CN102331590A

CN102331590A - Laminate and process for preparing the same

Info

Publication number: CN102331590A
Application number: CN2011101865787A
Authority: CN
Inventors: 赤田胜己; 恒川和启; 美浓贵之; 柳濑幸一
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2010-07-05
Filing date: 2011-07-05
Publication date: 2012-01-25
Also published as: TW201213128A; KR20120003813A

Abstract

The present invention relates to a laminate formed by lamination of an extinction film and a protective film, and a process for preparing the same. By adopting the process of the present invention, the prepared laminate has the advantages of uniform peel strength for peeling the protective film from the extinction film, no adhesive deposition, no bucklings in the protective film, no increased processes, simpleness and low cost. In the laminate of the present invention, at least an extinction surface of the extinction film containing thermoplastic resins is directly laminated with the protective film prepared by resins at least containing polyolefin resins, and the extinction film and the protective film can be peeled off. In addition, the process for preparing the laminate comprises the steps of: fusing the resins at least containing the polyolefin resins with the thermoplastic resins and extruding together to obtain membranoid substance; and inserting a surface with the resins at least containing the polyolefin resins between a shaping roller and a contact roller in the way of contacting the surface with the shaping roller, and forming an extinction shape on a surface of the thermoplastic resins.

Description

Duplexer and manufacturing approach thereof

Technical field

The present invention relates to matt film and range upon range of duplexer that obtains of diaphragm and manufacturing approach thereof.

Background technology

The film surface has that the matt film of concaveconvex shape (delustring shape) is many to be used to as various optical diffusion films in the optical applications etc.For matt film, thus can enumerate usually utilize the knurling rolls transfer printing and formed the regulation concaveconvex shape matt film, cross-linked resin particle or inorganic particles are mixed in constitute in the resin of film base material and melt extrude and be shaped or matt film that the multilayered molten extrusion molding makes this particle expose on the film surface to have formed concave-convex surface or through UV curable resin that is dispersed with spherical pearl in the base material film surface coated or the matt film that heat-curing resin forms concaveconvex shape etc. through individual layer.

The situation that this matt film uses aspect liquid crystal indicator is many, and can be used to be configured between the backlight illuminating unit and liquid crystal panel of liquid crystal indicator aptly, is used to improve the diaphragm etc. of the polarisation separating sheet of brightness.Usually; Even if this polarisation separating sheet is thick also with regard to the thickness about 100 μ m; Thereby thereby become insufficient at the insufficient independence of sheet self rigidity when the large tracts of land, receive light source etc. heat influence that sheet self bends sometimes or wrinkling or when contacting, interfere rainbow decorative pattern due to the striped etc. with liquid crystal panel; Therefore in order to suppress above-mentioned situation, the matt film that coating surface has concaveconvex shape (delustring shape) on the two sides of polarisation separating sheet usually.

Above-mentioned matt film might sustain damage at the delustring face of matt film with the range upon range of applying of polarisation separating sheet the time or when transporting etc. or adhere to dust.Therefore, usually at the delustring face of the matt film strippable diaphragm of fitting, and after with polarisation separating sheet and the range upon range of applying of matt film, diaphragm is peeled off from the delustring face of matt film.The terminal stage of the many assemblings at liquid crystal indicator of this diaphragm is stripped from, so need have the cohesive or the fissility of appropriateness with respect to matt film.Consider cohesive or fissility, diaphragm uses usually at single face the applying of matt film and has been coated with the diaphragm of adhesive or bonding agent or has had the diaphragm of the adhesiveness resin bed that added adhesive etc.

On the other hand, be known in the past through extrusion molding with the range upon range of surface of diaphragm in blooming.That is, record in the patent documentation 1 resin extruded and be laminated in the single face at least of blooming and form the content of diaphragm.In addition, record in the patent documentation 2 through fusion coextrusion shaping optical isotropy macromolecule layer and the range upon range of content of polymer protective layer.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2010-38924 communique

Patent documentation 2: TOHKEMY 2003-240953 communique.

Summary of the invention

The problem that invention will solve

As stated, when the delustring face applying diaphragm of matt film, particularly when the film of applying wide cut, two intermembranous peel strengths when peeling off might become inhomogeneous.In addition, when fitting, then become defective products, the product loss might take place if diaphragm produces fold.And then when diaphragm was peeled off, at residual a part of adhesive of matt film or bonding agent, this might become optical defect sometimes.In addition, owing to need bonding process, process number increases, bothers and aspect cost, is disadvantageous.

On the other hand; In aforementioned patent document 1; The single face at least of the blooming of other system film is extruded and be laminated in to the molten resin that forms diaphragm, perhaps on the diaphragm of system film in addition, extrude and the molten resin of range upon range of formation blooming, thus the blooming of forming belt diaphragm.In this film forming method; The face that contacts with diaphragm of making the blooming of film in addition is concaveconvex shape, or the face that contacts with diaphragm that melt extrudes the blooming to the diaphragm of other system film when being concaveconvex shape, has diaphragm to the inadequate situation of the cohesive of blooming.

In addition; In the patent documentation 2 record fit in film that polarizer P sheet uses, be that so-called polarization board protective film requires the surface very level and smooth usually; The fusion coextrusion is shaped and direct range upon range of optical isotropy polymer resin layer A and the duplexer of polymer protective layer B for pass through of using in the patent documentation 2, and the surface of not considering optical isotropy polymer resin layer A fully is the concaveconvex shape this point.

Therefore, problem of the present invention is to provide does not have binder deposition (adhesive deposit) and diaphragm not to produce the duplexer of fold when matt film is peeled off diaphragm.Further, the manufacturing approach that can in an operation, make this duplexer is provided.

Further, problem of the present invention is to provide except when matt film is peeled off, not having binder deposition and diaphragm not to produce the fold diaphragm, has also suppressed the duplexer of buckling deformation.The manufacturing approach of the duplexer that can in an operation, make the range upon range of delustring face in matt film of diaphragm also is provided in addition.

Be used to solve the means of problem

The inventor etc. are further investigation repeatedly in order to solve above-mentioned problem, and the result finds to comprise the solution of following formation, thereby accomplished the present invention.

(1) strippable duplexer is characterized in that, on the delustring face at least of the matt film of processing with thermoplastic resin, and the direct diaphragm processed of the range upon range of useful resin that contains polyolefin-based resins at least, this matt film and this diaphragm are strippable.

(2) aforementioned (1) described duplexer, wherein, the resin that contains polyolefin-based resins at least is to be selected from polyethylene-based resin, polypropylene-based resin and is at least a in the resin as their improved polyalkene of modification body.

(3) aforementioned (1) described duplexer, wherein, the resin that contains polyolefin-based resins at least is the resin combination that contains following compositions (a) and composition (b),

Composition (a): crystalline polyolefin

Composition (b): be selected from amorphism polymkeric substance and the tree oil lipid more than a kind.

(4) aforementioned (3) described duplexer, wherein, crystalline polyolefin be be selected from ethene, propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and the 1-octene a kind of homopolymerization or more than 2 kinds copolymerization and.

(5) aforementioned (3) or (4) described duplexer, wherein, the amorphism polymkeric substance be selected from polypropylene-based polymkeric substance and the polyethylene-based polymkeric substance more than a kind.

(6) each described duplexer in aforementioned (3)～(5), wherein, when being 100 weight % with the total amount of composition (a) and composition (b), resin combination contains composition (a) 80～99 weight %, composition (b) 1～20 weight %.

(7) each described duplexer in aforementioned (1)～(6); Wherein, thermoplastic resin be selected from polycarbonate-based resin, acrylic resin, cyclic olefine resin, polyester based resin, phenylethylene resin series, methyl methacrylate-phenylethylene resin series, ABS be resin and AS be in the resin more than a kind.

(8) each described duplexer in aforementioned (1)～(7), wherein, aforementioned matt film is that the layer that comprises acrylic resin is formed with comprising the folded layer by layer of polycarbonate-based resin, and at least one surface is delustring face.

(9) each described duplexer in aforementioned (1)～(8), wherein, the face that does not contact with aforementioned matt film of aforementioned diaphragm is a delustring face.

(10) each described duplexer in aforementioned (1)～(9), wherein, the mist degree of aforementioned matt film is below 90%.

(11) each described duplexer in aforementioned (1)～(10), wherein, the interior phase differential (retardation) of the face of aforementioned matt film is below the 30nm and surface gloss is below 60%.

(12) each described duplexer in the claim 1～11, wherein, the splitting power of aforementioned matt film and aforementioned diaphragm is 5～50g/25mm width.

(13) each described duplexer in aforementioned (1)～(12), wherein, aforementioned diaphragm and aforementioned matt film are range upon range of through fusion coextrusion shaping.

(14) each described duplexer in aforementioned (1)～(13), wherein, aforementioned matt film is used for liquid crystal indicator.

(15) aforementioned (14) described duplexer, wherein, aforementioned matt film is used for the protection of the polarisation separating sheet of foregoing liquid crystal display device.

(16) manufacturing approach of duplexer; It is characterized in that; With the resin that contains polyolefin-based resins at least and thermoplastic resin fusion coextrusion and obtain membranoid substance; And insert between excipient roller and the touch roll so that the face of aforementioned resin contacts with the excipient roller, and on the face of aforementioned thermoplastic resin formation delustring shape.

(17) matt film, its each described duplexer from aforementioned (1)～(15) is peeled off aforementioned diaphragm and is got.

The invention effect

According to the present invention; The inequality of the diaphragm peel strength due to the difference of the position when duplexer is wide cut reduces, since matt film and diaphragm do not fit through adhesive etc.; After so diaphragm is peeled off, so-called binder deposition disappearance; In addition, also can eliminate the fold of incidental diaphragm when fitting.

In addition, according to the present invention, through fusion coextrusion the range upon range of of the shaping in an operation, to accomplish matt film and diaphragm and two films that be shaped.

Further; According to the present invention; Because matt film and diaphragm are not fitted through adhesive etc.; After so diaphragm is peeled off, so-called binder deposition disappearance, the resin that contains polyolefin-based resins at least is when containing the resin combination of following compositions (a) and composition (b), can further suppress buckling deformation.

Description of drawings

Fig. 1] the diagrammatic illustration figure of an embodiment of manufacturing approach of expression duplexer of the present invention.

Symbol description

1,2 melt extrude machine

3 allocation blocks

4 branch manifold moulds

5 touch rolls

6 excipient rollers

7 mirror rollers

8 duplexers.

Embodiment

Below, the present invention is elaborated.

Duplexer of the present invention comprises matt film and diaphragm, and diaphragm directly is laminated in the delustring face at least of matt film.Here, direct range upon range of expression matt film and diaphragm are through adhesive phase or adhesive agent layer and range upon range of.Diaphragm is to process with the resin that contains polyolefin-based resins at least.Matt film is processed with thermoplastic resin.Below, the resin and the duplexer that contain polyolefin-based resins to thermoplastic resin, at least describe successively.

[thermoplastic resin]

Thermoplastic resin is preferably and is selected from polycarbonate-based resin, acrylic resin, cyclic olefine resin, polyester based resin, phenylethylene resin series, methyl methacrylate-phenylethylene resin series, ABS (acrylonitrile-butadiene-styrene copolymer) is that resin, AS (acrylonitritrile-styrene resin) are at least a in the resin; As resin, the resin that preferably clear property is good.Wherein, from having viewpoints such as high transparent, resistance to impact, thermotolerance, dimensional stability, excellent in flame retardance, optics impurity are few, preferably use polycarbonate-based resin.For thermoplastic resin, in the scope that does not hinder the transparency, can mix more than 2 kinds of above-mentioned resin.Matt film is that the layer that for example will comprise acrylic resin cascades with the layer that comprises polycarbonate-based resin, and at least one surface can be delustring face.The polyolefin-based resins that thermoplastic resin is stated after preferably not containing.

＜polycarbonate-based resin＞

As polycarbonate-based resin, for example preferably using, the aromatic copolycarbonate of excellences such as thermotolerance, physical strength, the transparency is a resin.

As aromatic copolycarbonate is resin; For example, can enumerate make dihydric phenol and carbonate precursor through interface polycondensation, melt transesterification process react the resin that gets, make resin that the carbonic ester prepolymer obtains through the polymerization of solid phase ester-interchange method, cyclic carbonate compound carries out resin that polymerization gets etc. through the ring-opening polymerization method.

As dihydric phenol, for example can enumerate p-dihydroxy-benzene, resorcinol, 4,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) methane, two { (4-hydroxyl-3; The 5-dimethyl) phenyl } methane, 1, two (4-hydroxy phenyl) ethane, 1 of 1-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes, 2 of 1-, two (4-hydroxy phenyl) propane (common name bisphenol-A), 2 of 2-; Two { (4-hydroxy-3-methyl) phenyl } propane, 2 of 2-, two { (4-hydroxyl-3, the 5-dimethyl) phenyl } propane, 2 of 2-, two { (the 4-hydroxyls-3 of 2-; The 5-dibromo) phenyl } propane, 2, two { (3-isopropyl-4-hydroxyl) phenyl } propane, 2 of 2-, two { (4-hydroxyl-3-phenyl) phenyl } propane, 2 of 2-, two (4-hydroxy phenyl) butane, 2 of 2-; Two (4-the hydroxy phenyl)-3-methylbutanes, 2 of 2-, two (the 4-hydroxy phenyls)-3 of 2-, 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-2-methylbutanes, 2 of 4-; Two (4-hydroxy phenyl) pentanes, 2 of 2-, two (4-the hydroxy phenyl)-4-methylpentanes, 1 of 2-, 1-bis(4-hydroxyphenyl)cyclohexane, 1; Two (4-the hydroxy phenyl)-4-isopropyl cyclohexanes, 1 of 1-, two (the 4-hydroxy phenyls)-3,3 of 1-; 5-trimethyl-cyclohexane, 9, two (4-hydroxy phenyl) fluorenes, 9 of 9-, two { (4-hydroxy-3-methyl) phenyl } fluorenes of 9-, α; The adjacent diisopropyl benzene of α '-two (4-hydroxy phenyl), α, diisopropyl benzene, α between α '-two (4-hydroxy phenyl), α '-two (4-hydroxy phenyl) is to diisopropyl benzene, 1; Two (the 4-hydroxy phenyls)-5 of 3-, 7-dimethyladamantane, 4,4 '-dihydroxydiphenylsulisomer, 4; 4 '-dihydroxy diphenyl sulfoxide, 4,4 '-dihydroxy diphenyl sulfide, 4,4 '-dihydroxy benzophenone, 4; 4 '-dihydroxy diphenyl ether and 4,4 '-dihydroxy diphenyl ester etc., they can separately or mix use more than 2 kinds.

Wherein, preferred use is separately perhaps used and is selected from bisphenol-A, 2 more than 2 kinds, two { (4-hydroxy-3-methyl) phenyl } propane, 2 of 2-; Two (4-hydroxy phenyl) butane, 2 of 2-, two (4-the hydroxy phenyl)-3-methylbutanes, 2 of 2-, two (the 4-hydroxy phenyls)-3 of 2-; 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-4-methylpentanes, 1 of 2-, two (the 4-hydroxy phenyls)-3 of 1-; 3,5-trimethyl-cyclohexane and α, the dihydric phenol between α '-two (4-hydroxy phenyl) in the diisopropyl benzene; The independent use or 1 of preferred especially bisphenol-A, two (the 4-hydroxy phenyls)-3,3 of 1-; The 5-trimethyl-cyclohexane be selected from bisphenol-A, 2, two { (4-hydroxy-3-methyl) phenyl } propane and the α of 2-, the dihydric phenol more than a kind between α '-two (4-hydroxy phenyl) in the diisopropyl benzene and use.

As carbonate precursor, for example use carboxylic acid halides, carbonic ester or haloformate etc., specifically can enumerate two haloformates of phosgene, diphenyl carbonate or dihydric phenol etc.

＜acrylic resin＞

As acrylic resin, for example use methacrylic resin.Methacrylic resin is to be the polymkeric substance of main body with the methacrylate, can be the homopolymer of methacrylate, also can be the above and multipolymers below the monomer 50 weight % beyond it of methacrylate 50 weight %.Here, as methacrylate, use the Arrcostab of methacrylic acid usually.

The preferred set of monomers of methacrylic resin becomes; With whole monomers is benchmark; Alkyl methacrylate 50～100 weight %, alkyl acrylate 0～50 weight %, monomer 0～49 weight % beyond them, more preferably alkyl methacrylate 50～99.9 weight %, alkyl acrylate 0.1～50 weight %, monomer 0～49 weight % beyond them.

Here, as alkyl methacrylate, for example can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid 2-Octyl Nitrite etc., the carbon number of its alkyl is generally 1～8, is preferably 1～4.Wherein preferably use methyl methacrylate.

In addition, as alkyl acrylate, for example can enumerate methyl acrylate, ethyl acrylate, butyl acrylate, 2-EHA etc., the carbon number of its alkyl is generally 1～8, is preferably 1～4.

In addition; As the monomer beyond alkyl methacrylate and the alkyl acrylate; For example; Can be for monofunctional monomer, be the compound that has 1 polymerism carbon-to-carbon double bond in the molecule, also can be, be the compound that has at least 2 polymerism carbon-to-carbon double bonds in the molecule, but preferably use monofunctional monomer for polyfunctional monomer.

As this monofunctional monomer, for example can enumerate cyaniding alkene such as styrenic monomers such as styrene, AMS, vinyltoluene, vinyl cyanide, methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide amine etc.

In addition; As polyfunctional monomer, for example can enumerate aromatic polyene based compound such as polyene-based ester, divinylbenzene of the polyprotonic acid such as alkenyl esters, diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate of the unsaturated carboxylic acid such as many esters of unsaturated carboxylic acids, allyl acrylate, allyl methacrylate, cinnamic acid allyl ester of polyvalent alcohols such as ethylene glycol dimethacrylate, butanediol dimethylacrylate, trimethylolpropane triacrylate etc.

Should explain, above-mentioned alkyl methacrylate, alkyl acrylate and the monomer beyond their can use as required separately they more than 2 kinds.

For methacrylic resin, from stable on heating viewpoint, its glass transition temperature is preferably more than 70 ℃, more preferably more than 80 ℃, further is preferably more than 90 ℃.This glass transition temperature can suit to set through kind or its ratio of adjustment monomer.

Methacrylic resin can utilize methods such as suspension polymerization, emulsion polymerization, bulk polymerization to prepare through making above-mentioned monomer component polymerization.At this moment, for the glass transition temperature that obtains suiting, or for the melt viscosity that obtains showing the formability that is configured as suitable duplexer etc., preferably when polymerization, use suitable chain-transferring agent.The addition of chain-transferring agent can the suitable decision corresponding to the kind of monomer or its ratio etc.

＜rubber particles＞

But also compound rubber particle in the acrylic resin.Here, as rubber particles, for example can use acrylic rubber particle, butadiene-based rubber particle, styrene-butadiene is rubber particles etc., but wherein, from against weather, permanance aspect, preferably uses the acrylic rubber particle.

The acrylic rubber particle is that to contain with the acrylic ester be the particle that the elastomeric polymer of main body is used as rubber constituent; It can be the particle that only comprises the single layer structure of this elastomeric polymer; Also can be layer with this elastomeric polymer, with the particle of sandwich construction of layer that for example is the polymkeric substance of main body with the methacrylate; But from the skin hardness aspect of the matt film that comprises acrylic resin, the particle of preferred sandwich construction.

In addition, this elastomeric polymer can be the homopolymer of acrylic ester, also can be the above and multipolymers below the monomer 50 weight % beyond it of acrylic ester 50 weight %.Here, as acrylic ester, use acrylic acid Arrcostab usually.

The preferred set of monomers that with the acrylic ester is the elastomeric polymer of main body becomes; With whole monomers is benchmark, alkyl acrylate 50～99.9 weight %, alkyl methacrylate 0～49.9 weight %, monofunctional monomer 0～49.9 weight % and polyfunctional monomer 0.1～10 weight % beyond them.

Here, as the alkyl acrylate in the above-mentioned elastomeric polymer, for example, previous crops is that the example of the alkyl acrylate enumerated of the composition of methacrylic resin is identical with it, and the carbon number of its alkyl is generally 1～8, is preferably 4～8.

In addition, as the alkyl methacrylate in the above-mentioned elastomeric polymer, for example, previous crops is that the example of the alkyl methacrylate enumerated of the monomer component of methacrylic resin is identical with it, and the carbon number of its alkyl is generally 1～8, is preferably 1～4.

As the monofunctional monomer beyond alkyl acrylate in the above-mentioned elastomeric polymer and the alkyl methacrylate; For example, with it previous crops to be the alkyl methacrylate enumerated of the monomer component of methacrylic resin identical with the example of monofunctional monomer beyond the alkyl acrylate.Wherein preferably use styrenic monomers such as styrene, AMS, vinyltoluene.

As the polyfunctional monomer in the above-mentioned elastomeric polymer, for example, previous crops is that the example of the polyfunctional monomer enumerated of the monomer component of methacrylic resin is identical with it, wherein preferably uses the alkenyl esters of unsaturated carboxylic acid or the polyene-based ester of polyprotonic acid.

Alkyl acrylate in the above-mentioned elastomeric polymer, alkyl methacrylate, the monofunctional monomer beyond them and polyfunctional monomer can use as required separately they more than 2 kinds.

When using the particle of sandwich construction as the acrylic rubber particle; As its suitable example; Can enumerate above-mentioned be the particle of sandwich construction of layer that the outside of layer of the elastomeric polymer of main body has with the methacrylate polymkeric substance that is main body with the acrylic ester, be about to above-mentioned with the acrylic ester be the elastomeric polymer of main body as internal layer, will be the particle of the polymkeric substance of main body with the methacrylate as the sandwich construction of outer field, at least 2 layers of structure.Here, as the methacrylate of outer field polymer monomer composition, use alkyl methacrylate usually.

In addition, outer field polymkeric substance can be that the ratio of common 10～400 weight portions, preferred 20～200 weight portions forms with elastomeric polymer 100 weight portions with respect to internal layer.Is more than 10 weight portions through making outer field polymer phase for elastomeric polymer 100 weight portions of internal layer, and the cohesion of this elastomeric polymer becomes and is difficult to take place, and it is good that the transparency of acrylic resin layer becomes.

The preferred set of monomers of above-mentioned outer field polymkeric substance becomes, and is benchmark with whole monomers, alkyl methacrylate 50～100 weight %, alkyl acrylate 0～50 weight %, monomer 0～50 weight % and polyfunctional monomer 0～10 weight % beyond them.

As the alkyl methacrylate in the above-mentioned outer field polymkeric substance, for example, previous crops is that the example of the alkyl methacrylate enumerated of the monomer component of methacrylic resin is identical with it, and the carbon number of its alkyl is generally 1～8, is preferably 1～4.Wherein preferably use methyl methacrylate.

As the alkyl acrylate in the above-mentioned outer field polymkeric substance, for example, previous crops is that the example of the alkyl acrylate enumerated of the monomer component of methacrylic resin is identical with it, and the carbon number of its alkyl is generally 1～8, is preferably 1～4.

As the monomer beyond alkyl methacrylate in the above-mentioned outer field polymkeric substance and the alkyl acrylate; For example; To be the alkyl methacrylate enumerated of the monomer component of methacrylic resin identical with the example of monofunctional monomer beyond the alkyl acrylate for previous crops with it, in addition, and as polyfunctional monomer; For example, previous crops is that the example of the polyfunctional monomer enumerated of the monomer component of methacrylic resin is identical with it.

Should explain, the alkyl methacrylate in the above-mentioned outer field polymkeric substance, alkyl acrylate, the monomer beyond them and polyfunctional monomer can use as required separately they more than 2 kinds.

In addition; Suitable example as the acrylic rubber particle of sandwich construction; Can enumerate the acrylic rubber particle of layer that further has with the methacrylate polymkeric substance that is main body in the inboard of layer that as the internal layer of above-mentioned 2 layers of structure above-mentioned is the elastomeric polymer of main body with the acrylic ester; Promptly; With this with the methacrylate be the polymkeric substance of main body as internal layer, with above-mentioned with the acrylic ester be the elastomeric polymer of main body as the middle layer, with before be that the polymkeric substance of main body is as acrylic rubber particle outer field, 3-tier architecture at least with the methacrylate.Here, the methacrylate as the polymer monomer composition of internal layer uses alkyl methacrylate usually.In addition, the polymkeric substance of internal layer can be that the ratio of common 10～400 weight portions, preferred 20～200 weight portions forms with elastomeric polymer 100 weight portions with respect to the middle layer.

The preferred set of monomers of the polymkeric substance of above-mentioned internal layer becomes, and is benchmark with whole monomers, alkyl methacrylate 70～100 weight %, alkyl acrylate 0～30 weight %, monomer 0～30 weight % and polyfunctional monomer 0～10 weight % beyond them.

As the alkyl methacrylate in the polymkeric substance of above-mentioned internal layer, for example, previous crops is that the example of the alkyl methacrylate enumerated of the monomer component of methacrylic resin is identical with it, and the carbon number of its alkyl is generally 1～8, is preferably 1～4.Wherein preferably use methyl methacrylate.

In addition, as the alkyl acrylate in the polymkeric substance of above-mentioned internal layer, for example, previous crops is that the example of the alkyl acrylate enumerated of the monomer component of methacrylic resin is identical with it, and the carbon number of its alkyl is generally 1～8, is preferably 1～4.

As the monomer beyond alkyl methacrylate in the polymkeric substance of above-mentioned internal layer and the alkyl acrylate; For example; To be the alkyl methacrylate enumerated of the monomer component of methacrylic resin identical with the example of monofunctional monomer beyond the alkyl acrylate for previous crops with it; In addition, as the example of polyfunctional monomer, previous crops is that the example of the polyfunctional monomer enumerated of the monomer component of methacrylic resin is identical with it.

Should explain, the alkyl methacrylate in the polymkeric substance of above-mentioned internal layer, alkyl acrylate, the monomer beyond them and polyfunctional monomer can use as required separately they more than 2 kinds.

The acrylic rubber particle can utilize emulsion polymerization method etc., through said before making it be that the monomer component of the elastomeric polymer of main body carries out polymerization and prepares with the acrylic ester in being at least 1 section reaction.At this moment; As described before; Form with the methacrylate in the outside of the layer of above-mentioned elastomeric polymer when being the layer of polymkeric substance of main body, can be in the presence of above-mentioned elastomeric polymer, utilize emulsion polymerization method etc. being at least to carry out polymerization in 1 section the reaction and graft on above-mentioned elastomeric polymer through the monomer component that makes this outer field polymkeric substance.

In addition; As described before; Further form when being the layer of polymkeric substance of main body at the layer of above-mentioned elastomeric polymer inboard, at first, utilize emulsion polymerization method etc. to make the monomer component of the polymkeric substance of this internal layer in being at least 1 section reaction, carry out polymerization with the methacrylate; Then; In the presence of resulting polymers, utilize the monomer component through making above-mentioned elastomeric polymer such as emulsion polymerization method in being at least 1 section reaction, to carry out the polymkeric substance that polymerization grafts on above-mentioned internal layer, and then; In the presence of the gained elastomeric polymer, utilize the monomer component through making above-mentioned outer field polymkeric substance such as emulsion polymerization method in being at least 1 section reaction, to carry out polymerization and graft on above-mentioned elastomeric polymer and get final product.Should explain, with the polymerization of each layer separately with 2 sections with on when carrying out, all be to make as a whole monomer form (rather than the monomer of each section is formed) in the scope of regulation, to get final product.

For the particle diameter of acrylic rubber particle, in this rubber particles with the acrylic ester be main body elastomeric polymer the layer mean grain size be preferably 0.01～0.4 μ m, more preferably 0.05～0.3 μ m further is preferably 0.07～0.25 μ m.The mean grain size of the layer of this elastomeric polymer is during greater than 0.4 μ m, and the transparency that then comprises the matt film of acrylic resin reduces, and is concerning that transmissivity reduces, so not preferred.In addition, the mean grain size of the layer of this elastomeric polymer is during less than 0.01 μ m, and then the skin hardness of matt film reduces the easy damaged that becomes, so not preferred.

Should explain; For above-mentioned mean grain size, can the acrylic rubber particle be mixed with methacrylic resin and membranization, in its section, utilize ruthenium-oxide that the layer of above-mentioned elastomeric polymer is implemented dyeing; Through electron microscope observation, obtain by the diameter of dyed part.

That is, with the acrylic rubber mix particles in methacrylic resin, when its section is dyeed with ruthenium-oxide; The methacrylic resin of parent phase can not be colored; With the methacrylate be main body polymkeric substance the layer be present in above-mentioned elastomeric polymer the layer the outside time, this outer field polymkeric substance can not be colored yet and since only above-mentioned elastomeric polymer the layer can be colored; Like this, can obtain particle diameter from diameter dyed, that be viewed as the part of circular shape with electron microscope.When being the layer of the polymkeric substance of the main body layer that is present in above-mentioned elastomeric polymer inboard with the methacrylate; The polymkeric substance of this internal layer can not be colored yet; Then under the state of 2 layers of structure being colored of layer of the above-mentioned elastomeric polymer in its outside, observe; At this moment, with the outside of 2 layers of structure, be that the external diameter of the layer of above-mentioned elastomeric polymer is considered to get final product.

Rubber particles is proportional for below the 40 all weight % of acrylic resin, below the preferred 30 weight % with respect to containing of acrylic resin.Containing of rubber particles is proportional during greater than all 40 weight % of acrylic resin, and the skin hardness of matt film reduces the easy damaged that becomes.

＜cyclic olefine resin＞

As the cyclic olefine resin; It is selected from the hydride of the ring-opening polymerization polymer of bicyclopentadiene be the various cyclic olefin polymers of representative, with the multipolymer of bicyclopentadiene or tetracyclododecane and ethene be in various cyclic olefine copolymers and hydride, the norbornene-based polymer etc. of representative more than a kind; For example; Be to have like ENB or the thermoplastic resin of the unit of the monomer that encircles the norborneol alkene monomer more, constitute by cycloolefin; Except being the hydrogenation thing of the ring-opening polymerization polymer of above-mentioned cycloolefin or the ring opening copolymer thing that uses cycloolefin more than 2 kinds, can also be cycloolefin and chain alkene or addition copolymer with aromatics of vinyl.In addition, can also import polar group.

When being made as cycloolefin and chain alkene or having the multipolymer of aromatics of vinyl; Example as chain alkene; Can enumerate ethene or propylene etc.; And, can enumerate styrene, AMS, phenyl ring by substituted styrene of alkyl etc. as the example of aromatics with vinyl.In this analog copolymer, the unit of the monomer that is made up of cycloolefin is 50 moles below the %, for example, and can be for about 15～50 moles of %.Especially, when being made as cycloolefin, chain alkene and having the terpolymer of aromatics of vinyl, the unit of the monomer that is made up of cycloolefin can be so less amount.In the said terpolymer, the unit of the monomer that is made up of chain alkene is generally 5～80%, and the unit of the monomer that is made up of the aromatics with vinyl is generally 5～80%.

As commercially available thermoplasticity cyclic olefine resin, " Topas " of the Ticona company sale of Germany, " アート Application ", " ゼオノア (ZEONOR) " and " ゼオネッ Network ス (ZEONEX) ", (being trade name) such as " アペ Le " that Mitsui Chemicals (strain) is sold that Japanese ゼオ Application (strain) is sold that JSR (strain) sells are arranged.

Should explain, as the cyclic olefine resin, preferably glass transition temperature be more than 100 ℃, preferred more than 130 ℃.

＜polyester based resin＞

As polyester based resin, for example can enumerate polyethylene terephthalate, PEN etc., can enumerate crystallinity polyester or non-crystalline polyester, but, be preferably non-crystalline from the viewpoint of the transparency.

Polyester based resin can be made up of the polyester resin composition that comprises crystallinity polyester and non-crystalline polyester.Polyester based resin is meant dibasic acid and polyvalent alcohol polycondensation and the material of making.

As dibasic acid, for example can enumerate terephthalic acid (TPA), m-phthalic acid, 2, aliphatic dicarboxylic acid such as aromatic dicarboxylic acid such as 6-naphthalenedicarboxylic acid or hexane diacid etc.

In addition,, for example can enumerate monoethylene glycol, 1,4-butylene glycol, 1,4 cyclohexane dimethanol, five glycol, 2, glycol such as 2-dimethyl trimethylene, hexamethylene glycol, neopentyl glycol as polyvalent alcohol.

Above-mentioned dibasic acid and polyvalent alcohol use through combination arbitrarily.Specifically can enumerate terephthalic acid (TPA)/glycol copolymer or terephthalic acid (TPA)/monoethylene glycol/1,4 cyclohexane dimethanol terpolymer, 2,6-naphthalenedicarboxylic acid/glycol copolymer, terephthalic acid (TPA)/1,4-butylene glycol multipolymer etc.

As the crystallinity polyester, for example can enumerate as trade name " バイロ Application " (Japan weaving (strain) system) and commercially available resin etc.

As non-crystalline polyester; For example can enumerate amorphism polyethylene terephthalate (so-called APET) or terephthalic acid (TPA)/monoethylene glycol/1,4 cyclohexane dimethanol terpolymer (example: trade name " PETG "! イーストマ Application ケミカ Le (strain) system)) etc.

＜phenylethylene resin series＞

As phenylethylene resin series; It is the polymkeric substance more than the styrene units 50 quality % that contain as its formation unit, more than the preferred 70 quality %; As long as contain more than the styrene units 50 quality %, then also can for one of which part by the multipolymer that can replace with styrene copolymerized simple function unsaturated monomer unit.

But, for example can enumerate methyl acrylic esters such as Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, methacrylic acid phenylester, methacrylic acid benzyl ester, methacrylic acid 2-Octyl Nitrite, 2-hydroxyethyl methacrylate as the simple function unsaturated monomer of copolymerization; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, acrylic acid benzyl ester, 2-EHA, acrylic acid 2-hydroxy methacrylate; Unsaturated acids such as methacrylic acid, acrylic acid; AMS, methacrylonitrile, maleic anhydride, phenyl maleimide, cyclohexyl maleimide etc.In addition, this multipolymer also can further contain glutaric anhydride unit, glutarimide unit.

And then, also can contain blend in aforementioned polymer, the multipolymer as the blend of the diene series rubber of rubber-like polymer, acrylic rubber etc.

＜methyl methacrylate-phenylethylene resin series＞

As methyl methacrylate-phenylethylene resin series, for example can enumerate the multipolymer of styrene units content 20 quality %～95 quality % and methyl methacrylate units content 80 quality %～5 quality %, the multipolymer that content 70 quality % in optimization styrene unit are above and methyl methacrylate units content 30 quality % are following etc.

＜AS be resin＞

As AS (acrylonitrile-styrene) is resin, for example can enumerate the monomeric unit of deriving by vinyl cyanide with the monomeric unit random copolymerization of deriving by styrene multipolymer etc.The content of the monomeric unit of being derived by vinyl cyanide is generally 2～50 weight % (promptly, the content of the monomeric unit of being derived by styrene be generally 98～50 weight %), is preferably 20～30 weight % (content of the monomeric unit of promptly, being derived by styrene is preferably 80～70 weight %).Wherein, the monomeric unit that is in the resin to be contained with AS add up to 100 weight.

＜ABS be resin＞

As ABS (acrylonitrile-butadiene-styrene (ABS)) is resin, for example can enumerate aforementioned AS be the following degree of graft polymerization 40 weight % in the resin ethylene series rubber (for example, polybutadiene rubber) and multipolymer etc.

In addition; Approach the viewpoint of the refractive index value of rubber constituent from the refractive index value that makes resinous principle in order to obtain the good transparency; As resinous principle, but preferably as the so-called transparent ABS of the multipolymer of the monomer of styrene and methyl methacrylate and other copolymerization.

But, for example can enumerate vinyl cyanide as the monomer of copolymerization.In addition, for transparent ABS, for example can enumerate among the JP2006-265406A disclosed.

" diaphragm " according to the invention is to process with the resin that contains polyolefin-based resins at least." resin that contains polyolefin-based resins at least " can only contain polyolefin-based resins, formed by a kind of resin basically, also can in polyolefin-based resins, contain the combination of all kinds resin, also can contain other resin beyond the polyolefin-based resins." resin that contains polyolefin-based resins at least " when containing the resin more than 2 kinds, and when containing resin additive, be resin combination then, but be referred to as " resin " in this instructions.

[polyolefin-based resins]

" polyolefin-based resins " is to say the polymkeric substance that contains the monomeric unit of being derived by alkene, do not contain above-mentioned " cyclic olefine resin ".

As alkene, be preferably at least a kind that is selected from ethene, propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, the 1-octene.

" polyolefin-based resins " also can carry out modification with other monomer (below be also referred to as " compound is used in modification ") with olefinic double bond.

" polyolefin-based resins " of the present invention is preferably and is selected from polyethylene-based resin, polypropylene-based resin and is at least a in the resin as their improved polyalkene of modification body.When duplexer of the present invention is used for liquid crystal indicator, owing to diaphragm finally can be stripped from, so polyethylene-based resin that preferred use can obtain at lower cost or polypropylene-based resin.

＜polyethylene-based resin＞

As polyethylene-based resin, for example can enumerate Alathon, ethylene-propylene random copolymer, ethene-alpha-olefin copolymer etc.

As the alpha-olefin that is used for ethene-alpha-olefin copolymer; Can enumerate 1-butylene, 2-methyl isophthalic acid-propylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butylene, 2; 3-dimethyl-1-butylene, 1-amylene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butylene, 1-heptene, methyl isophthalic acid-hexene, dimethyl-1-amylene, ethyl-1-amylene, trimethyl-1-butylene, Methylethyl-1-butylene, 1-octene, Methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl group-1-heptene, Methylethyl-1-heptene, trimethyl-1-amylene, propyl group-1-amylene, diethyl-1-butylene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene etc.Wherein, preferably use 1-butylene, 1-amylene, 1-hexene, 1-octene.

＜polypropylene-based resin＞

As polypropylene-based resin, for example can enumerate Noblen, propylene-ethylene random copolymers, propylene-alpha-olefin random copolymers, propylene-ethylene-alpha olefin copolymer, comprise the Noblen composition or mainly comprise the polypropylene-based multipolymer etc. of multipolymer composition of multipolymer composition and propylene and the ethene and/or the alpha-olefin of propylene.These polypropylene-based resins can use separately or and with more than 2 kinds the use.

As the alpha-olefin that is used for polypropylene-based resin, for example can enumerate the compound identical etc. with the alpha-olefin that is used for ethene-alpha-olefin copolymer.

＜improved polyalkene be resin＞

Improved polyalkene is that resin can pass through; For example, polyolefin is carried out modification with modifications such as maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, GMA, methacrylic acid hydroxyl ethyl ester, methyl methacrylates with compound and get.Polyolefin used herein can be known polyolefin, for example can enumerate vinylite, isotactic polypropylene, syndiotactic polypropylenes, contain comonomer the random polypropylene, utilize multi-stage polymeric the block type polypropylene, gather (4-methyl-1-pentene), gather (1-butylene) etc.

" resin that contains polyolefin-based resins at least " of the present invention can be the resin combination that contains following compositions (a) and composition (b).

Composition (a): crystalline polyolefin and

Below, " resin combination ", " crystalline polyolefin " and " amorphism polymkeric substance " and " tree oil lipid " etc. are described.

[resin combination]

Resin combination contains 2 kinds of component of polymer.Preferably 2 kinds of component of polymer are composition (a) and composition (b), composition (a) be crystalline polyolefin, composition (b) for be selected from amorphism polymkeric substance and the tree oil lipid more than a kind.

＜crystalline polyolefin＞

Crystalline polyolefin is the polymkeric substance that contains the monomeric unit of being derived by alkene, be in differential scanning calorimetric determination (DSC) according to JIS K7122, to observe the crystallization melting caloric-100～200 ℃ scopes be that crystallization fusion peak or crystallization heat more than the 30J/g is any one the polymkeric substance in the crystallization peak more than the 30J/g.

Crystalline polyolefin be preferably with a kind that is selected from ethene, propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene carry out homopolymerization or carry out copolymerization more than 2 kinds and crystalline polyolefin.As crystalline polyolefin, optimization polypropylene based polymer or polyethylene-based polymkeric substance, more preferably polypropylene-based polymkeric substance.As polypropylene-based polymkeric substance; Specifically can enumerate Noblen, propylene-ethylene copolymers, propylene-butene-1 copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-butene-1 copolymer, propylene-ethylene-1-hexene copolymer etc.; Wherein, Preferred Noblen or the alkene beyond the propylene and the multipolymer of propylene; As the alkene beyond the propylene and the multipolymer of propylene, preferred propylene-ethylene copolymers, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer.These crystalline polyolefins can use a kind, also can mix more than 2 kinds and use.In addition, as these polymkeric substance, can use these polymkeric substance of various structures such as random, block type.

The melt flow rate of crystalline polyolefin (MFR) is generally 0.1～50g/10 branch, from extruding the viewpoint of processability, is preferably 0.5～30g/10 branch.Should explain that this MFR measures according to JIS K7210, under 230 ℃ of temperature, loading 21.18N.

As the manufacturing approach of crystalline polyolefin, can use the known polymerization that utilizes known catalyst for olefines polymerizing.For example; Can enumerate used Ziegler-Natta series catalysts, metallocene be complex compound or Nonmetallocene be complex compound series catalysts such as complex compound, slurry polymerization process, solution polymerization process, mass polymerization, gaseous polymerization etc.; And, used mass polymerization, solution polymerization process of radical initiator etc.

In addition, also can use commercially available correspondence article.

In addition, also can use commercially available polyolefin polymkeric substance, for example, can enumerate the crystalline polypropylene based polymer “ ノー Block レ Application W151 of Sumitomo Chemical (strain) society system corresponding to crystalline polyolefin of the present invention " etc.

< amorphism polymkeric substance >

The amorphism polymkeric substance means the polymkeric substance of amorphism or low-crystalline, be the melting caloric that in differential scanning calorimetric determination ,-50～200 ℃ scopes, both do not observed the crystallization of observation according to JIS K7122 be more than the 30J/g crystallization fusion peak, do not observe the polymkeric substance that the crystallization heat is the crystallization peak more than the 30J/g yet.

From reducing the viewpoint of warpage, it is 60 moles below the % that the amorphism polymkeric substance preferably contains structural unit, this content of deriving from ethene, more preferably 50 moles below the %, further is preferably 30 moles below the %.

The amorphism polymkeric substance is preferably olefin polymer; As the alkene that is used to obtain this polymkeric substance; For example can enumerate the alpha-olefin of ethene, propylene, carbon number 4～20; Alpha-olefin as carbon number 4～20; For example can enumerate alpha-olefin, 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, the 2-ethyl-1-hexene, 2 of straight chain shapes such as 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene; 2, the alpha-olefin of 4-trimethyl-branched such as 1-amylene etc.

The amorphism polymkeric substance also can contain the monomeric unit that derives from the monomer beyond the alpha-olefin, as the monomer beyond the alpha-olefin, for example can enumerate polyenic compounds, cycloolefin, vinyl aromatic compounds etc.Derive from the content of the monomeric unit of the monomer beyond the alpha-olefin, when all being 100 moles of %, be preferably 20 moles below the % with composition (b).

As polyenic compounds, for example can enumerate conjugated polyene compound, unconjugated polyene compound etc.As conjugated polyene compound; For example can enumerate aliphatics conjugated polyene compound or ester ring type conjugated polyene compound etc.; As the unconjugated polyene compound, for example can enumerate aliphatics unconjugated polyene compound, ester ring type unconjugated polyene compound, aromatic series unconjugated polyene compound etc.Substituting groups such as they also can alkoxy, aryl, aryloxy group, aralkyl, aralkoxy replace.

As cycloolefin, for example can enumerate ENB, 5-methyl ENB, 5-ethyl ENB, 5-propyl group ENB, 5,6-dimethyl ENB, 1-methyl ENB, 7-methyl ENB, 5,5,6-trimethyl ENB, 5-phenyl ENB, 5-benzyl ENB, 5-ethylidene norbornene, 5-vinyl norbornene, 1,4,5,8-dimethylene-1,2,3; 4,4a, 5,8,8a-octahydro naphthalene, 2-methyl isophthalic acid, 4,5,8-dimethylene-1,2,3; 4,4a, 5,8,8a-octahydro naphthalene, 2-ethyl-1,4,5,8-dimethylene-1,2,3; 4,4a, 5,8,8a-octahydro naphthalene, 2,3-dimethyl-1,4,5,8-dimethylene-1,2; 3,4,4a, 5,8,8a-octahydro naphthalene, 2-hexyl-1,4,5,8-dimethylene-1,2; 3,4,4a, 5,8,8a-octahydro naphthalene, 2-ethylidene-1,4,5,8-dimethylene-1,2; 3,4,4a, 5,8,8a-octahydro naphthalene, 2-fluoro-1,4,5,8-dimethylene-1,2; 3,4,4a, 5,8,8a-octahydro naphthalene, 1,5-dimethyl-1,4,5,8-dimethylene-1; 2,3,4,4a, 5,8,8a-octahydro naphthalene, 2-cyclohexyl-1,4,5,8-dimethylene-1; 2,3,4,4a, 5,8,8a-octahydro naphthalene, 2,3-two chloro-1,4; 5,8-dimethylene-1,2,3,4,4a, 5,8,8a-octahydro naphthalene, 2-isobutyl-1; 4,5,8-dimethylene-1,2,3,4,4a, 5,8; 8a-octahydro naphthalene, 1,2-dihydro bicyclopentadiene, 5-chlorine ENB, 5,5-dichloro ENB, 5-fluorine ENB, 5,5,6-three fluoro-6-trifluoromethyl ENBs, 5-chloromethyl ENB, 5-methoxyl ENB, 5,6-dicarboxyl ENB dehydrate (ア Application Ha イ De レート), 5-dimethylamino ENB, 5-cyanic acid ENB, cyclopentene, 3-methyl cyclopentene, 4-methyl cyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorine cyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethyl cyclohexene, 3-chlorine cyclohexene, cycloheptene etc.

As vinyl aromatic compounds, for example can enumerate styrene, AMS, p-methylstyrene, vinyl-dimethyl benzene, monochloro styrene, dichlorostyrene, single bromstyrol, Dowspray 9, fluorobenzene ethene, to t-butyl styrene, ethyl styrene, vinyl naphthalene etc.

As the amorphism polymkeric substance; For example can enumerate hydrogenation thing, ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer, ethene-1-heptene multipolymer, ethene-1-octene copolymer, ethene-1-nonene multipolymer, ethene-1-decene multipolymer, ethene-1-undecylene multipolymer, ethene-1-dodecylene multipolymer, ethene-1-tridecylene multipolymer, ethene-tetradecene multipolymer, ethene-1-15 carbene multipolymers, ethene-cetene multipolymer, ethene-1-heptadecene multipolymer, ethene-1-vaccenic acid multipolymer, ethene-1-19 carbene multipolymers, ethene-1-eicosylene multipolymer, propylene-butene-1 copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-1-heptene multipolymer, propylene-1-octene copolymer, propylene-1-nonene multipolymer, propylene-1-decene multipolymer, propylene-1-undecylene multipolymer, propylene-1-dodecylene multipolymer, propylene-1-tridecylene multipolymer, propylene-tetradecene multipolymer, propylene-1-15 carbene multipolymers, propylene-cetene multipolymer, propylene-1-heptadecene multipolymer, propylene-1-vaccenic acid multipolymer, propylene-1-19 carbene multipolymers, propylene-1-eicosylene multipolymer, ethylene-propylene-butene-1 copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethene-1-butene-1-hexene copolymer of vinyl aromatic compounds-conjugated diene compound multipolymer, vinyl aromatic compounds-conjugated diene compound multipolymer etc.; Wherein, Preferred propylene-butene-1 copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, ethylene-propylene-butene-1 copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer; More preferably propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, further preferred propylene-butene-1 copolymer.These amorphism polymkeric substance can use separately or mix more than 2 kinds and use.

The limiting viscosity of amorphism polymkeric substance [η] is preferably 0.5～10dl/g, and more preferably 0.9～5dl/g further is preferably 1.2～3dl/g.[η] is too small for limiting viscosity, then can produce in the gained duplexer and be clamminess, and can only obtain low-value product sometimes, and excessive then sheet adds the moment of torsion that has extruder man-hour and increases, and is difficult to the situation of processability variation such as extruding.Should explain that limiting viscosity [η] is in 135 ℃ tetralin solvent, to measure.

From improving the viewpoint that warpage suppresses effect, the molecular weight distribution of amorphism polymkeric substance is preferably 1～3.Should explain that this molecular weight distribution is a weight-average molecular weight (Mw) and the ratio (Mw/Mn) of number-average molecular weight (Mn), is to utilize gel permeation chromatography (GPC), measure for the molecular weight standard material with the polystyrene standard.

As the polymerization of amorphism polymkeric substance, for example can adopt slurry polymerization process, solution polymerization process, mass polymerization, gaseous polymerization etc., can make through the monomer that utilizes the metallocene catalyst polymerisation regulation.As metallocene catalyst, for example can enumerate the metallocene series catalysts of record among JP58-19309A, JP60-35005A, JP60-35006A, JP60-35007A, JP60-35008A, JP61-130314A, JP3-163088A, JP4-268307A, JP9-12790A, JP9-87313A, JP11-80233A, the JP10-508055A etc.

In addition, as the manufacturing approach of the amorphism polymkeric substance that has used metallocene catalyst, the manufacturing approach of putting down in writing among the preferred EP1211287A.

As the amorphism polymkeric substance, for example can enumerate the polymkeric substance of putting down in writing among the JP11-193309A.As commercially available article; Can enumerate タ Off セレ Application T3712, T3722 that ダイ Na ロ Application 6200P, 1320P, 1321P, Sumitomo Chemical (strain) that BL series, JSR (strain) such as タフマー P series, A that Mitsui Chemicals (strain) makes are serial, BL4000, BL3450, BL2481 make are made, T3522, etc.Wherein, From viewpoint excellent with the intermiscibility of composition of the present invention (B), that can obtain the excellent film of the transparency, タフマー XM-7070, XM-7080 that the タ Off セレ Application T3722 that preferred Sumitomo Chemical (strain) is made, T3712, T3522, H5002, Mitsui Chemicals (strain) are made.

Should explain; The amorphism polymkeric substance can be mixed with crystalline polymer; For example, can be with amorphism polymkeric substance and the mixing composition that obtains of crystalline polymer or use crystalline polymer lining amorphism polymkeric substance, internal layer to be amorphism polymkeric substance, the outer polymkeric substance that constitutes as the multilayer of crystalline polymer.In the polymkeric substance that multilayer constitutes; Viewpoint from the buckling deformation that suppresses plywood; During as 100 weight %, preferred amorphism polymkeric substance is that 80～99 weight %, crystalline polymer are 1～20 weight % with the total of the amorphism polymkeric substance of internal layer and outer field crystalline polymer.

＜tree oil lipid＞

Tree oil lipid be the melting caloric that in differential scanning calorimetric determination ,-50～200 ℃ scopes, both do not observed the crystallization of observing according to JIS K7122 be more than the 30J/g crystallization fusion peak, do not observe the resin that the crystallization heat is the crystallization peak more than the 30J/g yet.

As tree oil lipid, can enumerate synthesizing petroleum resin, rosin series resin, terpenic series resin.As synthesizing petroleum resin, for example can enumerate homopolymer or multipolymer, aliphatics through-stone oleoresin, aromatic series through-stone oleoresin, ester ring type through-stone oleoresin, the aliphatics-ester ring type multipolymer of C 5 fraction, C6～C11 cut and other ethylene series cut of naphtha pyrolysis oil etc. as the hydride of these homopolymer or multipolymer.As synthesizing petroleum resin, and then can enumerate the multipolymer of above-mentioned naphtha pyrolysis oil and terpenes or as the copolymerization through-stone oleoresin of the hydride of this multipolymer etc.

As the C 5 fraction of naphtha pyrolysis oil, for example can enumerate amylene class, bicyclopentadiene etc. such as methyl butene classes such as isoprene, cyclopentadiene, 1,3-pentadiene, 2-methyl-1-butene alkene, 2-methyl-2-butene, 1-amylene, 2-amylene.As C6～C11 cut, for example can enumerate indenes, styrene, adjacent vinyltoluene, a vinyltoluene, to methyl styrene classes such as vinyltoluene, AMS, Beta-methyl styrene, methyl indenes, ethyl indenes, vinyl-dimethyl benzene, propenylbenzene etc.As other ethylene series cut, for example can enumerate butylene, hexene, heptene, octene, butadiene, octadiene etc.The synthesizing petroleum resin that uses among the present invention is preferably the synthesizing petroleum resin through hydrogenation.The cyclopentadiene that hydrogenated petroleum resin, ア Le コ Application P-115, P-125, the P140 、トーネッ Network ス (strain) that particularly, can use waste river chemistry (strain) to make is hydrogenated petroleum resin, エスコレッ Star 5320HC etc.

＜rosin series resin＞

As the rosin series resin, for example can enumerate by natural material, be pine tree obtain gum rosin, wood rosin and toll oil rosin etc.As this rosin series resin, preferably utilize methods such as hydrogenation, disproportionation and dimerization and stabilized rosin series resin.Particularly, can use disproportionated rosin 、スーパーエステ Le A-115 that waste river chemistry (strain) makes etc.

< terpenic series resin >

As the terpenic series resin, for example can enumerate with the terpenic series resin that is the terpenic series resin made of raw material by natural material gained terpinol, makes by orange peel etc.This terpenic series resin is preferably the terpenic series resin through hydrogenation.Particularly, can use hydrogenated terpene resin that ヤス Ha ラケミカ Le (strain) makes, Network リアロ Application P-115, P-125 etc.

With composition (a) and composition (b) add up to 100 weight % the time; Viewpoint from the buckling deformation that suppresses plywood; Resin combination preferably contains composition (a) 80～99 weight %, composition (b) 1～20 weight %, more preferably contains composition (a) 90～99 weight, composition (b) 1～10 weight %.

Should explain, in thermoplastic resin and the resin combination, also can cooperate other composition as required, for example, light diffusing agent, ultraviolet light absorber, organic system dyestuff, inorganic based dye, pigment, anti-oxidant, antistatic agent, surfactant etc.

The preparation method of resin combination so long as with composition (a) and composition (b) evenly mixing method get final product, for example, can enumerate the method for following (1) or (2).

(1) composition (a) and composition (b) are stirred the method that (Ha Application De Block レ Application De) etc. mixes, the gained potpourri is carried out with single shaft extruder or biaxial extruder etc. melting mixing through ribbon blender, Henschel mixer, drum mixer or hand-held.

(2) part of composition (a) is used with above-mentioned (1) identical method with composition (b) mixed; And then melting mixing; Obtain containing the masterbatch pellet of the above composition (b) of 20 weight %, follow, this masterbatch pellet and remaining composition (a) are used with above-mentioned (1) identical method mixed; So that composition in the resin combination (a) and amount (b) reach ormal weight, and then carry out the method for melting mixing.

Contain the method for above-mentioned (2) of the masterbatch pellet of the composition (b) more than the 20 weight % as preparation, for example, can enumerate the method for putting down in writing among the JP2000-72923A.In addition, in the gained masterbatch pellet, in the scope of not damaging effect of the present invention, also can carry out processing such as sulfur-crosslinked processing, peroxide crosslinking processing, peroxide breakdown processing, metal ion crosslinked processing, crosslinked with silicane processing.And then, can also spread the shop on the surface of this masterbatch pellet as required and be selected from least a powder in anti-oxidant, lime carbonate, barium sulphate, silicon dioxide, talcum, stearic acid and the polyolefin powder.

[duplexer]

Duplexer of the present invention is that diaphragm directly is laminated in the duplexer on the delustring face at least of matt film.

Further, duplexer of the present invention is preferred also is not delustring face (male and fomale(M&F)) with the protection face of matt film.

The thickness of duplexer is 30～400 μ m, is preferably 50～300 μ m, more preferably 70～250 μ m.Thickness is during less than 30 μ m, and then the duplexer self rigidity can reduce, so becomes in the duplexer and be easy to generate fold, under solid state, becomes to be easy to generate to heave (floating I) etc.When thickness was thicker than 400 μ m, then the manufacturing cost of duplexer uprised, and when gained duplexer and polarisation separating sheet are fitted, the thickness thickening of the polarisation separating sheet after the applying was arranged then, and so the situation of the thickness thickening of liquid crystal panel as a result is not preferred.

The thickness of the preferred matt film of duplexer is the thickness more than 60% with respect to the duplexer gross thickness, the more preferably thickness more than 70%.The thickness of matt film with respect to the duplexer gross thickness less than 60% o'clock, for example, across diaphragm with the delustring shape transferred thereon during in matt film, then might can't be with sufficient delustring shape transferred thereon in matt film.

In addition, the thickness of diaphragm is preferably 5～50 μ m, further is preferably 10～40 μ m.When thickness is thicker than 50 μ m, for example, across diaphragm with the delustring shape transferred thereon during in matt film, then might be with sufficient delustring shape transferred thereon in matt film, during less than 5 μ m, then the defencive function of diaphragm reduces, and might rupture when peeling off.

In addition, the mist degree of the matt film after diaphragm peeled off from duplexer is preferably below 90%, more preferably below 85%.Mist degree did not then show sufficient antiglare effect sometimes less than 25% o'clock.In addition, surpass at 90% o'clock, then when this film was used for liquid crystal indicator, picture can fade sometimes, caused that image quality reduces.

Phase difference value is preferably below the 30nm in the face of the incident light under the wavelength 590nm of matt film, further is preferably below the 20nm.

For example, when the matt film of having peeled off the diaphragm among the present invention is used for liquid crystal indicator, because the only polarisation that utilizes in the liquid crystal display, so require the little film of optical strain, the phase difference value below the preferred 30nm.Even if in liquid crystal indicator is used, it is low being used to protect the also preferred phase difference value of polarisation separating sheet diaphragm of polarisation separating sheet, so that do not upset the polarization direction of the polarisation that is come by the outgoing of polarisation separating sheet as far as possible, phase difference value is more preferably below the 20nm.

In the delustring face of matt film 60 degree mirror surface luster is preferably below 60%, more preferably below 50%.60 degree mirror surface lusters surpass at 60% o'clock, when then matt film contacts with liquid crystal panel, might interfere the rainbow decorative pattern due to the striped.

In the duplexer, matt film and diaphragm are peelable.Here, peelable being illustrated in directly range upon range of matt film and diaphragm can be peeled off the opposing party's film from a side film, and be divided into each film.

In the duplexer, the splitting power of matt film and diaphragm is preferably 5～50g/25mm width, 7～40g/25mm width more preferably.

Splitting power is during less than the 5g/25mm width; When duplexer applies external force when reeling or in transporting and then when cutting etc.; Diaphragm might be peeled off from duplexer, when higher than 50g/25mm width, then might when peeling off diaphragm, cause damage to matt film.

Matt film is used for diffusion, angle (angle) to be acted on, prevents with the adhesion of other member or through various purposes such as diaphragm surface such as contacting; For example; In liquid crystal indicator, can be used for being integrated in diaphragm, reflectance coating or the LGP etc. of light diffusing sheet, optical diffusion film, polarization board protective film, phase retardation film, brightness enhancement film etc. or polarisation separating sheet of backlight illuminating unit.In addition, also applicable to CD or automotive interior trim with film, illumination with film, building materials with in the film etc., the present invention is not limited to such use.The optical applications of diaphragm etc. that wherein, can be used for the polarisation separating sheet (brightness enhancement film) of liquid crystal indicator especially aptly.

Matt film or diaphragm are not limited to individual layer and constitute, and as required, also can constitute for the multilayer more than 2 layers.As matt film, for example can enumerate layer that comprises acrylic resin and cascade the 2 layers formation of layer that comprise polycarbonate-based resin etc.

The manufacturing approach of＜duplexer＞

The manufacturing approach of duplexer of the present invention (below; Be sometimes referred to as manufacturing approach of the present invention) have usually: thermoplastic resin and the resin that contains polyolefin-based resins are at least melt extruded respectively, and the thermoplastic resin (A) of fusion is range upon range of and obtain the operation (1) of membranoid substance with the resin bed that contains polyolefin-based resins at least (B) of fusion; And membranoid substance inserted between excipient roller and the touch roll; So that the face of the resin that contains polyolefin-based resins at least of membranoid substance contacts with the excipient roller; And contain the resin of polyolefin-based resins at least via this that joins with this excipient roller; Make the delustring shape transferred thereon that is formed at excipient roller surface to the face of the thermoplastic resin that joins with the resin that contains polyolefin-based resins at least, to form the operation (2) of delustring shape.

Through adopting above-mentioned manufacturing approach, can suppress the generation of fold on the diaphragm.

As the formation method of the delustring shape of using the excipient roller, it is that the use outer peripheral face is formed with the method that the metallic roll of concaveconvex shape is carried out transfer printing when coextrusion is shaped, for example can enumerate the method put down in writing among JP2009-196327A, the JP2009-202382A etc.

Below, with reference to accompanying drawing manufacturing approach of the present invention is elaborated.

Fig. 1 is the diagrammatic illustration figure of an embodiment of expression manufacturing approach of the present invention.

As shown in the drawing; For this embodiment; Being fed into the resin that melt extrudes the thermoplastic resin in the

machine

1,2 and contain polyolefin-based resins at least is melted mixing; After being supplied to allocation block 3 separately and being assigned with,, and be extruded as membranoid substance from branch manifold mould 4 front ends in branch manifold mould 4 (T mould) inner stacks with the mode that the layer that forms expectation constitutes.

In this embodiment, the resin bed (B) that usually will contain polyolefin-based resins at least with mould inner stacks mode is laminated in thermoplastic resin (A), and integrated.Particularly; For example; The thermoplastic resin and the polyolefin-based resins that are supplied to the allocation block 3 of two kinds of three layers or two kinds two-layer distribution type distribute in allocation block 3, so that contain the two sides that the resin bed (B) of polyolefin-based resins is dispensed to thermoplastic resin (A) at least, and perhaps so that contain the one side that the resin bed (B) of polyolefin-based resins is dispensed to thermoplastic resin (A) at least; In branch manifold mould 4, carry out range upon range ofly, and turned to 3-tier architecture or 2 layers of structure by one.

The temperature of extruder 1, extruder 2 and branch manifold mould 4 is set and can suited to adjust according to used resin; Use polycarbonate-based resin as thermoplastic resin, use polyethylene-based resin when containing the resin of polyolefin-based resins at least, preferred extruder 1 is that 220～300 ℃, extruder 2 are that 210～300 ℃, the temperature of branch manifold mould 4 are set at 260～300 ℃.

In addition; Use polycarbonate-based resin as thermoplastic resin, use polypropylene-based resin when containing the resin of polyolefin-based resins at least, preferred extruder 1 is that 210～290 ℃, extruder 2 are that 210～280 ℃, the temperature of branch manifold mould 4 are set at 250～290 ℃.

If outside above-mentioned scope, then might form the film in uneven thickness of each layer because of viscosity ratio.In addition, polyethylene-based resin might form impurity such as flake etc. because of the gelation due to crosslinked, and polypropylene-based resin then can might form bad order etc. because of the foaming due to decomposing, and is inappropriate for optical applications so become.

Further; At least the resin that contains polyolefin-based resins is when containing the resin combination of mentioned component (a) and composition (b); Use polycarbonate-based resin as thermoplastic resin, use the crystalline polypropylene based polymer in as resin combination during contained composition (a), preferred extruder 1 is that 210～290 ℃, extruder 2 are that 210～280 ℃, the temperature of branch manifold mould 4 are set at 250～290 ℃.In addition; Using polycarbonate-based resin as thermoplastic resin, the polyethylene-based polymkeric substance of crystallinity in as above-mentioned resin combination during contained composition (a), preferred extruder 1 is that 220～300 ℃, extruder 2 are that 210～300 ℃, the temperature of branch manifold mould 4 are set at 260～300 ℃.

If outside above-mentioned scope, then might form the film in uneven thickness of each layer because of viscosity ratio.In addition, the crystalline polypropylene based polymer then can might form bad order etc. because of the foaming due to decomposing, and the polyethylene-based polymkeric substance of crystallinity can might form impurity such as flake etc. because of the gelation due to crosslinked, is inappropriate for optical applications so become.

Should explain, in this embodiment, use the branch manifold method of utilizing allocation block 3 and branch manifold mould 4, but also can replace it and use for example as the feed piece! フィー De Block ロッ Network) the double slit mould etc. of overlapped way or mould outer stack mode.Wherein, because the thickness and precision of each layer is excellent more, so the preferred branch manifold mode of using.

Then; At least contain the side that resin bed (B) conduct of polyolefin-based resins contacts with excipient roller 6 (chill roll); And will sandwich by the resin that branch manifold mould 4 is extruded between the touch roll 5 (chill roll 5) and excipient roller 6 of subtend configuration on the general horizontal direction; With on the resin bed that contains polyolefin-based resins at least (B) at least one surface with delustring shape transferred thereon to thermoplastic resin (A), thus the shaping duplexer.And then volume is taken in the duplexer on the excipient roller 6 through between excipient roller 6 and the mirror roller 7 (chill roll), and utilizes mirror roller 7 and be slowly cooled, and can obtain duplexer 8 with the haulage speed of stipulating.

Touch roll 5 general diameters are about 200～1000mm, for example, comprise rubber rollers or metallic elastic roller.

The temperature of touch roll 5 can for example, using polycarbonate-based resin as thermoplastic resin, when using the polyethylene-based resin conduct to contain the resin of polyolefin-based resins at least, be generally 10～160 ℃ according to the suitable adjustment of used resin, is preferably 15～150 ℃.In addition,, be generally 10～170 ℃, be preferably 15～160 ℃, further be preferably 20～150 ℃ using polycarbonate-based resin as thermoplastic resin, when using the polypropylene-based resin conduct to contain the resin of polyolefin-based resins at least.

For example, use polycarbonate-based resin as thermoplastic resin, use the crystalline polypropylene based polymer in as above-mentioned resin combination during contained composition (a), be generally 10～170 ℃, be preferably 15～160 ℃.In addition, use polycarbonate-based resin as thermoplastic resin, use the polyethylene-based polymkeric substance of crystallinity in as above-mentioned resin combination during contained composition (a), be generally 10～160 ℃, be preferably 15～150 ℃.

When the temperature of touch roll 5 is too low, then since resin can be cooled sharp and easily at duplexer 8 residual strains, in addition, when the temperature of touch roll 5 is too high, then because cooling becomes insufficient and duplexer 8 and roller driving fit are reeled.

As rubber rollers, for example can enumerate silica gel roller or fluororubber roller, mix the rubber rollers of sand etc. for the raising release property.

The hardness of rubber rollers is preferably in A60 ° of measuring according to JIS K6253～A90 ° the scope.For the hardness that makes rubber rollers in aforementioned range, for example, can be through the degree of crosslinking of the rubber that constitutes rubber rollers or composition being adjusted and at random being carried out.

As the metallic elastic roller, for example, roller that constitutes by rubber for the inside of roller or the roller that is injected with fluid, and be the roller that its peripheral part is made up of the metallic film with bendability.Particularly; The inside that can enumerate roller constitute by silica gel roller and thickness 0.2～1mm about columnar stainless steel made membrane be coated on the roller of the peripheral part of this roller; Perhaps be injected with the roller of water or wet goods fluid for the inside of roller; Can enumerate the reel like film of the stainless steel about thickness 2～5mm is fixed with roll end, and enclose roller that fluid is arranged etc. in inside.

As this type touch roll 5, for example, be the touch roll that constitutes by metal material or elastic body, can use the touch roll that waits finishing as mirror-like through gold-plated.Should explain that the metallic film of metallic elastic roller or the surface of rubber rollers not necessarily must be level and smooth, also have no problem even if with the excipient roller 6 of following explanation concaveconvex shape is set on the surface identically.

Excipient roller 6 general diameters are about 200～1000mm, for example, comprise that outer peripheral face is formed with the metallic roll of concaveconvex shape.

The temperature of excipient roller 6 can suit to adjust according to used resin, for example, using polycarbonate-based resin as thermoplastic resin, when using polyethylene-based resin as polyolefin-based resins, is generally 10～80 ℃, is preferably 20～60 ℃.In addition,, be generally 10～100 ℃, be preferably 20～80 ℃ using polycarbonate-based resin as thermoplastic resin, when using polypropylene-based resin as polyolefin-based resins.

Further, for example, use polycarbonate-based resin as thermoplastic resin, use the crystalline polypropylene based polymer in as above-mentioned resin combination during contained composition (a), be generally 10～100 ℃, be preferably 20～80 ℃.In addition,, be generally 10～80 ℃, be preferably 20～60 ℃ using polycarbonate-based resin as thermoplastic resin, when using the polyethylene-based polymkeric substance of crystallinity as composition (a).

When the temperature of excipient roller 6 is too low, then since resin can be cooled sharp and easily at duplexer 8 residual strains, in addition, when the temperature of excipient roller 6 is too high, then because cooling becomes insufficient and duplexer 8 and roller driving fit are reeled.

As excipient roller 6; For example; Can enumerate that roller or the propellers of hollow structure etc. through the boring that have cut derby can pass through fluid, steam etc. in roller inside and the metallic roll of control roll surface temperature etc., can use the metallic roll of utilizing sandblast or engraving etc. to form the concaveconvex shape of expecting at the outer peripheral face of these metallic roll.

As the concaveconvex shape of the outer peripheral face that is formed on excipient roller 6, for example, can enumerate to have and count delustring shape about 0.1～15 μ m etc., specific spacing (ピッチ) or the concaveconvex shape of height etc. with arithmetic average roughness (Ra).Should explain that arithmetic average roughness (Ra) is to measure the value that gets with surface roughometer according to JIS B0601-2001.

For the resin of extruding by branch manifold mould 4 (or membranoid substance); When it is range upon range ofly on the two sides of thermoplastic resin (A) the range upon range of resin of the resin bed (B) that contains polyolefin-based resins at least to be arranged and make the delustring shape transferred thereon across the resin bed that contains polyolefin-based resins at least (B) when of thermoplastic resin (A) is surperficial; Be to contain the resin bed (B) of polyolefin-based resins at least and when making the delustring shape be formed at the face of layer (A) perhaps at the folded range upon range of resin that the resin bed (B) that contains polyolefin-based resins at least arranged of a surface layer of thermoplastic resin (A) and across this when it; Through sandwiching between above-mentioned touch roll 5 and the excipient roller 6; The concaveconvex shape of excipient roller 6 is needed on the face of thermoplastic resin (A), thus shaping duplexer 8.At this moment, the face of the resin bed that contains polyolefin-based resins at least (B) of matt film is extruded with the mode that contacts with excipient roller 6.

In addition; When it is range upon range of when the range upon range of resin of the resin bed (B) that contains polyolefin-based resins at least being arranged and making the delustring shape be formed at the two sides of thermoplastic resin (A) across the resin bed that contains polyolefin-based resins at least (B) on the two sides of thermoplastic resin (A), can this range upon range of resin be sandwiched chill roll that side face outside is formed with concaveconvex shape each other.

The duplexer 8 that has been transferred concaveconvex shape is being taken to excipient roller 6 by volume, and available carry-over pinch rolls traction is also reeled.

The haulage speed of carry-over pinch rolls can suit to adjust according to used resin, is generally 0.5～80m/ branch, is preferably 2～60m/ branch.Be slower than the 0.5m/ timesharing, then might aspect manufacturing cost, become unfavorable, faster than the 80m/ timesharing, then the film visual examination on the production line of having supposed optical applications (イ Application ライ Application) might become insufficient.

At this moment, after the excipient roller 6 mirror roller 7 can be set.Thus, duplexer 8 is slowly cooled, thereby can reduce the optical strain of duplexer 8, and then can also stablize and guarantee the duration of contact with excipient roller 6, thereby can make the concaveconvex shape that is imparted to excipient roller 6 stably carry out transfer printing.Mirror roller 7 is not special to be limited, and can adopt the common metallic roll of in the past in extrusion molding, using.As concrete example, can enumerate roller or propellers etc. through boring.The surface state of mirror roller 7 is preferably minute surface.

Make volume take to the duplexer 8 of excipient roller 6 through between excipient roller 6 and the mirror roller 7 and rolled up and take to mirror roller 7.Predetermined gap can be set to form free state, also can be clipped between two rollers between excipient roller 6 and mirror roller 7.Should explain, from cooling off duplexer 8 more lentamente, 1 or many chill rolls are set after mirror roller 7, thus make volume take to the mirror roller 7 matt film successively by volume take to after chill roll on.

Should explain; Matt film be with the layer that comprises acrylic resin with comprise folding layer by layer of polycarbonate-based resin and form; And at least one surface situation for the duplexer of delustring face, except shown in Figure 1 melt extruding the

machine

1,2, what other can newly be set melt extrudes machine (not shown); Can make allocation block 3 is three kinds of three layers of distribution type pieces or three kinds of five layers of distribution type pieces, and all the other can make duplexer with aforementioned embodiments identically.

[embodiment]

Below, embodiments of the invention are shown, but the present invention does not receive their qualification.Should explain that among the following embodiment, part of expression content or use amount is if no specified otherwise then is a weight basis.

The mensuration at crystallization melting caloric and crystallization peak is described below and carries out.

＜crystallization melting caloric and crystallization peak＞

According to JIS K7122, (" DSC6200 " of セイコーイ Application ス Star Le (strain) system) measures through differential scanning calorimetry.Particularly,, sample polymer is warming up to 200 ℃ from room temperature with 30 ℃/minute, kept 5 minutes down at 200 ℃ as the state adjustment.Then, be cooled to-50 ℃ with 10 ℃/minute ,-50 ℃ keep 5 minutes down after, be warming up to 200 ℃ with 10 ℃/minute from-50 ℃, carry out the mensuration at crystallization melting caloric and crystallization peak.

Being constructed as follows of the extrusion device that uses in following embodiment and the comparative example is said.

Extruder 1: the single shaft extruder (toshiba machine (strain) system) of the screw rod footpath 65mm of band vent port

Extruder 2: the single shaft extruder (toshiba machine (strain) system) of the screw rod footpath 45mm of band vent port

3: two kinds of two-layer distribution type pieces of allocation block (toshiba machine (strain) system)

Extruder

1 and 2, allocation block 3, branch manifold mould the 4, the 1st～the 3rd chill roll 5～7 are disposed as illustrated in fig. 1, each chill roll 5～7 is constituted like the following stated.

＜roller formation＞

Touch roll 5 and excipient roller 6, mirror roller 7 are constituted like the following stated:

Touch roll 5: external diameter 250mm φ and hardness A70 ° silica gel roller

Excipient roller 6: external diameter 250mm φ and by blasting treatment be formed with the concaveconvex shape of arithmetic average roughness (Ra) 3.5 μ m stainless steel metallic roll (through boring roller)

Mirror roller 7: the accurately machined stainless steel metallic roll of external diameter 250mm φ and minute surface (through the roller of boring).

(embodiment 1)

As layer (A); (" カリバー 301-10 ", the heat distortion temperature of Sumitomo ダウ (strain) system: the 140 ℃) fusion of polycarbonate-based resin is supplied to allocation block 3 by extruder 1 (barrel temperature: 230～280 ℃, screw rod revolution: 40rpm, extrusion capacity: 50kg/ hour); As layer (B); Polyvinyl resin (low density polyethylene " スミカセ Application L211 ", the vicat softening temperature of Sumitomo Chemical (strain) system: 98 ℃) fusion is supplied to allocation block 3 by extruder 2 (barrel temperature: 210～265 ℃, screw rod revolution: 18rpm, extrusion capacity 3kg/ hour); After allocation block 3 distributes with the mode of 2 layers of formation of cambium layer (B)/layer (A), carry out range upon range of and extrude at branch manifold mould 4 (mould temperature: 270 ℃).

Then, will sandwich between touch roll 5 (design temperature: 35 ℃) and the excipient roller 6 (design temperature: 35 ℃) the shaping duplexer by the membranoid substance that branch manifold mould 4 is extruded.And then, volume is taken duplexer to the excipient roller 6 through between excipient roller 6 and the mirror roller 7, volume is taken to mirror roller 7 (design temperature: 35 ℃), and draws with haulage speed 11m/ branch, the duplexer 8 of concaveconvex shape that obtained on the face transfer printing.In the gained duplexer, do not see fold in layer (B) (diaphragm), in addition, having peeled off in the layer behind the diaphragm (A) (matt film) does not have binder deposition.

The thickness of gained duplexer is shown in table 1.

(embodiment 2)

Screw rod revolution in making extruder 2 is that 36rpm, extrusion capacity are 9kg/ hour, carries out with embodiment 1 identically and obtains duplexer.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 1.

(comparative example 1)

Stop supply from the resin of extruder 2; Except the piece that the individual layer of allocation block being replaced by cambium layer (A) (being polycarbonate-based resin: 140 ℃ of " ガリバー 301-10 ", the heat distortion temperatures of Sumitomo ダウ (strain) system) constitutes; Carry out with embodiment 1 identically, obtain comprising the matt film of polycarbonate-based resin individual layer.With respect to the gained matt film; Diaphragm (mask at polypropylene-based resin layer (thickness=36 μ m) has the co-extruded films that contains the rubber resin (thickness=4 μ m) that adheres to imparting agent) with total thickness 40 μ m; Utilize make-up machine; Make the rubber resin face driving fit that adheres to imparting agent containing of diaphragm in the delustring face of matt film, and fit down at normal temperatures, obtain having the duplexer that contains the rubber resin that adheres to imparting agent.

In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm has binder deposition.

The thickness of gained duplexer is shown in table 1.

[table 1]

(embodiment 3)

[making of the masterbatch of resin combination]

With the crystalline polypropylene based polymer (the “ ノー Block レ Application W151 of Sumitomo Chemical (strain) system ", the crystallization melting caloric=49.6J/g) 80 weight portions mix with hydrogenated petroleum resin (" ア Le コ Application P125 " that waste river chemistry (strain) is made) 20 weight portions; carry out melting mixing with biaxial extruder (not shown), obtain the masterbatch pellet of resin combination.Should explain that hydrogenated petroleum resin had not both observed crystallization fusion peak and do not observed the crystallization peak yet.

[making of duplexer]

As thermoplastic resin (A); Polycarbonate-based resin (Sumitomo ダウ (strain) system " カリバー 301-15 ") is carried out melting mixing and is supplied to allocation block 3 at extruder 1 (barrel temperature: 230～260 ℃, screw rod revolution: 35rpm, extrusion capacity: 50kg/ hour); As resin combination layer (B); With the crystalline polypropylene based polymer (the “ ノー Block レ Application W151 of Sumitomo Chemical (strain) system ", the crystallization melting caloric=49.6J/g) 90 weight portions mix with aforementioned masterbatch pellet 10 weight portions; carry out melting mixing and be supplied to allocation block 3 at extruder 2 (barrel temperature: 210～260 ℃, screw rod revolution: 30rpm, extrusion capacity 7kg/ hour); after in allocation block 3, distributing, in branch manifold mould 4 (mould temperature: 260 ℃), carry out range upon range of and extrude with the mode of 2 layers of formation of cambium layer (B)/layer (A).

Then, the membranoid substance that will be extruded by branch manifold mould 4 with layer (B) and the mode that the excipient roller contacts, sandwiches between touch roll 5 (design temperature: 35 ℃) and the excipient roller 6 (design temperature: 35 ℃) the shaping duplexer.And then, volume is taken duplexer to the excipient roller 6 through between excipient roller 6 and the mirror roller 7, volume is taken to mirror roller 7 (design temperature: 50 ℃), and draws with haulage speed 9m/ branch, has obtained a face transfer printing duplexer 8 of concaveconvex shape.In the gained duplexer, do not see fold at layer (B) (diaphragm), in addition, having peeled off in the layer behind the diaphragm (A) (matt film) does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

(embodiment 4)

Except the combined amount that makes crystalline polypropylene based polymer and masterbatch pellet is crystalline polypropylene based polymer 75 weight portions, masterbatch pellet 25 weight portions, carries out with embodiment 3 and obtain duplexer identically.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

(embodiment 5)

Except the combined amount that makes crystalline polypropylene based polymer and masterbatch pellet is crystalline polypropylene based polymer 60 weight portions, masterbatch pellet 40 weight portions, carries out with embodiment 3 and obtain duplexer identically.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

(embodiment 6)

Except make hydrogenated petroleum resin (" the ア Le コ Application P125 " of waste river chemistry (strain) system) (" the Network リアロ Application P125 " of ヤス Ha ラケミカ Le (strain) system, carry out with embodiment 3 and obtain duplexer identically for hydrogenated terpene resin.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.Should explain that the terpenic series resin had not both observed crystallization fusion peak and do not observed the crystallization peak yet.

The thickness of gained duplexer is shown in table 2.

(embodiment 7)

Except the combined amount that makes crystalline polypropylene based polymer and masterbatch pellet is crystalline polypropylene based polymer 75 weight portions, masterbatch pellet 25 weight portions, carries out with embodiment 6 and obtain duplexer identically.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

(embodiment 8)

Except the combined amount that makes crystalline polypropylene based polymer and masterbatch pellet is crystalline polypropylene based polymer 60 weight portions, masterbatch pellet 40 weight portions, carries out with embodiment 6 and obtain duplexer identically.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

(embodiment 9)

[making of duplexer]

As layer (B); ((containing of " the タ Off セレ Application H5002 ", the crystallization melting caloric=8.5J/g that make of Sumitomo Chemical (strain), the polypropylene-based component of polymer of amorphism is proportional: 92 weight %) 2.2 weight portions mix; carry out melting mixing and be supplied to allocation block 3 with extruder 2 (barrel temperature: 210～260 ℃, screw rod revolution: 30rpm, extrusion capacity 7kg/ hour), in addition carry out with embodiment 3 identically and obtain duplexer for 97.8 weight portions of " ノー Block レ Application W151 ", the crystallization melting caloric of Sumitomo Chemical (strain) system=49.6J/g) and the polypropylene-based polymkeric substance of amorphism with the crystalline polypropylene based polymer.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

(embodiment 10)

Except the combined amount that makes crystalline polypropylene based polymer and the polypropylene-based polymkeric substance of amorphism is: crystalline polypropylene based polymer 94.6 weight portions, beyond polypropylene-based polymkeric substance 5.4 weight portions of amorphism, carry out with embodiment 9 identically and obtain duplexer.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

(embodiment 11)

Except not mixing masterbatch, and only with beyond the crystalline polypropylene based polymer melting mixing, carry out with embodiment 3 identically and obtain duplexer at extruder 2.In the gained duplexer, do not see fold in the diaphragm, in addition, having peeled off in the matt film behind the diaphragm does not have binder deposition.

The thickness of gained duplexer is shown in table 2.

[table 2]

Carry out following evaluation for each duplexer of gained with by layer (A) (matt film) that each duplexer has been peeled off layer (B) (diaphragm).The result is shown in table 3 and 4.

＜60 degree mirror surface lusters＞

According to JIS Z8741, measure 60 degree mirror surface lusters of the delustring face of matt film.

＜surfaceness＞

The average length (RSm) of the arithmetic average roughness of the delustring face of matt film (Ra), maximum height (Rz) and contour curve key element is according to JIS B0601-2001, utilizes surface roughometer (the “ サー Off テスト SJ-201 of ミ Star トヨ (strain) system ") to measure.

＜phase difference value＞

Cut out test film from matt film with the square size of 50mm, utilize small area birefraction meter (" KOBRA-CCO/X " of prince's instrumentation machine (strain) system) to measure the phase difference value under the 590nm.

＜full light transmittance (Tt) and mist degree (H)＞

Measure the full light transmittance (Tt) of matt film according to JIS K7361-1.

According to JIS K7136, measure the mist degree (H) of matt film.

＜peel strength＞

In 23 ℃ atmosphere, peel off under the condition of width 25mm, 180 ° of peel angle, peeling rate 300mm/min, measure and to peel off the needed power of diaphragm from the gained duplexer, with it as the peel strength (g/25mm) under 23 ℃.

＜buckling deformation amount＞

With extrude 297mm on the direction, the size of 210mm is cut off on the direction vertical with extruding direction, is made as test film.At first, test film carried place on the platform, through desk-top extensometry device! キーエ Application ス (strain) system) measure the amount of floating at 4 angles, the mean value of calculating the amount of floating at 4 angles, with it as the buckling deformation amount.

[table 3]

[table 4]

Claims

1. strippable duplexer is characterized in that, the delustring face at least of the matt film of processing with thermoplastic resin is the diaphragm processed of the range upon range of useful resin that contains polyolefin-based resins at least directly, and this matt film and this diaphragm are strippable.

2. the described duplexer of claim 1, wherein, the resin that contains polyolefin-based resins at least is to be selected from polyethylene-based resin, polypropylene-based resin and is at least a in the resin as their improved polyalkene of modification body.

3. the described duplexer of claim 1, wherein, the resin that contains polyolefin-based resins at least is the resin combination that contains following compositions (a) and composition (b),

Composition (a): crystalline polyolefin

4. the described duplexer of claim 3, wherein, crystalline polyolefin be be selected from ethene, propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and the 1-octene a kind of homopolymerization or more than 2 kinds copolymerization and.

5. claim 3 or 4 described duplexers, wherein, the amorphism polymkeric substance be selected from polypropylene-based polymkeric substance and the polyethylene-based polymkeric substance more than a kind.

6. each described duplexer in the claim 3～5, wherein, when being 100 weight % with the total amount of composition (a) and composition (b), resin combination contains composition (a) 80～99 weight %, composition (b) 1～20 weight %.

7. each described duplexer in the claim 1～6; Wherein, thermoplastic resin be selected from polycarbonate-based resin, acrylic resin, cyclic olefine resin, polyester based resin, phenylethylene resin series, methyl methacrylate-phenylethylene resin series, ABS be resin and AS be in the resin more than a kind.

8. each described duplexer in the claim 1～7, wherein, aforementioned matt film is that the layer that comprises acrylic resin is formed with comprising the folded layer by layer of polycarbonate-based resin, and at least one surface is a delustring face.

9. each described duplexer in the claim 1～8, wherein, the face that does not contact with aforementioned matt film of aforementioned diaphragm is a delustring face.

10. each described duplexer in the claim 1～9, wherein, the mist degree of aforementioned matt film is below 90%.

11. each described duplexer in the claim 1～10, wherein, phase differential is below the 30nm in the face of aforementioned matt film, and surface gloss is below 60%.

12. each described duplexer in the claim 1～11, wherein, the splitting power of aforementioned matt film and aforementioned diaphragm is 5～50g/25mm width.

13. each described duplexer in the claim 1～12, it is that aforementioned diaphragm and aforementioned matt film are shaped and the range upon range of duplexer that obtains through the fusion coextrusion.

14. each described duplexer in the claim 1～13, wherein, aforementioned matt film is used for liquid crystal indicator.

15. the described duplexer of claim 14, wherein, aforementioned matt film is used for the protection of the polarisation separating sheet of foregoing liquid crystal display device.

16. the manufacturing approach of duplexer; It is characterized in that; With the resin combination that contains polyolefin-based resins at least and thermoplastic resin fusion coextrusion and obtain membranoid substance; And insert between excipient roller and the touch roll with the mode that the face of aforementioned resin contacts with the excipient roller, the delustring shape is formed at the face of aforementioned thermoplastic resin.

17. matt film, it is that each described duplexer is peeled off aforementioned diaphragm and got in the accessory rights requirement 1～15.