CN106715078B - 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
CN106715078B
CN106715078B CN201580050630.2A CN201580050630A CN106715078B CN 106715078 B CN106715078 B CN 106715078B CN 201580050630 A CN201580050630 A CN 201580050630A CN 106715078 B CN106715078 B CN 106715078B
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Prior art keywords
resin
layer containing
mass
polycarbonate
methacrylic
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CN106715078A (en
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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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides the manufacturing method of resin plate that superficiality is good and is inhibited by the generation of warpage caused by residual stress.It is set as -10%~+5% by the difference of the linear expansion coefficient (S1) of the layer containing polycarbonate and the linear expansion coefficient (S2) of the layer containing methacrylic resin, with the ratio between the linear expansion coefficient of layer containing polycarbonate ((S2-S1)/S1), the glass transition temperature of the layer containing methacrylic resin is set as 120~160 DEG C.The thermoplastic resinous laminate (resin plate (16)) for being laminated with the layer containing polycarbonate and the layer containing methacrylic resin is squeezed out with molten condition from T-die (11), it is clamped between first and second chill roll (12,13), after being wound up on the second chill roll (13), it is wound up on third chill roll (14) and is cooled down, deflected from using roller (15) is deflected from.In resin plate (16) at the position that third chill roll (14) is removed, the temperature of resin entirety is set as range of the glass transition temperature relative to the layer containing polycarbonate from 0 DEG C to+15 DEG C.

Description

The manufacturing method and extruded resin sheet of extruded resin sheet
Technical field
The present invention relates to resin plates.More specifically, the present invention relates to manufacture superficiality well and because residual stress causes Warpage generation inhibited, the protective cover that is suitable for touch panel etc. has containing methacrylic resin The method of the resin plate of layer and the layer containing polycarbonate.
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, portable data assistance (PDA), digital audio-frequency player, portable game machine, plate PC, is answered at mobile phone Print machine, facsimile machine, auto navigation digital information equipment etc..
In the input operation using touch panel, scratch is generated on surface sometimes or inside is damaged by pressure.In order to Above situation is prevented, transparent protective cover is set on the surface of touch panel.As protective cover, strengthened glass system is mainly used Protective cover.In addition, having carried out the exploitation of the protective cover of transparent resin from the viewpoint of processability, lightweight.For this Protective 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 the layer comprising polycarbonate resin The resin plate constituted with the layer comprising methacrylic resin.In the heating melting forming of such resin plate, due to two It plants the difference of the characteristic of resin and makes to remain many distortional stresses in obtained formed products.This is remained in formed products Distortional 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 as the above-mentioned resin plate, because warpage 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, 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 2) comprising polycarbonate on it.But for the resin plate and Speech, even if in this way, the heat resistance and moisture-proof of methacrylic resin or insufficient, even if having the methacrylic Resin can not be solved the problem above-mentioned fully.
In addition, in order to solve this problem, it is also known that following method: being conceived to the linear expansion coefficient reduced between two resin sheets Difference, control the generation (for example, referenced patent document 3) of warpage.But it when only realizing the regulation of linear expansion coefficient, can not solve The certainly above problem.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-185956 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2009-248416 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2007-118597 bulletin
Summary of the invention
Problem to be solved by the invention
In resin plate, the degree of remaining stress is different in each resin layer.Therefore, it has attempted by adjusting in extrusion molding The rotation speed of the chill roll used reduces remaining stress.But when formed products leave chill roll, shaping sometimes The surface of product generates the striated defect for being referred to as the line that quivers, and superficiality reduces.The resin plate is being used for touch panel by the phenomenon Protective cover etc. in the case where become problem.
It is good the purpose of the present invention is to provide manufacture superficiality and because the generation of warpage caused by residual stress obtains The method and resin plate of the resin plate of inhibition.
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 following manner.
The manufacturer of extruded resin sheet (hereinafter, " extruded resin sheet " is suitably also recorded as " resin plate ") of the invention One mode of method is that the extrusion of the layer containing methacrylic resin is laminated on the single side of the layer containing polycarbonate The manufacturing method of resin plate applies process below in fact.
The thermoplastic resin of the layer containing methacrylic resin is laminated on the single side of the layer containing polycarbonate The process that laminated body is squeezed out with molten condition from T-die.
The process of 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 On carry out cooling process.
The process that above-mentioned thermoplastic resinous laminate is deflected from using roller is deflected from.
In addition to this, condition below is met in above-mentioned each process.
By the linear expansion coefficient (S1) of the above-mentioned layer containing polycarbonate and the above-mentioned layer containing methacrylic resin Linear expansion coefficient (S2) difference (S2-S1), with the ratio between the linear expansion coefficient (S1) of the above-mentioned layer containing polycarbonate ((S2- S1)/S1) it is set as -10%~+5%.Hereinafter, will be suitably recorded as than ((S2-S1)/S1) " line expansion ratio (SR) ".
The glass transition temperature of the above-mentioned layer containing methacrylic resin is set as 120~160 DEG C.
In above-mentioned thermoplastic resinous laminate at the position that above-mentioned third chill roll is removed, the temperature of resin entirety is set It is set to range of the glass transition temperature (Tg) relative to polycarbonate from 0 DEG C to+15 DEG C.
By meeting these conditions, good and small because of warpage caused by the residual stress resin plate of superficiality can be realized.
In addition, in a mode of the resin plate obtained by the manufacturing method of above-mentioned extruded resin sheet, it is preferably above-mentioned Structural unit from methyl methacrylate of the layer containing methacrylic resin containing 40~80 mass %, and contain There is the structural unit for deriving from methacrylate represented by the following general formula (I) of 20~60 mass %.
(in formula, Cy indicates alicyclic type hydrocarbon.)
In addition, the Cy in logical formula (I) is more preferably multicyclic aliphatic alkyl.
In addition, in a mode of the resin plate obtained by the manufacturing method of above-mentioned extruded resin sheet, it is preferably above-mentioned Layer containing methacrylic resin contains methacrylic resin and 20 mass % or more lower than 80 mass % At least origin is derived from the structural unit of aromatic ethenyl compound represented by the following general formula (II) and derives from the following general formula (III) copolymer that the structural unit of the acid anhydrides represented by is formed.
(in formula, R1And R2Each independently represent hydrogen atom or alkyl.)
(in formula, R3And R4Each independently represent hydrogen atom or alkyl.)
Furthermore it is preferred that above-mentioned copolymer contains the knot from above-mentioned aromatic ethenyl compound of 50~84 mass % Structure unit, the structural unit from above-mentioned acid anhydrides containing 15~49 mass %, and the metering system containing 1~25 mass % Acid ester monomer, above-mentioned methacrylate monomers are more preferably methyl methacrylate.
Above-mentioned resin plate is preferably further equipped with marresistance layer at least one surface.
Invention effect
The superficiality of resin plate of the invention is good, because the generation of warpage caused by residual stress is inhibited.In addition, Resin plate of the invention is suitable for requiring gloss, marresistance and impact resistance, such as touch panel protective cover.
Detailed description of the invention
Fig. 1 is the figure for indicating the manufacturing method of the resin plate using coextrusion of an embodiment of the invention.
Specific embodiment
Hereinafter, with reference to attached drawing, embodiments of the present invention will be described.In order to be clearly stated, it is below record and Attached drawing is suitably omitted and has been simplified.In the accompanying drawings, to the constituent element and corresponding portion of composition having the same or function Identical symbol is marked, and the description thereof will be omitted.
Embodiment 1
Resin plate of the invention is in the layer (hereinafter, being also suitably recorded as " polycarbonate contains layer ") containing polycarbonate A face on layer of the stacking containing methacrylic resin (hereinafter, being also suitably recorded as that " methacrylic resin contains Have layer ").
The layer containing methacrylic resin is laminated on the layer containing polycarbonate, thus the transparency, impact resistance Property, excellent abrasion.
Resin plate is manufactured by extrusion molding method, and production efficiency is excellent as a result,.
In resin plate, linear expansion coefficient (S1) and the layer containing methacrylic resin of the layer containing polycarbonate Line expansion ratio (SR) represented by the relational expression of linear expansion coefficient (S2) is set as -10%~+5% range, good from obtaining Warpage from the viewpoint of, line expansion ratio (SR) be more preferably -5%~+2% range.
Line expansion ratio (SR) is the linear expansion coefficient (S1) of the layer containing polycarbonate and contains methacrylic resin Layer linear expansion coefficient (S2) difference (S2-S1), with the ratio between linear expansion coefficient (S1) ((S2-S1)/S1).In other words, at this In specification, line expansion ratio (SR) is set as the linear expansion coefficient (S1) and methacrylic resin that polycarbonate is contained layer The ratio that the relationship of linear expansion coefficient (S2) containing layer is indicated with calculating formula ((S2-S1)/S1).
In addition, the lower limit for constituting the glass transition temperature (Tg) of the resin of the layer containing methacrylic resin is usual It is 120 DEG C, preferably 125 DEG C, more preferably 130 DEG C, the upper limit of glass transition temperature (Tg) is usually 160 DEG C, preferably It is 155 DEG C, more preferably 150 DEG C.The glass transition temperature of line expansion ratio (SR) and the layer containing methacrylic resin (Tg) in the range when, superficiality is good, because warpage caused by residual stress is small, thus it is preferred that.
[methacrylic resin]
In an embodiment of the invention, methacrylic resin contains the structure list from methacrylate Member.
Content from the structural unit of methacrylate is preferably 50 mass % or more, more preferably 80 mass % More than, further preferably 90 mass % or more are preferred.It can be 100 mass %.From the structure list of methacrylate The content of member within the above range when, the transparency is good.
The methacrylate is indicated by logical formula (IV).
Lead in formula (IV), R indicates alkyl.Alkyl can be saturated hydrocarbyl, or unsaturated alkyl.
Alkyl shown in R can be the Noncyclic aliphatics alkyl such as methyl, ethyl, propyl, or alicyclic type hydrocarbon, It can also be the aromatic hydrocarbyls such as phenyl.Here, methacrylate is by leading to formula (I) table in the case where R is alicyclic type hydrocarbon Show.Hereinafter, methacrylate represented by logical formula (I) is suitably recorded as " methacrylate (I) ".
It as methacrylate (I), can enumerate: cyclohexyl methacrylate, methacrylic acid ring pentyl ester, methyl-prop The methacrylic acids monocyclic aliphatic such as olefin(e) acid cycloheptyl ester race hydrocarbon ester；Methacrylic acid 2- norbornyl ester, methacrylic acid 2- methyl -2- Norbornyl ester, methacrylic acid 2- ethyl -2- norbornyl ester, methacrylic acid 2- isobornyl thiocyanoacetate, methacrylic acid 2- methyl -2- Isobornyl thiocyanoacetate, methacrylic acid 2- ethyl -2- isobornyl thiocyanoacetate, methacrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester, metering system Sour 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, methyl-prop Olefin(e) acid 2- Buddha's warrior attendant alkyl ester, 2-Methacryloyloxy-2-methyladamantane, 2-Ethyl-2-adamantyl methacrylate, methyl-prop Olefin(e) acid 1- Buddha's warrior attendant alkyl ester, methacrylic acid 2- benzene oxygen ester, methacrylic acid 2- methyl -2- benzene oxygen ester or methacrylic acid 2- second The methacrylic acids multicyclic aliphatic hydrocarbon esters such as base -2- benzene oxygen ester；Deng.Wherein, preferred methacrylic acid multicyclic aliphatic hydrocarbon ester, more It is preferred that methacrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester.
Methacrylic resin used in the present invention is preferably comprised from methyl methacrylate (hereinafter, also fitting Locality is recorded as " MMA ") structural unit and derive from methacrylate (I) structural unit, further preferably derive from The structural unit of methyl methacrylate and structural unit from methacrylic acid multicyclic aliphatic hydrocarbon ester, further preferably Containing the structural unit from methyl methacrylate and derive from methacrylic acid 8- tricyclic [5.2.1.02,6] last of the ten Heavenly stems ester knot Structure unit.
In methacrylic resin used in the present invention, from the viewpoint of hardness, 40~80 matter are preferably comprised The structural unit from methyl methacrylate of amount %, further preferably 50~80 mass %, further preferably 50 ~60 mass %.
In methacrylic resin used in the present invention, from the viewpoint for reducing line expansion ratio (SR) and turn vitrifying From the viewpoint of temperature (Tg) is 120 DEG C or more, preferably comprise 20~60 mass % derives from methacrylate (I) Structural unit, further preferably 20~50 mass %, further preferably 40~50 mass %.From methacrylate (I) when structural unit is more than 60 mass %, there are the tendencies that the impact resistance of methacrylic resin layer reduces.
Methacrylic resin used in the present invention passes through by above-mentioned methacrylate and as any ingredient Other monomers polymerize and obtained.In the case where using various of monomer in the polymerization, usually above-mentioned various of monomer is mixed It closes and prepares monomer mixture, then for polymerization.Polymerization is not particularly limited, from the viewpoint of productivity, preferably Free radical polymerization is carried out by the methods of mass polymerization, suspension polymerization, solution polymerization process, emulsion polymerization.
The weight average molecular weight (hereinafter, being also suitably recorded as " Mw ") of methacrylic resin used in the present invention is excellent It is selected as 40000~500000.By making 40000 or more the Mw, resin plate of the invention becomes marresistance, excellent heat resistance Resin plate the productivity of resin plate of the invention can be improved by making the Mw 500000 hereinafter, shaping processability is excellent.
It should be noted that Mw refers to the standard polyphenyl second measured using gel permeation chromatography (GPC) in this specification Alkene scaled value.
In an embodiment of the invention, the resin for constituting the layer containing methacrylic resin is containing lower than 80 At least origin of the methacrylic resin of quality % and 20 mass % or more are derived from virtue represented by the following general formula (II) The structural unit of fragrant race's vinyl compound (hereinafter, being also suitably recorded as " aromatic ethenyl compound (II) ") and source What the structural unit of the acid anhydrides represented by the following general formula (III) (hereinafter, being also suitably recorded as " acid anhydrides (III) ") was formed is total to The resin combination of polymers (hereinafter, being also suitably recorded as " SMA resin ") is (hereinafter, be also suitably recorded as " resin combination (1)”)。
(in formula, R1And R2Each independently represent hydrogen atom or alkyl.)
(in formula, R3And R4Each independently represent hydrogen atom or alkyl.)
The methacrylic resin contained in resin combination (1) is containing the structure list for deriving from methacrylate The resin of member.
It as the methacrylate, can enumerate: methyl methacrylate, ethyl methacrylate, methacrylic acid N-propyl, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, first Base amyl acrylate, hexyl methacrylate, metering system heptyl heptylate, 2-Ethylhexyl Methacrylate, methacrylic acid nonyl The alkyl methacrylates such as ester, decyl-octyl methacrylate, lauryl ester；Using as above-mentioned methacrylic acid The substance that ester (I) is recorded is the cycloalkyl methacrylate of representative；The aryl methacrylates such as phenyl methacrylate；First The methacrylic acids aralkyl ester such as base benzyl acrylate；Deng, from the viewpoint of availability, preferably MMA, methacrylic acid second Ester, n propyl methacrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate and methyl Tert-butyl acrylate, most preferably MMA.The content of the structural unit from methacrylate in methacrylic resin Preferably 90 mass % or more, more preferably 95 mass % or more, further preferably 98 mass % or more, can be to have contained only From the structural unit of methacrylate.
In addition, the methacrylic resin contained in resin combination (1) preferably comprises from the viewpoint of heat resistance The structural unit from MMA of 90 mass % or more, further preferably 95 mass % or more, further preferably 98 matter % or more is measured, can be the structural unit contained only from MMA.
In addition, other than the methacrylic resin contained in resin combination (1) can be containing methacrylate From the structural unit of other monomers.As the other monomers, methyl acrylate can be enumerated (hereinafter, also suitably recording For " MA "), ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid The tert-butyl ester, Hexyl 2-propenoate, 2-EHA, nonyl acrylate, decyl acrylate, lauryl ester, propylene Sour stearyl ester, acrylic acid 2- hydroxy methacrylate, acrylic acid 2- hydroxy propyl ester, acrylic acid 4- hydroxybutyl, cyclohexyl acrylate, propylene Sour 2- methoxy acrylate, acrylic acid 3- methoxybutyl, acrylic acid trifluoromethyl ester, acrylic acid trifluoro ethyl ester, five fluorine second of acrylic acid Ester, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluene toluene, benzyl acrylate, acrylic acid are different The acrylate such as norbornene ester, acrylic acid 3- dimethylamino ethyl ester, from the viewpoint of availability, preferably MA, ethyl acrylate, The acrylate such as n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, more It is preferred that MA and ethyl acrylate, most preferably MA.The structural unit from above-mentioned other monomers in methacrylic resin The total preferably 10 mass % of content hereinafter, more preferably 5 mass % hereinafter, further preferably 2 mass % or less.
The methacrylic resin contained in resin combination (1) passes through by above-mentioned methacrylate and as appointing The other monomers of meaning ingredient, which are polymerize, to be obtained.It, usually will be above-mentioned a variety of in the case where using various of monomer in the polymerization Monomer mixes and prepares monomer mixture, then for polymerization.Polymerization is not particularly limited, and examines from the viewpoint of productivity Consider, free radical polymerization is preferably carried out by the methods of mass polymerization, suspension polymerization, solution polymerization process, emulsion polymerization.
The weight average molecular weight of the methacrylic resin contained in resin combination (1) is (hereinafter, be also suitably recorded as " Mw ") it is preferably 40000~500000.By making 40000 or more the Mw, resin plate of the invention becomes marresistance, resistance to Hot excellent resin plate can be improved by making the Mw 500000 hereinafter, the shaping processability of resin combination (1) is excellent The productivity of resin plate of the invention.
The content of SMA resin in the resin combination used in the present invention (1), from reduction line expansion ratio (SR) Viewpoint and make glass transition temperature (Tg) be 120 DEG C or more from the viewpoint of, be preferably set to 20 mass % or more, more preferably Range for 45 mass % more than or lower than 95 mass %, model of the further preferably 50 mass % more than or lower than 90 mass % It encloses.
Above-mentioned SMA resin is at least origin derived from the structural unit of aromatic ethenyl compound (II) and from acid anhydrides (III) copolymer that structural unit is formed.
As the R in logical formula (II)1And R2And the R in logical formula (III)3And R4The alkyl each independently represented, preferably Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, just oneself The alkyl below of the carbon atom numbers such as base, n-heptyl, n-octyl, 2- ethylhexyl, nonyl, decyl, dodecyl 12, more preferable first The alkyl below of the carbon atom numbers such as base, 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~ The range of 85 mass %, more preferably 55~82 mass %, the further preferably range of 60~80 mass %.The content is 50 When the range of~85 mass %, resin combination (1) becomes the composition of moisture-proof and excellent transparency.
As aromatic ethenyl compound (II), can enumerate for example: styrene；2-methyl styrene, 3- methylbenzene The cores alkyl-substituted styrenes such as ethylene, 4- methyl styrene, 4- ethyl styrene, 4- t-butyl styrene；α-methylstyrene, The alpha-alkyls substituted phenylethylene such as 4- methyl-alpha-methyl, from the viewpoint of availability, optimization styrene.These fragrance Race's 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 the model of 15~50 mass % It encloses, more preferably the range of 18~45 mass %, further preferably the range of 20~40 mass %.By making the content 15 The range of~50 mass %, resin combination (1) become the composition of heat resistance and excellent transparency.
As acid anhydrides (III), can enumerate such as maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, from availability From the viewpoint of, preferred maleic anhydride.These acid anhydrides (III) can be used alone, and can also be applied in combination a variety of.
In above-mentioned SMA resin, in addition to aromatic ethenyl compound (II) and acid anhydrides (III), preferably also contain source In the structural unit of methacrylate monomers.The structural unit from methacrylate monomers in above-mentioned SMA resin Content be preferably 1~35 mass % range, the more preferably range of 3~30 mass %, further preferably 5~26 matter Measure the range of %.By making the range of 1~35 mass % of the content, make bendability, excellent transparency.
As methacrylate, can enumerate for example: MMA, ethyl methacrylate, propyl methacrylate, methyl The positive fourth of isopropyl acrylate, n-BMA, propyl methacrylate, isopropyl methacrylate, methacrylic acid Ester, Isobutyl methacrylate, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, cyclohexyl methacrylate, first Base phenyl acrylate, benzyl methacrylate, methacrylic acid 1- phenyl chlorocarbonate；Deng.In these methacrylates, preferred alkane The alkyl methacrylate that the carbon atom number of base is 1~7, from the sight of the heat resistance, excellent transparency of obtained SMA resin Point consideration, 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 methacrylic acid The structural unit of other monomers other than ester.As the other monomers, can enumerate MA, 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.These other monomers can be used alone, and can also be applied in combination a variety of.It is in SMA resin, from upper The content for stating the structural unit of other monomers is preferably 10 mass % hereinafter, more preferably 5 mass % are hereinafter, further preferably 2 mass % or less.
Above-mentioned SMA resin is by by above-mentioned aromatic ethenyl compound (II), acid anhydrides (III) and methacrylate And the other monomers as any ingredient 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 is preferably 40000~300000 range.By making 40000 or more the Mw, the present invention Resin plate become marresistance, excellent impact resistance resin plate, by making the Mw 300000 hereinafter, shaping processability is excellent It is good, the productivity of resin plate of the invention can be improved.
Resin combination (1) is by the way that above-mentioned methacrylic resin and SMA resin to be obtained by mixing.The mixing can To use such as melt mixing methods, solution mixing method.It is mixed using such as single screw rod kneading machine or multiscrew in melt mixing methods The melting mixing machines such as mill, open roll, banbury mixers, kneader, as needed in indifferent gas such as nitrogen, argon gas, helium Melting mixing is carried out under body atmosphere.In solution mixing method, methacrylic resin and SMA resin is made to be dissolved in toluene, tetrahydro It is mixed after in the organic solvents such as furans, methyl ethyl ketone.
The resin that the layer containing methacrylic resin is constituted used in an embodiment of the invention can be It does not damage in the range of effect of the present invention containing the other polymers other than methacrylic resin and SMA resin.As this Other polymers can be enumerated: the polyolefin such as polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether-ether-ketone, polyester, polysulfones, The thermoplastic resins such as polyphenylene oxide, polyimides, polyetherimide, polyacetals；Phenolic resin, melamine resin, organosilicon tree The thermosetting resins such as rouge, epoxy resin；Acrylic rubbers such as particle having multilayer structure, block copolymer etc..Other above-mentioned polymerizations Object can be used alone, and can also be applied in combination a variety of.
It is constituted used in an embodiment of the invention upper in the resin of the layer containing methacrylic resin The content for stating other polymers is preferably 10 mass % hereinafter, more preferably 5 mass % are hereinafter, further preferably 2 mass % Below.
It, can be by methacrylic when containing other polymers and/or additive in methacrylic resin Addition when resin is polymerize can also be added after polymerisation.
It, can be by methacrylic resin when containing other polymers and/or additive in resin combination (1) And/or addition when being polymerize of SMA resin, it can also add when mixing methacrylic resin and SMA resin, may be used also To be added again after mixing methacrylic resin and SMA resin.
The resin that the layer containing methacrylic resin is constituted used in an embodiment of the invention can root According to needing containing various additives.As the additive, such as antioxidant, heat deterioration preventing agent, ultraviolet light can be enumerated and inhaled Receive agent, light stabilizer, lubricant, release agent, polymer processing aid, antistatic agent, fire retardant, dyes/pigments, light diffusion Agent, delustering agent, impact resistance modification agent, fluorophor etc..The content of these additives can be in the model for not damaging effect of the present invention It is suitably set in enclosing, preferably with respect to 100 mass parts of resin for constituting the layer containing methacrylic resin, for example, antioxygen The content of agent is 0.01~1 mass parts, the content of ultraviolet absorbing agent is 0.01~3 mass parts, the content of light stabilizer is 0.01~3 mass parts, the content of lubricant are 0.01~3 mass parts, the content of dyes/pigments is 0.01~3 mass parts.
The melt of the resin of the layer containing methacrylic resin is constituted used in an embodiment of the invention Flow rate (hereinafter, being also suitably recorded as " MFR ") is preferably 1~10g/10 minutes ranges, more preferably 1.5~7g/ 10 minutes ranges, further preferably 2~4g/10 minute.When the range that MFR is 1~10g/10 minutes, heating melting forming Have good stability.
It should be noted that the MFR of the resin of layer of the composition containing methacrylic resin in this specification is to make It is worth obtained from being measured under 230 DEG C of temperature, 3.8kg load with fusion index instrument.
[polycarbonate]
Dihydric phenol and carbonate precursor preferably and being copolymerized by polycarbonate used in laminated body of the invention It obtains.
As above-mentioned dihydric phenol, bis- (4- hydroxy phenyl) propane of 2,2- (common name bisphenol-A), bis- (the 4- hydroxyls of 1,1- can be enumerated Base phenyl) ethane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 2,2- it is bis- (3, 5- dimethyl -4- hydroxy phenyl) propane, bis- (4- hydroxy phenyl) sulfites, bis- (4- hydroxy phenyl) sulfones etc., wherein preferably Bisphenol-A.These dihydric phenols can be used alone, and can also be applied in combination a variety of.
As above-mentioned carbonate precursor, can enumerate the carbonic esters such as the halo carbonyl compounds such as phosgene, diphenyl carbonate, Haloformates such as the bishaloformate of dihydric phenol etc..These carbonate precursors can be used alone, and can also combine Using a variety of.
The manufacturing method of above-mentioned polycarbonate is not particularly limited, and can enumerate for example: making the aqueous solution and carbon of dihydric phenol Interfacial polymerization of the organic solvent solution of acid esters precursor in interfacial reaction；Make dihydric phenol and carbonate precursor high temperature, decompression, The ester-interchange method etc. reacted under the conditions of solvent-free.
The Mw of above-mentioned polycarbonate is preferably 10000~100000 range, more preferably 20000~70000 range. By making 10000 or more the Mw, the impact resistance of laminated body of the invention, excellent heat resistance, by making the Mw 100000 Hereinafter, the shaping processability of polycarbonate is excellent, the productivity of laminated body of the invention can be improved.
Above-mentioned polycarbonate can contain other polymers within the scope of the effect of the invention.As this, other gather Object is closed, its that can contain with methacrylic resin, resin combination (1) and above-mentioned resin combination (1) can be used The identical polymer of his polymer.Above-mentioned other polymers can be used alone, and can also be applied in combination a variety of.Poly- carbonic acid The content of above-mentioned other polymers in ester is preferably 15 mass % hereinafter, more preferably 10 mass % are hereinafter, further preferably For 5 mass % or less.
Above-mentioned polycarbonate can according to need containing various additives.As additive, can be used and above-mentioned composition The identical additive of the additive that the resin of layer containing methacrylic resin can contain.The content of these additives can To suitably set within the scope of the effect of the invention, preferably with respect to 100 mass parts of polycarbonate, antioxidant contains Amount is 0.01~1 mass parts, the content of ultraviolet absorbing agent is 0.01~3 mass parts, the content of light stabilizer is 0.01~3 matter Measure part, the content of lubricant is 0.01~3 mass parts, the content of dyes/pigments is 0.01~3 mass parts.
It, can be before by dihydric phenol and carbonic ester when containing other polymers and/or additive in above-mentioned polycarbonate Addition when body is copolymerized can also add simultaneously melting mixing after terminating the copolymerization.
The glass transition temperature (Tg) of above-mentioned polycarbonate is preferably 120~160 DEG C of range, more preferably 135~ 155 DEG C of range, further preferably 140~150 DEG C of range.
The MFR of above-mentioned polycarbonate is preferably 1~30g/10 minutes ranges, more preferably 3~20g/10 minutes model It encloses, further preferably 5~10g/10 minutes range.When the range that MFR is 1~30g/10 minutes, heating melting forming It has good stability.
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, and it is preferable to use for example live to change Si Tailong polycarbonate Co., Ltd. " the ユ that " the カ リ バ ー (registered trademark) " and " SD Port リ カ (registered trademark) " of manufacture, Mitsubishi engineering Plastics Co., Ltd manufacture " タ Off ロ Application (registered trademark) ", the Supreme Being that ー ピ ロ Application/ノ バ レ ッ Network ス (registered trademark) ", Idemitsu Kosen Co., Ltd. manufacture People is melted into " the パ Application ラ イ ト (registered trademark) " etc. of Co., Ltd.'s manufacture.
[thickness of resin plate]
The thickness of resin plate in an embodiment of the invention is preferably 0.1~2mm, more preferably 0.5~ 1.5mm.When excessively thin, there is the tendency rigidly become inadequate.When blocked up, there is the lightweight that can interfere liquid crystal display device etc. Tendency.
The thickness of the layer containing methacrylic resin of resin plate in an embodiment of the invention is preferably 20~200 μm.In the range, the balance of marresistance and impact resistance is excellent.It is more preferably 25~150 μm, further excellent It is selected as 30~100 μm.
The thickness of layer containing polycarbonate is preferably 0.1~2mm, more preferably 0.5~1.5mm.When excessively thin, there are resistance to The tendency that impact becomes inadequate.When blocked up, there is the light-weighted tendency that can interfere liquid crystal display device etc..
In the resin plate that an embodiment through the invention obtains, solidification can be set at least one surface thereof Overlay film.By the way that curing overlay film is arranged, the functions such as marresistance, low reflectivity can be assigned.
For example, the thickness of marresistance (hard painting propert) curing overlay film is preferably 2~30 μm, more preferably 5~20 μm.It is excessively thin When, surface hardness becomes inadequate, and when blocked up, may be cracked due to the bending in manufacturing process.
In addition, the thickness of for example low reflexive curing overlay film is preferably 80~200nm, more preferably 100~150nm.It crosses It is thin or blocked up all low reflecting properties can be made to become inadequate.
[manufacturing process]
Resin plate in an embodiment of the invention is manufactured by being coextruded.Polycarbonate and composition are contained into first The resin heating melting of the layer of base acrylic resin, to be laminated on at least single side of the layer containing polycarbonate containing first The state of the thermoplastic resinous laminate of the layer of base acrylic resin, from the discharge opening of the wide cut shape of referred to as T-die It is squeezed out with molten condition, is clamped using a pair of rolls being made of the first chill roll and the second chill roll and be formed as sheet.Then, It after further thermoplastic resinous laminate is wound up on the second chill roll, is wound up on third chill roll, thus carries out cold But.In addition, thermoplastic resinous laminate (resin plate 16) is further carried out using more chill rolls after this sometimes cold But.
In Fig. 1, show as an embodiment using by T-die 11, first to 12~14 and of third chill roll Deflect from the summary of the manufacturing method of the resin plate of the co-extrusion device of the composition of roller 15.From T-die 11 squeeze out resin utilize by A pair of rolls clamping that first chill roll 12 and the second chill roll 13 are constituted, is formed as the resin plate 16 of sheet.Then, further will Resin plate 16 is cooling using third chill roll 14, is deflected from using the roller 15 that deflects from being made of a pair of rolls.Third chill roll with draw From roller can in addition be arranged between roller.It should be noted that the present invention is not limited to which.
As the mode of T-die at this time, it can use the methacrylic resin of heating melting state and gather Carbonic ester flow into T-die front laminate supply head mode, by methacrylic resin and polycarbonate in T-die The branch manifold mode etc. of portion's stacking.It is preferably more from the viewpoint of the flatness for improving the interface of each interlayer for constituting resin plate Manifold mode.
In addition, metallic roll can be enumerated as polishing roll at this time, have the resilient roller of metal made membrane in peripheral part (hereinafter, sometimes referred to as metallic elastic roller) etc..As metallic roll, as long as high rigidity is not particularly limited, example can be enumerated Such as hollow rolls, propellers.The surface state of metallic roll is not particularly limited, for example, can be mirror surface, or decorative pattern Or bumps etc..Metallic elastic the roller such as beaming roller by being rotatably arranged substantially cylindricly, the periphery to cover the beaming roller The mode in face configures and the columnar metal made membrane that contacts with flaked thermoplastic's resin and is enclosed in above-mentioned beaming roller and metal Fluid between made membrane is constituted, and so that metallic elastic roller is shown elasticity using fluid.Beaming roller is not particularly limited, such as by stainless Steel etc. is constituted.Metal made membrane is for example made of stainless steel etc., and thickness is preferably from about 2mm~about 5mm.Metal made membrane is preferred With bendability, pliability etc., the preferably not no jointless structure of welding seam part.The metallic elastic for having such metal made membrane Roller becomes excellent durability and to made of metal film mirror-polishing when is able to carry out and similarly handles with common mirror roller, is right Metal made membrane can transfer the roller of its shape when assigning decorative pattern or bumps, therefore easy to use.
The resin and polycarbonate for constituting the layer containing methacrylic resin are preferably before multilevel shaping and/or multilayer Melt filteration is carried out using filter when forming.Multilevel shaping is carried out by using each resin combination after melt filteration, it can The few resin plate of defect caused by obtain because of foreign matter, gel.The filter material of used filter is not particularly limited, according to making It is suitably selected, be can be used for example comprising polypropylene, cotton, polyester, artificial silk, glass fibre with temperature, viscosity, filtering accuracy Deng non-woven fabrics；It is impregnated with the tablet of the cellulose of phenolic resin；Metallic fiber nonwoven fabric sintered sheet object；Metal powder Sintered sheet object；Metal mesh；Or their combination.Wherein, from the viewpoint of heat resistance and durability, preferably by metal fibre Tieing up non-woven fabrics sintered sheet object, multiple are laminated to use.
The filtering accuracy of above-mentioned filter is not particularly limited, preferably 30 μm hereinafter, more preferably 10 μm hereinafter, into one Preferably 5 μm or less of step.
The resin plate of an embodiment of the invention is preferably by the temperature for the resin entirety removed from third chill roll 14 It is set as range of the glass transition temperature (Tg) relative to polycarbonate from 0 DEG C to+15 DEG C.The reason for this is that from third When the temperature for the resin entirety that chill roll 14 is removed is lower than glass transition temperature (Tg) of polycarbonate, resin plate is cold by third But the shape transfer of roller, warpage increase.On the other hand, the temperature ratio and third for the resin entirety removed from third chill roll 14 are cold But when the glass transition temperature (Tg) of the resin layer of roller contact is high too many, resin plate is unable to get beautiful superficiality.It needs Illustrate, the temperature of resin entirety and any one face of resin plate are unrelated, to being laminated with polycarbonate resin and methyl-prop The temperature of the resin plate entirety of olefin(e) acid resinoid is measured to use.
The range that the preferred line expansion ratio (SR) of the resin plate of an embodiment of the invention is -10%~+5%, contains The glass transition temperature (Tg) of the resin layer of methacrylic resin is 120~160 DEG C.Its reason is as described below.
The resin plate stripped down from third chill roll 14 be clamped into deflect from roller 15 before in a period of, sandwich respectively It third chill roll 14 and deflects from roller 15, therefore forms the shape of general planar.The tree just stripped down from third chill roll 14 Range of the temperature of rouge plate for the glass transition temperature (Tg) relative to polycarbonate from 0 DEG C to+15 DEG C, but it is attached to deflect from roller 15 The temperature of close resin plate is cooled to room temperature, therefore approximately reaches room temperature.
For example, the temperature of the resin plate stripped down from third chill roll 14 is 150 DEG C, the resin plate near roller is deflected from Temperature is 25 DEG C.The linear expansion coefficient (S1) of layer containing polycarbonate and the line of the layer containing methacrylic resin expand When coefficient (S2) has differences, specifically, shrinking and generating in the big side of linear expansion coefficient when (S1-S2)/S1 is not zero Warpage.
In addition, for example, the glass transition temperature (Tg) of the layer containing methacrylic resin is 120 DEG C, containing poly- The glass transition temperature (Tg) of the layer of carbonic ester is 150 DEG C.In this case, the resin plate stripped down from third chill roll 14 Temperature be 150 DEG C, therefore, 150 DEG C of the layer containing polycarbonate from glass transition temperature (Tg) are cooled to room temperature.Cause This, in the layer containing polycarbonate, forms the contraction approximately along linear expansion coefficient.
On the other hand, the layer containing methacrylic resin is from the region (150 DEG C) than glass transition temperature high temperature It is cooled near 120 DEG C of glass transition temperature (Tg).Therefore, though the layer containing polycarbonate linear expansion coefficient (S1) when there is no difference with the linear expansion coefficient (S2) for the resin for constituting the layer containing methacrylic resin, containing methyl In the layer of acrylic resin, the big contraction more than linear expansion coefficient can be also generated.
Here, general resin is in glass transition temperature, the following are elastomers, but more than glass transition temperature temporarily And become the viscoelastic body for having both the function of viscosity and elasticity.
Above-mentioned elastomer is deformed when applying stress, when discharging, eliminating deformation, in contrast, viscoelastic Property body when being cooled to glass transition temperature in the state of being applied with stress, form residual deformation.From third chill roll 14 The temperature of the resin plate stripped down is such as 150 DEG C, the layer containing methacrylic resin and the layer containing polycarbonate When for above-mentioned glass transition temperature, for resin plate after just stripping down from third chill roll 14, Polycarbonate Layer is bullet Property body, in contrast, the layer containing methacrylic resin be viscoelastic body.That is, by resin plate just from third chill roll 14 After stripping down, contraction distortion only is generated in the layer containing methacrylic resin as viscoelastic body.In other words, make Stress is reversible for the Polycarbonate Layer of elastomer, therefore, even if there are the load of stress, releasing, will not be generated Deformation.In contrast, it is generated as the layer containing methacrylic resin of viscoelastic body due to load, the releasing of stress Residual deformation.
Based on the above reasons, the linear expansion coefficient (S1) of the layer containing polycarbonate and containing methacrylic resin The linear expansion coefficient (S2) of layer when having differences, in other words, when the absolute value of online expansion ratio (SR) is big, can generate because of elasticity Therefore warpage caused by contraction difference in body generates warpage at the time of deflecting from roller 15 and discharging resin plate.It should be noted that So far, to simplify the explanation, it is sometimes denoted as the difference of line expansion.In the case where illustrating simple size, it is poor to use When fully indicating, but wanting to indicate quantitative amount of warpage, need to be discussed with line expansion ratio (SR).
In addition, the layer containing methacrylic resin glass transition temperature (Tg) lower than containing polycarbonate The temperature of the glass transition temperature (Tg) of layer and the resin plate stripped down from third chill roll 14 is containing metering system When between the glass transition temperature (Tg) of the layer of acid resin and the glass transition temperature (Tg) of the layer containing polycarbonate, Due to the contraction difference in elastomer and viscoelastic body in the layer residual deformation containing methacrylic resin.The residual deformation In the presence of following tendency: deformation is discharged and being exposed under the conditions of high temperature and high temperature and humidity, to generate warpage.Here, just The temperature of the resin plate stripped down from third chill roll 14 relative to polycarbonate glass transition temperature (Tg) be 0 DEG C extremely + 15 DEG C, therefore, there is also the states of viscoelastic body for polycarbonate.Here, the temperature of resin plate quilt before arrival deflects from roller 15 It is cooled to room temperature, but the layer containing methacrylic resin and the layer containing polycarbonate are all cooled to room temperature simultaneously.Cause This, has just included the glass of polycarbonate to the temperature for reaching the resin plate before deflecting from roller 15 from stripping down third chill roll 14 The glass transition temperature (Tg) of glass transition temperature (Tg) and the layer containing methacrylic resin.That is, by resin plate Temperature is cooled to the glass transition of the layer containing methacrylic resin from the glass transition temperature (Tg) of polycarbonate During temperature (Tg), in the layer residual deformation containing methacrylic resin.
On the other hand, in principle, when making the temperature of the resin plate stripped down from third chill roll 14 lower than 150 DEG C, line The tendency that warpage and residual stress caused by expansion ratio (SR) are reduced, therefore, warpage becomes smaller.But as noted previously, as The warpage that resin plate generates the shape transfer of third chill roll 14 increases, thus not preferably.
It follows that the temperature for the resin removed from third chill roll 14 is set as in order to achieve the purpose that the application Range of the glass transition temperature (Tg) from 0 DEG C to+15 DEG C relative to polycarbonate, line expansion ratio (SR) is set as- The glass transition temperature (Tg) of layer containing methacrylic resin is set as 120~160 by 10%~+5% range DEG C, thus, it is possible to obtain the small good resin plate of warpage.
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 resin plate is measured by the following method.
[glass transition temperature (Tg)]
Obtained resin plate is cut into the test film of 10mg after 80 DEG C 24 hours dry under reduced pressure (1kPa), benefit It is sealed with aluminium dish, uses differential scanning calorimeter (" DSC-50 ", Co., Ltd. Neo-Confucianism's manufacture), progress 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, keeps 10 Minute, it is cooled to 25 DEG C (single pass).Then, 200 DEG C (rescans) are warming up to 10 DEG C/min of speed.In utilization Point method calculates glass transition temperature (Tg).
[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 ", the manufacture of Block Le カ ー エ イ エ ッ Network ス エ ス Co., Ltd.) is set according to JIS K7197 to be measured. That is, using gold in order to which the resin plate for carrying out sheet obtained from press molding to the resin of each measurement is formed smooth end face Hard rock saw, the length for being processed into one side is 5mm × 5mm, is highly the prism-shaped of 10mm, by each sample after processing so that 5mm The mode that the surface of × 5mm is contacted with quartz plate is placed on the plate of quartz, is placed cylindric stick on it, is applied the pressure of 5g Contracting load and fix.Then, in air atmosphere, each sample is warming up to from 25 DEG C (room temperature) with 3 DEG C/min of heating rate Minus 10 DEG C of glass transition temperature (Tg) are cooled to 25 DEG C (room temperature) (single pass).Then, with 3 DEG C/min of heating speed Degree is warming up to positive 20 DEG C (rescans) of the glass transition temperature (Tg) of each sample from 25 DEG C (room temperature).When to rescan Each temperature in the coefficient of expansion be measured, find out the average linear expansion coefficient in the range of 30 DEG C~80 DEG C.
[amount of warpage]
By the resin plate of embodiment and comparative example so that the direction parallel with Extrusion Flow direction is short side and Extrusion Flow The vertical direction in direction is that the mode of long side is cut into rectangle, the test film of production short side 65mm, long side 110mm.By production Test film is be placed into the layer containing methacrylic resin on platform in a manner of upward, in 23 DEG C of temperature, relative humidity It is placed 24 hours in 50% environment.Then, using feeler gauge, the maximum value in the gap of measurement test piece and platform, by the value As initial stage amount of warpage.Then, in the environment chambers for being set as 85 DEG C of temperature, relative humidity 85%, by above-mentioned test film Be placed into the layer containing methacrylic resin in glass platform in a manner of upward, place 72 hours in this state Afterwards, it is placed 4 hours under 25 DEG C of environment.Then, it is measured in the same manner as described above measurement, using the value as the warpage after high temperature and humidity Amount.By test film be placed into the layer containing methacrylic resin on platform in a manner of upward, by downwardly convex warpage Symbol be set as just, the symbol of upward convex warpage is set as negative.It is that ± 0.5mm or less is set as qualified by amount of warpage.
[superficiality]
In the interior for being provided with fluorescent lamp, the two sides of resin plate is visually observed, according to following benchmark to superficiality It is evaluated.
Zero: not observing the line that quivers in resin board surface.
△: the line that quivers is observed in resin board surface, but unobvious.
×: in resin board surface, the line that quivers is obvious.
[resin temperature]
At the position that third chill roll 14 is removed, the whole temperature of infrared emission thermometer measurement resin plate 16 is utilized Degree.The temperature measured in this way is known as resin temperature (TT).
[methacrylic resin A]
Prepare " パ ラ ペ ッ ト (registered trademark) HR " of Kuraray Co., Ltd.'s manufacture (under 230 DEG C of temperature, 3.8kg load MFR=2.4g/10 minute) be used as methacrylic resin A.
[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 is 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.
[methacrylic resin C]
Prepare from central side by 35 mass % of hard layer (first layer: 94 mass parts of MMA unit, methyl acrylate units 6 Mass parts, 0.2 mass parts of allyl methacrylate unit), soft layer 45 mass % (second layer, rubber layer: butyl acrylate 82.2 mass parts of unit, 17.8 mass parts of styrene units, 2 mass parts of allyl methacrylate unit) and 20 matter of hard layer Measure % (third layer: 94 mass parts of MMA unit, 6 mass parts of methyl acrylate units, 0.2 mass parts of n octylmercaptan unit) structure The acrylic compounds three-decker rubber particles for being 0.23 μm at, average grain diameter.
Prepare the above-mentioned of the methacrylic resin B and 8.5 mass % of the 35 mass % of TC ratio of 91.5 mass % Average grain diameter is the resin combination that mixes of 0.23 μm of acrylic compounds three-decker rubber particles as methacrylic acid Resinoid C.
[resin combination (1)]
In Production Example, methacrylic resin as follows and SMA resin are used.
<methacrylic resin>
About methacrylic resin, prepare " the パ ラ ペ ッ ト (registered trademark) of above-mentioned Kuraray Co., Ltd.'s manufacture HR " is (identical as methacrylic resin A) to be used as methacrylic resin.
<SMA resin>
SMA resin can be obtained by the following method.
For example, the method by recording in WO2010/013557, available total as phenylethylene-maleic anhydride-MMA The SMA resin of polymers.
The quality ratio of components of the SMA resin used and weight average molecular weight (Mw) are shown in Table 1.
[table 1]
<quality ratio of components>
The copolymerization composition of SMA resin is found out according to following steps by 13C-NMR method.
13C-NMR spectrum uses nuclear magnetic resonance device (Japan Electronics Corporation manufactures, GX-270).Dissolve SMA resin 1.5g In deuterated chloroform 1.5ml, sample solution is prepared, under room temperature environment, under conditions of cumulative number is 4000~5000 times It is measured.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=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, the TSKgel for manufacturing TOSOH Co., Ltd is used as column using tetrahydrofuran Two columns being connected in series with SuperHZ4000 of SuperMultipore HZM-M.It is poor using having as GPC device Show the HLC-8320 (model) of TOSOH Co., Ltd's manufacture of refractive index detector (RI detector).It is dissolved in SMA resin 4mg In tetrahydrofuran 5ml, sample solution is prepared.The temperature of column oven is set as 40 DEG C, with 0.35ml/ minutes elution flow quantities 20 μ l of sample solution is injected, chromatogram is measured.Utilize standard polyphenyl of GPC measurement molecular weight in the range of 400~5000000 10 points of ethylene, production indicates the standard curve of the relationship of retention time and molecular weight.Mw is determined based on the standard curve.
SMA resin in resin combination (1) is shared in the total amount of methacrylic resin A and SMA resin The ratio that feeds intake (quality percentage) be known as SMA ratio.
[polycarbonate]
Prepare firmly to change " SD Port リ カ (registered trademark) PCX " that Si Tailong polycarbonate Co., Ltd. makes (300 DEG C of temperature, 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 resin plate)
By the methacrylic resin B of 20 mass % of TC ratio (glass transition temperature: 120 degree, linear expansion coefficient: 7.30×10-5/ K) it is melted using 150mm φ single screw extrusion machine [Toshiba Machinery Co., Ltd.'s system], polycarbonate is utilized The two is laminated via branch manifold pattern tool for 150mm φ single screw extrusion machine [Toshiba Machinery Co., Ltd.'s system] melting.It will Resin (thermoplastic resinous laminate of resin plate 16, molten condition) after stacking is clamped into the first chill roll 12 shown in FIG. 1 It between the second chill roll 13, after being wound up on the second chill roll 13, is wound up on third chill roll 14, thus carries out cold But, resin plate 16 is deflected from using deflecting from roller 15, manufactures resin plate.Resin temperature (TT) passes through the second chill roll 13 of control and the The temperature of three chill rolls 14 and adjust to 150 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[embodiment 2]
The methacrylic resin B and polycarbonate for using 35 mass % of TC ratio as described above, manufacture resin Plate.Resin temperature (TT) is adjusted as described above to 150 DEG C.The evaluation result of manufacturing condition and obtained resin plate is shown In table 2.
[embodiment 3]
The methacrylic resin B and polycarbonate of 45 mass % of TC ratio are manufactured as described above.Resin temperature (TT) it adjusts as described above to 155 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[embodiment 4]
The methacrylic resin B and polycarbonate of 60 mass % of TC ratio are manufactured as described above.Resin temperature (TT) it adjusts as described above to 155 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[embodiment 5]
The resin combination (1) and polycarbonate of 20 mass % of SMA ratio are manufactured as described above.Resin temperature (TT) It is adjusted as described above to 150 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[embodiment 6]
The resin combination (1) and polycarbonate of 50 mass % of SMA ratio are manufactured as described above.Resin temperature (TT) It is adjusted as described above to 150 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[embodiment 7]
The resin combination (1) and polycarbonate of 70 mass % of SMA ratio are manufactured as described above.Resin temperature (TT) It is adjusted as described above to 155 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[embodiment 8]
The resin combination (1) and polycarbonate of 100 mass % of SMA ratio are manufactured as described above.Resin temperature (TT) it adjusts as described above to 155 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[embodiment 9]
The resin combination (1) and polycarbonate of 70 mass % of SMA ratio are manufactured as described above.Resin temperature (TT) It is adjusted as described above to 165 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[comparative example 1]
Methacrylic resin A and polycarbonate are manufactured as described above.Resin temperature (TT) is as described above It adjusts to 150 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[comparative example 2]
The resin combination (1) and polycarbonate of 70 mass % of SMA ratio are manufactured as described above.Resin temperature (TT) It is adjusted as described above to 145 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[comparative example 3]
The resin combination (1) and polycarbonate of 70 mass % of SMA ratio are manufactured as described above.Resin temperature (TT) It is adjusted as described above to 170 DEG C.By manufacturing condition and obtained resin plate evaluation result is shown in table in 2.
[comparative example 4]
Other than the methacrylic resin B of 35 mass % of TC ratio is changed into methacrylic resin C, with Embodiment 2 similarly manufactures resin plate.Resin temperature (TT) is adjusted as described above to 150 DEG C.By manufacturing condition and gained To resin plate evaluation result is shown in table in 2.
In table 2, for embodiment and comparative example, resin temperature (TT), glass transition temperature (Tg), resin is shown respectively Amount of warpage and prima facie measurement result after the linear expansion coefficient of plate, line expansion ratio (SR), initial stage and high temperature and humidity.
In Examples 1 to 4, manufacture is laminated with the layer of the methacrylic resin B containing 20~60 mass % of TC ratio It is tested with the resin plate of the layer containing polycarbonate.As shown in table 2, containing TC ratio 45% using embodiment 3 Methacrylic resin B layer in the case where, it is contemplated that glass transition temperature (Tg), linear expansion coefficient ratio (SR) and stick up Qu Liang has obtained most preferred result.
In embodiment 5~9, manufacture be laminated with the resin combination (1) containing 20~100 mass % of SMA ratio layer and The resin plate of layer containing polycarbonate is tested.As shown in table 2, containing 70 matter of SMA ratio using embodiment 7,9 In the case where the layer for measuring the resin combination (1) of %, the absolute value of amount of warpage is small, has obtained most preferred result.
On the other hand, in comparative example 1, glass transition temperature (Tg) is low, and the warpage after high temperature and humidity is big.In comparative example 2, Reduce resin temperature (TT), as a result, the resin plate big as amount of warpage.It in comparative example 3, improves resin temperature (TT), ties Fruit becomes the resin plate of superficiality difference.In comparative example 4, the condition of linear expansion coefficient is unsatisfactory for the application, therefore, initial stage warpage It is big with the warpage after high temperature and humidity.
Industrial availability
Resin plate of the invention can be used in the protective cover of such as liquid crystal display protection board, touch panel, be suitable for vehicle It carries with display device, portable phone, smart phone, PC, 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.
This application claims preferential based on the Japanese publication Patent 2014-190029 proposed by September 18th, 2014 Power, its entire disclosure is incorporated in this specification.
Symbol description
11 T-dies
12 first chill rolls
13 second chill rolls
14 third chill rolls
15 deflect from roller
16 resin plates

Claims (7)

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
By the line of the linear expansion coefficient (S1) of the layer containing polycarbonate and the layer containing methacrylic resin The ratio between the difference (S2-S1) of the coefficient of expansion (S2) and the linear expansion coefficient (S1) of the layer containing polycarbonate ((S2-S1)/S1) It is set as -10%~+5%,
The glass transition temperature of the layer containing methacrylic resin is set as 120~160 DEG C,
The manufacturing method comprises the following steps:
The layer containing methacrylic resin will be laminated on at least single side of the layer containing polycarbonate Thermoplastic resinous laminate is squeezed out with molten condition from T-die,
The thermoplastic resinous laminate is sandwiched between the first chill roll and the second chill roll,
By by the thermoplastic resinous laminate be wound up on second chill roll after be wound up on third chill roll come It is cooled down,
Thermoplastic resinous laminate utilization is deflected from roller to deflect from；
In the thermoplastic resinous laminate at the position that the third chill roll is removed, the temperature of resin entirety is set as Range of the glass transition temperature from 0 DEG C to+15 DEG C relative to the layer containing polycarbonate.
2. a kind of extruded resin sheet, it includes the extruded resin sheet obtained by manufacturing method described in claim 1,
Structure from methyl methacrylate of the layer containing methacrylic resin containing 40~80 mass % Unit, and the structural unit for deriving from methacrylate represented by the following general formula (I) containing 20~60 mass %,
In formula, Cy indicates alicyclic type hydrocarbon.
3. extruded resin sheet as claimed in claim 2, wherein the Cy in logical formula (I) is multicyclic aliphatic alkyl.
4. a kind of extruded resin sheet, it includes the extruded resin sheet obtained by manufacturing method described in claim 1,
The layer containing methacrylic resin contains methacrylic resin and 20 matter lower than 80 mass % At least origin for measuring % or more is derived from structural unit and the source of aromatic ethenyl compound represented by the following general formula (II) The copolymer that the structural unit of the acid anhydrides represented by the following general formula (III) is formed,
In formula, R1And R2Hydrogen atom or alkyl are each independently represented,
In formula, R3And R4Each independently represent hydrogen atom or alkyl.
5. extruded resin sheet as claimed in claim 4, which is characterized in that the copolymer contains the source of 50~84 mass % In the structural unit of the aromatic ethenyl compound, the structure list from the acid anhydrides containing 15~49 mass % Member, and the methacrylate monomers containing 1~25 mass %.
6. extruded resin sheet as claimed in claim 5, which is characterized in that the methacrylate monomers are methacrylic acid Methyl esters.
7. the extruded resin sheet as described in any one of claim 2~6, wherein be further equipped at least one surface Marresistance layer.
CN201580050630.2A 2014-09-18 2015-09-04 The manufacturing method and extruded resin sheet of extruded resin sheet Active CN106715078B (en)

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JP2014-190029 2014-09-18
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