CN105899360A - Thermoplastic resin laminate - Google Patents
Thermoplastic resin laminate Download PDFInfo
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- CN105899360A CN105899360A CN201580003929.2A CN201580003929A CN105899360A CN 105899360 A CN105899360 A CN 105899360A CN 201580003929 A CN201580003929 A CN 201580003929A CN 105899360 A CN105899360 A CN 105899360A
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- thermoplastic resin
- resin composition
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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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
Abstract
The present invention provides a thermoplastic resin laminate having: a layer (A) containing a thermoplastic resin composition; and a layer (B) provided to at least one surface of the layer (A) and containing an acrylic resin composition. The thermoplastic resin composition contains: a polyester resin (a) having dicarboxylic acid structural units and diol structural units, 10-60mol% of the total diol structural units being derived from a diol having a cyclic acetal skeleton represented by formula (1) or formula (2); and a polycarbonate resin (b). The ratio of polycarbonate resin (b) in the thermoplastic resin composition relative to the total of the polyester resin (a) and the polycarbonate resin (b) is 5-50 wt%. The acrylic resin composition contains: at least one selected from the group consisting of an acrylic resin (c) and a styrene-methylmethacrylate copolymer (d); and a styrene-anhydrous maleic acid copolymer (e).
Description
Technical field
The present invention relates to thermoplastic resin laminate, particularly relate to the transparency, thermostability, resistance to
The thermoplastic resin of the excellent in dimensional stability under scratch resistance, resistance to impact, hot and humid environment
Laminated body.
Background technology
Resin-made lamella lucida is at outdoor billboard, the outward appearance purposes of bicycle shed or OA equipment, portable
The optical applications of the display part front surface panel of electronic equipment etc. are widely used.In recent years,
Such portable at portable telephone terminal, Portable electronic game machine, portable data assistance
In the front surface panel of formula display device, do not require nothing more than the transparency and visibility, marresistance,
Also require dimensional stability high when using under harsh and unforgiving environments.As such front surface panel
The transparent resin used, is widely used the propylene of the transparency, weatherability, excellent scratch resistance
Acid resin.But, acrylic resin lacks resistance to impact, at the easily quilt such as touch-screen display
Apply, in the purposes of impact, have front surface panel to be susceptible to the problem ruptured.
Patent documentation 1 is recorded by 10～60 moles of % with dihydroxylic alcohols construction unit are contained
Have the glycol unit with cyclic acetal skeleton shown in formula (1) or formula (2),
Or contain formula (3) or formula (4) institute with 10～60 moles of % of dicarboxylic acid structural units
The polyester resin (a) of the dicarboxylic acid units with cyclic acetal skeleton shown makes as central core
With and use the structure of acrylic resin at surface layer, it is possible to obtain the transparency, thermostability, resistance to
Scratch resistance, the multi-layer sheet of excellent impact resistance.
(in formula (1), (2), R1、R2And R3Independently, represent selected from carbon number and be
The aliphatic group of 1～10, carbon number be 3～10 ester ring type group and carbon number be
Organic group in the aromatic group of 6～10.)
(in formula (3), (4), R4And R5Independently, represent selected from carbon number be 1～
The aliphatic group of 10, carbon number be 3～10 ester ring type group and carbon number be 6～
Organic group in the aromatic group of 10, R6And R7Independently, represent hydrogen atom, methyl,
Ethyl or isopropyl.)
But, although the multi-layer sheet disclosed in this publication is at the excellent heat resistance of low-humidity environment,
But in temperature 85 DEG C, the dimensional stability of the such hot and humid environment of humidity 85% insufficient.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-182014 publication
Summary of the invention
Invent problem to be solved
The problem of the present invention is at least one problem solving in above-mentioned existing issue.It addition,
The problem of the present invention be to provide a kind of transparency, thermostability, marresistance, resistance to impact and
The thermoplastic resin laminate of the excellent in dimensional stability under hot and humid environment.
For the method solving problem
The present inventor conducts in-depth research, it was found that by the following present invention,
Can solve the problem that above-mentioned problem.
That is, the present invention is as described below.
<1>a kind of thermoplastic resin laminate, it is characterised in that:
There is the layer (A) comprising thermoplastic resin composition and be arranged at described layer (A) extremely
Lack a face and the layer (B) comprising acrylic resin composition,
Above-mentioned thermoplastic resin composition contains polyester resin (a) and polycarbonate resin (b),
This polyester resin (a) contains dihydroxylic alcohols construction unit and dicarboxylic acid structural units, wherein, all
10～60 moles of % in dihydroxylic alcohols construction unit are from shown in following formula (1) or following formula (2)
The dihydroxylic alcohols construction unit of the dihydroxylic alcohols with cyclic acetal skeleton, relative to above-mentioned thermoplastic
Property resin combination in polyester resin (a) and the total of polycarbonate resin (b), poly-carbon
The ratio of acid ester resin (b) is 5～50 weight %,
(in formula (1) and (2), R1、R2And R3Independently, represent selected from carbon number
Be 1～10 aliphatic group, carbon number be 3～10 ester ring type group and carbon number
It it is the organic group in the aromatic group of 6～10.)
Aforesaid propylene acrylic resin composition contains selected from acrylic resin (c) and methacrylic acid
At least one in methyl ester-styrol copolymer (d) and styrene-maleic anhydride copolymer
E (), relative to the knot from methyl methacrylate in aforesaid propylene acrylic resin composition
Structure unit, from cinnamic construction unit and the total of the construction unit from maleic anhydride,
Ratio from the construction unit of methyl methacrylate is 70～95 moles of %, from maleic acid
The ratio of the construction unit of acid anhydride is 1～5 mole of %.
<2>thermoplastic resin laminate as described in above-mentioned<1>, wherein, relative to styrene-
In copolymer-maleic anhydride (e) from cinnamic construction unit with from the knot of maleic anhydride
The total of structure unit, the ratio from cinnamic construction unit is 75～95 weight %.
<3>thermoplastic resin laminate as described in above-mentioned<1>or<2>, wherein, above-mentioned have
The dihydroxylic alcohols of cyclic acetal skeleton is double (1,1-dimethyl-2-the ethoxy)-2,4,8,10-four of 3,9-
Oxaspiro [5.5] hendecane.
<4>thermoplastic resin laminate as according to any one of above-mentioned<1>～<3>, wherein,
The structure from p-phthalic acid in polyester resin (a), in whole dicarboxylic acid structural units
The ratio of unit is 70 moles of more than %.
<5>thermoplastic resin laminate as according to any one of above-mentioned<1>～<4>, wherein,
One face or two faces are implemented hard conating and process.
<6>thermoplastic resin laminate as according to any one of above-mentioned<1>～<5>, wherein,
One face or two faces are implemented selected from antireflection process, antifouling process, antistatic treatment,
Any one above process in weatherability treatment and anti-dazzle process.
<7>a kind of thermoplastic resin laminate comprised according to any one of above-mentioned<1>～<6>
Transparent substrate material.
<8>a kind of thermoplastic resin laminate comprised according to any one of above-mentioned<1>～<6>
The transparency protection material.
The effect of invention
Optimal way according to the present invention, using the teaching of the invention it is possible to provide the transparency, thermostability, marresistance,
The thermoplastic resin laminate of the excellent in dimensional stability under resistance to impact and hot and humid environment,
This thermoplastic resin laminate can make as transparent substrate material, transparency protection material etc.
With, it is especially suitable for for requiring the portable of high dimensional stability under hot and humid environment
The front surface panel etc. of escope equipment.
Detailed description of the invention
Hereinafter the present invention is described in detail.The feature of the thermoplastic resin laminate of the present invention
It is there is the layer (A) comprising thermoplastic resin composition and comprise acrylic resin combination
The layer (B) of thing, at least one mask at above-mentioned layer (A) has above-mentioned layer (B), above-mentioned heat
Thermoplastic resin composition comprises polyester resin (a) and polycarbonate resin (b), above-mentioned polyester tree
In the dihydroxylic alcohols construction unit of fat (a), containing from the dihydroxylic alcohols with cyclic acetal skeleton
Dihydroxylic alcohols construction unit, aforesaid propylene acrylic resin composition contains selected from acrylic resin (c)
With at least one in copolymer of methyl methacrylatestyrene (d) and styrene-horse
Carry out acid anhydride copolymer (e).
Polyester resin (a) used in the present invention comprises in whole dihydroxylic alcohols construction unit
10～60 moles of % are for from having cyclic acetal bone shown in following formula (1) or following formula (2)
The dihydroxylic alcohols construction unit of the dihydroxylic alcohols of frame and the polyester resin of dicarboxylic acid structural units.
(in formula (1) and (2), R1、R2And R3Independently, represent selected from carbon number
Be 1～10 aliphatic group, carbon number be 3～10 ester ring type group and carbon number
It it is the organic group in the aromatic group of 6～10.)
In the dihydroxylic alcohols with cyclic acetal skeleton shown in above-mentioned formula (1) or formula (2),
R1、R2It is preferably methylene, ethylidene, propylidene, butylidene or their isomer,
Such as, isopropylidene, isobutylene etc..R3Preferably represent methyl, ethyl, propyl group, butyl
Or their isomer, such as isopropyl, isobutyl group etc..Wherein, as above-mentioned, there is ring
The dihydroxylic alcohols of shape acetal skeleton, double (1, the 1-dimethyl-2-ethoxy)-2,4,8,10-of more preferably 3,9-
Four oxaspiros [5.5] hendecane, 5-methylol-5-ethyl-2-(1,1-dimethyl-2-ethoxy)-1,3-
Dioxane, double (1,1-dimethyl-2-ethoxy)-2,4,8,10-tetra-oxaspiros [5.5] of particularly preferred 3,9-
Hendecane.
As in the polyester resin (a) used in the present invention from having cyclic acetal skeleton
Dihydroxylic alcohols dihydroxylic alcohols construction unit beyond dihydroxylic alcohols construction unit, be not particularly limited,
Can illustrate ethylene glycol, trimethylene, 1,4-butanediol, 1,5-pentanediol, 1,6-HD,
The aliphatic diol class of diethylene glycol, propylene glycol, neopentyl glycol etc.；Polyethylene Glycol, polypropylene glycol,
The polyether compound class of polytetramethylene glycol etc.；1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol,
1,2-decahydronaphthalenes dimethanol, 1,3-decahydronaphthalenes dimethanol, 1,4-decahydronaphthalenes dimethanol, 1,5-
Decahydronaphthalenes dimethanol, 1,6-decahydronaphthalenes dimethanol, 2,7-decahydronaphthalenes dimethanol, tetrahydro
Naphthalene dimethanol, norborene dimethanol, Tricyclodecane Dimethanol, five cyclododecane dimethanols etc.
Ester ring type glycols；4,4'-(1-methyl ethylidene) bis-phenol, methylene bis-phenol (Bisphenol F),
The bisphenols of 4,4'-cyclohexylidene bisphenol (bisphenol Z), 4,4'-sulfonyldiphenol (bisphenol S) etc.；
The alkylene oxide adduct of above-mentioned bisphenols；Hydroquinone, resorcinol, 4,4' dihydroxy diphenyl,
The aromatic series dihydroxy of 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl benzophenone etc.
Compound；Dihydroxylic alcohols structure with the alkylene oxide adduct from above-mentioned aromatic dihydroxy compound
Unit.Beyond the dihydroxylic alcohols construction unit from the dihydroxylic alcohols with cyclic acetal skeleton
Dihydroxylic alcohols construction unit, among these, particularly preferably from the construction unit of ethylene glycol.
As the dicarboxylic acid structural units of the polyester resin (a) used in the present invention, there is no spy
Do not limit, it is possible to illustrate from succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid,
Azelaic Acid, decanedioic acid, dodecanedicarboxylic acid, cyclohexane dicarboxylic acid, decane dicarboxylic acid, fall ice
The aliphatic dicarboxylic acid of sheet docosene dicarboxylic acid, tricyclodecane-dicarboxylic acid, five rings dodecanedicarboxylic acid etc.
Ester formative derivant with them；P-phthalic acid, M-phthalic acid, phthalic acid,
The fragrance of 2-methylterephthalic acid, naphthalene dicarboxylic acids, diphenyl dicarboxylic acid, tetrahydronaphthalene dicarboxylic acids etc.
Race's dicarboxylic acids and the dicarboxylic acid structural units of their ester formative derivant.Among these, more
It is preferred from p-phthalic acid, the dicarboxylic acid structural units of 3 naphthalene dicarboxylic acids, particularly preferably to benzene two
Formic acid.
In polyester resin (a) used in the present invention, coming in whole dihydroxylic alcohols construction units
From the ratio of the dihydroxylic alcohols construction unit of the dihydroxylic alcohols with cyclic acetal skeleton be preferably 10～
60 moles of %, more preferably 15～50 moles %.When aforementioned proportion is less than 10 moles of %, polyester
Resin (a) can not show sufficient thermostability sometimes, so the most preferred.It addition, more than 60
During mole %, resistance to impact reduces sometimes, so the most preferred.
The knot from p-phthalic acid in polyester resin (a), in whole dicarboxylic acid structural units
The ratio of structure unit is preferably 70 moles of %～100 moles of %, more preferably 90 moles %～100
Mole %.When polyester resin (a) has above-mentioned dihydroxylic alcohols construction unit with dicarboxylic acid structural units,
The thermostability of the thermoplastic resin laminate of the present invention, mechanical performance and economy are more excellent.
The method manufacturing the polyester resin (a) used in the present invention is not particularly limited, it is possible to
It is suitable for existing known method.For instance, it is possible to enumerate the molten of ester-interchange method, direct esterification etc.
Melt polymerization or solution polymerization process etc..In polyester resin (a), it is also possible to add generally
The various additive used, as additive, it is possible to enumerate ester exchange catalyst, esterification is urged
The various stabilizers of agent, anti-ether agent, heat stabilizer, light stabilizer etc., polymerization regulator etc..
Polycarbonate resin (b) used in the present invention be by aromatic dihydroxy compound or
That itself and a small amount of polyol are obtained by interfacial polymerization with phosgene or by upper
The aromatic dihydroxy compound stated can be had by what ester exchange reaction produced with the diester of carbonic acid
There is the thermoplastic poly carbonic ether polymer of side chain, such as, use the carbon using bisphenol-A as main material
Acid ester polymer.The molecular weight of the polycarbonate resin (b) used, is preferably capable passing through
Common extrusion molding manufactures the molecular weight of sheet material, and during with polystyrene conversion, preferably weight average divides
Son amount is 45,000～70,000.In the range of this weight average molecular weight, polycarbonate resin substrate
Linear expansivity 6 × 10-5/ DEG C～8 × 10-5/ DEG C in the range of.Polycarbonate resin (b)
In, it is also possible to add normally used various additive, as additive, for instance, it is possible to row
Lift antioxidant, stainblocker, UV absorbent, light diffusing agent, fire retardant, releasing agent,
Lubricant, antistatic additive, dye pigment etc..
As the polyester resin (a) in above-mentioned thermoplastic resin composition and polycarbonate resin (b)
Ratio, relative to the total of polyester resin (a) He polycarbonate resin (b), poly-carbonic acid
The ratio of ester resin (b) is preferably 5～50 weight %.Polycarbonate resin (b) is less than 5
During weight %, the dimensional stability under hot and humid environment is deteriorated, during more than 50 weight %,
The Tg of thermoplastic resin composition uprises, with the layer (B) comprising acrylic resin composition
Between the difference of Tg become big, accordingly, it is difficult to be shaped to smooth products formed.By making thermoplasticity
The ratio of the polyester resin (a) in resin combination and polycarbonate resin (b) is at above-mentioned model
Enclosing, the thermoplastic resin laminate of the present invention can obtain under resistance to impact and hot and humid environment
The such advantage of excellent in dimensional stability.Relative to polyester resin (a) and polycarbonate resin
B the total of (), the ratio of polycarbonate resin (b) is more preferably at the model of 10～50 weight %
Enclose, more preferably in the scope of 20～50 weight %.
Above-mentioned thermoplastic resin composition can be containing polyester resin (a) and polycarbonate resin (b)
Resin in addition.As the resin beyond polyester resin (a) and polycarbonate resin (b),
For instance, it is possible to enumerate polyethylene terephthalate, PEN, isophthalic
The modified poly-terephthaldehyde of dioctyl phthalate modification polyethylene terephthalate, 1,4 cyclohexane dimethanol
Polyester resin beyond the polyester resin (a) of acid glycol ester, polyarylate etc..
Acrylic resin (c) used in the present invention comprises methyl methacrylate polymer.
During with polystyrene conversion, the weight average molecular weight of acrylic resin (c) be preferably 10000～
30000。
Copolymer of methyl methacrylatestyrene (d) used in the present invention be comprise 5～
The construction unit from methyl methacrylate of 99 weight % and 95～1 weight % from benzene
The copolymer of the construction unit of ethylene.Preferably comprise 50～95 weight % from metering system
The construction unit of acid methyl ester and the copolymer from cinnamic construction unit of 50～5 weight %,
More preferably comprise the construction unit from methyl methacrylate of 60～90 weight % and 40～
The copolymer from cinnamic construction unit of 10 weight %.From methyl methacrylate
Construction unit less than 5 weight % and from cinnamic construction unit more than 95 weight % time, thoroughly
Bright property reduces, degraded appearance.During with polystyrene conversion, Methyl Methacrylate-Styrene
The weight average molecular weight of copolymer (d) is preferably 10000～30000.
From can be the most compatible with styrene-maleic anhydride copolymer (e) viewpoint and anti-scratch
From the viewpoint of wound property, be preferably used acrylic resin (c) and/or methyl methacrylate-
Styrol copolymer (d), the thermoplastic resin laminate of the present invention can obtain transparent and resistance to
The advantage of scratch resistance excellence.
Styrene-maleic anhydride copolymer (e) used in the present invention is to comprise 75～95
The copolymerization from cinnamic construction unit He the maleic anhydride accounting for 25～5 weight % of weight %
Thing.Preferably comprise 78～92 weight % from cinnamic construction unit and 22～8 weight %
The copolymer of maleic anhydride, more preferably comprise 80～90 weight % from cinnamic knot
The copolymer of the maleic anhydride of structure unit and 20～10 weight %.During with polystyrene conversion, benzene
The weight average molecular weight of ethylene maleic acid anhydride copolymer (e) is preferably 10000～30000.From
When cinnamic construction unit is less than 75 weight % and maleic anhydride more than 25 weight %, the most thoroughly
Bright property reduces, degraded appearance.It addition, from cinnamic construction unit more than 95 weight % and
When maleic anhydride is less than 5 weight %, the transparency reduces, additionally thermostability, hygroscopic improvement effect
Fruit is few.By being above-mentioned composition, the thermoplastic resin laminate of the present invention can obtain
The advantage of the excellent in dimensional stability under hot and humid environment.
Aforesaid propylene acrylic resin composition can contain acrylic resin (c), methacrylic acid
Other beyond methyl ester-styrol copolymer (d), styrene-maleic anhydride copolymer (e)
Resinous principle.Resinous principle as other, it is possible to enumerate the polyester beyond polyester resin (a),
Merlon, polystyrene, acrylonitrile-butadiene-styrene copolymer, methacrylic acid
Methyl ester-methacrylic acid copolymer, methyl methacrylate-acrylic acid copolymer, methyl-prop
E pioic acid methyl ester-acrylonitrile copolymer, methyl methacrylate-methacrylonitrile copolymers, first
Base acrylic acid methyl ester. and the copolymer of N-phenylmaleimide, methyl methacrylate and N
The copolymer of-N-cyclohexylmaleimide, styrene methyl methacrylate-metering system
Acid copolymer, styrene methyl methacrylate-acrylic copolymer, styrene-methyl
Acrylic acid methyl ester .-acrylonitrile copolymer, styrene methyl methacrylate-methacrylonitrile
The copolymer of copolymer, styrene and methyl methacrylate and N-phenylmaleimide,
Styrene and methyl methacrylate and the copolymer of N-N-cyclohexylmaleimide, vinyl chloride
Resin, ester ring type vistanex etc..As the polyester resin beyond above-mentioned polyester resin (a),
Specifically, it is possible to enumerate polyethylene terephthalate, PEN,
Isophthalate modified polyethylene terephthalate, 1,4 cyclohexane dimethanol modification gather benzene
Naphthalate, polyarylate etc..Other resinous principle above-mentioned can be used alone, also
Can be applied in combination two or more.Other resinous principle in aforesaid propylene acrylic resin composition
Shared ratio is less than 10 weight %.
Copolymer of methyl methacrylatestyrene (d) used in the present invention and styrene
The polymerization of-copolymer-maleic anhydride (e) is not particularly limited, and organic peroxy is preferably used
The radical polymerization of compound, additionally as manufacturing process, has been preferably used the entirety of a small amount of solvent
Continuous polymerization technique.The method that the technique being polymerized by suspension polymerisation or emulsion is obtained, the most not
The sufficient transparency can be obtained.The organic peroxide added during as polymerization, it is possible to used
Oxybenzene t-butyl formate, peroxide-2-ethyl hexanoic acid tert-butyl, 1,1-are double (tert-butyl hydroperoxide)
Double (the tert-butyl hydroperoxide)-hexamethylene of-3,3,5-trimethyl-cyclohexane, 1,1-, the double (4,4-of 2,2-
Dibutyl peroxidating cyclohexyl) propane, t-butylperoxyisopropyl monocarbonate, two tertiary fourths
Base peroxide, cumyl peroxide, ethyl-3,3-two (tert-butyl hydroperoxide) butyrate
Deng known material.Relative to total 100 weight portion of monomer, the interpolation of organic peroxide
Amount is preferably 0.001～5 weight portions.As solvent, it is possible to use butane, pentane, hexane,
The aliphatic hydrocarbon of isopentane, heptane, octane, isobutyltrimethylmethane. etc.；Pentamethylene., methyl cyclopentane,
The ester ring type hydrocarbon of hexamethylene, hexahydrotoluene, ethyl cyclohexane etc.；Or benzene, toluene, second
The aromatic hydrocarbon etc. of base benzene, dimethylbenzene etc., relative to total 100 weight portion of monomer, solvent
Addition be preferably 5～20 weight portions.It addition, during polymerization, add 4-methyl-2,4-hexichol
The known molecular weight regulator such as base amylene-1, tertiary lauryl mercaptan, n-dodecyl mercaptan is also
Harmless.Polymerization temperature is preferably 80～170 DEG C, more preferably 100～160 DEG C.
In aforesaid propylene acrylic resin composition, relative to selected from acrylic resin (c) and methyl
At least one in acrylate-styrene copolymer (d) is with phenylethylene-maleic anhydride altogether
The total of polymers (e), the ratio of styrene-maleic anhydride copolymer (e) is preferably 1～35
Weight %.When styrene-maleic anhydride copolymer (e) is less than 1 weight %, hot and humid
Dimensional stability under environment reduces, and during more than 35 weight %, marresistance reduces.By making
It becomes above-mentioned composition, it is possible to do not make the anti-scratch of the layer (B) comprising acrylic resin composition
Wound property improves thermostability, hygroscopicity with being deteriorated, and makes the thermoplastic resin laminate of the present invention obtain
This advantage of excellent in dimensional stability under marresistance, hot and humid environment.Relative to being selected from
In acrylic resin (c) and copolymer of methyl methacrylatestyrene (d) at least one
Plant the total with styrene-maleic anhydride copolymer (e), styrene-maleic anhydride copolymer
E the ratio of () is more preferably the scope of 5～30 weight %.
Relative to the structure from methyl methacrylate in aforesaid propylene acrylic resin composition
Unit, from cinnamic construction unit and the total of the construction unit from maleic anhydride, come
It is preferably 70～95 moles of %, from Malaysia from the ratio of the construction unit of methyl methacrylate
The ratio of the construction unit of anhydride is preferably 1～5 mole of %.Aforesaid propylene acrylic resin composition
In the ratio of these construction unit when above-mentioned scope, the thermoplastic resin lamination of the present invention
Body dimensional stability under hot and humid environment, excellent scratch resistance.Relative to from methyl
The construction unit of acrylic acid methyl ester., from cinnamic construction unit with from the knot of maleic anhydride
The total of structure unit, the ratio from the construction unit of methyl methacrylate be more preferably 70～
90 moles of %.It addition, relative in aforesaid propylene acrylic resin composition from metering system
The construction unit of acid methyl ester, from cinnamic construction unit with from the structure list of maleic anhydride
The total of unit, the ratio from cinnamic construction unit is preferably 4～29 moles of %, more preferably
It is 5～25 moles of %.
Above-mentioned thermoplastic resin composition and/or aforesaid propylene acrylic resin composition can contain
Various additives.As above-mentioned various additives, for instance, it is possible to enumerate antioxidant, ultraviolet
Light absorbers, stainblocker, antistatic additive, releasing agent, lubricant, dyestuff, pigment, nothing
Machine filler, resin extender etc..The method of mixing is not particularly limited, it is possible to use total amount blending
Method, the method etc. that is dry mixed of the method that masterbatch is dry mixed, total amount.
Above-mentioned thermoplastic resin composition can be manufactured by known technology.It is not particularly limited,
For instance, it is possible to by the composition containing polyester resin (a) and polycarbonate resin (b) is done
Carry out melting mixing after formula mixing to obtain.Aforesaid propylene acrylic resin composition also is able to pass through
Same procedure obtains.
The thermoplastic resin laminate of the present invention has the layer (A) comprising thermoplastic resin composition
With at least one face being arranged at above-mentioned layer (A) and the layer comprising acrylic resin composition
(B)。
Manufacture method as the thermoplastic resin laminate of the present invention, it is possible to use coetrusion,
The known laminating technology of coextruded layer platen press, extruding layer platen press, dry lamination method etc..Separately
Outward, in order to carry out the laminating of these, it is also possible to use between resin suitable bonding agent or
Adhesive resin.
The layer (A) comprising thermoplastic resin composition comprises acrylic resin group with multiple stratification
Kind and the Rotating fields (laminated layer sequence, the number of plies) of the layer (B) of compound select i.e. according to purposes
Can.Such as, the use of case hardness and the dimensional stability under hot and humid environment is needed at the same time
In Tu, it is possible to by be formed in surface layer use comprise acrylic resin composition layer (B),
Rotating fields (the bag of two kinds of two-layers of the layer (A) comprising thermoplastic resin composition is used at central core
The layer (A) of the layer (B) containing acrylic resin composition/comprise thermoplastic resin composition)
Rotating fields (the layer (B) comprising acrylic resin composition/comprise thermoplastic with two kinds three layers
The layer (B) of the layer (A) of property resin combination/comprise acrylic resin composition), obtain
Dimensionally stable under the transparency, thermostability, marresistance, resistance to impact and hot and humid environment
Property excellent thermoplastic resin laminate.
The thickness of the thermoplastic resin laminate in the present invention is preferably the scope of 0.1～10.0mm.
During for scope less than 0.1mm, sometimes due to bleed-through (バ Application Network け) occurs transfer bad
Or thickness and precision is bad.It addition, during scope more than 10.0mm, the most after shaping due to cold
The most unequal generation thickness and precision is bad or bad order.The scope of more preferably 0.3～5.0mm,
Further it is preferably the scope of 0.3～3.0mm.
Thermoplastic resin laminate in the present invention comprises the layer of acrylic resin composition
(B) thickness (side) is preferably less than the 25% of the overall thickness of thermoplastic resin laminate,
It is preferably the scope of 10～500 μm.The thickness (side) of layer (B) exceedes thermoplastic resin
The thickness that laminated body is overall 25% time, under hot and humid environment, sometimes there is prying.It addition,
During less than the scope of 10 μm, sometimes marresistance, weatherability is not enough, more than the model of 500 μm
When enclosing, under hot and humid environment, sometimes there is prying.The more preferably scope of 30～200 μm.
Hard conating can be implemented in the thermoplastic resin laminate of the present invention a face or two faces
Process.Such as, the photonasty coating firmly utilizing luminous energy to solidify by use forms hard conating.
As the photonasty utilizing luminous energy to solidify coating firmly, it is possible to be set forth in and comprise as simple function group
And/or the resin combination of multi-functional acrylate monomer and/or oligomer adds light
The Photocurable resin composition etc. that polymerization initiator obtains.Three are comprised for example, it is possible to be set forth in
(acryloyl-oxyethyl) chlorinated isocyanurates (f1) 40～80 weight % and can with (f1) altogether
Two poly-functional groups and/or methacrylate compound (f2) 20～40 weight of trifunctional
Resin combination 100 weight portion of amount % adds Photoepolymerizationinitiater initiater (f3) 1～10 weight portion
The Photocurable resin composition etc. obtained.
The hard method being coated with coating in the coating present invention is not particularly limited, it is possible to use known
Method.For example, it is possible to enumerate brushing, intaglio plate roller coat, dip-coating, flow coat, spraying, ink-jet painting
Cloth etc..
The synthetic resin laminated body of the present invention can be applied antireflection in one face or two faces
Any one in process, antifouling process, antistatic treatment, weatherability treatment and anti-dazzle process
Above process.Antireflection process, antifouling process, antistatic treatment, weatherability treatment and anti-
The method that dizziness processes is not particularly limited, it is possible to use known method.For example, it is possible to row
Lift the method for coating reflection reducing coating, the method for evaporation thin dielectric film, coating antistatic coating
Method etc..
The thermoplastic resin laminate of the present invention total light penetration when thickness 1.0mm is preferred
It is more than 90%.
The thermoplastic resin laminate of the optimal way of the present invention has the transparency, thermostability, resistance to
The scratch resistance feature with the excellent in dimensional stability under hot and humid environment, this thermoplastic resin is folded
Layer body can use as transparent substrate material, transparency protection material etc., the most applicable
The front surface face of the display apparatus of the high dimensional stability under requiring at hot and humid environment
Plate.
Embodiment
Hereinafter, by embodiment, the present invention is specifically explained.But, the present invention not because of
These embodiments and make its scope by any restriction.
Polyester resin (a), copolymer of methyl methacrylatestyrene (d), styrene-
Copolymer-maleic anhydride (e), the evaluation of acrylic resin composition, by embodiment with compare
The evaluation of the thermoplastic resin laminate that example obtains is carried out as follows.
<structural analysis of resinous principle>
About polyester resin (a), copolymer of methyl methacrylatestyrene (d), benzene second
The structural determination of alkene-copolymer-maleic anhydride (e), is dissolved in the deuterated of 1g by resin 20mg
Chloroform, measures through 1H-NMR, calculates from the area ratio at peak.Determinator uses NEC
(strain) manufactures JNM-AL400, is measured with 400MHz.
<mensuration of mean molecule quantity>
About molecular weight (number-average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw
/ Mn), resin 2mg is dissolved in the chloroform of 20g, uses gel permeation chromatography (GPC)
It is measured, by the value in terms of polystyrene standard as Mn, Mw, Mw/Mn.About
GPC, connects two TOSOH (strain) colors processed at TOSOH (strain) TOSOH processed 8020
A spectrum post GMHHR-L and TSK G5000HR, is surveyed chromatogram column temperature 40 DEG C
Fixed.For eluent, chloroform is injected with the flow velocity of 1.0mI/min, uses UV detector
It is determined.
<evaluation of the component molar ratio of acrylic resin composition>
The thermoplastic resin laminate obtained in below example, comparative example comprised propylene
From methyl methacrylate in layer (B) the inner acrylic based resin composition of acrylic resin composition
The construction unit (hreinafter referred to as " MMA unit ") of ester, from cinnamic construction unit
(hreinafter referred to as " St unit "), from maleic anhydride construction unit (hereinafter referred to as
For " MAH unit ") mol ratio analyzed.
About component molar ratio, only cut lower acrylic compounds from the layer (B) of thermoplastic resin laminate
Resin combination 20mg, is dissolved in the deuterochloroform of 1g, is surveyed by 13C-NMR (i.g.)
Fixed, calculate from the area ratio at peak.Determinator uses Bruker Biospin (strain) system
AVANCEII, is determined with 600MHz.The thermoplasticity obtained in embodiment, comparative example
MMA unit in the acrylic resin composition of resin laminate body, St unit, MAH are mono-
The mol ratio of unit is remembered respectively in table 1.
<transparency is evaluated>
For the thermoplastic resin laminate obtained in below example, comparative example, about always
Light penetration, according to JIS K 7105, ASTM D1003, uses color difference meter (Japan's electricity color
Industry (strain) system: COH-400) be determined.By saturating for total light during thickness 1.0mm
The rate of mistake be more than 90% laminated body be designated as qualified.
<Evaluation of Heat Tolerance>
For the thermoplastic resin laminate obtained in below example, comparative example, from 1.0mm
In thick thermoplastic resin laminate, with extrude direction as longitudinal direction, width be horizontal, cut
Go out the rectangle test film of longitudinal 90mm, horizontal 60mm, will be until minor face central part 5mm
Part use width to be that the clip of 13mm is clamped, test film is sling into plumbness,
Temperature heats 48 hours in being set as the baking box of 90 DEG C.By recessed with upper surface for the test film after test
The mode fallen into is statically placed in horizontal plane, puts a φ 38mm at test film central part, weight is 300g
Weight and fix, determine the deflection at four angles of test film and the gap length of horizontal plane,
It is qualified the value of the summation of this deflection laminated body less than 0.5mm to be designated as.
<marresistance evaluation>
For the thermoplastic resin laminate obtained in below example, comparative example, about lead
Hardness, according to JIS K 5600-5-4, uses pencil (the Rhizoma Sparganii pencil (strain) of various hardness
Manufacture UNI) pencil hardness of the layer (B) comprising acrylic resin composition is carried out
Measure.It is qualified the laminated body that pencil hardness is more than 3H to be designated as.
<resistance to impact test>
For the thermoplastic resin laminate obtained in below example, comparative example, about resistance to
Impact, makes the layer (B) comprising acrylic resin composition be upside, comprise thermoplastic resin
The layer (A) of oil/fat composition, as downside, is evaluated by falling ball impact test.In falling ball impact test,
Sample is fixed between the flange of φ 50, makes φ 25, the metal ball of 63.7g falls, with 10cm
The method measurement of interval measurement is arranged on the height during test film fracture of bottom, during this fracture
The highest survey is to 150cm.It is designated as closing by the laminated body that height is more than 100cm during fracture
Lattice.
<the dimensional stability evaluation under hot and humid environment>
For the thermoplastic resin laminate obtained in below example, comparative example, from 1.0mm
Thick thermoplastic resin laminate, with extrude direction as longitudinal direction, width be horizontal, cut out
Longitudinal 90mm, the rectangle test film of horizontal 60mm, by until minor face central part 5mm's
The clip that part uses width to be 13mm is clamped, and test film is sling into plumbness, is setting
Heat 120 hours in being set to the constant temperature and humidity machine of temperature 85 DEG C, humidity 85%.After test
The mode of the above surface indentation of test film is statically placed in horizontal plane, puts a φ at test film central part
38mm, weight are the weight of 300g and fix, and determine four angles and the horizontal plane of test film
The deflection of gap length, by the aggregate value of this deflection laminated body note less than 0.5mm
For qualified.
<mouldability evaluation>
For the thermoplastic resin laminate obtained in below example, comparative example, from 1.0mm
Thick thermoplastic resin laminate, with extrude direction as longitudinal direction, width be horizontal, cut out
Longitudinal 90mm, the rectangle test film of horizontal 60mm, be adjusted to temperature 23 DEG C, humidity 50%.
The mode of the above surface indentation of test film after test is statically placed in horizontal plane, in test film central authorities
A φ 38mm is put in portion, weight is the weight of 300g and fixes, and determines the corner of test film
With the deflection of the gap length of horizontal plane, the aggregate value of this deflection is less than 0.3mm's
Laminated body is designated as qualified.
[synthesis example 1]
Employ dimethyl terephthalate (DMT) as dicarboxylic acid component, use as glycol component
Double (1,1-dimethyl-2-ethoxy)-2,4,8,10-four oxaspiro [5.5] hendecane of 3,9-and second two
Alcohol is respectively 45 moles of %, the starting monomer of 55 moles of %, relative to dicarboxylic acid component 100
In the case of mole there is manganese acetate tetrahydrate 0.03 mole, it is warming up in a nitrogen atmosphere
200 DEG C, carry out ester exchange reaction.After the quantity of distillate of methanol reaches more than 90% relative to theoretical amount,
Relative to dicarboxylic acid component 100 moles, add stibium oxide (III) 0.01 mole and phosphoric acid triphen
Ester 0.06 mole, slowly carries out liter gentle decompression, finally 280 DEG C, below 0.1MPa carries out
Polymerization.Terminate reaction in the moment of the melt viscosity reaching appropriateness, obtain polyester resin (a).
The ratio of the glycol unit having cyclic acetal skeleton in obtained polyester resin (a) is
45 moles of %, Mn are 16500, and Mw/Mn is 3.6.
[synthesis example 2]
By the type that the is thoroughly mixed reactor of the volume with blender about 20 liters, volume about 40 liters
Tower plug flow type reactor, devolatilization groove with preheater be connected in series composition.Preparation contains
Styrene 11 mass parts, methyl methacrylate 89 mass parts, the list of ethylo benzene 8 mass parts
Body mixed liquor, it addition, mixing 1, (Japan's oils and fats is public for double (the tert-butyl hydroperoxide)-hexamethylene of 1-
Take charge of PERHEXA C processed) 0.02 mass parts and n-dodecyl mercaptan (KAO. Corp. SA's system
THIOKALCOL 20) 0.02 mass parts, make material solution.By this material solution with the least
Time 6kg import temperature and control to be the type that the is thoroughly mixed reactor of 130 DEG C.Additionally, to be thoroughly mixed
Stirred for several 180rpm of type reactor is implemented.Then, from being thoroughly mixed type reactor continuously
Take out reactant liquor, import the direction along flowing and be adjusted to the gradient with temperature 130 DEG C to 160 DEG C
Tower plug flow type reactor in.While using preheater to heat this reactant liquor, import
Control, in the devolatilization groove for temperature 235 DEG C and pressure 1.0kPa, to remove waving of unreacted monomer etc.
Send out composition.Take out this resin liquid with gear pump, obtain Methyl Methacrylate-Styrene copolymerization
Thing (d).The methacrylic acid of obtained copolymer of methyl methacrylatestyrene (d)
The ratio of methyl ester unit is 89 weight %, and the ratio of styrene units is 11 weight %, and Mn is
17000, Mw/Mn is 2.4.
[synthesis example 3]
Making monomer mixed solution is styrene 84 mass parts, maleic anhydride 16 mass parts, makes addition
The n-dodecane mercaptan of material solution is 0.2 mass parts, in addition, all as synthesis example 2
Ground is implemented, and has obtained phenylethylene-maleic anhydride based copolymer (e).Obtained styrene-
The styrene units of copolymer-maleic anhydride (e) is 84 weight %, and maleic anhydride units is 16
Weight %, Mn=17000, Mw/Mn=2.4.
[embodiment 1]
Use have the single axle extruding machine of diameter of axle 32mm, the single axle extruding machine of diameter of axle 65mm,
The feed unit being connected with full extruder and the multilayer extrusion device of the T die head with feed unit,
It is shaped to thermoplastic resin laminated plate.Be continuously introduced in the single axle extruding machine of diameter of axle 32mm by
Acrylic resin [Asahi Chemical Industry Chemicals (strain) makes, trade name: DELPET 80NH] (c),
In the copolymer of methyl methacrylatestyrene (d) that obtains in synthesis example 2, synthesis example 3
The styrene-maleic anhydride copolymer (e) obtained is 90 2.5 7.5 dry with respective weight ratio
The propylene resin mixture that formula is mixed to get, with barrel temperature 250 DEG C, discharging speed 4.8kg
The condition extrusion of/h.To synthesize it addition, be continuously introduced in the single axle extruding machine of diameter of axle 65mm
The polyester resin (a) obtained in example 1 and polycarbonate resin [Rhizoma Sparganii gas chemistry (strain) system,
Trade name: IUPILON S-3000] (b) be that 60 40 dry types are mixed to get with respective weight ratio
Thermoplastic resin intermixture, extrude with barrel temperature 260 DEG C, discharging speed 67kg/h.
The feed unit being connected with full extruder possesses the shunting pin of two kinds of two-layers, temperature 260 DEG C,
One face of thermoplastic resin composition (A1) layer imports acrylic resin composition (B1)
Layer carries out lamination.The T die head being used in the temperature 260 DEG C that its front end connects is extruded into sheet, with
3 polishing rolls transfer minute surface while cooling down, and obtain at thermoplastic resin composition (A1)
One face lamination of layer has the thermoplastic resin laminate of acrylic resin composition (B1) layer.
The design temperature of roller now starts to be followed successively by 85 DEG C, 85 DEG C, 107 DEG C from upstream side.Obtained by
The thickness of thermoplastic resin laminate be 1.0mm, acrylic resin composition (B1) layer
Thickness be 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability under impact evaluation, hot and humid environment, mouldability are evaluated is respectively
For well, synthetic determination is qualified.
[embodiment 2]
Replace the acrylic resin composition (B1) used in embodiment 1, use acrylic acid
Resin [Asahi Chemical Industry Chemicals (strain) makes, trade name: DELPET 80NH] (c), methyl
Acrylate-styrene copolymer (d), styrene-maleic anhydride copolymer (e) are with respectively
It is the propylene resin mixture that 80 5 15 dry types are mixed to get from weight ratio, in addition,
Operate similarly to Example 1, obtain folded in a face of thermoplastic resin composition (A1) layer
Layer has the thermoplastic resin laminate of acrylic resin composition (B2) layer.Obtained heat
The thickness of plastic resin laminated body is 1.0mm, the thickness of acrylic resin composition (B2) layer
Degree is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability evaluation under impact evaluation, hot and humid environment, mouldability are evaluated
Being respectively good, synthetic determination is qualified.
[embodiment 3]
Replace the acrylic resin composition (B1) used in embodiment 1, use acrylic acid
Resin [Asahi Chemical Industry Chemicals (strain) makes, trade name: DELPET 80NH] (c), methyl
Acrylate-styrene copolymer (d), styrene-maleic anhydride copolymer (e) are with respectively
Be the propylene resin mixture that 70 7.5 22.5 dry types are mixed to get from weight ratio, except this with
Outward, operate similarly to Example 1, obtain at thermoplastic resin composition (A1) layer
Face lamination has the thermoplastic resin laminate of acrylic resin composition (B3) layer.Obtained by
The thickness of thermoplastic resin laminate be 1.0mm, acrylic resin composition (B3) layer
Thickness be 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability evaluation under impact evaluation, hot and humid environment, mouldability are evaluated
Being respectively good, synthetic determination is qualified.
[embodiment 4]
Replace the acrylic resin composition (B1) used in embodiment 1, use acrylic acid
Resin [Asahi Chemical Industry Chemicals (strain) makes, trade name: DELPET 80NH] (c), benzene second
Alkene-copolymer-maleic anhydride (e) with respective weight ratio be 90 10 dry types be mixed to get third
Vinyl resin mixture, in addition, operates similarly to Example 1, obtains at thermoplastic resin
One face lamination of oil/fat composition (A1) layer has the heat of acrylic resin composition (B4) layer
Plastic resin laminated body.The thickness of obtained thermoplastic resin laminate is 1.0mm, propylene
The thickness of acrylic resin composition (B4) layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability evaluation under impact evaluation, hot and humid environment, mouldability are evaluated
Being respectively good, synthetic determination is qualified.
[embodiment 5]
Replace the thermoplastic resin composition (A1) used in embodiment 2, use polyester resin
(a), carbonate resin [Rhizoma Sparganii gas chemistry (strain) system, trade name: IUPILON S-3000]
B (), with the thermoplastic resin intermixture that respective weight ratio is that 90 10 dry types are mixed to get, removes
Beyond this, operate similarly to Example 2, obtain at thermoplastic resin composition (A2) layer
One face lamination has the thermoplastic resin laminate of acrylic resin composition (B2) layer.Institute
The thickness of the thermoplastic resin laminate obtained is 1.0mm, acrylic resin composition (B2)
The thickness of layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability evaluation under impact evaluation, hot and humid environment, mouldability are evaluated
Being respectively good, synthetic determination is qualified.
[embodiment 6]
Replace the thermoplastic resin composition (A1) used in embodiment 2, use polyester resin
(a), polycarbonate resin [Rhizoma Sparganii gas chemistry (strain) system, trade name: IUPILON S-3000]
B (), with the thermoplastic resin intermixture that respective weight ratio is that 75 25 dry types are mixed to get, removes
Beyond this, operate similarly to Example 2, obtain at thermoplastic resin composition (A3) layer
One face lamination has the thermoplastic resin laminate of acrylic resin composition (B2) layer.Institute
The thickness of the thermoplastic resin laminate obtained is 1.0mm, acrylic resin composition (B2)
The thickness of layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability evaluation under impact evaluation, hot and humid environment, mouldability are evaluated
Being respectively good, synthetic determination is qualified.
[embodiment 7]
Replace the thermoplastic resin composition (A1) used in embodiment 2, use polyester resin
(a), polycarbonate resin [Rhizoma Sparganii gas chemistry (strain) system, trade name: IUPILON S-3000]
B (), with the thermoplastic resin intermixture that respective weight ratio is that 50 50 dry types are mixed to get, removes
Beyond this, operate similarly to Example 2, obtain at thermoplastic resin composition (A4) layer
One face lamination has the thermoplastic resin laminate of acrylic resin composition (B2) layer.Institute
The thickness of the thermoplastic resin laminate obtained is 1.0mm, acrylic resin composition (B2)
The thickness of layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability evaluation under impact evaluation, hot and humid environment, mouldability are evaluated
Being respectively good, synthetic determination is qualified.
[embodiment 8]
Replace the thermoplastic resin composition (A1) used in embodiment 3, use polyester resin
(a), polycarbonate resin [Rhizoma Sparganii gas chemistry (strain) system, trade name: IUPILON S-3000]
B (), with the thermoplastic resin intermixture that respective weight ratio is that 90 10 dry types are mixed to get, removes
Beyond this, operate similarly to Example 3, obtain at thermoplastic resin composition (A2) layer
One face lamination has the thermoplastic resin laminate of acrylic resin composition (B3) layer.Institute
The thickness of the thermoplastic resin laminate obtained is 1.0mm, acrylic resin composition (B3)
The thickness of layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that dimensional stability evaluation under impact evaluation, hot and humid environment, mouldability are evaluated
Being respectively good, synthetic determination is qualified.
[comparative example 1]
Replace the acrylic resin composition (B1) used in embodiment 1, use acrylic acid tree
Fat [Asahi Chemical Industry Chemicals (strain) make, trade name: DELPET 80NH] (c), except this with
Outward, operate similarly to Example 1, obtain at thermoplastic resin composition (A1) layer
Face lamination has the thermoplastic resin laminate of acrylic resin (c) layer.Obtained thermoplastic resin
The thickness of fat laminated body is 1.0mm, and the thickness of acrylate resin layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that impact is evaluated, mouldability is evaluated is respectively good, but the chi under hot and humid environment
The result of very little estimation of stability is bad, and synthetic determination is defective.
[comparative example 2]
Replace the acrylic resin composition (B1) used in embodiment 1, use acrylic acid
Resin [Asahi Chemical Industry Chemicals (strain) makes, trade name: DELPET 80NH] (c), methyl
Acrylate-styrene copolymer (d), styrene-maleic anhydride copolymer (e) are with respectively
It is the propylene resin mixture that 50 12.5 37.5 dry types are mixed to get from weight ratio, except this
In addition, operate similarly to Example 1, obtain at the one of thermoplastic resin composition (A1) layer
Individual face lamination has the thermoplastic resin laminate of acrylic resin composition (B5) layer.Gained
To the thickness of thermoplastic resin laminate be 1.0mm, acrylic resin composition (B5)
The thickness of layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Under Evaluation of Heat Tolerance, resistance to impact evaluation, hot and humid environment
Dimensional stability evaluation, the result evaluated of mouldability be respectively good, but the transparency is evaluated,
The result of marresistance evaluation is bad, and synthetic determination is defective.
[comparative example 3]
Replace the acrylic resin composition (B2) used in embodiment 5, use acrylic acid
Resin [Asahi Chemical Industry Chemicals (strain) makes, trade name: DELPET 80NH] (c), methyl
Acrylate-styrene copolymer (d), styrene-maleic anhydride copolymer (e) are with respectively
It is the propylene resin mixture that 50 12.5 37.5 dry types are mixed to get from weight ratio, except this
In addition, operate similarly to Example 5, obtain at the one of thermoplastic resin composition (A2) layer
Individual face lamination has the thermoplastic resin laminate of acrylic resin composition (B5) layer.Gained
To the thickness of thermoplastic resin laminate be 1.0mm, acrylic resin composition (B5)
The thickness of layer is 70 μm near central authorities.
Evaluation result is shown in table 1.The knot that Evaluation of Heat Tolerance, resistance to impact evaluation, mouldability are evaluated
Fruit is respectively good, but the chi under the transparency evaluation, marresistance evaluation, hot and humid environment
The result of very little estimation of stability is bad, and synthetic determination is defective.
[comparative example 4]
Replace the thermoplastic resin composition (A1) used in embodiment 2, use polyester resin
A (), in addition, operates similarly to Example 1, obtain at the one of polyester resin (a) layer
Individual face lamination has the thermoplastic resin laminate of acrylic resin composition (B2) layer.Gained
To the thickness of thermoplastic resin laminate be 1.0mm, acrylic resin composition (B2)
The thickness of layer is 70 μm near central authorities.
Evaluation result is shown in table 1.Transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, resistance to
The result that impact is evaluated, mouldability is evaluated is respectively good, but the chi under hot and humid environment
The result of very little estimation of stability is bad, and synthetic determination is defective.
[comparative example 5]
Replace the thermoplastic resin composition (A1) used in embodiment 2, use polycarbonate resin
Fat [Rhizoma Sparganii gas chemistry (strain) system, trade name: IUPILON S-3000] (b), in addition,
Operating similarly to Example 1, obtaining a face lamination at polycarbonate resin (b) layer has third
The thermoplastic resin laminate of olefin(e) acid based resin composition (B2) layer.Obtained thermoplastic resin
The thickness of fat laminated body is 1.0mm, the thickness of acrylic resin composition (B2) layer in
It is 70 μm near centre.
Evaluation result is shown in table 1.The transparency evaluation, Evaluation of Heat Tolerance, resistance to impact evaluation, height
The result that dimensional stability under temperature high humidity environment is evaluated is respectively good, but marresistance evaluation,
The result of mouldability evaluation is bad, and synthetic determination is defective.
[comparative example 6]
Use and there is the single axle extruding machine of diameter of axle 65mm and the monolayer extrusion device of T die head, become
Type is thermoplastic resin board.It is continuously introduced into polyester resin in the single axle extruding machine of diameter of axle 65mm
A (), extrudes with barrel temperature 250 DEG C, discharging speed 70kg/h.It is used in its front end even
The T die head of the temperature connect 250 DEG C is extruded into sheet, with 3 polishing roll transfer minute surfaces one
Limit cools down, and obtains the thermoplastic resin board of polyester resin (a).Obtained thermoplastic resin board
Thickness be 1.0mm.
Evaluation result is shown in table 1.The transparency evaluation, Evaluation of Heat Tolerance, resistance to impact evaluation, one-tenth
The result that type is evaluated is respectively good, but the chi under marresistance evaluation, hot and humid environment
The result of very little estimation of stability is bad, and synthetic determination is defective.
[comparative example 7]
Replace the polyester resin (a) used in comparative example 6, use polycarbonate resin [Rhizoma Sparganii watt
This chemistry (strain) system, trade name: IUPILON S-3000] (b), in addition, and compare
Example 6 operates equally, obtains the thermoplastic resin board of polycarbonate resin (b).Obtained heat
The thickness of plastic resin plate is 1.0mm.
Evaluation result is shown in table 1.Under Evaluation of Heat Tolerance, resistance to impact evaluation, hot and humid environment
The result evaluated of dimensional stability be respectively good, but transparency evaluation, marresistance evaluation,
The result of mouldability evaluation is bad, and synthetic determination is defective.
[comparative example 8]
Replace the polyester resin (a) used in comparative example 6, use acrylic resin [Asahi Chemical Industry
Chemicals (strain) make, trade name: DELPET 80NH] (c), in addition, with than
Relatively example 6 operates equally, obtains the thermoplastic resin board of acrylic resin (c).Obtained heat
The thickness of plastic resin plate is 1.0mm.
Evaluation result is shown in table 1.The transparency evaluation, Evaluation of Heat Tolerance, marresistance evaluation, one-tenth
The result that type is evaluated is respectively good, but the chi under resistance to impact evaluation, hot and humid environment
The result of very little estimation of stability is bad, and synthetic determination is defective.
[comparative example 9]
Replace the polyester resin (a) used in comparative example 6, use methyl methacrylate-benzene
Ethylene copolymer (d), in addition, operates as comparative example 6, obtains methacrylic acid
The thermoplastic resin board of methyl ester-styrol copolymer (d).Obtained thermoplastic resin board
Thickness is 1.0mm.
Evaluation result is shown in table 1.The result that transparency evaluation, Evaluation of Heat Tolerance, mouldability are evaluated
It is respectively good, but the chi under marresistance evaluation, resistance to impact evaluation, hot and humid environment
The result of very little estimation of stability is bad, and synthetic determination is defective.
[comparative example 10]
Replace the polyester resin (a) used in comparative example 6, use phenylethylene-maleic anhydride altogether
Polymers (e), in addition, operates as comparative example 6, obtains phenylethylene-maleic anhydride
The thermoplastic resin board of copolymer (e).The thickness of obtained thermoplastic resin board is 1.0mm.
Evaluation result is shown in table 1.Dimensional stability under Evaluation of Heat Tolerance, hot and humid environment is commented
The result that valency, mouldability are evaluated is respectively good, but transparency evaluation, marresistance evaluation,
The result of resistance to impact evaluation is bad, and synthetic determination is defective.
[table 1]
Claims (8)
1. a thermoplastic resin laminate, it is characterised in that:
There is the layer (A) comprising thermoplastic resin composition and be arranged at described layer (A) extremely
Lack a face and the layer (B) comprising acrylic resin composition,
Described thermoplastic resin composition contains polyester resin (a) and polycarbonate resin (b),
This polyester resin (a) contains dihydroxylic alcohols construction unit and dicarboxylic acid structural units, wherein, all
10～60 moles of % in dihydroxylic alcohols construction unit are from shown in following formula (1) or following formula (2)
The dihydroxylic alcohols construction unit of the dihydroxylic alcohols with cyclic acetal skeleton, relative to described thermoplastic
Property resin combination in polyester resin (a) and the total of polycarbonate resin (b), poly-carbon
The ratio of acid ester resin (b) is 5～50 weight %,
In formula (1) and (2), R1、R2And R3Independently, represent selected from carbon number and be
The aliphatic group of 1～10, carbon number be 3～10 ester ring type group and carbon number be
The organic group of the aromatic group of 6～10,
Described acrylic resin composition contains selected from acrylic resin (c) and methacrylic acid
At least one in methyl ester-styrol copolymer (d) and styrene-maleic anhydride copolymer
E (), relative to the knot from methyl methacrylate in described acrylic resin composition
Structure unit, from cinnamic construction unit and the total of the construction unit from maleic anhydride,
Ratio from the construction unit of methyl methacrylate is 70～95 moles of %, from maleic acid
The ratio of the construction unit of acid anhydride is 1～5 mole of %.
2. thermoplastic resin laminate as claimed in claim 1, it is characterised in that:
Relative in described styrene-maleic anhydride copolymer (e) from cinnamic structure
Unit and the total of the construction unit from maleic anhydride, from the ratio of cinnamic construction unit
Example is 75～95 weight %.
3. thermoplastic resin laminate as claimed in claim 1 or 2, it is characterised in that:
The described dihydroxylic alcohols with cyclic acetal skeleton is the double (1,1-dimethyl-2-hydroxyl second of 3,9-
Base)-2,4,8,10-four oxaspiro [5.5] hendecane.
4. the thermoplastic resin laminate as according to any one of claims 1 to 3, its feature exists
In:
In described polyester resin (a), in whole dicarboxylic acid structural units from terephthaldehyde
The ratio of the construction unit of acid is 70 moles of more than %.
5. the thermoplastic resin laminate as according to any one of Claims 1 to 4, its feature exists
In:
One face or two faces are implemented hard conating and process.
6. the thermoplastic resin laminate as according to any one of Claims 1 to 5, its feature exists
In:
One face or two faces are implemented at antireflection process, antifouling process, antistatic
Any one above process in reason, weatherability treatment and anti-dazzle process.
7. a transparent substrate material, it is characterised in that:
Comprise the thermoplastic resin laminate according to any one of claim 1～6.
8. a transparency protection material, it is characterised in that:
Comprise the thermoplastic resin laminate according to any one of claim 1～6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-006720 | 2014-01-17 | ||
| JP2014006720 | 2014-01-17 | ||
| PCT/JP2015/050773 WO2015108064A1 (en) | 2014-01-17 | 2015-01-14 | Thermoplastic resin laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105899360A true CN105899360A (en) | 2016-08-24 |
Family
ID=53542952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580003929.2A Pending CN105899360A (en) | 2014-01-17 | 2015-01-14 | Thermoplastic resin laminate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5930138B2 (en) |
| KR (1) | KR20160108378A (en) |
| CN (1) | CN105899360A (en) |
| TW (1) | TW201532815A (en) |
| WO (1) | WO2015108064A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112912247A (en) * | 2018-10-26 | 2021-06-04 | 三菱瓦斯化学株式会社 | Thermoplastic resin laminate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7356304B2 (en) * | 2019-09-11 | 2023-10-04 | 三菱瓦斯化学株式会社 | Resin laminates, transparent substrate materials containing the same, and transparent protective materials |
| KR102541655B1 (en) * | 2020-12-18 | 2023-06-14 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Multilayers and molded articles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471464A (en) * | 2000-10-27 | 2004-01-28 | 3M创新有限公司 | Method and materials for preventing warping in optical films |
| JP2008268913A (en) * | 2007-03-29 | 2008-11-06 | Asahi Kasei Chemicals Corp | Laminated optical film |
| JP4196154B2 (en) * | 2001-12-19 | 2008-12-17 | 三菱瓦斯化学株式会社 | Multilayer sheet |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008188875A (en) * | 2007-02-05 | 2008-08-21 | Mitsubishi Gas Chem Co Inc | Multi-layer sheet |
| JP2011099046A (en) * | 2009-11-06 | 2011-05-19 | Mitsubishi Gas Chemical Co Inc | Polyester resin composition |
| JP2011219667A (en) * | 2010-04-13 | 2011-11-04 | Mitsubishi Gas Chemical Co Inc | Decorative film |
| JP6295659B2 (en) * | 2012-12-27 | 2018-03-20 | 三菱ケミカル株式会社 | Molded resin laminate and molded body |
| JP6295660B2 (en) * | 2012-12-27 | 2018-03-20 | 三菱ケミカル株式会社 | Molded resin laminate and molded body |
| JP2014148165A (en) * | 2013-01-10 | 2014-08-21 | Mitsubishi Plastics Inc | Formed article and method for producing the same |
| JP2014205342A (en) * | 2013-03-19 | 2014-10-30 | 三菱樹脂株式会社 | Formed body and manufacturing method of the same |
| JP6201404B2 (en) * | 2013-04-30 | 2017-09-27 | 三菱ケミカル株式会社 | Scratch resistant resin laminate |
-
2015
- 2015-01-14 KR KR1020167020563A patent/KR20160108378A/en not_active Application Discontinuation
- 2015-01-14 CN CN201580003929.2A patent/CN105899360A/en active Pending
- 2015-01-14 WO PCT/JP2015/050773 patent/WO2015108064A1/en active Application Filing
- 2015-01-14 JP JP2015557845A patent/JP5930138B2/en active Active
- 2015-01-16 TW TW104101420A patent/TW201532815A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471464A (en) * | 2000-10-27 | 2004-01-28 | 3M创新有限公司 | Method and materials for preventing warping in optical films |
| JP4196154B2 (en) * | 2001-12-19 | 2008-12-17 | 三菱瓦斯化学株式会社 | Multilayer sheet |
| JP2008268913A (en) * | 2007-03-29 | 2008-11-06 | Asahi Kasei Chemicals Corp | Laminated optical film |
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| 陈平等: "《高分子合成材料学》", 31 August 2010, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112912247A (en) * | 2018-10-26 | 2021-06-04 | 三菱瓦斯化学株式会社 | Thermoplastic resin laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201532815A (en) | 2015-09-01 |
| JP5930138B2 (en) | 2016-06-08 |
| WO2015108064A1 (en) | 2015-07-23 |
| JPWO2015108064A1 (en) | 2017-03-23 |
| KR20160108378A (en) | 2016-09-19 |
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