other copolymers as desired. Examples thereof include copolymers with unsaturated monomers, and metal salts (ionomers), amides, and imides thereof.
Specific examples of the α, β-unsaturated carboxylic acid that is a copolymer component include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.
Specific examples of the derivatives include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, and n methacrylate. -Butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. Specific examples of these copolymers include ethylene- (meth) acrylic acid copolymers, ethylene-maleic anhydride copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-acrylic acid-vinyl acetate. Examples thereof include binary or multi-component copolymers such as a copolymer and an ethylene-ethyl acrylate-maleic anhydride copolymer.

Other unsaturated monomers in the above are olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, C2 (Meth) acrylic acid esters such as vinyl esters of C3 alkanecarboxylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid , At least one selected from the group of ethylenically unsaturated carboxylic acids such as maleic acid, fumaric acid and maleic anhydride, or anhydrides thereof.
Specific examples of the above products include ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., ACLIFT (registered trademark) CM502), ethylene-ethyl acrylate copolymer (manufactured by Nihon Unicar, NUC (registered trademark) 6570) is commercially available.

The ethylene copolymer is preferably a copolymer comprising 65 to 99.5% by weight of ethylene, 0.5 to 35% by weight of an unsaturated carboxylic acid or ester thereof, and 0 to 25% by weight of other unsaturated monomers. .
The MFR of these copolymers is selected in the range of 0.5 to 20 g / 10 minutes, preferably 1 to 15 g / 10 minutes, more preferably 1.5 to 10 g / 10 minutes.

  In addition, when the high-pressure radical polyethylene resin (B) is used alone as the polyethylene resin (X) which is a raw material for the functional film, it is important to select it within the range of MFR 1 to 10 g / 10 min. is there.

[Other polyolefin resin (C)]
The other polyolefin resin (C) is a polyolefin resin other than the above (A) or (B), and is an optional component of the polyolefin resin (Y) in the present invention.
Specifically, polypropylene resins (C3 such as medium / high density polyethylene (C1), ethylene-α-olefin copolymer rubber (C2), propylene homopolymer or propylene and other α-olefin copolymers. And at least one polyolefin resin selected from the functional group-containing polyolefin resin (C4).

[Medium / High-density polyethylene (C1)]
In the present invention, the medium / high density polyethylene (C1) is a polyethylene selected in the range of density 0.94 to 0.97 g / cm ³ , preferably density 0.945 to 0.965 g / cm ³ . The melt flow rate (MFR: measured at 190 ° C. under a load of 21.18 N) is 0.5 to 20 g / 10 minutes, preferably MFR is 1 to 15 g / 10 minutes, more preferably MFR 1.5 to It is selected in the range of 10 g / 10 minutes.

[Ethylene-α-olefin copolymer rubber (C2)]
Examples of the ethylene-α-olefin copolymer rubber (C2) include copolymer rubbers of ethylene and α-olefins having 3 to 10 carbon atoms, such as ethylene-propylene copolymer rubber, ethylene-propylene-diene (EPDM). ) Copolymer rubber, ethylene-1-butene copolymer rubber and the like.
These rubber components fulfill the effect of improving the performance of the sealant film such as impact strength and pinhole resistance.
Examples of the copolymer obtained by copolymerizing a diene monomer include an ethylene / propylene / dicyclopentadiene copolymer, an ethylene / propylene / 5-ethylidene-2-norbornene copolymer, and an ethylene / propylene / 1,6-hexadiene. A copolymer etc. can be illustrated.

[Polyolefin resin (Y)]
In the present invention, the polyolefin resin (Y) is a melt flow rate composed of an ion-polymerized polyethylene resin (A) and / or a high-pressure radical polyethylene resin (B) (measured under MFR: 190 ° C. and 21.18 N load). Is composed of 100 to 50% by weight of polyethylene resin (X) of 1.0 to 10 g / 10 min and 0 to 50% by weight of other polyolefin resin (C).
Hereinafter, the constituent materials of the present invention will be described in detail.

[Polypropylene resin (C3)]
In the present invention, the polypropylene resin is a polypropylene homopolymer such as syndiotactic polypropylene resin or isotactic polypropylene resin, a random copolymer of propylene and other α-olefin, a block copolymer, an amorphous polypropylene, or the like. Is mentioned.
The polypropylene resin has a melt flow rate (MFR: measured at 230 ° C. under a load of 21.60 g) of 0.5 to 20 g / 10 minutes, preferably 1 to 15 g / 10 minutes, more preferably 1.5 to It is desirable to use 10 g / 10 min.

[Functional group-containing polyolefin resin (C4)]
Furthermore, the functional group-containing polyolefin resin (C4) according to the present invention is a copolymer of any of the following functional group-containing compounds (a), (d), (e), and (f) and an olefin, or a polyolefin resin. And a functional group-modified polyolefin resin obtained by modifying and grafting any one of the functional group-containing compounds (a) to (f) in the presence of a radical generator.
The functional group-containing polyolefin resin (C4) may be a single type or a combination of two or more types.

(1) Functional group-containing compound The functional group-containing compound of the functional group-containing polyolefin resin (C4) according to the present invention includes an epoxy group-containing compound (a), an unsaturated carboxylic acid group-containing compound or a derivative thereof (b), and an ester. It is at least one compound selected from the group consisting of a group-containing compound (c), a hydroxyl group-containing compound (d), an amino group-containing compound (e), and a silane group-containing compound (f), and an epoxy group-containing compound ( a), or an unsaturated carboxylic acid group-containing compound or a derivative thereof (b) is preferred.

(A) Epoxy group-containing compound Examples of the epoxy group-containing compound include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, adipic acid diglycidyl ester, methacrylic acid glycidyl ester, and trimethylolpropane triglycidyl ether. , Polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, butanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, phenol novolac polyglycidyl ether, epoxidized vegetable oil, and the like.

  Among these epoxy group-containing compounds, polyvalent epoxy compounds having a molecular weight of 3000 or less and containing at least two epoxy groups (oxirane groups) in the molecule are preferable. Since this epoxy compound contains two or more epoxy groups in the molecule, the adhesive strength is remarkably improved as compared with the case where there is one epoxy group in the molecule. The molecular weight of the epoxy compound is preferably 3000 or less, and particularly preferably 1500 or less. When the molecular weight exceeds 3000, there is a possibility that sufficient adhesive strength cannot be obtained when the composition is formed.

As the epoxy group-containing compound, an epoxidized vegetable oil can be selected from the viewpoint of ease of handling and safety. Epoxidized vegetable oil is an epoxidized unsaturated double bond of natural vegetable oil with peracid, for example, epoxidized soybean oil, epoxidized linseed oil, epoxidized olive oil, epoxidized safflower oil, epoxidized Examples include corn oil.
These epoxidized vegetable oils are commercially available as, for example, O-130P (epoxidized soybean oil), O-180A (epoxidized linseed oil), manufactured by Asahi Denka Kogyo Co., Ltd.
It should be noted that an oil component that is not epoxidized or is insufficiently epoxidized as a by-product when epoxidizing vegetable oil does not hinder the effects of the present invention even if it is present.

  In this invention, content of an epoxy-group containing compound is 0.01-5 weight% in a functional group containing polyolefin-type resin (C4), 0.01-3 weight% is preferable, 0.01-1 Weight percent is more preferred. If the content of the epoxy group-containing compound is within this range, problems such as insufficient adhesive strength with the substrate do not occur.

(B) Unsaturated carboxylic acid group-containing compound or derivative thereof The unsaturated carboxylic acid or derivative thereof used in the present invention is at least one compound selected from a carboxylic acid group or an acid anhydride group-containing compound. preferable.
Examples include monobasic unsaturated carboxylic acids, dibasic unsaturated carboxylic acids, and their metal salts, amides, imides, esters and anhydrides. The number of carbon atoms of the monobasic unsaturated carboxylic acid is 20 or less, preferably 15 or less, and the number of carbon atoms of the dibasic unsaturated carboxylic acid is 30 or less, preferably 25 or less. 30 or less, preferably 25 or less. Among these unsaturated carboxylic acid group-containing compounds and derivatives thereof, acrylic acid, methacrylic acid, maleic acid and its anhydride, 5-norbornene-2,3-dicarboxylic acid and its anhydride, and glycidyl methacrylate are particularly preferable. Maleic anhydride and 5-norbornene anhydride are preferred because of excellent adhesion performance of the resin composition.

  Preferred functional group-modified polyolefin polymers include (meth) acrylic acid glycidyl grafted ethylene copolymer, (meth) acrylic acid grafted ethylene copolymer, maleic anhydride grafted ethylene copolymer, maleic anhydride / graft. Examples thereof include binary or ternary copolymers such as ethylene / vinyl acetate copolymer, maleic anhydride / grafted ethylene / methyl acrylate copolymer, and maleic anhydride / grafted ethylene / ethyl acrylate copolymer.

  The content of the unsaturated carboxylic acid group-containing compound or derivative thereof is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight in the functional group-containing polyolefin resin (C4). Especially preferably, it is 0.2 to 2 weight%. If it is the range of this content, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(C) Ester group-containing compound Examples of the ester group-containing compound grafted onto the polyethylene chain include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate, and are particularly preferred. Examples thereof include methyl acrylate and ethyl acrylate.
The content of the ester group-containing compound is preferably 5.0 to 40.0% by weight, more preferably 10 to 30.0% by weight, and particularly preferably 15.0% in the functional group-containing polyolefin resin (C4). ˜25.0% by weight. If it is content of this range, the softness | flexibility and adhesiveness of a functional group containing polyolefin resin (C4) will express.

(D) Hydroxyl group-containing compound Examples of the hydroxyl group-containing compound include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
The content of the hydroxyl group-containing compound is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.2% in the functional group-containing polyolefin resin (C4). ~ 2% by weight. If it is content of this range, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(E) Amino group-containing compound Examples of the amino group-containing compound include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, and the like.
The content of the amino group-containing compound is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.2% in the functional group-containing polyolefin resin (C4). ~ 2% by weight. If it is content of this range, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(F) Silane group-containing compound Examples of the silane group-containing compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, vinyltrichlorosilane, vinyltriisopropoxysilane, vinyltrismethylethylketoximesilane, and vinyltriisopropenoxy. Vinyl silanes such as silane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethyldimethylmethoxysilane, γ-acryloxypropyltri Methoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldi Acrylic silanes such as toxisilane, γ-acryloxypropyldimethylmethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethyldimethylmethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, methacrylsilanes such as γ-methacryloxypropyldimethylmethoxysilane, styryltrimethoxysilane, Styryltriethoxysilane, styrylmethyldimethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, N-vinyl And unsaturated silane compounds such as styrylsilanes such as benzyl-γ-aminopropylmethyldimethoxysilane.
These unsaturated silane compounds can be used singly or in combination of two or more, and are a copolymer of a silane compound and an ethylene-α-olefin, a silane group-modified ethylene-α-olefin copolymer. A polymer.
In the present invention, the content of the silane group-containing compound is 0.01 to 5% by weight in the functional group-containing polyolefin resin (C). Preferably, it is 0.01 to 3 weight%, More preferably, it is 0.01 to 1 weight%. When the content is in this range, sufficient adhesion with a protective material such as glass can be obtained, and a decrease in the volume resistivity can be suppressed.

(2) Production of functional group-containing polyolefin resin (C4) The functional group-containing polyolefin resin (C4) is a copolymer of a functional group-containing compound and an olefin, or a polyolefin resin in the presence of a radical initiator. It can be produced by grafting reaction with the functional group-containing compound capable of grafting.

  In the case of a copolymer of the functional group-containing compound and the olefin that can be copolymerized, the functional group-containing compound includes an epoxy group-containing compound (a), a hydroxyl group-containing compound (d), an amino group-containing compound (e), And at least one compound selected from the group of silane group-containing compounds (f). The amount of copolymerization varies depending on the type of the functional group-containing compound, but the functional group-containing compound unit is contained in an amount of 0.5 to 30% by weight in 100% by weight of the copolymer.

In the case of a functional group-modified polyolefin resin obtained by grafting a polyolefin resin with a functional group-containing compound, specific examples of the functional group-containing compound include maleic anhydride, (meth) acrylic acid, (meth) acrylic acid. Examples thereof include glycidyl and acrylic silane.
The functional group-modified polyolefin polymer is prepared by melt-kneading a polyolefin polymer in the presence of a radical initiator, in the presence of a solvent or in a kneader such as an extruder, and grafting the functional group-containing compound capable of grafting. Manufactured by modification.

[Raw material resin for functional film]
The raw material resin for the functional film of the present invention includes (i) an ion polymerization polyethylene resin (A), (ii) a high pressure radical polyethylene resin (B), and (iii) an ion polymerization ethylene resin (A) + Mixed resin (A + B) with high pressure radical method polyethylene resin (iv) Ion polymerization method polyethylene resin (A) + other polyolefin resin (C), (v) High pressure radical method polyethylene resin (B) + other Polyolefin resin (C), (vi) ion-polymerized ethylene resin (A) + mixed resin with high-pressure radical polyethylene resin (B) + other polyolefin resin (C), (vii) (A) and / or Combinations of (B) + functional group-containing polyolefin resin (C4) and the like can be mentioned.

[Rating ratio of raw resin]
In the present invention, the polyethylene resin (X) is an ion polymerization polyethylene resin (A) and a high-pressure radical polyethylene resin (B) based on 90% to 10% by weight of the resin (A). ) 10 to 90 wt%, preferably resin (A) 80 to 20 wt% / resin (B) 20 to 80 wt%, more preferably resin (A) 75 to 25 wt% / resin (B) 25 to 75 wt% % In a proportion in the range of%.
Moreover, when resin (C) is mix | blended and it is set as polyolefin resin (Y), the polyethylene-type resin (X) which consists of said resin (A) and / resin (B) 100-50 weight% / resin ( C) It mix | blends in the ratio of the range of 0-50 weight%. Preferably, the resin (X) is 95 to 55% by weight / resin (C) 5 to 45% by weight, and more preferably the resin (X) 90 to 60% by weight / resin (C) 10 to 40% by weight is selected. It is desirable.

  The melt flow rate (MFR: measured at 190 ° C., 21.18 N load) of the polyethylene resin (X) constituting the functional film of the present invention is 1.0 to 10 g / 10 min, preferably 1 .3 to 8.0 g / 10 min, more preferably 1.5 to 7.0 g / 10 min. When the MFR is less than 1.0 g / 10 min, the extrusion load during low-temperature molding increases and the heat generated by the resin becomes excessive, causing a foaming phenomenon. Moreover, when MFR exceeds 10 g / 10min, film-forming stability deteriorates and there exists a concern about the fall of the intensity | strength of a film.

[Wavelength conversion substance (D)]
In the present invention, the wavelength converting substance (D) is not particularly limited. Specifically, in addition to a fluorescent agent conventionally used, a rare earth element or an ion thereof or an organometallic complex thereof and / or ( Organic) fluorescent dyes, and condensation products of barbituric acid and p-dimethylaminobenzaldehyde.

  Examples of the inorganic phosphor include inorganic phosphors such as calcium halophosphate, cadmium telluride, and ZnS: Cu.

  In the present invention, the rare earth element or an ion thereof or an organometallic complex thereof includes a rare earth element or an element obtained by activating the metal ion as an emission center in an inorganic base crystal, an organometallic complex thereof, or the like.

Examples of the rare earth metal include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Of these, europium, terbium, samarium and the like are preferable. Examples of activated rare earth elements or their metal ions into an inorganic host crystal as luminescent centers include Y ₂ O ₃ : Eu, SrAl ₂ O ₄ : Eu, Dy, LaF ₃ : Yb, and the like. .

An organometallic complex is a complex of the rare earth element ion and an organic compound. In recent years, an organic / inorganic hybrid material that can be absorbed over the entire wavelength range of sunlight (300 nm to 10 μm) has also been developed. This is also a kind of organometallic complex.
Examples of the organic compound forming the rare earth metal complex include carboxylic acids, β-diketones, and nitrogen-containing organic compounds.
Examples of the carboxylic acid include aliphatic carboxylic acids such as butyric acid, stearic acid, oleic acid, coconut oil fatty acid, t-butyl carboxylic acid, and succinic acid, aromatic carboxylic acids such as benzoic acid, naphthoic acid, and quinoline carboxylic acid. Can be mentioned.

  β-diketones include 1,3-diphenyl-1,3-propanedione, acetylacetone, benzoylacetone, dibenzoylacetone diisobutyromethane, dibiparoylmethane, 3-methylpentane-2,4dione, 2,2- Dimethylpentane-3,5-dione, 2-methyl-1,3-butanedione, 1,3-butanedione, 3-phenyl-2.4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 3-methyl-2,4-pentanedione 2-acetylcyclopentanone, 2-acetylcyclohexanone, 1-heptafluoropropyl-3-t-butyl-1,3-propanedione, , 3-diphenyl-2-methyl-1,3-propane dione (diphenyl acetylacetone), and 1-ethoxy-1,3-butanedione can be exemplified. Among these, 1,3-diphenyl-1,3-propanedione, acetylacetone, and benzoylacetone are preferable.

  Examples of the nitrogen-containing organic compound include aromatic amines such as alkylamines and anilines, nitrogen-containing aromatic heterocyclic compounds, and the like, specifically 1,10-phenanthroline or bipyridyl. In addition, imidazole, triazole, pyrimidine, pyrazine, aminopyridine, pyridine and derivatives thereof, nucleobases such as adenine, thymine, guanine and cytosine and derivatives thereof can also be used.

Specific examples of the metal complex include [Ru (III) (Phen) ₃ ] (ClO ₄ ) ₃ (Phen: 1,10-phenanthrolin), [Ru (III) (bipy) ₃ ] (ClO ₄ ) ₃ (bipy : 2,2′-bipyridyl), K ₂ [W (II) ₆ Cl14], K ₂ [Mo (II) ₆ Cl14], and a lanthanoid metal complex, [Tb (bpy) ₂ ] Cl ₃ complex, [Eu ( phen) ₂ ] Cl ₃ complex, [Tb (terpy) ₂ ] Cl _{3 and the} like.

  Organic fluorescent dyes include fluoranthene dyes, perylene dyes, perylimide dyes, naphthalimide dyes, acridine orange dyes, rhodamine 6G dyes, rhodamine B dyes, brilliant sulfoflavin FF dyes, basic yellow HG dyes , Eosin dyes, ruthenium dyes, coumarin dyes, porphyrin dyes, fluorescein dyes (490 nm → 520 nm), phthalocyanine dyes, naphthoquinone dyes, anthraquinone dyes, naphthalene tetracarboxylic acid diimide dyes, perylene tetracarboxylic acid It is at least one selected from the group consisting of diimide dyes, merocyanine dyes, indigo dyes, oligothiophene dyes, violanthrone dyes, fullerene dyes and squarylium dyes. Of these, perylene dyes, coumarin dyes, and rhodamine dyes are preferred.

In the present invention, as the wavelength conversion substance (D), a condensation product type wavelength conversion substance is preferable, and it is particularly desirable to use a condensation product that is a barbituric acid derivative, which is a kind of organic luminescent pigment.
In particular, a condensation product of barbituric acid and p-dimethylaminobenzaldehyde is used in combination with a polyethylene resin (X) having a melt flow rate (MFR) of 1.0 to 10 g / 10 min and a molding temperature of 160 ° C. or less. By doing so, it is possible to expect a remarkable effect that a homogeneous sheet can be obtained without generation of bubbles.
Examples of the condensation product of the barbituric acid derivative include a condensation product of barbituric acid (d2) and p- (dialkyl) methylaminobenzaldehyde (d1) represented by the following formula.

(In the formula, R1 and R2 are independently a hydrogen atom or, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a secondary butyl group, an isobutyl group, or a tertiary butyl group. , N-amyl group, tertiary-amyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group or octadecyl group Represents an alkyl group of 18 to 18)). Preferably R1 and R2 are methyl groups.

  The condensation product is represented by, for example, the following formula (D1) or (D2).

  This condensation reaction and product (D1) are no. No. 1753-47-5 and (D2) is No. It has a CAS number of 152734-34-4. Specifically, it is a compound prepared as described in, for example, European Patent No. 1413599, and its trade name includes trade name of Ciba Specialty Chemicals Co., Ltd .: Smart Light RL1000.

  The blending amount of the wavelength converting substance (D) is 0.01 to 5 parts by weight, preferably 0.02 to 4 parts by weight, more preferably 0.03 to 100 parts by weight of the polyolefin resin (Y). The range is 3 parts by weight. If the wavelength converting substance (D) is less than 0.01 parts by weight, the light quality conversion effect is not exhibited, and even if an amount exceeding 5 parts by weight is added, the light quality conversion effect is not exhibited, and if the amount is excessive, light Since the phenomenon that the quality conversion efficiency falls occurs, it is not preferable.

2. [Manufacture of functional films]
The method for producing the functional film of the present invention is not particularly limited, and the polyolefin resin composition (Z) is kneaded or dry blended, etc., by extrusion molding such as inflation molding, T-die molding, and calendar molding. Molded.
In the present invention, when the polyolefin resin composition (Z) comprising the polyolefin resin (Y) and the wavelength converting substance (D) is extruded, the molding temperature is 160 ° C. or less, preferably the polyolefin resin composition (Y). It is important that the molding is performed at a melting point of 155 ° C., more preferably at a melting point of 150 ° C. The kneading or molding temperature is preferably 140 to 160 ° C, and more preferably 145 to 155 ° C.
When the kneading or molding temperature is within this range, it is possible to provide a functional film that is homogeneous and rich in flexibility without generating bubbles and is excellent in mechanical strength such as piercing strength.

The functional film produced under the above conditions desirably has 2 or less, preferably 1 or less bubbles per 1 m ² in the functional film with an average diameter of 0.5 mm or more.
Since such a functional film with few bubbles improves the performance, it is preferably applied to a solar cell encapsulant or the like.

  Although the thickness of the functional film of the present invention varies depending on the application, it is generally desirable to select the thickness in the range of 10 μm to 200 mm. If the thickness is 10 μm or less, it is too thin, the workability during molding deteriorates, and the mechanical strength decreases, which is not preferable. Moreover, what exceeds 200 mm will be a thing with bad handleability.

3. [Laminated film]
The functional film of the present invention is applied to a solar cell encapsulant, an optical film, an intermediate film of laminated glass for automobiles, and the like after being monolayered or multilayered.

  The functional film of the present invention can be applied as a single layer or a laminated multilayer film. Specific examples of the laminated or multilayered film include a base film / functional film and a base film / functional film. / Polyolefin film, base film / functional film / reinforcing material / polyolefin film, polyolefin film / functional film / polyolefin film, glass / functional film / back film and the like.

As base film, polyester resin, polyamide resin, polycarbonate resin, polychlorinated resin, polyvinylidene chloride resin, polyolefin resin, saponified ethylene / vinyl acetate copolymer or stretched product thereof, inorganic oxide vapor deposition A film, metal foil, etc. are mentioned.
In addition, the functional film of the present invention may be a structure in which a single layer or a laminated multilayer film is further laminated on a substrate such as a nonwoven fabric, paper, metal, or glass.

Moreover, although the wavelength conversion substance is contained in the functional film, it may be contained in any layer of the laminated film.
Furthermore, in this invention, you may mix | blend an ultraviolet absorber, a sterically hindered amine light stabilizer, a phenolic antioxidant, a phosphite or phosphonite, an antistatic agent, a processing aid, a filler or a reinforcing material.

In addition, it contains a condensation product-based wavelength conversion material, in particular, a condensation product of barbituric acid and p-dimethylaminobenzaldehyde, as a wavelength conversion material, so that the molding temperature of a normal polyolefin film, particularly the molding Although air bubbles are likely to be generated at a relatively medium / high temperature of 160 ° C. or higher, in the present invention, since a specific resin that can be molded at a low temperature of 160 ° C. or lower is selected, the manufacturing temperature is set to 160 ° C. or lower. The method can prevent such problems from occurring.
The amount of the wavelength converting substance is in the range of 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight, more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the resin constituting the layer. is there. If the amount of the wavelength converting substance is too small, the light quality conversion effect is not exhibited. If the amount is too large, a phenomenon that the light quality conversion efficiency is lowered is not preferable.

[Manufacture of laminated film]
The production method of the laminated film is not particularly limited. For example, an ethylene / α-olefin copolymer composition, a polyethylene resin, and an ethylene / α-olefin copolymer blended with a predetermined wavelength converting substance are used. Using a multi-layered T-die, it can be manufactured by being molded by a known molding method.
The manufacturing method includes an air-cooled or water-cooled blown film molding, a T-die film molding, a calendar using an extrusion machine according to the number of stacks, and a normal die with a feed block type, multi-manifold type, and multi-slot type joining / merging section. A suitable laminated film can be obtained by any one of these methods.
The molding temperature needs to be not less than the melting point of the polyolefin resin (Y) and not more than 160 ° C., preferably not less than the melting point and not more than 155 ° C., more preferably not less than the melting point and not more than 150 ° C. When the molding temperature is within this range, a foaming phenomenon (bubbles) does not occur, and a homogeneous functional film can be continuously formed.

  Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. In addition, the physical-property measuring method and raw material which were used by each Example and the comparative example are as follows.

1. Evaluation Method of Resin Physical Properties (1) Melt Flow Rate (MFR): MFR of polyethylene resin was measured according to JIS-K6922-2: 1997 appendix (190 ° C., 21.18 N load).
(2) Density: Measured according to JIS K-7112.
(3) Mw / Mn: Measured by GPC shown below.
Apparatus: Waters GPC 150C type Detector: MIRAN 1A infrared spectrophotometer (measurement wavelength, 3.42 μm)
Column: Showa Denko Co., Ltd. AD806M / S 3 (column calibration is Tosoh monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, F288 each 0.5 mg / ml solution) The logarithm of the elution volume and molecular weight was approximated by a quadratic equation, and the molecular weight of the sample was converted to polyethylene using the viscosity equation of polystyrene and polyethylene, where the coefficient of the viscosity equation of polystyrene was α = 0. .723, log K = −3.967, and polyethylene has α = 0.723 and log K = −3.407.)
Measurement temperature: 140 ° C
Injection volume: 0.2ml
Concentration: 20 mg / 10 mL
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min

2. Raw material (1) Ion polymerization method polyethylene PE-1 (A1): linear low density polyethylene: MFR 2.1 g / 10 min, density 0.920 g / cm ³ ,
Mw / Mn: 3.82 (trade name: Novatec LL UF240, manufactured by Nippon Polyethylene Co., Ltd.)
PE-2 (A2): linear low density polyethylene: MFR 0.3 g / 10 min, density 0.924 g / cm ³ ,
Mw / Mn: 3.95 (Nippon Polyethylene Co., Ltd., Novatec LL UH411)
PE-4 (A3) linear low density polyethylene: MFR 13 g / 10 min, density 0.920 g / cm ³ ,
(Product name: Novatec LD LJ700 manufactured by Nippon Polyethylene Co., Ltd.)
(2) High-pressure radical polyethylene / PE-3 (B1): low density polyethylene: MFR 2.8 g / 10 min, density 0.925 g / cm ³ ,
Mw / Mn: 4.43 (Novatech LL LF440B, manufactured by Nippon Polyethylene Co., Ltd.)
(3) Wavelength converting substance D1: condensation product of barbituric acid and p-dimethylaminobenzaldehyde Ciba Specialty Chemicals Co., Ltd., SMARTLIGHT RL1000

3. Evaluation Method of Film (1) Evaluation of Foaming Property (Bubble) Ten samples of 1 m 2 were randomly collected from a 100 μm thick film formed by the inflation film forming method. Thereafter, bubbles with a size of 0.5 mm or more in the collected film were visually counted, and the average value of 10 sheets was evaluated as the number of bubbles generated. The smaller the number of bubbles generated, the better the film, and the larger the number of bubbles, the less filmed.
(2) Evaluation of fluorescence characteristics (light quality conversion) The reflectance of a film having a thickness of 100 μm formed by the inflation film forming method was measured with a spectrocolorimeter manufactured by Konica Minolta: CM-2600d. When the reflectance of 620 nm to 680 nm when a white plate is measured on the opposite side of the film and the light source is 120% or more when the reflectance when no wavelength converting substance is added is 100%, it is good. A circle indicates that light quality conversion has been performed. Since the reflectance lower than 120% is not suitable as a wavelength conversion film, it was evaluated as x.

Example 1
A polyolefin resin composition was prepared by adding 1 part by weight of a wavelength converting substance (dry blending) to 100 parts by weight of linear low-density polyethylene: PE-1 (A1).
Next, this polyolefin resin composition was supplied to an MK50 blown film molding machine (extruder diameter: 50 mmφ, die diameter: 75 mmφ) manufactured by Mitsubishi Chemical Engineering Co., Ltd. at a molding temperature of 150 ° C., a folded film width of 235 mm, and a film thickness of 100 μm. The film was formed. The resulting film was evaluated for foamability and fluorescent properties, and the results are shown in Table 1.

(Example 2)
Molding and evaluation were performed in the same manner as in Example 1 except that PE-3 (B1) was used instead of PE-1 (A1) as a polyethylene resin and molding was performed at a temperature of 140 ° C. The results are shown in Table 1.

(Example 3)
Molding and evaluation were performed in the same manner as in Example 1 except that 80% by weight of PE-1 (A1) and 20% by weight of PE-3 (B1) were used as the polyethylene resin. The results are shown in Table 1.

(Comparative Example 1)
Molding and evaluation were performed in the same manner as in Example 1 except that the polyolefin resin composition was molded at a molding temperature of 170 ° C. The results are shown in Table 1.

(Comparative Example 2)
Molding and evaluation were performed in the same manner as in Example 1 except that the wavelength conversion agent was not added to the polyethylene resin. The results are shown in Table 1.

(Comparative Example 3)
Molding and evaluation were performed in the same manner as in Example 1 except that 0.005 part by weight of the wavelength conversion agent was added to the polyethylene resin. The results are shown in Table 1.

(Comparative Example 4)
Molding and evaluation were performed in the same manner as in Example 1 except that 6 parts by weight of the wavelength converting agent was added to the polyethylene resin. The results are shown in Table 1.

(Comparative Example 5)
Molding was performed in the same manner as in Example 1 using PE-2 (A2) instead of PE-1 (A1) as the polyethylene resin. However, since the MFR was as low as 0.3 g / 10 min, the heat generation in the extruder was intense, the temperature could not be controlled, the temperature rose to 190 ° C., and foaming (bubbles) was very large.

(Comparative Example 6)
The polyethylene resin was molded in the same manner as in Example 1 using PE-4 (A3) instead of PE-1 (A1). Although not shown in Table 1, the MFR was high, the film formation stability was poor, normal film formation was not possible, and the film was extremely uneven, and was not practically usable.

(Evaluation results)
From the results shown in Table 1, Examples 1 to 3 are blended with a predetermined amount of wavelength converting substance in a resin in a specific MFR range, all of which are homogeneous with no bubbles by molding at a molding temperature of 160 ° C. or lower. Thus, a functional film having good fluorescence characteristics (light quality conversion ability) was obtained.
On the other hand, Comparative Example 1 had many bubbles because the polyolefin resin composition was molded at 170 ° C. outside the range of the present invention.
Moreover, as for Comparative Examples 2-4, all the compounding quantities of the wavelength conversion substance were outside the range of this invention, and the effect was not exhibited. Particularly, in Comparative Example 4, the compounding amount of the wavelength converting substance was an excessive compounding amount of 6 parts by weight, and the fluorescence characteristics (light quality conversion ability) were lowered.
Further, Comparative Example 5 deviated from the lower limit of the MFR range of the present invention, where the MFR was 0.3 g / 10 minutes, the heat generated in the extruder was intense, the temperature could not be controlled, and foaming (bubbles) was very large. .

  The functional film of the present invention uses a polyolefin resin composition in which a wavelength conversion substance is blended with a polyethylene resin (X) made of a polyethylene resin and / or a high-pressure radical polyethylene resin produced with a specific ion catalyst. Because there is no generation of bubbles at the time of molding, it is homogeneous, flexible, and excellent in light quality conversion, so that it can be used as a sealing material for solar cells, optical films, interlayer films in laminated glass of window glass for automobiles, etc. Useful for.

Claims (9)

In the functional film formed by molding a polyolefin resin composition (Z) containing 0.01 to 5 parts by weight of the wavelength converting substance (D) with respect to 100 parts by weight of the polyolefin resin (Y),
The melt flow rate (measured under a load of MFR: 190 ° C. and 21.18 N), in which the polyolefin resin (Y) is composed of a polyethylene resin (A) by ion polymerization and / or a high-pressure radical polyethylene resin (B). Has a polyethylene resin (X) of 1.0 to 10 g / 10 min as a main component, and the content of the wavelength converting substance (D) is 0.01 to 5 weights per 100 parts by weight of the polyolefin resin (Y). Part,
A functional film, wherein the polyolefin resin composition (Z) is molded at a molding temperature of not less than the melting point of the polyolefin resin (Y) and not more than 160 ° C.   The functional film according to claim 1, wherein the polyethylene resin (A) by an ionic polymerization method is an ethylene-α-olefin copolymer produced by a single site catalyst.   The functional film according to claim 1 or 2, wherein the wavelength converting substance (D) is one or more substances selected from an inorganic phosphor, an organometallic complex, or an organic luminescent pigment.   The functional film according to claim 3, wherein the organic luminescent pigment is a condensation product of barbituric acid and p- (dimethyl) aminobenzaldehyde.   The polyethylene resin (X) is a mixture of 90 to 10% by weight of an ion polymerization polyethylene resin (A) and 10 to 90% by weight of a high pressure radical polyethylene resin (B). 5. The functional film according to any one of 4 above.   The polyolefin resin (Y) further contains another polyolefin resin (C), and the content thereof is 0 to 50% by weight with respect to 100 to 50% by weight of the polyethylene resin (X). The functional film according to any one of claims 1 to 5. The functional film according to any one of claims 1 to 6, wherein the number of bubbles having an average diameter of 0.5 mm or more contained in the functional film is 2 or less per 1 m ^2. .   Melt flow rate (MFR: measured at 190 ° C., 21.18 N load) composed of polyethylene resin (A) and / or high-pressure radical polyethylene resin (B) by ion polymerization is 1.0 to 10 g / 10 min. Polyolefin resin (Y) having a polyethylene resin (X) as a main component, a polyolefin obtained by adding 0.01 to 5 parts by weight of a wavelength converting substance (D) to 100 parts by weight of a polyolefin resin (Y) A method for producing a functional film, wherein the resin composition (Z) is extruded at a molding temperature of not less than the melting point of the polyolefin resin (Y) and not more than 160 ° C.   A laminated film comprising at least one layer of the functional film according to claim 1.