CN109562553A - The manufacturing method and extruded resin sheet of extruded resin sheet - Google Patents

The manufacturing method and extruded resin sheet of extruded resin sheet Download PDF

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Publication number
CN109562553A
CN109562553A CN201780049200.8A CN201780049200A CN109562553A CN 109562553 A CN109562553 A CN 109562553A CN 201780049200 A CN201780049200 A CN 201780049200A CN 109562553 A CN109562553 A CN 109562553A
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China
Prior art keywords
resin sheet
resin
extruded resin
chill roll
delay
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Granted
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CN201780049200.8A
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CN109562553B (en
Inventor
船崎男
船崎一男
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Kuraray Co Ltd
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Kuraray Co Ltd
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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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/885—External treatment, e.g. by using air rings for cooling tubular films
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • 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
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability

Abstract

The manufacturing method and extruded resin sheet of the few extruded resin sheet of the mechanical periodicity of good, in face the length of delay of offer superficiality.A kind of manufacturing method of extruded resin sheet (16), wherein, include: the thermoplastic resinous laminate for being laminated with the above-mentioned layer containing methacrylic resin on at least single side of the layer containing polycarbonate is coextruded with molten condition from T-die (11), above-mentioned thermoplastic resinous laminate is sandwiched into the process between the first chill roll (12) and the second chill roll (13), the temperature (TX) for the resin entirety being sandwiched between above-mentioned second chill roll and third chill roll (14) is set as to+10 DEG C of glass transition temperature or more relative to the above-mentioned layer containing polycarbonate, in above-mentioned thermoplastic resinous laminate at the position that the chill roll finally wound is removed, the temperature (TT) of resin entirety is set as -2 DEG C~+19 DEG C of glass transition temperature relative to the above-mentioned layer containing polycarbonate Range.

Description

The manufacturing method and extruded resin sheet of extruded resin sheet
Technical field
The present invention relates to extruded resin sheets.More specifically, the week for the length of delay that the present invention relates to superficiality well, in face The protective cover that phase is consistent, is suitable for touch panel etc. has the layer containing methacrylic resin and containing poly- carbonic acid The extruded resin sheet and its manufacturing method of the layer of ester.
Background technique
Touch panel (or touch screen) is the electronic component that combination has display device and positioning input device.Use can be passed through Finger or pen contact touch panel to operate electronic equipment.Touch panel is used for the ATM of bank and other financial mechanism, automatic vending Machine, mobile phone, portable data assistance (PDA), digital audio-frequency player, portable game machine, tablet-type personal computer, Duplicator, facsimile machine, auto navigation digital information equipment etc..
Due to being operated using the input of touch panel, scratch is generated on surface sometimes or internal generate is damaged by pressure.In order to The situation is prevented, transparent protective cover is set on the surface of touch panel.As protective cover, the main guarantor for using strengthened glass Shield.In addition, having carried out the exploitation of the protective cover of transparent resin from the viewpoint of processability, lightweight.For the protection Cover, it is desirable that gloss, marresistance, impact resistance etc..
Polycarbonate is suitable for obtaining one of resin of formed products of excellent impact resistance.Methacrylic resin is It is suitable for obtaining one of the resin of formed products of high glaze and excellent abrasion.In addition, by polycarbonate and methyl-prop Olefin(e) acid resinoid carries out heating melting forming (such as coextrusion forming) simultaneously, can manufacture by layer and packet comprising polycarbonate The resin plate that layer containing methacrylic resin is constituted.In the heating melting forming of such resin plate, due to two kinds of trees The difference of the characteristic of rouge and make to remain many distortional stresses in obtained formed products.This is remained in the deformation in formed products Stress is known as residual stress, and the formed products with the residual stress can generate warpage because of heat etc., shrink.
For the plate formed products of above-mentioned resin plate etc, the warpage as caused by residual stress especially becomes problem. Inhibit one of the method for generation of warpage as the residual stress reduced in plate formed products, it is known that using in extrusion molding Chill roll the method (for example, referenced patent document 1) that is adjusted of rotation speed.In addition, it is known that as with polycarbonate The vinyl copolymer resin being laminated, using to make methyl methacrylate and it is styrene copolymerized made of resin aromatic series The resin (for example, patent document 2) that double bond is hydrogenated.
In addition, in order to solve this problem, being ground to the raising of the heat resistance and moisture-proof of methacrylic resin Study carefully.Such as, it was recently reported that a kind of two layers of resin plate, wherein using with methyl methacrylate units and selected from methyl-prop Olefin(e) acid unit, acrylic acid units, maleic anhydride units, N- maleimide amine unit substituted or unsubstituted, glutaric anhydride structure list The methacrylic resin that unit and glass transition temperature in member and glutarimide structural unit are 110 DEG C or more comes First layer is formed, has the layer (for example, referenced patent document 3) comprising polycarbonate on it.But even if in this way, tree The heat resistance and moisture-proof of the methacrylic resin of rouge plate are also insufficient, even if can not fully be solved using the program The above problem.
In addition, in order to solve this problem, it is also known that the difference for being conceived to the linear expansion coefficient between two resin sheets of reduction is come Control the method (for example, referenced patent document 4) of the generation of warpage.But when only realizing the regulation of linear expansion coefficient, fail to solve The certainly above problem.
As above-mentioned protective cover, following scheme is had studied: in order to improve marresistance, identification and use at least one The resin plate of marresistance (hard painting propert), low reflexive hardening overlay film is formed on face.
For example, Patent Document 5 discloses: hardening, which is formed, at least one face of methacrylic resin plate covers The display window protective panel of film, the portable data assistance as crystal liquid mode uses.
In addition, Patent Document 6 discloses: stacking contains methacrylic on a face of polycarbonate resin The layer of resin forms hardening overlay film on the layer containing methacrylic resin for be formed by plywood, is used for liquid crystal display Device cover.
In addition, above-mentioned protective cover is set to the front side (identification person side) of liquid crystal display, identification person penetrates the protective cover It watches the picture of liquid crystal display, but for previous protective cover, hardly makes as polarisation from liquid crystal Show that the polarity of the emergent light of device changes, therefore, has on polarized sunglasses come when watching picture, according to the polarisation of emergent light The axis of homology of axis and polarized sunglasses is formed by angle, and picture is dimmed and be difficult to see that image sometimes.Therefore, to can inhibit The liquid crystal display that image recognition when crossing the picture of the polarities optical filter such as polarized sunglasses viewing liquid crystal display reduces Protective cover is studied.
For example, Patent Document 7 discloses: the length of delay in face is set as 85~300nm.
The hardening overlay film of marresistance (hard painting propert) and low reflectivity is formed on the surface of resin plate as described above In process, resin plate is heated to about 100 DEG C of temperature sometimes.For example, being covered in the case where covering material is heat cured situation The curing process of film is heated.In addition, being heated in the case where covering material is light solidity with the irradiation of light.In addition, In the case where covering material contains organic solvent equal solvent, it is heated due to dry.
But due to resin plate is exposed under high temperature and length of delay reduce, be unable to control sometimes in the desired range in.
In addition to this, on-vehicle displays, portable phone, the intelligence such as the auto-navigation system of liquid crystal display are being used In the case that mobile phone is placed in automobile under the sunshine of summer, liquid crystal display protection board remain on sometimes can be heated it is supreme The length of delay of temperature, resin plate may reduce.About the project that the length of delay reduces, it is conceived to the peripheral speed of roller and discloses Solution (such as patent document 8,9)
As described previously for above-mentioned resin plate, various technical problems and solution are disclosed.Here, above-mentioned resin plate There are following situations: when having on polarized sunglasses to watch picture, due to the mechanical periodicity of length of delay, the light and shade and face of picture Color change becomes uneven, is difficult to see that image.But not yet notice this point, also without open solution.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-185956 bulletin
Patent document 2:WO2011/145630
Patent document 3: Japanese Unexamined Patent Publication 2009-248416 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2007-118597 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2004-299199 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2006-103169 bulletin
Patent document 7: Japanese Unexamined Patent Publication 2010-085978 bulletin
Patent document 8:WO2015/093037
Patent document 9:WO2016/038868
Summary of the invention
Problem to be solved by the invention
In extruded resin sheet, the degree for remaining on the stress of each resin layer is different.Therefore, it has attempted by adjusting being extruded into The rotation speed of chill roll used in shape reduces remaining stress.But when formed products leave chill roll, exist sometimes The surface of formed products generates the striated defect for being referred to as the line that quivers, and superficiality reduces.The phenomenon is used for by the extruded resin sheet Become problem in the case where protective cover of touch panel etc..
The few extruded resin sheet of the mechanical periodicity for the length of delay that the object of the present invention is to provide superficiality well, in face Manufacturing method and extruded resin sheet.
The method for solving problem
The present inventor is studied in order to achieve the above object, as a result, it has been found that the present invention comprising following manner. That is, the present invention includes mode below.
[1] a kind of manufacturing method of extruded resin sheet, to be laminated on at least single side of the layer containing polycarbonate The manufacturing method of the extruded resin sheet of layer containing methacrylic resin, wherein
Include following process:
It will be laminated on at least single side of the above-mentioned layer containing polycarbonate above-mentioned containing methacrylic resin The thermoplastic resinous laminate of layer is coextruded with molten condition from T-die,
Above-mentioned thermoplastic resinous laminate is sandwiched between the first chill roll and the second chill roll,
By being wound up into third chill roll after above-mentioned thermoplastic resinous laminate is wound up on above-mentioned second chill roll Above cooled down,
The utilization of above-mentioned thermoplastic resinous laminate is deflected from roller to deflect from,
By the temperature (TX) for the resin entirety being sandwiched between above-mentioned second chill roll and third chill roll be set as relative to + 10 DEG C of glass transition temperature or more of the above-mentioned layer containing polycarbonate,
In above-mentioned thermoplastic resinous laminate at the position that the chill roll finally wound is removed, by the temperature of resin entirety (TT) it is set as -2 DEG C~+19 DEG C of glass transition temperature of the range relative to the above-mentioned layer containing polycarbonate.
[2] manufacturing method of the extruded resin sheet according to [1], wherein
The glass transition temperature of the above-mentioned layer containing methacrylic resin is 110 DEG C or more,
The linear expansion coefficient (S1) of the above-mentioned layer containing polycarbonate and the above-mentioned layer containing methacrylic resin The ratio between the difference (S2-S1) of linear expansion coefficient (S2) and the linear expansion coefficient (S1) of the above-mentioned layer containing polycarbonate ((S2-S1)/ It S1) is -10%~+10%.
[3] manufacturing method of the extruded resin sheet according to [1] or [2], wherein by the above-mentioned peripheral speed for deflecting from roller (V4) 0.98 or more and 1.01 or less is set as with the peripheral speed ratio (V4/V2) of the peripheral speed (V2) of above-mentioned second chill roll.
[4] manufacturing method of the extruded resin sheet according to any one of [1]~[3], wherein above-mentioned methacrylic acid Resinoid contains 40~80 mass % of structural unit from methyl methacrylate and comes from methyl shown in the following general formula (I) 60~20 mass % of structural unit of acrylate.
(in formula, Cy indicates alicyclic type hydrocarbon.)
[5] manufacturing method of the extruded resin sheet according to [4], wherein the Cy in above-mentioned logical formula (I) is polycyclic aliphatic Race's alkyl.
[6] manufacturing method of the extruded resin sheet according to [1]~[3], wherein above-mentioned to contain methacrylic tree The layer of rouge contains 95~20 mass % of 5~80 mass % of methacrylic resin and copolymer, and the copolymer, which contains, to be come from The structural unit of aromatic ethenyl compound shown in the following general formula (II) and the acid anhydrides shown in the following general formula (III) Structural unit.
(in formula,R1And R2Each independently represent hydrogen atom or alkyl.)
(in formula,R3And R4Each independently represent hydrogen atom or alkyl.)
[7] manufacturing method of the extruded resin sheet according to [6], wherein above-mentioned copolymer contains from above-mentioned fragrance It 50~84 mass % of structural unit of race's vinyl compound, 15~49 mass % of structural unit from above-mentioned acid anhydrides and comes from 1~35 mass % of structural unit of methacrylate.
[8] manufacturing method of the extruded resin sheet according to [7], wherein the above-mentioned structure from methacrylate Unit is methyl methacrylate.
[9] a kind of manufacturing method of extruded resin sheet, wherein
Comprising obtaining extruded resin sheet by manufacturing method described in any one of [1]~[8], further by above-mentioned extrusion At a temperature of heating 1~30 hour process of the resin plate at 65 DEG C~110 DEG C,
Before and after above-mentioned heating at least in a part of width direction, the length of delay in face is 50~600nm, above-mentioned to add The reduced rate of the above-mentioned length of delay of hot front and back is less than 30%.
[10] a kind of extruded resin sheet, to be laminated on at least single side of the layer containing polycarbonate containing methyl-prop The extruded resin sheet of the layer of olefin(e) acid resinoid, wherein
The glass transition temperature of the above-mentioned layer containing methacrylic resin is 110 DEG C or more,
Standard deviation obtained from length of delay on Extrusion Flow direction in 50mm length in aspect of measure is less than 2.5nm
When being heated 5 hours under any stationary temperature in 75 DEG C~100 DEG C, before heating after at least in width direction A part in, length of delay in face is 50~600nm,
The reduced rate of above-mentioned length of delay before and after above-mentioned heating less than 30%,
The linear expansion coefficient (S1) of the above-mentioned layer containing polycarbonate and the above-mentioned layer containing methacrylic resin The ratio between the difference (S2-S1) of linear expansion coefficient (S2) and the linear expansion coefficient (S1) of the above-mentioned layer containing polycarbonate ((S2-S1)/ It S1) is -10%~+10%.
[11] extruded resin sheet according to [10], wherein by above-mentioned extruded resin sheet in 75 DEG C or 100 DEG C of temperature At lower heating 5 hours, before heating after at least in a part of width direction, length of delay in face is 50~600nm,
The reduced rate of above-mentioned length of delay before and after above-mentioned heating is less than 30%.
[12] extruded resin sheet according to [10] or [11], wherein at least in width direction before and after above-mentioned heating A part in, length of delay in face is 80~350nm.
[13] extruded resin sheet according to any one of [10]~[12], wherein above-mentioned before and after above-mentioned heating prolongs The reduced rate being worth late is less than 15%.
[14] extruded resin sheet according to any one of [10]~[13], wherein also have at least one surface Standby marresistance layer.
Invention effect
The superficiality of the extruded resin sheet obtained using the manufacturing method of extruded resin sheet of the invention is good.In addition, by It is few in the mechanical periodicity of the length of delay in face, therefore the light and shade and color change of picture when through polarized sunglasses identification can be inhibited The unevenness of change.Extruded resin sheet of the invention is suitable for for example requiring gloss, scratch resistance since the identification of picture is excellent The purposes such as the touch panel protective cover of property and impact resistance.
Detailed description of the invention
Fig. 1 be show an embodiment of the invention, using coextrusion extruded resin sheet manufacturing method figure.
Fig. 2 is the polarisation photo of the mechanical periodicity of the delay of the extruded resin sheet of comparative example.
Specific embodiment
Extruded resin sheet of the invention is in the layer containing polycarbonate (hereinafter, being also suitably recorded as that " polycarbonate contains Layer ") at least single side on be laminated with the layer containing methacrylic resin (hereinafter, being also suitably recorded as " methacrylic acid Resinoid contains layer ").
It is laminated with methacrylic resin on layer contains layer by containing in polycarbonate, thus the transparency, impact resistance Property, excellent abrasion.Extruded resin sheet is manufactured by extrusion molding method, and thus production efficiency is excellent.
In extruded resin sheet, the lower limit for the glass transition temperature (Tg) that methacrylic resin contains layer is preferably 110 DEG C, more preferably 115 DEG C are even more preferably 120 DEG C, most preferably 125 DEG C；Its glass transition temperature (Tg) The upper limit is preferably 160 DEG C, and more preferably 155 DEG C, be even more preferably 150 DEG C.Methacrylic resin contains the glass of layer Glass transition temperature (Tg) in the range when, superficiality is good, and the warpage as caused by residual stress is small, thus it is preferred that.
[methacrylic resin]
In the present invention, methacrylic resin contains the structural unit from methacrylate.Methacrylic acid In resinoid, the content preferably from the structural unit of methacrylate is preferably 50 mass % or more, more preferably 80 mass % or more, further preferably 90 mass % or more.It can be 100 mass %.In the knot from methacrylate The content of structure unit within the above range in the case where, the transparency is good.
The methacrylate is indicated by logical formula (IV).
In logical formula (IV), R indicates alkyl.Alkyl can be saturated hydrocarbyl, or unsaturated alkyl.
Alkyl represented by R can be the Noncyclic aliphatics alkyl such as methyl, ethyl, propyl, or ester ring type hydrocarbon Base can also be the aromatic hydrocarbyls such as phenyl.Here, methacrylate is by general formula in the case where R is alicyclic type hydrocarbon (I) it indicates.Hereinafter, methacrylate represented by logical formula (I) is suitably also recorded as " methacrylate (I) ".
(in formula, Cy indicates alicyclic type hydrocarbon.)
It as methacrylate (I), can enumerate: cyclohexyl methacrylate, methacrylic acid ring pentyl ester, metering system The methacrylic acids monocyclic aliphatic such as sour cycloheptyl ester race hydrocarbon ester；Methacrylic acid 2- norbornyl ester, methacrylic acid 2- methyl -2- drop Norbornene ester, methacrylic acid 2- ethyl -2- norbornyl ester, methacrylic acid 2- isobornyl thiocyanoacetate, methacrylic acid 2- methyl -2- are different Norbornene ester, methacrylic acid 2- ethyl -2- isobornyl thiocyanoacetate, methacrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester, methacrylic acid 8- methyl -8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester, methacrylic acid 8- ethyl -8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester, metering system Sour 2- Buddha's warrior attendant alkyl ester, 2-Methacryloyloxy-2-methyladamantane, 2-Ethyl-2-adamantyl methacrylate, metering system Sour 1- Buddha's warrior attendant alkyl ester, methacrylic acid 2- turnip ester, methacrylic acid 2- methyl -2- turnip ester or methacrylic acid 2- ethyl -2- turnip The methacrylic acids multicyclic aliphatic hydrocarbon ester such as ester；Deng.Wherein, preferred methacrylic acid multicyclic aliphatic hydrocarbon ester, more preferable methyl Acrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester.
Methacrylic resin can contain the structural unit of other monomers other than methacrylate.As Other monomers, can enumerate: methyl acrylate (being also suitably recorded as " MA " below), ethyl acrylate, n-propyl, Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Hexyl 2-propenoate, acrylic acid 2- ethyl hexyl Ester, nonyl acrylate, decyl acrylate, lauryl ester, stearyl acrylate, acrylic acid 2- hydroxy methacrylate, acrylic acid 2- hydroxy propyl ester, acrylic acid 4- hydroxybutyl, cyclohexyl acrylate, acrylic acid 2- methoxy acrylate, acrylic acid 3- methoxyl group fourth Ester, acrylic acid trifluoromethyl ester, acrylic acid trifluoro ethyl ester, five fluorine ethyl ester of acrylic acid, glycidyl acrylate, acrylic acid allyl Ester, phenyl acrylate, toluene toluene, benzyl acrylate, isobornyl acrylate, acrylic acid 3- dimethylamino ethyl ester etc. Acrylate, from the viewpoint of availability, preferably MA, ethyl acrylate, n-propyl, isopropyl acrylate, propylene The acrylate such as sour N-butyl, isobutyl acrylate, tert-butyl acrylate, more preferable MA and ethyl acrylate, most preferably MA.First The total preferably 10 mass % of the content of the structural unit from above-mentioned other monomers in base acrylic resin are hereinafter, more excellent 5 mass % are selected as hereinafter, further preferably 2 mass % or less.
Methacrylic resin used in the present invention passes through by above-mentioned methacrylate and as optional member Other monomers, which are polymerize, to be obtained.In the case where using various of monomer in the polymerization, usually the various of monomer is mixed and Monomer mixture is prepared, then for polymerization.Polymerization is not particularly limited, and from the viewpoint of productivity, preferably passes through The methods of mass polymerization, suspension polymerization, solution polymerization process, emulsion polymerization carry out free radical polymerization.
The weight average molecular weight (being also suitably recorded as " Mw " below) of methacrylic resin used in the present invention is excellent It is selected as 40000~500000.By making 40000 or more the Mw, extruded resin sheet of the invention becomes marresistance, heat resistance Excellent extruded resin sheet；By making the Mw 500000 hereinafter, shaping processability is excellent, extrusion tree of the invention can be improved The productivity of rouge plate.
It should be noted that Mw refers to the standard polyphenyl second measured using gel permeation chromatography (GPC) in this specification Alkene scaled value.
[methacrylic resin (B)]
In one embodiment, methacrylic resin used in the present invention is preferably comprised from methyl methacrylate The structural unit of ester (being also suitably recorded as " MMA " below) and from methacrylate (I) structural unit (below sometimes Referred to as methacrylic resin (B)), wherein structural unit further preferably from MMA and polycyclic from methacrylic acid The structural unit of aliphatic hydrocarbon ester, further preferably the structural unit from MMA and come from methacrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester structural unit.
From the viewpoint of hardness, methacrylic resin (B) used in the present invention preferably comprises 40~80 matter Measure the structural unit from MMA of %, further preferably 50~80 mass %, further preferably 50~60 mass %.
From the viewpoint for reducing aftermentioned line expansion ratio (SR) and glass transition temperature (Tg) is made to be 110 DEG C or more of viewpoint Set out, methacrylic resin (B) used in the present invention preferably comprise 20~60 mass % from methacrylate (I) structural unit, further preferably 20~50 mass %, further preferably 40~50 mass %.From metering system When the structural unit of acid esters (I) is more than 60 mass %, have the tendency that the impact resistance that methacrylic resin contains layer reduces.
[resin combination (1) containing methacrylic resin]
In yet another embodiment of the present invention, it is containing 5~80 mass %'s that methacrylic resin, which contains layer, The resin combination of the copolymer (being suitably recorded as " SMA resin " below) of methacrylic resin and 95~20 mass % (being suitably recorded as " resin combination (1) " below), the copolymer at least contain the virtue shown in the following general formula (II) It the structural unit of fragrant race's vinyl compound (being also suitably recorded as " aromatic ethenyl compound (II) " below) and comes from The structural unit of acid anhydrides shown in the following general formula (III) (being also suitably recorded as " acid anhydrides (III) " below).
(in formula,R1And R2Each independently represent hydrogen atom or alkyl.)
(in formula,R3And R4Each independently represent hydrogen atom or alkyl.)
Methacrylic resin contained in resin combination (1) (is also suitably recorded as " methacrylic below Resin (A) ") it is the resin containing the structural unit for carrying out methacrylate shown in self-drifting (IV).
As the methacrylate, it is not particularly limited, from the viewpoint of availability, preferably MMA, methacrylic acid Ethyl ester, n propyl methacrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate and first Base tert-butyl acrylate, most preferably MMA.The structural unit from methacrylate in the methacrylic resin (A) Content be preferably 90 mass % or more, more preferably 95 mass % or more, further preferably 98 mass % or more can be only For the structural unit from methacrylate.
In addition, methacrylic resin (A) preferably comprises coming from for 90 mass % or more from the viewpoint of heat resistance The structural unit of MMA, further preferably 95 mass % or more, further preferably 98 mass % or more can be only to come from The structural unit of MMA.
In addition, methacrylic resin (A) can contain the structure of other monomers other than methacrylate Unit.As other monomers, the other monomers addressed in the explanation of methacrylic resin can be used.Methyl-prop The total preferably 10 mass % of the content of the structural unit from above-mentioned other monomers in olefin(e) acid resinoid (A) are hereinafter, more excellent 5 mass % are selected as hereinafter, further preferably 2 mass % or less.
From the viewpoint for reducing aftermentioned line expansion ratio (SR) and glass transition temperature (Tg) is made to be 110 DEG C or more Viewpoint is set out, and the content of the SMA resin in resin combination (1) used in the present invention is preferably set to 20 mass % or more, more It is preferred that in the range of 45~95 mass %, further preferably in the range of 50~90 mass %.
The content of methacrylic resin (A) in resin combination used in the present invention (1) be preferably 80% with Under, more preferably in the range of 5~55 mass %, further preferably in the range of 10~50 mass %.
Above-mentioned SMA resin is at least containing the structural unit from aromatic ethenyl compound (II) and from acid anhydrides (III) copolymer of structural unit.
As the R in logical formula (II)1And R2And the R in logical formula (III)3And R4The alkyl each independently represented, it is excellent Select methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, just The alkyl below of the carbon atom numbers such as hexyl, n-heptyl, n-octyl, 2- ethylhexyl, nonyl, decyl, dodecyl 12, more preferably The alkyl below of the carbon atom numbers such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl 4.
As R1, preferably hydrogen atom, methyl, ethyl and tert-butyl.As R2、R3、R4, preferably hydrogen atom, methyl and second Base.
The content of the structural unit from aromatic ethenyl compound (II) in above-mentioned SMA resin is preferably 50~85 In the range of quality %, more preferably 55~82 mass %, further preferably in the range of 60~80 mass %.The content When in the range of 50~85 mass %, the moisture-proof and excellent transparency of resin combination (1).
As aromatic ethenyl compound (II), it can be mentioned, for example: styrene；2-methyl styrene, 3- methylbenzene second The cores alkyl-substituted styrenes such as alkene, 4- methyl styrene, 4- ethyl styrene, 4- t-butyl styrene；α-methylstyrene, 4- The alpha-alkyls substituted phenylethylene such as methyl-alpha-methyl, from the viewpoint of availability, optimization styrene.These aromatic series Vinyl compound (II) can be used alone, and can also be applied in combination a variety of.
The content of the structural unit from acid anhydrides (III) in above-mentioned SMA resin is preferably in the range of 15~50 mass % It is interior, more preferably in the range of 18~45 mass %, further preferably in the range of 20~40 mass %.The content is 15 When in the range of~50 mass %, the heat resistance and excellent transparency of resin combination (1).
As acid anhydrides (III), it can be mentioned, for example: maleic anhydride, citraconic anhydride, dimethyl maleic anhydride etc., from availability From the perspective of, preferred maleic anhydride.These acid anhydrides (III) can be used alone, and can also be applied in combination a variety of.
Above-mentioned SMA resin is preferably other than containing aromatic ethenyl compound (II) and acid anhydrides (III) also containing next From the structural unit of methacrylate monomers.The structural unit from methacrylate monomers in above-mentioned SMA resin Content is preferably in the range of 1~35 mass %, more preferably in the range of 3~30 mass %, further preferably in 5~26 matter In the range of amount %.By making the content in the range of 1~35 mass %, bendability, excellent transparency.This feelings Under condition, the content of the structural unit from aromatic ethenyl compound (II) preferably in the range of 50~84 mass %, is come From the content of the structural unit of acid anhydrides (III) preferably in the range of 15~49 mass %.
As the methacrylate, it can be mentioned, for example: MMA, ethyl methacrylate, propyl methacrylate, first Base isopropyl acrylate, n-BMA, propyl methacrylate, isopropyl methacrylate, methacrylic acid are just Butyl ester, Isobutyl methacrylate, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, cyclohexyl methacrylate, Phenyl methacrylate, benzyl methacrylate, methacrylic acid 1- phenyl chlorocarbonate；Deng.In these methacrylates, preferably Alkyl methacrylate that the carbon atom number of alkyl is 1~7, from the heat resistance of obtained SMA resin, excellent transparency Viewpoint is set out, particularly preferred MMA.In addition, methacrylate can be used alone, can also be applied in combination a variety of.
Above-mentioned SMA resin can have from aromatic ethenyl compound (II), acid anhydrides (III) and methacrylate The structural unit of other monomers in addition.As other monomers, can be used in the explanation of methacrylic resin The other monomers addressed.The content of the structural unit from other monomers in SMA resin be preferably 10 mass % hereinafter, More preferably 5 mass % are hereinafter, further preferably 2 mass % or less.
Above-mentioned SMA resin by by above-mentioned aromatic ethenyl compound (II), acid anhydrides (III) and methacrylate with And other monomers as optional member are polymerize and are obtained.In the polymerization, usually the monomer used is mixed and is made Standby monomer mixture, then for polymerization.Polymerization is not particularly limited, and from the viewpoint of productivity, preferably passes through this The methods of body polymerization, solution polymerization process carry out free radical polymerization.
The Mw of above-mentioned SMA resin preferably 40000~300000 range.By making 40000 or more the Mw, the present invention The marresistance of extruded resin sheet, excellent impact resistance can by making the Mw 300000 hereinafter, shaping processability is excellent To improve the productivity of extruded resin sheet of the invention.
Above-mentioned resin combination (1) is by the way that above-mentioned methacrylic resin (A) and above-mentioned SMA resin to be obtained by mixing It arrives.The mixing can be used such as melt mixing methods, solution mixing method.It is mixed using such as single screw rod in melt mixing methods The melting mixing machines such as mill or multiscrew kneading machine, open roll, banbury mixers, kneader, as needed in nitrogen, argon Melting mixing is carried out under the inert gas atmospheres such as gas, helium.In solution mixing method, make methacrylic resin (A) and SMA tree Rouge is dissolved in the organic solvents such as toluene, tetrahydrofuran, methyl ethyl ketone and is mixed.
[methacrylic resin contains layer]
Methacrylic resin contains layer can be only by above-mentioned methacrylic resin (preferably methacrylic Resin (A) or (B)) it constitutes, above-mentioned methacrylic resin and other polymer can also be contained, or above-mentioned resin Composition (1) can also further contain other polymer in above-mentioned resin combination (1).As other polymer, There is no limit can enumerate: the polyolefin such as polyethylene, polypropylene, polyamide, polyphenylene sulfide as long as not damaging effect of the invention The thermoplastic resins such as ether, polyether-ether-ketone, polyester, polysulfones, polyphenylene oxide, polyimides, polyetherimide, polyacetals；Phenolic resin, Heat-curing resins such as melamine resin, organic siliconresin, epoxy resin etc..Above-mentioned other polymer can be used alone one Kind, it can also be applied in combination a variety of.Composition methacrylic resin used in an embodiment of the invention contains layer Resin in the contents of above-mentioned other polymer be preferably 10 mass % hereinafter, more preferably 5 mass % are hereinafter, further excellent It is selected as 2 mass % or less.
When containing other polymer and/or additive in methacrylic resin, it can polymerize by monomer Shi Tianjia can also be added after polymerisation.
When containing other polymer and/or additive in resin combination (1), methacrylic can will be being constituted The addition when monomer of resin (A) and/or SMA resin is polymerize, can also be by methacrylic resin (A) and SMA tree Rouge adds when mixing, and can also add again after mixing methacrylic resin (A) with SMA resin.
Methacrylic resin used in an embodiment of the invention, which contains layer, can according to need containing each Kind additive.As the additive, it can be mentioned, for example: antioxidant, heat deterioration preventing agent, ultraviolet absorbing agent, light are stablized Agent, lubricant, release agent, polymer processing aid, antistatic agent, fire retardant, dyes/pigments, light diffusing agent, delustering agent, core The impact resistances such as shell particles and block copolymer modification agent, fluorophor etc..The content of these additives can not damage this hair It is suitably set in the range of obvious results fruit, 100 mass parts of resin of layer is contained relative to composition methacrylic resin, for example, The content of antioxidant is preferably 0.01~1 mass parts, and the content of ultraviolet absorbing agent is preferably 0.01~3 mass parts, and light is steady The content for determining agent is preferably 0.01~3 mass parts, and the content of lubricant is preferably 0.01~3 mass parts, the content of dyes/pigments Preferably 0.01~3 mass parts.
Composition methacrylic resin used in an embodiment of the invention contains the melt flow of the resin of layer Dynamic rate (being suitably recorded as " MFR " below) preferably in the range of 1~10g/10 minutes, more preferably divides in 1.5~7g/10 In the range of clock, further preferably at 2~4g/10 minutes.When MFR is in the range of 1~10g/10 minutes, heating melting forming Have good stability.
It should be noted that the MFR for the resin that the composition methacrylic resin in this specification contains layer be using Fusion index instrument is worth obtained from measuring under 230 DEG C of temperature, 3.8kg load.
[polycarbonate]
Polycarbonate used in extruded resin sheet of the invention is preferably by the way that dihydric phenol and carbonate precursor to be total to It is poly- to obtain.
It as above-mentioned dihydric phenol, can enumerate: 2,2- bis- (4- hydroxy phenyl) propane (common name bisphenol-A), bis- (the 4- hydroxyls of 1,1- Phenyl) ethane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, the bis- (3,5- of 2,2- Dimethyl -4- hydroxy phenyl) propane, bis- (4- hydroxy phenyl) thioethers, bis- (4- hydroxy phenyl) sulfones etc., wherein preferred bisphenol-A. These dihydric phenols can be used alone, and can also be applied in combination a variety of.
As above-mentioned carbonate precursor, the carbonic esters such as the halo carbonyl compounds such as phosgene, diphenyl carbonate, binary can be enumerated Haloformates such as the bishaloformate of phenol etc..These carbonate precursors can be used alone, and can also be applied in combination It is a variety of.
The manufacturing method of above-mentioned polycarbonate is not particularly limited, it can be mentioned, for example: make the aqueous solution and carbonic acid of dihydric phenol The interfacial polymerization that the organic solvent solution of ester precursor is reacted at interface；Make dihydric phenol and carbonate precursor in high temperature, subtract Pressure, it is solvent-free under the conditions of the ester-interchange method that reacts etc..
The Mw of above-mentioned polycarbonate preferably 10000~100000 range, more preferably 20000~70000 range. By making 10000 or more the Mw, the impact resistance of extruded resin sheet of the invention, excellent heat resistance；By making the Mw For 100000 hereinafter, the shaping processability of polycarbonate is excellent, the productivity of extruded resin sheet of the invention can be improved.
[polycarbonate contains layer]
Above-mentioned polycarbonate contains layer can contain other polymer within the scope of the effect of the invention.As institute Other polymer are stated, can be used and contain saying for layer in methacrylic resin, SMA resin and methacrylic resin The identical polymer of the polymer addressed in bright.Above-mentioned other polymer can be used alone, and can also be applied in combination more Kind.The content of above-mentioned other polymer in polycarbonate be preferably 15 mass % hereinafter, more preferably 10 mass % hereinafter, into One step is preferably 5 mass % or less.
Above-mentioned polycarbonate, which contains layer, can according to need containing various additives.As additive, can be used with it is upper It states methacrylic resin and contains the identical additive of the additive that can contain in layer.The content of these additives can be It does not damage in the range of effect of the present invention and suitably sets, relative to 100 mass parts of polycarbonate, the content of antioxidant is preferably 0.01~1 mass parts, the content of ultraviolet absorbing agent are preferably 0.01~3 mass parts, and the content of light stabilizer is preferably 0.01 ~3 mass parts, the content of lubricant are preferably 0.01~3 mass parts, and the content of dyes/pigments is preferably 0.01~3 mass parts.
It, can be before by dihydric phenol and carbonic ester when adding other polymer and/or additive into above-mentioned polycarbonate Body carries out addition when polycondensation, and simultaneously melting mixing can also be added after terminating the polycondensation.
The glass transition temperature (Tg) of above-mentioned polycarbonate is preferably in the range of 120~160 DEG C, more preferably 135 In the range of~155 DEG C, further preferably in the range of 140~150 DEG C.
The MFR of above-mentioned polycarbonate is preferably in the range of 1~30g/10 minutes, more preferably at 3~20g/10 minutes In range, further preferably in the range of 5~10g/10 minutes.When MFR is in the range of 1~30g/10 minutes, heating is molten Melt having good stability for forming.
It should be noted that the MFR of the polycarbonate in this specification be using fusion index instrument 300 DEG C of temperature, It is worth obtained from being measured under conditions of under 1.2kg load.
Commercially available product can be used in above-mentioned polycarbonate, such as it is preferable to use live to change Si Tailong polycarbonate strain formula meeting " CALIBRE (registered trademark) " and " SD POLYCA (registered trademark) " of society's manufacture, Mitsubishi engineering Plastics Co., Ltd manufacture " TARFLON (registered trademark) ", the Supreme Being's peopleization of " IUPILON/NOVAREX (registered trademark) ", Idemitsu Kosen Co., Ltd. manufacture At " PANLITE (registered trademark) " etc. of Co., Ltd.'s manufacture.
[extruded resin sheet]
In extruded resin sheet, the linear expansion coefficient (S1) and methacrylic resin for containing layer by polycarbonate contain layer Linear expansion coefficient (S2) relational expression indicate line expansion ratio (SR) be defined as the linear expansion coefficient that polycarbonate contains layer (S1) and methacrylic resin contain layer linear expansion coefficient (S2) difference (S2-S1) and the ratio between linear expansion coefficient (S1), The value indicated by calculating formula ((S2-S1) × 100/S1).
Line expansion ratio (SR) is in the range of -10%~+10%, good from realizing preferably in the range of -10%~+5% From the perspective of good warpage reduces, line expansion ratio (SR) is more preferably in the range of -5%~+2%.Line expansion ratio (SR) can Think -10%~-0.1%, -5%~-0.1% ,+0.1%~+10% ,+0.1%~+5% or+0.1%~+2%.Line is swollen It is swollen in the range than (SR) when, be easy to get the extruded resin sheet that superficiality is good, the warpage as caused by residual stress is small.
The thickness of extruded resin sheet of the invention is preferably 0.1~3.0mm, more preferably 0.5~2.0mm.When excessively thin, have The tendency rigidly become inadequate.When blocked up, there is the light-weighted tendency for interfering liquid crystal display device etc..
The thickness that the methacrylic resin of extruded resin sheet of the invention contains layer is preferably 20~200 μm.At this When range, the balance of marresistance and impact resistance is excellent.More preferably 25~150 μm, further preferably 30~100 μm.
The thickness that the polycarbonate of extruded resin sheet of the invention contains layer is preferably 0.1~3.0mm, and more preferably 0.5 ~2.0mm.When excessively thin, have the tendency that impact resistance becomes inadequate.When blocked up, there is the lightweight for interfering liquid crystal display device etc. Tendency.
As long as extruded resin sheet of the invention is laminated with methacrylic on at least single side that polycarbonate contains layer Resin contains layer, then can have other resin layers.It can be mentioned, for example following compositions: polycarbonate contains layer-methacrylic acid Resinoid contains two layers of layer；Methacrylic resin, which contains layer-polycarbonate and contains layer-methacrylic resin, to be contained Three layers of layer；Methacrylic resin contains three layers that layer-polycarbonate contains the other resin layers of layer-；Other resin layer-first Base acrylic resin contains three layers that layer-polycarbonate contains layer；Deng.
In extruded resin sheet of the invention, hardening overlay film can be set on its at least one face.It is covered by the way that hardening is arranged Film can assign the functions such as marresistance, low reflectivity.
For example, the thickness of marresistance (hard painting propert) hardening overlay film is preferably 2~30 μm, more preferably 5~20 μm.It is excessively thin When, surface hardness becomes inadequate；When blocked up, it may be cracked due to the bending in manufacturing process.
In addition, the thickness of for example low reflexive hardening overlay film is preferably 80~200nm, more preferably 100~150nm.This Be because, it is excessively thin or blocked up all low reflecting properties can be made to become inadequate.
[manufacturing process]
Extruded resin sheet in an embodiment of the invention is manufactured by being coextruded.Polycarbonate will be constituted to contain Layer and methacrylic resin contain the resin heating melting of layer, to be laminated on at least single side that polycarbonate contains layer Methacrylic resin contains the discharge of the state of the thermoplastic resinous laminate of layer from the wide cut shape of referred to as T-die Mouth is squeezed out with molten condition, is sandwiched using a pair of rolls being made of the first chill roll and the second chill roll and is formed as sheet.Heat Hereafter plastic resin laminated body is further winding on the second chill roll after, at least it is wound up on third chill roll, thus It is cooled down.In addition, sometimes that thermoplastic resinous laminate (extruded resin sheet 16) is further cold using hereafter after this But roller is cooled down.
It should be noted that will consolidate here, the substance of heating melting state is mainly expressed as thermoplastic resinous laminate Substance after change is expressed as extruded resin sheet, but the two does not have specific boundary.
In Fig. 1, show as an embodiment using by T-die 11, first~third chill roll, 12~14 and Deflect from the summary of the manufacturing method of the extruded resin sheet of the co-extrusion device of the composition of roller 15.The thermoplasticity squeezed out from T-die 11 A pair of rolls clamping that laminated resin body is made of the first chill roll 12 and the second chill roll 13, is configured to the extrusion resin of sheet Plate 16.Then, further that extruded resin sheet 16 is cooling using third chill roll 14, roller 15 is deflected from using what is be made of a pair of rolls It deflects from.In this case, third chill roll 14 becomes the chill roll finally wound.
As the mode other than Fig. 1, in third chill roll and it can deflect from addition roller is set between roller.In this case, The roller finally wound, which becomes third chill roll or third chill roll is arranged in and deflects from the roller between roller, winds thermoplastic resin The last roller of rouge laminated body.
Hereinafter, to put it more simply, being illustrated in such a way that the chill roll finally wound is Fig. 1 of third chill roll. It should be noted that the present invention is not limited to which.
As the mode of T-die at this time, can using by the composition polycarbonate of heating melting state contain layer and The molten resin that methacrylic resin contains layer is in the supply head mode for flowing into the front laminate of T-die or will constitute Polycarbonate contains resin that layer and methacrylic resin contain layer in the branch manifold mode etc. of T-die inner laminated. From the viewpoint of the flatness for improving the interface of each interlayer for constituting extruded resin sheet, preferred branch manifold mode.
In addition, as polishing roll at this time, can enumerate metallic roll, peripheral part have metal made membrane resilient roller (with Under, sometimes referred to as metallic elastic roller) etc..As metallic roll, as long as high rigidity is not particularly limited, it can be mentioned, for example drillings Roller, propellers etc..The surface state of metallic roll is not particularly limited, for example, can be mirror surface, can also there is decorative pattern or bumps Deng.Metallic elastic roller is for example by the side of the generally cylindrical beaming roller being rotatably arranged, outer peripheral surface to cover the beaming roller Formula configures and the columnar metal made membrane that contacts with flaked thermoplastic's resin and is enclosed in above-mentioned beaming roller and metal made membrane Between fluid constitute, using fluid make metallic elastic roller show elasticity.Beaming roller is not particularly limited, such as by structures such as stainless steels At.Metal made membrane is for example made of stainless steel etc., and thickness is preferably from about 2mm~about 5mm.Metal made membrane preferably has curved Qu Xing, flexibility etc., the preferably not no jointless structure of welding seam part.The metallic elastic roller for having such metal made membrane becomes resistance to Long property is excellent and to made of metal film mirror-polishing when is able to carry out processing identical with common mirror roller, thin to made of metal Film can transfer the roller of its shape when assigning decorative pattern or bumps, therefore easy to use.
Composition polycarbonate contains the molten resin that layer and methacrylic resin contain layer and preferably utilizes before stacking Filter carries out melt filteration.Multilevel shaping is carried out by using each molten resin after melt filteration, this makes it possible to obtain by different The few extruded resin sheet of defect caused by object, gel.The filter material of used filter is not particularly limited, according to using temperature Degree, viscosity, filtering accuracy suitably select, and can be used for example: comprising polypropylene, cotton, polyester, artificial silk, glass fibre etc. Non-woven fabrics；It is impregnated with the tablet of the cellulose of phenolic resin；Metallic fiber nonwoven fabric sintered sheet object；Metal powder is burnt Tie tablet；Metal mesh；Or their combination.Wherein, from the viewpoint of heat resistance and durability, preferably by multiple metals Fabric nonwoven cloth sintered sheet nitride layer is folded to use.
The filtering accuracy of above-mentioned filter is not particularly limited, preferably 30 μm hereinafter, more preferably 15 μm hereinafter, into one Preferably 5 μm or less of step.
The extruded resin sheet of an embodiment of the invention preferably will (be third in Fig. 1 from the chill roll finally wound Chill roll 14) removing resin entirety temperature (TT) be set as -2 DEG C of the glass transition temperature (Tg) relative to polycarbonate~ + 19 DEG C of range, preferably -2 DEG C~-0.1 DEG C or+0.1 DEG C~+19 DEG C of the temperature range, more preferably -2 DEG C~+15 DEG C, Further preferably+0.1 DEG C~+15 DEG C.The reason is that temperature and the poly- carbon of the resin entirety removed from third chill roll 14 When the glass transition temperature (Tg) of acid esters compares too low, extruded resin sheet increases the shape transfer of third chill roll, warpage. On the other hand, the temperature for the resin entirety removed from third chill roll 14 with and the vitrifying of resin layer that contacts of third chill roll When transition temperature (Tg) compares excessively high, extruded resin sheet is unable to get good superficiality.It should be noted that resin entirety Temperature is unrelated with any one face of extruded resin sheet, the tree being laminated to polycarbonate resin and methacrylic resin The temperature of rouge entirety is measured to use.Infrared radiation thermometer can be used in temperature measuring.
The small good extruded resin sheet of warpage, the extruded resin sheet of an embodiment of the invention are preferred in order to obtain Line expansion ratio (SR) is located in the range of -10%~+10%；Additionally, it is preferred that methacrylic resin to be contained to the glass of layer Glass transition temperature (Tg) is set as 110 DEG C or more.
Then, delay refers to the phase of the light and the light in the direction perpendicular to the molecular backbone direction in molecular backbone direction Difference.Known macromolecule usually can obtain arbitrary shape by carrying out thermoforming, but produce in its heating, cooling procedure Raw certain stress, molecule are orientated and generate delay.Therefore, it in order to control delay, needs to control the orientation of molecule System.Molecule orientation for example due to the forming near high molecular glass transition temperature when stress and generate.It needs Bright, the delay in the present invention refers to the delay in face.
The inventors discovered that being taken and carrying out various adjustment to manufacturing condition during extrusion molding to molecule To controlled, to caused by the heating after preventing extruded resin sheet from shaping at least in the face of a part of width direction The method of the mechanical periodicity of length of delay in the reduction and face of length of delay (hereinafter, " length of delay in face " for only recording sometimes). Hereinafter, being divided into the influence of peripheral speed ratio, heating condition is illustrated.
Influence > of the < about peripheral speed ratio
Peripheral speed is than referring to any chill roll in addition to the second chill roll 13 and deflecting from roller relative to the second chill roll The ratio between 13 peripheral speed.Hereinafter, the peripheral speed of the second chill roll is expressed as V2, by the peripheral speed table of third chill roll It is shown as V3, the peripheral speed for deflecting from roller is expressed as V4.
Peripheral speed ratio to third chill roll 14 relative to the second chill roll 13 under the defined conditions in the following manner (V3/V2) relationship with the length of delay in face is evaluated, as a result, even if increasing the peripheral speed ratio (V3/V2), prolonging in face Slow value is not also significantly increased.Speculate that its reason is as follows.
The temperature for the resin removed from above-mentioned third chill roll 14 is adjusted to the glass transition temperature relative to polycarbonate The range of -2 DEG C to+19 DEG C of degree (Tg).
About the temperature (TX) for the resin that resin is contacted with third chill roll 14, since resin is cooled down by third chill roll, Therefore it is higher than the temperature (TT) for the resin removed from third chill roll 14.That is, the resin that resin is contacted with third chill roll 14 Temperature (TX) is higher than TT in the range of -2 DEG C to+19 DEG C of glass transition temperature (Tg) relative to polycarbonate, example It such as can be near relative to+20 DEG C of glass transition temperature (Tg).Therefore, in this case, even if increasing third chill roll 14 peripheral speed ratio (V3/V2) and apply big tensile stress to extruded resin sheet, can also become due to being in resin point Son is difficult to the temperature of the resin for the high temperature range being orientated, the therefore not substantially increased tendency of the length of delay in face.
To deflect from roller 15 relative to the second chill roll 13 peripheral speed ratio (V4/V2) and face in length of delay relationship into It has gone evaluation, has as a result known, the peripheral speed ratio (V4/V2) is bigger, and the length of delay in face more increases.
Think the reason is that the temperature of resin entirety when resin is removed from third chill roll 14 is adjusted to than poly- carbon The slightly higher temperature of the glass transition temperature (Tg) of acid esters, specifically relative to -2 DEG C of the glass transition temperature (Tg)~ + 19 DEG C of range increases the peripheral speed ratio for deflecting from roller 15 and applies big tensile stress to extruded resin sheet, thus reaches tree The molecule of rouge is easy the temperature range being orientated.
Then, the degree reduced to the length of delay in face when heating extruded resin sheet is studied.
Know: vitrifying of the temperature of the resin entirety when resin is removed from third chill roll 14 lower than polycarbonate turns Slowly increase when temperature (Tg) the second chill roll 13 with deflect from roller 15 peripheral speed ratio (V4/V2) in the case where, in face Length of delay slowly increases, but the reduced rate of the length of delay in the face after heating becomes larger and (refers to aftermentioned Comparative Examples 1 and 2).
Vitrifying of the temperature of resin entirety when removing resin from third chill roll 14 relative to polycarbonate Peripheral speed ratio (the V4/ for slowly increasing the second chill roll 13 when the range of -2 DEG C~+19 DEG C of transition temperature (Tg) and deflecting from roller 15 V2 in the case where), the length of delay in face slowly increases, but the reduction amount of the length of delay in face when heating will not significantly change (referring to aftermentioned embodiment 10,11,12).
Think the reason is that by resin from third chill roll 14 remove when resin entirety temperature adjust to relative to The range of -2 DEG C~+19 DEG C of the glass transition temperature (Tg) of polycarbonate, increase deflect from roller 15 peripheral speed ratio and to squeeze Resin plate applies big tensile stress out, and the molecule of resin is orientated or is lower than the glass of polycarbonate in heating temperature as a result, Implement at a temperature of glass transition temperature (Tg), therefore, the orientation of resin is not easy to mitigate.
It follows that by the temperature control of resin entirety when being removed from third chill roll 14 for relative to polycarbonate The range of -2 DEG C~+19 DEG C of glass transition temperature (Tg) is adjusted chill roll 13 with the peripheral speed ratio for deflecting from roller 15, The reduction amount of the length of delay in face when then can control length of delay and the heating in face.
Specifically, for example, the peripheral speed ratio (V4/V2) for deflecting from roller and the second chill roll can be set as 0.98 with It is upper and 1.01 or less.
It should be noted that having prolonging in face when the second chill roll 13 is more than 1.01 with the peripheral speed ratio for deflecting from roller 15 Value is more than the tendency (referring to aftermentioned embodiment 18) of 600nm late；When less than 0.98, there is length of delay the inclining less than 50nm in face To (referring to aftermentioned embodiment 19).Making the length of delay in face in preferred scope, the second chill roll 13 with The peripheral speed of roller 15 is deflected from than more preferably 0.985~0.995 (referring to aftermentioned embodiment 10,14~17).
Mechanical periodicity > of the < about the length of delay in face
When being cooled down when sandwiching between the first chill roll and the second chill roll, there are following situations: flowing in resin Direction (squeeze out direction) on periodically, generate phase on the entire width in the direction (width direction) orthogonal with direction is squeezed out Same band-like bumps are uneven.It is thought that due to the periodicity of the peripheral speed variation of the first chill roll and the second chill roll Variation and generate.The periodic peripheral speed variation of each roller is sometimes due to the control of the motor of control roller peripheral speed It is uneven, generate from motor to gear of roller transmitting rotation etc..
Here, the mechanical periodicity of length of delay when being transmitted sometimes from the second chill roll to third chill roll in forming face, from And the bumps that resin surface is generated when sandwiching between the first chill roll and the second chill roll are uneven (with reference to Fig. 2).
The temperature that the present inventor is conceived to the resin being sandwiched between the second chill roll and third chill roll has carried out various Research, as a result know, when resin entirety being sandwiched between the second chill roll and third chill roll temperature (TX) for relative to When the glass transition temperature (Tg) of polycarbonate is less than 10 DEG C, can length of delay in generation face mechanical periodicity；When being sandwiched into The temperature (TX) of resin entirety between second chill roll and third chill roll is the glass transition temperature relative to polycarbonate When+10 DEG C of degree (Tg) or more, it is not likely to produce the mechanical periodicity of the length of delay in face；It is cooling with third when being sandwiched into the second chill roll It is several when the temperature (TX) of resin entirety between roller is more than+20 DEG C for the glass transition temperature (Tg) relative to polycarbonate Will not length of delay in generation face mechanical periodicity.Herein it may be speculated that the temperature of polycarbonate is to turn relative to vitrifying In the case where+10 DEG C of temperature (Tg) or more, due to being high temperature range that the molecule of polycarbonate is not easy to be orientated, because This is not likely to produce the mechanical periodicity of the length of delay in face.
Extrusion resin can be evaluated with the standard deviation (σ) that is measured in 50mm length on Extrusion Flow direction The length of delay in the Extrusion Flow direction of plate is uneven.The standard deviation (σ) is less than 2.5nm, preferably 2.0nm or less.
That is, being sandwiched into the second chill roll from the viewpoint of the mechanical periodicity of the length of delay in inhibition face and third being cooling The temperature (TX) of resin entirety between roller is+10 DEG C of the glass transition temperature (Tg) or more relative to polycarbonate, preferably It is+15 DEG C or more.The upper limit value of the temperature is not particularly limited, preferably+35 DEG C, more preferably+30 DEG C.The reason is that It is easy to make the temperature (TT) for the resin entirety removed from third chill roll for the glass transition temperature relative to polycarbonate (Tg) -2 DEG C to+19 DEG C of range, and when the temperature of resin entirety (TX) is excessively high, it becomes difficult to it is shelled from the second chill roll From, be difficult to obtain beautiful planar.
Length of delay > in the face <
In the present invention, the length of delay in the face of extruded resin sheet is not particularly limited.It should be noted that liquid crystal display When length of delay in the face of protection board is more than 600nm, through the viewing of the polarizing filters such as polarized sunglasses, it is seen that The difference of the transmissivity of each wavelength of optical range becomes larger, and therefore, it is difficult to recognize various colors.On the other hand, when being less than 50nm, Transmissivity under whole wavelength of visible-range is greatly reduced, and forms completely black image and is difficult to recognize.In 50nm~600nm In the range of when, be worth bigger, then form brighter image, be worth smaller, then color more shoals.Especially the length of delay in face is set When for 80nm~350nm, the balance of brightness and color is good, and identification is excellent, thus it is preferred that.
< heating condition >
About the heating condition that the length of delay for evaluating obtained extruded resin sheet in the present invention reduces, it is set as 75 DEG C~100 DEG C in the range of any steady temperature, when being measured, using at 5 hours at 75 DEG C and 100 DEG C in 5 hours One of.Above-mentioned heating environment is preferably able to reference to the common acid extraction formed during hardening overlay film It is resistant to the heating environment and maintains length of delay.
Specifically, by by test film put into management for 5 hours in 100 DEG C ± 3 DEG C or 75 DEG C ± 3 DEG C of baking oven come It is measured.
As discussed above, in the manufacturing method of above-mentioned extruded resin sheet, preferably so that manufactured extrusion There is resin plate the mode of characteristic below to be controlled.
For extruded resin sheet, preferably according to making extruded resin sheet is 5 small in 75 DEG C~100 DEG C of at a temperature of heating Constantly, before heating after length of delay at least in a part of width direction in face be 50~600nm, at 75 DEG C~100 DEG C At least one of at a temperature of heating before and after face in length of delay mode of the reduced rate less than 30% to manufacturing process into Row control.
Furthermore it is preferred that according to make extruded resin sheet before heating after delay at least in a part of width direction in face Value is that the mode of 80~350nm controls manufacturing process.
Furthermore it is preferred that according to make extruded resin sheet before heating after face in length of delay side of the reduced rate less than 15% Formula controls manufacturing process.
In the manufacturing method of extruded resin sheet of the invention, due to assigning above-mentioned characteristic, can by 65 DEG C~ 1~30 hour process is heated at a temperature of 110 DEG C and the extruded resin sheet for being suitable for liquid crystal display protection board etc. is made.
[purposes]
The superficiality of extruded resin sheet of the invention is good, and the mechanical periodicity of delay is inhibited.And suitably inhibit The generation of warpage, even if being heated to high temperature, the reduced rate of the length of delay in face is also small, with the length of delay in suitable face. Therefore, the extruded resin sheet and by the extruded resin sheet heating made of resin plate be resistant to heating process, hot environment, produce Rate, excellent durability, can be used for various uses.In particular, ATM, automatic vending machine, movement as bank and other financial mechanism Phone, portable data assistance (PDA), digital audio-frequency player, portable game machine, tablet-type personal computer, duplicator, Facsimile machine, the protection board of the touch panel of auto navigation digital information equipment, liquid crystal display protection board are particularly useful.
Embodiment
Hereinafter, showing embodiment, the present invention is illustrated in more details.But the present invention is not by the embodiment Any restriction.
The physical property of extruded resin sheet is measured by the following method.
[glass transition temperature (Tg)]
Obtained extruded resin sheet is cut into the test of 10mg after 80 DEG C 24 hours dry under reduced pressure (1kPa) Piece is sealed using aluminium dish, using differential scanning calorimeter (" DSC-50 ", Co., Ltd. Neo-Confucianism's system), carry out 30 minutes or more Nitrogen displacement.Then, in 10ml/ minutes stream of nitrogen gas, it is first warming up to 200 DEG C from 25 DEG C with 20 DEG C/min of speed, protects It holds 10 minutes, is cooled to 25 DEG C (single pass).Then, 200 DEG C (rescans) are warming up to 10 DEG C/min of speed, by It is that rescan obtains as a result, utilize mid-point method calculate glass transition temperature (Tg).It should be noted that due to containing two Kind or more resin and in the case where obtaining multiple glass transition temperatures, using the value of the resin from main component as glass Glass transition temperature.
[linear expansion coefficient]
Linear expansion coefficient is defined as the tensile strain rate of temperature change per unit.Linear expansion coefficient is filled using thermo-mechanical analysis (" TMA4000 ", BRUKER AXS Co. Ltd. system) is set according to JIS K7197 to be measured.That is, in order to make to survey each The extruded resin sheet of sheet obtained from fixed resin press molding forms smooth end face, using diamond saw, is processed into one The length on side is 5mm × 5mm, is highly the prism-shaped of 10mm, by each sample after processing so that surface and the stone of 5mm × 5mm The mode of English plate contact is placed on the plate of quartz, is placed cylindric stick on it, is applied the compressive load of 5g and fix.It connects , in air atmosphere, the glass transition temperature of each sample is warming up to from 25 DEG C (room temperature) with 3 DEG C/min of heating rate (Tg) minus 10 DEG C, 25 DEG C (room temperature) (single pass) are cooled to.Then, with 3 DEG C/min of heating rate from 25 DEG C (room temperature) It is warming up to positive 20 DEG C (rescans) of the glass transition temperature (Tg) of each sample.At each temperature swollen when to rescan Swollen coefficient is measured, and finds out the average linear expansion coefficient in the range of 30 DEG C~80 DEG C.
[amount of warpage]
By the extruded resin sheet of embodiment and comparative example so that the direction parallel with Extrusion Flow direction (squeezing out direction) is Short side, the mode that the direction vertical with Extrusion Flow direction (width direction) is long side are cut into rectangle, make short side 65mm, length The test film of side 110mm.The test film of production is placed into platform in a manner of making methacrylic resin contain layer upward On, 23 DEG C of temperature, relative humidity 50% environment in place 24 hours.Then, using feeler gauge, measurement test piece and platform Gap maximum value, using the value as initial amount of warpage.Then, in the environment for being set as 85 DEG C of temperature, relative humidity 85% In testing machine, above-mentioned test film is placed into glass platform in a manner of making methacrylic resin contain layer upward, After being placed 72 hours under the state, placed 4 hours under 50%, 23 DEG C of environment of relative humidity.Then, it is measured in the same manner as described above Measurement, using the value as the amount of warpage after high temperature and humidity.By test film so that methacrylic resin contains the side of layer upward Formula is placed on platform, and the symbol of downwardly convex warpage is set as just, and the symbol of upward convex warpage is set as negative.
[heating condition]
About test film, the test film of 100mm square is cut and made using reciprocating saw.About heating, will test Piece puts into management as 5 hours in 100 DEG C ± 3 DEG C of baking oven.
[measurement of length of delay]
About test film, the test film of 100mm square is cut and made using reciprocating saw.About the delay in face Value, test film is placed 10 minutes or more in the environment of 23 DEG C ± 3 DEG C, is manufactured using Photonic Lattice, Inc. WPA-100 (- L) is measured.About locating, the center of test film is nearby measured.
In addition, the test film after heating condition above-mentioned for experience, is carried out similarly measurement.
The change rate of delay is found out by following formula.
Change rate (%)=100 × ([length of delay before heating]-[length of delay after heating])/[length of delay before heating]
[mechanical periodicity (visual) of delay]
For the evaluation method of the mechanical periodicity of delay, test film, polarizer are set gradually on liquid crystal display device, Polarizer is set to tilt and observe picture again.
Zero: not observing delay period variation.
△: slightly observe that delay period changes.
×: equally observe that delay period changes with Fig. 2.
[the not mean value of length of delay measures]
Length of delay is measured in 50mm length on Extrusion Flow direction, not as length of delay by its standard deviation (σ) ?.It is uneven larger when the value of standard deviation is big；It is the value hour of standard deviation, uneven smaller.Standard deviation reaches 2.5nm or more When, it is judged as uneven big, unacceptable；It is then the level slightly observed if it is less than 2.5nm；Then if it is 2.0nm or less Do not observe.
[superficiality]
In the interior for being provided with fluorescent lamp, the two sides of extruded resin sheet is visually observed, according to following benchmark to table Face property is evaluated.
Zero: not observing the line that quivers in extrusion resin plate surface.
△: the line that quivers is observed in extrusion resin plate surface, but unobvious.
×: in extrusion resin plate surface, the line that quivers is obvious.
[temperature (TT) of resin entirety]
At the position that third chill roll 14 is removed, 16 entirety of infrared radiation thermometer measurement extruded resin sheet is utilized Temperature.Measure object is set as the central part of the width direction of extruded resin sheet.The temperature measured in this way is known as resin entirety Temperature (TT).
[temperature (TX) of resin entirety]
The temperature for being sandwiched into the resin entirety between the second chill roll and third chill roll is difficult to straight due to being stopped by roller It connects and is measured with infrared radiation thermometer.Therefore, with infrared radiation thermometer measurement, will to be transferred to third from the second chill roll cold But the temperature of 16 entirety of extruded resin sheet before roller and the just temperature of 16 entirety of extruded resin sheet after transmitting.Measure object is set For the central part of the width direction of extruded resin sheet.The average value of temperature before will transmitting and the temperature after rigid transmitting is known as It is sandwiched into the temperature (TX) of the resin entirety between the second chill roll and third chill roll.
[methacrylic resin (B)]
It is ready to pass through methyl methacrylate and methacrylic acid 8- tricyclic [5.2.1.02,6] free radical polymerization of last of the ten Heavenly stems ester obtains The copolymer arrived, as methacrylic resin (B).
It should be noted that by methacrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester is in methyl methacrylate and methyl Acrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester total amount in the shared ratio that feeds intake (quality percentage) be known as TC ratio.
[resin combination (1)]
Used in Production Example it is following shown in methacrylic resin (A) and SMA resin.
< methacrylic resin (A) >
Prepare " PARAPET (registered trademark) HR " of Kuraray Co., Ltd.'s manufacture (under 230 DEG C of temperature, 3.8kg load MFR=2.0cm3/ 10 minutes), as methacrylic resin (A).
< SMA resin >
SMA resin can be obtained with the following method.
It is available as phenylethylene-maleic anhydride-MMA copolymer according to the method recorded in WO2010/013557 SMA resin.
The quality ratio of components of the SMA resin used and weight average molecular weight (Mw) is shown in table 1.
[table 1]
< mass ratio of components >
The copolymerization composition of SMA resin passes through according to following steps13C-NMR method is found out.
13C-NMR spectrum uses nuclear magnetic resonance device (Japan Electronics Corporation manufactures, GX-270).It is dissolved in SMA resin 1.5g In deuterated chloroform 1.5ml, prepare sample solution, under room temperature environment, cumulative number be 4000~5000 times under conditions of into Row measurement.The following value is found out by measurement result.
[integral at the carbon peak (127,134,143ppm near) of the phenyl ring (carbon atom number 6) in styrene units is strong Degree]/6
[integrated intensity at the carbon peak (near 170ppm) at the carbonyl position (carbon atom number 2) in maleic anhydride units]/2
[integrated intensity at the carbon peak (near 175ppm) at the carbonyl position (carbon atom number 1) in MMA unit]/1
Mole of styrene units in sample, maleic anhydride units, MMA unit is found out by the area ratio of above value Than.By obtained molar ratio and each monomeric unit mass ratio (styrene units: maleic anhydride units: MMA unit= 104:98:100) find out the quality composition of each monomer in SMA resin.
< weight average molecular weight (Mw) >
The Mw of SMA resin is found out according to following steps by GPC method.
As eluent, two TSKgel for manufacturing TOSOH Co., Ltd are used as column using tetrahydrofuran The column that SuperMultipore HZM-M and SuperHZ4000 are connected in series.As GPC device, rolled over using with differential Penetrate the HLC-8320 (model) of TOSOH Co., Ltd's manufacture of rate detector (RI detector).SMA resin 4mg is set to be dissolved in tetrahydro In furans 5ml, sample solution is prepared.The temperature of column oven is set as 40 DEG C, the flow of eluent is 0.35ml/ minutes, note Enter 20 μ l of sample solution, measures chromatogram.Utilize standard polyphenyl second of GPC measurement molecular weight in the range of 400~5000000 10 points of alkene, production indicate the standard curve of the relationship of retention time and molecular weight.Mw is determined based on the standard curve.
By the SMA resin in resin combination (1) in total amount of methacrylic resin (A) and SMA resin institute The ratio that feeds intake (quality percentage) accounted for is known as SMA ratio.
[polycarbonate]
Prepare " SD POLYCA (registered trademark) the PCX " (temperature 300 for firmly changing the manufacture of Si Tailong polycarbonate Co., Ltd. DEG C, the MFR=6.7g/10 minute under 1.2kg load, glass transition temperature (Tg)=150 DEG C, linear expansion coefficient=6.93 × 10-5/ K) it is used as polycarbonate.
[embodiment 1]
(manufacturing method of extruded resin sheet)
By methacrylic resin (the B) (glass transition temperature: 120 degree, line expansion system of 20 mass % of TC ratio Number: 7.30 × 10-5/ K) it is melted using 65mm φ single screw extrusion machine [Toshiba Machinery Co., Ltd.'s manufacture], by polycarbonate benefit It is melted with 150mm φ single screw extrusion machine [Toshiba Machinery Co., Ltd. manufactures], the two is had via branch manifold pattern and carries out layer It is folded.Resin (thermoplastic resinous laminate of extruded resin sheet 16, molten condition) after stacking is clamped into shown in FIG. 1 first Between chill roll 12 and the second chill roll 13, after being wound up on the second chill roll 13, it is wound up on third chill roll 14, thus It is cooled down, extruded resin sheet 16 is deflected from using roller 15 is deflected from, is thus manufactured.The temperature (TT) of resin entirety passes through control It makes the temperature of the second chill roll 13 and third chill roll 14 and adjusts to 150 DEG C.In addition, by the second chill roll 13 and deflecting from roller 15 Peripheral speed ratio (V4/V2) adjust to 0.995, by the peripheral speed ratio (V3/ of the second chill roll 13 and third chill roll 14 V2 it) adjusts to 1.005.Polycarbonate is set to contain layer side and 14 side contacts of third chill roll.Methacrylic resin is contained The thickness of layer is set as 0.075mm, the thickness that polycarbonate contains layer is set as 0.925mm, to make with a thickness of 1mm.It will Manufacturing condition and obtained extruded resin sheet evaluation result is shown in table 3.
[embodiment 2~4]
Use the methacrylic for the TC ratio recorded in " methacrylic resin contains layer " column with table 2 Resin B replaces the methacrylic resin (B) of 20 mass % of TC ratio, and the temperature (TT) and resin of resin entirety is whole Temperature (TX) be adjusted as documented by table 2, in addition to this, manufacture extruded resin sheet similarly to Example 1.It will Manufacturing condition and obtained extruded resin sheet evaluation result is shown in table 3.
[embodiment 5]
The methacrylic of 20 mass % of TC ratio is replaced using the resin combination (1) of 20 mass % of SMA ratio Resin (B) manufactures extruded resin sheet as documented by table 2 similarly to Example 1.Show the results of the evaluation table 3.
[embodiment 6~14,18~19, comparative example 2,3]
Come using the resin combination (1) for the SMA ratio recorded in " methacrylic resin contains layer " with table 2 Instead of the resin combination (1) of 20 mass % of SMA ratio, each condition is changed as documented by table 2, except this with Outside, extruded resin sheet is manufactured similarly to Example 5.Show the results of the evaluation table 3.
[embodiment 15, comparative example 1]
The methacrylic resin (B) that 20 mass % of TC ratio is replaced using methacrylic resin (A), will be each Condition is changed as documented by table 2, in addition to this, manufactures extruded resin sheet similarly to Example 1.Evaluation is tied Fruit is shown in table 3.
[embodiment 16~17, comparative example 4]
So that the methacrylic resin of extruded resin sheet is contained layer and be configured to surface and the back side, formed successively with a thickness of The methacrylic resin of 0.075mm contains layer, contains layer, with a thickness of the polycarbonate of 0.850mm with a thickness of 0.075mm's Methacrylic resin contains three layers of composition of layer, to make with a thickness of 1mm.Layer is contained with regard to methacrylic resin and It says, uses methacrylic resin (A) in embodiment 16 and comparative example 4, use 70 mass %'s of SMA ratio in embodiment 17 Each condition is changed as documented by table 2, in addition to this, is manufactured similarly to Example 1 by resin combination (1) Extruded resin sheet.Show the results of the evaluation table 3.
[table 2]
[table 3]
In embodiment 1 to 19, by the temperature (TX) for the resin entirety being sandwiched between the second chill roll and third chill roll It is set as 165 DEG C or more.As a result, showing good result in the evaluation of the mechanical periodicity of delay.On the other hand, compare In example 1,2,4, the temperature (TX) of resin entirety is low, shows the mechanical periodicity of length of delay and is not good.
In embodiment 1 to 4, by the layer of the methacrylic resin (B) containing 20~60 mass % of TC ratio and poly- carbon Acid esters contains layer stackup and manufactures extruded resin sheet, and is tested.As shown in table 2 and table 3, in containing using embodiment 3 The methacrylic of TC ratio 45%Resin BLayer in the case where, it is contemplated that glass transition temperature (Tg), linear expansion coefficient Than the value and change rate of (SR), amount of warpage and delay, most preferred result has been obtained.
In embodiment 5 to 14,17 to 19, by the layer of the resin combination (1) containing 10~70 mass % of SMA ratio and gather Carbonic ester contains layer stackup and manufactures extruded resin sheet, and is tested.As shown in table 2 and table 3, especially embodiment is being used In the case where the layer of 7 and 9 resin combination (1) containing 70 mass % of SMA ratio, the value and change rate of delay are suitable, stick up The absolute value of song amount is also small, has obtained most preferred result.
In addition, in Examples 1 to 9, peripheral speed ratio (V4/V2) is set as 0.995 and constant.Embodiment 9~14,17~ In 19, using the layer of the resin combination (1) containing 70 mass % of SMA ratio, make the temperature (TT) of resin entirety as table 2 It is fixed, peripheral speed ratio (V4/V2) is set as 0.98~1.015.In embodiment 18, peripheral speed ratio (V4/V2) is improved, knot Fruit forms the high extruded resin sheet of length of delay.In embodiment 19, makes peripheral speed ratio (V4/V2) reduction, as a result form and prolong It is worth low extruded resin sheet late.
In comparative example 3, the temperature (TT) of resin entirety is improved, the not good extrusion resin of superficiality is as a result formd Plate.Comparative Examples 1 and 2 in 4, reduces the temperature (TX) of resin entirety, as a result forms the mechanical periodicity for showing delay and is Not good extruded resin sheet.
Industrial availability
The extruded resin sheet that manufacturing method through the invention obtains can be used in such as liquid crystal display protection board, touch-control The protective cover of panel is suitable for on-vehicle display, portable phone, smart phone, personal computer, television set etc..
It should be noted that the present invention is not limited to the above embodiments, can be fitted in the range of not departing from purport Work as change.
It is claimed priority based on the Japanese publication Patent 2016-158357 that the application was proposed by August 12nd, 2016, it will Its entire disclosure is introduced into the application.
Symbol description
11 T-dies
12 first chill rolls
13 second chill rolls
14 third chill rolls
15 deflect from roller
16 extruded resin sheets (thermoplastic resinous laminate)
22 squeeze out direction
23 width directions

Claims (14)

1. a kind of manufacturing method of extruded resin sheet, to be laminated on at least single side of the layer containing polycarbonate containing first The manufacturing method of the extruded resin sheet of the layer of base acrylic resin, wherein
Include following process:
The layer containing methacrylic resin will be laminated on at least single side of the layer containing polycarbonate Thermoplastic resinous laminate is coextruded with molten condition from T-die,
The thermoplastic resinous laminate is sandwiched between the first chill roll and the second chill roll,
And being wound up on third chill roll after being wound up into the thermoplastic resinous laminate on second chill roll It is cooled down,
Thermoplastic resinous laminate utilization is deflected from roller to deflect from,
The temperature (TX) for the resin entirety being sandwiched between second chill roll and third chill roll is set as relative to described + 10 DEG C of glass transition temperature or more of layer containing polycarbonate,
In the thermoplastic resinous laminate at the position that the chill roll finally wound is removed, by the temperature (TT) of resin entirety It is set as -2 DEG C~+19 DEG C of glass transition temperature of the range relative to the layer containing polycarbonate.
2. the manufacturing method of extruded resin sheet according to claim 1, wherein
The glass transition temperature of the layer containing methacrylic resin is 110 DEG C or more,
The linear expansion coefficient (S1) and the line of the layer containing methacrylic resin of the layer containing polycarbonate are swollen The ratio between the difference (S2-S1) of swollen coefficient (S2) and the linear expansion coefficient (S1) of the layer containing polycarbonate ((S2-S1)/S1) It is -10%~+10%.
3. the manufacturing method of extruded resin sheet according to claim 1 or 2, wherein by the peripheral speed for deflecting from roller (V4) 0.98 or more and 1.01 or less is set as with the peripheral speed ratio (V4/V2) of the peripheral speed (V2) of second chill roll.
4. the manufacturing method of extruded resin sheet described in any one of claim 1 to 3, wherein the methacrylic acid Resinoid contains 40~80 mass % of structural unit from methyl methacrylate and comes from methyl shown in the following general formula (I) 60~20 mass % of structural unit of acrylate,
In formula, Cy indicates alicyclic type hydrocarbon.
5. the manufacturing method of extruded resin sheet according to claim 4, wherein the Cy in the logical formula (I) is polycyclic rouge Fat race alkyl.
6. the manufacturing method of extruded resin sheet according to claims 1 to 3, wherein described to contain methacrylic tree The layer of rouge contains 95~20 mass % of 5~80 mass % of methacrylic resin and copolymer, and the copolymer, which contains, to be come from The structural unit of aromatic ethenyl compound shown in the following general formula (II) and the acid anhydrides shown in the following general formula (III) Structural unit,
In formula, R1And R2Hydrogen atom or alkyl are each independently represented,
In formula,R3And R4Each independently represent hydrogen atom or alkyl.
7. the manufacturing method of extruded resin sheet according to claim 6, wherein the copolymer contains from the fragrance It 50~84 mass % of structural unit of race's vinyl compound, 15~49 mass % of structural unit from the acid anhydrides and comes from 1~35 mass % of structural unit of methacrylate.
8. the manufacturing method of extruded resin sheet according to claim 7, wherein the structure from methacrylate Unit is methyl methacrylate.
9. a kind of manufacturing method of extruded resin sheet, wherein
Comprising obtaining extruded resin sheet by manufacturing method according to any one of claims 1 to 8, further by the extrusion At a temperature of heating 1~30 hour process of the resin plate at 65 DEG C~110 DEG C,
Before and after the heating at least in a part of width direction, the length of delay in face is 50~600nm, before the heating The reduced rate of the length of delay afterwards is less than 30%.
10. a kind of extruded resin sheet, to be laminated on at least single side of the layer containing polycarbonate containing methacrylic acid The extruded resin sheet of the layer of resinoid, wherein
The glass transition temperature of the layer containing methacrylic resin is 110 DEG C or more,
Standard deviation obtained from length of delay on Extrusion Flow direction in 50mm length in aspect of measure is less than 2.5nm,
When being heated 5 hours under 75 DEG C~100 DEG C of any stationary temperature, before heating after at least at one of width direction In point, the length of delay in face is 50~600nm,
The reduced rate of the length of delay before and after the heating less than 30%,
The linear expansion coefficient (S1) and the line of the layer containing methacrylic resin of the layer containing polycarbonate are swollen The ratio between the difference (S2-S1) of swollen coefficient (S2) and the linear expansion coefficient (S1) of the layer containing polycarbonate ((S2-S1)/S1) It is -10%~+10%.
11. extruded resin sheet according to claim 10, wherein by the extruded resin sheet in 75 DEG C or 100 DEG C of temperature At the lower heating of degree 5 hours, before heating after at least in a part of width direction, the length of delay in face is 50~600nm,
The reduced rate of the length of delay before and after the heating is less than 30%.
12. extruded resin sheet described in 0 or 11 according to claim 1, wherein at least in width direction before and after the heating In a part, the length of delay in face is 80~350nm.
13. extruded resin sheet described in any one of 0~12 according to claim 1, wherein the delay before and after the heating The reduced rate of value is less than 15%.
14. extruded resin sheet described in any one of 0~13 according to claim 1, wherein be also equipped at least one surface Marresistance layer.
CN201780049200.8A 2016-08-12 2017-08-10 Method for producing extruded resin sheet and extruded resin sheet Active CN109562553B (en)

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