KR20120003813A - Laminate and process for preparing the same - Google Patents

Abstract

PURPOSE: A laminate is provided to prevent complicated process without adhesive residue and to ensure simplicity and low cost. CONSTITUTION: A releasable laminate(8) has a protection film with resin containing polyolefin resin on a mat side of a mat film formed of thermoplastic resin. The mat film and protection film are releasable. The resin containing polyolefin resin is polyethylene resin, polypropylene resin, or modified polyolefin resin. The resin contains 80-99 wt% of crystalline polyolefin ingredients and 1-20 wt% of non-crystalline polymer or petroleum resins.

Description

Laminated body and its manufacturing method {LAMINATE AND PROCESS FOR PREPARING THE SAME}

This invention relates to the laminated body which laminated | stacked the mat film and the protective film, and its manufacturing method.

The mat film which has uneven | corrugated shape (mat shape) on a film surface is used for optical use etc. in many cases as various light-diffusion films. The matte film is usually formed with a predetermined concave-convex shape by emboss roll transfer, or crosslinked resin particles or inorganic fine particles are mixed in the resin constituting the film base material, and the film is formed on the film surface by single layer melt extrusion molding or multilayer melt extrusion molding. The surface irregularities are formed by the particles coming out, or the irregularities are formed by coating a UV curable resin or a thermosetting resin in which spherical beads are dispersed on the surface of the base film.

This mat film is often used for a liquid crystal display device, and is preferably used for a protective film of 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 the polarizing separation sheet is usually about 100 µm thick even when thick, the sheet itself is not sufficiently rigid when the surface area becomes large, and its self-reliability is insufficient, or the sheet itself bends or waves due to heat effects such as a light source. In order to suppress these, it may be bent as if it hits, or a rainbow pattern by an interference fringe may arise when it contacts with a liquid crystal panel. The mat film which has is bonded together.

The above-mentioned mat film may have a scratch or dust adhere to the mat surface of a mat film at the time of lamination bonding with a polarizing separation sheet, conveyance, etc. Therefore, after bonding together the protective film which can peel on the mat surface of a mat film normally, and laminating and bonding a polarization separating sheet and a mat film, a protective film is peeled off from the mat surface of a mat film. The protective film is often peeled off at the final stage of assembling the liquid crystal display device, and therefore, it is necessary to have appropriate adhesiveness and peelability to the mat film. Bonding of the protective film with respect to a mat film normally uses the protective film which has a protective film which apply | coated the adhesive or adhesive to single side | surface in consideration of adhesiveness, or peelability, the adhesive resin layer which added the adhesive, etc.

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

Japanese Unexamined Patent Publication No. 2010-38924 Japanese Laid-Open Patent Publication 2003-240953

As mentioned above, when bonding a protective film to the mat surface of a mat film, especially when bonding a wide film, there existed a possibility that the peeling strength between both films at the time of peeling may become nonuniform. Moreover, when wrinkles generate | occur | produce in the protective film at the time of bonding, there exists a possibility that it may become a defective article and lead to product loss. In addition, a part of an adhesive and an adhesive agent may remain in a mat film at the time of peeling of a protective film, and there existed a possibility that this might become an optical defect. In addition, since the bonding step is required, the number of steps increases, which is complicated and costly.

On the other hand, in the said patent document 1, by extruding laminated | stacking the molten resin which forms a protective film on the at least single side | surface of the optical film manufactured separately, or extrusion-laminating the molten resin which forms an optical film on the protective film which separately manufactured The optical film with a protective film is shape | molded. In this film forming method, when the surface which contacts the protective film of the optical film manufactured separately is uneven | corrugated shape, or when the surface which contacts the protective film of the optical film melt-extruded on the protective film manufactured separately, is uneven | corrugated shape, The adhesiveness of the protective film to an optical film may not be enough.

Moreover, what is called a polarizing plate protective film which is a film used by bonding to the polarizer P sheet of patent document 2 is generally required to be very smooth, and isotropically laminated directly by melt coextrusion molding used by patent document 2 With respect to the laminate of the polymer resin layer A and the polymer protective layer B, the fact that the surface of the optically isotropic polymer resin layer A is uneven is not considered at all.

Then, the subject of this invention is providing the laminated body which does not have an adhesive residue when peeling a protective film from a mat film, and does not produce wrinkles in a protective film. Moreover, it is providing the manufacturing method which can manufacture this laminated body in one process.

Moreover, the subject of this invention is providing the laminated body in which curvature distortion was suppressed in addition to having no adhesive residue and when wrinkles do not arise in a protective film when peeling a protective film from a mat film. Moreover, it is providing the manufacturing method which can manufacture the laminated body which laminated | stacked the protective film on the mat surface of the mat film by one process.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors discovered the solution which consists of the following structures, and came to complete this invention.

(1) A protective film made of a resin containing at least a polyolefin resin is directly laminated on at least a mat surface of a mat film made of a thermoplastic resin, and the mat film and the protective film can be peeled off. Laminate.

(2) The laminated body as described in said (1) whose resin containing at least polyolefin resin is at least 1 sort (s) chosen from the group which consists of polyethylene resin, polypropylene resin, and modified polyolefin resin which is those modified bodies.

(3) The laminated body as described in said (1) whose resin containing polyolefin resin at least is a resin composition containing the following component (a) and a component (b).

Component (a): crystalline polyolefin

Component (b): 1 or more types chosen from the group which consists of an amorphous polymer and petroleum resins

(4) The crystalline polyolefin is one 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 laminated body as described in said (3) whose homopolymerization or 2 or more types are copolymerized.

(5) The laminate according to the above (3) or (4), wherein the amorphous polymer is at least one member selected from the group consisting of polypropylene polymers and polyethylene polymers.

(6) The resin composition contains 80 to 99% by weight of component (a) and 1 to 20% by weight of component (b) when the total amount of component (a) and component (b) is 100% by weight. The laminated body in any one of said (3)-(5).

(7) The thermoplastic resin is 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 laminated body in any one of said (1)-(6) which is 1 or more types to become.

(8) The said laminated body in any one of said (1)-(7) whose layer which consists of acrylic resin and the layer which consists of polycarbonate resin is laminated | stacked, and at least one surface is a mat surface.

(9) The laminated body in any one of said (1)-(8) whose surface which is not in contact with the said mat film of the said protective film is a mat surface.

The laminated body in any one of said (1)-(9) whose haze of the said mat film is 90% or less.

The laminated body in any one of said (1)-(10) whose in-plane retardation of the said mat film is 30 nm or less, and surface glossiness is 60% or less.

The laminated body in any one of said (1)-(11) whose interlayer peeling force of the said mat film and the said protective film is 5-50 g / 25mm width.

(13) The laminate according to any one of the above (1) to (12), wherein the protective film and the mat film are laminated by melt coextrusion.

The laminated body in any one of said (1)-(13) whose said mat film is used for a liquid crystal display device.

The laminated body as described in said (14) in which the said matte film is used for protection of the polarization separation sheet in the said liquid crystal display device.

(16) Melt coextrusion of a resin containing at least a polyolefin resin and a thermoplastic resin to obtain a film-like product, and is inserted between the mold roll and the touch roll so that the surface of the resin in contact with the mold roll, to the surface of the thermoplastic resin A mat shape is formed, The manufacturing method of the laminated body characterized by the above-mentioned.

The mat film obtained by peeling the said protective film from the laminated body in any one of said (1)-(15).

According to this invention, since the variation of the peeling strength of the protective film by the positional difference in the case where a laminated body is wide is small, and a mat film and a protective film are not bonded via an adhesive etc., after protective film peeling off, So-called adhesive residues are eliminated, and wrinkles of the protective film that are likely to occur at the time of bonding can also be eliminated.

Moreover, according to this invention, shaping | molding of a mat film and a protective film and lamination | stacking of both films can be made into one process by melt coextrusion molding.

Moreover, according to this invention, since the mat film and the protective film are not bonded together via an adhesive etc., what is called adhesive residue after peeling of a protective film disappears, and resin containing at least polyolefin resin contains the following component (a ) And the resin composition containing the component (b), further curvature deformation can be suppressed.

Moreover, according to this invention, shaping | molding of a mat film and a protective film and lamination | stacking of both films can be made into one process by melt coextrusion molding.

BRIEF DESCRIPTION OF THE DRAWINGS 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 laminated body of this invention consists of a mat film and a protective film, and a protective film is laminated | stacked directly on at least the mat surface of a mat film. Here, direct lamination shows that the mat film and the protective film are laminated | stacked without interposing an adhesive bond layer or an adhesive layer. The protective film is resin containing at least polyolefin resin. The mat film is made of thermoplastic resin. Hereinafter, a thermoplastic resin, resin containing at least polyolefin resin, and a laminated body are demonstrated in order.

[Thermoplastic resin]

The thermoplastic resin is polycarbonate resin, acrylic resin, cyclic olefin resin, polyester resin, styrene resin, methyl methacrylate-styrene resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, It is preferable that it is at least 1 sort (s) chosen from the group which consists of AS (acrylonitrile-styrene copolymer) system resin, and it is preferable that it is resin with favorable transparency as resin. Especially, it is preferable to use a polycarbonate resin from a viewpoint of having high transparency, excellent impact resistance, heat resistance, dimensional stability, and flame retardancy, and few optical foreign substances. A thermoplastic resin may mix 2 or more types of said resin in the range which does not impair transparency. For example, the mat film may be formed by stacking a layer made of acrylic resin and a layer made of polycarbonate resin, and at least one surface may be a mat surface. It is preferable that a thermoplastic resin does not contain the polyolefin resin mentioned later.

<Polycarbonate-based resin>

As polycarbonate resin, it is preferable to use aromatic polycarbonate resin excellent in heat resistance, mechanical strength, transparency, etc., for example.

As aromatic polycarbonate resin, For example, resin obtained by reacting dihydric phenol and a carbonate precursor by the interfacial polycondensation method and the melt transesterification method, resin which superposed | polymerized the carbonate prepolymer by the solid-state transesterification method, and cyclic carbonate compound Resin obtained by superposing | polymerizing by the ring-opening polymerization method of this etc. is mentioned.

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 known as 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-hydroxy Yl) 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'-di Hydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, and the like, and these may be used alone. Or it can mix and use 2 or more types.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy Phenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1- Divalent phenols selected from the group consisting of bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene alone Or 2 or more types, and it is preferable to use bisphenol A alone, or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2- in particular. With at least one divalent phenol selected from the group consisting of bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene Combination is preferable.

Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

<Acrylic resin>

As acrylic resin, methacryl resin is used, for example. Methacrylic resin is a polymer mainly composed of methacrylic acid ester, and may be a homopolymer of methacrylic acid ester, or may be a copolymer of 50% by weight or more of methacrylic acid ester and other monomers by weight of 50% or less. Here, as methacrylic acid ester, the alkyl ester of methacrylic acid is used normally.

The preferred monomer composition of the methacryl 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 monomers other than these, more preferably based on all monomers. Preferably it is 50-99.9 weight% of alkyl methacrylates, 0.1-50 weight% of alkyl acrylates, and 0-49 weight% of monomers other than these.

Here, as alkyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc. are mentioned, for example, Carbon number of this alkyl group is 1-8, Usually, Preferably it is 1-4. Especially, methyl methacrylate is used preferably.

Moreover, as alkyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. are mentioned, for example, Carbon number of this alkyl group is 1-8 normally, Preferably it is 1-4.

Moreover, as monomers other than alkyl methacrylate and alkyl acrylate, a monofunctional monomer, ie, the compound which has one polymerizable carbon-carbon double bond in a molecule | numerator, may be sufficient, for example, a polyfunctional monomer, ie, a polymer in a molecule | numerator, may be sufficient as it. Although the compound which has at least two carbon-carbon double bonds may be sufficient, a monofunctional monomer is used preferably.

As this monofunctional monomer, For example, styrene monomers, such as styrene, (alpha) -methylstyrene, and vinyltoluene, alkenyl cyanide, such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide etc. are mentioned.

Moreover, as a polyfunctional monomer, For example, polyunsaturated carboxylic acid ester of polyhydric alcohols, such as ethylene glycol dimethacrylate, butanediol dimethacrylate, a trimethylol propane triacrylate, allyl acrylate, allyl methacrylate. And aromatic polys such as polyalkenyl esters of polybasic acids such as alkenyl esters of unsaturated carboxylic acids such as allyl cinnamic acid, diallyl phthalate, diallyl maleic acid, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene Alkenyl compounds etc. are mentioned.

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

It is preferable that the glass transition temperature of a methacryl resin is 70 degreeC or more from a viewpoint of heat resistance, It is more preferable that it is 80 degreeC or more, Furthermore, it is preferable that it is 90 degreeC or more. This glass transition temperature can be set suitably by adjusting the kind of monomer and its ratio.

Methacrylic resin can be prepared by superposing | polymerizing the said monomer component by methods, such as suspension polymerization, emulsion polymerization, and block polymerization. In that case, it is preferable to use a suitable chain transfer agent at the time of superposition | polymerization, in order to obtain preferable glass transition temperature, or to obtain melt viscosity which shows moldability with respect to a preferable laminated body. 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 particle>

You may mix | blend rubber particle with 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. Among them, acrylic rubber particles are preferably used in terms of weather resistance and durability. .

The acrylic rubber particles are particles containing an elastomer mainly composed of an acrylate ester as a rubber component, and may be particles having a single layer structure containing only this elastomer, and mainly the elastomer layer and methacrylic acid ester, for example. Although the particle | grains of the multilayered structure which has a polymer layer made into may be sufficient, it is preferable that it is particle | grains of a multilayered structure from the point of the surface hardness of the mat film containing acrylic resin.

Moreover, the homopolymer of acrylate ester may be sufficient as this elastic polymer, and the copolymer of 50 weight% or more of acrylate ester and 50 weight% or less of monomers other than this may be sufficient as it. Here, as acrylic ester, the alkyl ester of acrylic acid is used normally.

Preferred monomer composition of the elastomer mainly composed of acrylate ester is from 50 to 99.9% by weight of alkyl acrylate, from 0 to 49.9% by weight of alkyl methacrylate, and from 0 to 4% of monofunctional monomers other than these. 49.9 weight% and a polyfunctional monomer are 0.1-10 weight%.

Here, as alkyl acrylate in the said elastic polymer, it is the same as the example of the alkyl acrylate previously illustrated as a monomer component of a methacrylic resin, for example, The carbon number of this alkyl group is 1-8 normally, Preferably it is 4 ~ 8

Moreover, as alkyl methacrylate in the said elastic polymer, it is the same as the example of the alkyl methacrylate illustrated previously as a monomer component of methacrylic resin, for example, The carbon number of this alkyl group is 1-8 normally, Preferably Is 1-4.

As monofunctional monomers other than alkyl acrylate and alkyl methacrylate in the said elastic polymer, For example, the examples of monofunctional monomers other than the alkyl methacrylate and alkyl acrylate which were previously illustrated as a monomer component of a methacryl resin same. Especially, styrene monomers, such as styrene, (alpha) -methylstyrene, and vinyltoluene, are used preferably.

As a polyfunctional monomer in the said elastic polymer, it is the same as the example of the polyfunctional monomer illustrated previously as a monomer component of methacryl resin, Especially, the alkenyl ester of unsaturated carboxylic acid, and the polybasic acid Polyalkenyl esters are preferably used.

Alkyl acrylate, alkyl methacrylate, monofunctional monomers other than these, and a polyfunctional monomer in the said elastic polymer may respectively use these 2 or more types as needed.

When using what has a multilayered structure as an acrylic rubber particle, As the preferable example, what has a polymer layer which mainly has a methacrylic acid ester on the outer side of the elastomer layer which mainly has the above-mentioned acrylic acid ester, ie, the said The thing of the at least 2-layered structure which makes an inner layer the elastic polymer which mainly has the above-mentioned acrylate ester as an inner layer, and makes an outer layer the polymer which mainly has a methacrylic acid ester is mentioned. Here, as methacrylic acid ester which is a monomer component of an outer layer polymer, alkyl methacrylate is used normally.

Moreover, it is preferable to form an outer layer polymer in the ratio of 10-400 weight part normally, Preferably it is 20-200 weight part with respect to 100 weight part of inner layer elastomers. By setting the outer layer polymer to 10 parts by weight or more with respect to 100 parts by weight of the inner layer elastomer, aggregation of the elastomer is less likely to occur, and transparency of the acrylic resin layer becomes good.

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

As alkyl methacrylate in the said outer layer polymer, it is the same as the example of the alkyl methacrylate illustrated previously as a monomer component of methacrylic resin, for example, The carbon number of this alkyl group is 1-8 normally, Preferably it is 1 It is -4. Especially, methyl methacrylate is used preferably.

As alkyl acrylate in the said outer layer polymer, it is the same as the example of the alkyl acrylate previously illustrated as a monomer component of methacryl resin, for example, The carbon number of this alkyl group is 1-8 normally, Preferably it is 1-4. .

As monomers other than the alkyl methacrylate and alkyl acrylate in the said outer-layer polymer, it is the same as the example of the monofunctional monomers other than the alkyl methacrylate and alkyl acrylate which were previously illustrated as a monomer component of a methacrylic resin, for example. Moreover, as a polyfunctional monomer, it is the same as the example of the polyfunctional monomer mentioned above as a monomer component of methacryl resin, for example.

In addition, the alkyl methacrylate, the alkyl acrylate, monomers other than these, and a polyfunctional monomer in the said outer layer polymer may respectively use these 2 or more types as needed.

Moreover, as a preferable example of the acrylic rubber particle of a multilayered structure, it has a polymer layer which mainly has methacrylic acid ester inside the elastic polymer layer mainly having the above-mentioned acrylic acid ester which is an inner layer of the said two-layered structure. That is, the polymer mainly having this methacrylic acid ester as an inner layer, the above-mentioned elastic polymer mainly as the acrylate ester as an intermediate | middle layer, and the polymer mainly having the methacrylic acid ester as an outer layer And at least a three-layer structure. Here, as methacrylic acid ester which is a monomer component of an inner layer polymer, alkyl methacrylate is used normally. Moreover, it is preferable to form an inner layer polymer in the ratio of 10-400 weight part normally, Preferably it is 20-200 weight part with respect to 100 weight part of elastic polymer of an intermediate | middle layer.

The preferred monomer composition of the inner layer polymer is 70 to 100% by weight of alkyl methacrylate, 0 to 30% by weight of alkyl acrylate, 0 to 30% by weight of monomers other than this, and polyfunctionality based on all monomers. The monomer is 0 to 10% by weight.

As alkyl methacrylate in the said inner layer polymer, it is the same as the example of the alkyl methacrylate illustrated previously as a monomer component of methacrylic resin, for example, The carbon number of this alkyl group is 1-8 normally, Preferably it is 1 It is -4. Especially, methyl methacrylate is used preferably.

Moreover, as alkyl acrylate in the said inner layer polymer, it is the same as the example of the alkyl acrylate previously illustrated as a monomer component of methacryl resin, for example, Carbon number of this alkyl group is 1-8 normally, Preferably it is 1-. 4

As monomers other than alkyl methacrylate and alkyl acrylate in the said inner layer polymer, it is the same as the example of the monofunctional monomers other than the alkyl methacrylate and alkyl acrylate which were previously illustrated as a monomer component of methacrylic resin, for example. Moreover, the example of a polyfunctional monomer is the same as the example of the polyfunctional monomer mentioned above as a monomer component of methacryl resin.

In addition, the alkyl methacrylate, alkyl acrylate, monomers other than these, and a polyfunctional monomer in the said inner layer polymer may respectively use 2 or more types of those as needed.

An acrylic rubber particle can be prepared by superposing | polymerizing the monomer component of the elastic polymer which mainly has the above-mentioned acrylate ester by reaction of at least 1 stage by emulsion polymerization method etc. In that case, as mentioned above, when forming the polymer layer mainly having methacrylic acid ester on the outer side of the said elastic polymer layer, the monomer component of this outer layer polymer is emulsion-polymerized in presence of the said elastic polymer. What is necessary is just to graft to the said elastic polymer by superposing | polymerizing in at least 1 step reaction by the method etc ..

Moreover, as mentioned above, when forming the polymer layer which mainly has methacrylic acid ester inside the said elastic polymer layer, the monomer component of this inner layer polymer is first made into an emulsion polymerization method etc. at least. In the presence of the polymer to be polymerized by one-stage reaction, the monomer component of the elastomer is polymerized in at least one-stage reaction by an emulsion polymerization method or the like to be grafted to the inner layer polymer, and further, In the presence, the monomer component of the outer layer polymer may be grafted to the elastic polymer by polymerizing the monomer component of the outer layer polymer in at least one stage by an emulsion polymerization method or the like. In addition, when superposing | polymerizing each layer in 2 or more steps, respectively, what is necessary is not only the monomer composition of each step, but the monomer composition as a whole should just exist in a predetermined range.

About the particle diameter of an acrylic rubber particle, it is preferable that the average particle diameter of the elastomer layer mainly having the acrylate ester in the rubber particle is 0.01-0.4 micrometer, More preferably, it is 0.05-0.3 micrometer, More preferably, 0.07 -0.25 micrometer. When the average particle diameter of this elastic polymer layer is larger than 0.4 micrometer, since the transparency of the mat film which consists of acrylic resin falls, and it leads to the transmittance | permeability fall, it is unpreferable. Moreover, when the average particle diameter of this elastomer layer is smaller than 0.01 micrometer, since the surface hardness of a mat film falls and a scratch will become easy to produce, it is unpreferable.

The average particle diameter is obtained by mixing acrylic rubber particles with methacryl resin to form a film, dyeing the elastomer layer with ruthenium oxide in the cross section, and observing with an electron microscope to determine from the diameter of the dyed portion. You can get it.

That is, when acrylic rubber particles are mixed with methacryl resin and the cross section is dyed with ruthenium oxide, the mother methacryl resin is not dyed, and a polymer layer mainly composed of methacrylic acid ester is formed on the outer side of the elastomer layer. If present, the outer layer polymer is also not dyed, and only the elastomer layer is dyed. Thus, the particle diameter can be obtained from the diameter of the portion which is dyed in this way and observed in a nearly circular shape with an electron microscope. When a polymer layer mainly composed of methacrylic acid ester is present inside the elastomer layer, the inner layer polymer is also not dyed, and the outer elastomer layer is observed in a dyed two-layer structure state. In this case, what is necessary is just to think about the outer side of a two-layered structure, ie, the outer diameter of the said elastic polymer layer.

The content rate of the rubber particle with respect to acrylic resin is 40 weight% or less of the whole acrylic resin, Preferably it is 30 weight% or less. When the content rate of rubber particle is larger than 40 weight% of the whole acrylic resin, the surface hardness of a mat film will fall and it will become easy to produce a scratch.

<Cyclic olefin resin>

Examples of the cyclic olefin resin include various cyclic olefin polymers including hydrides of ring-opening polymers of dicyclopentadiene, various cyclic olefin copolymers including dicyclopentadiene or copolymers of tetracyclododecene and ethylene, and the number thereof. Opening of the cyclic olefin as a thermoplastic resin having a unit composed of only a cyclic olefin such as norbornene or a polycyclic norbornene monomer, for example, at least one selected from a digested product and a norbornene-based polymer. In addition to being a hydrogenated product of a ring-opening copolymer using a polymer or two or more kinds of cyclic olefins, an addition copolymer of an cyclic olefin, an aromatic compound having a chain olefin or a vinyl group may be used. Moreover, the polar group may be introduce | transduced.

In the case of using 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 include styrene and α-. Methyl styrene, styrene in which the benzene ring was substituted by the alkyl group, etc. are mentioned. In such a copolymer, 50 mol% or less, for example, about 15-50 mol% may be sufficient as the unit of the monomer comprised only from a cyclic olefin. In particular, in the case of using a ternary copolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group, the unit of the monomer composed of only the cyclic olefin can be relatively small in this way. In such a terpolymer, the unit of the monomer which consists of a linear olefin is 5 to 80% normally, and the unit of the monomer which consists of an aromatic compound which has a vinyl group is 5 to 80% normally.

Commercially available thermoplastic cyclic olefin resins include `` Topas '' sold by Ticona of Germany, `` Aton '' sold by JSR, and `` ZEONOR '' sold by Nippon Xeon Co., Ltd. And ZEONEX, and "Apel" sold by Mitsui Chemicals, Inc. (both trade names).

Moreover, 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 resins include polyethylene terephthalate, polyethylene naphthalate, and the like, and crystalline polyesters and amorphous polyesters are preferred, but from the viewpoint of transparency, it is preferable to be amorphous.

Polyester-based resin can be comprised by the polyester-based resin composition containing crystalline polyester and amorphous polyester. Polyester-based resin is produced by polycondensing dibasic acid and a polyhydric alcohol.

As a dibasic acid, aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, 2, 6- naphthalenedicarboxylic acid, aliphatic dicarboxylic acids, such as adipic acid, etc. are mentioned, for example.

Moreover, as polyhydric alcohol, For example, ethylene glycol, 1, 4- butanediol, 1, 4- cyclohexane dimethanol, pentaethylene glycol, 2, 2- dimethyl trimethylene glycol, hexamethylene glycol, neopentyl glycol, etc. And diols.

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, terphthalic acid / 1, 4- Butanediol copolymer etc. are mentioned.

As crystalline polyester, resin etc. marketed as a brand name "Bylon" (Toyo Spinning Co., Ltd. product) are mentioned, for example.

As amorphous polyester, For example, amorphous polyethylene terephthalate (so-called APET), terephthalic acid / ethylene glycol / 1, 4- cyclohexane dimethanol terpolymer (for example; brand name "PETG" (Eastman Chemical Co., Ltd.) ) Production)).

<Styrene-based resin>

As styrene resin, it is a polymer containing 50 mass% or more of styrene units, Preferably it is 70 mass% or more as the structural unit, The monofunctional which can be copolymerized with styrene a part of them as long as it contains 50 mass% or more of styrene units. The copolymer substituted by the unsaturated monomeric unit may be sufficient.

As a monofunctional unsaturated monomer which can be copolymerized, for example, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic Methacrylic acid esters such as acid 2-hydroxyethyl; Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate; Unsaturated acids such as methacrylic acid and acrylic acid; (alpha) -methylstyrene, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexyl maleimide, etc. are mentioned. Moreover, this copolymer may further contain the glutaric anhydride unit and the glutarimide unit.

Moreover, you may contain what mixed the diene rubber, acrylic rubber, etc. as a rubbery polymer in the above-mentioned polymer and copolymer.

<Methyl methacrylate-styrene resin>

As a methyl methacrylate-styrene resin, For example, the copolymer of 20 mass%-95 mass% of styrene unit content, and 80 mass%-5 mass% of methyl methacrylate unit content, Preferably styrene unit content 70 The copolymer etc. of mass% or more and methyl methacrylate unit content 30 mass% or less are mentioned.

<AS-based resin>

As AS (acrylonitrile- styrene) type resin, the copolymer etc. which the monomer unit derived from acrylonitrile and the monomer unit derived from styrene were copolymerized randomly are mentioned, for example. The content of monomer units derived from acrylonitrile is usually 2 to 50% by weight (ie, the content of monomer units derived from styrene is usually 98 to 50% by weight), and preferably 20 to 30% by weight (ie, styrene The content of the monomer unit derived from is preferably 80 to 70% by weight). However, the sum total of the monomer units contained in AS type resin shall be 100 weight%.

<ABS type resin>

As an ABS (acrylonitrile-butadiene-styrene) resin, For example, the copolymer etc. which graft-polymerized olefinic rubber (for example, polybutadiene rubber) to about 40 weight% or less to the AS-type resin mentioned above are mentioned, for example. Can be mentioned.

In order to obtain good transparency, from the viewpoint of bringing the refractive index value of the resin component close to the refractive index value of the rubber component, so-called transparent ABS made of a copolymer of styrene, methyl methacrylate and other copolymerizable monomers is preferable as the resin component. .

As a monomer which can be copolymerized, an acrylonitrile is mentioned, for example. Moreover, about transparent ABS, what was disclosed by JP2006-265406A is mentioned, for example.

"Protective film" which concerns on this invention becomes resin containing polyolefin resin at least. "Resin containing at least polyolefin resin" may be substantially a kind of resin containing only polyolefin resin, may contain a combination of various types of resin among polyolefin resins, and contains other resins other than polyolefin resin. You may also When "resin containing polyolefin resin at least" contains 2 or more types of resins, and when it contains a resin additive, it becomes a resin composition, but all are called "resin" in this specification.

[Polyolefin resin]

"Polyolefin resin" means the polymer containing the monomeric unit derived from an olefin, and does not contain the above-mentioned "cyclic olefin resin".

As the olefin, at least one member 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 is preferable.

"Polyolefin resin" may be modified with a monomer having another ethylenic double bond (hereinafter also referred to as "modified compound").

The "polyolefin resin" according to the present invention is preferably at least one selected from the group consisting of polyethylene resins, polypropylene resins and modified polyolefin resins which are modified substances thereof. When using the laminated body of this invention for a liquid crystal display device, since a protective film finally peels, it is preferable to use polyethylene resin or polypropylene resin which can be obtained at comparatively low cost.

<Polyethylene-based resin>

As polyethylene-type resin, an ethylene homopolymer, an ethylene propylene random copolymer, an ethylene-alpha-olefin copolymer, etc. are mentioned, for example.

Examples of the α-olefins used in the ethylene-α-olefin copolymers include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 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-1-butene, 1-nonene, 1- Decene, 1-undecene, 1-dodecene and the like. Especially, it is preferable to use 1-butene, 1-pentene, 1-hexene, 1-octene.

<Polypropylene resin>

Examples of the polypropylene-based resin include propylene homopolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, propylene-ethylene-α-olefin copolymer, propylene homopolymer component or mainly propylene. The polypropylene type copolymer etc. which contain the copolymer component mentioned above, and the copolymer component of propylene, ethylene, and / or alpha-olefin are mentioned. You may use these polypropylene resin individually or in combination of 2 or more types.

As an alpha olefin used for polypropylene resin, the compound similar to the alpha olefin used for an ethylene- alpha olefin copolymer, etc. are mentioned, for example.

<Modified polyolefin resin>

Modified polyolefin resins include, for example, maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, and methyl methacrylate. It is obtained by modifying with a compound for modification such as acrylate. The polyolefin used here may be a well-known polyolefin, for example, ethylene resin, isotactic polypropylene, syndiotactic polypropylene, random type polypropylene containing comonomer, block type polypropylene by multistage polymerization, poly (4-methyl-1-pentene), poly (1-butene), and the like.

The resin composition containing the following component (a) and component (b) may be sufficient as "resin containing polyolefin resin at least" which concerns on this invention.

Component (a): crystalline polyolefin, and

Component (b): 1 or more types chosen from the group which consists of an amorphous polymer and petroleum resins.

Hereinafter, "resin composition", "crystalline polyolefin", "amorphous polymer", "petroleum resins", etc. are demonstrated.

[Resin composition]

The resin composition contains two kinds of polymer components. It is preferable that two types of polymer components are a component (a) and a component (b), a component (a) is a crystalline polyolefin, a component (b) is 1 or more types chosen from the group which consists of an amorphous polymer and petroleum resins. .

<Crystalline polyolefin>

Crystalline polyolefin is a polymer containing a monomer unit derived from an olefin, and in a differential scanning calorimetry (DSC) according to JIS K7122, a crystal melting peak whose crystal melting heat is 30 J / g or more in the range of -100 to 200 ° C. Or any of crystallization peaks having a heat of crystallization of 30 J / g or more is observed.

The crystalline polyolefin is homopolymerized or two kinds selected from ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene It is preferable that the above copolymerized. As crystalline polyolefin, it is preferable that it is a polypropylene polymer or a polyethylene polymer, and it is more preferable that it is a polypropylene polymer. Specifically as a polypropylene polymer, a propylene homopolymer, a propylene ethylene copolymer, a propylene-1- butene copolymer, a propylene-1-hexene copolymer, a propylene-1- octene copolymer, propylene-ethylene-1 -Butene copolymer, propylene-ethylene-1-hexene copolymer, etc. are mentioned, Especially, the propylene homopolymer or the copolymer of olefin other than propylene and propylene is preferable, As a copolymer of olefin other than propylene, and propylene , Propylene-ethylene copolymer, propylene-1-butene copolymer and propylene-ethylene-1-butene copolymer are preferable. These crystalline polyolefins may be used by 1 type, and may mix and use 2 or more types. Moreover, as these polymers, things of various structures, such as a random type and a block type, can be used.

Melt flow rate (MFR) of a crystalline polyolefin is 0.1-50 g / 10min normally, and it is preferable that it is 0.5-30 g / 10min from an extrusion workability viewpoint. In addition, the MFR is measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K7210.

As a manufacturing method of a crystalline polyolefin, the well-known polymerization method using the well-known catalyst for olefin polymerization is used. For example, a radical initiator such as slurry polymerization method, solution polymerization method, bulk polymerization method, gas phase polymerization method using a complex catalyst such as a Ziegler-Natta catalyst, a metallocene complex or a nonmetallocene complex, may be used. The used block polymerization method, the solution polymerization method, etc. are mentioned.

Moreover, the said commercial item can also be used.

Moreover, you may use the commercially available polyolefin polymer corresponding to the crystalline polyolefin of this invention, For example, the crystalline polypropylene polymer "noblen W151" by Sumitomo Chemical Co., Ltd. is mentioned.

<Amorphous Polymer>

An amorphous polymer means an amorphous or low crystalline polymer, and in the differential scanning calorimetry according to JIS K7122, a crystal melting peak of 30 J / g or more in terms of heat of fusion observed in the range of -50 to 200 ° C, Or a polymer in which no crystallization peak of 30 J / g or more of heat of crystallization is observed.

From the viewpoint of reducing the warpage, the amorphous polymer contains a structural unit derived from ethylene, the content thereof is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less. .

It is preferable that an amorphous polymer is an olefin type polymer, As an olefin used in order to obtain this polymer, ethylene, a propylene, alpha-olefin of 4-20 carbon atoms is mentioned, for example, 4 carbon atoms As an alpha olefin of -20, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene , Linear α-olefins such as 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicosene, 3 Branched α-olefins such as -methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene, and the like Can be mentioned.

The amorphous polymer may contain monomer units derived from monomers other than the α-olefin, and examples of the monomers other than the α-olefin include polyene compounds, cyclic olefins, vinyl aromatic compounds, and the like. . When content of the monomeric unit derived from monomers other than an alpha olefin is 100 mol% of the whole component (b), it is preferable that it is 20 mol% or less.

As a polyene compound, a conjugated polyene compound, a nonconjugated polyene compound, etc. are mentioned, for example. As a conjugated polyene compound, an aliphatic conjugated polyene compound or an alicyclic conjugated polyene compound etc. are mentioned, for example, As a nonconjugated polyene compound, an aliphatic nonconjugated polyene compound, an alicyclic type is mentioned, for example. Non-conjugated polyene compounds, aromatic nonconjugated polyene compounds, and the like. These may be substituted by substituents, such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.

As the cyclic olefin, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene , 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1, 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5, 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4 , 4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5 , 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3, 4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5 , 5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxynorbornene anhydrate, 5-dimethyl Aminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, Cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cyclopentene and the like.

As a vinyl aromatic compound, For example, styrene, (alpha) -methylstyrene, p-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert -Butyl styrene, ethyl styrene, vinyl naphthalene, etc. are mentioned.

As an amorphous polymer, For example, the hydrogenated substance of a vinyl aromatic compound conjugated diene compound copolymer, a vinyl aromatic compound conjugated diene compound copolymer, an ethylene propylene copolymer, ethylene-1-butene copolymer, ethylene-1 -Hexene copolymer, ethylene-1-octene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer, ethylene-1-nonene copolymer, ethylene-1-decene copolymer, ethylene-1-undene Ene copolymer, ethylene-1-dodecene copolymer, ethylene-1-tridecene copolymer, ethylene-1-tetradecene copolymer, ethylene-1-pentadecene copolymer, ethylene-1-hexadecene copolymer, ethylene -1-heptadecene copolymer, ethylene-1-octadecene copolymer, ethylene-1-nanodecene copolymer, ethylene-1-ecocene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer , Propylene-1-octene copolymer, propylene-1-heptene copolymer, pro Pylene-1-octene copolymer, propylene-1-nonene copolymer, propylene-1-decene copolymer, propylene-1-undecene copolymer, propylene-1-dodecene copolymer, propylene-1-tridecene copolymer , Propylene-1-tetradecene copolymer, propylene-1-pentadecene copolymer, propylene-1-hexadecene copolymer, propylene-1-heptadecene copolymer, propylene-1-octadecene copolymer, propylene-1- Nanodecene copolymer, propylene-1-eicosene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-1-butene- 1-hexene copolymer etc. are mentioned, Especially, the propylene-1- butene copolymer, the propylene-1- hexene copolymer, the propylene-1- octene copolymer, the ethylene- propylene-1- butene copolymer, and ethylene- Propylene-1-hexene copolymer and ethylene-propylene-1-octene copolymer are preferred. , Propylene-1-butene copolymer, ethylene-propylene-1-butene copolymer is more preferred, and a propylene-1-butene is more preferably a copolymer. These amorphous polymers can be used individually or in mixture of 2 or more types.

It is preferable that the intrinsic viscosity [(eta)] of an amorphous polymer is 0.5-10 dl / g, It is more preferable that it is 0.9-5 dl / g, It is further more preferable that it is 1.2-3 dl / g. If the intrinsic viscosity [η] is too small, stickiness may occur in the laminate to be obtained, and only a low product value may be obtained. If the intrinsic viscosity [η] is too large, the torque of the extruder rises and is difficult to extrude during sheet processing. Workability may be inferior. In addition, intrinsic viscosity [(eta)] is measured in 135 degreeC tetralin solvent.

It is preferable that the molecular weight distribution of an amorphous polymer is 1-3 from a viewpoint of improving a curvature suppression effect. In addition, the molecular weight distribution measures standard polystyrene as a molecular weight standard substance by gel permeation chromatography (GPC) by ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn).

As a polymerization method of an amorphous polymer, slurry polymerization method, solution polymerization method, block polymerization method, gas phase polymerization method, etc. can be employ | adopted, for example, It can manufacture by superposing | polymerizing a predetermined monomer by a metallocene catalyst. have. As a metallocene catalyst, for example, JP58-19309A, JP60-35005A, JP60-35006A, JP60-35007A, JP60-35008A, JP61-130314A, JP3-163088A, JP4-268307A, JP9-12790A, JP9-87313A And metallocene catalysts described in JP11-80233A, JP10-508055A and the like.

Moreover, as a manufacturing method of the amorphous polymer using a metallocene catalyst, the manufacturing method of EP1211287A is preferable.

As an amorphous polymer, the polymer of JP11-193309A is mentioned, for example. As a commercial item, Tafuma P series, A series, BL series, BL4000, BL3450, BL2481, etc. of the Mitsui Chemicals Co., Ltd. Dynaron 6200P, 1320P, 1321P, Sumitomo Chemical Co., Ltd. Tough selenium T3712, T3722, T3522 etc. are mentioned. Among them, tough selenium T3722, T3712, T3522, H5002, Mitsui Chemical Co., Ltd. product made by Sumitomo Chemical Co., Ltd. from the viewpoint of obtaining a film excellent in compatibility with the component (B) of the present invention and excellent in transparency. Fuma XM-7070 and XM-7080 are preferable.

The amorphous polymer may be a mixture of crystalline polymers, for example, a composition in which an amorphous polymer and a crystalline polymer are kneaded, or the amorphous polymer is coated with a crystalline polymer, and the inner layer is an amorphous polymer, The polymer of the multilayer structure whose outer layer is a crystalline polymer may be sufficient. In the polymer having a multilayered structure, from the viewpoint of suppressing warpage deformation of the laminate, when the total of the amorphous polymer of the inner layer and the crystalline polymer of the outer layer is 100% by weight, the amorphous polymer is 80 to 99% by weight and the crystalline property It is preferable that a polymer is 1-20 weight%.

<Petroleum resins>

Petroleum resins are crystal melting peaks of 30 J / g or more, or crystallization calories of 30 J / g or more, in the differential scanning calorimetry according to JIS K7122, in which the heat of fusion of crystals observed in the range of −50 to 200 ° C. is 30 J / g or more. It is a resin in which neither peak is observed.

Examples of the petroleum resins include synthetic petroleum resins, rosin-based resins, and terpene-based resins. As a synthetic petroleum resin, For example, aliphatic petroleum which is a homopolymer or copolymer of C5 fraction of naphtha cracked oil, C6 to C11 fraction, and other olefinic fraction, and hydrogenated products of these homopolymers and copolymers. Resins, aromatic petroleum resins, alicyclic petroleum resins, aliphatic-alicyclic copolymers, and the like. As a synthetic petroleum resin, the copolymer of said naphtha decomposition oil and terpene, the copolymer type petroleum resin which is a hydrogenated substance of this copolymer, etc. are mentioned further.

Examples of the C5 fraction of naphtha decomposition oil include methyl butenes such as isoprene, cyclopentadiene, 1,3-pentadiene, 2-methyl-1-butene, and 2-methyl-2-butene, 1-pentene, Pentenes, such as 2-pentene, dicyclopentadiene, etc. are mentioned. As the C6 to C11 fraction, for example, methyl styrene such as indene, styrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, α-methyl styrene, β-methyl styrene, methyl indene, ethyl Indene, vinyl xylene, propenylbenzene and the like. As other olefin fraction, butene, hexene, heptene, octene, butadiene, octadiene etc. are mentioned, for example. The synthetic petroleum resin used in the present invention is preferably hydrogenated. Specifically, Arakawa Chemical Co., Ltd. hydrogenated petroleum resin, Alcon P-115, P-125, P140, Tonex Co., Ltd. cyclopentadiene type hydrogenated petroleum resin, Escort 5320HC, etc. can be used.

<Rosin-based resin>

Examples of the rosin-based resins include gum rosin, wood rosin, tall oil rosin and the like obtained from a natural material, that is, pine. As the rosin-based resin, one stabilized by a method such as hydrogenation, disproportionation, and dimerization is preferable. Specifically, Arakawa Chemical Co., Ltd. disproportionation rosin, super ester A-115, etc. can be used.

<Terpene-based resin>

As terpene-type resin, the thing produced by terepene oil obtained from a natural material as a raw material, the thing manufactured with orange peel, etc. are mentioned, for example. The terpene-based resin is preferably hydrogenated. Specifically, the hydrogenated terpene resin, Clearon P-115, P-125, etc. made by Yashara Chemical Co., Ltd. can be used.

When the total amount of the component (a) and the component (b) is 100% by weight, the resin composition has 80 to 99% by weight of the component (a) and 1 component (b) from the viewpoint of suppressing warpage deformation of the laminate. It is preferable to contain-20 weight%, and it is more preferable to contain 90-99 weight of a component (a) and 1-10 weight% of a component (b).

Moreover, you may mix | blend another component with a thermoplastic resin and a resin composition as needed, for example, a light diffusing agent, a ultraviolet absorber, an organic type dye, an inorganic type dye, a pigment, antioxidant, an antistatic agent, surfactant, etc.

The preparation method of a resin composition should just be a method by which a component (a) and a component (b) are knead | mixed uniformly, For example, the method of following (1) or (2) is mentioned.

(1) A method of mixing components (a) and (b) with a ribbon blender, Henschel mixer, tumbler mixer, hand blend, or the like, and melt-kneading the obtained mixture by a single screw extruder or a twin screw extruder or the like.

(2) A part of component (a) and a component (b) are mixed by the same method as said (1), and melt-kneading again, and the master batch pellet containing 20 weight% or more of component (b) is obtained, and then, The master batch pellet and the remaining component (a) are mixed in the same manner as in (1) above so that the amounts of the components (a) and (b) in the resin composition are a predetermined amount, followed by melt kneading.

As a method of said (2) which prepares the masterbatch pellet containing 20 weight% or more of component (b), the method described in JP2000-72923A is mentioned, for example. In addition, the master batch pellet obtained may be treated with a sulfur crosslinking treatment, a peroxide crosslinking treatment, a peroxide decomposition treatment, a metal ion crosslinking treatment, a silane crosslinking treatment and the like within a range that does not impair the effects of the present invention. In addition, at least one kind of powder selected from antioxidant, calcium carbonate, barium sulfate, silica, talc, stearic acid, and polyolefin powder may be powdered on the surface of this masterbatch pellet as needed.

[Laminated body]

In the laminate of the present invention, the protective film is directly laminated on at least the mat surface of the mat film.

Moreover, it is preferable that the laminated body of this invention is a mat surface (uneven surface) also the protective film surface which is not in contact with a mat film.

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 is lowered, so that wrinkles are likely to occur in the laminate, or lift is likely to occur in a set state. When the thickness is thicker than 400 μm, the manufacturing cost of the laminate becomes high, or when the obtained laminate is bonded to the polarization separation sheet, the thickness of the polarization separation sheet after bonding becomes thick, and as a result, the thickness of the liquid crystal panel becomes thick. It is not desirable to have.

It is preferable that the thickness of a mat film is 60% or more with respect to the thickness of the whole laminated body, More preferably, it is more preferable that it is 70% or more of thickness. If the thickness of the mat film is less than 60% with respect to the thickness of the whole laminate, for example, when transferring the mat shape to the mat film via the protective film, there is a fear that a sufficient mat shape to the mat film cannot be transferred.

Moreover, it is preferable that the thickness of a protective film is 5-50 micrometers, Furthermore, it is preferable that it is 10-40 micrometers. If the thickness is thicker than 50 μm, for example, when transferring the mat shape to the mat film through the protective film, there is a fear that sufficient mat shape may not be transferred to the mat film, and if it is less than 5 μm, the protective function of the protective film. There is a fear that this is lowered or broken during peeling.

Moreover, it is preferable that it is 90% or less, and, as for the haze of the mat film after peeling a protective film from a laminated body, it is more preferable that it is 85% or less. When haze is lower than 25%, sufficient anti-glare effect may not appear. Moreover, when it exceeds 90%, when this film is used for a liquid crystal display device, the whitening unevenness of a screen and the image quality fall may be caused.

It is preferable that the in-plane retardation value of incident light in the wavelength of 590 nm of a mat film is 30 nm or less, Furthermore, it is preferable that it is 20 nm or less.

For example, when using the mat film which peeled off the protective film in this invention for a liquid crystal display device, since the light used for liquid crystal display is polarized light, the film with small optical deformation is calculated | required, and a rita of 30 nm or less It is preferable that it is a date value. Among the liquid crystal display devices, it is preferable that the retardation value is low so as not to disturb the polarization direction of the polarization emitted from the polarization separation sheet as much as possible about the polarization separation sheet protective film used for the polarization separation sheet protection, and the retardation value is It is more preferable that it is 20 nm or less.

It is preferable that it is 60% or less, and, as for the 60 degree mirror glossiness in the mat surface of a mat film, it is more preferable that it is 50% or less. When 60-degree mirror glossiness exceeds 60%, when a mat film and a liquid crystal panel contact, there exists a possibility that the rainbow shape by an interference fringe may generate | occur | produce.

The laminated body can peel a mat film and a protective film. Here, peelable means that the other film can be peeled and divided into each film from one film among the directly laminated | stacked mat film and protective film.

It is preferable that the interlayer peeling force of a mat film and a protective film is 5-50 g / 25 mm width, and, as for a laminated body, it is more preferable that it is 7-40 g / 25 mm width.

If the interlaminar peeling force is lower than 5 g / 25 mm width, the protective film may peel off from the laminate when an external force is applied, such as during winding or conveyance of the laminate, or even during cutting, and more than 50 g / 25 mm width. If it is high, there is a risk of damaging the mat film when the protective film is peeled off.

The matte film is used for various purposes such as diffusion action, alteration action, prevention of sticking with other members, protection of the film surface by contact, and the like. For example, in a liquid crystal display device, a light diffusion sheet and a light mounted on a backlight unit are used. It can be used for a diffusion film, a polarizing plate protective film, a retardation film, a brightness improving film, etc., a protective film of a polarization separating sheet, a reflective film, a light guide plate, etc. Moreover, it is applicable also to an optical disk, the film for automobile interiors, the film for lighting, the film for building materials, etc., This invention is not limited to these uses. Especially, it can use suitably for optical uses, such as a protective film of the polarization separating sheet (brightness improvement film) in a liquid crystal display device.

A mat film or a protective film is not limited to single layer structure, The multilayer structure of two or more layers may be sufficient as needed. As a mat film, the 2-layered constitution etc. which the layer which consists of acrylic resin, and the layer which consists of polycarbonate resin are laminated | stacked are mentioned, for example.

<Method for Manufacturing Laminate>

The manufacturing method of the laminated body of this invention (Hereinafter, it may be called the manufacturing method of this invention.) Melt-extrudes resin containing a thermoplastic resin and at least polyolefin resin, respectively, and melted thermoplastic resin layer (A ) And a step (1) of laminating a resin layer (B) containing molten at least polyolefin resin to obtain a film-like article, and the film so that the surface of the resin containing at least polyolefin-based resin of the film-like article contacts the shaping roll. The surface of a shaping | molding roll is inserted in the surface of the thermoplastic resin which inserts a shaped object between a shaping | molding roll and a touch roll, and contacts the resin containing at least polyolefinic resin through the resin containing the at least polyolefinic resin contacting the shaping | molding roll. It has a process (2) which transfers the mat shape formed in this and forms a mat shape.

By employ | adopting the manufacturing method mentioned above, wrinkle generation with respect to a protective film can be suppressed.

As a mat-shaped formation method using an shaping | molding roll, it transfers using the metal roll in which the uneven | corrugated shape was formed in the outer peripheral surface at the time of coextrusion molding, For example, the method of JP2009-196327A, JP2009-202382A, etc. are mentioned. have.

EMBODIMENT OF THE INVENTION Hereinafter, the manufacturing method of this invention is demonstrated in detail with reference to drawings.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic explanatory drawing which shows one Embodiment of the manufacturing method of this invention.

As shown in the figure, in this embodiment, the thermoplastic resin injected into the melt extruder 1, 2 and the resin containing at least polyolefin resin are melt-kneaded, and are respectively supplied to the distribution block 3, and the desired layer structure is provided. After dispensing as much as possible, it is laminated in the multi-manifold die 4 (T die), and extruded into a film-like material from the tip of the multi-manifold die 4.

In this embodiment, the resin layer (B) containing at least a polyolefin resin is laminated | stacked and integrated in a thermoplastic resin layer (A) by a die-in-die lamination system normally. Specifically, for example, the thermoplastic resin and the polyolefin-based resin supplied to the distribution block 3, which is a two-layer three-layer or two-layer two-layer distribution type, are both surfaces of the thermoplastic resin layer (A) in the distribution block (3). Are distributed so that the resin layer (B) containing at least polyolefin resin is arrange | positioned to the resin layer, or the resin layer (B) containing at least polyolefin resin is arrange | positioned to one surface of a thermoplastic resin layer (A), and is multi-manifold Stacked in die 4 and integrated as a three or two layer structure.

The temperature setting of the extruder 1, the extruder 2, and the multi-manifold die 4 may be appropriately adjusted according to the resin to be used, but the polyethylene-based resin may be a polycarbonate-based resin or at least a polyolefin-based resin in the thermoplastic resin. When using resin, it is preferable that the extruder 1 is 220-300 degreeC, the extruder 2 is 210-300 degreeC, and the temperature setting of the multi-manifold die 4 is 260-300 degreeC.

Moreover, when polypropylene resin is used for resin containing polycarbonate resin and at least polyolefin resin for a thermoplastic resin, the extruder 1 is 210-290 degreeC, and the extruder 2 is 210-280 degreeC, multi It is preferable that the temperature setting of the manifold die 4 is 250-290 degreeC.

If it is out of the said range, there exists a possibility that it may become a film whose thickness of each layer is nonuniform according to a viscosity ratio. In addition, polyethylene resins may become foreign matters such as fisheye due to gelation by crosslinking, and polypropylene resins may be deteriorated in appearance by foaming due to decomposition, and thus are not suitable for optical applications. .

In addition, when the resin containing at least a polyolefin resin is a resin composition containing the above-mentioned component (a) and a component (b), it is made to the component (a) contained in a polycarbonate resin and a resin composition in a thermoplastic resin. When using a crystalline polypropylene polymer, it is preferable that the extruder 1 is 210-290 degreeC, the extruder 2 is 210-280 degreeC, and the temperature setting of the multi-manifold die 4 is 250-290 degreeC. Do. Moreover, when using a crystalline polyethylene polymer for the polycarbonate resin and the component (a) contained in the resin composition mentioned above for a thermoplastic resin, the extruder 1 is 220-300 degreeC, and the extruder 2 is 210 It is preferable that the temperature setting of -300 degreeC and the multi-manifold die 4 is 260-300 degreeC.

If it is out of the said range, there exists a possibility that it may become a film whose thickness of each layer is nonuniform according to a viscosity ratio. In addition, in the crystalline polypropylene polymer, the appearance may be poor due to foaming due to decomposition, and the crystalline polyethylene polymer may be foreign matter such as fisheye due to gelation by crosslinking. It is not suitable.

In addition, in this embodiment, although the multi-manifold method using the distribution block 3 and the multi-manifold die 4 was used, instead of this, the dual slot which is a feed block stacking system or the die-die stacking system is used instead. Die or the like can be used. Especially, it is preferable to use the multi-manifold system from the point which the thickness precision of each layer is more excellent.

Next, the resin extruded from the multi-manifold die 4 is a touch in which the resin layer B containing at least the polyolefin-based resin is disposed in contact with the shaping roll 6 (cooling roll) in the substantially horizontal direction. Mat shape is formed on at least one surface of the thermoplastic resin layer (A) via the resin layer (B) which is clamped between the roll 5 (cooling roll 5) and the shaping | molding roll 6, and contains at least polyolefin resin. This transfer is carried out, and a laminated body is shape | molded. Furthermore, the laminated body wound on the shaping roll 6 passes between the shaping roll 6 and the mirror surface roll 7 (cooling roll), is gently cooled by the mirror surface roll 7, and laminated at a predetermined take-up speed. (8) can be obtained.

The touch roll 5 is about 200-1000 mm in diameter normally, For example, it consists of a rubber roll or a metal elastic roll.

What is necessary is just to adjust the temperature of the touch roll 5 suitably according to resin to be used, For example, when using a polyethylene-type resin for resin containing a polycarbonate resin and at least polyolefin resin in a thermoplastic resin, it is normally 10 -160 degreeC, Preferably it is 15-150 degreeC. Moreover, when polypropylene resin is used for resin containing polycarbonate resin and at least polyolefin resin for a thermoplastic resin, it is 10-170 degreeC normally, Preferably it is 15-160 degreeC, More preferably, it is 20-150 ℃.

For example, when using a crystalline polypropylene polymer for the polycarbonate resin and the component (a) contained in the resin composition mentioned above for a thermoplastic resin, it is 10-170 degreeC normally, Preferably it is 15-160 degreeC to be. Moreover, when a crystalline polyethylene polymer is used for a polycarbonate resin and the component (a) contained in the resin composition mentioned above for a thermoplastic resin, it is 10-160 degreeC normally, Preferably it is 15-150 degreeC.

If the temperature of the touch roll 5 is too low, the resin is rapidly cooled, so that deformation is likely to remain in the laminate 8, or if the temperature of the touch roll 5 is too high, cooling is insufficient, resulting in a laminate ( 8) may adhere to a roll and wind up.

As a rubber roll, a silicone rubber roll, a fluororubber roll, the rubber roll which mixed sand in order to raise mold release property, etc. are mentioned, for example.

It is preferable that the hardness of a rubber roll exists in the range of A60 degrees-A90 degrees measured based on JISK6253. In order to make the hardness of a rubber roll into the said range, it can implement arbitrarily by adjusting the crosslinking degree and composition of the rubber which comprises a rubber roll, for example.

As a metal elastic roll, the inside of a roll is comprised from rubber | gum, or the fluid is inject | poured, and the outer periphery part is comprised from the metal thin film which has flexibility. 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 circumference of the roll, or in which fluid such as water or oil is injected into the inside of the roll, A stainless steel cylindrical thin film having a thickness of about 2 to 5 mm is fixed at the roll end, and a fluid is enclosed therein.

As such a touch roll 5, what consists of a metal material and an elastic body, for example, and finishes in mirror shape by plating etc. is used. In addition, the surface of the metal thin film and rubber roll of a metal elastic roll does not necessarily need to be smooth, and there exists no problem even if it forms uneven | corrugated shape in the surface like the shaping | molding roll 6 demonstrated below.

The shaping | molding roll 6 is about 200-1000 mm in diameter normally, For example, it consists of a metal roll in which the uneven shape was formed in the outer peripheral surface.

What is necessary is just to adjust the temperature of the shaping | molding roll 6 suitably according to resin to be used, For example, when using a polyethylene resin for polycarbonate resin and polyolefin resin for a thermoplastic resin, it is 10-80 degreeC normally, Preferably Preferably it is 20-60 degreeC. Moreover, when polypropylene resin is used for polycarbonate resin and polyolefin resin for thermoplastic resin, it is 10-100 degreeC normally, Preferably it is 20-80 degreeC.

For example, when a crystalline polypropylene polymer is used for a polycarbonate resin and the component (a) contained in the resin composition mentioned above for a thermoplastic resin, it is 10-100 degreeC normally, Preferably it is 20- 80 ° C. Moreover, when using a crystalline polyethylene polymer for polycarbonate resin and component (a) for a thermoplastic resin, it is 10-80 degreeC normally, Preferably it is 20-60 degreeC.

If the temperature of the shaping roll 6 is too low, the resin is rapidly cooled, so that deformation is likely to remain in the laminated body 8, or if the temperature of the shaping roll 6 is too high, the cooling becomes insufficient and the laminate ( 8) may adhere to a roll and wind up.

As the shaping | molding roll 6, for example, the drilled roll which cut out the metal lump, the metal roll etc. which can control the temperature of a roll surface by letting fluid, steam, etc. pass inside the roll, such as a spiral roll of a hollow structure, etc. These are mentioned, The thing in which desired uneven | corrugated shape was formed in the outer peripheral surface of these metal rolls by sandblasting, engraving, etc. can be used.

As the uneven | corrugated shape formed in the outer peripheral surface of the shaping | molding roll 6, the mat shape of about 0.1-15 micrometers, etc. in arithmetic mean roughness Ra, the uneven | corrugated shape which has a specific pitch or height, etc. are mentioned, for example. have. In addition, arithmetic mean roughness Ra is a value obtained by measuring with a surface roughness meter based on JISB0601-2001.

The resin (or film-like article) extruded from the multi-manifold die 4 is a laminated resin in which a resin layer (B) containing at least a polyolefin resin is laminated on both surfaces of the thermoplastic resin layer (A), and at least polyolefin resin is used. Resin layer (B) which contains a polyolefin resin at least in the case where a mat shape is transferred to one surface of a thermoplastic resin layer (A) via the resin layer (B) to contain, or one surface of a thermoplastic resin layer (A). ) Is a laminated resin laminated, and in the case of forming a mat shape on the surface of the layer (A) through the resin layer (B) containing at least the polyolefin-based resin, such a touch roll 5 and a shaping roll 6 ), The concave-convex shape of the shaping roll 6 is transferred to the surface of the thermoplastic resin layer A and molded into the laminated body 8 by sandwiching between the layers. In that case, the surface of the resin layer (B) containing at least polyolefin resin of a mat film is extruded so that it may contact with the shaping | molding roll 6.

Moreover, it is a laminated resin in which the resin layer (B) containing at least polyolefin resin was laminated | stacked on both surfaces of a thermoplastic resin layer (A), and is a thermoplastic resin layer (A) via the resin layer (B) containing at least polyolefin resin. What is necessary is just to sandwich the laminated resin between the cooling rolls in which the uneven shape was formed in the outer peripheral surface when forming a mat shape on both surfaces of the.

The laminated body 8 to which the uneven | corrugated shape was transferred is wound up by the take-up roll, after winding up to the shaping | molding roll 6, and wound up.

What is necessary is just to adjust the pulling speed of a take-up roll suitably according to resin to be used, and it is 0.5-80 m / min normally, Preferably it is 2-60 m / min. When it is slower than 0.5 m / min, there exists a possibility that it may become disadvantageous in terms of manufacturing cost, and when it is faster than 80 m / min, there exists a possibility that the inspection of the film appearance in the inline which assumed an optical use may become inadequate.

At this time, the mirror surface roll 7 may be formed after the shaping roll 6. Thereby, since the laminated body 8 is cooled slowly, since the optical deformation of the laminated body 8 can be made small, and also the contact time with respect to the shaping roll 6 can be ensured stably, the shaping roll 6 It becomes possible to stably transfer the uneven shape given to). It does not specifically limit as the mirror surface roll 7, The conventional metal roll conventionally used by extrusion molding can be employ | adopted. As a specific example, a drilled roll, a spiral roll, etc. are mentioned. It is preferable that the surface state of the mirror surface roll 7 is mirror surface.

The laminated body 8 wound around the shaping roll 6 is passed between the shaping roll 6 and the mirror surface roll 7 so as to be wound around the mirror roll 7. Between the shaping | molding roll 6 and the mirror surface roll 7, you may make it a release state with a predetermined clearance gap, and may sandwich between both rolls. In addition, in cooling the laminated body 8 more gently, one or more cooling rolls are formed after the mirror surface roll 7, and the mat film wound on the mirror surface roll 7 is sequentially cooled next. You may make it roll on a roll.

Moreover, in the case of the laminated body in which the mat film consists of a layer which consists of acrylic resin, and the layer which consists of polycarbonate resins, and at least one surface is a mat surface, it melts to the melt-extruder (1, 2) shown in FIG. In addition, another melt extruder (not shown) may be newly formed, and the distribution block 3 may be a three-layer three-layer distribution block or a three-layer five-layer distribution block, and otherwise laminated in the same manner as in the above-described embodiment. Sieves can be prepared.

Example

Hereinafter, although the Example of this invention is shown, this invention is not limited by these. In addition, the part which shows content-usage-amount in a following example is a basis of weight unless there is particular notice.

The measurement of the heat of fusion and the crystallization peak was performed as follows.

<Crystal Melting Calorie and Crystallization Peak>

According to JIS K7122, it measured by the differential scanning calorimeter ("DSC6200" by Seiko Instruments Co., Ltd. product). Specifically, the sample polymer was heated to 30 ° C./min from room temperature to 200 ° C. as a condition adjustment, and held at 200 ° C. for 5 minutes. Subsequently, the temperature was lowered to −50 ° C. at 10 ° C./min, held at −50 ° C. for 5 minutes, the temperature was raised from −50 ° C. to 200 ° C. at 10 ° C./min, and the heat of crystal melting and the crystallization peak were measured. .

The structure of the extrusion apparatus used by the following example and the comparative example is as follows.

Extruder (1): screw diameter 65 mm single screw extruder with vent (manufactured by Toshiba Machine Co., Ltd.)

Extruder (2): screw diameter 45 mm single screw extruder with vent (manufactured by TOSHIBA Machinery Co., Ltd.)

Distribution block 3: two two-layer distribution block (manufactured by TOSHIBA Machinery Co., Ltd.)

Extruder (1) and (2), distribution block (3), multi-manifold die (4), 1st-3rd cooling rolls (5)-(7) are arrange | positioned as shown in FIG. 1, and each cooling roll (5)-(7) was comprised as follows.

<Roll structure>

The touch roll 5, the shaping | molding roll 6, and the mirror surface roll 7 were comprised as follows.

Touch roll (5): Silicone rubber roll with an outer diameter of 250 mmφ and a hardness of A70 °

Shaping roll (6): A stainless steel metal roll (drilled roll) having an outer diameter of 250 mmφ and having an uneven shape having an arithmetic mean roughness (Ra) of 3.5 μm by blasting.

Mirror surface roll 7: Stainless steel roll (drilled roll) with an outer diameter of 250 mmφ and mirror finish

(Example 1)

As the layer (A), the polycarbonate resin ("Caliber 301-10", Sumitomo Dow Co., Ltd. product, heat deformation temperature: 140 degreeC) was melted, and the extruder 1 (cylinder temperature: 230-280 degreeC, screw rotation) Water: 40 rpm, extrusion amount: 50 kg / hr., Supplied to the distribution block 3, the polyethylene resin (Sumitomo Chemical Co., Ltd. low density polyethylene "Sumikasen L211" manufactured by Sumitomo Chemical Co., Ltd. as a layer B), Vicat softening temperature: 98 degreeC) is melted, and it supplies to the distribution block 3 from the extruder 2 (cylinder temperature: 210-265 degreeC, screw rotation speed: 18 rpm, extrusion amount 3 kg / hour), and layered in the distribution block 3 After distributing so as to have a two-layer constitution of (B) / layer (A), it was laminated and extruded in a multi-manifold die 4 (die temperature: 270 ° C).

Next, the film-form extruded from the multi-manifold die 4 was sandwiched between the touch roll 5 (set temperature: 35 degreeC) and the shaping roll 6 (set temperature: 35 degreeC), and the laminated body was shape | molded. . In addition, the laminated body wound around the shaping roll 6 is passed between the shaping roll 6 and the mirror surface roll 7 to be wound around the mirror roll 7 (set temperature: 35 ° C), and a take-up speed of 11 m / min. The laminated body 8 in which the uneven | corrugated shape was transcribe | transferred by one side to the surface of the sheet | seat was obtained. In the obtained laminated body, wrinkles were not observed in the layer (B) (protective film), and there was no adhesive residue in the layer (A) (mat film) after peeling off the protective film.

Table 1 shows the thickness of the obtained laminate.

(Example 2)

A laminated body was obtained in the same manner as in Example 1 except that the screw rotation speed in the extruder 2 was 36 rpm and the extrusion amount was 9 kg / hour. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 1 shows the thickness of the obtained laminate.

(Comparative Example 1)

The resin supply from the extruder 2 was stopped, and the distribution block was formed with a single layer structure of the layer (A) (i.e., polycarbonate-based resin: "Caliber 301-10", manufactured by Sumitomo Dow Co., Ltd., heat deformation temperature 140 deg. A mat film made of a polycarbonate-based resin single layer was obtained in the same manner as in Example 1, except that the blocks were replaced with the resulting blocks. About the obtained mat film, the protective film (co-extrusion film which has a tackifier containing rubber type resin layer (thickness = 4 micrometer) in one surface of a polypropylene resin layer (thickness = 36 micrometer)) with a total thickness of 40 micrometers Using the bonding machine, the tackifier-containing rubber-based resin layer surface of the protective film was brought into close contact with the mat surface of the mat film, and bonded at normal temperature to obtain a laminate with a tackifier-containing rubber-based resin layer.

In the obtained laminated body, wrinkles were observed in the protective film, and there was adhesive residue in the mat film after peeling off the protective film.

Table 1 shows the thickness of the obtained laminate.

(Example 3)

[Production of master batch of resin composition]

Crystalline polypropylene-based polymer ("Noblen W151" manufactured by Sumitomo Chemical Co., Ltd., crystal melting heat = 49.6 J / g) 80 parts by weight and hydrogenated petroleum resin (`` Alcon P125 '' manufactured by Arakawa Chemical Co., Ltd.) 20 The parts by weight were mixed and melt kneaded with a twin screw extruder (not shown) to obtain a master batch pellet of the resin composition. In addition, neither hydrogenated crystallization peak nor crystallization peak was observed for the hydrogenated petroleum resin.

[Production of laminated body]

As the thermoplastic resin layer (A), a polycarbonate resin ("Calibar 301-15" manufactured by Sumitomo Dow Co., Ltd.) was extruded into the extruder 1 (cylinder temperature: 230 to 260 ° C, screw rotation speed: 35 rpm, extrusion). Amount: melt kneaded at 50 kg / hr and supplied to distribution block 3, and as a resin composition layer (B), crystalline polypropylene polymer ("Noblen W151" manufactured by Sumitomo Chemical Co., Ltd.), crystal melting Calories = 49.6 J / g) 90 parts by weight and 10 parts by weight of the master batch pellets were mixed and melted with an extruder 2 (cylinder temperature: 210 to 260 ° C, screw rotation speed: 30 rpm, extrusion amount 7 kg / hr). After kneading and supplying to the distribution block 3 and distributing in a two-layer configuration of layer (B) / layer (A) in the distribution block 3, the multi-manifold die 4 (die temperature: 260 ° C.) Laminated and extruded.

Next, the film shape extruded from the multi-manifold die 4 is made to contact the shaping | molding roll with the layer B, and the touch roll 5 (setting temperature: 35 degreeC) and the shaping roll 6 (setting temperature: It sandwiched between 35 degreeC), and the laminated body was shape | molded. Moreover, the laminated body wound around the shaping roll 6 is made to pass between the shaping roll 6 and the mirror surface roll 7, and it winds around on the mirror surface roll 7 (set temperature: 50 degreeC), and the take-up speed is 9 m. The laminated body 8 in which the uneven | corrugated shape was transferred to one surface by pulling by / minute was obtained. In the obtained laminated body, wrinkles were not observed in the layer (B) (protective film), and there was no adhesive residue in the layer (A) (mat film) after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

(Example 4)

A laminated body was obtained in the same manner as in Example 3 except that the mixed amount of the crystalline polypropylene polymer and the master batch pellet was 75 parts by weight of the crystalline polypropylene polymer and 25 parts by weight of the master batch pellet. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

(Example 5)

A laminated body was obtained in the same manner as in Example 3 except that the mixed amount of the crystalline polypropylene polymer and the master batch pellet was 60 parts by weight of the crystalline polypropylene polymer and 40 parts by weight of the master batch pellet. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

(Example 6)

A laminate was obtained in the same manner as in Example 3 except that the hydrogenated petroleum resin (“Alcon P125” manufactured by Arakawa Chemical Co., Ltd.) was used as a hydrogenated terpene resin (“Clearlon P125” manufactured by Yashara Chemical Co., Ltd.). . In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film. In addition, neither the terpene type resin nor the crystal melting peak or the crystallization peak was observed.

Table 2 shows the thickness of the obtained laminate.

(Example 7)

A laminated body was obtained in the same manner as in Example 6 except that the mixed amount of the crystalline polypropylene polymer and the master batch pellet was 75 parts by weight of the crystalline polypropylene polymer and 25 parts by weight of the master batch pellet. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

(Example 8)

A laminated body was obtained in the same manner as in Example 6 except that the mixed amount of the crystalline polypropylene polymer and the master batch pellet was 60 parts by weight of the crystalline polypropylene polymer and 40 parts by weight of the master batch pellet. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

(Example 9)

[Production of laminated body]

As the layer (B), 97.8 parts by weight of a crystalline polypropylene polymer ("Noblen W151" manufactured by Sumitomo Chemical Co., Ltd., crystal melting amount = 49.6 J / g) and an amorphous polypropylene polymer (Sumitomo Chemical Co., Ltd.) ) "Tough selenium H5002" manufactured, calorific value of crystal melting = 8.5 J / g, content of amorphous polypropylene-based polymer component: 92% by weight) 2.2 parts by weight of the extruder (2) (cylinder temperature: 210 to 260) The laminate was obtained in the same manner as in Example 3 except that the mixture was melt-kneaded at a screw rotation speed of 30 rpm and an extrusion amount of 7 kg / hr) and fed to the distribution block 3. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

(Example 10)

Laminated in the same manner as in Example 9 except that the mixed amount of the crystalline polypropylene polymer and the amorphous polypropylene polymer was 94.6 parts by weight of the crystalline polypropylene polymer and 5.4 parts by weight of the amorphous polypropylene polymer. Got a sieve. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

(Example 11)

In the extruder 2, the laminated body was obtained like Example 3 except having melt-kneaded only the crystalline polypropylene-type polymer, without mixing a masterbatch. In the obtained laminated body, wrinkles were not observed in the protective film, and there was no adhesive residue in the mat film after peeling off the protective film.

Table 2 shows the thickness of the obtained laminate.

The following evaluation was performed about the layer (A) (mat film) which peeled layer (B) (protective film) from each obtained laminated body and each laminated body. The results are shown in Tables 3 and 4.

<60 degree mirror glossiness>

In accordance with JIS Z8741, 60 degree mirror glossiness of the mat surface of the mat film was measured.

<Surface roughness>

Arithmetic mean roughness (Ra), maximum height (Rz), and average length (RSm) of contour curve elements of the mat surface of the matte film are based on JIS B0601-2001 based on surface roughness meter (Mitsutoyo Co., Ltd. Surf test SJ-201 ").

<Retardation value>

The test piece was cut out from the mat film by 50 mm in size, and the retardation value in 590 nm was measured with the micro area birefringence meter ("KOBRA-CCO / X" by Oji Measuring Instruments Co., Ltd. product).

<Total Light Transmittance (Tt) and Haze (H)>

In accordance with JIS K7361-1, the total light transmittance (Tt) of the mat film was measured.

In accordance with JIS K7136, the haze (H) of the mat film was measured.

<Peel strength>

In 23 degreeC atmosphere, the force required to peel a protective film from the laminated body obtained on 25 mm of peeling widths, peel angle 180 degrees, and peeling speed of 300 mm / min was measured, and this was measured in 23 degreeC. It was set as peeling strength (g / 25mm).

<Deformation amount of warpage>

It cut into 297 mm in the extrusion direction, and 210 mm in the direction orthogonal to the extrusion direction, and set it as the test piece. First, the test piece was placed on a surface plate, and the floating amount of the four corners was measured by a table strain measuring instrument (manufactured by Keyence Co., Ltd.), and the average value of the floating amount of the four corners was calculated, which was defined as the amount of warpage deformation.

1, 2 melt extruder
3 distribution blocks
4 multi manifold dies
5 touch rolls
6 inch rolls
7 mirror roll
8 laminate

Claims (17)

A peelable laminated body, wherein a protective film made of a resin containing at least polyolefin resin is directly laminated on at least a mat surface of a mat film made of a thermoplastic resin, and the mat film and the protective film can be peeled off. The method of claim 1,
The resin containing at least polyolefin resin is at least one selected from the group consisting of polyethylene resin, polypropylene resin and modified polyolefin resin which is a modified product thereof. The method of claim 1,
Resin containing at least polyolefin resin is a laminated body which is a resin composition containing the following component (a) and component (b).
Component (a): crystalline polyolefin
Component (b): 1 or more types chosen from the group which consists of an amorphous polymer and petroleum resins The method of claim 3, wherein
Homopolymerization of 1 type of crystalline polyolefin 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 a laminate obtained by copolymerizing two or more kinds. The method according to claim 3 or 4,
A laminate wherein the amorphous polymer is at least one member selected from the group consisting of polypropylene polymers and polyethylene polymers. 6. The method according to any one of claims 3 to 5,
When a resin composition makes the total amount of a component (a) and a component (b) 100 weight%, the laminated body containing 80 to 99 weight% of a component (a) and 1 to 20 weight% of a component (b). . The method according to any one of claims 1 to 6,
The thermoplastic resin is one 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 above laminated body. The method according to any one of claims 1 to 7,
The laminated body in which the said mat film consists of a layer containing acrylic resin and the layer containing polycarbonate resin laminated | stacked, and at least one surface is a mat surface. The method according to any one of claims 1 to 8,
The laminated body whose surface which is not in contact with the said mat film of the said protective film is a mat surface. The method according to any one of claims 1 to 9,
The laminated body whose haze of the said mat film is 90% or less. The method according to any one of claims 1 to 10,
The laminated body whose in-plane retardation of the said mat film is 30 nm or less, and surface glossiness is 60% or less. The method according to any one of claims 1 to 11,
The laminated body whose interlayer peeling force of the said mat film and the said protective film is 5-50 g / 25mm width. The method according to any one of claims 1 to 12,
The laminated body in which the said protective film and the said mat film are laminated | stacked by melt coextrusion molding. The method according to any one of claims 1 to 13,
The laminated body in which the said matte film is used for a liquid crystal display device. The method of claim 14,
The laminated body in which the said matte film is used for protection of the polarization separation sheet in the said liquid crystal display device. Melt coextrusion of a resin composition and at least a thermoplastic resin containing at least a polyolefin resin to obtain a film-like product, and inserted between the mold roll and the touch roll so that the surface of the resin composition in contact with the mold roll, the mat on the surface of the thermoplastic resin Forming shape, The manufacturing method of the laminated body characterized by the above-mentioned. The mat film obtained by peeling the said protective film from the laminated body in any one of Claims 1-15.

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