JP2012171260A - Laminate and method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which shows no uneven defects on the surface and has a satisfactory appearance.SOLUTION: This laminate has a protective film composed of a polyolefin resin composition, containing a polyolefin and an antioxidant, directly laminated on the matted surface of a matte film made of a thermoplastic resin. The matte film and the protective film are releasable from each other. In addition, the matte film and the protective film are preferably laminated by melt coextrusion molding.

Description

  The present invention relates to a laminate in which a mat film and a protective film are laminated and a method for producing the same.

A mat film having a mat shape (uneven shape) on the film surface is often used as an optical application as various light diffusion films. The matte film is usually formed by embossing roll transfer to form a predetermined matte shape, or cross-linked resin particles or inorganic fine particles are mixed into the resin constituting the film substrate, and then by single layer melt extrusion molding or multilayer melt extrusion molding. A mat shape is formed on the surface of the film when the particles come out, and a mat shape is formed by coating the surface of the base film with a UV curable resin or thermosetting resin in which spherical beads are dispersed. And the like that form
This mat film is often used for a liquid crystal display device, and is used as a protective film for a polarized light separating sheet which is disposed between a backlight unit of a liquid crystal display device and a liquid crystal panel and used for improving luminance. . Since this polarized light separating sheet is usually about 100 μm thick even when it is thick, the rigidity of the sheet itself is not sufficient when it becomes a large area, and the self-supporting property becomes insufficient. In order to suppress these, it is usually the case that the sheet itself is bent or wavy due to the effect of heat, or that a rainbow pattern is generated due to interference when it comes into contact with the liquid crystal panel. A matte film made of a polycarbonate resin and having a matte surface on one side is bonded to both sides of the sheet as a polarizing separation sheet protective film.

  The mat film described above may be damaged or dust may adhere to the mat surface of the mat film when laminated with the polarized light separating sheet or during transport. Therefore, usually, after the protective film made of a detachable polyolefin resin is bonded to the mat surface, and then the surface of the mat film that is not bonded to the protective film is bonded to the polarized light separating sheet, The protective film is peeled from the surface. In many cases, the protective film is peeled off at the final stage of assembly of the liquid crystal display device, and accordingly, it is necessary to have appropriate adhesiveness and peelability to the matte film. Bonding the protective film to the matte film is a protective film with a pressure-sensitive adhesive or adhesive coated on one side in consideration of adhesiveness or peelability, or a protective film with a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive. Usually used.

  It is also known to laminate an optical film and a protective film by extrusion. Patent Document 1 describes that an optical film made of an acrylic resin is laminated on one surface of a protective film made of polypropylene resin by extrusion melt lamination. Patent Document 2 discloses that a polyethylene terephthalate resin is formed on both sides of the polymer resin layer (A) made of a norbornene resin by melt-kneading each of a norbornene resin and a polyethylene terephthalate resin and performing melt coextrusion molding. It is described that the sheet | seat on which the polymer protective layer (B) which consists of was obtained was obtained.

JP 2010-38924 A JP 2003-240953 A

  When a protective film is bonded to the matte surface of the matte film, the protective film is wrinkled at the time of bonding, which may result in a defective product and a product loss. Furthermore, when the protective film is peeled off, a part of the pressure-sensitive adhesive or adhesive may remain on the mat film, which may become an optical defect. Moreover, since a bonding step is required, the number of steps is increased, which is complicated and disadvantageous in terms of cost.

  The present inventors found that a laminate in which a protective film is directly laminated on the mat surface of the mat film by melt coextrusion molding has no adhesive residue when the protective film is peeled off from the mat film, and wrinkles are generated on the protective film. Protective film made of polyolefin resin on the mat surface of the matte film made of polycarbonate resin by melting and kneading each of polycarbonate resin and polyolefin resin under the idea that the As a result, it was found that uneven defects may occur on the protective film surface of the laminate.

  Accordingly, an object of the present invention is to provide a laminate in which there is no adhesive residue when the protective film is peeled off from the mat film, and furthermore, the occurrence of uneven defects on the protective film surface is suppressed. Moreover, another subject of this invention is providing the manufacturing method which can manufacture the laminated body by which the protective film was laminated | stacked on the mat | matte surface of the mat film in one process.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, the present invention relates to the following inventions.
(1) A protective film made of a polyolefin resin composition containing a polyolefin resin and an antioxidant is directly laminated on the mat surface of a matte film made of a thermoplastic resin, and the mat film and the protective film can be peeled off. A laminate characterized by the above.
(2) The thermoplastic resin is selected from the group consisting of polycarbonate resin, acrylic resin, cyclic olefin resin, polyester resin, polystyrene resin, methyl methacrylate-styrene resin, ABS resin, and AS resin. The laminate according to (1), which is one or more kinds.
(3) One type of polyolefin resin selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene The laminate according to the above (1) or (2), which is obtained by homopolymerization or copolymerization of two or more.
(4) The above (1) to (3), wherein the antioxidant is one or more selected from the group consisting of phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants and phosphites. The laminated body in any one of.
(5) When the total amount of the polyolefin resin and the antioxidant is 100% by weight in the polyolefin resin composition, the polyolefin resin is 99.6 to 99.9% by weight, and the antioxidant is 0.1 to 0.4. The laminate according to any one of (1) to (4), which is contained by weight%.
(6) The laminate according to any one of (1) to (5), wherein both surfaces of the protective film are mat surfaces.
(7) The laminate according to any one of (1) to (6), wherein the haze of the matte film is 90% or less.
(8) The laminate according to any one of (1) to (7), wherein the in-plane retardation of the matte film is 30 nm or less and the 60 ° specular gloss is 60% or less.
(9) The laminate according to any one of (1) to (8), wherein the delamination force between the mat film and the protective film is 3 to 50 g / 25 mm width.
(10) The laminate according to any one of (1) to (9), which is produced by melt coextrusion of a thermoplastic resin and a polyolefin resin composition.
(11) The laminate according to any one of (1) to (10), wherein a matte film obtained by peeling a protective film from the laminate is used for a liquid crystal display device.
(12) The laminate according to (11), wherein the matte film is used as a polarization separation sheet protective film in a liquid crystal display device.
(13) A polyolefin resin composition and a thermoplastic resin are melt-coextruded to obtain a film-like material, and the layer (B) of the polyolefin resin composition is contacted with the shaping roll so that the surface of the shaping roll and the touch roll A method for producing a laminate, wherein the mat is formed on the surface of the layer (A) made of a thermoplastic resin, inserted between them.
(14) A matte film obtained by peeling a protective film from the laminate according to any one of (1) to (12).

According to the present invention, since the mat film and the protective film are not bonded via an adhesive or the like, there is no so-called adhesive residue after the protective film is peeled off, and the occurrence of uneven defects on the protective film surface is further eliminated. Can be suppressed.
Moreover, according to the manufacturing method of this invention, shaping | molding of a mat | matte film and a protective film and lamination | stacking of both films can be carried out in one process.

It is a schematic explanatory drawing which shows one Embodiment of the manufacturing method of the laminated body of this invention.

Hereinafter, the present invention will be described in detail.
The laminate of the present invention has a mat film and a protective film, and the protective film is directly laminated on the mat surface of the mat film. Here, the direct lamination means that the mat film and the protective film are laminated without using an adhesive layer or a pressure-sensitive adhesive layer. The mat film is made of a thermoplastic resin. The protective film is made of a polyolefin resin composition containing a polyolefin resin and an antioxidant. Hereinafter, a thermoplastic resin, a polyolefin resin composition, and a laminated body are demonstrated in order.

[Thermoplastic resin]
The thermoplastic resin is composed of a resin other than the polyolefin resin described later, and is a polycarbonate resin, acrylic resin, cyclic olefin resin, polyester resin, polystyrene resin, methyl methacrylate-styrene resin, ABS (acrylonitrile-butadiene- It is preferably at least one selected from the group consisting of a styrene copolymer) resin and an AS (acrylonitrile-styrene copolymer) resin, and the resin is preferably a resin with good transparency. Among them, it is preferable to use a polycarbonate-based resin from the viewpoints of high transparency, excellent impact resistance, heat resistance, dimensional stability, flame retardancy, and few optical foreign matters. Two or more of the above resins may be mixed as long as the thermoplastic resin does not impair transparency. In the following description, the term “thermoplastic resin” means a thermoplastic resin that does not contain a polyolefin resin.

<Polycarbonate resin>
As the polycarbonate resin, for example, it is preferable to use an aromatic polycarbonate resin excellent in heat resistance, mechanical strength, transparency, and the like.
As an aromatic polycarbonate resin, for example, a resin obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, a carbonate prepolymer was polymerized by a solid phase transesterification method. Examples thereof include a resin and a resin obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.

  Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis { (4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) ) Phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4 Hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy 3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, etc., and these may be used alone or in combination of two or more. can do.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) It is preferable to use a dihydric phenol selected from the group consisting of −3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene alone or in combination, Use of bisphenol A alone, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, At least one selected from the group consisting of enol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene. The combined use with a monohydric phenol is preferred.

  As the carbonate precursor, for example, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

<Acrylic resin>
For example, methacrylic resin is used as the acrylic resin. The methacrylic resin is a polymer mainly composed of a methacrylic acid ester, and may be a homopolymer of a methacrylic acid ester, or a methacrylic acid ester of 50% by weight or more and other monomers of 50% by weight or less. A copolymer may also be used. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used.

  The preferred monomer composition of the methacrylic resin is 50 to 100% by weight of alkyl methacrylate, 0 to 50% by weight of alkyl acrylate, and 0 to 49% by weight of other monomers based on all monomers. More preferably, the alkyl methacrylate is 50 to 99.9% by weight, the alkyl acrylate is 0.1 to 50% by weight, and other monomers are 0 to 49% by weight.

  Here, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. It is. Of these, methyl methacrylate is preferably used.

  Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. is there.

The monomer other than alkyl methacrylate and alkyl acrylate may be, for example, a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, Although it may be a polyfunctional monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used.
Examples of the monofunctional monomer include styrene monomers such as styrene, α-methylstyrene, and vinyl toluene, alkenyl cyanide such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N -Substituted maleimide and the like.
Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamon. Alkenyl esters of unsaturated carboxylic acids such as allyl acids, polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, aromatic polyalkenyl compounds such as divinylbenzene, etc. Can be mentioned.

  In addition, as for said alkyl methacrylate, alkyl acrylate, and monomers other than these, respectively, you may use those 2 or more types as needed.

  From the viewpoint of heat resistance, the methacrylic resin preferably has a glass transition temperature of 70 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 90 ° C. or higher. This glass transition temperature can be appropriately set by adjusting the type of monomer and the ratio thereof.

  The methacrylic resin can be prepared by polymerizing the monomer component by a method such as suspension polymerization, emulsion polymerization, or bulk polymerization. At that time, it is preferable to use an appropriate chain transfer agent at the time of polymerization in order to obtain a suitable glass transition temperature or to obtain a melt viscosity exhibiting a moldability to a suitable laminate. What is necessary is just to determine the addition amount of a chain transfer agent suitably according to the kind of monomer, its ratio, etc.

<Rubber particles>
Rubber particles can also be blended with the acrylic resin. Here, as the rubber particles, for example, acrylic rubber particles, butadiene rubber particles, styrene-butadiene rubber particles and the like can be used, and among them, acrylic rubber particles from the viewpoint of weather resistance and durability. Is preferably used.

The acrylic rubber particle is a particle containing an elastic polymer mainly composed of an acrylate ester as a rubber component, and may be a particle having a single layer structure made of only this elastic polymer, or a layer of this elastic polymer. For example, it may be a multi-layered particle having a polymer layer mainly composed of a methacrylic acid ester, but it may be a multi-layered particle in terms of the surface hardness of a mat film made of an acrylic resin. preferable.
The elastic polymer may be a homopolymer of an acrylate ester or a copolymer of 50% by weight or more of an acrylate ester and 50% by weight or less of other monomers. . Here, as the acrylic ester, an alkyl ester of acrylic acid is usually used.

  A preferable monomer composition of the elastic polymer mainly composed of an acrylate ester is 50 to 99.9% by weight of alkyl acrylate, 0 to 49.9% by weight of alkyl methacrylate, based on all monomers, The monofunctional monomer other than these is 0 to 49.9% by weight, and the polyfunctional monomer is 0.1 to 10% by weight.

Here, the alkyl acrylate in the elastic polymer is, for example, the same as the examples of the alkyl acrylate previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms. Preferably it is 4-8.
The alkyl methacrylate in the elastic polymer is, for example, the same as the examples of alkyl methacrylates previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably Is 1-4.

  Examples of the monofunctional monomer other than alkyl acrylate and alkyl methacrylate in the elastic polymer include, for example, monofunctional monomers other than alkyl methacrylate and alkyl acrylate mentioned above as the monomer component of methacrylic resin. This is the same as the example. Of these, styrene monomers such as styrene, α-methylstyrene and vinyltoluene are preferably used.

  The polyfunctional monomer in the elastic polymer is, for example, the same as the examples of the polyfunctional monomer previously mentioned as the monomer component of the methacrylic resin, among them, an alkenyl ester of an unsaturated carboxylic acid, Polyalkenyl esters of polybasic acids are preferably used.

  The alkyl acrylate, the alkyl methacrylate, the monofunctional monomer other than these, and the polyfunctional monomer in the elastic polymer may each be used in combination of two or more as necessary.

When the acrylic rubber particles having a multilayer structure are used, as a suitable example, a polymer layer mainly composed of methacrylic acid ester is provided outside the above-mentioned elastic polymer layer mainly composed of acrylate ester. That is, the above-mentioned elastic polymer mainly composed of an acrylate ester is used as an inner layer, and the polymer mainly composed of a methacrylic ester is used as an outer layer. Here, as the methacrylic acid ester which is a monomer component of the polymer in the outer layer, alkyl methacrylate is usually used.
The outer layer polymer is usually formed at a ratio of 10 to 400 parts by weight, preferably 20 to 200 parts by weight with respect to 100 parts by weight of the inner layer elastic polymer. By setting the polymer of the outer layer to 10 parts by weight or more with respect to 100 parts by weight of the elastic polymer of the inner layer, the elastic polymer is less likely to aggregate and the transparency of the acrylic resin layer is improved.

  The preferred monomer composition of the polymer of the outer layer is based on all monomers, the alkyl methacrylate is 50 to 100% by weight, the alkyl acrylate is 0 to 50% by weight, and other monomers are 0 to 0% by weight. 50% by weight, and 0 to 10% by weight of the polyfunctional monomer.

  The alkyl methacrylate in the polymer of the outer layer is, for example, the same as the examples of alkyl methacrylate previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1-4. Of these, methyl methacrylate is preferably used.

  The alkyl acrylate in the polymer of the outer layer is, for example, the same as the examples of the alkyl acrylate mentioned above as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1-4.

  Examples of monomers other than alkyl methacrylate and alkyl acrylate in the polymer of the outer layer include, for example, monofunctional monomers other than alkyl methacrylate and alkyl acrylate mentioned above as the monomer component of methacrylic resin. It is the same as that of an example, and as a polyfunctional monomer, it is the same as that of the example of the polyfunctional monomer previously mentioned as a monomer component of a methacryl resin, for example.

  In addition, as for the alkyl methacrylate, the alkyl acrylate, the monomer other than these, and the polyfunctional monomer in the polymer of the outer layer, two or more kinds thereof may be used as necessary.

  Further, as a suitable example of the acrylic rubber particles having a multilayer structure, a polymer mainly composed of a methacrylic acid ester is further provided inside the elastic polymer layer mainly composed of the above-mentioned acrylic ester which is the inner layer of the above two-layer structure In other words, the polymer mainly composed of the methacrylic acid ester is used as the inner layer, the above-mentioned elastic polymer mainly composed of the acrylate ester is used as the intermediate layer, and the polymer mainly composed of the above methacrylic acid ester. It is also possible to include those having at least a three-layer structure, wherein Here, as a methacrylic acid ester which is a monomer component of the polymer of the inner layer, alkyl methacrylate is usually used. The polymer of the inner layer is usually formed at a ratio of 10 to 400 parts by weight, preferably 20 to 200 parts by weight, with respect to 100 parts by weight of the elastic polymer of the intermediate layer.

  A preferable monomer composition of the polymer of the inner layer is 70 to 100% by weight of alkyl methacrylate, 0 to 30% by weight of alkyl acrylate, and 0 to 30% of other monomers based on all monomers. 30% by weight, and 0 to 10% by weight of the polyfunctional monomer.

The alkyl methacrylate in the polymer of the inner layer is, for example, the same as the examples of alkyl methacrylate previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1-4. Of these, methyl methacrylate is preferably used.
In addition, the alkyl acrylate in the polymer of the inner layer is, for example, the same as the examples of the alkyl acrylate previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms. Preferably it is 1-4.

  Examples of monomers other than alkyl methacrylate and alkyl acrylate in the polymer of the inner layer include, for example, monofunctional monomers other than alkyl methacrylate and alkyl acrylate mentioned above as the monomer component of methacrylic resin. The examples are the same as the examples, and examples of the polyfunctional monomer are the same as the examples of the polyfunctional monomer described above as the monomer component of the methacrylic resin.

  In addition, as for the alkyl methacrylate, the alkyl acrylate, the monomer other than these, and the polyfunctional monomer in the polymer of the inner layer, two or more kinds thereof may be used as necessary.

Acrylic rubber particles can be prepared by polymerizing the monomer component of the above-mentioned elastic polymer mainly composed of an acrylate ester by at least one stage reaction by an emulsion polymerization method or the like. At this time, as described above, when a polymer layer mainly composed of methacrylic acid ester is formed outside the elastic polymer layer, the monomer component of the outer layer polymer is added to the elastic polymer layer. What is necessary is just to graft to the said elastic polymer by making it superpose | polymerize by reaction of at least 1 step | paragraph by emulsion polymerization method etc. in presence of a polymer.
Further, as described above, when a polymer layer mainly composed of methacrylic acid ester is formed inside the elastic polymer layer, first, the monomer component of the polymer in the inner layer is Polymerization is performed by at least one stage reaction by an emulsion polymerization method or the like, and then the monomer component of the elastic polymer is polymerized by at least one stage reaction by an emulsion polymerization method or the like in the presence of the resulting polymer. In the presence of the resulting elastic polymer, the monomer component of the outer layer polymer is polymerized in an at least one-stage reaction by an emulsion polymerization method or the like. To be grafted to the elastic polymer. When the polymerization of each layer is performed in two or more stages, it is sufficient that the monomer composition as a whole is within a predetermined range, not the monomer composition of each stage.

  Regarding the particle diameter of the acrylic rubber particles, the average particle diameter of the elastic polymer layer mainly composed of acrylic acid ester in the rubber particles is preferably 0.01 to 0.4 μm, and more preferably 0. It is 05-0.3 micrometer, More preferably, it is 0.07-0.25 micrometer. If the average particle size of the elastic polymer layer is larger than 0.4 μm, the transparency of the matte film made of acrylic resin is lowered and the transmittance is lowered. Further, if the average particle size of the elastic polymer layer is smaller than 0.01 μm, the surface hardness of the mat film is lowered and the surface is easily damaged, which is not preferable.

The average particle diameter was determined by mixing acrylic rubber particles with a methacrylic resin to form a film, dyeing the elastic polymer layer with ruthenium oxide in the cross section, and observing with an electron microscope. It can be determined from the diameter.
That is, when acrylic rubber particles are mixed with methacrylic resin and the cross section thereof is dyed with ruthenium oxide, the methacrylic resin of the parent phase is not dyed, and the polymer mainly composed of methacrylic acid ester is outside the elastic polymer layer. If there is a layer, the polymer of this outer layer is not dyed, only the elastic polymer layer is dyed. The diameter can be determined. When a polymer layer mainly composed of methacrylic acid ester is present inside the elastic polymer layer, the polymer of the inner layer is not dyed and the outer elastic polymer layer is dyed 2 In this case, the outer diameter of the two-layer structure, that is, the outer diameter of the elastic polymer layer may be considered.

  The content ratio of the rubber particles with respect to the acrylic resin is 40% by weight or less, preferably 30% by weight or less of the entire acrylic resin. If the content ratio of the rubber particles is larger than 40% by weight of the whole acrylic resin, the surface hardness of the mat film is lowered and the surface is easily damaged.

<Cyclic olefin resin>
Cyclic olefin resins include various cyclic olefin polymers including hydrides of ring-opening polymers of dicyclopentadiene, and various cyclic olefin copolymers including copolymers of dicyclopentadiene or tetracyclododecene and ethylene. One or more selected from hydrides thereof, norbornene polymers, and the like, for example, a thermoplastic resin having a monomer unit composed of a cyclic olefin, such as norbornene and polycyclic norbornene monomers, In addition to the cyclic olefin ring-opening polymer and the hydrogenated product of the ring-opening copolymer using two or more kinds of cyclic olefins, the cyclic olefin and the aromatic compound having a chain olefin or vinyl group It may be an addition copolymer. In addition, a polar group may be introduced.
In the case of a copolymer of a cyclic olefin and a chain olefin or an aromatic compound having a vinyl group, examples of the chain olefin include ethylene and propylene, and examples of the aromatic compound having a vinyl group Examples thereof include styrene, α-methylstyrene, and nuclear alkyl-substituted styrene. In such a copolymer, the unit of the monomer comprising the cyclic olefin may be 50 mol% or less, for example, about 15 to 50 mol%. In particular, when a terpolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group is used, the monomer unit composed of the cyclic olefin can have a relatively small amount. In such a ternary copolymer, the monomer unit composed of a chain olefin is usually 5 to 80%, and the monomer unit composed of an aromatic compound having a vinyl group is usually 5 to 80%.
Commercially available thermoplastic cyclic olefin-based resins include “Topas” sold by Ticona, Germany, “Arton” sold by JSR Corporation, and “Zeonoa” sold by Nippon Zeon Corporation. ZEONOR ”and“ ZEONEX ”,“ Apel ”sold by Mitsui Chemicals, Inc. (all are trade names).
In addition, as cyclic olefin resin, glass transition point is 100 degreeC or more, Preferably 130 degreeC or more is preferable.

<Polyester resin>
Examples of the polyester-based resin include polyethylene terephthalate and polyethylene naphthalate, and examples thereof include crystalline polyester and amorphous polyester. From the viewpoint of transparency, an amorphous resin is preferable.
The polyester resin can be composed of a polyester resin composition composed of a crystalline polyester and an amorphous polyester. The polyester resin is produced by polycondensation of a dibasic acid and a polyhydric alcohol.
Examples of the dibasic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid.
Examples of the polyhydric alcohol include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, pentaethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene glycol, neopentyl glycol. Diols such as
Said dibasic acid and polyhydric alcohol are used by arbitrary combinations. Specifically, terephthalic acid / ethylene glycol copolymer, terephthalic acid / ethylene glycol / 1,4-cyclohexane dimethanol terpolymer, 2,6-naphthalenedicarboxylic acid / ethylene glycol copolymer, terephthalate Examples include acid / 1,4-butanediol copolymer.
Examples of the crystalline polyester include a resin marketed under the trade name “Byron” (manufactured by Toyobo Co., Ltd.).
Examples of the amorphous polyester include amorphous polyethylene terephthalate (so-called APET) and terephthalic acid / ethylene glycol / 1,4-cyclohexanedimethanol terpolymer (example: trade name “PETG” (yeast Man Chemical Co., Ltd.)).

<Polystyrene resin>
The polystyrene-based resin is a polymer containing 50% by mass or more, preferably 70% by mass or more of styrene units as a structural unit, and a part thereof can be copolymerized with styrene as long as it contains 50% by mass or more of styrene units. Such a copolymer may be substituted with a monofunctional unsaturated monomer unit.

Examples of the copolymerizable monofunctional unsaturated monomer include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and the like. Methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc .; methacryl Examples thereof include unsaturated acids such as acid and acrylic acid; α-methylstyrene, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like. Moreover, this copolymer may further contain a glutaric anhydride unit and a glutarimide unit.
Further, a blend of a diene rubber, an acrylic rubber or the like as a rubbery polymer may be contained in the polymer or copolymer described above.

<Methyl methacrylate-styrene resin>
Examples of the methyl methacrylate-styrene resin include, for example, a styrene unit content of 20% by mass to 95% by mass and a methyl methacrylate unit content of 80% by mass to 5% by mass, preferably a styrene unit content of 70% by mass or more. And a copolymer having a methyl methacrylate unit content of 30% by mass or less.

<AS resin>
Examples of the AS (acrylonitrile-styrene) resin include a copolymer in which a monomer unit derived from acrylonitrile and a monomer unit derived from styrene are randomly copolymerized. The content of monomer units derived from acrylonitrile is usually 2 to 50% by weight (that is, the content of monomer units derived from styrene is usually 98 to 50% by weight), preferably 20 to 30% by weight. (That is, the content of monomer units derived from styrene is preferably 80 to 70% by weight). However, the total of the monomer units contained in the AS resin is 100% by weight.

<ABS resin>
Examples of the ABS (acrylonitrile-butadiene-styrene) resin include a copolymer obtained by graft polymerization of the olefin rubber (for example, polybutadiene rubber) to about 40% by weight or less on the AS resin described above.
In addition, in order to obtain good transparency, from the viewpoint of bringing the refractive index value of the resin component closer to the refractive index value of the rubber component, a copolymer of styrene, methyl methacrylate and other copolymerizable monomers as the resin component. A so-called transparent ABS which is a polymer is preferred.
Examples of the copolymerizable monomer include acrylonitrile. Moreover, about transparent ABS, what was disclosed by Unexamined-Japanese-Patent No. 2006-265406 is mentioned, for example.

[Polyolefin resin composition]
The polyolefin resin composition contains a polyolefin resin and an antioxidant.

<Polyolefin resin>
As the polyolefin resin, for example, one kind selected from ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is homopolymerized. Or what copolymerized 2 or more types is mentioned. Among these, a polyethylene resin or a polypropylene resin is preferable, and a polyethylene resin is more preferable.

<Polyethylene resin>
Examples of the polyethylene resin include an ethylene homopolymer, an ethylene-propylene random copolymer, and an ethylene-α-olefin copolymer.
Examples of the α-olefin used in the ethylene-α-olefin copolymer include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2 -Ethyl-1-butene, 2,3-dimethyl-1-butene, 1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl -1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, Ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl Examples include -1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Of these, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferably used.

<Polypropylene resin>
Examples of the polypropylene resin include propylene homopolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, propylene-ethylene-α-olefin copolymer, propylene homopolymer component or mainly. Examples thereof include a polypropylene-based copolymer composed of a copolymer component composed of propylene and a copolymer component of propylene and ethylene and / or α-olefin. These polypropylene resins may be used alone or in combination of two or more.

  Examples of the α-olefin used for the polypropylene resin include compounds similar to the α-olefin used for the ethylene-α-olefin copolymer.

As a method for producing the polyolefin resin, a known polymerization method using a known olefin polymerization catalyst is used. For example, slurry polymerization method, solution polymerization method, bulk polymerization method, gas phase polymerization method, etc. using complex catalysts such as Ziegler-Natta catalysts, metallocene complexes and nonmetallocene complexes, and radical initiators are used. Examples thereof include bulk polymerization and solution polymerization.
A commercially available polyolefin resin corresponding to the polyolefin resin of the present invention may be used. For example, a polyethylene resin “Sumikasen L705” manufactured by Sumitomo Chemical Co., Ltd., a polyethylene resin “Sumikasen” manufactured by Sumitomo Chemical Co., Ltd. FV405 "etc. are mentioned.

<Antioxidant>
The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants and phosphites.

<Phenolic antioxidant>
Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, and 2-t. -Butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl -4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2,4,6 -Tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6 1'-methylundecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl) Alkylated monophenols such as tridecyl-1′-yl) phenol and mixtures thereof;

  2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -Alkylthiomethylphenols such as nonylphenol and mixtures thereof;

  2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- ( α-methylcyclohexyl) phenol]], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-methylenebis (4 , 6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4-isobutyl-6-t-butylphenol), 2, 2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4 Nonylphenol], 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis ( 3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- Bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis-3′-t-butyl 4'-hydroxyphenyl] butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-t-butyl-2'-hydroxy-5'-) Methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-t-) Butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5 Alkylidene bisphenol and its derivatives, such as -t-butyl-4-hydroxy-2-methylphenyl) pentane and mixtures thereof,

  Acylaminophenol derivatives such as 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbanate and mixtures thereof;

  β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane And so Esters of mono- or polyhydric alcohols, such as mixtures of al,

  2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis Hydroxylated thiodiphenyl ether such as (2-methyl-6-tert-butylphenol), 4,4 ′-(2,6-dimethyl-4-hydroxyphenyl) disulfide,

  3,5,3 ′, 5′-tetra-t-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris (3,5-di-t -Butyl-4-hydroxybenzyl) amine, bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide Benzyl derivatives such as O-benzyl derivatives, N-benzyl derivatives, S-benzyl derivatives, etc., isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate and mixtures thereof

  2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4 -Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylphenoxy)- 1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, tris (4-tert-butyl-3-hydroxy) -2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4) -Hydroxyphenylethyl) -1,3,5 Triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate , Triazine derivatives such as tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof;

  Dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) malonate, di Dodecyl mercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2 Hydroxybenzylated malonate derivatives such as hydroxybenzylated malonate derivatives such as bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate and mixtures thereof,

  1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,4-bis (3,5-di-t-butyl-4 -Hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-tert-butyl-4-hydroxybenzyl) phenol and mixtures thereof, aromatic hydroxybenzyl derivatives,

  Dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4 -Hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, and mixtures thereof Benzylphosphonate derivatives,

  β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane And Esters of mono- or polyhydric alcohols such as mixtures thereof,

  β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3- Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and Esters of mono- or polyhydric alcohols such as a mixture of these,

  3,5-di-t-butyl-4-hydroxyphenylacetic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof Esters of mono- or polyhydric alcohol,

  N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-) t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] trimethylenediamine and Β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amides such as mixtures thereof, etc.

  Examples include tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof.

  Examples of hydroquinone and alkylated hydroquinone antioxidants include 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, and 2,5-di-t-amylhydroquinone. 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4 -Hydroxyphenyl stearate, bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate and mixtures thereof.

  The phenolic antioxidants exemplified above can be used alone or in admixture of two or more.

<Sulfur-based antioxidant>
Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, tridecyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl 3,3′-. Examples include thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), and these may be used alone or in combination of two or more. Can do.

<Phosphorus antioxidant>
Examples of phosphorus antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl. Pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphos Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4 -Di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphite, etc. These are independent It can be used by mixing two or more kinds.

<Phosphorous esters>
As phosphites, for example, 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d , F] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propoxy] -12 Til-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyloxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-pentyl-6- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4 8,10-Tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxa Phosphepine, 2,10-dimethyl-4,8-di-t-butyl 6- (3,5-di-tert-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra- t-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2, 10-dimethyl-4,8-di-t-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3 , 2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [ d, g] [1,3,2] dioxaphosphocin, 2,10-di Ethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2 Dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy]- Examples thereof include dibenzo [d, f] [1,3,2] dioxaphosphine, and these can be used alone or in admixture of two or more.

  As the antioxidant of the present invention, commercially available antioxidants corresponding to the antioxidants exemplified above may be used. For example, the phenolic antioxidant “H-BHT” manufactured by Honshu Chemical Industry Co., Ltd. ”, Phosphorous acid esters“ Sumilyzer GP ”manufactured by Sumitomo Chemical Co., Ltd., and the like.

  When the total of the polyolefin resin and the antioxidant is 100% by weight, the polyolefin resin composition contains 99.6 to 99.9% by weight of the polyolefin resin and an antioxidant from the viewpoint of suppressing the occurrence of uneven defects. The content is preferably 0.1 to 0.4% by weight, more preferably 99.7 to 99.9% by weight of the polyolefin resin and 0.1 to 0.3% by weight of the antioxidant.

  The thermoplastic resin and the polyolefin resin composition may contain other components as necessary, for example, a light diffusing agent, an ultraviolet absorber, an organic dye, an inorganic dye, a pigment, an antistatic agent, a surfactant, and the like. You may mix | blend.

The preparation method of polyolefin resin composition should just be a method by which polyolefin resin and antioxidant are knead | mixed uniformly, for example, the method of following (1) or (2) is mentioned.
(1) A method in which a polyolefin resin and an antioxidant are mixed by a ribbon blender, a Henschel mixer, a tumbler mixer, hand blending, or the like, and the resulting mixture is melt-kneaded with a single screw extruder or a twin screw extruder.
(2) A part of the polyolefin resin and the antioxidant are mixed in the same manner as in the above (1), and further melt-kneaded to obtain a master batch pellet containing 10% by weight or more of the antioxidant, The master batch pellet and the remaining polyolefin resin are mixed by the same method as in the above (1) so that the amount of the polyolefin resin and the antioxidant in the polyolefin resin composition is a predetermined amount, and further melt-kneaded. Method.

  Examples of the method (2) for preparing master batch pellets containing 10% by weight or more of an antioxidant include the method described in JP-A No. 2000-72923. In addition, the obtained master batch pellets are subjected to treatments such as sulfur crosslinking treatment, peroxide crosslinking treatment, peroxide decomposition treatment, metal ion crosslinking treatment, and silane crosslinking treatment within a range not impairing the effects of the present invention. Also good. Furthermore, the surface of the master batch pellet may be dusted with at least one powder selected from an antioxidant, calcium carbonate, barium sulfate, silica, talc, stearic acid, and polyolefin powder, if necessary. Good.

[Laminate]
In the laminate of the present invention, a protective film is directly laminated on the mat surface of the mat film. In the laminate of the present invention, it is preferable that both surfaces of the protective film are mat surfaces.

  The thickness of the laminate is 30 to 400 μm, preferably 50 to 300 μm, and more preferably 70 to 250 μm. If the thickness is less than 30 μm, the rigidity of the laminate itself becomes low, so that wrinkles are likely to enter the laminate, and floating or the like tends to occur in the set state. When the thickness is thicker than 400 μm, the manufacturing cost of the laminate is increased, and when the obtained laminate is bonded to the polarization separation sheet, the thickness of the polarization separation sheet after bonding is increased, and as a result The liquid crystal panel may become thick, which is not preferable.

In the laminate, the thickness of the mat film is preferably 60% or more, more preferably 70% or more, and 80% or more of the thickness of the entire laminate. More preferably, it is. When the thickness of the mat film is less than 60% of the total thickness of the laminate, for example, when transferring the mat shape to the mat film through the protective film, a sufficient mat shape cannot be transferred to the mat film. There is a fear.
Moreover, it is preferable that the thickness of a protective film is 5-50 micrometers, and it is more preferable that it is 10-40 micrometers. If the thickness is larger than 50 μm, for example, when transferring the mat shape to the mat film through the protective film, there is a possibility that a sufficient mat shape cannot be transferred to the mat film. If the thickness is less than 5 μm, the protective function of the protective film is There is a risk of lowering or breaking during peeling.

  Moreover, it is preferable that the haze of the matte film after peeling a protective film from a laminated body is 90% or less, and it is more preferable that it is 85% or less. If the haze is lower than 25%, a sufficient antiglare effect may not appear. On the other hand, if it exceeds 90%, when this film is used in a liquid crystal display device, the screen may be tinted and image quality may be deteriorated.

The in-plane retardation value of incident light at a wavelength of 590 nm of the mat film is preferably 30 nm or less, and more preferably 20 nm or less.
For example, when the mat film from which the protective film in the present invention is peeled is used for a liquid crystal display device, since the light used for the liquid crystal display is polarized light, a film with small optical distortion is required, and the retardation value is 30 nm or less. Preferably there is. The polarization separation sheet protective film used for protecting the polarization separation sheet among liquid crystal display devices preferably has a low retardation value so as not to disturb the polarization direction of the polarized light emitted from the polarization separation sheet as much as possible. Is more preferably 20 nm or less.

  The 60-degree specular gloss on the matte surface of the matte film is preferably 60% or less, and more preferably 50% or less. If the 60-degree specular gloss exceeds 60%, a rainbow pattern due to interference may occur when the mat film and the liquid crystal panel come into contact with each other.

  In the surface roughness on the mat surface of the mat film, the arithmetic average roughness (Ra) is preferably 0.2 to 6 μm, more preferably 0.7 to 6 μm, and the maximum height roughness ( Rz) is preferably 0.7 to 30 μm, more preferably 3 to 30 μm, and the average length (RSm) of the contour curve element is preferably 80 to 320 μm, preferably 80 to 300 μm. More preferably. If each of the roughness values is lower than a predetermined range, a sufficient antiglare effect may not appear. Moreover, when it exceeds each predetermined range, there exists a possibility that transparency may fall.

  In the laminate, the matte film and the protective film can be peeled off. Here, peelable means that the matte film and the protective film directly laminated can be peeled off from one film and separated into separate films.

In the laminate, the delamination force between the mat film and the protective film is preferably 5 to 50 g / 25 mm width, and more preferably 7 to 45 g / 25 mm width.
If the delamination force is lower than 5 g / 25 mm width, the protective film may be peeled off from the laminate when an external force is applied such as when the laminate is wound, transported, or cut. If it is too high, the matte film may be damaged when the protective film is peeled off.

A mat film in which a protective film is peeled off from a laminate is used in a liquid crystal display device for the purpose of diffusing action, variable angle action, prevention of sticking with other members and protection of the film surface by contact, etc. It is used as a light diffusion sheet, a light diffusion film, a polarizing plate protective film, a retardation film, a brightness enhancement film, a reflection film, a light guide plate, or a polarization separation sheet protective film incorporated into a light unit. Among these, the use as a polarizing separation sheet protective film is preferable.
To use a mat film as a polarizing separation sheet protective film, first, the protective film laminated on the mat surface of the mat film is peeled from the mat surface to obtain a mat film, and then the obtained mat film is separated by polarization. What is necessary is just to paste on at least one surface of the sheet. When one surface of the mat film is a mat surface, the mat surface may be the outermost surface, that is, a surface that is not the mat surface may be bonded to the polarization separation sheet, and both surfaces of the mat film may be mat surfaces. In this case, either one of the mat surfaces may be bonded to the polarization separation sheet. Further, the mat film bonded to the polarization separation sheet may be damaged or dust may be attached to the mat surface when it is bonded to the polarization separation sheet or transported. Therefore, first, the laminate is bonded to the polarization separation sheet so that the mat film surface of the laminate becomes the bonding surface, and then in the final stage of assembly of the liquid crystal display device, the mat surface of the mat film in the laminate You may peel the protective film currently laminated | stacked on this mat | matte surface.

  The laminate or matte film is bonded to the polarized light separating sheet by applying an adhesive or adhesive to the laminated surface of the laminated body or matte film, and sticking between the polarized light separating sheet and the laminate or matte film. It is preferable to interpose an agent layer or an adhesive layer. Moreover, you may interpose the adhesive resin layer which added the adhesive. The pressure-sensitive adhesive or adhesive is not particularly limited, and may be appropriately selected according to the required pressure-sensitive adhesive force or adhesive force.

  The matte film formed by peeling off the protective film from the laminate is not limited to use in the above-described liquid crystal display device, and can be applied to optical disks, automobile interior films, lighting films, building material films, and the like. it can.

  The mat film or the protective film is not limited to a single layer configuration, and may have a multilayer configuration of two or more layers as necessary. Examples of the matte film include a two-layer configuration in which a layer made of an acrylic resin and a layer made of a polycarbonate resin are laminated.

<Method for producing laminate>
The method for producing a laminate of the present invention (hereinafter sometimes referred to as the production method of the present invention) usually involves melt extrusion of a thermoplastic resin and a polyolefin resin composition, respectively, and a layer (A) (hereinafter referred to as thermoplastic resin). A layer (A)) and a layer (B) made of a polyolefin resin composition (hereinafter also referred to as layer (B)) to obtain a film-like product (1), The film-like material is inserted between the shaping roll and the touch roll so that the layer (B) surface of the shaped product is in contact with the shaping roll, and the layer ( A step (2) in which the mat shape formed on the surface of the shaping roll is transferred to the layer (A) surface in contact with B) to form the mat shape, and the layer (A) surface is used as the mat surface. It is. In the laminate produced by such a production method, the layer (B) made of the polyolefin resin composition, that is, the protective film is directly laminated on the mat surface of the layer (A) made of the thermoplastic resin, that is, the mat surface of the mat film. The mat film and the protective film are peelable.

  A method for forming a mat shape using a shaping roll is a method by transfer using a metal roll having a mat shape formed on the outer peripheral surface at the time of coextrusion molding. For example, JP 2009-196327 A, JP 2009 The method described in -202382 gazette etc. can be mentioned.

Hereinafter, the production method of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic explanatory view showing one embodiment of the production method of the present invention.
As shown in the figure, in this embodiment, the thermoplastic resin and the polyolefin resin composition charged into the melt extruders 1 and 2 are melt-kneaded and supplied to the distribution block 3 to form a desired layer structure. After being distributed in this manner, they are stacked in a multi-manifold die 4 (T-die) and extruded from the tip of the multi-manifold die 4 as a film.

  In this embodiment, the layer (B) is usually laminated and integrated with the layer (A) by an in-die lamination method. Specifically, for example, the thermoplastic resin and the polyolefin resin composition supplied to the distribution block 3 that is a two-type three-layer or two-type two-layer distribution type are layered on both sides of the layer (A) in the distribution block 3. (B) is arranged, or is distributed so that the layer (B) is arranged on one surface of the layer (A), and is laminated in the multi-manifold die 4 to have a three-layer structure or a two-layer structure. Integrated as

The temperature settings of the extruder 1, the extruder 2 and the multi-manifold die 4 may be adjusted as appropriate depending on the resin used. However, when a polycarbonate resin is used as the thermoplastic resin and a polyethylene resin is used as the polyolefin resin, the extruder 1 is It is preferable that 220-300 degreeC, the extruder 2 is 210-300 degreeC, and the temperature setting of the multi-manifold die 4 is 260-300 degreeC. When a polycarbonate resin is used as the thermoplastic resin and a polypropylene resin is used as the polyolefin resin contained in the polyolefin resin composition, the extruder 1 is 210-290 ° C., the extruder 2 is 210-280 ° C., and the multi-manifold die The temperature setting of 4 is preferably 250 to 290 ° C.
If it is out of the above range, the thickness of each layer may be non-uniform depending on the viscosity ratio. In addition, the polyethylene resin may become a foreign substance due to gelation by crosslinking, and the polypropylene resin may have a poor appearance due to foaming due to decomposition.

  In the present embodiment, the multi-manifold method using the distribution block 3 and the multi-manifold die 4 is used, but instead of this, for example, a dual-slot die that is a feed block stacking method or an external die stacking method is used. be able to. Among them, it is preferable to use a multi-manifold system because the thickness accuracy of each layer is more excellent.

  Next, the resin extruded from the multi-manifold die 4 includes a touch roll 5 (cooling roll 5) disposed so as to face the layer (B) in a substantially horizontal direction as a side in contact with the shaping roll 6 (cooling roll). The mat shape is transferred to the surface of the layer (B) by being sandwiched between the shaping rolls 6, and the mat shape is also formed on the layer (A) surface in contact with the layer (B) through the layer (B). Is transferred to form a laminate. At this time, a mat shape is also formed on the layer (B) surface in contact with the layer (A) surface. Further, the laminate wound around the shaping roll 6 is passed between the shaping roll 6 and the mirror surface roll 7 (cooling roll), and is gently cooled by the mirror surface roll 7 and laminated at a predetermined take-up speed. The body 8 can be obtained.

The touch roll 5 usually has a diameter of about 200 to 1000 mm, and is made of, for example, a rubber roll or a metal elastic roll.
What is necessary is just to adjust the temperature of the touch roll 5 suitably with resin to be used, for example, when using a polycarbonate-type resin for a thermoplastic resin and a polyethylene-type resin for a polyolefin resin, it is 10-160 degreeC normally, Preferably it is 15-150 degreeC. is there. Moreover, when using a polycarbonate-type resin for a thermoplastic resin and a polypropylene-type resin for the polyolefin resin contained in a polyolefin resin composition, it is 10-170 degreeC normally, Preferably it is 15-160 degreeC.
If the temperature of the touch roll 5 is too low, the resin is rapidly cooled, so that the laminate 8 is likely to remain distorted. If the temperature of the touch roll 5 is too high, the cooling is insufficient. The laminated body 8 may be tightly wound on the roll and wound up.

Examples of the rubber roll include a silicone rubber roll, a fluororubber roll, and a rubber roll mixed with sand to improve releasability.
The hardness of the rubber roll is preferably in the range of A60 ° to A90 ° measured according to JIS K6253. In order to make the hardness of the rubber roll within the above range, for example, it can be arbitrarily performed by adjusting the degree of crosslinking and composition of the rubber constituting the rubber roll.

  As the metal elastic roll, for example, the inside of the roll is made of rubber or a fluid is injected, and the outer peripheral part is made of a metal thin film having flexibility. is there. Specifically, the inside of the roll is composed of a silicone rubber roll, and a cylindrical stainless steel thin film having a thickness of about 0.2 to 1 mm is coated on the outer periphery of the roll, In a case where a fluid such as oil is injected, a cylindrical thin film made of stainless steel having a thickness of about 2 to 5 mm is fixed at the end of the roll, and the fluid is sealed inside.

  As such a touch roll 5, for example, a touch roll 5 made of a metal material or an elastic body and finished in a mirror shape with a plating or the like is used. The surface of the metal thin film or rubber roll of the metal elastic roll is not necessarily smooth, and there is no problem even if a mat shape is provided on the surface in the same manner as the shaping roll 6 described below.

The shaping roll 6 usually has a diameter of about 200 to 1000 mm, and is made of, for example, a metal roll having a mat shape formed on the outer peripheral surface.
What is necessary is just to adjust the temperature of the shaping roll 6 suitably with resin to be used, for example, when using a polycarbonate-type resin for a thermoplastic resin and a polyethylene-type resin for a polyolefin resin, it is 10-80 degreeC normally, Preferably it is 20-60 degreeC. It is. Moreover, when using a polycarbonate-type resin for a thermoplastic resin and a polypropylene-type resin for the polyolefin resin contained in a polyolefin resin composition, it is 10-100 degreeC normally, Preferably it is 20-80 degreeC.
When the temperature of the shaping roll 6 is too low, the resin is rapidly cooled, so that the laminate 8 is likely to remain distorted. When the temperature of the shaping roll 6 is too high, the cooling is insufficient. As a result, the laminate 8 may be in close contact with the roll and wound up.

  Examples of the shaping roll 6 include a drilled roll obtained by shaving a metal lump, a metal roll capable of controlling the temperature of the roll surface through fluid, steam, etc. inside the roll such as a spiral roll having a hollow structure. A roll having a desired mat shape formed on the outer peripheral surface of the roll by sandblasting or engraving can be used.

  Examples of the mat shape formed on the outer peripheral surface of the shaping roll 6 include a mat shape having a specific arithmetic average roughness (Ra) and an uneven shape having a specific pitch and height. By appropriately adjusting the mat shape, the surface roughness of the mat surface of the mat film can be made desired.

The film-like material extruded from the multi-manifold die 4 is a film-like material in which the layer (B) is laminated on both sides of the layer (A), and over the layer (B), the layer (B) and When the mat shape is transferred to the surface of the layer (A) that is in contact, or a film-like product in which the layer (B) is laminated on one surface of the layer (A), and the layer (B) is passed through the layer (B). When the mat shape is formed on the surface (A) in contact with the layer (B), the mat shape of the shaping roll 6 becomes a layer by sandwiching between the touch roll 5 and the shaping roll 6. (A) It is transferred to the surface and formed into a laminate 8. In that case, it extrudes so that the layer (B) surface of a film-form thing may contact the shaping roll 6. FIG.
In addition, when it is a film-like product in which the layer (B) is laminated on both sides of the layer (A) and the mat shape is formed on both sides of the layer (A) through the layer (B), the mat What is necessary is just to pinch | interpose this film-form thing between the cooling rolls formed in the outer peripheral surface.

The laminated body 8 to which the mat shape is transferred is wound around the shaping roll 6 and then taken up and taken up by the take-up roll.
The take-up speed of the take-up roll may be appropriately adjusted depending on the resin used, and is usually 0.5 to 80 m / min, preferably 2 to 60 m / min. If it is slower than 0.5 m / min, it may be disadvantageous in terms of production cost, and if it is faster than 80 m / min, there is a risk that in-line film appearance inspection assuming an optical application will be insufficient.
At this time, the mirror roll 7 may be provided after the shaping roll 6. Thereby, since the laminated body 8 is cooled slowly, the optical distortion of the laminated body 8 can be reduced, and furthermore, the contact time to the shaping roll 6 can be stably secured. The mat shape thus formed can be stably transferred. The mirror roll 7 is not particularly limited, and a normal metal roll conventionally used in extrusion molding can be employed. Specific examples include a drilled roll and a spiral roll. The surface state of the mirror surface roll 7 is preferably a mirror surface.

  The laminate 8 wound around the shaping roll 6 is passed between the shaping roll 6 and the mirror roll 7 so as to be wound around the mirror roll 7. A predetermined gap may be provided between the shaping roll 6 and the mirror roll 7 so as to be in a released state or may be sandwiched between both rolls. In order to cool the laminate 8 more gently, one or a plurality of cooling rolls are provided after the mirror roll 7, and the mat film wound around the mirror roll 7 is sequentially wound around the next cooling roll. May be.

  In addition, in the laminated body in which the mat film or the protective film has a multilayer structure, another melt extruder (not shown) is newly provided in addition to the melt extruders 1 and 2 shown in FIG. A seed 3 layer distribution type block or a 3 type 5 layer distribution type block may be used, and the others may be melt coextruded in the same manner as in the above-described embodiment.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

The structure of the extrusion apparatus used in the following examples and comparative examples is as follows.
Extruder 1: Single screw extruder with vented screw diameter 65mm (manufactured by Toshiba Machine Co., Ltd.)
Extruder 2: Single screw extruder with vented screw diameter 45mm (manufactured by Toshiba Machine Co., Ltd.)
Distribution block 3: 2-type, 2-layer distribution block (manufactured by Toshiba Machine Co., Ltd.)

  Extruders 1 and 2, distribution block 3, multi-manifold die 4, first to third cooling rolls 5-7 were arranged as shown in FIG. 1, and each cooling roll 5-7 was configured as follows.

<Roll configuration>
The touch roll 5, the shaping roll 6, and the mirror surface roll 7 were configured as follows.
Touch roll 5: Silicone rubber roll shaped roll 6 having an outer diameter of 250 mmφ and a hardness of A70 ° 6: A stainless steel metal roll having an outer diameter of 250 mmφ and a matte shape having an arithmetic average roughness (Ra) of 3.5 μm formed by blasting ( Drilled roll)
Mirror roll 7: Stainless steel metal roll (drilled roll) with an outer diameter of 250 mmφ and a mirror finish

Resins used in Examples and Comparative Examples are the following three types.
Resin a: A polycarbonate resin “Caliver 301-10” manufactured by Sumitomo Dow Co., Ltd. was used.
Resin b: A polyethylene resin “Sumikasen L705” manufactured by Sumitomo Chemical Co., Ltd. was used.
Resin c: A polyethylene resin “Sumikasen FV405” manufactured by Sumitomo Chemical Co., Ltd. was used. Sumikasen FV405 contains polyethylene resin and phosphite ester "Sumilyzer GP" manufactured by Sumitomo Chemical Co., Ltd. When the total amount of polyethylene resin and Sumilyzer GP is 100% by weight, Sumilyser GP is 0.2. It is contained by weight.

Example 1
[Preparation of master batch of polyolefin resin composition]
90 parts by weight of the resin b and 10 parts by weight of a phenolic antioxidant “H-BHT” manufactured by Honshu Chemical Industry Co., Ltd. are mixed and melt-kneaded with a twin screw extruder (not shown) to obtain a polyolefin resin composition. A master batch pellet of the product was obtained.

[Production of laminate]
As the layer (A), the resin a is melted and kneaded in the extruder 1 (cylinder temperature: 230 to 280 ° C., screw rotation speed: 35 rpm, extrusion rate: 50 kg / hour) and supplied to the distribution block 3, and the layer ( As B), 98 parts by weight of resin b and 2 parts by weight of the master batch pellet are mixed and melt-kneaded in an extruder 2 (cylinder temperature: 230 to 280 ° C., screw rotation speed: 30 rpm, extrusion rate 7 kg / hour). Are supplied to the distribution block 3 and distributed in the distribution block 3 so as to have a two-layer structure of layer (B) / layer (A), and then stacked on the multi-manifold die 4 (die temperature: 280 ° C.). Extruded.

Next, the film-like material extruded from the multi-manifold die 4 is touched with the touch roll 5 (set temperature: 35 ° C.) and the shaping roll 6 (set temperature: 35) so that the layer (B) is in contact with the shaping roll. C.) to form a laminate. Furthermore, the laminated body wound around the shaping roll 6 is passed between the shaping roll 6 and the mirror roll 7 and wound around the mirror roll 7 (set temperature: 50 ° C.), and the take-up speed is 9 m / min. The laminated body 8 with the mat shape transferred on one surface was obtained. In the obtained laminate, no wrinkles were found in the layer (B) (protective film), and there was no adhesive residue on the layer (A) (mat film) after the layer (B) was peeled from the laminate. . Further, the layer (A) had a mat surface on the surface in contact with the layer (B), and the layer (B) had a mat surface on both surfaces.
Table 1 shows the thickness of the obtained laminate. The “total thickness” indicates the total thickness of the obtained laminate. In Table 1, the antioxidant content is the content of the antioxidant when the total amount of the resin and the antioxidant in the layer (B) is 100% by weight.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that the resin c was melted and kneaded in the extruder 2. In the obtained laminate, no wrinkles were observed in the layer (B) (protective film), and there was no adhesive residue in the layer (A) (matte film) after the layer (B) was peeled off. Further, the layer (A) had a mat surface on the surface in contact with the layer (B), and the layer (B) had a mat surface on both surfaces.
Table 1 shows the thickness of the obtained laminate.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1 except that the resin b was melted and kneaded in the extruder 2. On the layer (B) (protective film) surface of the obtained laminate, many irregular defects were generated. Furthermore, when the layer (B) was peeled from the obtained laminate, the mat shape was not sufficiently formed on the surface of the layer (A) (mat film) that was in contact with the layer (B).
Table 1 shows the thickness of the obtained laminate.

  The following evaluation was performed about each layered product obtained and layer (A) (mat film) which peeled layer (B) (protective film) from each layered product. The results are shown in Table 2.

<Retardation value>
A test piece was cut out from the mat film in a size of 50 mm square, and the retardation value at 590 nm was measured with a micro-area birefringence meter (“KOBRA-CCO / X” manufactured by Oji Scientific Instruments).

<Total light transmittance (Tt) and haze (H)>
Based on JIS K7361-1, the total light transmittance (Tt) of the mat film was measured.
The haze (H) of the matte film was measured according to JIS K7136.

<60 degree specular gloss>
Based on JIS Z8741, the 60 degree specular glossiness of the matte surface of the matte film was measured.

<Surface roughness>
The arithmetic average roughness (Ra), the maximum height roughness (Rz) and the average length (RSm) of the contour curve element of the matte surface of the mat film were measured according to JIS B0601-2001 by a surface roughness meter (Mitutoyo ( Measured by “Surf Test SJ-201”).

<Peel strength>
In an atmosphere at 23 ° C., the force required to peel the protective film from the obtained laminate was measured under the conditions of a peeling width of 25 mm, a peel angle of 180 °, and a peeling speed of 300 mm / min. (G / 25 mm).

<Occurrence of irregularities>
Generation | occurrence | production of the uneven | corrugated defect in the layer (B) surface of the obtained laminated body was evaluated by visual observation. The case where a small number of irregular defects were confirmed on the surface of the layer (B) was evaluated as “◯”, and the case where many irregular defects were confirmed was evaluated as “x”.

DESCRIPTION OF SYMBOLS 1, 2 Melt extruder 3 Distribution block 4 Multi manifold die 5 Touch roll 6 Shaping roll 7 Mirror roll 8 Laminated body

Claims (14)

  A protective film made of a polyolefin resin composition containing a polyolefin resin and an antioxidant is directly laminated on the mat surface of a matte film made of a thermoplastic resin, and the mat film and the protective film are peelable. Laminated body.   The thermoplastic resin is one or more selected from the group consisting of polycarbonate resins, acrylic resins, cyclic olefin resins, polyester resins, polystyrene resins, methyl methacrylate-styrene resins, ABS resins, and AS resins. The laminate according to claim 1.   The polyolefin resin is a single polymer selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Or the laminated body of Claim 1 or 2 which copolymerized 2 or more types.   The antioxidant according to any one of claims 1 to 3, wherein the antioxidant is at least one selected from the group consisting of phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, and phosphites. Laminated body.   When the total amount of the polyolefin resin and the antioxidant is 100% by weight, the polyolefin resin composition contains 99.6 to 99.9% by weight of the polyolefin resin and 0.1 to 0.4% by weight of the antioxidant. The laminate according to any one of claims 1 to 4.   The laminate according to any one of claims 1 to 5, wherein both surfaces of the protective film are mat surfaces.   The laminate according to any one of claims 1 to 6, wherein the mat film has a haze of 90% or less.   The laminate according to any one of claims 1 to 7, wherein the in-plane retardation of the mat film is 30 nm or less and the 60 ° specular gloss is 60% or less.   The laminate according to any one of claims 1 to 8, wherein the delamination force between the mat film and the protective film is 3 to 50 g / 25 mm width.   The laminate according to any one of claims 1 to 9, which is produced by melt coextrusion of a thermoplastic resin and a polyolefin resin composition.   The laminated body according to any one of claims 1 to 10, wherein a matte film obtained by peeling a protective film from the laminated body is used for a liquid crystal display device.   The laminate according to claim 11, wherein the mat film is used as a polarizing separation sheet protective film in a liquid crystal display device.   A polyolefin resin composition and a thermoplastic resin are melt-coextruded to obtain a film-like material, and inserted between the shaping roll and the touch roll so that the layer (B) surface made of the polyolefin resin composition is in contact with the shaping roll. And forming a mat shape on the surface of the layer (A) made of the thermoplastic resin.   The mat | matte film obtained by peeling a protective film from the laminated body in any one of Claims 1-12.

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