CN104703796A - Laminate - Google Patents
Laminate Download PDFInfo
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- CN104703796A CN104703796A CN201380053406.XA CN201380053406A CN104703796A CN 104703796 A CN104703796 A CN 104703796A CN 201380053406 A CN201380053406 A CN 201380053406A CN 104703796 A CN104703796 A CN 104703796A
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- Prior art keywords
- resin
- duplexer
- resin bed
- thermoplastic resin
- laminated
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Abstract
The present invention is a laminate comprising a resin layer (A) obtained from a thermoplastic resin layer (A) and a resin layer (B) laminated on at least one side thereof and obtained from a different thermoplastic resin, wherein: (i) the thickness of the resin layer (B) is 40 - 150 [mu]m, and the total thickness of the resin layer (A) and the resin layer (B) is 0.8 mm - 3.0 mm, (ii) the respective glass transition points TgA and TgB of the thermoplastic resin (A) and thermoplastic resin (B) are both 115 DEG C or more and the difference between TgA and TgB is 30 DEG C or less, (iii) the water absorption rates of the thermoplastic resin (A) and the thermoplastic resin (B) are both 0.7% or less and the difference in water absorption rates is 0.5% or less, and (iv) the warping rate after the resin laminate is left for 120 hours in a high temperature, high humidity environment of 85 DEG C temperature and 85% RH humidity is 0.2% or less.
Description
Technical field
The present invention relates to that pencil hardness is high, the duplexer of excellent heat resistance, not easily buckling deformation.
Background technology
The transparency of polycarbonate resin plate, heat resistance, resistance to impact, mechanical strength, for the display, touch panel front panel etc. of OA electronic equipment.But polycarbonate resin has following shortcoming: because pencil hardness is low, so resin surface easily scratches, because weatherability is low so easily cause variable color when outdoor application.As the method improving these problems, propose at the layer be made up of polycarbonate resin (following, referred to as PC layer) go up the stacked layer (following, sometimes referred to as PMMA layer) be made up of the methacrylic resin of weatherability, pencil hardness excellence or the layer be made up of the polycarbonate resin of modification.
But, PMMA layer have lack heat resistance, water imbibition high, there is the warpage of duplexer itself because humidity change or under hot and humid environment, cause the shortcoming of buckling deformation.Significant deficiency is become in the electronic equipment associated uses such as touch panel front panel, lcd cover of this shortcoming under environment for use is high temperature, under high humidity.Therefore, the trial of the buckling deformation of the duplexer produced under having carried out suppressing environment for use.
For example, Patent Document 1 discloses on PC layer the stacked PMMA layer that has excellent weather resistance and the duplexer obtained.According to patent document 1, describe this duplexer not easily because water suction causes warpage, weatherability is also excellent.But in patent document 1, do not study the suppression of the buckling deformation of duplexer under hot and humid environment.
Patent Document 2 discloses by when sheet is shaping in advance with the duplexer that certain radius of curvature makes bending tablet suppress the warpage under hot and humid environment to change.But, the principal component of the thermoplastic resin used in duplexer is methyl methacrylate, under long-term hot and humid environment (temperature 85 DEG C, the humidity condition of 85%, 120 hours), in heat resistance, water imbibition etc., the suppression of buckling deformation is insufficient.
Describe in patent document 3 and the warpage after being heated to 80 DEG C can be suppressed to change more than making the peripheral speed of the 2nd chill roll and the ratio of the peripheral speed of the 3rd chill roll be certain when duplexer is shaping with 3 rollers.But for the duplexer recorded in patent document 3, under long-term hot and humid environment (temperature 85 DEG C, the humidity condition of 85%, 120 hours), in heat resistance, water imbibition etc., the suppression of buckling deformation is insufficient.
In addition, Patent Document 4 discloses the modified polycarbonate resin layer of stacked heat resistance, pencil hardness excellence on PC layer and the duplexer obtained.But, in patent document 4, do not study the suppression of the buckling deformation of duplexer under hot and humid environment.
, there is the problem causing because of the buckling deformation of the front panel under hot and humid environment peeling off in the display screen cover of smart mobile phone etc., touch panel front panel.
Patent document 1: JP 2006-205478 publication
Patent document 2: JP 2012-051311 publication
Patent document 3: JP 2012-096357 publication
Patent document 4: JP 2010-188719 publication
Summary of the invention
The object of the present invention is to provide a kind of pencil hardness, marresistance, heat resistance, low water absorbable excellent, the little and duplexer that buckling deformation under long-term hot and humid environment is few of the buckling deformation under ambient temperature and moisture environment.When the object of the present invention is to provide a kind of display screen cover for smart mobile phone etc., touch panel front panel in addition, the duplexer that the stripping caused by buckling deformation is few.
The present inventor etc. find the duplexer comprising resin bed (A) and the resin bed (B) be made up of 2 kinds of different thermoplastic resins with specific glass transition temperature and water absorption rate to melt extrude, when cooling with 3 chill rolls, by the peripheral speed of the carry-over pinch rolls relative to the 2nd roller peripheral speed is set as specific scope, the warpage rate of placing after 120 hours under the hot and humid environment of temperature 85 DEG C, humidity 85%RH can be made to be less than 0.2%, thus to complete the present invention.Visible, the present invention is based on following discovery: by carrying out micro-stretching to the duplexer be made up of specific 2 kinds of thermoplastic resins, be reduced in the warpage rate under hot and humid environment.
Namely the present invention is the duplexer comprising the resin bed (A) be made up of thermoplastic resin (A) and the resin bed (B) be made up of thermoplastic resin (B) being laminated in its at least one face,
I the thickness of () resin bed (B) is 40 ~ 150 μm, the aggregate thickness of resin bed (A) and resin bed (B) is 0.8mm ~ 3.0mm,
(ii) thermoplastic resin (A) and the respective glass transition temperature Tg A of thermoplastic resin (B) and TgB are more than 115 DEG C, and the difference of TgA and TgB is less than 30 DEG C,
(iii) water absorption rate of thermoplastic resin (A) and thermoplastic resin (B) is less than 0.7%, and water suction rate variance is less than 0.5%,
(iv) be less than 0.2% by this duplexer warpage rate of placing after 120 hours under the hot and humid environment of temperature 85 DEG C, humidity 85%RH.
In addition, the present invention is the manufacture method of above-mentioned duplexer, comprises following operation: the duplexer of the resin bed (B) comprising resin bed (A) and be laminated in its at least one face is extruded from die head with molten condition by (i),
(ii) duplexer utilizing carry-over pinch rolls to draw to be extruded while utilize the 1st ~ 3rd chill roll to cool,
Here, for the 1st ~ 3rd chill roll, rotary middle spindle is parallel, at grade, and closely configures, and makes the peripheral speed of carry-over pinch rolls be 0.996 ~ 1.010 times relative to the 2nd roller peripheral speed, carries out as follows:
A the duplexer extruded from die head is clipped between the 1st chill roll and the 2nd chill roll by (),
B () is wound in the 2nd chill roll,
C () is wound in the 3rd chill roll.
Accompanying drawing explanation
Fig. 1 is the figure representing the device used in embodiment.
Detailed description of the invention
Below, the present invention is described in detail.
< resin bed (A) >
Resin bed (A) is made up of thermoplastic resin (A).The glass transition temperature Tg A of thermoplastic resin (A) is more than 115 DEG C, and water absorption rate is less than 0.7%.Glass transition temperature Tg A is preferably 115 ~ 180 DEG C, is more preferably 130 ~ 160 DEG C, more preferably 140 ~ 150 DEG C.Glass transition temperature of the present invention uses differential scanning calorimetric analysis device (DSC), with what obtain according to the programming rate 20 DEG C/min mensuration of JIS K7121.In addition, water absorption rate is preferably less than 0.5%, is more preferably less than 0.4%.
As thermoplastic resin (A), be preferably principal component with polycarbonate resin.The content of the polycarbonate resin in thermoplastic resin (A) is preferably more than 50 % by weight, be more preferably more than 70 % by weight, more preferably more than 80 % by weight, be particularly preferably more than 90 % by weight, most preferably be and be made up of polycarbonate resin in fact.
Polycarbonate resin utilizes the such as known method such as interface polycondensation, melt transesterification process that dihydric phenol and carbonate precursor are reacted and the aromatic polycarbonate resin of manufacture.
As the representative example of dihydric phenol, can 2 be enumerated, two (4-hydroxy phenyl) propane (common name bisphenol-A), 1 of 2-, two (4-hydroxy phenyl) ethane, 1 of 1-, 1-bis(4-hydroxyphenyl)cyclohexane, 2,2-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane, 2,2-two (4-hydroxyl-3,5-dibromo phenyl) propane, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfones etc.Preferred dihydric phenol is two (4-hydroxy phenyl) alkanes, particularly preferably bisphenol-As.
As carbonate precursor, carboxylic acid halides, carbonic ester, haloformate etc. can be enumerated, specifically, two haloformates etc. of phosgene, diphenyl carbonate, dihydric phenol can be enumerated.
When manufacturing polycarbonate resin, above-mentioned dihydric phenol can be used alone or two kinds more than also use, in addition, molecular weight regulator, branching agent, catalyst etc. can be used as required.
The viscosity average molecular weigh of the polycarbonate resin used in resin bed (A) is preferably 1.0 × 10
4~ 10.0 × 10
4, be more preferably 1.5 × 10
4~ 4.5 × 10
4, more preferably 1.8 × 10
4~ 3.0 × 10
4.Viscosity average molecular weigh is the specific viscosity (η will obtained by the solution at 20 DEG C of dissolved polycarbonate resin 0.7g in 100ml carrene
sp) bring the value obtained in following formula into.
η
sp/ c=[η]+0.45 × [η]
2c (wherein, [η] is inherent viscosity)
[η]＝1.23×10
-4M
0.83
c＝0.7
In addition, additive can be coordinated as required, releasing agent (0.005 ~ 2.0 % by weight), the fire retardant such as low-molecular polycarbonate, deca-BDE (3 ~ 15 % by weight) of tetrabromobisphenol A, tetrabromobisphenol A, colouring agent, the fluorescent whitening agents etc. such as the ester of the heat stabilizers such as such as phosphite ester, phosphate, phosphonate ester (0.001 ~ 0.2 % by weight), alcohol and aliphatic acid in polycarbonate resin.
The thickness of resin bed (A) is the scope of 0.65mm ~ 2.96mm.Be preferably the scope of 0.8mm ~ 2.5mm.
< resin bed (B) >
Resin bed (B) is made up of thermoplastic resin (B).The glass transition temperature Tg B of thermoplastic resin (B) is more than 115 DEG C, and water absorption rate is less than 0.7%.Glass transition temperature Tg B is preferably 115 ~ 150 DEG C, is more preferably 117 ~ 140 DEG C, more preferably 120 ~ 130 DEG C.In addition, water absorption rate is preferably less than 0.6%, is more preferably less than 0.5%.If TgB lower than when 115 DEG C or the water absorption rate of resin bed (B) more than 0.7%, then under the hot and humid environment of temperature 85 DEG C, humidity 85%RH, due to heat and moisture absorption cause duplexer easily warpage to occur.
In addition, the difference (TgA-TgB) of glass transition temperature Tg A and glass transition temperature Tg B is less than 30 DEG C.If the difference of TgA and TgB is more than 30 DEG C, then under the hot and humid environment of temperature 85 DEG C, humidity 85%RH, the contraction rate variance of the thermoplastic resin of resin bed (A) and the thermoplastic resin of resin bed (B) becomes greatly, and duplexer easily produces warpage.The difference of glass transition temperature Tg A and glass transition temperature Tg B is preferably less than 28 DEG C, is more preferably less than 25 DEG C.
Further, thermoplastic resin (A) is less than 0.5% with the difference (water absorption rate of the water absorption rate-thermoplastic resin (A) of thermoplastic resin (B)) of the water absorption rate of thermoplastic resin (B).If water suction rate variance more than 0.5%, then under the hot and humid environment of temperature 85 DEG C, humidity 85%RH because moisture expantion causes size to change, also easily there is warpage.The difference of the water absorption rate of thermoplastic resin (A) and thermoplastic resin (B) is preferably less than 0.4%, is more preferably less than 0.3%, and more preferably less than 0.2%, be particularly preferably less than 0.1%.
The pencil hardness of resin bed (B) measures according to JIS K5600-5-4.The pencil hardness of resin bed (B) is preferably more than F, is more preferably more than H, more preferably more than 2H.
The thickness of resin bed (B) is 40 ~ 150 μm, is preferably 50 ~ 120 μm, is more preferably 60 ~ 100 μm.The thickness of if tree lipid layer (B) is excessively thin, then can not get sufficient pencil hardness, if more than 150 μm, is then difficult to make the warpage rate under the hot and humid environment of temperature 85 DEG C, humidity 85%RH be less than 0.2%.
As thermoplastic resin (B), can enumerate unit [2] that the unit [1] that represents containing following formula and following formula represent, unit [1] ratio relative to whole unit be 50 ~ 100 % by mole, viscosity average molecular weigh is 1.0 × 10
4~ 8.0 × 10
4modified polycarbonate resin.
In unit [1], W represents the cycloalkylidene of the alkane 2 basis of singly-bound, carbon number 1 ~ 6, the arlydene of carbon number 6 ~ 10 or carbon number 3 ~ 8.
As the alkane 2 basis of carbon number 1 ~ 6, methylene, ethylidene, propane two base, propane-2,2-bis-base, butane two base etc. can be enumerated.As the arlydene of carbon number 6 ~ 10, phenylene, naphthalene two base, bis-phenol two base, toluene two base etc. can be enumerated.As the cycloalkylidene of carbon number 3 ~ 8, cyclopentylene, cyclohexylidene, sub-ring octyl group can be enumerated.
Unit [1] is preferably by being selected from two (the 4-hydroxy-3-methyl phenyl) cyclohexane of 1,1-, 2,2-two (4-hydroxy-3-methyl phenyl) propane and 2, the unit that at least one in 2 '-methyl-4,4 '-biphenyl glycol is derivative.It is particularly preferably the unit derived by two (the 4-hydroxy-3-methyl phenyl) cyclohexane of 1,1-or two (the 4-hydroxy-3-methyl phenyl) propane of 2,2-.
In addition, the ratio of the unit [1] in whole unit preferably more than 60 % by mole, more preferably more than 80 % by mole, preferably more than 90 % by mole further, particularly preferably in fact 100%.When the content of unit [1] is more than 50 % by mole, pencil hardness is high, and heat resistance is also good, therefore preferably.Should illustrate, as long as modified polycarbonate resin meets the ratio of said units [1], then can be copolymer also can be polyblend resin.
The manufacture method of modified polycarbonate resin can use following methods: utilize the known method such as interface polycondensation, melt transesterification process that dihydric phenol and carbonate precursor are reacted in the same manner as above-mentioned polycarbonate resin.The viscosity average molecular weigh of modified polycarbonate resin is preferably 1.1 × 10
4~ 6.0 × 10
4, be more preferably 1.3 × 10
4~ 4.5 × 10
4, more preferably 1.5 × 10
4~ 3.0 × 10
4.
In addition, as thermoplastic resin (B), can to enumerate containing aromatic series (methyl) acrylic ester unit of 5 ~ 80 % by weight and (methyl) methyl acrylate units of 20 ~ 95 % by weight and weight average molecular weight is acrylic copolymer 20 ~ 60 weight portion of 5000 ~ 30000 and the blending resin of polycarbonate resin 40 ~ 80 weight portion (wherein, acrylate copolymer and polycarbonate resin add up to 100 weight portions).The pencil hardness of above-mentioned blending resin is high, and heat resistance is also good, therefore preferably.
Acrylic copolymer, preferably containing 10 ~ 60 % by weight aromatic series (methyl) acrylic ester unit and 40 ~ 90 % by weight (methyl) methyl acrylate units, more preferably contains 20 ~ 50 % by weight aromatic series (methyl) acrylic ester unit and 50 ~ 80 % by weight (methyl) methyl acrylate units.In addition, the weight average molecular weight of acrylic copolymer preferably 8000 ~ 28000 scope, the more preferably scope of 10000 ~ 25000.
The mixture of blending resin preferred acrylic copolymer 25 ~ 55 weight portion and polycarbonate resin 45 ~ 75 weight portion, the more preferably mixture of acrylic copolymer 30 ~ 50 weight portion and polycarbonate resin 50 ~ 70 weight portion.Polyblend can be implemented by arbitrary method, suitably uses such as by the method for the mixing such as rotary drum mixer, V-Mixer, nauta mixer, mixing roller, extruder.
In addition, thermoplastic resin (B) is preferably containing ultra-violet absorber.By in the resin bed (B) on most top layer becoming duplexer containing ultra-violet absorber, absorb ultraviolet with resin bed (B), can suppress thus resin bed (A) because of the decomposition deterioration caused by luminous energy.Thus, even if when being subject to sunshine etc. and there is ultraviolet light-struck place use, the long-time stability of duplexer can be improved.The content of ultra-violet absorber relative to the scope of preferred 0.5 ~ 5.0 weight portion of thermoplastic resin (B) 100 weight portion, the more preferably scope of 1.0 ~ 4.0 weight portions.
As ultra-violet absorber, BTA system, benzophenone series, benzo can be enumerated
piperazine system, triazine system etc.
As BTA system ultra-violet absorber, can 2 be enumerated, 2 '-di-2-ethylhexylphosphine oxide [6-(BTA-2-base)-4-tert-octyl phenol], 2-[2-hydroxyl-3, two (the α of 5-, α-dimethylbenzyl) phenyl]-2H-BTA, 2-[2-hydroxyl-3, two (alpha, alpha-dimethylbenzyl) phenyl of 5-]-2H-BTA etc.
As triazine system ultra-violet absorber, 2,4-diphenyl-6-(2-hydroxyl-4-methoxyphenyl)-1,3 can be enumerated, 5-triazine, 2-[4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazines-2-base]-5-(octyloxy) phenol etc.
In addition, other additives can be added in thermoplastic resin (B).Such as antioxidant can use known antioxidant.The content of antioxidant relative to thermoplastic resin (B) 100 weight portion, the preferably scope of 0.001 ~ 0.2 weight portion.
As phenol system antioxidant, n-octadecane base-3-(3 can be enumerated, 5-bis--tert-butyl-hydroxy phenyl)-propionic ester, n-octadecane base-3-(3,5-bis--tert-butyl-hydroxy phenyl)-acetic acid esters, n-octadecane base-3,5-bis--tertiary butyl-4-hydroxy benzoic ether, n-hexyl-3,5-bis--tert-butyl-hydroxy phenyl benzoic ether, dodecyl-3,5-bis--tert-butyl-hydroxy phenyl benzoic ether, new dodecyl-3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester.
As phosphorous antioxidant, three (2,4-, bis--tert-butyl-phenyl) phosphite ester, 2-[[2,4,8,10-tetra-(1,1-dimethyl ethyl) dibenzo [d, f] [1,3,2] two can be enumerated
phospha English in heptan-6-base] oxygen base] two [2-[[2,4,8,10-tetra-(1,1 dimethyl ethyl) dibenzo [d, f] [1,3,2] two of-N, N-
phospha English in heptan-6-base] oxygen base]-ethyl] ethamine, diphenyl tridecyl phosphite.
< hard conating >
Duplexer of the present invention can at the upper stacked hard conating of resin (B).Hard conating, when not damaging the transparency, as long as have sufficient adaptation, is just not particularly limited material, adding method etc.As the formation method of hard conating, the method that coating utilizes the curable coating of the solidifications such as heat, ultraviolet, electron beam can be enumerated, physical vapor vapour deposition method, chemical vapor coating method etc.From the view point of in manufacture, the method for preferred coated UV line curable coating.
Ultraviolet-curable coating, as long as the composition containing uv curing resin and Photoepolymerizationinitiater initiater, is just not particularly limited.As uv curing resin, urethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate, glycidyl compound, fat cyclic epoxy compound, oxetane compound etc. can be enumerated.
As Photoepolymerizationinitiater initiater, 1-hydroxycyclohexylphenylketone, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-methyl isophthalic acid-((4-methyl mercapto) phenyl)-2-morpholino propane-1-ketone, benzophenone, 4-benzoyl-4 can be enumerated '-aminomethyl phenyl thioether, 2,4-diethyl thioxanthones etc.In addition, retarder thinner, defoamer, levelling agent, antistatic additive etc. can be added in the composition.
As the painting method using ultraviolet-curable coating to form hard conating, such as, can use any means such as micro-gravure coating process, spin-coating method, cast transfer printing, spraying rubbing method, flow coat method, dip coating, rolling method, stick coating method.From the view point of coating proterties, more preferably micro-gravure coating process, rolling method, stick coating method.In addition, identical method coating can be reinstated in two sides one when coated on both sides, also can apply with diverse ways respectively.The minimizing of warpage rate of hard conating to the duplexer being laminated with hard conating is formed with the almost identical thickness difference of the thickness (be 5 μm within) favourable on two sides.
The thickness of the hard conating preferably scope of 1 ~ 30 μm, the more preferably scope of 3 ~ 25 μm, the further preferred scope of 5 ~ 20 μm.If the Thickness Ratio of hard conating 1 μm is thin, then can not get sufficient marresistance, in addition, if thicker than 30 μm, then easily produce the crackle caused by stress, be not suitable for the purposes such as display screen cover, touch panel.
The pencil hardness of hard conating is preferably more than 3H, is more preferably more than 4H, more preferably more than 5H.The pencil hardness of hard conating measures according to JIS K5600-5-4.
< duplexer >
Duplexer of the present invention is laminated with resin bed (B) at least one face of resin bed (A).
The aggregate thickness of resin bed (A) and resin bed (B) is 0.8mm ~ 3.0mm.The aggregate thickness of resin bed (A) and resin bed (B) is preferably 0.9mm ~ 2.5mm, is more preferably 1.0 ~ 2.0mm.If the Thickness Ratio 3.0mm of duplexer is thick, then when being used as display cover, weight becomes heavy, and it is unfavorable that cost becomes, therefore not preferred.If be less than 0.8mm, then not enough as display cover rigidity, in addition, be difficult to warpage rate to be suppressed to less than 0.2% as duplexer.
Duplexer of the present invention is placed the warpage rate after 4 hours and is preferably less than 0.2% under temperature 23 DEG C, humidity 50%RH environment, is more preferably less than 0.15%.
In addition, it is less than 0.2% that duplexer of the present invention places the warpage rate after 120 hours under the hot and humid environment of temperature 85 DEG C, humidity 85%RH, is preferably less than 0.15%.
The duplexer warpage rate after 4 hours of placing under temperature 23 DEG C, humidity 50%RH environment being laminated with hard conating of the present invention is preferably less than 0.2%, is more preferably less than 0.15%.In addition, it is less than 0.2% that the duplexer being laminated with hard conating of the present invention places the warpage rate after 120 hours under the hot and humid environment of temperature 85 DEG C, humidity 85%RH, is preferably less than 0.15%.
The manufacture method > of < duplexer
Duplexer of the present invention can be manufactured by following operation: the duplexer of the resin bed (B) comprising resin bed (A) and be laminated in its at least one face is extruded from die head with molten condition by (i),
(ii) duplexer utilizing carry-over pinch rolls to draw to be extruded is while utilize the 1st ~ 3rd chill roll to cool.
(extruding operation (i))
It is the operation that the duplexer of resin bed (B) comprising resin bed (A) and be laminated in its at least one face is extruded from die head with molten condition.This operation makes thermoplastic resin (A) and thermoplastic resin (B) melting with extruder, uses material feeding block (feed block) method or manifold (multi-manifold) method to carry out stacked co-extrusion modling method.Co-extrusion modling method is by thermoplastic resin (A) and thermoplastic resin (B) melting, the resin of multiple integral and roller is snugly carried out shaping.Specifically, can extrude from manifold die head, material feeding block die head.
Even if thermoplastic resin (A) and thermoplastic resin (B) mixing also maintain the transparency, so when recovery layer lamination is shaping produce end cutting part and pulverize, with specific ratio, to be preferably relative to thermoplastic resin (A) 100 weight portion before reclaiming be that the ratio of below 50 weight portions is mixed in resin bed (A), when not damaging the characteristic as laminates, material unaccounted-for (MUF) ground can be reduced and extrudes.
(refrigerating work procedure (ii))
This operation is that the duplexer that utilizes carry-over pinch rolls to draw to be extruded is while utilize the 1st ~ 3rd chill roll to carry out the operation cooled.
As shown in Figure 1, the 1st ~ 3rd chill roll, rotary middle spindle is parallel, at grade, and closely configures.The interval of the 1st ~ 3rd chill roll is corresponding with the thickness of duplexer.Be cooled through (a) to be clipped in by the duplexer extruded between the 1st chill roll and the 2nd chill roll, (b) is wound in thereafter the 2nd chill roll, and (c) is wound in thereafter the 3rd chill roll and carries out.
(peripheral speeds relative to the carry-over pinch rolls of the 2nd roller peripheral speed)
In the present invention, by the peripheral speed of carry-over pinch rolls is set as 0.996 ~ 1.010 times relative to the 2nd roller peripheral speed, the warpage rate of placing after 120 hours under the hot and humid environment of temperature 85 DEG C, humidity 85%RH that can realize is less than 0.2%.Usually, about 0.990 ~ 0.995 times is set to relative to the peripheral speed of the carry-over pinch rolls of the 2nd roller peripheral speed because of the contraction caused by the cooling of resin.The present invention is based on following discovery: by by micro-for duplexer stretching, thus the warpage rate under being reduced in hot and humid environment.0.997 ~ 1.005 times is preferably, more preferably 0.998 ~ 1.000 times relative to the peripheral speed of the carry-over pinch rolls of the 2nd roller peripheral speed.
If be less than the lower limit of above-mentioned scope relative to the peripheral speed of the carry-over pinch rolls of the 2nd roller peripheral speed, deformation during then sheet direct of travel (MD direction) shaping becomes large, produce the warpage variation caused by deformation relaxes under hot and humid environment, be difficult to for practicality, therefore not preferred.In addition, if exceed the upper limit of above-mentioned scope relative to the peripheral speed of the carry-over pinch rolls of the 2nd roller peripheral speed, then negative effect is caused to the outward appearance of sheet, therefore not preferred.The uneven thickness of such as sheet becomes large, and in addition, phase difference uprises, and causes negative effect to optical characteristics.
(peripheral speed relative to the 3rd roller of the 2nd roller peripheral speed)
Usually, the peripheral speed of the 3rd roller is identical speed relative to the 2nd roller peripheral speed.In the present invention, by the peripheral speed of the 3rd roller relative to the 2nd roller peripheral speed is set as specific scope, warpage rate can be reduced further.That is, be preferably 1.001 ~ 1.030 times relative to the peripheral speed of the 3rd roller of the 2nd roller peripheral speed, be more preferably 1.002 ~ 1.020 times, more preferably 1.003 ~ 1.010 times.
If be in above-mentioned scope relative to the peripheral speed of the 3rd roller of the 2nd roller peripheral speed, then deformation during sheet direct of travel (MD direction) shaping diminishes, and the warpage variation caused by deformation relaxes not easily occurs under hot and humid environment.In addition, if be in above-mentioned scope relative to the peripheral speed of the carry-over pinch rolls of the 2nd roller peripheral speed, then the outward appearance of sheet becomes good.
(hard conating stacked)
Resin bed (B) the above stacked hard conating of the duplexer obtained can cooled.Hard conating and laminating method described above.
< purposes >
Duplexer of the present invention can be used as display screen cover or touch panel front panel.
Embodiment
Below, the present invention is described in detail to enumerate embodiment.
Embodiment 1 ~ 10, comparative example 1 ~ 3
The evaluation method > of < characteristic
(glass transition temperature: Tg)
According to JIS K7121, use the thermoplastic resin of each layer, measure glass transition temperature with Shimadzu Scisakusho Ltd DSC-60A.In the test flume of 50ml nitrogen stream environment per minute, thermoplastic resin 10 ~ 20mg is warming up to 200 DEG C with 20 DEG C per minute and makes its melting, be cooled to 35 DEG C and obtain sample, baseline when again heating up using 20 DEG C per minute the intermediate point of " departing from " is occurred as glass transition temperature.
(water absorption rate)
Make profiled sheeting (the vertical 80mm of the thermoplastic resin of each layer, horizontal 10mm, thickness 4mm), use as test film, take out after test film is left standstill 24 hours in the constant temperature and humidity cabinet of temperature 85 DEG C, humidity 0%RH, at room temperature leave standstill after 10 minutes again, use balance gravimetry, it can be used as dry weight.Next, take out after test film is left standstill 120 hours in the constant temperature and humidity cabinet of temperature 85 DEG C, humidity 85%RH, more at room temperature leave standstill after 10 minutes, use balance gravimetry, it can be used as water suction weight.Water absorption rate is obtained by following formula.
Water absorption rate [%]=(water suction weight [g]-dry weight [g])/dry weight [g] × 100 [%]
(pencil hardness)
The mensuration that the weight of 750g carries out pencil hardness is applied, by using the hardness of the pencil of the non-scratch surface of visualization as evaluation result according to the face being laminated with resin bed (B) of JIS K5600-5-4 to duplexer.Pencil uses Mitsubishi pencil Uni (trade name).
(the warpage rate after ambient temperature and moisture test)
The mode that sheet direct of travel during by duplexer to manufacture is long limit cuts out the size of 3 vertical 50mm × horizontal 100mm, duplexer is cut out the size of 3 vertical 50mm × horizontal 100mm in the mode that sheet width is long limit, after these 6 test films are placed 4 hours under temperature 23 DEG C, humidity 50%RH environment, mode on resin bed (B) side being keeps flat, and mensuration corner and intermediate point thereof amount to the floatation volume of 8.Obtain maximum floatation volume (maximum amount of warpage) in 6 of mensuration, using the value that is calculated as follows as warpage rate (%).
Warpage rate (%)=100 × maximum amount of warpage (mm)/100 (mm)
Should illustrate, with resin bed (B) side be depression floatation volume on the occasion of.
(the warpage rate after damp heat test)
The mode that sheet direct of travel during by duplexer to manufacture is long limit cuts out the size of 3 vertical 50mm × horizontal 100mm, duplexer is cut out the size of 3 vertical 50mm × horizontal 100mm in the mode that sheet width is long limit, these 6 test films are placed 120 hours under temperature 85 DEG C, humidity 85%RH environment, then place under temperature 23 DEG C, humidity 50%RH environment after 4 hours, mode on resin bed (B) side being keeps flat, and mensuration corner and intermediate point thereof amount to the floatation volume of 8.Obtain maximum floatation volume (maximum amount of warpage) in 6 of mensuration, using the value that is calculated as follows as warpage rate (%).
Warpage rate (%)=100 × maximum amount of warpage (mm)/100 (mm)
Should illustrate, with resin bed (B) side be depression floatation volume on the occasion of.
(stripping after damp heat test confirms)
Cut out the sample of vertical 50mm × horizontal 100mm from duplexer, use Sumitomo 3M Co., Ltd. two-sided tape, production code member Y4914, be fixed on the housing of smart mobile phone with 4 limits.Place 120 hours under temperature 85 DEG C, humidity 85%RH environment, then place after 4 hours under temperature 23 DEG C, humidity 50%RH environment, the state of visualization front panel standing part, confirm that two-sided tape occurs with or without stripping.Zero for peel off, × for peeling off, be shown in table 1.
The manufacture > of < resin 1 ~ 5
The resin 1 ~ 5 forming resin bed (B) manufactures by the following method.
(Production Example 1 of modified polycarbonate resin: resin 1)
48% sodium hydrate aqueous solution and 18182 parts of ion exchange waters of 3845 parts are loaded in the reactor of band thermometer, mixer and reflux condenser, dissolve 3984 part 2 wherein, after two (the 4-hydroxy-3-methyl phenyl) propane of 2-and 8.37 parts of dithionite, add 10567 parts of carrene, under stirring, be blown into 2000 parts of phosgene at 15 ~ 25 DEG C with about 60 minutes.
After phosgene is blown into end, adds 48% sodium hydrate aqueous solution and 58.28 parts of p-t-butyl phenols of 897 parts, then open stirring, after emulsification, add 5.39 parts of triethylamines, then stir end reaction in 1 hour at 28 ~ 33 DEG C.By after product dchloromethane also washing after reaction terminates, make hydrochloric acid acidity and wash, then washing, until the conductance of aqueous phase is almost identical with ion exchange water, obtains the dichloromethane solution of polycarbonate resin repeatedly.
Then, make this solution by the filter of bore size 0.3 μm, be added drop-wise to again in the warm water had in the kneader of the band isolation ward of foreign body mouth at bearing portion, heat up in a steamer carrene and make polycarbonate resin plate shape, then this pulverized dry containing liquid tablet and obtain powder.Thereafter, three (2 are added in the mode becoming 0.0025 % by weight in this powder, 4-bis--tert-butyl-phenyl) phosphite ester, glyceryl monostearate is added in the mode becoming 0.05 % by weight, after Homogeneous phase mixing, utilized by this powder exhaust biaxial extruder [Kobe Steel Ltd KTX-46] degassed while melting mixing, obtain the modified polycarbonate resin particle (viscosity average molecular weigh 25000) be made up of unit [1].It can be used as resin 1.
(Production Example 2 of modified polycarbonate resin: resin 2)
48% sodium hydrate aqueous solution of 4485 parts and the ion exchange water of 22377 parts is loaded in the reactor of band thermometer, mixer and reflux condenser, dissolve 2 of 1992 parts (7.9 moles) wherein, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 1773 parts (7.8 moles) 2, after two (4-hydroxy phenyl) propane of 2-and 7.53 parts of dithionite, add 13209 parts of carrene, under stirring, be blown into 2000 parts of phosgene at 15 ~ 25 DEG C with about 60 minutes.
After phosgene is blown into end, adds 48% sodium hydrate aqueous solution and 97.90 parts of p-t-butyl phenols of 640 parts, then open stirring, after emulsification, add 5.39 parts of triethylamines, then stir end reaction in 1 hour at 28 ~ 33 DEG C.By after product dchloromethane also washing after reaction terminates, make hydrochloric acid acidity and wash, then washing, until the conductance of aqueous phase is almost identical with ion exchange water, obtains the dichloromethane solution of polycarbonate resin repeatedly.
Then, make this solution by the filter of bore size 0.3 μm, be added drop-wise to again in the warm water had in the kneader of the band isolation ward of foreign body mouth at bearing portion, heat up in a steamer carrene and by polycarbonate resin plate shape, then this pulverized dry containing liquid tablet and obtain powder.Thereafter, three (2 are added in the mode becoming 0.0025 % by weight in this powder, 4-bis--tert-butyl-phenyl) phosphite ester, glyceryl monostearate is added in the mode becoming 0.05 % by weight, after Homogeneous phase mixing, utilized by this powder exhaust biaxial extruder [Kobe Steel Ltd KTX-46] degassed while melting mixing, obtain the modified polycarbonate resin particle (viscosity average molecular weigh 19500) be made up of unit [1] and [2].It can be used as resin 2.
(Production Example 3 of modified polycarbonate resin: resin 3)
By dried powder 50 weight portion of resin 1 that obtains by the operation identical with Production Example 1 and the polycarbonate resin (polycarbonate resin of Teijin Chemicals, Ltd.'s bisphenol A-type, viscosity average molecular weigh 24000) 50 weight portions are dry mixed, thereafter, three (2 are added in the mode becoming 0.0025 % by weight in this powder, 4-bis--tert-butyl-phenyl) phosphite ester, glyceryl monostearate is added in the mode becoming 0.05 % by weight, after Homogeneous phase mixing, utilized by this powder exhaust biaxial extruder [Kobe Steel Ltd KTX-46] degassed while melting mixing, obtain the modified polycarbonate resin particle (viscosity average molecular weigh 24500) be made up of unit [1] and [2].It can be used as resin 3.
(Production Example of the blending resin of acrylic copolymer and polycarbonate resin: resin 4 and resin 5)
In the heatable reaction vessel possessing thermometer, nitrogen ingress pipe, reflux condensing tube and agitating device, load following compositions, with in nitrogen displacement reaction container, be warming up to 80 DEG C.Import deionized water 200 parts, dispersant 0.3 part, 0.5 part, sodium sulphate, 2,2 '-azodiisobutyronitrile 0.3 part, phenyl methacrylate 33 parts, methyl methacrylate 66 parts, methyl acrylate 1 part, n octylmercaptan 2.5 parts, continue stirring 4 hours, by the polymer of the pearl that obtains washing, dry, obtain acrylic copolymer (weight average molecular weight 19200).Should illustrate, as dispersant, 1:1 mixing is by the polymer of 70 parts, methacrylic acid potassium, methyl methacrylate 30 parts of copolymerization with by the polymer of methacrylic acid 2-ethanesulfonic acid ester sodium salt 65 parts, 10 parts, methacrylic acid potassium, methyl methacrylate 25 parts of copolymerization in mass ratio, uses 10% aqueous solution of the polymer of this mixing.
By the acrylic copolymer that obtains and the polycarbonate resin (polycarbonate resin of Teijin Chemicals, Ltd.'s bisphenol A-type, viscosity average molecular weigh 22200) be supplied to biaxial extruder [Kobe Steel Ltd KTX-46], at 280 DEG C of melting mixings, obtain resin composition pellet.Using the ratio of acrylic copolymer and polycarbonate resin be the resin particle of 50:50 as resin 4, be that the resin particle of 30:70 is as resin 5 using the ratio of acrylic copolymer and polycarbonate resin.
Embodiment 1
1st, the 2nd extruder 1A, 1B, die head 2 and the 1st ~ 3rd roller 4 ~ 6 and a pair carry-over pinch rolls 7 are configured by shown in Fig. 1, the mode supplying stub bar to contact the 2nd roller with resin bed (A) of 2 kind of 2 Layer assignment is configured.
Single axle extruding machine (1A of Fig. 1) extruder forming the polycarbonate resin screw diameter 40mm of resin bed (A) carries out melting, in addition, the thermoplastic resin forming resin bed (B) uses the single axle extruding machine (1B of Fig. 1) of screw diameter 30mm to carry out melting, be laminated into 2 layers with for stub bar method, the die head via design temperature 280 DEG C is extruded.Prolong with the 1st roller and the 2nd roll-in, cool with the 3rd roller and draw.
Use polycarbonate resin (polycarbonate resin of Teijin Chemicals, Ltd.'s bisphenol A-type, viscosity average molecular weigh 23300) as resin bed (A).Use resin 1 as resin bed (B), manufacture duplexer in the mode that the thickness of the gross thickness 1.0mm of duplexer, resin bed (B) is 100 μm.
By the water absorption rate (%) of the glass transition temperature (Tg) of the thickness of the gross thickness of the duplexer obtained, resin bed (B), resin bed (A) and resin bed (B), resin bed (A) and resin bed (B), pencil hardness, shaping time the 3rd roller peripheral speed ratio relative to the 2nd roller and the peripheral speed ratio relative to the carry-over pinch rolls of the 2nd roller, warpage rate (%) and damp heat test after the result of warpage rate (%) be shown in table 1.
Embodiment 2
Use resin 2 as resin bed (B), in addition, obtain duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 3
Use resin 3 as resin bed (B), in addition, obtain duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 4
Use resin 4 as resin bed (B), in addition, obtain duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 5
Use resin 5 as resin bed (B), in addition, obtain duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 6
The thickness of resin bed (B) is set to 60 μm, in addition, obtains duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 7
The gross thickness of duplexer is set to 2.0mm, in addition, obtains duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 8
The peripheral speed ratio of the 3rd roller relative to the 2nd roller time shaping is set to 1.005 times, in addition, obtains duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 9
The peripheral speed ratio of the 3rd roller relative to the 2nd roller time shaping is set to 1.003 times, is set to 0.996 times relative to the peripheral speed ratio of the carry-over pinch rolls of the 2nd roller, in addition, obtains duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Embodiment 10
1.0 weight portions are added as 2 of ultra-violet absorber relative to the resin 1 of 100 weight portions, 2 '-di-2-ethylhexylphosphine oxide [4-(1,1,3,3-tetramethyl butyl)-6-[2H-BTA-2-base] phenol]] (ADEKA Inc., trade name: Adekastab LA-31), in addition, obtain duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Comparative example 1
Use commercially available acrylic resin (Mitsubishi Rayon Co., Ltd. trade name: ACRYPET VH001) as resin bed (B), the thickness of resin bed (B) is set to 60 μm, in addition, duplexer is obtained similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Comparative example 2
Use commercially available acrylic resin (Arkema Inc., trade name: Altuglas HT-121) as resin bed (B), the thickness of resin bed (B) is set to 60 μm, in addition, obtains duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
Comparative example 3
The peripheral speed ratio of the carry-over pinch rolls relative to the 2nd roller time shaping is set to 0.992 times, in addition, obtains duplexer similarly to Example 1.The evaluation result of the duplexer obtained is shown in table 1.
[table 1]
As shown in Table 1, the warpage rate after the ambient temperature and moisture test of embodiment 1 ~ 10, warpage rate after damp heat test are less than 0.2%.When particularly using resin 1 as resin bed (B), obtain high pencil hardness.
On the other hand, use Tg be less than 115 DEG C, the resin of water absorption rate more than 0.7% as the comparative example 1 of resin bed (B), use Tg to be more than 115 DEG C but the resin of water absorption rate more than 0.7% as the comparative example 2 of resin bed (B) obtain ambient temperature and moisture test after warpage rate, result that warpage rate after damp heat test is all large.In addition, layer forms identical with embodiment 1 but carry-over pinch rolls obtain the large result of the warpage rate after damp heat test relative to the peripheral speed of the 2nd roller than low comparative example 3.
Embodiment 11 ~ 22, comparative example 4 ~ 6
The evaluation method > of < characteristic
(glass transition temperature: Tg)
According to JIS K7121, use the thermoplastic resin of each layer, measure glass transition temperature with Shimadzu Scisakusho Ltd DSC-60A.In the test flume of 50ml nitrogen stream environment per minute, thermoplastic resin 10 ~ 20mg is made its melting with 20 DEG C per minute to heating up 200 DEG C and is cooled to 35 DEG C, obtain sample, baseline when again heating up using 20 DEG C per minute the intermediate point of " departing from " is occurred as glass transition temperature.
(water absorption rate)
Make profiled sheeting (the vertical 80mm of the thermoplastic resin of each layer, horizontal 10mm, thickness 4mm), use as test film, test film is taken out after the constant temperature and humidity cabinet of temperature 85 DEG C, humidity 0%RH leaves standstill 24 hours, at room temperature leave standstill after 10 minutes again, use balance gravimetry, it can be used as dry weight.Next, test film is taken out after the constant temperature and humidity cabinet of temperature 85 DEG C, humidity 85%RH leaves standstill 120 hours, more at room temperature leaves standstill after 10 minutes, use balance gravimetry, it can be used as water suction weight.Water absorption rate is obtained by following formula.
Water absorption rate [%]=(water suction weight [g]-dry weight [g])/dry weight [g] × 100 [%]
(pencil hardness)
The mensuration of pencil hardness is carried out, using the hardness of the pencil of non-for visualization scratch surface as evaluation result according to the weight of JIS K5600-5-4 to the face applying 750g of the hard conating on the resin bed (B) of the duplexer before and after stacked hard conating and resin bed (B).Pencil uses Mitsubishi pencil Uni (trade name).
(marresistance)
To be laminated with hard conating duplexer resin bed (B) on the face of hard conating, apply the weight of 500g, after reciprocal wiping 20 steel wire lumps (Nippon Steel Wool Co., Ltd. Bonstar#0000), be confirmed whether wound by visualization.Using do not produce wound as zero, using produce wound as ×.Should illustrate, to resin bed (B) face of the duplexer before stacked hard conating, if implement the test of above-mentioned marresistance, be judged to be "×".
(the warpage rate after ambient temperature and moisture test)
The mode that sheet direct of travel during by the duplexer being laminated with hard conating to manufacture is long limit cuts out the size of 3 vertical 50mm × horizontal 100mm, the mode being long limit with sheet width cuts out the size of 3 vertical 50mm × horizontal 100mm, after these 6 test films are placed 4 hours under temperature 23 DEG C, humidity 50%RH environment, mode on resin bed (B) side being keeps flat, and mensuration corner and intermediate point thereof amount to the floatation volume of 8.Obtain maximum floatation volume (maximum amount of warpage) in 6 of mensuration, using the value that is calculated as follows as warpage rate (%).
Warpage rate (%)=100 × maximum amount of warpage (mm)/100 (mm)
Should illustrate, with resin bed (B) side be depression floatation volume on the occasion of.
(the warpage rate after damp heat test)
The mode that sheet direct of travel during by the duplexer being laminated with hard conating to manufacture is long limit cuts out the size of 3 vertical 50mm × horizontal 100mm, the mode being long limit with sheet width cuts out the size of vertical 50mm × horizontal 100mm, these 6 test films are placed 120 hours under temperature 85 DEG C, humidity 85%RH environment, then place under temperature 23 DEG C, humidity 50%RH environment after 4 hours, mode on resin bed (B) side being keeps flat, and mensuration corner and intermediate point thereof amount to the floatation volume of 8.Obtain maximum floatation volume (maximum amount of warpage) in 6 of mensuration, using the value that is calculated as follows as warpage rate (%).
Warpage rate (%)=100 × maximum amount of warpage (mm)/100 (mm)
Should illustrate, with resin bed (B) side be depression floatation volume on the occasion of.
(stripping after damp heat test confirms)
Cut out the sample of vertical 50mm × horizontal 100mm from the duplexer being laminated with hard conating, use Sumitomo 3M Co., Ltd. two-sided tape, production code member Y4914, be fixed on the housing of smart mobile phone with 4 limits.Place 120 hours under temperature 85 DEG C, humidity 85%RH environment, then place after 4 hours under temperature 23 DEG C, humidity 50%RH environment, the state of visualization front panel standing part, confirm that two-sided tape occurs with or without stripping.Zero for peel off, × for peeling off, be shown in table 2.
< resin 1 ~ 5 >
The resin forming resin bed (B) uses the resin 1 ~ 5 identical with embodiment 1 ~ 10.
Embodiment 11
1st, the 2nd extruder 1A, 1B, die head 2 and the 1st ~ 3rd roller 4 ~ 6 and a pair carry-over pinch rolls 7 are configured by shown in Fig. 1, the mode supplying stub bar to contact the 2nd roller with resin bed (A) of 2 kind of 2 Layer assignment is configured.
Single axle extruding machine (1A of Fig. 1) extruder forming the polycarbonate resin screw diameter 40mm of resin bed (A) carries out melting, in addition, the single axle extruding machine (1B of Fig. 1) forming the thermoplastic resin screw diameter 30mm of resin bed (B) carries out melting, 2 layers are laminated for for stub bar method, die head via design temperature 280 DEG C is extruded, while prolong with the 1st roller and the 2nd roll-in, with the 3rd roller cooling, utilize a pair carry-over pinch rolls traction.
Use the polycarbonate resin (polycarbonate resin of Teijin Chemicals, Ltd.'s bisphenol A-type, viscosity average molecular weigh 23300) as resin bed (A), use resin 1 as resin bed (B), with the aggregate thickness of the thickness of resin bed (A) and resin bed (B) be 1.0mm, the thickness of resin bed (B) is that the mode of 100 μm manufactures duplexer.
Use metal bar coater on the two sides of the duplexer obtained with the mode coated UV line curable coating (Arakawa Chemical Industries, Ltd. BEAMSET575CL) of the thickness of thickness 10 μm, after drying, use ultraviolet lamp with accumulative light quantity 600mJ/cm
2mode be cured, obtain the duplexer being laminated with hard conating.
For the duplexer obtained, by the water absorption rate (%) of the glass transition temperature (Tg) of the thickness of the thickness of resin bed (A)+resin bed (B), resin bed (B), resin bed (A) and resin bed (B), resin bed (A) and resin bed (B), shaping time the 3rd roller peripheral speed ratio relative to the 2nd roller and be shown in table 2 relative to the peripheral speed ratio of the carry-over pinch rolls of the 2nd roller, the measurement result of pencil hardness.In addition, for the duplexer being laminated with hard conating, the result of the warpage rate (%) after the thickness of hard conating, pencil hardness, marresistance, warpage rate (%) and damp heat test is shown in table 2.
Embodiment 12
With the mode coated UV line curable coating (Arakawa Chemical Industries, Ltd. BEAMSET 575CL) that the thickness of hard conating is 5 μm, in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 13
With the mode coated UV line curable coating (Arakawa Chemical Industries, Ltd. BEAMSET 575CL) that the thickness of hard conating is 20 μm, in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 14
Use resin 2 as resin bed (B), in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 15
Use resin 3 as resin bed (B), in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 16
Use resin 4 as resin bed (B), in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 17
Use resin 5 as resin bed (B), in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 18
The thickness of resin bed (B) is set to 60 μm, in addition, obtains the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 19
The aggregate thickness of the thickness of resin bed (A) and resin bed (B) is set to 2.0mm, in addition, obtains the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 20
The 3rd roller time shaping is set to 1.005 times relative to the peripheral speed ratio of the 2nd roller, in addition, obtains the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 21
The 3rd roller time shaping is set to 1.003 times relative to the peripheral speed ratio of the 2nd roller, and carry-over pinch rolls are set to 0.996 times relative to the peripheral speed ratio of the 2nd roller, in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Embodiment 22
Be 100 weight portions relative to resin 1, add 1.0 weight portions as 2 of ultra-violet absorber, 2 '-di-2-ethylhexylphosphine oxide [4-(1,1,3,3-tetramethyl butyl)-6-[2H-BTA-2-base] phenol]] (ADEKA Inc., trade name: Adekastab LA-31), in addition, the duplexer being laminated with hard conating is obtained similarly to Example 11.Evaluation result is shown in table 2.
Comparative example 4
Use commercially available acrylic resin (Mitsubishi Rayon Co., Ltd. trade name: ACRYPET VH001) as resin bed (B), the thickness of resin bed (B) is set to 60 μm, in addition, the duplexer being laminated with hard conating is obtained similarly to Example 11.Evaluation result is shown in table 2.
Comparative example 5
Use commercially available acrylic resin (Arkema Inc., trade name: AltuglasHT-121) as resin bed (B), the thickness of resin bed (B) is set to 60 μm, in addition, obtains the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
Comparative example 6
Carry-over pinch rolls time shaping are set to 0.992 times relative to the peripheral speed ratio of the 2nd roller, in addition, obtain the duplexer being laminated with hard conating similarly to Example 11.Evaluation result is shown in table 2.
[table 2]
Table 2 continued
As shown in Table 2, the warpage rate after the ambient temperature and moisture test of embodiment 11 ~ 22, warpage rate after damp heat test are less than 0.2%.When particularly using resin 1 as resin bed (B), obtain high pencil hardness.
On the other hand, use Tg be less than 115 DEG C, the resin of water absorption rate more than 0.7% as the comparative example 4 of resin bed (B), use Tg to be more than 115 DEG C but the resin of water absorption rate more than 0.7% as the comparative example 5 of resin bed (B) obtain ambient temperature and moisture test after warpage rate, result that warpage rate after damp heat test is all large.In addition, layer form identical with embodiment 11 but shaping time carry-over pinch rolls obtain the large result of the warpage rate after damp heat test relative to the peripheral speed of the 2nd roller than low comparative example 6.
The pencil hardness of duplexer of the present invention is high, excellent scratch resistance, excellent heat resistance, and the buckling deformation under ambient temperature and moisture environment is little, and also not easily buckling deformation under long-term hot and humid environment.According to the manufacture method of duplexer of the present invention, the duplexer of not easily buckling deformation under the little and long-term hot and humid environment of buckling deformation under ambient temperature and moisture environment can be manufactured.
Utilizability in industry
Duplexer of the present invention is useful as the display screen cover of OA electronic equipment, touch panel front panel.
Symbol description
1A the 1st extruder
1B the 2nd extruder
2 die heads
The duplexer of 3 molten conditions
4 the 1st rollers
5 the 2nd rollers
6 the 3rd rollers
7 carry-over pinch rolls
As concrete mode of the present invention, there is following invention.
1. a laminated resin body, it is the laminated resin body folding the gross thickness 0.8mm ~ 3.0mm of the resin bed (B) be made up of other thermoplastic resins different from resin bed (A) of thickness 40 ~ 150 μm at least one surface layer of thermoplastic resin (A), it is characterized in that, the respective glass transition temperature Tg A of the thermoplastic resin of resin bed (A) and the thermoplastic resin of resin bed (B) and TgB is more than 115 DEG C, and the difference of TgA and TgB is less than 30 DEG C, the water absorption rate of the thermoplastic resin of resin bed (A) and the thermoplastic resin of resin bed (B) is less than 0.7%, and water suction rate variance is less than 0.5%, by this laminated resin body temperature 85 DEG C, under the hot and humid environment of humidity 85%RH, the warpage rate of placing after 120 hours is less than 0.2%.
2. according to the laminated resin body that preceding paragraph 1 is recorded, wherein, the thermoplastic resin of resin bed (A) is polycarbonate resin, the thermoplastic resin of resin bed (B) is modified polycarbonate resin, this modified polycarbonate resin contains Component units [1] that following formula [1] represents and the Component units [2] that following formula [2] represents, the ratio of the Component units [1] in whole Component units is 50 ~ 100 % by mole, and viscosity average molecular weigh is 1.0 × 10
4~ 8.0 × 10
4.
(in formula, W represents the cyclic alkyl of the alkyl of singly-bound, carbon number 1 ~ 6, the aryl of carbon number 6 ~ 10 or carbon number 3 ~ 8.)
3. according to the laminated resin body that preceding paragraph 1 is recorded, wherein, the thermoplastic resin of resin bed (A) is polycarbonate resin, the thermoplastic resin of resin bed (B) is the acrylic copolymer of 20 ~ 60 weight portions and the polyblend resin of 40 ~ 80 weight part polycarbonate resins, this acrylic copolymer contains 5 ~ 80 % by weight aromatic series (methyl) acrylic ester unit and 20 ~ 95 % by weight (methyl) methyl acrylate units, and weight average molecular weight is 5000 ~ 30000.
4. according to the laminated resin body that preceding paragraph 1 is recorded, wherein, relative to thermoplastic resin 100 weight portion of resin bed (B), the ultra-violet absorber containing 0.5 ~ 5.0 weight portion.
5., according to the laminated resin body that preceding paragraph 1 is recorded, wherein, the pencil hardness of resin bed (B) is more than F.
6., according to the laminated resin body that preceding paragraph 1 is recorded, wherein, it is less than 0.2% that laminated resin body places the warpage rate after 4 hours under temperature 23 DEG C, humidity 50%RH environment.
7. the manufacture method of the laminated resin body of preceding paragraph 1 record, it is characterized in that, use and there is the parallel and position relationship at grade of rotary middle spindle and 3 chill rolls closely configured, the laminated resin body that at least one side at thermoplastic resin (A) is laminated with other thermoplastic resins (B) different from resin bed (A) is extruded from die head with molten condition, by being clipped between the 1st chill roll and the 2nd chill roll, after being wound in the 2nd chill roll, be wound in the 3rd chill roll and cool, the at least one side being manufactured on resin bed (A) is laminated with the laminated resin body of resin bed (B), when as above manufacturing, making relative to the peripheral speed of the carry-over pinch rolls of the 2nd roller peripheral speed is 0.996 ~ 1.010 times.
8., according to the laminated resin body that preceding paragraph 1 is recorded, it is used as display screen cover, touch panel front panel.
In addition, as the mode with hard conating, there is following invention.
1. one kind is laminated with the laminated resin body of hard conating, it is the resin bed (B) be made up of other thermoplastic resins different from resin bed (A) folding thickness 40 ~ 150 μm at least one surface layer of thermoplastic resin (A), the laminated resin body of hard conating is laminated with further on resin bed (B), it is characterized in that, the aggregate thickness of the thickness of resin bed (A) and resin bed (B) is 0.8mm ~ 3.0mm, the respective glass transition temperature Tg A of the thermoplastic resin of resin bed (A) and the thermoplastic resin of resin bed (B) and TgB is more than 115 DEG C, and the difference of TgA and TgB is less than 30 DEG C, the water absorption rate of the thermoplastic resin of resin bed (A) and the thermoplastic resin of resin bed (B) is less than 0.7%, and water suction rate variance is less than 0.5%, to the laminated resin body of this hard conating be laminated with temperature 85 DEG C, the warpage rate of hot and humid lower placement after 120 hours of humidity 85%RH is less than 0.2%.
2. according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, wherein, the thermoplastic resin of resin bed (A) is polycarbonate resin, the thermoplastic resin of resin bed (B) is modified polycarbonate resin, this modified polycarbonate resin contains Component units [1] that following formula [1] represents and the Component units [2] that following formula [2] represents, the ratio of the Component units [1] in whole Component units is 50 ~ 100 % by mole, and viscosity average molecular weigh is 1.0 × 10
4~ 8.0 × 10
4.
(in formula, W represents the cyclic alkyl of the alkyl of singly-bound, carbon number 1 ~ 6, the aryl of carbon number 6 ~ 10 or carbon number 3 ~ 8.)
3. according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, wherein, the thermoplastic resin of resin bed (A) is polycarbonate resin, the thermoplastic resin of resin bed (B) is the polyblend resin of 20 ~ 60 parts by weight propylene acid copolymers and 40 ~ 80 weight part polycarbonate resins, described acrylic copolymer contains 5 ~ 80 % by weight aromatic series (methyl) acrylic ester unit and 20 ~ 95 % by weight (methyl) methyl acrylate units, and weight average molecular weight is 5000 ~ 30000.
4. according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, wherein, relative to thermoplastic resin 100 weight portion of resin bed (B), containing 0.5 ~ 5.0 weight portion ultra-violet absorber.
5., according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, wherein, the pencil hardness being layered in the hard conating on resin bed (B) is more than 3H.
6. according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, wherein, under temperature 23 DEG C, humidity 50%RH environment, the warpage rate of placing after 4 hours is less than 0.2%.
7., according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, wherein, hard conating is formed by ultraviolet curing coating.
8., according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, wherein, the thickness of hard conating is 1 ~ 30 μm.
9. the manufacture method being laminated with the laminated resin body of hard conating of preceding paragraph 1 record, comprise following operation: use and there is the parallel and position relationship at grade of rotary middle spindle and 3 chill rolls closely configured, the laminated resin body that at least one side at thermoplastic resin (A) is laminated with other thermoplastic resins (B) different from resin bed (A) is extruded from die head with molten condition, be clipped between the 1st chill roll and the 2nd chill roll, after being wound in the 2nd chill roll, be wound in the 3rd chill roll and cool, the at least one side being manufactured on resin bed (A) is laminated with the laminated resin body of resin bed (B), when as above manufacturing, it is 0.996 ~ 1.010 times by making relative to the peripheral speed of the carry-over pinch rolls of the 2nd roller peripheral speed, obtain the operation of laminated resin body, with the operation at the upper stacked hard conating of the resin bed (B) of the laminated resin body obtained.
10., according to the laminated resin body being laminated with hard conating that preceding paragraph 1 is recorded, it is used as display screen cover, touch panel front panel.
Claims (13)
1. a duplexer, comprise resin bed (A) and resin bed (B), described resin bed (A) is made up of thermoplastic resin (A), described resin bed (B) is laminated at least one face of described resin bed (A) and is made up of different other thermoplastic resins (B)
I the thickness of () resin bed (B) is 40 ~ 150 μm, the aggregate thickness of resin bed (A) and resin bed (B) is 0.8mm ~ 3.0mm,
(ii) thermoplastic resin (A) and the respective glass transition temperature Tg A of thermoplastic resin (B) and TgB are more than 115 DEG C, and the difference of TgA and TgB is less than 30 DEG C,
(iii) water absorption rate of thermoplastic resin (A) and thermoplastic resin (B) is less than 0.7%, and water suction rate variance is less than 0.5%,
(iv) be less than 0.2% by this duplexer warpage rate of placing after 120 hours under the hot and humid environment of temperature 85 DEG C, humidity 85%RH.
2. duplexer according to claim 1, wherein, thermoplastic resin (A) is polycarbonate resin, thermoplastic resin (B) is modified polycarbonate resin, this modified polycarbonate resin contains unit [1] that following formula represents and the unit [2] that following formula represents, relative to whole unit, the ratio of unit [1] is 50 ~ 100 % by mole, and viscosity average molecular weigh is 1.0 × 10
4~ 8.0 × 10
4,
(in formula, W represents the cycloalkylidene of the alkane 2 basis of singly-bound, carbon number 1 ~ 6, the arlydene of carbon number 6 ~ 10 or carbon number 3 ~ 8),
3. duplexer according to claim 1, wherein, thermoplastic resin (A) is polycarbonate resin, and thermoplastic resin (B) is the blending resin of the acrylic copolymer of 20 ~ 60 weight portions and the polycarbonate resin of 40 ~ 80 weight portions,
Described acrylic copolymer contains aromatic series (methyl) acrylic ester unit of 5 ~ 80 % by weight and (methyl) methyl acrylate units of 20 ~ 95 % by weight, and weight average molecular weight is 5000 ~ 30000.
4. duplexer according to claim 1, wherein, relative to thermoplastic resin (B) 100 weight portion, resin bed (B) is containing 0.5 ~ 5.0 weight portion ultra-violet absorber.
5. duplexer according to claim 1, wherein, the pencil hardness of resin bed (B) is more than F.
6. duplexer according to claim 1, wherein, it is less than 0.2% that duplexer places the warpage rate after 4 hours under temperature 23 DEG C, humidity 50%RH environment.
7. duplexer according to claim 1, wherein, resin bed (B) is laminated with hard conating.
8. duplexer according to claim 7, wherein, the pencil hardness of hard conating is more than 3H.
9. duplexer according to claim 7, wherein, hard conating is formed by ultraviolet curing coating.
10. a manufacture method for duplexer according to claim 1, comprises following operation:
I the duplexer of the resin bed (B) comprising resin bed (A) and be laminated in its at least one face is extruded from die head with molten condition by (),
(ii) duplexer utilizing carry-over pinch rolls to draw to be extruded is while utilize the 1st ~ 3rd chill roll to cool;
Wherein, for the 1st ~ 3rd chill roll, rotary middle spindle is parallel, at grade, and closely configures, and makes the peripheral speed of carry-over pinch rolls be 0.996 ~ 1.010 times relative to the 2nd roller peripheral speed, carries out as follows:
A the duplexer extruded from die head is clipped between the 1st chill roll and the 2nd chill roll by (),
B () is wound in the 2nd chill roll,
C () is wound in the 3rd chill roll.
11. manufacture methods according to claim 10, wherein, make the peripheral speed of the 3rd roller be 1.001 ~ 1.030 times relative to the 2nd roller peripheral speed.
12. manufacture methods according to claim 10, are included in the operation of the upper stacked hard conating of the resin bed (B) cooling the duplexer obtained.
13. duplexers according to claim 1, it is used as display screen cover or touch panel front panel.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012228002 | 2012-10-15 | ||
| JP2012-228002 | 2012-10-15 | ||
| JP2012-246311 | 2012-11-08 | ||
| JP2012246311 | 2012-11-08 | ||
| PCT/JP2013/078395 WO2014061817A1 (en) | 2012-10-15 | 2013-10-11 | Laminate |
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| Publication Number | Publication Date |
|---|---|
| CN104703796A true CN104703796A (en) | 2015-06-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380053406.XA Pending CN104703796A (en) | 2012-10-15 | 2013-10-11 | Laminate |
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| Country | Link |
|---|---|
| JP (1) | JP5872058B2 (en) |
| KR (1) | KR102139840B1 (en) |
| CN (1) | CN104703796A (en) |
| TW (1) | TWI617445B (en) |
| WO (1) | WO2014061817A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102258868B1 (en) * | 2013-12-19 | 2021-05-31 | 주식회사 쿠라레 | Method of manufacturing extruded resin plate and liquid crystal display protective plate |
| JP2015208961A (en) * | 2014-04-28 | 2015-11-24 | 住友ベークライト株式会社 | Multilayer resin sheet, liquid crystal protective sheet, window material for building base material, window material for industrial machinery or window material for merchandise display furniture |
| JP2015208962A (en) * | 2014-04-28 | 2015-11-24 | 住友ベークライト株式会社 | Multilayer resin sheet, liquid crystal protective sheet, window material for building base material, window material for industrial machinery and window material for merchandise display furniture |
| CN106573454B (en) * | 2014-07-09 | 2018-09-18 | 三菱瓦斯化学株式会社 | Synthetic resin laminated body |
| KR101949458B1 (en) | 2016-03-11 | 2019-02-18 | 주식회사 엘지화학 | Preparation method of super absorbent polymer, and super absorbent polymer |
| TWI729089B (en) * | 2016-03-23 | 2021-06-01 | 日商可樂麗股份有限公司 | Manufacturing method of extruded resin board and extruded resin board |
| JP6627608B2 (en) * | 2016-03-30 | 2020-01-08 | 三菱エンジニアリングプラスチックス株式会社 | Laminate |
| JP7120225B2 (en) * | 2017-05-31 | 2022-08-17 | 日本ゼオン株式会社 | Touch sensor substrate and manufacturing method thereof, touch sensor member and manufacturing method thereof, and display device |
| JP7065633B2 (en) * | 2018-02-14 | 2022-05-12 | 三菱瓦斯化学株式会社 | Resin laminate and resin molded product using it |
| JPWO2021241426A1 (en) * | 2020-05-27 | 2021-12-02 | ||
| KR102467377B1 (en) * | 2020-12-30 | 2022-11-16 | (주)아이컴포넌트 | Coextruded film and manufacturing method of the same |
| JP7427730B1 (en) | 2022-08-23 | 2024-02-05 | 三菱瓦斯化学株式会社 | Multilayer bodies and molded products |
| JP7427731B1 (en) | 2022-08-23 | 2024-02-05 | 三菱瓦斯化学株式会社 | Multilayer bodies and molded products |
| WO2024043180A1 (en) * | 2022-08-23 | 2024-02-29 | 三菱瓦斯化学株式会社 | Multilayer body and molded article |
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- 2013-10-11 WO PCT/JP2013/078395 patent/WO2014061817A1/en active Application Filing
- 2013-10-11 JP JP2014542207A patent/JP5872058B2/en active Active
- 2013-10-11 KR KR1020157009005A patent/KR102139840B1/en active IP Right Grant
- 2013-10-11 CN CN201380053406.XA patent/CN104703796A/en active Pending
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| CN101786361A (en) * | 2009-01-22 | 2010-07-28 | 帝人化成株式会社 | Polycarbonate resin stackup body |
| JP2012096357A (en) * | 2010-10-29 | 2012-05-24 | Sumitomo Chemical Co Ltd | Method for producing extruded resin plate |
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|---|---|
| KR102139840B1 (en) | 2020-07-30 |
| TWI617445B (en) | 2018-03-11 |
| JPWO2014061817A1 (en) | 2016-09-05 |
| KR20150070136A (en) | 2015-06-24 |
| JP5872058B2 (en) | 2016-03-01 |
| WO2014061817A1 (en) | 2014-04-24 |
| TW201429714A (en) | 2014-08-01 |
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Application publication date: 20150610 |