JP2012011732A - Laminate and method for producing the same - Google Patents

Abstract

An object of the present invention is to easily remove a protective film from a matte film with little variation in peel strength, no adhesive residue, no wrinkles on the protective film, and no increase in the number of steps. A laminate that can be produced at low cost and a method for producing the same are provided.
In the laminate of the present invention, a protective film made of a polyolefin resin is directly laminated on at least the mat surface of a mat film made of a thermoplastic resin other than a polyolefin resin, and the mat film and the protective film are peeled off. Is possible. In the production method of the present invention, a polyolefin resin and a thermoplastic resin other than the polyolefin resin are melt-coextruded to obtain a film-like product, and the surface of the polyolefin resin is adjusted so as to contact the shaping roll. Inserted between a mold roll and a touch roll, a mat shape is formed on the surface of the thermoplastic resin.
[Selection] Figure 1

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 concavo-convex shape (mat shape) on the film surface is often used for optical applications as various light diffusion films. The matte film is usually formed by embossing roll transfer with a predetermined concavo-convex shape, cross-linked resin particles or inorganic fine particles are mixed into the resin constituting the film substrate, and single layer melt extrusion molding or multilayer melt extrusion molding. Surface irregularities are formed by the appearance of the particles on the film surface, and irregularities are formed by coating the surface of the base film with UV curable resin or thermosetting resin in which spherical beads are dispersed. And what to do.
This mat film is often used for a liquid crystal display device, and is preferably 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 mat film having an uneven shape (mat shape) on the surface is bonded to both surfaces of the sheet.

  However, there is a possibility that the mat surface of the mat film may be scratched or dust may be adhered during lamination lamination with the polarization separation sheet or during transportation. Therefore, usually, a protective film that can be peeled is bonded to the mat surface of the mat film, and the polarizing film and the mat film are laminated and bonded, and then the protective film is peeled off from the mat surface of the mat film. 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.

  On the other hand, it is also conventionally known to laminate a protective film on the surface of an optical film by extrusion molding. That is, Patent Document 1 describes that a protective film is formed by extrusion laminating a resin on at least one surface of an optical film. Patent Document 2 describes that an optically isotropic polymer layer and a polymer protective layer are laminated by melt coextrusion molding.

JP 2010-38924 A JP 2003-240953 A

  As described above, when the protective film is bonded to the mat surface of the mat film, particularly when a wide film is bonded, the peeling strength between the two films at the time of peeling may be uneven. Moreover, if wrinkles were formed on the protective film at the time of pasting, there was a possibility of becoming a defective product and resulting in 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.

On the other hand, in Patent Document 1 described above, a molten resin that forms a protective film is extruded and laminated on at least one surface of an optical film that is separately formed, or a molten resin that forms an optical film on a protective film that is separately formed is formed. An optical film with a protective film is formed by extrusion lamination. In this film forming method, the surface that comes into contact with the protective film of the optical film separately formed is uneven, or the surface that comes into contact with the protective film of the optical film melt-extruded on the protective film formed separately is In the case of the concavo-convex shape, the adhesion of the protective film to the optical film may not be sufficient.
In addition, a so-called polarizing plate protective film, which is a film used by being bonded to the polarizer P sheet described in Patent Document 2, is usually required to have a very smooth surface, and is used in Patent Document 2. Regarding the laminated body of the optically isotropic polymer resin layer A and the polymer protective layer B directly laminated by coextrusion molding, the point that the surface of the optically isotropic polymer resin layer A is uneven is completely taken into consideration. It has not been.

  Then, the subject of this invention is the manufacturing method which can manufacture the laminated body which does not have a glue residue when peeling a protective film from a mat | matte film, and does not wrinkle a protective film, and this laminated body in one process. Is to provide.

  In order to solve the above problems, the laminate of the present invention and the method for producing the same have the following configurations.

(1) A protective film made of a polyolefin resin is directly laminated on at least a mat surface of a mat film made of a thermoplastic resin other than a polyolefin resin, and the mat film and the protective film are peelable. A peelable laminate.
(2) The thermoplastic resin is selected from the group consisting of polycarbonate resins, acrylic resins, cyclic olefin resins, polyester resins, styrene resins, methyl methacrylate-styrene resins, ABS resins, and AS resins. The laminate according to (1), which is at least one kind.
(3) The laminate according to (1) or (2), wherein the mat film is formed by laminating a layer made of an acrylic resin and a layer made of a polycarbonate resin, and at least one surface is a mat surface.
(4) The polyolefin resin according to any one of (1) to (3), wherein the polyolefin resin is at least one selected from the group consisting of a polyethylene resin, a polypropylene resin, and a modified polyolefin resin that is a modified body thereof. Laminated body.
(5) The laminate according to any one of (1) to (4), wherein a surface of the protective film that is not in contact with the mat film is a mat surface.
(6) The laminate according to any one of (1) to (5), wherein the mat film has a haze of 90% or less.
(7) The laminate according to any one of (1) to (6), wherein the in-plane retardation of the mat film is 30 nm or less and the surface glossiness is 60% or less.
(8) The laminate according to any one of (1) to (7), wherein an interlayer peeling force between the mat film and the protective film is 5 to 50 g / 25 mm width.
(9) The laminate according to any one of (1) to (8), wherein the protective film and the matte film are laminated by melt coextrusion molding.
(10) The laminate according to any one of (1) to (9), wherein the mat film is used in a liquid crystal display device.
(11) The laminate according to (10), wherein the mat film is used for protecting a polarization separation sheet in the liquid crystal display device.
(12) A polyolefin resin and a thermoplastic resin other than the polyolefin resin are melt-coextruded to obtain a film-like product, and the shaping roll and the touch roll are made so that the surface of the polyolefin resin contacts the shaping roll. A method for producing a laminate, wherein the laminate is inserted in between to form a mat shape on the surface of the thermoplastic resin.
(13) A matte film obtained by peeling the protective film from the laminate according to any one of (1) to (11).

According to the present invention, there is little variation in the peel strength of the protective film due to the difference in position when the laminate is wide, and the mat film and the protective film are not bonded via an adhesive or the like. There is no so-called adhesive residue after peeling, and it is possible to eliminate wrinkles of the protective film that is likely to occur during bonding.
Further, according to the present invention, molding of the mat film and the protective film and lamination of both films can be performed in one step by melt coextrusion molding.

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 comprises a mat film and a protective film, and the protective film is directly laminated on at least 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 protective film is made of a polyolefin resin. The mat film is made of a thermoplastic resin other than the polyolefin resin. Hereinafter, the thermoplastic resin, the polyolefin resin, and the laminate will be described in order. In the following description, the term “thermoplastic resin” means a thermoplastic resin that does not contain a polyolefin resin.

[Thermoplastic resin]
The thermoplastic resin is made of a resin other than the polyolefin resin described later, and is a polycarbonate resin, acrylic resin, cyclic olefin resin, polyester resin, styrene 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 having good transparency. Among these, 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. For example, the mat film may be formed by laminating a layer made of an acrylic resin and a layer made of a polycarbonate resin, and at least one surface may be a matte surface.

<Polycarbonate resin>
As the polycarbonate resin, for example, an aromatic polycarbonate resin excellent in heat resistance, mechanical strength, transparency and the like is preferably used.
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) ) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used alone or in combination of two or more. 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 acid, 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.)).

<Styrene resin>
The styrene resin is a polymer containing 50% by mass or more, preferably 70% by mass or more of styrene units as a constituent unit, and a part of the polymer 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 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 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]
The polyolefin resin is preferably at least one selected from the group consisting of a polyethylene resin, a polypropylene resin, and a modified polyolefin resin that is a modified product thereof. When the laminate of the present invention is used in a liquid crystal display device, since the protective film is finally peeled off, it is preferable to use a polyethylene resin or a polypropylene resin available at a relatively low cost.

<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.

<Modified polyolefin resin>
For example, the modified polyolefin resin is obtained by modifying a polyolefin with a modifying compound such as maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, or methyl methacrylate. can get. The polyolefin used here may be a known polyolefin. For example, ethylene-based resin, isotactic polypropylene, syndiotactic polypropylene, random type polypropylene containing a comonomer, block type polypropylene by multistage polymerization, poly (4-methyl- 1-pentene), poly (1-butene) and the like.

[Laminate]
The laminate of the present invention is obtained by directly laminating a protective film on at least the mat surface of the mat film.
Furthermore, in the laminate of the present invention, the protective film surface not in contact with the mat film also becomes a mat surface (uneven surface).

  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.

The laminate preferably has a mat film thickness of 60% or more, more preferably 70% or more of the thickness of the entire laminate. 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 also it is 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, the haze of the matte film after peeling the protective film from the laminate is 90% or less, preferably 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 ° specular glossiness on the matte surface of the matte film is 60% or less, 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.

The laminate preferably has a delamination force between the mat film and the protective film of 5 to 50 g / 25 mm width, preferably 7 to 40 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.

  The mat film is used for various purposes such as diffusion action, angle change action, prevention of sticking with other members and protection of the film surface by contact, etc. For example, a light diffusion sheet incorporated in a backlight unit in a liquid crystal display device , A light diffusion film, a polarizing plate protective film, a retardation film, a brightness enhancement film, a polarizing separation sheet protective film, a reflective film, a light guide plate, and the like. The present invention can also be applied to optical disks, automobile interior films, lighting films, building material films, and the like, and the present invention is not limited to these applications. Especially, it can use suitably for optical uses, such as a protective film of the polarization separation sheet (brightness improvement film) in a liquid crystal display device especially.

<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, respectively, and fusion with a molten thermoplastic resin layer (A). Step (1) of laminating the polyolefin-based resin layer (B) thus obtained to obtain a film-like material, and shaping the film-like material so that the surface of the polyolefin-based resin of the film-like material is in contact with the shaping roll The mat shape formed on the surface of the shaping roll is transferred to the surface of the thermoplastic resin in contact with the polyolefin resin through the polyolefin resin in contact with the shaping roll, inserted between the roll and the touch roll. And a step (2) of forming a mat shape.

  As a forming method of the mat shape using the shaping roll, there is a method by transfer using a metal roll having a concavo-convex shape formed on the outer peripheral surface at the time of co-extrusion 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 polyolefin resin charged into the melt extruders 1 and 2 are melt-kneaded and supplied to the distribution block 3 to form a desired layer structure. Are distributed in the multi-manifold die 4 (T die) and extruded from the tip of the multi-manifold die 4 as a film.

  In the present embodiment, the polyolefin resin layer (B) is usually laminated and integrated with the thermoplastic resin layer (A) by an in-die lamination method. Specifically, for example, the thermoplastic resin and the polyolefin resin supplied to the distribution block 3 that is a two-type three-layer or two-type two-layer distribution type are both surfaces of the thermoplastic resin layer (A) in the distribution block 3. Are distributed so that the polyolefin resin layer (B) is disposed on the surface of the thermoplastic resin layer (A) or the polyolefin resin layer (B) is disposed on one surface of the thermoplastic resin layer (A). And are integrated as a three-layer structure or a two-layer structure.

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 used. 220 to 300 ° C., the extruder 2 is preferably 210 to 300 ° C., and the temperature setting of the multi-manifold die 4 is preferably 260 to 300 ° C.
When a polycarbonate resin is used as the thermoplastic resin and a polypropylene resin is used as the polyolefin resin, the extruder 1 is 210-290 ° C., the extruder 2 is 210-280 ° C., and the temperature of the multi-manifold die 4 is 250- It is preferable that it is 290 degreeC.
If it is out of the above range, the thickness of each layer may be non-uniform depending on the viscosity ratio. In addition, polyethylene-based resins may be a foreign matter such as fish eye due to gelation by crosslinking, and polypropylene-based resins may be poor in appearance due to foaming due to decomposition, and are not suitable for optical applications.

  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. Especially, since the thickness accuracy of each layer is more excellent, it is preferable to use a multi-manifold method.

  Subsequently, the resin extruded from the multi-manifold die 4 is a touch roll 5 (cooling roll 5) that is disposed so as to face the substantially horizontal direction as the side on which the polyolefin-based resin layer (B) contacts the shaping roll 6 (cooling roll). ) And the shaping roll 6, the mat shape is transferred to at least one surface of the thermoplastic resin layer (A) through the polyolefin resin layer (B), and a laminate is formed. 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. It is. Moreover, when using a polycarbonate-type resin for a thermoplastic resin and a polypropylene-type resin for a polyolefin resin, it is 10-170 degreeC normally, Preferably it is 15-160 degreeC, More preferably, it is 20-150 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 silicon 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 silicon 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. In addition, 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 the surface is provided with an uneven shape as in 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 an uneven shape formed on the outer peripheral surface.
What is necessary is just to adjust suitably the temperature of the shaping roll 6 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. ° C. Moreover, when using a polycarbonate-type resin for a thermoplastic resin and a polypropylene-type resin for a polyolefin resin, 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. It is possible to use a roll having a desired concavo-convex shape formed by sandblasting or engraving on the outer peripheral surface of the roll.

  As an uneven | corrugated shape formed in the outer peripheral surface of the shaping roll 6, for example, the mat | matte shape of about 0.1-15 micrometers in arithmetic mean roughness (Ra) etc., the uneven | corrugated shape which has specific pitch and height, etc. Can be mentioned. The arithmetic average roughness (Ra) is a value obtained by measuring with a surface roughness meter in accordance with JIS B0601-2001.

The resin extruded from the multi-manifold die 4 is a laminated resin in which the polyolefin resin layer (B) is laminated on both sides of the thermoplastic resin layer (A), and the thermoplastic resin passes through the polyolefin resin layer (B). When the mat shape is transferred to one surface of the resin layer (A), or a laminated resin in which the polyolefin resin layer (B) is laminated on one surface of the thermoplastic resin layer (A), the polyolefin resin When the mat shape is formed on the surface of the layer (A) over the resin layer (B), the uneven shape of the shaping roll 6 is heated by being sandwiched between the touch roll 5 and the shaping roll 6. It is transferred to the surface of the plastic resin layer (A) and molded into the laminate 8. In that case, it extrudes so that the surface of the polyolefin-type resin layer (B) of a mat | matte film may contact the shaping roll 6. FIG.
A laminated resin in which a polyolefin resin layer (B) is laminated on both surfaces of a thermoplastic resin layer (A), and a mat shape is formed on both surfaces of the thermoplastic resin layer (A) through the polyolefin resin layer (B). Is formed, the laminated resin may be sandwiched between cooling rolls having a concavo-convex shape formed on the outer peripheral surface.

The laminated body 8 to which the concavo-convex 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. It is possible to stably transfer the uneven shape. 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 the case where the mat film is a laminate in which a layer made of an acrylic resin and a layer made of a polycarbonate resin are laminated and at least one surface is a mat surface, the melt extruder 1 shown in FIG. In addition to 2, another melt extruder (not shown) may be newly provided, and the distribution block 3 may be a three-type three-layer distribution type block or a three-type five-layer distribution type block. In the same manner, a laminate can be produced.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the following examples, the parts representing the content or amount used are based on weight unless otherwise specified.

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: Silicon rubber roll shaped roll 6 having an outer diameter of 250 mmφ and a hardness of A70 ° 6: Stainless steel metal roll having an outer diameter of 250 mmφ and an irregular 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

Example 1
As the layer (A), a polycarbonate resin (“Caliber 301-10” manufactured by Sumitomo Dow Co., Ltd., heat distortion temperature: 140 ° C.) is melted and the extruder 1 (cylinder temperature: 230 to 280 ° C., screw rotation speed). : 40 rpm, extrusion rate: 50 kg / hour) is supplied to the distribution block 3, and a polyethylene resin (low density polyethylene “Sumikasen L211” manufactured by Sumitomo Chemical Co., Ltd., Vicat softening temperature: 98 ° C.) is used as the layer (B). It is melted and supplied to the distribution block 3 from the extruder 2 (cylinder temperature: 210 to 265 ° C., screw rotation speed: 18 rpm, extrusion rate 3 kg / hour), and in the distribution block 3, the layer (B) / layer (A) After being distributed so as to have a two-layer structure, they were stacked and extruded by a multi-manifold die 4 (die temperature: 270 ° C.).
Next, the film-like product extruded from the multi-manifold die 4 was sandwiched between the touch roll 5 (set temperature: 35 ° C.) and the shaping roll 6 (set temperature: 35 ° 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 surface roll 7 and wound around the mirror surface roll 7 (set temperature: 35 ° C.) at a take-up speed of 11 m / min. The laminated body 8 with the uneven shape transferred on one surface was obtained. 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 protective film was peeled off.
Table 1 shows the thickness of the obtained laminate.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that the screw speed in the extruder 2 was 36 rpm and the extrusion rate was 9 kg / hour. In the obtained laminate, no wrinkles were found on the protective film, and no adhesive residue was left on the matte film after the protective film was peeled off.
Table 1 shows the thickness of the obtained laminate.

(Comparative example)
The supply of resin from the extruder 2 is stopped, and the distribution block has a single-layer configuration of layer (A) (ie, polycarbonate resin: “Gulliver 301-10” manufactured by Sumitomo Dow Co., Ltd., heat distortion temperature 140 ° C.) A mat film made of a polycarbonate resin single layer was obtained in the same manner as in Example 1 except that the block was replaced. A protective film having a total thickness of 40 μm (coextruded film having a tackifier-containing rubber-based resin layer (thickness = 4 μm) on one surface of a polypropylene-based resin layer (thickness = 36 μm) with respect to the obtained matte film ) Is adhered to the matte surface of the matte film using a laminating machine, and the tackifier-containing rubber-based resin layer surface of the protective film is adhered and bonded at room temperature to obtain a laminate with a tackifier-containing rubber-based resin layer. Obtained.
In the obtained laminate, wrinkles were found on the protective film, and there was adhesive residue on the mat film after the protective film was peeled off.
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.

<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>
Arithmetic average roughness (Ra), maximum height (Rz) and average length (RSm) of contour curve elements of the matte surface of the mat film are measured according to JIS B0601-2001 (Mitutoyo Corporation). “Surf Test SJ-201”).

<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.

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

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

(Comparative Example 1 )
The supply of the resin from the extruder 2 is stopped, and the distribution block has a single-layer configuration of a layer (A) (that is, polycarbonate resin: “Gulliver 301-10” manufactured by Sumitomo Dow Co., Ltd., heat distortion temperature 140 ° C.) A mat film made of a polycarbonate resin single layer was obtained in the same manner as in Example 1 except that the block was replaced. A protective film having a total thickness of 40 μm (coextruded film having a tackifier-containing rubber-based resin layer (thickness = 4 μm) on one surface of a polypropylene-based resin layer (thickness = 36 μm) with respect to the obtained matte film ) Is adhered to the matte surface of the matte film using a laminating machine, and the tackifier-containing rubber-based resin layer surface of the protective film is adhered and bonded at room temperature to obtain a laminate with a tackifier-containing rubber-based resin layer. Obtained.
In the obtained laminate, wrinkles were found on the protective film, and there was adhesive residue on the mat film after the protective film was peeled off.
Table 1 shows the thickness of the obtained laminate.

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

Claims (13)

  A protective film made of a polyolefin resin is directly laminated on at least the mat surface of a mat film made of a thermoplastic resin other than a polyolefin resin, and the mat film and the protective film are peelable. Laminated body.   The thermoplastic resin is at least one selected from the group consisting of polycarbonate resin, acrylic resin, cyclic olefin resin, polyester resin, styrene resin, methyl methacrylate-styrene resin, ABS resin, and AS resin. The laminate according to claim 1, which is a seed.   The laminate according to claim 1 or 2, wherein the mat film is formed by laminating a layer made of an acrylic resin and a layer made of a polycarbonate resin, and at least one surface is a mat surface.   The laminate according to any one of claims 1 to 3, wherein the polyolefin resin is at least one selected from the group consisting of a polyethylene resin, a polypropylene resin, and a modified polyolefin resin that is a modified product thereof.   The laminate according to any one of claims 1 to 4, wherein a surface of the protective film that is not in contact with the mat film is a mat surface.   The laminate according to any one of claims 1 to 5, wherein the mat film has a haze of 90% or less.   The laminate according to any one of claims 1 to 6, wherein the in-plane retardation of the mat film is 30 nm or less and the surface glossiness is 60% or less.   The laminate according to any one of claims 1 to 7, wherein the delamination force between the mat film and the protective film is 5 to 50 g / 25 mm width.   The laminate according to any one of claims 1 to 8, wherein the protective film and the matte film are laminated by melt coextrusion molding.   The laminate according to any one of claims 1 to 9, wherein the mat film is used in a liquid crystal display device.   The laminate according to claim 10, wherein the mat film is used for protecting a polarization separation sheet in the liquid crystal display device.   A polyolefin resin and a thermoplastic resin other than the polyolefin resin are melt-coextruded to obtain a film, and inserted between the shaping roll and the touch roll so that the surface of the polyolefin resin is in contact with the shaping roll. And the mat | matte shape is formed in the surface of the said thermoplastic resin, The manufacturing method of the laminated body characterized by the above-mentioned.   The mat | matte film obtained by peeling the said protective film from the laminated body in any one of Claims 1-11.

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