CN102129092A - Coarse film for optical use - Google Patents
Coarse film for optical use Download PDFInfo
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- CN102129092A CN102129092A CN2011100251133A CN201110025113A CN102129092A CN 102129092 A CN102129092 A CN 102129092A CN 2011100251133 A CN2011100251133 A CN 2011100251133A CN 201110025113 A CN201110025113 A CN 201110025113A CN 102129092 A CN102129092 A CN 102129092A
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- layer
- optics
- rough textured
- particle
- film
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
The present invention provides a coarse film for optical use, which has excellent surface hardness, excellent optical deformability and excellent heat resistance. The coarse film for optical use according to the invention is obtained through stacking a layer (B) which is composed of acrylic acid series thermoplastic resin composition that comprises acrylic acid series resins on at least one surface of a layer (A) which is composed of polycarbonate series thermoplastic resin composition that comprises polycarbonate series resins. The surface of at least one layer (B) is a coarse surface. The whole thickness of the film is 30-300 mu m. The thickness of the layer (A) accounts for more than 30% of that of the whole film. The thickness of the layer (B) is more than 8 mu m. A delay value of the coarse film for the incident light with a wavelength of 590nm is less than 30 nm.
Description
Technical field
The present invention relates to the optics rough textured film.
Background technology
The rough textured film that the film surface has concaveconvex shape (rough form) uses in the optical applications of optical diffusion film, polarisation separating sheet diaphragm etc.; for this film; in order to prevent to require to improve its skin hardness by the damage on the film surface that causes with contacting of miscellaneous part etc.
In addition; for example; when on the exit facet that this rough textured film is layered in the polarisation separating sheet in order to protect the polarisation separating sheet in the liquid crystal indicator, using, require to reduce its optical skew, make can not change from the polarization direction of the polarized light of polarisation separating sheet outgoing.And then, because rough textured film is in the environment of heating for a long time, therefore require patience to this heating in liquid-crystal apparatus.
As the rough textured film that uses in the above-mentioned optical applications, proposed to be formed with by the knurling rolls transfer printing rough textured film (patent documentation 1,2) of the concaveconvex shape of regulation, be dispersed with the rough textured film (patent documentation 3) of the acrylic acid series heat-curing resin of spherical microballon in the surface coated of the layer that forms by polycarbonate resin on the surface of the film that forms by polycarbonate resin.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-53998 communique
Patent documentation 2: international disclosing No. 2008/081953
Patent documentation 3: TOHKEMY 2001-42108 communique
Summary of the invention
But, for the rough textured film of record in the above-mentioned patent documentation 1～3, may not be enough satisfactory aspect skin hardness, optical skew and the thermotolerance of film.
Therefore, problem of the present invention is to provide the equal good optical rough textured film of either side in the skin hardness, optical skew, thermotolerance of film.
The inventor etc. further investigate in order to solve above-mentioned problem, found that, by forming at the folded layer (B) that forms by the acrylic acid series thermoplastic resin composition of containing acrylic resin of at least one surface layer of the layer (A) that forms by the polycarbonate-based thermoplastic resin composition that contains polycarbonate-based resin and the surface of at least 1 layer (B) is the rough textured film of uneven surface, can solve above-mentioned problem, thereby finish the present invention.
That is, the present invention includes following formation.
(1) a kind of optics rough textured film, it is characterized in that, one side at least at the layer (A) that forms by the polycarbonate-based thermoplastic resin composition that contains polycarbonate-based resin, the stacked layer (B) that is formed by the acrylic acid series thermoplastic resin composition of containing acrylic resin forms, the surface of at least 1 layer (B) is a uneven surface
The thickness of film integral body is 30～300 μ m, and the thickness of layer (A) is more than 30% with respect to the thickness of film integral body, and the thickness of layer (B) is more than the 8 μ m,
The length of delay of the incident light of the wavelength 590nm of film is below the 30nm.
(2) above-mentioned (1) described optics rough textured film, aforesaid propylene acid based thermoplastic resin composition contains rubber particles.
(3) above-mentioned (2) described optics rough textured film, above-mentioned rubber particles is the acrylic rubber particle.
(4) each described optics rough textured film in above-mentioned (1)～(3), above-mentioned uneven surface forms by the matte roll transfer printing.
(5) above-mentioned (1) described optics rough textured film, aforesaid propylene acid based thermoplastic resin composition contains the roughening agent
(6) above-mentioned (5) described optics rough textured film, above-mentioned roughening agent are to be selected from least a kind of transparent particulate as main body in methyl methacrylate based polymer particle, styrenic particle, the siloxane-based polymers particle.
(7) the described optics rough textured film in above-mentioned (1)～(6) forms above-mentioned polycarbonate-based thermoplastic resin composition and described acrylic acid series thermoplastic resin composition coextrusion shaping.
(8) each described optics rough textured film in above-mentioned (1)～(7) is used for liquid crystal indicator.
(9) above-mentioned (8) described optics rough textured film is used for protecting the polarisation separating sheet of described liquid crystal indicator.
Optics of the present invention is little owing to optical skew with rough textured film, therefore the polarization direction of polarized light is changed, and, because film skin hardness height, therefore be difficult for because of producing damage with contacting of miscellaneous part etc., and then, because patience height to heating, shrink, size changing rate is few, when therefore in liquid-crystal apparatus, using, can use for a long time.
Description of drawings
Fig. 1 is the diagrammatic illustration figure of expression optics of the present invention with an example of the manufacturing process of rough textured film.
Fig. 2 is expression is used as optics of the present invention one example of the polarisation separating sheet diaphragm in the liquid crystal indicator with rough textured film diagrammatic illustration figure.
Symbol description
1,2 melt extrude machine
3 feed pieces
4 membrana oralis
5 the 1st chill rolls
6 the 2nd chill rolls
7 the 3rd chill rolls
8 optics rough textured films
9 backlight units
10 polarisation separating sheet
11 polarisation separating sheet diaphragms
12 liquid crystal panels
Embodiment
Below, at length describe for the present invention.Optics rough textured film of the present invention, one side at least at the layer (A) that forms by the polycarbonate-based thermoplastic resin composition that contains polycarbonate-based resin, the stacked layer (B) that is formed by the acrylic acid series thermoplastic resin composition of containing acrylic resin and rubber particles as required forms, and the surface of at least 1 layer (B) is a uneven surface.
＜polycarbonate-based thermoplastic resin composition 〉
Above-mentioned polycarbonate-based thermoplastic resin composition as the formation material of layer (A) contains polycarbonate-based resin as resinous principle.
As this polycarbonate-based resin, for example preferably use good aromatic polycarbonate resins such as thermotolerance, physical strength, the transparency.Aromatic polycarbonate resin normally adopts interface polycondensation, melt transesterification process that dihydric phenol and carbonate precursor reaction are obtained, in addition, also the polymerization of carbonic ester prepolymer is obtained, perhaps carry out polymerization and obtain by the ring-opening polymerization method of cyclic carbonate compound by the solid phase ester-interchange method.
As above-mentioned dihydric phenol, can enumerate for example p-dihydroxy-benzene, resorcinol, 4,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) methane, two { (4-hydroxyls-3, the 5-dimethyl) phenyl } methane, 1, two (4-hydroxy phenyl) ethane of 1-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 2, two (4-hydroxy phenyl) propane (common name bisphenol-A) of 2-, 2, two { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, two { (the 4-hydroxyls-3 of 2-, the 5-dimethyl) phenyl } propane, 2, two { (the 4-hydroxyls-3 of 2-, the 5-dibromo) phenyl } propane, 2, two { (3-isopropyl-4-hydroxyl) phenyl } propane of 2-, 2, two { (4-hydroxyl-3-phenyl) phenyl } propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-the hydroxy phenyl)-3-methylbutanes of 2-, 2, two (the 4-hydroxy phenyls)-3 of 2-, the 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-2-methylbutanes of 4-, 2, two (4-hydroxy phenyl) pentanes of 2-, 2, two (4-the hydroxy phenyl)-4-methylpentanes of 2-, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 1, two (4-the hydroxy phenyl)-4-isopropyl cyclohexanes of 1-, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two { (4-hydroxy-3-methyl) phenyl } fluorenes of 9-, α, α '-two (4-hydroxy phenyl)-adjacent diisopropyl benzene, α, α '-two (4-hydroxy phenyl)-diisopropyl benzene, α, α '-two (4-hydroxy phenyl)-to diisopropyl benzene, 1, two (the 4-hydroxy phenyls)-5 of 3-, the 7-dimethyladamantane, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxy diphenyl sulfoxide, 4,4 '-dihydroxy diphenylsulfide, 4,4 '-dihydroxy diphenylketone, 4,4 '-dihydroxydiphenyl ether and 4,4 '-dihydroxy diphenyl etc.They may be used singly or as a mixture of two or more.
Wherein, preferably use separately or use more than 2 kinds from bisphenol-A, 2, two { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-the hydroxy phenyl)-3-methylbutanes of 2-, 2, two (the 4-hydroxy phenyls)-3 of 2-, the 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-4-methylpentanes of 2-, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane and α, the dihydric phenol of selecting in α '-two (4-the hydroxy phenyl)-diisopropyl benzene, the independent use of preferred especially bisphenol-A, 1, 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 also usefulness of the dihydric phenol of more than one in α '-two (4-the hydroxy phenyl)-diisopropyl benzene.
As above-mentioned carbonate precursor, can use for example carboxylic acid halides, carbonic ester ester or haloformate etc., specifically can enumerate the bishaloformate of phosgene, diphenyl carbonate or dihydric phenol etc.
＜acrylic acid series thermoplastic resin composition 〉
Aforesaid propylene acid based thermoplastic resin composition as the formation material of layer (B) contains acrylic resin as resinous principle.
As this acryl resin, use for example methacrylic resin.Methacrylic resin is the polymkeric substance based on methacrylate, can be the homopolymer of methacrylate, can also be the multipolymer of the following monomer except that methacrylate of above methacrylate of 50 weight % and 50 weight %.Here, as methacrylate, use the Arrcostab of methacrylic acid usually.
The preferred monomers of methacrylic resin is formed, with whole monomers is benchmark, alkyl methacrylate be 50～100 weight %, alkyl acrylate be 0～50 weight %, except that the monomer them be 0～49 weight %, more preferably alkyl methacrylate be 50～99.9 weight %, alkyl acrylate be 0.1～50 weight %, except that the monomer them be 0～49 weight %.
Here, as the example of alkyl methacrylate, 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 the example of alkyl acrylate, 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 except that alkyl methacrylate and alkyl acrylate, both can be monofunctional monomer, promptly in molecule, have a compound of 1 polymerism carbon-to-carbon double bond, also can be polyfunctional monomer, promptly in molecule, have the compound of at least 2 polymerism carbon-to-carbon double bonds, preferably use monofunctional monomer.
In addition, as the example of this monofunctional monomer, can enumerate styrenic monomers compounds such as styrene, α-Jia Jibenyixi, vinyltoluene; Cyaniding such as vinyl cyanide, methacrylonitrile thiazolinyl; Acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide amine etc.
In addition, as the example of polyfunctional monomer, can enumerate many esters of unsaturated carboxylic acids of the polyvalent alcohol of Ethylene glycol dimethacrylate, tetramethylene dimethacrylate, trimethylolpropane triacrylate and so on; The alkenyl esters of unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, cinnamic acid allyl ester; The polyene-based ester of polyprotonic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, cyamelide triallyl; Aromatic polyene based compounds such as divinylbenzene etc.
In addition, above-mentioned alkyl methacrylate, alkyl acrylate and except that the monomer them can use as required separately in them more than 2 kinds.
From stable on heating angle, the glass transition temperature of methacrylic resin is preferably more than 70 ℃, and is more preferably more than 80 ℃, further preferred more than 90 ℃.This glass transition temperature can suitably be set by adjusting monomeric species, its ratio.
Methacrylic resin can prepare the polymerization of monomer whose composition by methods such as suspension polymerization, emulsion polymerization, bulk polymerizations.At this moment, plywood is shown the viscosity etc. of formability, preferably when polymerization, use suitable chain-transferring agent for the glass transition temperature that obtains suiting or for what obtain suiting.The amount of chain-transferring agent can suitably be determined according to the kind of monomer, its ratio etc.
＜rubber particles 〉
Can also the compound rubber particle among the acrylic acid series thermoplastic resin composition.Here, as rubber particles, for example can use acrylic rubber particle, butadiene-based rubber particle, styrene-butadiene is rubber particles etc., wherein, from the aspect of weatherability, permanance, preferably uses the acrylic rubber particle.
The acrylic rubber particle is to contain particle based on the elastomeric polymer of acrylate as rubber constituent, it can be the single layer structure particle that only constitutes by this elastomeric polymer, also can be to have this elastomeric polymer layer and, be preferably the particle of sandwich construction from the aspect of the skin hardness of the layer (B) that forms by the acrylic acid series thermoplastic resin for example based on the particle having multilayer structure of the polymeric layer of methacrylate.
In addition, this elastomeric polymer can be the homopolymer of acrylate, also can be above acrylate of 50 weight % and the following multipolymer except that the monomer it of 50 weight %.Here, as acrylate, usually, use acrylic acid Arrcostab.
Preferred monomers based on the elastomeric polymer of acrylate is formed, with whole monomers is benchmark, alkyl acrylate be 50～99.9 weight %, alkyl methacrylate be 0～49.9 weight %, except that the monofunctional monomer them is 0～49.9 weight %, and polyfunctional monomer is 0.1～10 weight %.
Here, as the example of the alkyl acrylate in the above-mentioned elastomeric polymer, as the monomer component of methacrylic resin and the example of the alkyl acrylate of enumerating is identical, the carbon number of its alkyl is generally 1～8 with formerly, and preferred 4～8.
In addition, as the example of the alkyl methacrylate in the above-mentioned elastomeric polymer, as the monomer component of methacrylic resin and the example of the alkyl methacrylate of enumerating is identical, the carbon number of its alkyl is generally 1～8 with formerly, and preferred 1～4.
As the example of the monofunctional monomer except that alkyl acrylate and alkyl methacrylate in the above-mentioned elastomeric polymer, and formerly as the monomer component of methacrylic resin and the example of the monofunctional monomer of enumerating except that alkyl methacrylate and alkyl acrylate is identical.Wherein, preferably use styrenic monomers such as styrene, α-Jia Jibenyixi, vinyltoluene.
As the example of the polyfunctional monomer in the above-mentioned elastomeric polymer, as the monomer component of methacrylic resin and the example of the polyfunctional monomer of enumerating is identical, wherein, preferably use the alkenyl esters of unsaturated carboxylic acid, the polyalkenyl ester of polyprotonic acid with formerly.
Alkyl acrylate in the above-mentioned elastomeric polymer, alkyl methacrylate, except that the monofunctional monomer them and polyfunctional monomer can use as required respectively in them more than 2 kinds.
When using the rubber particles of sandwich construction as the acrylic rubber particle, as its preference, can enumerate the outside in above-mentioned elastomeric polymer layer based on acrylate, has particle based on the polymeric layer of methacrylate, that is, with above-mentioned elastomeric polymer based on acrylate as internal layer, and will be based on the polymkeric substance of methacrylate particle as outer field at least 2 layers of structure.Here, the methacrylate as the monomer component of outer field polymkeric substance uses alkyl methacrylate usually.
In addition, with respect to elastomeric polymer 100 weight portions of internal layer, outer field polymkeric substance is usually with 10～400 weight portions, preferably form with the ratio of 20～200 weight portions.Is more than 10 weight portions by making outer field polymer phase for the elastomeric polymer of the internal layer of 100 weight portions, and this elastomeric polymer is difficult for condensing, and the transparency of acrylic resin layer is good.
The preferred monomers of above-mentioned outer field polymkeric substance is formed, with whole monomers is benchmark, alkyl methacrylate be 50～100 weight %, alkyl acrylate be 0～50 weight %, except that the monomer them is 0～50 weight %, and polyfunctional monomer is 0～10 weight %.
As the example of the alkyl methacrylate in the above-mentioned outer field polymkeric substance, as the monomer component of methacrylic resin and the example of the alkyl methacrylate of enumerating is identical, the carbon number of its alkyl is generally 1～8 with formerly, and preferred 1～4.Wherein, preferably use methyl methacrylate.
As the example of the alkyl acrylate in the above-mentioned outer field polymkeric substance, as the monomer component of methacrylic resin and the example of the alkyl acrylate of enumerating is identical, the carbon number of its alkyl is generally 1～8 with formerly, and preferred 1～4.
Example as the monomer except that alkyl methacrylate and alkyl acrylate in the above-mentioned outer field polymkeric substance, with formerly as the monomer component of methacrylic resin and the example of the monofunctional monomer of enumerating except that alkyl methacrylate and alkyl acrylate is identical, in addition, as the example of polyfunctional monomer, and formerly as the monomer component of methacrylic resin and the example of the polyfunctional monomer of enumerating is identical.
In addition, the alkyl methacrylate in the above-mentioned outer layer copolymer, alkyl acrylate, except that the monomer them and polyfunctional monomer can use as required respectively in them more than 2 kinds.
In addition, preference as the acrylic rubber particle of sandwich construction, can enumerate in the outside as the above-mentioned elastomeric polymer layer based on acrylate of the internal layer of above-mentioned 2 layers of structure, further has particle based on the polymeric layer of methacrylate, that is, with this based on the polymkeric substance of methacrylate as internal layer, with above-mentioned elastomeric polymer based on acrylate as the middle layer, and will be formerly based on the polymkeric substance of methacrylate particle as outer field 3-tier architecture at least.Here, the methacrylate as the monomer component of internal layer polymer uses alkyl methacrylate usually.In addition, with respect to elastomeric polymer 100 weight portions in middle layer, the polymkeric substance of internal layer forms with the ratio of 10～400 weight portions, preferred 20～200 weight portions usually.
The preferred monomers of above-mentioned internal layer polymer is formed, with whole monomers is benchmark, alkyl methacrylate be 70～100 weight %, alkyl acrylate be 0～30 weight %, except that the monomer them is 0～30 weight %, and polyfunctional monomer is 0～10 weight %.
As the example of the alkyl methacrylate in the above-mentioned internal layer polymer, as the monomer component of methacrylic resin and the example of the alkyl methacrylate of enumerating is identical, the carbon number of its alkyl is generally 1～8 with formerly, and preferred 1～4.Wherein, preferably use methyl methacrylate.
As the example of the alkyl acrylate in the above-mentioned internal layer polymer, as the monomer component of methacrylic resin and the example of the alkyl acrylate of enumerating is identical, the carbon number of its alkyl is generally 1～8 with formerly, and preferred 1～4.
Example as the monomer except that alkyl methacrylate and alkyl acrylate in the above-mentioned internal layer polymer, with formerly as the monomer component of methacrylic resin and the example of the monofunctional monomer of enumerating except that alkyl methacrylate and alkyl acrylate is identical, in addition, as the example of polyfunctional monomer, and formerly as the monomer component of methacrylic resin and the example of the polyfunctional monomer of enumerating is identical.
In addition, the alkyl methacrylate in the above-mentioned internal layer polymer, alkyl acrylate, except that the monomer them and polyfunctional monomer can use as required respectively in them more than 2 kinds.
The acrylic rubber particle can be by adopting emulsion polymerization etc., the monomer component of formerly describing based on the elastomeric polymer of acrylate is carried out polymerization with the reaction at least 1 step and prepares.At this moment, as mentioned above, when forming the polymeric layer based on methacrylate in the outside of above-mentioned elastomeric polymer layer, can be in the presence of above-mentioned elastomeric polymer, adopt emulsion polymerization etc., the monomer component of this outer layer copolymer is carried out polymerization with the reaction at least 1 step, thus with above-mentioned elastomeric polymer grafting.
In addition, as mentioned above, when above-mentioned elastomeric polymer layer inboard further forms polymeric layer based on methacrylate, can be at first, employing emulsion polymerizations etc. carry out polymerization with the monomer component of this internal layer polymer with the reaction at least 1 step, then, in the presence of the polymkeric substance that obtains, adopt emulsion polymerization etc., the monomer component of above-mentioned elastomeric polymer is carried out polymerization with the reaction at least 1 step, thereby with above-mentioned internal layer polymer grafting, and then, in the presence of the polymkeric substance that obtains, adopt emulsion polymerization etc., the monomer component of above-mentioned outer layer copolymer is carried out polymerization with the reaction at least 1 step, with above-mentioned elastomeric polymer grafting.In addition, when carrying out more than the polymerization of each layer goes on foot with 2 respectively, monomer composition is as a whole got final product within the limits prescribed, rather than the monomer in each step is formed within the limits prescribed.
For the particle diameter of acrylic rubber particle, preferred 0.01～0.4 μ m of mean grain size in this rubber particles, more preferably 0.05～0.3 μ m, further preferred 0.07～0.25 μ m based on the elastomeric polymer layer of acrylate.The mean grain size of this elastomeric polymer layer is during greater than 0.4 μ m, causes the transparency of the layer (B) that formed by the acrylic acid series thermoplastic resin composition to reduce, and transmissivity reduces, thereby not preferred.In addition, the mean grain size of this elastomeric polymer layer is during less than 0.01 μ m, and the skin hardness of layer (B) reduces and is easy to sustain damage, thereby not preferred.
In addition, above-mentioned mean grain size can followingly be obtained: the acrylic rubber particle is mixed the back membranization with methacrylic resin, its cross section implemented the dyeing of the above-mentioned elastomeric polymer layer of carrying out, observe, obtain by the diameter of the part that is colored with electron microscope with ruthenium-oxide.
Promptly, the acrylic rubber particle is mixed with methacrylic resin, when dyeed with ruthenium-oxide in its cross section, the methacrylic resin of parent phase is not colored, when having the polymeric layer based on methacrylate in the outside of above-mentioned elastomeric polymer layer, this outer layer copolymer is not colored yet, and only above-mentioned elastomeric polymer layer is colored, therefore observe the diameter of the part of circular by being colored like this with electron microscope, can obtain particle diameter.When having the polymeric layer based on methacrylate in the inboard of above-mentioned elastomeric polymer layer, with this internal layer polymer be not colored yet, the state of 2 layers of structure being colored of above-mentioned elastomeric polymer layer in its outside is observed, at this moment, with the outside of 2 layers of structure, be that the external diameter of above-mentioned elastomeric polymer layer is considered to get final product.
Rubber particles is with respect to overall the containing below the 40 overall weight % of the proportional acrylic acid series thermoplastic resin composition of being, below the preferred 30 weight % of acrylic acid series thermoplastic resin composition.Containing of rubber particles is proportional during more than the overall 40 weight % of acrylic acid series thermoplastic resin composition, and the skin hardness of layer (B) reduces and sustains damage easily.
In addition, among polycarbonate-based thermoplastic resin composition and the acrylic acid series thermoplastic resin composition, can cooperate other compositions as required, for example, ultraviolet light absorber, organic system dyestuff, inorganic based dye, pigment, antioxidant, antistatic agent, surfactant etc.
＜optics the manufacturing process of rough textured film 〉
As optics rough textured film of the present invention, one side at least at the layer (A) that forms by above-mentioned polycarbonate-based thermoplastic resin composition, the stacked layer (B) that is formed by the acrylic acid series thermoplastic resin composition forms, and the surface of at least 1 layer (B) is a uneven surface.
As the formation method of this uneven surface, can enumerate when coextrusion is shaped to use and be formed with the method that the metallic roll of concaveconvex shape, so-called matte roll are carried out transfer printing at outer peripheral face; When using the composition that in the acrylic acid series thermoplastic resin composition, contains the transparent particulate that becomes the roughening agent to carry out the coextrusion shaping as skin-material, form concavo-convex method etc. on the surface.
The formation method of the uneven surface of＜use roller 〉
Formation method as the uneven surface that uses so-called matte roll, be when coextrusion is shaped, to use at outer peripheral face to be formed with the method that the metallic roll of concaveconvex shape is carried out transfer printing, can enumerate the method put down in writing in for example TOHKEMY 2009-196327 communique, the TOHKEMY 2009-202382 communique etc.
Fig. 1 is an expression optics of the present invention with the diagrammatic illustration figure of an example of the manufacturing process of rough textured film (below, be called manufacturing process of the present invention).
As shown in the drawing, this manufacturing process is, prepare 2 and melt extrude machine 1,2, the polycarbonate-based thermoplastic resin composition and the acrylic acid series thermoplastic resin composition melting mixing of each extruder will be dropped into, be supplied to respectively feed piece 3 and fusion stacked integrated after, resin is situated between and is launched by single manifold ports mould 4 (T type mouth mould), is extruded as membranaceous from mouth mould front end.
In the manufacturing process of the present invention, overlapped way is in layer (A) top laminate (B) and integrated before the through port mould.Particularly, for example, be supplied to the polycarbonate-based thermoplastic resin composition and the acrylic acid series thermoplastic resin composition of the feed piece 3 of two kinds 3 layers and two kinds 2 layers of distribution type, in feed piece 3 as at the 3-tier architecture of the two sides layer laminate (B) of layer (A) or in 2 layers of structure of the one side layer laminate (B) of layer (A) and integrated.
For above-mentioned manufacturing process, be to use the example of feed piece 3 and mouthful mould 4, but also can have replaced them and for example use as mouthful branch manifold mouth mould of mould inner stacks mode, as mouthful double slit mouth mould of mould outer stack mode etc.
Then, the resin of extruding from mouth mould 4 is clamped in along between the 1st chill roll 5 and the 2nd chill roll 6 of the relative configuration of general horizontal direction, at least 1 surface at the layer (B) that is formed by the acrylic acid series thermoplastic resin composition forms uneven surface, slowly cool off by the 3rd chill roll 7, thereby can obtain optics rough textured film 8.
The diameter of the 1st chill roll 5 is about 25～100cm, is made of rubber rollers or metallic elastic roller.
As above-mentioned rubber rollers, for example can enumerate silica gel roller, fluororubber roller etc., in order to improve release property, also can adopt the rubber rollers that is mixed with sand.The hardness of rubber rollers is preferably in the scope of the A60 that measures according to JISK6253 °～A90 °.For the hardness that makes rubber rollers in above-mentioned scope, degree of crosslinking that for example can be by adjusting the rubber that constitutes rubber rollers, composition and carry out arbitrarily.
The inside that above-mentioned metallic elastic roller is a roller is injected with fluid with the roller that rubber constitutes, and its peripheral part constitutes with the metallic film with bendability.Particularly, the inside that can enumerate roller constitute with silica gel roller and thickness 0.2～1mm about cylindrical shape stainless steel made membrane be coated on the roller of the peripheral part of this roller; Be injected with in the roller of water, wet goods fluid in the inside of roller, the stainless steel rounding cylindrical membrane about thickness 2～5mm is fixed in roll end, enclose the roller of fluid etc. in inside.
As the 1st such chill roll 5, use to constitute, and be processed as the roller of mirror-like by plating etc. by metal material, elastic body.In addition, the metallic film of metallic elastic roller, the surface of rubber rollers needn't be necessarily level and smooth, even be provided with concaveconvex shape equally on the surface also without any problem with the 2nd chill roll 6 of following explanation.
The diameter of the 2nd chill roll 6 is about 25～100cm, is made of the metallic roll that is formed with concaveconvex shape at outer peripheral face.Particularly, the metallic roll etc. that the slotter (drilled roll) of cutting metal piece, the propellers of hollow structure etc. can wait the temperature on control roll surface at roller internal circulation fluid, steam can be enumerated, the roller that is formed with required concaveconvex shape by sandblast, engraving etc. at the outer peripheral face of these metallic roll can be used.
As the concaveconvex shape that forms at the outer peripheral face of the 2nd chill roll 6, can enumerate in the rough form about arithmetic mean rugosity (Ra) 0.1～10 μ m etc., have specific spacing, concaveconvex shape highly etc.Above-mentioned arithmetic mean rugosity (Ra) is according to the JIS B0601-2001 fixed value that gets of surface roughness instrumentation.
The resin of extruding from mouth mould 3 is when forming uneven surface at the stacked resin of the two sides layer laminate (B) of layer (A) and on a surface of this layer (B), or when forming uneven surface at the stacked resin of the one side layer laminate (B) of layer (A) and on the surface of this layer (B), by being clamped between such the 1st chill roll 5 and the 2nd chill roll 6, above-mentioned concaveconvex shape that can transfer printing the 2nd chill roll 6 is configured as film.At this moment, the mode that becomes a side that contacts with the 2nd roller 6 with layer (B) side of rough textured film is extruded.
In addition, be when forming uneven surfaces at the stacked resin of the two sides layer laminate (B) of layer (A) and on two surfaces of this layer (B), this stacked resin clip is held in the above-mentioned chill roll that is formed with concaveconvex shape at outer peripheral face gets final product each other.
After transfer printing has the resin molding of concaveconvex shape to be wound in the 2nd chill roll 6, reeled by the carry-over pinch rolls traction.At this moment, can after the 2nd chill roll 6, the 3rd chill roll 7 be set.Therefore thus, resin molding is slowly cooled, and can reduce the optical skew of resin molding, and then owing to can also stably guarantee duration of contact with the 2nd chill roll 6, therefore the concaveconvex shape that the 2nd chill roll 6 is given of transfer printing stably.As the 3rd chill roll 7, be not particularly limited the common metallic roll of in extrusion molding, having used since adopting in the past.As concrete example, can enumerate slotter, propellers etc.The surface state of the 3rd chill roll 7 is preferably minute surface.
Make the resin molding that is wound in the 2nd chill roll 6 between the 2nd chill roll 6 and the 3rd chill roll 7 by after be wound in the 3rd chill roll 7.Become open state even be provided with specified gap between the 2nd chill roll 6 and the 3rd chill roll 7, also can be held on two rollers.In addition, for further slowly cooling of resin molding, can also after the 3rd chill roll 7, the 4th chill roll, the 5th chill roll be set ... several chill rolls are wound in next chill roll successively with the rough textured film that is wound in the 3rd chill roll 7.
The formation method of the uneven surface of＜use roughening agent 〉
In addition,, can enumerate when using the acrylic acid series thermoplastic resin composition of containing the particle that becomes the roughening agent to carry out the coextrusion shaping as skin-material, form concavo-convex method on the surface as other formation methods of uneven surface.As coextrusion shaping method at this moment, for example can enumerate the method for putting down in writing in aforesaid TOHKEMY 2009-196327 communique, the TOHKEMY 2009-202382 communique, at this moment, therefore effect by the roughening agent forms concave-convex surface, and also can to adopt common surface state be the metallic roll of minute surface to the 2nd chill roll 6.
In addition, at this moment the general particle that is commonly called so-called light diffusing agent that uses of the roughening agent of Shi Yonging, as light diffusing agent, for example can enumerate organic system particles such as methyl methacrylate based polymer particle, styrenic particle, siloxane-based polymers particle; Lime carbonate, barium sulphate, titanium dioxide, aluminium hydroxide, silicon dioxide (monox), unorganic glass, talcum, mica, white carbon, magnesium oxide, zinc paste etc. are inorganic to be particle etc.In addition, for evenly dispersion in thermoplastic resin, inorganic is that particle can carry out surface treatment with surface conditioning agents such as fatty acid.
Optics of the present invention requires the high light line transmissivity with rough textured film as optical characteristics more, therefore as the roughening agent, can preferably use the good particle of the transparency.In addition, from the roughening agent of adding the degree that to guarantee the concave-convex surface sense and the viewpoint that keeps the high light line transmissivity, preferably with particle that can be not excessive as the refringence of the acrylic resin of substrate resin, the preferred index difference is in about 0.1 usually.From above viewpoint,, preferably use organic system particles such as methyl methacrylate based polymer particle, styrenic particle, siloxane-based polymers particle as the roughening agent among the present invention.These particles can use separately, also can use more than 2 kinds.
The methyl methacrylate based polymer particle that uses as above-mentioned roughening agent is with the particle of methyl methacrylate as the polymkeric substance of main body, this polymkeric substance can be make methyl methacrylate, except that it in molecule, have 1 can free radical polymerization two keys monofunctional monomer and in molecule, have more than 2 the cross-linked polymer that the polyfunctional monomer copolymerization of two keys that can free radical polymerization forms.
Example as the monofunctional monomer except that methyl methacrylate in the above-mentioned methyl methacrylate based polymer particle, can enumerate and be (methyl) acrylate except that methyl methacrylate, styrenic monomers and the identical monomer of the monomer except that (methyl) acrylate and styrenic monomers that the example of the monomer of resin is enumerated formerly, preferably use styrene as methyl methacrylate.
Example as the polyfunctional monomer in the above-mentioned methyl methacrylate based polymer particle, can enumerate dimethacrylate 1, the 4-butanediol ester, the dimethacrylate DOPCP, Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylidene ethylidene glycol dimethacrylate (プ ロ ピ レ Application エ チ レ Application グ リ コ one Le ジ メ タ Network リ レ one ト), four propylidene ethylidene glycol dimethylacrylates (テ ト ラ プ ロ ピ レ Application エ チ レ Application グ リ コ one Le ジ メ タ Network リ レ one ト), trimethylol-propane trimethacrylate, the methyl acrylic ester of polyvalent alcohols such as pentaerythrite tetramethyl acrylate; Diacrylate 1, the methyl acrylic ester of polyvalent alcohols such as 4-butanediol ester, diacrylic acid pentyl diol ester, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, propylidene ethylidene glycol diacrylate (プ ロ ピ レ Application エ チ レ Application グ リ コ one Le ジ Network リ レ one ト), four propylidene ethylidene glycol diacrylates (テ ト ラ プ ロ ピ レ Application エ チ レ Application グ リ コ one Le ジ Network リ レ one ト), trimethylolpropane triacrylate, tetramethylol methane tetraacrylate; Aromatic series such as divinylbenzene, diallyl phthalate polyfunctional compound etc.This polyfunctional monomer can be used alone or in combination of two or more kinds respectively.
The refractive index of this methyl methacrylate based polymer particle is generally about 1.46～1.55, exists the content of benzene skeleton, halogen atom to demonstrate the trend of big more refractive index more at most.This methyl methacrylate based polymer particle for example can pass through manufacturings such as suspension polymerization, microsuspension polymerization method, emulsion polymerization, dispersion copolymerization method.
The styrenic particle that uses as above-mentioned roughening agent is with the particle of styrene as the polymkeric substance of main body, this polymkeric substance can be make styrene, except that it in molecule, have 1 can free radical polymerization two keys monofunctional monomer and in molecule, have more than 2 the cross-linked polymer that the polyfunctional monomer copolymerization of two keys that can free radical polymerization forms.
Example as the monofunctional monomer except that styrene in the above-mentioned styrenic particle, except methyl methacrylate, can also enumerate with formerly as methyl methacrylate be resin monomer example and (methyl) acrylate except that methyl methacrylate, styrenic monomers and the identical monomer of the monomer except that (methyl) acrylate and styrenic monomers enumerated preferably use methyl methacrylate.
Example as the polyfunctional monomer in the above-mentioned styrenic particle, can enumerate and the identical monomer of formerly enumerating of monomer as the example of the polyfunctional monomer of methyl methacrylate based polymer particle, can be respectively separately or will be used in combination more than 2 kinds.
The refractive index of this styrenic particle is generally about 1.53～1.61, exists the content of benzene skeleton, halogen atom to demonstrate the trend of big more refractive index more at most.This styrenic particle for example can pass through manufacturings such as suspension polymerization, microsuspension polymerization method, emulsion polymerization, dispersion copolymerization method.
As the ratio of the polyfunctional monomer that uses in the methyl methacrylate based polymer particle of above-mentioned roughening agent and the styrenic particle, be benchmark with whole monomers, be generally about 0.05～15 quality % preferred 0.1～10 quality %.When the amount of polyfunctional monomer was very few, the crosslinking degree of particle was insufficient, was heated when extrusion molding, particle is easy to significantly be out of shape when shearing, and the result is difficult to obtain required light diffusion effect.In addition, when the amount of multi-functional monomer is too much, bad order takes place easily when extrusion molding.
The siloxane-based polymers particle that uses as above-mentioned roughening agent for example is the particle of the polymkeric substance made by the method that makes the hydrolysis of chlorosilane class, condensation.
As the chlorosilane class, for example can enumerate dimethyldichlorosilane, diphenyl dichlorosilane, phenylmethyldichloroislane, methyl trichlorosilane, phenyl trichlorosilane etc.Siloxane-based polymers can be crosslinked.In order to make it crosslinked, can for example make benzoyl peroxide, peroxidating 2,4-dichloro-benzoyl, chloro benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide-2,5-dimethyl-2, superoxide and siloxane-based polymers effects such as 5-(tert-butyl hydroperoxide) hexane.In addition, when having terminal silanol group, can carry out condensation cross-linking with the alkoxyl silicone alkanes.Be preferably with respect to 1 silicon atom through crosslinked polymkeric substance, be combined with the structure of the organic residue about 2～3.
This siloxane-based polymers is the polymkeric substance that is also referred to as silicone rubber, silicone resin, preferably uses under the normal temperature polymkeric substance as solid.The siloxane polymer particle can obtain by this siloxane polymer is pulverized.By curable polymer, its composition with wire organosiloxane block are solidified with atomize, can make granular particle.In addition, by hydrolytic condensation in the aqueous solution of ammonia or amine, can be used as the form of granular particle and obtain alkyltrialkoxysilaneand or its partial hydrolysis condensation product.
The refractive index of this siloxane-based polymers particle is generally about 1.40～1.47.
The weight average particle diameter of the particle that uses as the roughening agent can suitably be selected according to required concave-convex surface shape, in order to have required concave-convex surface shape, and has good optical characteristics, preferred 0.5～50 μ m, more preferably 1～40 μ m, further preferred 2～30 μ m.In addition, particle is generally spherical, but also can use the square shape, the particle of flakey, needle-like, shape such as tabular.
The particle that uses as the roughening agent with respect to overall the containing of acrylic acid series thermoplastic resin composition proportionally is, below the overall 35 weight % of acrylic acid series thermoplastic resin composition, below the preferred 30 weight %.Containing of the particle that uses as the roughening agent is proportional during greater than the overall 35 weight % of acrylic acid series thermoplastic resin composition, is difficult to carry out the shaping that melt extrudes of composition, thereby not preferred.
＜optics rough textured film 〉
Optics of the present invention is 30～300 μ m with the thickness of rough textured film, preferred 30～200 μ m, more preferably 30～100 μ m.Thickness is during less than 30 μ m, and the film self rigidity reduces, and therefore produces fold easily in film, and it is moving etc. perhaps to issue capture at the state of installing.When thicker than 300 μ m, the length of delay height of incident light, thereby not preferred.
Optics rough textured film of the present invention, the length of delay of the incident light under the wavelength 590nm of film is preferably below the 30nm, more preferably below the 20nm.As the optics rough textured film, for example when being used for the rough textured film of liquid crystal indicator, because liquid crystal is represented the only polarized light that utilized therefore to require the little film of optical skew as rough textured film, the following length of delay of preferred 30nm.In liquid crystal indicator was used, for the polarisation separating sheet diaphragm that is used to protect the polarisation separating sheet, because following reason, length of delay was more preferably below the 20nm equally.
As shown in Figure 2, liquid crystal indicator constitutes as follows: backlight unit 9 is provided with liquid crystal panel 12, from the light of backlight unit 9 outgoing to liquid crystal panel 12 incidents.Polarisation separating sheet 10 is configured between backlight unit 9 and the liquid crystal panel 12 usually, to be separated into 2 polarized lights from the nonpolarized light of backlight unit 9 outgoing with orthogonality relation, only optionally see through a side polarized light and outgoing to liquid crystal panel 12 sides, the opposing party's polarized light returns backlight unit 9 sides, after in backlight unit, reflecting, be incident to polarisation separating sheet 10 once again and utilize again, thus the utilization ratio of raising light.Therefore; as be used to protect polarisation separating sheet 10 on the two sides of this sheet 10 or one side stacked, fit and the polarisation separating sheet diaphragm 11 that uses; not chaotic as far as possible in order to make from the polarization direction of the polarisation of this sheet 10 outgoing, preferred length of delay is low, more preferably the following length of delay of 20nm.
Optics rough textured film of the present invention, the uneven surface on layer (B) surface is preferably more than the B with the surperficial pencil hardness that JIS K5600 measures.The surperficial pencil hardness of uneven surface is during less than B, in film is produced, film handle medium, when contact etc., be easy to the generation of film surface is damaged with miscellaneous part.In addition, in order to prevent damage, can also be at the uneven surface diaphragm of fitting, but must the diaphragm bonding process, it is numerous and diverse also to become on operation, also unfavorable on cost.
Optics of the present invention is preferably more than 90% according to total light transmittance that JIS K7361-1 measures with rough textured film.Total light transmittance of this rough textured film is crossed when low, with respect to the rough textured film quantity of incident light, reduces from the ratio of the light quantity of rough textured film outgoing, and is unfavorable from the utilization ratio aspect of light.
Optics rough textured film of the present invention, the thickness of layer (A) is preferably thickness more than 30%, the more preferably thickness more than 40% with respect to the thickness of film integral body.Less than 30% o'clock, the thermotolerance of film reduced the thickness of layer (A) with respect to the thickness of film integral body, kept estimating in (keeping 30 minutes 120 ℃ baking oven in) at high temperature, sometimes the change in size increase of accompanying with the contraction of this film.Heat distortion temperature (Th) according to ASTM D-648 mensuration, for the polycarbonate-based resin of resinous principle as layer (A) is about 140 ℃, relative therewith, for the acrylic resin of resinous principle as layer (B) is about 100 ℃, therefore, from stable on heating viewpoint, be more than the 9 μ m as the thickness of the layer (A) of resinous principle preferably with polycarbonate-based resin with higher Th.
As optics of the present invention is carried out the size changing rate (shrinkage factor) of high temperature when keep estimating with rough textured film, preferably film extrude direction (MD), Width (TD) is below 7.0%, and is more preferably below 6.0%, further preferred below 5.0%.When size changing rate is big, when using this film in liquid crystal indicator, owing to the heating in the liquid crystal indicator, the change in size of film may take place, floating, rising and falling of film taken place.
In addition, the thickness of layer (B) is preferably more than the 8 μ m, more preferably more than the 10 μ m.Thickness is during less than 8 μ m, and the skin hardness of this layer (B) may reduce sometimes.
Optics of the present invention is formed with concaveconvex shape with rough textured film on the surface; be endowed the function that makes light scattering; therefore; for example in liquid crystal indicator, light diffusing sheet, optical diffusion film, polaroid protective film, phase retardation film, the briliancy that can be used for being installed on backlight unit improves the diaphragm of film etc., polarisation separating sheet etc.In addition, also be applicable to CD, automobile inside with film, illumination with film, building materials with film etc., the present invention is not limited to these purposes.
Embodiment
Below, embodiments of the invention are shown, but the present invention is not limited thereto.In addition, among the following embodiment, part of expression content or use amount is weight basis unless otherwise specified.
Being constructed as follows of the extrusion device that uses in following embodiment and the comparative example.
Extruder 1: the single shaft extruder (toshiba machine (strain) system) of the screw diameter 115mm of band air vent
Extruder 2: the band air vent screw diameter 90mm, single shaft extruder (toshiba machine (strain) system)
3: two kinds 3 layers and two kinds 2 layers distribution type feed piece of feed piece (toshiba machine (strain) system)
Mouth mould 4:T type mouth mould
＜roller constitutes 1 〉
The 1st chill roll 5 and the 2nd chill roll the 6, the 3rd chill roll 7 formations as follows.
The 1st chill roll 5: external diameter 450mm φ, hardness A70 ° silica gel roller
The 2nd chill roll 6: external diameter 450mm φ, be formed with the stainless steel metallic roll (slotter) that arithmetic mean rugosity (Ra) is the concaveconvex shape of 3.5 μ m by blasting treatment
The 3rd chill roll 7: the stainless steel metallic roll (slotter) of external diameter 450mm φ, mirror finish
＜roller constitutes 2 〉
The 1st chill roll 5 and the 2nd chill roll the 6, the 3rd chill roll 7 formations as follows.
The 1st chill roll 5: external diameter 450mm φ, hardness A70 ° silica gel roller
The 2nd chill roll 6: the stainless steel metallic roll (slotter) of footpath 450mm φ, mirror finish
The 3rd chill roll 7: the stainless steel metallic roll (slotter) of footpath 450mm φ, mirror finish
In embodiment and the comparative example,, use following methacrylic resin, roughening agent (transparent particulate) and acrylic rubber particle as methacrylic resin, roughening agent (transparent particulate) and acrylic rubber particle.
＜methacrylic resin 〉
As methacrylic resin, using that polymerization by the monomer component that is made of methyl methacrylate 97.8 weight % and methyl acrylate 2.2 weight % gets, heat distortion temperature (Th) is the particle of 100 ℃ thermoplastic polymer.
＜roughening agent (transparent particulate) 〉
As roughening agent (transparent particulate), use that polymerization by methyl methacrylate 95% and divinylbenzene 5% (mass ratio) gets, refractive index is 1.49, weight average particle diameter is the methyl methacrylate based thermoplastic polymer particle of 5 μ m.
＜acrylic rubber particle 〉
As the acrylic rubber particle, the acrylic rubber particle of the 3-tier architecture that the following manufacture method of use employing obtains.
According to the method for putting down in writing among Japanese Patent Publication 55-27576 number the embodiment, at first, in the glass reaction vessel of internal volume 5L, add ion exchange water 1700g, sodium carbonate 0.7g, sodium peroxydisulfate 0.3g, nitrogen flow down stir after, after adding PELEX OT-P (flower king (strain) system) 4.46g, ion exchange water 150g, methyl methacrylate 150g, allyl methacrylate 0.3g, be warming up to 75 ℃ and continue to stir 150 minutes.
Then, from different inlets with the potpourri that added butyl acrylate 689g, styrene 162g and allyl methacrylate 17g in 90 minutes, and the potpourri of sodium peroxydisulfate 0.85g, PELEX OT-P 7.4g and ion exchange water 50g, further proceed polymerization in 90 minutes.
After polymerization finishes, from different inlets with 30 minutes further potpourris of interpolation methyl acrylate 326g and ethyl acrylate 14g, and the ion exchange water 30g that is dissolved with sodium peroxydisulfate 0.34g.
After adding end, further kept 60 minutes, finish polymerization.The latex that obtains dropped into make polymkeric substance cohesion in 0.5% aluminum chloride aqueous solution.With its with about 50 ℃ warm water washing 5 times after, carry out drying, obtain the acrylic rubber particle of 3-tier architecture.
(embodiment 1, embodiment 7 and comparative example 1)
As layer (A), with polycarbonate resin (" Calibre303-10 " of Sumitomo Dow corporate system, 140 ℃ of Th) melting mixing, be supplied to feed piece 3 from extruder 1, as layer (B), to contain the acrylic acid series thermoplastic resin composition melting mixing of methacrylic resin, roughening agent (transparent particulate) and acrylic rubber particle with the ratio shown in the table 1, be supplied to feed piece 3 from extruder 2, it is stacked integrated to carry out fusion, 3 layers of formation of cambium layer (B)/layer (A)/layer (B) are extruded from mouth mould 4.In addition, for comparative example 1, stop from the supply of extruder 2, only extrusion molding layer (A) to feed piece 3.Then, make the above-mentioned roller of constituting of chill roll constitute 1, to be held in from the membranaceous resin clip that mouth mould 4 is extruded between the 1st chill roll 5 (design temperature: 45 ℃) and the 2nd chill roll 6 (design temperature: 100 ℃), be wound in the 3rd chill roll 7 (design temperature: 100), obtain having the optics rough textured film 8 of concaveconvex shape in the one side transfer printing.
(embodiment 2～6, comparative example 2 and 3)
For embodiment 2～6 and comparative example 3, constitute 2 except making chill roll constitute above-mentioned roller, adopt method similarly to Example 1 to obtain optics rough textured film 8.In addition,, stop the monofilm that is shaped and only constitutes by layer (B) from the supply of extruder 1 to feed piece 3 for comparative example 4.
Table 1
※ is by the thickness of the film integral body of layer (B)/layer (A)/layer (B) formation
Each optics rough textured film for obtaining carries out following evaluation.Show the result in table 2
＜skin hardness (pencil hardness) 〉
According to JIS K5600, the skin hardness of the outermost concaveconvex shape face of the rough textured film that obtains is measured.
＜surface gloss 〉
According to JIS Z8741, to the outermost concaveconvex shape face of the rough textured film that obtains and with 60 degree glossiness of the face of this face opposition side.
＜surface roughness 〉
Use surface roughness meter (" the Surftest sj-201 " of Mitutoyo corporate system),, arithmetic mean rugosity (Ra) and 10 average boldness (Rz) of the outermost concaveconvex shape face of the rough textured film that obtains are measured according to JIS B0601-1994.
＜length of delay 〉
The size square with 50mm cuts out test film by the rough textured film that obtains, and uses the length of delay of small area birefraction meter (" KOBRA-CCO/X " of prince's instrumentation machine (strain) system) when measuring 590nm.
(total light transmittance (Tt) and mist degree (H))
Measure according to JISK7361-1.
＜shrinkage factor 〉
At first, the size square with about 10cm cuts out test film by the rough textured film that obtains, and measures the size (MD that extrudes direction of this test film respectively
0) and the size (TD of Width
0).Then, in metal tubbing, be coated with baby powder (with " the Siccarol Hi " of light hall corporate system), place above-mentioned test film thereon, dropped in 120 ℃ the baking oven 30 minutes.
Then, measure the size of extruding direction (MD) of the test film behind the natural cooling and the size (TD) of Width respectively, with each size substitution formula: the shrinkage factor S that obtains
1={ 1-(MD/MD
0) * 100, formula: shrinkage factor S
2={ 1-(TD/TD
0) * 100 in, calculate shrinkage factor S
1, S
2In addition, by the shrinkage factor S that calculates
1, S
2Calculate than (S
1/ S
2).
Table 2
※ 1 extrudes the size of direction
The size of ※ 2 Widths
The arithmetic mean rugosity of stipulating among the ※ 3JIS B0601-1994
10 average boldness stipulating among the ※ 4JIS B0601-1994.
Claims (9)
1. optics rough textured film, it is characterized in that, one side at least at the layer (A) that forms by the polycarbonate-based thermoplastic resin composition that contains polycarbonate-based resin, the stacked layer (B) that is formed by the acrylic acid series thermoplastic resin composition of containing acrylic resin forms, the surface of at least 1 layer (B) is a uneven surface
The thickness of film integral body is 30～300 μ m, and the thickness of layer (A) is more than 30% with respect to the thickness of film integral body, and the thickness of layer (B) is more than the 8 μ m,
The length of delay of the incident light of the wavelength 590nm of film is below the 30nm.
2. optics rough textured film according to claim 1, described acrylic acid series thermoplastic resin composition is contained rubber particles.
3. optics rough textured film according to claim 2, described rubber particles are the acrylic rubber particle.
4. optics rough textured film according to claim 1, described uneven surface forms by the matte roll transfer printing.
5. optics rough textured film according to claim 1, described acrylic acid series thermoplastic resin composition is contained the roughening agent
6. optics rough textured film according to claim 5, described roughening agent are to be selected from least a kind of transparent particulate as main body in methyl methacrylate based polymer particle, styrenic particle, the siloxane-based polymers particle.
7. optics rough textured film according to claim 1 forms described polycarbonate-based thermoplastic resin composition and described acrylic acid series thermoplastic resin composition coextrusion shaping.
8. according to each described optics rough textured film in the claim 1～7, be used for liquid crystal indicator.
9. optics rough textured film according to claim 8 is used for protecting the polarisation separating sheet of described liquid crystal indicator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010010046A JP5149916B2 (en) | 2010-01-20 | 2010-01-20 | Optical matte film |
| JP2010-010046 | 2010-01-20 |
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| Publication Number | Publication Date |
|---|---|
| CN102129092A true CN102129092A (en) | 2011-07-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100251133A Pending CN102129092A (en) | 2010-01-20 | 2011-01-18 | Coarse film for optical use |
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| Country | Link |
|---|---|
| JP (1) | JP5149916B2 (en) |
| KR (1) | KR20110085899A (en) |
| CN (1) | CN102129092A (en) |
| TW (1) | TW201134662A (en) |
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| JP5139646B2 (en) * | 2006-05-16 | 2013-02-06 | 帝人化成株式会社 | Manufacturing method of light diffusion plate |
| JP5065664B2 (en) * | 2006-12-12 | 2012-11-07 | 恵和株式会社 | Light diffusion sheet for liquid crystal display |
| JP2009255522A (en) * | 2008-03-27 | 2009-11-05 | Sumitomo Chemical Co Ltd | Abrasion-resistant resin plate and portable information terminal display window protecting plate |
-
2010
- 2010-01-20 JP JP2010010046A patent/JP5149916B2/en not_active Expired - Fee Related
-
2011
- 2011-01-17 TW TW100101641A patent/TW201134662A/en unknown
- 2011-01-17 KR KR1020110004516A patent/KR20110085899A/en not_active Application Discontinuation
- 2011-01-18 CN CN2011100251133A patent/CN102129092A/en active Pending
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| CN104854490A (en) * | 2012-12-13 | 2015-08-19 | 日东电工株式会社 | Polarizing film production method |
| CN112394443A (en) * | 2013-08-22 | 2021-02-23 | 东洋钢钣株式会社 | Method for producing polarizing plate protective film and polarizing plate protective film |
| CN107850698A (en) * | 2015-07-23 | 2018-03-27 | 惠和株式会社 | Laminates, LCD MODULE, the manufacture method of back light unit and laminates |
| US10974483B2 (en) | 2015-07-23 | 2021-04-13 | Keiwa Inc. | Laminate sheet, liquid crystal display module, backlight unit, and production method of laminate sheet |
| CN113748020A (en) * | 2019-04-18 | 2021-12-03 | 大日本印刷株式会社 | Transparent resin film, method for producing transparent resin film, and decorative material |
| US11993063B2 (en) | 2019-04-18 | 2024-05-28 | Dai Nippon Printing Co., Ltd. | Transparent resin film, transparent resin film production method, and decorative material |
| WO2023082337A1 (en) * | 2021-11-15 | 2023-05-19 | 聊城鲁西聚碳酸酯有限公司 | Light diffusion agent, flame-retardant light diffusion polycarbonate composition and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110085899A (en) | 2011-07-27 |
| TW201134662A (en) | 2011-10-16 |
| JP5149916B2 (en) | 2013-02-20 |
| JP2011150074A (en) | 2011-08-04 |
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Application publication date: 20110720 |