CN106715078A

CN106715078A - Process for producing extruded resin sheet, and extruded resin sheet

Info

Publication number: CN106715078A
Application number: CN201580050630.2A
Authority: CN
Inventors: 船崎男; 船崎一男
Original assignee: Kuraray Co Ltd
Current assignee: Kuraray Co Ltd
Priority date: 2014-09-18
Filing date: 2015-09-04
Publication date: 2017-05-24
Anticipated expiration: 2035-09-04
Also published as: KR20170057301A; CN106715078B; WO2016042727A1; KR102365229B1; TWI683740B; TW201618930A; JP6545179B2; JPWO2016042727A1

Abstract

The present invention provides a process for producing a resin sheet which has satisfactory surface properties and is inhibited from suffering warpage due to residual stress. The ratio of the difference between the coefficient of linear expansion (S1) of a polycarbonate-containing layer and the coefficient of linear expansion (S2) of a methacrylic-resin-containing layer to the coefficient of linear expansion (S1) of the polycarbonate-containing layer, (S2-S1)/S1, is regulated to -10% to +5%. The glass transition temperature of the methacrylic-resin-containing layer is regulated to 120-160 DEG C. A thermoplastic resin laminate (resin sheet (16)) comprising the polycarbonate-containing layer and the methacrylic-resin-containing layer laminated thereto is extruded in a molten state through a T die (11), is sandwiched between first and second cooling rolls (12, 13), is wound on the second cooling roll (13), is then wound on a third cooling roll (14) to cool the sheet, and is hauled with hauling rolls (15). At the position where the resin sheet (16) separates from the third cooling roll (14), the temperature of the entire resin is regulated so as to be higher by 0-15 DEG C than the glass transition temperature of the polycarbonate-containing layer.

Description

The manufacture method and extruded resin sheet of extruded resin sheet

Technical field

The present invention relates to resin plate.More specifically, the present invention relates to manufacture superficiality well and because residual stress causes Warpage generation obtained suppression, possessing for the protective cover that is suitable for contact panel etc. contain methacrylic resin The method of the resin plate of layer and the layer containing makrolon.

Background technology

Contact panel (or touch-screen) is the electronic unit that combination has display device and positioning input device.Can by with Finger or pen contact contact panel to operate electronic equipment.Contact panel is used for the ATM of bank and other financial mechanism, automatic vending It is machine, mobile phone, portable data assistance (PDA), digital audio-frequency player, portable game machine, plate PC, multiple Print machine, facsimile machine, auto navigation digital information equipment etc..

In the input operation using contact panel, scratch or inside is produced to damage by pressure on surface sometimes.In order to Above-mentioned situation is prevented, transparent protective cover is set on the surface of contact panel.It is main to use strengthened glass system as protective cover Protective cover.In addition, from from the viewpoint of processability, lightweight, having carried out the exploitation of the protective cover of transparent resin.For this Protective cover, it is desirable to gloss, marresistance, impact resistance etc..

Makrolon is suitable for obtaining one of resin of formed products of excellent impact resistance.Methacrylic resin is It is suitable for obtaining one of resin of formed products of high glaze and excellent abrasion.In addition, by makrolon and methyl-prop Olefin(e) acid resinoid carries out heating melt-shaping (being for example coextruded shaping) simultaneously, can manufacture by the layer comprising polycarbonate resin The resin plate constituted with the layer comprising methacrylic resin.In the heating melt-shaping of such resin plate, due to two Plant the difference of the characteristic of resin and make to remain many distortional stresses in resulting formed products.During this is remained in into formed products Distortional stress is referred to as residual stress, and the formed products with the residual stress can produce warpage, shrink because heat is waited.

For tabular formed products as above-mentioned resin plate, because the warpage that residual stress causes especially turns into problem. Suppress one of method of generation of warpage as the residual stress reduced in tabular formed products, it is known that to being used in extrusion molding Chill roll the method (for example, referenced patent document 1) that is adjusted of rotary speed.

In addition, in order to solve the problem, the raising to the heat resistance and moisture-proof of methacrylic resin is ground Study carefully.For example, it was recently reported that a kind of resin plate of two-layer, wherein, using with methyl methacrylate units and selected from methyl-prop Olefin(e) acid unit, acrylic acid units, maleic anhydride units, N- substitutions or unsubstituted maleimide amine unit, glutaric anhydride structure list Unit and glass transition temperature in unit and glutarimide construction unit are that more than 110 DEG C of methacrylic resin comes Ground floor is formed, possesses the layer (for example, referenced patent document 2) comprising makrolon thereon.But, for the resin plate Speech, even if so, the heat resistance and moisture-proof of methacrylic resin or insufficient, even if having the methacrylic Resin, can not fully solve the problems, such as above-mentioned.

In addition, in order to solve the problem, it is also known that following method：It is conceived to the linear expansion coefficient reduced between two resin sheets Difference, control warpage generation (for example, referenced patent document 3).But, when only realizing the regulation of linear expansion coefficient, it is impossible to solve Certainly above mentioned problem.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2007-185956 publications

Patent document 2：Japanese Unexamined Patent Publication 2009-248416 publications

Patent document 3：Japanese Unexamined Patent Publication 2007-118597 publications

The content of the invention

Invent problem to be solved

In resin plate, the degree of the stress remained in each resin bed is different.Therefore, in having attempted by adjusting extrusion molding The rotary speed of the chill roll for using reduces the stress of residual.But, when formed products leave chill roll, sometimes in shaping The surface of product produces the striated defect of the line that is referred to as quivering, superficiality reduction.The resin plate is being used for contact panel by the phenomenon Protective cover etc. in the case of turn into problem.

The generation of warpage that is good it is an object of the invention to provide manufacture superficiality and causing by residual stress is obtained The method and resin plate of the resin plate of suppression.

For the method for solve problem

The present inventor is studied in order to achieve the above object, is as a result found that the present invention comprising in the following manner.

That is, the present invention includes in the following manner.

The manufacturer of extruded resin sheet (below, being also suitably recited as " resin plate " " extruded resin sheet ") of the invention One mode of method is the extrusion that the layer containing methacrylic resin is laminated with the one side of the layer containing makrolon The manufacture method of resin plate, the operation under imposing in fact.

The thermoplastic resin of the layer containing methacrylic resin is laminated with the one side of the layer containing makrolon The operation that layered product is extruded with molten condition from T-shaped mould head.

The operation of above-mentioned thermoplastic resinous laminate is sandwiched between the first chill roll and the second chill roll.

The 3rd chill roll is wound up into after by the way that above-mentioned thermoplastic resinous laminate is wound up on above-mentioned second chill roll On come the operation that is cooled down.

Above-mentioned thermoplastic resinous laminate is utilized and deflects from the operation that roller is deflected from.

In addition, following condition is met in above-mentioned each operation.

By the linear expansion coefficient (S1) of the above-mentioned layer containing makrolon and the above-mentioned layer containing methacrylic resin Linear expansion coefficient (S2) difference (S2-S1) and the ratio between linear expansion coefficient (S1) ((S2- of the above-mentioned layer containing makrolon S1)/S1) it is set as -10%~+5%.Hereinafter, will be suitably recited 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 from the position that above-mentioned 3rd chill roll is peeled off, the overall temperature of resin is set It is set to the scope that the glass transition temperature (Tg) relative to makrolon is from 0 DEG C to+15 DEG C.

By meeting these conditions, can realize that superficiality is good and because of the small resin plate of warpage that residual stress causes.

In addition, in a mode of the resin plate obtained by the manufacture method of above-mentioned extruded resin sheet, it is preferably above-mentioned Construction unit from methyl methacrylate of the layer containing methacrylic resin containing 40~80 mass %, and contain There is the construction unit from the methacrylate represented by following logical formula (I)s of 20~60 mass %.

(in formula, Cy represents alicyclic type hydrocarbon.)

Additionally, the Cy in logical formula (I) is more preferably multicyclic aliphatic alkyl.

In addition, in a mode of the resin plate obtained by the manufacture method of above-mentioned extruded resin sheet, it is preferably above-mentioned Layer containing methacrylic resin contains the methacrylic resin and more than 20 mass % less than 80 mass % At least origin comes from the construction unit of the aromatic ethenyl compound represented by following logical formula (II)s and from following formulas (III) copolymer that the construction unit of the acid anhydrides represented by is formed.

(in formula, R¹And R²Hydrogen atom or alkyl are represented independently of one another.)

(in formula, R³And R⁴Hydrogen atom or alkyl are represented independently of one another.)

Furthermore it is preferred that above-mentioned copolymer contains the knot from above-mentioned aromatic ethenyl compound of 50~84 mass % Structure unit, the construction unit from above-mentioned acid anhydrides containing 15~49 mass %, and contain the metering system of 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, and the generation of the warpage caused by residual stress is suppressed.In addition, Resin plate of the invention is suitable for requirement gloss, marresistance and impact resistance, such as contact panel protective cover.

Brief description of the drawings

Fig. 1 is the figure of the manufacture method using the resin plate being coextruded for representing an embodiment of the invention.

Specific embodiment

Hereinafter, refer to the attached drawing is illustrated to embodiments of the present invention.In order to be clearly stated, following record and Accompanying drawing is suitably omitted and simplified.In the accompanying drawings, to inscape and appropriate section with identical composition or function Mark identical symbol, and the description thereof will be omitted.

Implementation method 1

Resin plate of the invention is in the layer (below, being also suitably recited as " makrolon contains layer ") containing makrolon A face on be laminated the layer containing methacrylic resin and (below, be also suitably recited as that " methacrylic resin contains Have layer ").

The layer containing methacrylic resin is laminated with the layer containing makrolon, thus the transparency, impact resistance Property, excellent abrasion.

Resin plate is manufactured by extrusion molding method, and thus, production efficiency is excellent.

In resin plate, linear expansion coefficient (S1) and the layer containing methacrylic resin of the layer containing makrolon Line expansion ratio (SR) represented by the relational expression of linear expansion coefficient (S2) is set as -10%~+5% scope, good from obtaining Warpage from the viewpoint of, line expansion ratio (SR) is more preferably -5%~+2% scope.

Line expansion ratio (SR) is the linear expansion coefficient (S1) of the layer containing makrolon and contain methacrylic resin Layer linear expansion coefficient (S2) difference (S2-S1) and 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) that makrolon is contained into layer and methacrylic resin The ratio that the relation of the linear expansion coefficient (S2) containing layer is represented 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 it is 120 DEG C, preferably 125 DEG C, more preferably 130 DEG C, the upper limit of its 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) when within the range, superficiality is good, because the warpage that residual stress causes is small, so that it is preferred that.

[methacrylic resin]

In an embodiment of the invention, methacrylic resin contains the structure list from methacrylate Unit.

Content from the construction unit of methacrylate is preferably more than 50 mass %, more preferably 80 mass % More than, more preferably more than 90 mass % are preferably.Can be 100 mass %.From the structure list of methacrylate The content of unit within the above range when, the transparency is good.

The methacrylate is represented by logical formula (IV).

Lead in formula (IV), R represents alkyl.Alkyl can be saturated hydrocarbyl, or unsaturated alkyl.

Alkyl shown in R can be the Noncyclic aliphatic alkyl such as methyl, ethyl, propyl group, or alicyclic type hydrocarbon, Can also be the aromatic hydrocarbyls such as phenyl.Here, in the case where R is alicyclic type hydrocarbon, methacrylate is by logical formula (I) table Show.Hereinafter, suitably the methacrylate represented by logical formula (I) is recited as " methacrylate (I) ".

As methacrylate (I), can enumerate：Cyclohexyl methacrylate, methacrylic acid ring pentyl ester, methyl-prop The methacrylic acid monocyclic aliphatic such as olefin(e) acid cycloheptyl ester race hydrocarbon ester；Methacrylic acid 2- norborneols ester, methacrylic acid 2- methyl -2- Norborneol ester, methacrylic acid 2- ethyl -2- norborneols ester, methacrylic acid 2- isobornyl thiocyanoacetates, methacrylic acid 2- methyl -2- Isobornyl thiocyanoacetate, methacrylic acid 2- ethyl -2- isobornyl thiocyanoacetates, the ring [5.2.1.0 of methacrylic acid 8- tri-^2,6] last of the ten Heavenly stems ester, metering system Sour ring [the 5.2.1.0 of 8- methyl -8- three^2,6] last of the ten Heavenly stems ester, the ring [5.2.1.0 of methacrylic acid 8- ethyls -8- three^2,6] last of the ten Heavenly stems ester, methyl-prop Olefin(e) acid 2- Buddha's warrior attendants alkyl ester, 2-Methacryloyloxy-2-methyladamantane, 2-Ethyl-2-adamantyl methacrylate, methyl-prop Olefin(e) acid 1- Buddha's warrior attendants alkyl ester, methacrylic acid 2- benzene oxygen ester, methacrylic acid 2- methyl -2- benzene oxygen esters or methacrylic acid 2- second The methacrylic acid multicyclic aliphatic hydrocarbon esters such as base -2- benzene oxygen esters；Deng.Wherein, preferred methacrylic acid multicyclic aliphatic hydrocarbon ester, more It is preferred that ring [the 5.2.1.0 of methacrylic acid 8- tri-^2,6] last of the ten Heavenly stems ester.

The methacrylic resin used in the present invention is preferably comprised (below, also fits from methyl methacrylate Locality is recited as " MMA ") construction unit and the construction unit from methacrylate (I), further preferably derive from The construction unit of methyl methacrylate and the construction unit from methacrylic acid multicyclic aliphatic hydrocarbon ester, further preferably Containing the construction unit from methyl methacrylate and from the ring [5.2.1.0 of methacrylic acid 8- tri-^2,6] last of the ten Heavenly stems ester knot Structure unit.

In the methacrylic resin used in the present invention, from from the viewpoint of hardness, 40~80 matter are preferably comprised Measure the construction unit from methyl methacrylate of %, further preferably 50~80 mass %, further preferably 50 ~60 mass %.

In the methacrylic resin used in the present invention, from reduce line expansion ratio (SR) viewpoint and make vitrifying turn Temperature (Tg) be from the viewpoint of more than 120 DEG C preferably comprise 20~60 mass % from methacrylate (I) Construction unit, further preferably 20~50 mass %, further preferably 40~50 mass %.From methacrylate (I) when construction unit is more than 60 mass %, there is the tendency of the impact resistance reduction of methacrylic resin layer.

The methacrylic resin used in the present invention is by using above-mentioned methacrylate and as any condition Other monomers be polymerized and obtained.In the case of using various of monomer in the polymerization, generally above-mentioned various of monomer is mixed Close and prepare monomer mixture, then for polymerization.Polymerization is not particularly limited, from from the viewpoint of productivity ratio, preferably Radical polymerization is carried out by methods such as mass polymerization, suspension polymerization, solution polymerization process, emulsion polymerizations.

The weight average molecular weight (below, being also suitably recited as " Mw ") of the methacrylic resin used in the present invention is excellent Elect 40000~500000 as.By making the Mw be more than 40000, resin plate of the invention turns into marresistance, excellent heat resistance Resin plate, by making the Mw for less than 500000, shaping processability is excellent, can improve the productivity ratio of resin plate of the invention.

It should be noted that in this specification, Mw refers to the standard polyphenyl second determined using gel permeation chromatography (GPC) Alkene scaled value.

In an embodiment of the invention, the resin for constituting the layer containing methacrylic resin is containing less than 80 At least origin of the methacrylic resin of quality % and more than 20 mass % comes from the virtue represented by following logical formula (II)s The construction unit of fragrant race's vinyl compound (below, being also suitably recited as " aromatic ethenyl compound (II) ") and source In being total to that the construction unit of the acid anhydrides (below, being also suitably recited as " acid anhydrides (III) ") represented by following logical formula (III)s is formed The resin combination of polymers (below, being also suitably recited as " SMA resins ") (below, is also suitably recited as " resin combination (1)”)。

The methacrylic resin contained in resin combination (1) is to contain the structure list from methacrylate The resin of unit.

As the methacrylate, can enumerate：Methyl methacrylate, EMA, 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；As above-mentioned methacrylic acid The material that ester (I) is recorded is the cycloalkyl methacrylate of representative；The aryl methacrylates such as phenyl methacrylate；First The methacrylic acid aralkyl ester such as base benzyl acrylate；Deng, from 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 construction unit from methacrylate in methacrylic resin Preferably more than 90 mass %, more preferably more than 95 mass %, more preferably more than 98 mass %, can be only to contain From the construction unit of methacrylate.

In addition, from from the viewpoint of heat resistance, the methacrylic resin contained in resin combination (1) is preferably comprised The construction unit from MMA of more than 90 mass %, further preferably more than 95 mass %, further preferably 98 matter Amount more than %, can be only to contain the construction unit from MMA.

In addition, beyond the methacrylic resin contained in resin combination (1) can be containing methacrylate From the construction unit of other monomers.As the other monomers, methyl acrylate can be enumerated and (below, also suitably recorded Be " MA "), ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid The tert-butyl ester, Hexyl 2-propenoate, 2-EHA, acrylic acid nonyl ester, decyl acrylate, lauryl ester, propylene Sour stearyl ester, acrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl esters, acrylic acid 4- hydroxybutyls, cyclohexyl acrylate, propylene Sour 2- methoxy acrylates, acrylic acid 3- methoxybutyls, acrylic acid trifluoro methyl esters, acrylic acid trifluoro ethyl ester, the fluorine second of acrylic acid five Ester, glycidyl acrylate, allyl acrylate, phenyl acrylate, CA, benzyl acrylate, acrylic acid are different The acrylate such as norbornene ester, acrylic acid 3- dimethylamino ethyl esters, from 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 construction unit from above-mentioned other monomers in methacrylic resin Content total be preferably below 10 mass %, more preferably more preferably below 5 mass %, below 2 mass %.

The methacrylic resin contained in resin combination (1) is by using above-mentioned methacrylate and as appointing The other monomers of meaning composition are polymerized and are obtained.In the case of various of monomer being used in the polymerization, generally will be above-mentioned various Monomer mixes and prepares monomer mixture, then for polymerization.Polymerization is not particularly limited, and is examined from the viewpoint of productivity ratio Consider, radical polymerization is preferably carried out by methods such as mass polymerization, suspension polymerization, solution polymerization process, emulsion polymerizations.

The weight average molecular weight of the methacrylic resin contained in resin combination (1) (below, is also suitably recited as " Mw ") it is preferably 40000~500000.By making the Mw for more than 40000, resin plate of the invention turns into marresistance, resistance to Hot excellent resin plate, by making the Mw be less than 500000, the shaping processability of resin combination (1) is excellent, can improve The productivity ratio of resin plate of the invention.

Content on the SMA resins in the resin combination (1) that is used in the present invention, from reducing line expansion ratio (SR) Viewpoint and make glass transition temperature (Tg) from the viewpoint of more than 120 DEG C, to be preferably set to more than 20 mass %, more preferably It is 45 mass % less than the scope of 95 mass %, models of the more preferably 50 mass % less than 90 mass % Enclose.

Above-mentioned SMA resins are that at least origin comes from the construction unit of aromatic ethenyl compound (II) and from acid anhydrides (III) copolymer that construction unit is formed.

As the R in logical formula (II)¹And R²And the R in logical formula (III)³And R⁴The alkyl for representing independently of one another, preferably Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl, just oneself The alkyl of the carbon number below 12 such as base, n-heptyl, n-octyl, 2- ethylhexyls, nonyl, decyl, dodecyl, more preferably first Alkyl of the carbon numbers such as base, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group below 4.

As R¹, preferably hydrogen atom, methyl, ethyl and the tert-butyl group.As R²、R³、R⁴, preferably hydrogen atom, methyl and second Base.

The content of the construction unit from aromatic ethenyl compound (II) in above-mentioned SMA resins is preferably 50~ The scope of 85 mass %, more preferably 55~82 mass %, the more preferably scope of 60~80 mass %.The content is 50 During the scope of~85 mass %, composition of the resin combination (1) as moisture-proof and excellent transparency.

As aromatic ethenyl compound (II), can enumerate for example：Styrene；2-methyl styrene, 3- methylbenzenes The core alkyl-substituted styrenes such as ethene, 4- methyl styrenes, 4- ethyl styrenes, 4- t-butyl styrenes；AMS, The alpha-alkyl substituted phenylethylene such as 4- methyl-alpha-methyls, from from the viewpoint of availability, optimization styrene.These fragrance Race's vinyl compound (II) can be used alone one kind, it is also possible to be applied in combination various.

The content of the construction unit from acid anhydrides (III) in above-mentioned SMA resins is preferably the model of 15~50 mass % Enclose, more preferably the scope of 18~45 mass %, more preferably the scope of 20~40 mass %.By making the content be 15 The scope of~50 mass %, composition of the resin combination (1) as heat resistance and excellent transparency.

As acid anhydrides (III), such as maleic anhydride, citraconic anhydride, dimethyl maleic anhydride etc. can be enumerated, from availability From the viewpoint of, preferred maleic anhydride.These acid anhydrides (III) can be used alone one kind, it is also possible to be applied in combination various.

In above-mentioned SMA resins, in addition to aromatic ethenyl compound (II) and acid anhydrides (III), preferably also contain source In the construction unit of methacrylate monomers.The construction unit from methacrylate monomers in above-mentioned SMA resins Content be preferably the scope of 1~35 mass %, the more preferably scope of 3~30 mass %, more preferably 5~26 matter Measure the scope of %.By the scope for making the content be 1~35 mass %, make bendability, excellent transparency.

As methacrylate, can enumerate for example：MMA, EMA, 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 chlorocarbonates；Deng.In these methacrylates, preferred alkane The carbon number of base is 1~7 alkyl methacrylate, from the sight of the heat resistance, excellent transparency of resulting SMA resins Point consideration, particularly preferred MMA.In addition, methacrylate can be used alone one kind, it is also possible to be applied in combination various.

Above-mentioned SMA resins can have from aromatic ethenyl compound (II), acid anhydrides (III) and methacrylic acid The construction unit of the other monomers beyond 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 hexyls Ester, acrylic acid nonyl ester, decyl acrylate, lauryl ester, stearyl acrylate ester, acrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl esters, acrylic acid 4- hydroxybutyls, cyclohexyl acrylate, acrylic acid 2- methoxy acrylates, acrylic acid 3- methoxyl group fourths Ester, acrylic acid trifluoro methyl esters, acrylic acid trifluoro ethyl ester, the fluorine ethyl ester of acrylic acid five, glycidyl acrylate, acrylic acid allyl Ester, phenyl acrylate, CA, benzyl acrylate, isobornyl acrylate, acrylic acid 3- dimethylamino ethyl esters etc. Acrylate.These other monomers can be used alone one kind, it is also possible to be applied in combination various.It is in SMA resins, from upper The content for stating the construction unit of other monomers is preferably below 10 mass %, more preferably below 5 mass %, more preferably Below 2 mass %.

Above-mentioned SMA resins are by by above-mentioned aromatic ethenyl compound (II), acid anhydrides (III) and methacrylate And be polymerized and obtained as the other monomers of any condition.In the polymerization, the monomer that will generally use mixes and makes Standby monomer mixture, then for polymerization.Polymerization is not particularly limited, from from the viewpoint of productivity ratio, preferably by this The methods such as body polymerization, solution polymerization process carry out radical polymerization.

The Mw of above-mentioned SMA resins is preferably 40000~300000 scope.By making the Mw be more than 40000, the present invention Resin plate turn into marresistance, the resin plate of excellent impact resistance, by making the Mw for less than 300000, shaping processability is excellent It is good, the productivity ratio of resin plate of the invention can be improved.

Resin combination (1) is obtained by by above-mentioned methacrylic resin with SMA mixed with resin.The mixing can To use such as melt mixing methods, solution mixing method etc..It is mixed using such as single screw rod kneading machine or multiscrew in melt mixing methods The melting mixing machine 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 is set to be dissolved in toluene, tetrahydrochysene with SMA resins Mixed after in the organic solvents such as furans, MEK.

The resin of layer of the composition used in an embodiment of the invention containing methacrylic resin can be Do not damage and contain the other polymers beyond methacrylic resin and SMA resins in the range of effect of the present invention.As this Other polymers, can enumerate：The polyolefin such as polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether-ether-ketone, polyester, polysulfones, The thermoplastic resins such as polyphenylene oxide, polyimides, PEI, polyacetals；Phenolic resin, melmac, organosilicon tree The thermosetting resins such as fat, epoxy resin；Acrylic rubbers such as particle having multilayer structure, block copolymer etc..Above-mentioned other polymerizations Thing can be used alone one kind, it is also possible to be applied in combination various.

It is upper in the resin of layer of the composition used in an embodiment of the invention containing methacrylic resin The content for stating other polymers is preferably below 10 mass %, more preferably below 5 mass %, more preferably 2 mass % Below.

When containing other polymers and/or additive in methacrylic resin, can be by methacrylic Added when resin is polymerized, it is also possible to add after polymerisation.

When containing other polymers and/or additive in resin combination (1), can be by methacrylic resin And/or SMA resins are added when being polymerized, it is also possible to added when by methacrylic resin and SMA mixed with resin, may be used also Added again with after by methacrylic resin and SMA mixed with resin.

The resin of layer of the composition used in an embodiment of the invention containing methacrylic resin can be with root According to needing to contain various additives.As the additive, such as antioxidant, heat deterioration preventing agent, ultraviolet can be enumerated and inhaled Receive agent, light stabilizer, lubricant, releasing 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 not damage the model of effect of the present invention Interior appropriate setting is enclosed, preferably with respect to the mass parts of resin 100 for constituting the layer containing methacrylic resin, for example, antioxygen The content of agent is that 0.01~1 mass parts, the content of ultra-violet absorber are that 0.01~3 mass parts, the content of light stabilizer are 0.01~3 mass parts, the content of lubricant be 0.01~3 mass parts, the content of dyes/pigments be 0.01~3 mass parts.

The melt of the resin of layer of the composition used in an embodiment of the invention containing methacrylic resin Flow rate (below, being also suitably recited as " MFR ") is preferably the scope of 1~10g/10 minutes, more preferably 1.5~7g/ The scope of 10 minutes, more preferably 2~4g/10 minute.When MFR is the scope of 1~10g/10 minutes, melt-shaping is heated 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 determined under 230 DEG C of temperature, 3.8kg load with fusion index instrument.

[makrolon]

The makrolon used in layered product of the invention is preferably by by dihydric phenol and carbonate precursor carrying out copolymerization Obtain.

As above-mentioned dihydric phenol, double (4- hydroxy phenyls) propane (common name bisphenol-A) of 2,2-, double (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 double (3, 5- dimethyl -4- hydroxy phenyls) propane, double (4- hydroxy phenyls) sulfites, double (4- hydroxy phenyls) sulfones etc., wherein, preferably Bisphenol-A.These dihydric phenols can be used alone one kind, it is also possible to be applied in combination various.

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 one kind, it is also possible to combine Using various.

The manufacture method of above-mentioned makrolon is not particularly limited, and can enumerate for example：Make the aqueous solution of dihydric phenol and carbon Interfacial polymerization of the organic solvent solution of acid esters precursor in interfacial reaction；Make dihydric phenol and carbonate precursor high temperature, decompression, Ester-interchange method reacted under the conditions of solvent-free etc..

The Mw of above-mentioned makrolon is preferably 10000~100000 scope, more preferably 20000~70000 scope. By making the Mw be more than 10000, the impact resistance of layered product of the invention, excellent heat resistance, by making the Mw be 100000 Hereinafter, the shaping processability of makrolon is excellent, can improve the productivity ratio of layered product of the invention.

Above-mentioned makrolon can contain other polymers not damaging in the range of effect of the present invention.As this, other gather Compound, it is possible to use can contain with methacrylic resin, resin combination (1) and above-mentioned resin combination (1) its His polymer identical polymer.Above-mentioned other polymers can be used alone one kind, it is also possible to be applied in combination various.Poly- carbonic acid The content of the above-mentioned other polymers in ester is preferably below 15 mass %, more preferably below 10 mass %, further preferably It is below 5 mass %.

Above-mentioned makrolon can as needed contain various additives.As additive, it is possible to use with above-mentioned composition The additive identical additive that the resin of the layer containing methacrylic resin can contain.The content of these additives can Suitably set in the range of effect of the present invention with not damaging, preferably with respect to the mass parts of makrolon 100, antioxidant contains Measure for 0.01~1 mass parts, the content of ultra-violet absorber be 0.01~3 mass parts, the content of light stabilizer be 0.01~3 matter Amount part, the content of lubricant are that 0.01~3 mass parts, the content of dyes/pigments are 0.01~3 mass parts.

When containing other polymers and/or additive in above-mentioned makrolon, can be before by dihydric phenol and carbonic ester Body carries out addition during copolymerization, it is also possible to addition and melting mixing after the copolymerization is terminated.

The glass transition temperature (Tg) of above-mentioned makrolon is preferably 120~160 DEG C of scope, more preferably 135~ 155 DEG C of scope, more preferably 140~150 DEG C of scope.

The MFR of above-mentioned makrolon is preferably the scope of 1~30g/10 minutes, the model of more preferably 3~20g/10 minutes Enclose, the scope of more preferably 5~10g/10 minutes.When MFR is the scope of 1~30g/10 minutes, heating melt-shaping Have good stability.

It should be noted that the MFR of the makrolon in this specification be use fusion index instrument 300 DEG C of temperature, It is worth obtained from being determined under conditions of under 1.2kg load.

Above-mentioned makrolon can use commercially available product, it may be preferred to use and for example live to change Si Tailong makrolon Co., Ltd. " カリバー (registration mark) " and " SD Port リカ (registration mark) ", " ユ of Mitsubishi engineering Plastics Co., Ltd's manufacture of manufacture ーピロ Application/ノバレッ Network ス (registration mark) ", " タ Off ロ Application (registration mark) ", the Supreme Being of Idemitsu Kosen Co., Ltd.'s manufacture People is melted into " パ Application ライト (registration mark) " of Co., Ltd.'s manufacture etc..

[thickness of resin plate]

The thickness of the resin plate in an embodiment of the invention is preferably 0.1~2mm, more preferably 0.5~ 1.5mm.When excessively thin, there is rigidity becomes insufficient tendency.When blocked up, there is the lightweight that can hinder liquid crystal display device etc. Tendency.

The thickness of the layer containing methacrylic resin of the resin plate in an embodiment of the invention is preferably 20~200 μm.In the scope, marresistance is excellent with the balance of impact resistance.It is more preferably 25~150 μm, further excellent Elect 30~100 μm as.

The thickness of the layer containing makrolon is preferably 0.1~2mm, more preferably 0.5~1.5mm.When excessively thin, exist resistance to Impact becomes insufficient tendency.When blocked up, there is the light-weighted tendency that can hinder liquid crystal display device etc..

By in the resin plate that an embodiment of the invention is obtained, can at least one surface thereof set solidification Overlay film.By setting curing overlay film, 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, case hardness becomes insufficient, when blocked up, may be cracked due to the bending in manufacturing process.

In addition, the thickness of for example low reflectivity curing overlay film is preferably 80~200nm, more preferably 100~150nm.Cross It is thin or blocked up the low reflecting properties is become insufficient.

[manufacturing process]

Resin plate in an embodiment of the invention is manufactured by being coextruded.Makrolon and composition are contained into first The resin heating melting of the layer of base acrylic resin, first is contained to be laminated with least one side of the layer containing makrolon The state of the thermoplastic resinous laminate of the layer of base acrylic resin, from the discharge opening of the wide cut shape for being referred to as T-shaped mould head Extruded with molten condition, sheet is formed as using a pair of rolls clamping being made up of the first chill roll and the second chill roll.Then, After further thermoplastic resinous laminate is wound up on the second chill roll, it is wound up on the 3rd chill roll, thus carries out cold But.In addition, thermoplastic resinous laminate's (resin plate 16) is carried out further with more chill rolls after this sometimes cold But.

In Fig. 1, shown using by T-shaped mould first 11, first to the and of the 3rd chill roll 12~14 as an implementation method Deflect from the summary of the manufacture method of the resin plate of the co-extrusion device of the composition of roller 15.From T-shaped mould it is first 11 extrusion 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 cooled down using the 3rd chill roll 14, is deflected from using the roller 15 that deflects from being made up of a pair of rolls.The 3rd chill roll with draw Roller can be set in addition between roller.It should be noted that the invention is not restricted to which.

As the mode of T-shaped mould head now, using the methacrylic resin that will heat molten condition and can gather Carbonic ester is flowing into the supply head mode of T-shaped mould head front laminate, by methacrylic resin and makrolon in T-shaped mould head Branch manifold mode of portion's stacking etc..It is preferably many from from the viewpoint of the flatness at interface for improving each interlayer for constituting resin plate Manifold mode.

In addition, as polishing roll now, metallic roll can be enumerated, possess the resilient roller of metal made membrane in peripheral part (below, 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 minute surface, or decorative pattern Or concavo-convex etc..Beaming roller, the periphery to cover the beaming roller that metallic elastic roller is for example rotatably set by generally a cylindrical shape ground Columnar metal made membrane and be enclosed in above-mentioned beaming roller and metal that the mode in face is configured and contacted with flaked thermoplastic's resin Fluid between made membrane is constituted, and 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 up of stainless steel etc., and its thickness is preferably from about 2mm~about 5mm.Metal made membrane is preferred With bendability, pliability etc., the preferably jointless structure without welding seam part.Possesses the metallic elastic of such metal made membrane Roller turns into excellent durability and the treatment same with common mirror roller, right can be carried out during to metal made membrane mirror-polishing Metal made membrane assign decorative pattern or it is concavo-convex when can transfer the roller of its shape, it is therefore easy to use.

The resin and makrolon of the layer containing methacrylic resin are constituted preferably before multilevel shaping and/or multilayer During shaping melt filteration is carried out using filter.Multilevel shaping is carried out by using each resin combination after melt filteration, can The resin plate few to obtain the defect that causes by foreign matter, gel.The filter material of the filter for being used is not particularly limited, according to making Suitably selected with temperature, viscosity, filtering accuracy, for example, can used comprising polypropylene, cotton, polyester, artificial silk, glass fibre Deng non-woven fabrics；It is impregnated with the tablet of the cellulose of phenolic resin；Metallic fiber nonwoven fabric sintered sheet thing；Metal dust Sintered sheet thing；Wire netting；Or combinations thereof.Wherein, it is preferably that metal is fine from from the viewpoint of heat resistance and durability Multiple stackings of non-woven fabrics sintered sheet thing are tieed up to use.

The filtering accuracy of above-mentioned filter is not particularly limited, preferably less than 30 μm, more preferably less than 10 μm, enters one Step is preferably less than 5 μm.

The temperature of the resin entirety that the resin plate of an embodiment of the invention will preferably be peeled off from the 3rd chill roll 14 It is set as the glass transition temperature (Tg) relative to makrolon from 0 DEG C to+15 DEG C of scope.The reason for this is that from the 3rd When the temperature of the resin entirety that chill roll 14 is peeled off is less than glass transition temperature (Tg) of makrolon, resin plate is cold by the 3rd But the shape transfer of roller, warpage increase.On the other hand, the temperature ratio of the resin entirety peeled off from the 3rd chill roll 14 is cold with the 3rd But when the glass transition temperature (Tg) of the resin bed of roller contact is high too many, resin plate cannot obtain the superficiality of beauty.Need Illustrate, the overall temperature of resin is unrelated with any one face of resin plate, to being laminated with polycarbonate resin and methyl-prop The overall temperature of the resin plate of olefin(e) acid resinoid is measured to use.

The preferred line expansion ratio (SR) of resin plate of an embodiment of the invention is -10%~+5% scope, is contained The glass transition temperature (Tg) of the resin bed of methacrylic resin is 120~160 DEG C.Its reason is as described below.

The resin plate stripped down from the 3rd chill roll 14 is sandwiched respectively in a period of being clamped into before deflecting from roller 15 3rd chill roll 14 and roller 15 is deflected from, therefore form the shape of general planar.The tree for just being stripped down from the 3rd chill roll 14 The temperature of fat plate is that, relative to the glass transition temperature of makrolon (Tg) from 0 DEG C to+15 DEG C of scope, but it is attached to deflect from roller 15 The temperature of near resin plate is cooled to room temperature, therefore approximately reaches normal temperature.

For example, the temperature of the resin plate stripped down from the 3rd chill roll 14 is 150 DEG C, resin plate near roller is deflected from Temperature is 25 DEG C.The linear expansion coefficient (S1) of the layer containing makrolon expands with the line of the layer containing methacrylic resin When coefficient (S2) has differences, specifically, when (S1-S2)/S1 is not zero, is shunk in the big side of linear expansion coefficient and produced 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 the 3rd chill roll 14 Temperature be 150 DEG C, therefore, the layer containing makrolon is cooled to normal temperature from 150 DEG C of glass transition temperature (Tg).Cause This, in the layer containing makrolon, 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, even if in the linear expansion coefficient of the layer containing makrolon (S1) when the linear expansion coefficient (S2) with the resin for constituting the layer containing methacrylic resin does not have difference, methyl is being contained In the layer of acrylic resin, the big contraction more than linear expansion coefficient can be also produced.

Here, general resin is elastomer below glass transition temperature, but more than glass transition temperature temporarily And as the viscoelastic body of the function of having viscosity and elasticity concurrently.

Above-mentioned elastomer is deformed when stress is applied, when discharging, eliminating deformation, on the other hand, viscoelastic Gonosome forms residual deformation when glass transition temperature is cooled in the state of being applied with stress.From the 3rd chill roll 14 The temperature of the resin plate for stripping down is such as 150 DEG C, the layer containing methacrylic resin and the layer containing makrolon During for above-mentioned glass transition temperature, after just being stripped down from the 3rd chill roll 14, Polycarbonate Layer is bullet to resin plate Gonosome, on the other hand, the layer containing methacrylic resin is viscoelastic body.That is, by resin plate just from the 3rd chill roll 14 After stripping down, only contraction distortion is produced in the layer containing methacrylic resin as viscoelastic body.In other words, make For the Polycarbonate Layer of elastomer is reversible for stress, therefore, even if there is the load of stress, releasing, will not also produce Deformation.On the other hand, produced due to load, the releasing of stress as the layer containing methacrylic resin of viscoelastic body Residual deformation.

For the foregoing reasons, the linear expansion coefficient (S1) of the layer containing makrolon with contain 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 produce because of elasticity The warpage that contraction difference in body causes, therefore, produce warpage at the moment for deflecting from the release resin plate of roller 15.It should be noted that So far, for the purpose of simplifying the description, it is sometimes denoted as the difference of line expansion.In the case where simple size is illustrated, it is poor to use , it is necessary to be discussed with line expansion ratio (SR) when fully representing, but wanting to represent quantitative amount of warpage.

In addition, the layer containing methacrylic resin glass transition temperature (Tg) less than containing makrolon The glass transition temperature (Tg) and the temperature of the resin plate stripped down from the 3rd chill roll 14 of layer are 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 makrolon, 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：By be exposed to high temperature and it is hot and humid under the conditions of and discharge deformation, so as to produce warpage.Here, just The temperature of the resin plate stripped down from the 3rd chill roll 14 relative to makrolon glass transition temperature (Tg) for 0 DEG C extremely + 15 DEG C, therefore, makrolon there is also the state of viscoelastic body.Here, the temperature of resin plate quilt before arrival deflects from roller 15 Normal temperature is cooled to, but the layer containing methacrylic resin and the layer containing makrolon are all cooled to normal temperature simultaneously.Cause This, just from the 3rd chill roll 14 is stripped down to reaching glass of the temperature comprising makrolon that deflects from resin plate before roller 15 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 makrolon During temperature (Tg), in the layer residual deformation containing methacrylic resin.

On the other hand, in principle, when the temperature of the resin plate stripped down from the 3rd chill roll 14 is less than 150 DEG C, line The tendency that warpage and residual stress caused by expansion ratio (SR) are reduced, therefore, warpage diminishes.But, as noted previously, as The warpage increase that resin plate produces the shape transfer of the 3rd chill roll 14, from without preferred.

It follows that the purpose in order to reach the application, the temperature of the resin peeled off from the 3rd chill roll 14 is set as Relative to makrolon glass transition temperature (Tg) from 0 DEG C to+15 DEG C of scope, line expansion ratio (SR) is set as- 10%~+5% scope, 120~160 are set as by the glass transition temperature (Tg) of the layer containing methacrylic resin DEG C, thus, it is possible to obtain the small good resin plate of warpage.

Embodiment

Hereinafter, embodiment is shown, the present invention is illustrated in more detail.But, the present invention does not receive the embodiment Any restriction.

The physical property of resin plate is determined by the following method.

[glass transition temperature (Tg)]

By resulting resin plate, (1kPa) after 80 DEG C of dryings 24 hours, cuts the test film of 10mg under reduced pressure, profit Sealed with aluminium dish, using differential scanning calorimeter (" DSC-50 ", Co., Ltd. Neo-Confucianism's manufacture), carry out the nitrogen of more than 30 minutes Displacement.Then, in the stream of nitrogen gas of 10ml/ minutes, 200 DEG C are first warming up to from 25 DEG C with 20 DEG C/min of speed, keep 10 Minute, it is cooled to 25 DEG C (single passes).Then, it is warming up to 200 DEG C (rescans) with 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 per unit temperature change.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 put to be measured according to JIS K7197. That is, in order to the resin plate that sheet obtained from press molding is carried out to the resin of each measure is formed into smooth end face, gold is used Hard rock is sawed, be processed into the length on one side for 5mm × 5mm, be highly the prism-shaped of 10mm, by processing after each sample so that 5mm The mode that the surface of × 5mm contacts with quartz plate is placed on the plate of quartz, and the rod of cylindrical shape is placed thereon, applies the pressure of 5g Contracting load and fix.Then, in air atmosphere, each sample is warming up to from 25 DEG C (room temperatures) with 3 DEG C/min of programming rate Minus 10 DEG C of glass transition temperature (Tg), are cooled to 25 DEG C (room temperature) (single passes).Then, with 3 DEG C/min of intensification 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).During to rescan Each temperature in the coefficient of expansion be measured, obtain the average coefficient of linear expansion 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 on side long is cut into rectangle, makes short side 65mm, the test film of side 110mm long.By what is made Test film to make the layer containing methacrylic resin be placed on platform in the way of upward, in 23 DEG C of temperature, relative humidity Placed 24 hours in 50% environment.Then, using feeler gauge, the maximum in the gap of determination test piece and platform, by the value As initial stage amount of warpage.Then, in 85 DEG C of temperature, the environment chambers of relative humidity 85% are set as, by above-mentioned test film To make the layer containing methacrylic resin be placed into glass platform in the way of upward, place 72 hours in this condition Afterwards, placed 4 hours under 25 DEG C of environment.Then, it is measured as described above, using the value as the warpage after hot and humid Amount.By test film to make the layer containing methacrylic resin be placed on platform in the way of upward, by warpage convex downwards Symbol be set to just, the symbol of convex warpage is set to bear.By amount of warpage for ± below 0.5mm be set as it is qualified.

[superficiality]

In the interior for being provided with fluorescent lamp, the two sides to resin plate visually observes, according to following benchmark to superficiality Evaluated.

○：The line that quivers is not observed in resin board surface.

△：It is in resin board surface it was observed that the line that quivers but unobvious.

×：In resin board surface, the line that quivers is obvious.

[resin temperature]

At the position peeled off from the 3rd chill roll 14, the temperature of the entirety of resin plate 16 is determined using infrared emission thermometer Degree.Such temperature for determining is referred to as resin temperature (TT).

[methacrylic resin A]

" パラペット (registration mark) HR " of preparation Kuraray Co., Ltd. manufacture is (under 230 DEG C of temperature, 3.8kg load MFR=2.4g/10 minutes) as methacrylic resin A.

[methacrylic resin B]

It is ready to pass through methyl methacrylate and the ring [5.2.1.0 of methacrylic acid 8- tri-^2,6] radical polymerization of last of the ten Heavenly stems ester obtains The copolymer for arriving is used as methacrylic resin B.

It should be noted that by the ring [5.2.1.0 of methacrylic acid 8- tri-^2,6] last of the ten Heavenly stems ester is in methyl methacrylate and methyl Ring [the 5.2.1.0 of acrylic acid 8- tri-^2,6] last of the ten Heavenly stems ester total amount in the shared ratio that feeds intake (quality percentage) be referred to as TC ratios.

[methacrylic resin C]

Prepare from central side by the mass % (ground floors of hard layer 35：The mass parts of MMA units 94, methyl acrylate units 6 Mass parts, the mass parts of allyl methacrylate unit 0.2), soft layer 45 mass % (second layer, rubber layer：Butyl acrylate The mass parts of unit 82.2, the mass parts of styrene units 17.8, the mass parts of allyl methacrylate unit 2) and the matter of hard layer 20 Amount % (third layer：The mass parts of MMA units 94, the mass parts of methyl acrylate units 6, the mass parts of n octylmercaptan unit 0.2) structure Into, acrylic compounds three-decker rubber particles that average grain diameter is 0.23 μm.

Prepare the methacrylic resin B of the mass % of TC ratios 35 of 91.5 mass % is above-mentioned with 8.5 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 resins are used.

On methacrylic resin, prepare " パラペット (registration mark) of above-mentioned Kuraray Co., Ltd.'s manufacture HR " (identical with methacrylic resin A) is used as methacrylic resin.

SMA resins can be obtained by following method.

For example, by the method described in WO2010/013557, can obtain common as phenylethylene-maleic anhydride-MMA The SMA resins of polymers.

The quality ratio of components and weight average molecular weight (Mw) of the SMA resins that will be used are shown in Table 1.

[table 1]

The copolymerization composition of SMA resins is obtained according to following steps by 13C-NMR methods.

13C-NMR spectrums use nuclear magnetic resonance device (NEC company manufactures, GX-270).Dissolve SMA resins 1.5g In deuterochloroform 1.5ml, sample solution is prepared, under room temperature environment, under conditions of being 4000~5000 times in cumulative number It is measured.Following value is obtained by measurement result.

[integration at the carbon peak (127,134,143ppm near) of the phenyl ring (carbon number 6) in styrene units is strong Degree]/6

[integrated intensity at the carbon peak (near 170ppm) at the carbonyl position (carbon number 2) in maleic anhydride units]/2

[integrated intensity at the carbon peak (near 175ppm) at the carbonyl position (carbon number 1) in MMA units]/1

By more than value area than obtain the styrene units in sample, maleic anhydride units, MMA units mole Than.By resulting mol ratio and the mass ratio (styrene units of each monomeric unit:Maleic anhydride units:MMA=104: 98:100) the quality composition of each monomer in SMA resins is obtained.

The Mw of SMA resins is obtained according to following steps by GPC method.

As eluent, using tetrahydrofuran, as post, the TSKgel for manufacturing TOSOH Co., Ltd is used Two posts being connected in series with SuperHZ4000 of SuperMultipore HZM-M.As GPC devices, using with difference Show the HLC-8320 (model) of TOSOH Co., Ltd's manufacture of RI-detector (RI detectors).It is dissolved in SMA resins 4mg In tetrahydrofuran 5ml, sample solution is prepared.The temperature of column oven is set as 40 DEG C, with the wash-out flow quantity of 0.35ml/ minutes The injection μ l of sample solution 20, determine chromatogram.Standard polyphenyl of the molecular weight in the range of 400~5000000 is determined using GPC 10 points of ethene, makes the standard curve for representing retention time and the relation of molecular weight.Mw is determined based on the standard curve.

SMA resins in resin combination (1) is shared in the total amount of methacrylic resin A and SMA resins The ratio that feeds intake (quality percentage) be referred to as SMA ratios.

[makrolon]

Prepare firmly to change " SD Port リカ (registration mark) PCX " that Si Tailong makrolon Co., Ltd. makes (300 DEG C of temperature, MFR=6.7g/10 minutes under 1.2kg load, glass transition temperature (Tg)=150 DEG C, linear expansion coefficient=6.93 × 10^-5/ K) as makrolon.

[embodiment 1]

(manufacture method of resin plate)

By the methacrylic resin B (glass transition temperatures of the mass % of TC ratios 20：120 degree, linear expansion coefficient： 7.30×10^-5/ K) using 150mm φ single screw extrusion machines [Toshiba Machinery Co., Ltd.'s system] meltings, makrolon is utilized 150mm φ single screw extrusion machines [Toshiba Machinery Co., Ltd.'s system] are melted, and both are laminated via branch manifold pattern tool.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 Between the second chill roll 13, after being wound up on the second chill roll 13, it is wound up on the 3rd 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) is by controlling the second chill roll 13 and the The temperature of three chill rolls 14 and adjust to 150 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[embodiment 2]

As described above using the methacrylic resin B and makrolon of the mass % of TC ratios 35, resin is manufactured Plate.Resin temperature (TT) is adjusted to 150 DEG C as described above.The evaluation result of manufacturing condition and resulting resin plate is shown In table 2.

[embodiment 3]

The methacrylic resin B and makrolon of the mass % of TC ratios 45 are manufactured as described above.Resin temperature (TT) adjust as described above to 155 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[embodiment 4]

The methacrylic resin B and makrolon of the mass % of TC ratios 60 are manufactured as described above.Resin temperature (TT) adjust as described above to 155 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[embodiment 5]

The resin combination (1) and makrolon of the mass % of SMA ratios 20 are manufactured as described above.Resin temperature (TT) Adjust as described above to 150 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[embodiment 6]

The resin combination (1) and makrolon of the mass % of SMA ratios 50 are manufactured as described above.Resin temperature (TT) Adjust as described above to 150 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[embodiment 7]

The resin combination (1) and makrolon of the mass % of SMA ratios 70 are manufactured as described above.Resin temperature (TT) Adjust as described above to 155 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[embodiment 8]

The resin combination (1) and makrolon of the mass % of SMA ratios 100 are manufactured as described above.Resin temperature (TT) adjust as described above to 155 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[embodiment 9]

The resin combination (1) and makrolon of the mass % of SMA ratios 70 are manufactured as described above.Resin temperature (TT) Adjust as described above to 165 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[comparative example 1]

Methacrylic resin A and makrolon are manufactured as described above.Resin temperature (TT) is as described above Adjust to 150 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[comparative example 2]

The resin combination (1) and makrolon of the mass % of SMA ratios 70 are manufactured as described above.Resin temperature (TT) Adjust as described above to 145 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[comparative example 3]

The resin combination (1) and makrolon of the mass % of SMA ratios 70 are manufactured as described above.Resin temperature (TT) Adjust as described above to 170 DEG C.The evaluation result of manufacturing condition and resulting resin plate is shown in Table 2.

[comparative example 4]

In addition to the methacrylic resin B of the mass % of TC ratios 35 is changed into methacrylic resin C, with Embodiment 2 similarly manufactures resin plate.Resin temperature (TT) is adjusted to 150 DEG C as described above.By manufacturing condition and gained To the evaluation result of resin plate be shown in Table 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 embodiment 1~4, manufacture is laminated with the layer of the methacrylic resin B containing the mass % of TC ratios 20~60 Tested with the resin plate of the layer containing makrolon.As shown in table 2, TC ratios 45% are being contained using embodiment 3 Methacrylic resin B layer in the case of, 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 the mass % of SMA ratios 20~100 layer and The resin plate of the layer containing makrolon is tested.As shown in table 2, the matter of SMA ratios 70 is being contained using embodiment 7,9 In the case of the layer of the resin combination (1) for measuring %, 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, it is hot and humid after warpage it is big.In comparative example 2, Reduce resin temperature (TT), as a result, as the big resin plate of amount of warpage.In comparative example 3, resin temperature (TT) is improve, tied Really, as 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 warpage after hot and humid.

Industrial applicability

Resin plate of the invention can be used in the protective cover of such as liquid crystal display protection board, contact panel, be suitable for car Carry with display device, portable phone, smart mobile phone, PC, television set etc..

It should be noted that the invention is not restricted to above-mentioned implementation method, fitted in the range of purport that can not departed from Work as change.

This application claims preferential based on the Japanese publication Patent 2014-190029 of proposition on the 18th of September in 2014 Power, its entire disclosure is incorporated in this specification.

Symbol description

11 T-shaped mould heads

12 first chill rolls

13 second chill rolls

14 the 3rd chill rolls

15 deflect from roller

16 resin plates

Claims

1. a kind of manufacture method of extruded resin sheet, it is to be laminated with to contain first at least one side of the layer containing makrolon The manufacture 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 makrolon 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 makrolon ((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 manufacture method includes following operation：

The layer containing methacrylic resin will be laminated with least one side of the layer containing makrolon Thermoplastic resinous laminate is extruded with molten condition from T-shaped mould head,

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 the 3rd chill roll come Cooled down,

Thermoplastic resinous laminate utilization is deflected from into roller to deflect from；

In the thermoplastic resinous laminate from the position that the 3rd chill roll is peeled off, the overall temperature of resin is set as Relative to the layer containing makrolon glass transition temperature from 0 DEG C to+15 DEG C of scope.

2. a kind of extruded resin sheet, it includes the extruded resin sheet obtained by the manufacture method described in claim 1,

Structure from methyl methacrylate of the layer containing methacrylic resin containing 40~80 mass % Unit, and the construction unit from the methacrylate represented by following logical formula (I)s containing 20~60 mass %,

In formula, Cy represents alicyclic type hydrocarbon.

3. extruded resin sheet as claimed in claim 2, wherein, the Cy led in formula (I) is multicyclic aliphatic alkyl.

4. a kind of extruded resin sheet, it includes the extruded resin sheet obtained by the manufacture method described in claim 1,

The layer containing methacrylic resin contains the methacrylic resin and 20 matter less than 80 mass % At least origin of amount more than % comes from construction unit and the source of the aromatic ethenyl compound represented by following logical formula (II)s In the copolymer that the construction unit of the acid anhydrides represented by following logical formula (III)s is formed,

In formula, R¹And R²Hydrogen atom or alkyl are represented independently of one another,

In formula, R³And R⁴Hydrogen atom or alkyl are represented independently of one another.

5. extruded resin sheet as claimed in claim 4, it is characterised in that the copolymer contains the source of 50~84 mass % In the construction unit of the aromatic ethenyl compound, the structure list from the acid anhydrides containing 15~49 mass % Unit, and contain the methacrylate monomers of 1~25 mass %.

6. extruded resin sheet as claimed in claim 5, it is characterised in that the methacrylate monomers are methacrylic acid Methyl esters.

7. the extruded resin sheet as any one of claim 2~6, wherein, it is further equipped with least one surface Marresistance layer.