CN105555863A - Resin composition and molded article thereof - Google Patents
Resin composition and molded article thereof Download PDFInfo
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- CN105555863A CN105555863A CN201480051845.1A CN201480051845A CN105555863A CN 105555863 A CN105555863 A CN 105555863A CN 201480051845 A CN201480051845 A CN 201480051845A CN 105555863 A CN105555863 A CN 105555863A
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- 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
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
This resin composition contains: 100 parts by mass of a copolymer (a) formed from a constituent unit derived from a methacrylic acid alicyclic hydrocarbon ester, and a constituent unit derived from another monomer; 0.001 to 2 parts by mass, inclusive, of a lubricant (x) formed from at least one selected from the group consisting of a higher alcohol, a hydrocarbon, a fatty acid, an aliphatic amide, and a fatty acid ester not having 2 or more hydroxyls in one molecule; and 0.1 parts by mass or less of a lubricant (y2) formed from a fatty acid ester having 2 or more hydroxyls in one molecule. Said resin composition is melt-molded to obtain a molded article.
Description
Technology dividing line
The present invention relates to resin combination and products formed thereof.More specifically, not easily generate when the present invention relates to melt molding gel, the resin combination of excellent heat resistance and products formed thereof.
Background technology
The transparency, scuff resistance, weathering resistance etc. of methacrylic resin are excellent.In this methacrylic resin, it is sometimes made to contain lubricant (such as, patent documentation 1 etc.) for improving the objects such as release property.On the other hand, in order to improve the thermotolerance of methacrylic resin, propose the scheme (such as, patent documentation 2 etc.) making it contain the unit from (methyl) CALCIUM ACRYLATE ring type hydrocarbon ester.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-180454 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 61-176901 publication
Summary of the invention
Invent problem to be solved
When to make to improve in the methacrylic resin composition of thermotolerance containing lubricant and carry out melt molding, generate gel sometimes.This gel becomes the foreign matter defect of products formed or the outward appearance of infringement product.
Problem of the present invention not easily generate when being to provide a kind of melt molding gel, the resin combination of excellent heat resistance and products formed thereof.
For solving the means of problem
In order to solve above-mentioned problem, complete the present invention comprised with under type.
(1) resin combination, contains: multipolymer (a) 100 mass parts, and described multipolymer (a) comprises from the structural unit of methacrylic acid ester ring type hydrocarbon ester and the structural unit from other monomer;
More than lubricant (x) 0.001 mass parts, below 2 mass parts, be selected from least one in the group be made up of the fatty acid ester that in higher alcohols, hydrocarbon, lipid acid, fatty acid metal salt, aliphatic amide and 1 molecule, not there are more than 2 hydroxyls described lubricant (x) comprising; With
Lubricant (y1) 0 ~ 0.1 mass parts, described lubricant (y1) comprises the direactive glyceride that carbonatoms is the saturated fatty acid of 10 ~ 24.
(2) resin combination Gen Ju (1), wherein, the content of lubricant (y1) is 0 ~ 0.05 mass parts relative to multipolymer (a) 100 mass parts.
(3) resin combination Gen Ju (1), wherein, the content of lubricant (y1) is 0 ~ 0.01 mass parts relative to multipolymer (a) 100 mass parts.
(4) resin combination, contains: multipolymer (a) 100 mass parts, and described multipolymer (a) comprises from the structural unit of methacrylic acid ester ring type hydrocarbon ester and the structural unit from other monomer;
More than lubricant (x) 0.001 mass parts, below 2 mass parts, be selected from least one in the group be made up of the fatty acid ester that in higher alcohols, hydrocarbon, lipid acid, fatty acid metal salt, aliphatic amide and 1 molecule, not there are more than 2 hydroxyls described lubricant (x) comprising; With
Lubricant (y2) 0 ~ 0.1 mass parts, described lubricant (y2) comprises the fatty acid ester in 1 molecule with more than 2 hydroxyls.
(5) resin combination Gen Ju (4), wherein, the content of lubricant (y2) is 0 ~ 0.05 mass parts relative to multipolymer (a) 100 mass parts.
(6) resin combination Gen Ju (4), wherein, the content of lubricant (y2) is 0 ~ 0.01 mass parts relative to multipolymer (a) 100 mass parts.
(7) according to resin combination according to any one of (1) ~ (6), wherein, lubricant (x) comprise be selected from by carbonatoms be 12 ~ 18 aliphatic monobasic alcohol and carbonatoms be at least one in the group that forms of saturated fatty acid of 16 ~ 24.
(8) according to the resin combination according to any one of (1) ~ (7), its second-order transition temperature is more than 115 DEG C and less than 150 DEG C.
(9) according to resin combination according to any one of (1) ~ (8), its saturated water absorption in the water of 23 DEG C is 0.3 ~ 1.8 quality %.
(10) products formed, comprises the resin combination according to any one of aforementioned (1) ~ (9).
(11) duplexer, has: the layer comprising the resin combination according to any one of aforementioned (1) ~ (9), and
Comprise second-order transition temperature and be more than 130 DEG C and the layer of the thermoplastic resin composition of less than 160 DEG C.
(12) duplexer Gen Ju (11), wherein, second-order transition temperature is more than 130 DEG C and the thermoplastic resin composition of less than 160 DEG C is resin combination containing polycarbonate.
Invention effect
Resin combination of the present invention has excellent thermotolerance, does not generate gel during melt molding.And then resin combination of the present invention is good to the adaptation of format roll and release property (do not adhere on the surface of mould, deadlocked character of generating heat).The products formed that resin combination melt molding of the present invention is obtained because foreign matter defect is few, outward appearance is good, therefore, it is possible to be applicable to optics etc.
Embodiment
Resin combination of the present invention is the resin combination containing multipolymer (a) and lubricant (x).
Multipolymer (a) comprises from the structural unit of methacrylic acid ester ring type hydrocarbon ester and the structural unit from other monomer.
The methacrylic acid ester ring type hydrocarbon ester forming the multipolymer (a) used in the present invention is the compound represented by formula (I).
[changing 1]
(in formula (I), Cy represents ester ring type alkyl.)
As methacrylic acid ester ring type hydrocarbon ester, the methacrylic acid monocyclic aliphatic race hydrocarbon esters such as such as cyclohexyl methacrylate, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, methacrylic acid ring pentyl ester, methacrylic acid ring heptyl ester, Menthyl methacrylate can be enumerated; Methacrylic acid-2-norborneol ester, methacrylic acid-2-methyl-2-norborneol ester, methacrylic acid-2-ethyl-2-norborneol ester, methacrylic acid-2-isobornyl thiocyanoacetate, methacrylic acid-2-methyl-2-isobornyl thiocyanoacetate, methacrylic acid-2-ethyl-2-isobornyl thiocyanoacetate, methacrylic acid-8-three ring [5.2.1.0
2,6] last of the ten Heavenly stems ester, methacrylic acid 8-methyl-8-three ring [5.2.1.0
2,6] last of the ten Heavenly stems ester, methacrylic acid-8-ethyl-8-three ring [5.2.1.0
2,6] last of the ten Heavenly stems ester, methacrylic acid-2-adamantane esters, methacrylic acid-2-methyl-2-adamantane esters, methacrylic acid-2-ethyl-2-adamantane esters, methacrylic acid-1-adamantane esters, methacrylic acid-2-fenchyl ester, methacrylic acid-2-methyl-2-fenchyl ester, the methacrylic acid multicyclic aliphatic hydrocarbon ester such as methacrylic acid-2-ethyl-2-fenchyl ester.Among these, preferable methyl vinylformic acid multicyclic aliphatic hydrocarbon ester, more preferably methacrylic acid-8-three ring [5.2.1.0
2,6] ester in the last of the ten Heavenly stems (another name: methacrylic acid two ring pentyl ester).
In the multipolymer (a) used in the present invention, from containing ratio preferably 10 ~ 60 quality %, more preferably 20 ~ 50 quality % and then preferred 30 ~ 40 quality % of the structural unit of methacrylic acid ester ring type hydrocarbon ester.Time fewer than aforementioned range, the thermotolerance of resin combination has the time difference.Time more than aforementioned range, the shock-resistance of resin combination has the time difference.
About other monomer forming in the present invention the multipolymer (a) used, as long as can with the monomer of methacrylic acid ester ring type hydrocarbon ester copolymerization, be not particularly limited.As other monomer described, methyl acrylate can be enumerated, ethyl propenoate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, the just own ester of vinylformic acid, ethyl acrylate, vinylformic acid pentadecyl ester, lauryl acrylate, cyclohexyl acrylate, vinylformic acid norbornene ester, isobornyl acrylate, benzyl acrylate, acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-2-ethoxy ethyl ester, glycidyl acrylate, allyl acrylate, the acrylate such as phenyl acrylate, the alkyl methacrylates such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid secondary butyl ester, Tert-butyl Methacrylate, pentylmethacrylate, isopentyl methacrylate, the just own ester of methacrylic acid, methacrylic acid-2-ethylhexyl, methacrylic acid pentadecyl ester, lauryl methacrylate(LMA), phenyl methacrylate, the unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, maleic anhydride, toxilic acid, methylene-succinic acid, the alkene such as ethene, propylene, 1-butylene, iso-butylene, 1-octene, divinyl, isoprene, myrcene equiconjugate diene, the aromatic ethenyl compounds such as vinylbenzene, alpha-methyl styrene, p-methylstyrene, a vinyl toluene, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile, vinyl-acetic ester, vinyl pyridine, vinyl ketone, vinylchlorid, vinylidene chloride, vinylidene etc.Among these other monomers, the combination of preferable methyl methyl acrylate and acrylate, the more preferably combination of methyl methacrylate and methyl acrylate.
In the multipolymer (a) preferably used in the present invention, from containing ratio preferably 40 ~ 90 quality %, more preferably 50 ~ 80 quality % and then preferred 60 ~ 70 quality % of the structural unit of methyl methacrylate.When containing ratio from the structural unit of methyl methacrylate is fewer than aforementioned range, the transparency of resin combination, scuff resistance and weathering resistance have the time difference.When containing ratio from the structural unit of methyl methacrylate is more than aforementioned range, the thermotolerance of resin combination has the time difference.
In addition, from containing ratio preferably below 10 quality %, more preferably below 5 quality % and then preferred below the 2 quality % of the structural unit of the monomer except methacrylic acid ester ring type hydrocarbon ester and methyl methacrylate.
The second-order transition temperature of the multipolymer (a) used in the present invention is preferably more than more than 115 DEG C and less than 150 DEG C, more preferably 130 DEG C and less than 150 DEG C and then preferably more than 140 DEG C and less than 150 DEG C.When the second-order transition temperature of multipolymer (a) is in aforementioned range, thermotolerance and the shock-resistance of resin combination balance well, being inhibited of the sheet duplexer (hereinafter sometimes referred to lamination sheets) of such as this thermoplastic resin such as resin combination and the polycarbonate warpage under hot and humid.
The weight-average molecular weight of the multipolymer (a) used in the present invention preferably 40, more than 000 and 500, less than 000, more preferably 70, more than 000 and 300, less than 000 and then preferably 100, more than 000 and 200, less than 000.When the weight-average molecular weight of multipolymer (a) is in aforementioned range, the molding processibility of resin combination is excellent, the scuff resistance of the products formed of acquisition and the balance of thermotolerance excellent.
The weight-average molecular weight of the multipolymer (a) used in the present invention and the ratio (being sometimes recited as Mw/Mn) of number-average molecular weight preferably more than 1.7 and less than 2.6, more preferably more than 1.7 and less than 2.3 and then preferably more than 1.7 and less than 2.0.
It should be noted that, weight-average molecular weight and number-average molecular weight are the molecular weight converted with the polystyrene standard that GPC (gel permeation chromatography) measures.
In addition, the weight-average molecular weight of multipolymer (a), number-average molecular weight and Mw/Mn can be controlled by the kind, amount etc. adjusting polymerization starter described later and chain-transfer agent.
When obtaining in the present invention the multipolymer (a) used, for the yellowness index preferably less than 2 of the monomer mixture be polymerized, more preferably less than 1.If the yellowness index of monomer mixture is little, then by time shaping for the resin combination of acquisition, easily obtain the products formed of almost non-coloring with high efficiency.It should be noted that, yellowness index is the value of yellow chromaticity based on the value using the colour examining colour-difference-metre ZE-2000 of Japanese electricity Se Industrial Co., Ltd to measure based on JISZ8722, that calculate based on JISK7373.
Preferred below the 10ppm of dissolved oxygen amount of above-mentioned monomer mixture, more preferably below 5ppm and then preferably below 4ppm, particularly preferably below 3ppm.When being set to the dissolved oxygen amount of such scope, polyreaction is successfully carried out, and easily obtains the products formed without silvery white, non-coloring.
In the manufacture of the multipolymer (a) used in the present invention, polymerization process is not particularly limited.Such as, suspension polymerization, (continuously) mass polymerization, solution polymerization process, emulsion polymerization etc. can be enumerated.This polymerization preferably utilizes that radical polymerization is incompatible to carry out.Among described polymerization process, from the view point of productivity and resistance to pyrolytic, preferred suspension polymerization or (continuously) mass polymerization, more preferably suspension polymerization.
Polyreaction is caused by the polymerization starter added together with monomer mixture.In addition, by adding in monomer mixture by chain-transfer agent as required, the weight-average molecular weight of obtained multipolymer (a), number-average molecular weight, molecular weight distribution can be regulated.
As long as the polymerization starter used in the manufacture of multipolymer (a) produces the initiator of reactive free radical, be not particularly limited.The tertiary own ester of such as isopropyl peroxide list carbonic acid can be enumerated, the tertiary own ester of peroxidation-2 ethyl hexanoic acid, peroxidation-2 ethyl hexanoic acid-1, 1, 3, 3-tetramethyl-butyl ester, tert-Butyl peroxypivalate, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), new peroxide tert-butyl caprate, the tertiary own ester of peroxidation neodecanoic acid, peroxidation neodecanoic acid-1, 1, 3, 3-tetramethyl-butyl ester, 1, two (the tertiary hexyl peroxidation) hexanaphthene of 1-, benzoyl peroxide, peroxidation-3, 5, 5-trimethyl acetyl, lauroyl peroxide, 2, 2 '-azo two (2-methyl propionitrile), 2, 2 '-azo two (2-methylbutyronitrile), dimethyl-2, 2 '-azo two (2 Methylpropionic acid ester) etc.Wherein, the tertiary own ester of preferred peroxidation-2 ethyl hexanoic acid, 1,1-two (tertiary hexyl peroxidation) hexanaphthene, dimethyl-2,2 '-azo two (2 Methylpropionic acid ester).
1 hr half-life temperature preferably 60 ~ 140 DEG C of described polymerization starter, more preferably 80 ~ 120 DEG C.These polymerization starters can be used alone a kind or two or more combinationally used.In addition, the addition, addition means etc. of polymerization starter suitably can set according to object, are not particularly limited.Such as, about the amount of the polymerization starter used in suspension polymerization, relative to monomer mixture 100 mass parts preferably 0.0001 ~ 0.1 mass parts, more preferably 0.001 ~ 0.07 mass parts.
The chain-transfer agent used in the manufacture of multipolymer (a) is not particularly limited.Such as n octylmercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, 1 can be enumerated, 4-butanediethiol, 1,6-hexanedithiol, ethylene glycol bisthioglycolate thiopropionate, butyleneglycol methyl-carbithionic acid ester, butyleneglycol dithiopropionic acid ester, hexylene glycol methyl-carbithionic acid ester, hexylene glycol dithiopropionic acid ester, trimethylolpropane tris-alkyl sulfide alcohols such as (β-thiopropionate), tetramethylolmethane tetrathio propionic ester; Alpha-methyl styrene dimer; Terpinolene etc.Among these, the alkyl sulfhydryls such as preferred n octylmercaptan, tetramethylolmethane tetrathio propionic ester.These chain-transfer agents can be used alone a kind, also two or more can be combinationally used.About the usage quantity of chain-transfer agent, relative to monomer mixture 100 mass parts, preferably 0.1 ~ 1 mass parts, more preferably 0.2 ~ 0.8 mass parts and then preferably 0.3 ~ 0.6 mass parts.
About each monomer, polymerization starter and the chain-transfer agent that use in the manufacture of multipolymer (a), both by behind they all mixing, its mixture can be supplied to reactive tank, also they can be supplied to reactive tank respectively.In the present invention, after preferably all mixing, its mixture is supplied to the method for reactive tank.
Lubricant is to give antifriction quality, release property and the known additive added in resin.As lubricant, there will be a known higher alcohols base lubricant, hydrocarbon system lubricant, fatty acid series lubricant, fatty acid metal salt base lubricant, aliphatic amide base lubricant, ester base lubricant etc.
Among these, the lubricant (x) used in the present invention comprises at least one in the group being selected from and being made up of the fatty acid ester not having more than 2 hydroxyls in higher alcohols, hydrocarbon, lipid acid, fatty acid metal salt, aliphatic amide and 1 molecule, preferably comprise be selected from by carbonatoms be 12 ~ 18 aliphatic monobasic alcohol and carbonatoms be at least one in the group that forms of saturated fatty acid of 16 ~ 24, more preferably comprise the aliphatic monobasic alcohol that carbonatoms is 12 ~ 18.
As higher alcohols, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, oleyl alcohol etc. can be enumerated.From the view point of antifriction quality is high and mold fouling, roller pollute few, the higher alcohols preferred aliphat monohydroxy-alcohol used in the present invention, more preferably carbonatoms is the aliphatic monobasic alcohol of 12 ~ 18, and then preferably carbonatoms is the representative examples of saturated aliphatic monohydroxy-alcohol of 12 ~ 18, and then more preferably carbonatoms is the representative examples of saturated aliphatic monohydroxy-alcohol of 16 ~ 18.
High from the view point of antifriction quality, release property, as hydrocarbon, preferred carbonatoms is the aliphatic hydrocarbon of more than 12.In addition, the aliphatic hydrocarbon such as whiteruss, Microcrystalline Wax, native paraffin, synthesis paraffin, polyolefin-wax can be used; The partial oxide of aliphatic hydrocarbon; The commercial materials such as the halogenide of aliphatic hydrocarbon.Sometimes be also the mixture of these commercial materials, the average carbon atom number of now also preferably contained aliphatic hydrocarbon is more than 12.
As lipid acid, lauric acid, palmitinic acid, stearic acid, eicosanoic acid, behenic acid, lignoceric acid, oleic acid, erucic acid, arachidonic acid, 12-oxystearic acid etc. can be enumerated.From the view point of antifriction quality is high and mold fouling, roller pollute few, the preferred carbonatoms of the lipid acid used in the present invention is the lipid acid of more than 10, and more preferably carbonatoms is the lipid acid of 16 ~ 24, and then preferably carbonatoms is the saturated fatty acid of 16 ~ 24.
As fatty acid metal salts, cadmium stearate can be enumerated, cadmium laurate, cadmium ricinoleate, aphthenic acids cadmium, cadmium 2-ethylhexoate Application acid De system), barium stearate, barium laurate, barium ricinoleate, barium naphthanate, 2 ethyl hexanoic acid barium Application acid system), calcium stearate, calcium laurate, ricinoleic acid calcium, strontium stearate, zinc stearate, zinc laurate, zinc ricinoleate, 2 ethyl hexanoic acid zinc Application Suan Ami, lead stearate, binary lead stearate, lead naphthenate, stearic acid tin, aluminum stearate, dolomol etc.
From the view point of antifriction quality is high and mold fouling, roller pollute few, as the lipid acid forming fatty acid metal salt, preferred carbonatoms is the lipid acid of more than 10, and more preferably carbonatoms is the lipid acid of 16 ~ 24, and then preferably carbonatoms is the saturated fatty acid of 16 ~ 24.From the view point of stability, antifriction quality, as the metal forming fatty acid metal salt, preferably containing being selected from least one metal in the group that is made up of calcium, magnesium, zinc, lead, tin, iron, cadmium, aluminium, barium, cobalt, nickel, manganese, strontium, titanium, vanadium and copper, more preferably containing being selected from by least one metal in calcium, magnesium, zinc and the plumbous group formed.
As aliphatic amide, lauric amide, palmitic amide, stearic amide, arachidamide, behenamide, amine hydroxybenzene, eicosenoic acid acid amides, erucicamide (エ Le シ Application acid ア ミ De), erucicamide (エ Le カ acid ア ミ De), methylene bis stearic amide, ethylene bis stearic acid amide etc. can be enumerated.From the view point of antifriction quality is high and mold fouling, roller pollute few, the preferred carbonatoms of the aliphatic amide used in the present invention is the fatty acid amide of more than 12, more preferably carbonatoms is the fatty acid amide of 16 ~ 22, and then preferably carbonatoms is the unsaturated fatty acids acid amides of 16 ~ 22.
As the fatty acid ester in 1 molecule without more than 2 hydroxyls; the fatty acid ester of such as monohydroxy-alcohol, the fatty acid ester etc. of dibasic alcohol can be enumerated; specifically, two glyceryl ester, Witepsol W-S 55, acetylated monoglyceride, stearyl stearate, butyl stearate, ethylene glycol monostearate, Unister E 275 etc. can be enumerated.For not there is in 1 molecule used in the present invention the fatty acid ester of more than 2 hydroxyls, from the view point of antifriction quality is high and mold fouling, roller pollute few, the carbonatoms of the lipid acid in fatty acid ester preferably more than 10, more preferably 16 ~ 24.
The amount of lubricant (x) is more than 0.001 mass parts relative to multipolymer (a) 100 mass parts and below 2 mass parts, preferably more than 0.005 mass parts and below 1 mass parts and then preferably more than 0.01 mass parts and below 0.5 mass parts.Time fewer than 0.001 mass parts, the effect of above-mentioned lubricant (x) becomes insufficient, even if more than 2 mass parts, also the further effect of above-mentioned lubricant (x) cannot be obtained, moreover, these lubricants are also had to ooze out thus the worries such as the surfaces of tacky of products formed from products formed.Lubricant (x) can be used alone a kind, also two or more can be combinationally used.As lubricant (x), when the difference of use melting point is the multiple lubricant (x) of more than 5 DEG C, the effects such as antifriction quality can be played in wider temperature range, so preferably.
In the resin combination of one embodiment of the present invention as required and use lubricant (y1) comprise the direactive glyceride that carbonatoms is the saturated fatty acid of 10 ~ 24.Be the direactive glyceride of the saturated fatty acid of 10 ~ 24 as carbonatoms, the such as direactive glyceride such as glyceryl monostearate, single Glyceryl Behenate can be enumerated.
The lubricant (y2) used as required in the resin combination of another embodiment of the present invention comprises the fatty acid ester in 1 molecule with more than 2 hydroxyls.As the fatty acid ester in 1 molecule with more than 2 hydroxyls, polyol fat acid moieties ester can be enumerated, specifically, the sorbitan list/diester etc. such as tetramethylolmethane list/diester, sorbitan monostearate, sorbitan monopalmitate such as the direactive glyceride such as glyceryl monostearate, single Glyceryl Behenate, pentaerythritol monostearate, pentaerythritol stearic acid ester 2 can be enumerated.The carbonatoms in 1 molecule with the lipid acid of the fatty acid ester of more than 2 hydroxyls preferably 10 ~ 40, more preferably 10 ~ 24 and then preferably 14 ~ 24.In addition, this lipid acid can be unsaturated fatty acids, also can be saturated fatty acid.
The amount of lubricant (y1) or (y2) is below below below 0.1 mass parts, preferably 0.05 mass parts, more preferably 0.03 mass parts and then preferably below 0.01 mass parts relative to multipolymer (a) 100 mass parts.When the amount of lubricant (y1) or (y2) is too much, has generating gel during resin combination melt molding and cause the foreign matter defect of products formed, the tendency of bad order.
Resin combination of the present invention can contain various additive in addition as required.As described additive, thermo-stabilizer, antioxidant, thermal degradation when preventing agent, UV light absorber, photostabilizer, mineral filler, inorganic fibre or organic fibre, polymer processing aid, antistatic agent, fire retardant, dye pigment, tinting material, matting agent, light diffusing agent, shock-resistance modification agent, fluor, adhesive agent, tackifiers, softening agent, whipping agent etc. can be enumerated.The content of these additives suitably can set in the scope not damaging effect of the present invention.Such as, in resin combination 100 mass parts of the present invention, the content of antioxidant is preferably set to 0.01 ~ 1.0 mass parts, the content of UV light absorber is preferably set to 0.01 ~ 3.0 mass parts, the content of dye pigment is preferably set to 0.00001 ~ 0.01 mass parts.
In addition, resin combination of the present invention can in the scope not damaging effect of the present invention with multipolymer (a) beyond other mixed with polymers use.As other polymkeric substance described, the polyolefine such as polyethylene, polypropylene, poly-1-butylene, poly-4-methyl-1-pentene, polynorbornene can be enumerated; Ethene system ionomer; The phenylethylene resin series such as polystyrene, styrene-maleic anhydride copolymer, impact resistant polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; Copolymer of methyl methacrylatestyrene; The polyester such as polyethylene terephthalate, polybutylene terephthalate; The polymeric amide such as nylon 6, nylon66 fiber, polyamide elastomer; Polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene difluoride (PVDF), urethane, Noryl, polyphenylene sulfide, organic-silicon-modified resin; Acrylic rubber, organo-silicone rubber; The styrene series thermoplastic elastomers such as SEPS, SEBS, SIS; The ethylene series rubber etc. such as IR, EPR, EPDM.These other polymkeric substance can be used alone a kind, also multiple combination can be used.
Content in resin combination of the present invention, these other polymkeric substance preferably below 10 quality %, more preferably below 5 quality %, and then preferred below 2 quality %.
The preparation method of resin combination of the present invention is not particularly limited.Such as, can obtain as follows: mixing by carrying out at the temperature of multipolymer (a) more than softening temperature, add lubricant (x), the lubricant (y1) coordinated as required or lubricant (y2), the additive coordinated as required and other polymkeric substance wherein and mixing, thus obtain; Or can also obtain as follows: by multipolymer (a), lubricant (x), the lubricant (y1) coordinated as required or lubricant (y2), the additive coordinated as required and other polymer dissolution in a solvent, by this solution except desolventizing, thus obtain.
The second-order transition temperature of resin combination of the present invention is preferably more than more than 115 DEG C and less than 150 DEG C, more preferably 130 DEG C and less than 150 DEG C and then preferably more than 140 DEG C and less than 150 DEG C.When the second-order transition temperature of resin combination is in aforementioned range, thermotolerance and the shock-resistance of resin combination balance well, such as, being inhibited of the warpage of the lamination sheets of this thermoplastic resin such as resin combination and polycarbonate under hot and humid.
In addition, the saturated water absorption of resin combination of the present invention in the water of 23 DEG C preferably 0.3 ~ 1.8 quality %, more preferably 0.5 ~ 1.5 quality % and then preferred 0.5 ~ 1.0 quality %.When saturated water absorption is in aforementioned range, the warpage of the duplexer caused by moisture absorption can be suppressed.It should be noted that, saturated water absorption is the following value measured: this products formed to be immersed in the distilled water of 23 DEG C and through time ground quality measurement time in the increment rate of the quality of the quality in moment that the reaches balance products formed of more than three days relative to vacuum-drying.
Resin combination co-extrusion modling method of the present invention, T-shaped mold layer are folded the method for forming, extruded the extrusion mouldings such as cladding process, the injection mouldings such as inserts injection moulding, two-color injection-molded method, injection moulding of loosing core, sandwich injection moulding, injection extrusion forming method, blow molding method, rolling-molding method, extrusion forming method, the method heating and meltings such as slush moulding method are shaping, can obtain various products formed thus.Even if resin combination of the present invention at high temperature melt molding also not easily generates gel, be therefore also suitable for the manufacture of the products formed needing high-temperature molding condition.Resin combination of the present invention is suitable for the manufacture of the thin and broad products formed of sheet, film, plate etc. and so on.
Duplexer of the present invention comprises the duplexer of the layer of other material for having at least 1 layer of layer comprising resin combination of the present invention (hereinafter sometimes referred to resin combination [a]) and at least 1 layer.Other material used in duplexer of the present invention is not particularly limited.Such as, the organic materialss such as resin can be enumerated; The inorganic materials such as metal simple-substance, metal oxide.
The duplexer of one embodiment of the present invention comprises the duplexer of the layer of resin combination [b] for having at least 1 layer of layer comprising resin combination [a] and at least 1 layer.
The resin contained in resin combination [b] is not particularly limited.As this resin, the such as polyolefine such as polyethylene, polypropylene can be enumerated, polystyrene, (methyl) acrylic resin, polyester, polymeric amide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene difluoride (PVDF), urethane, Noryl, polyphenylene sulfide, organic-silicon-modified resin, polyether-ether-ketone, polysulfones, polyphenylene oxide, polyimide, polyetherimide; The heat-curing resins such as resol, melamine resin, silicone resin, epoxy; Energy ray-curable resin etc.These resins can be used alone a kind or two or more combinationally used.Among these, preferred thermoplastic resin, more preferably polycarbonate.
When using polycarbonate as resin, the amount of the polycarbonate contained in resin combination [b] is more than 90 quality %, more preferably more than 95 quality % and then preferred more than 98 quality % preferably.The weight-average molecular weight of described polycarbonate preferably 20, more than 000 and 100, less than 000.When the weight-average molecular weight of polycarbonate is in aforementioned range, the thermotolerance of resin combination [b] and shock-resistance improve, and can comprise the lamination sheets of resin combination [a] and resin combination [b] with excellent molding processibility and high productivity manufacture.In addition, the Mw/Mn of foregoing polycarbonates preferably 1.7 ~ 2.6, more preferably 1.7 ~ 2.3 and then preferably 1.7 ~ 2.0.It should be noted that, weight-average molecular weight Mw and number-average molecular weight Mn is the molecular weight converted with the polystyrene standard that GPC (gel permeation chromatography) measures.
The second-order transition temperature of the resin combination [b] used in the present invention preferably more than 130 DEG C and less than 160 DEG C.In addition, the second-order transition temperature of resin combination [b] is preferably same degree with the second-order transition temperature of resin combination [a].Specifically, the second-order transition temperature of resin combination [b] and the second-order transition temperature of resin combination [a] difference Δ Tg preferably less than 30 DEG C, more preferably less than 20 DEG C.When both second-order transition temperatures are same degree, inhibition layer lamination becomes higher in the effect of hot and humid lower generation warpage.
In order to improve resistance to pyrolytic, resistance to thermochromism, photostabilization etc., in the resin combination [b] used in the present invention, known additive can also be contained.As additive, antioxidant, thermal degradation when preventing agent, UV light absorber, photostabilizer, lubricant, releasing agent, polymer processing aid, antistatic agent, fire retardant, dye pigment, light diffusing agent, organic pigment, matting agent, shock-resistance modification agent, fluor etc. can be enumerated.
The duplexer of another embodiment of the present invention has the duplexer that at least 1 layer of layer comprising resin combination [a], at least 1 layer of layer comprising resin combination [b] and at least one layer function give layer [c].Functional imparting layer [c] is not particularly limited.Such as hard coat, antistatic backing, stain-proofing layer, friction can be enumerated and lower layer, antiglare layer, anti-reflection layer, adhesion layer, shock strength imparting layer etc.Functional imparting layer [c] can be formed by known method.Such as, hard coat can by the hard painting resin solution of coating, drying, solidification and obtaining.Low refractive index film and high refractive index film can be undertaken stacked by evaporation etc. and obtain by anti-reflection layer.Among functional imparting layer [c], the outermost that layer, antiglare layer, anti-reflection layer etc. are arranged on duplexer is usually lowered in such as hard coat, antistatic backing, stain-proofing layer, friction.Functional layer [c] both can only arrange a kind, also can arrange multiple.
Layer in duplexer of the present invention is formed and is not particularly limited.The layer comprising resin combination [a] is being denoted as [a] layer, the layer comprising resin combination [b] is denoted as [b] layer, when functional imparting layer [c] is denoted as " c " layer, as the lamination order of duplexer of the present invention, such as [a] layer/[b] layer can be enumerated, [a] layer/[b] layer/[a] layer, [b] layer/[a] layer/[b] layer, [a] layer/[b] layer/[a] layer/[b] layer/[a] layer, [a] layer/[b] layer/[c] layer, [c] layer/[a] layer/[b] layer, [c] layer/[a] layer/[b] layer/[c] layer, [c] layer/[a] layer/[b] layer/[a] layer/[c] layer, [a] layer/[b] layer/[c] layer/[b] layer/[a] layer etc.Such as, when [c] layer is hard coat, preferably [c] layer/[a] layer/[b] layer, [c] layer/[a] layer/[b] layer/[c] layer, [c] layer/[a] layer/[b] layer/[a] layer/[c] layer.
The present invention is useful in the lamination sheets of sheet, thin plate, film etc. and so on shape.When lamination sheets of the present invention being used as protection tectum, being preferably positioned at outermost mode according to resin combination [a] layer when observing from protected (protected face) and being configured.Such as; preferably the lamination sheets that the layer comprising [a] layer/[b] layer is formed is configured according to the order of [a] layer/[b] layer/protected, or the lamination sheets of the layer formation that will comprise [a] layer/[b] layer/[a] layer is configured according to the order of [a] layer/[b] layer/[a] layer/protected.
Total thickness preferably 0.2 ~ 2mm, the more preferably 0.5 ~ 1.5mm of lamination sheets of the present invention.When crossing thin, there is the tendency that rigidity becomes insufficient.Time blocked up, there is the tendency becoming the light-weighted obstacles such as liquid crystal indicator.
The thickness comprising the layer of resin combination [a] in lamination sheets of the present invention preferably in the scope of 0.02 ~ 0.5mm, more preferably in the scope of 0.03mm ~ 0.3mm, and then preferably in the scope of 0.05 ~ 0.1mm.When described thickness is less than 0.01mm, scuff resistance and weathering resistance deficiency sometimes.In addition, when more than 0.5mm, shock-resistance is not enough sometimes.
From the view point of the generation suppressing hot and humid lower warpage, lamination sheets of the present invention is preferably set to the lamination order of symmetry in a thickness direction, and then the thickness of more preferably each layer is also symmetrical.
The manufacture method of lamination sheets of the present invention is not particularly limited, such as, can the multi-layer forming method such as, inserts injection molding shaping by shaping, the multi-layer blow molding of multilayer extrusion, multilayer extrusion forming, multicolor injection manufactures.Among these multi-layer forming methods, from productive viewpoint, the multilayer extrusion of preferred resin composition [a] and resin combination [b] is shaping.
The method shaping to multilayer extrusion is not particularly limited, can adopt the known multilayer extrusion method of forming used in the manufacture of the multilayer layer lamination of thermoplastic resin, such as utilization possesses smooth T mould and the surperficial device having carried out the accurately machined polishing roll of minute surface carries out shaping.As the mode of T mould, can adopt the resin combination of heating and melting shape thing [a] and resin combination [b] before flowing into T mould stacked material feeding block formula or resin combination [a] and resin combination [b] at the multi-manifold etc. of T mould inner laminated.From the view point of the smoothness at the interface of each interlayer of raising constituting layer lamination, preferred multi-manifold.
Resin combination [a] and resin combination [b] preferably carry out melt filteration with strainer before carrying out multi-layer forming.Carry out multi-layer forming by each resin combination after using melt filteration, thus can obtain from the few lamination sheets of the defect such as foreign matter, gel.The strainer used in melt filteration is not particularly limited.This strainer suitably can be selected from known strainer based on viewpoints such as the filtering accuracies of use temperature, viscosity, requirement.As the concrete example of strainer, the non-woven fabrics formed by polypropylene, cotton, polyester, viscose rayon, glass fibre etc. can be enumerated; The cellulose membrane of impregnation resol; Metallic fiber nonwoven fabric sintered membrane; Metal powder sintering membrane; Wire netting; Or these combination.Wherein, from the view point of thermotolerance, weather resistance and carrying capacity, preferably by the stacked use of multi-disc metallic fiber nonwoven fabric sintered membrane.
The filtering accuracy of aforementioned filter is not particularly limited, preferably less than 30 μm, more preferably less than 10 μm, and then preferably less than 5 μm.
As the purposes of products formed of the present invention, duplexer or lamination sheets, the signboard parts such as such as advertising tower, vertical signboard, protruding-type signboard, fanlight signboard, roof signboard can be enumerated; The display members such as show window, dividing plate, shop displaying; The illuminace components such as fluorescent lamp shade, situation illuminating cover, lampshade, luminous ceiling, Guang Bi, chandelier; Pendant, the upholstery parts such as mirror; The building components such as the roof of door, cupola, safety window glass, partition, stair skirtboard, balcony skirtboard, leisure buildings; Aircraft window, pilot are with conveyor associated components such as sun visor, motorcycle, motorboat windsheild, motorbus tinted shade, automobile side sun visor, rear sun visor, front wing, head lamp cases; The e-machine parts such as sound equipment reflection label, three-dimensional acoustic shell, TV protective guard, vending machine; The medical machine parts such as foster-mother, roentgen machine parts; Machine associated components such as machinery cover, survey meter cover, experimental installation, scale, dial plate, viewing window etc.; The optical correlation parts such as front panel, diffuser plate of liquid crystal protecting sheet, light guiding plate, light guiding film, Fresnel lens, lens pillar, various indicating meter; The traffic associated components such as road sign, guide plate, bend convex mirror, sound proof panel; The film structural component such as surfacing, label film of automobile inside surfacing, mobile phone; The household appliances components such as the top panel of the cover material of washing machine, control panel, electric cooker; And greenhouse, large-scale tank, case tank, clock panel, bathtub, Public toilets, mat applying, game part, toy, welding time face protection face shield etc.
Products formed of the present invention can be used as the front panel of various indicating meter.Described front panel can by resin combination heating and melting and by the common forming method acquisition such as extrusion moulding, injection molding.
To using the display equipment of aforementioned front panel to be not particularly limited, the such as giant display device such as large screen television, advertisement indicating meter can be enumerated; The middle-size and small-size display equipment etc. of mobile phone, smart mobile phone and so on.
Aforementioned front panel is not limited only to plane, also can have curve form.Aforementioned curve form can be the shape bending along a direction, also can be along the bending shape of multiple directions.In order to make aforementioned front panel form curve form, aforementioned tabular formed body can have flexible nature, also can be shaped to the curve form of expectation in advance.
In addition, products formed of the present invention can also to have carried out the state of hard painting for aforementioned various uses by method effects on surfaces such as spraying, dip-coatings.By hard painting, the pencil hardness on surface uprises, and not easily scratches.In addition, except being firmly coated with, anti-dazzle photosphere can also be set, anti-reflection layer, intercept the functional layers such as the layer of hertzian wave, ultraviolet, near infrared ray etc.
Products formed of the present invention can be stacked via adhesive linkage, adhesion layer and other functional membrane, functional sheet, also can be undertaken stacked by film insert molding.As aforementioned functional membrane, functional sheet, light guiding plate, diffuser plate, anti-disperse film, nesa coating etc. can be enumerated.
Embodiment
Below illustrate that embodiment and comparative example further illustrate the present invention.But the present invention does not limit by these embodiments.
The methacrylic resin obtained in Production Example, embodiment 1a ~ 4a and comparative example 1a ~ 3a and the physical property of methacrylic resin composition measure by the following method.
< second-order transition temperature (Tg) >
Based on JISK7121, by methacrylic resin or methacrylic resin composition with 20 DEG C/min from room temperature to 200 DEG C, keep 10 minutes, cool to room temperature, then with 10 DEG C/min from room temperature to 200 DEG C, carry out under such temperature condition means of differential scanning calorimetry (DSC) analyze.Use the intermediate point second-order transition temperature obtained by the DSC curve measured during the 2nd intensification as the second-order transition temperature in the present invention.As determinator, use Shimadzu Seisakusho Ltd. DSC-50.
< saturated water absorption >
Use injection moulding machine (Sumitomo Heavy Industries, Ltd's system, SE-180DU-HP), under barrel temperature 280 DEG C, die temperature 75 DEG C and the shaping cycle condition of 1 minute, injection molding is carried out to methacrylic resin composition, acquisition thickness is 2mm, square test film that a limit is 50mm.By test film vacuum-drying 24 hours under the condition of temperature 80 DEG C, 5mmHg.Then, test film is placed cooling in moisture eliminator.Test film, immediately quality measurement (initial stage quality) is taken out from moisture eliminator.
Then, this test film is immersed in the distilled water of 23 DEG C.Test film is taken out from water, wipes the water of surface attachment away, quality measurement.This test film is immersed in distilled water, as described above quality measurement.Repeat to the dipping in distilled water, quality determination, till quality no longer changes.By following formula, the quality (water suction quality) when no longer being changed by quality and initial stage quality calculate saturated water absorption.
Saturated water absorption (%)=[(water suction quality-initial stage quality)/initial stage quality] × 100
< Production Example 1 >
The methacrylic acid three ring [5.2.1.0 of the methyl methacrylate of 63 mass parts, 35 mass parts is added in autoclave
2,6] last of the ten Heavenly stems-8-base ester, the methyl acrylate of 2 mass parts, the Diisopropyl azodicarboxylate of 0.06 mass parts, 1,1-bis-(tert-butyl hydroperoxide) hexanaphthene of 0.01 mass parts, the tetramethylolmethane tetrathio propionic ester of 0.47 mass parts, the water of 250 mass parts, the dispersion agent of 0.09 mass parts and 1.07 mass parts pH adjusting agent.
While stir in autoclave, make liquid temperature rise to 70 DEG C from room temperature, keep 120 minutes at 70 DEG C, then keep 60 minutes at 120 DEG C, carry out polyreaction.Make liquid temperature drop to room temperature, polymerization liquid is extracted out from autoclave.Taking out solids component by filtering from polymerization liquid, washing with water, warm air drying 24 hours at 80 DEG C.The solids component of acquisition is supplied to the hopper of twin screw extruder, at barrel temperature 230 DEG C, carries out melting mixing.Then, molten resin is extruded, obtain the granular methacrylic resin [A] that second-order transition temperature is 123 DEG C.
< Production Example 2 >
The pH adjusting agent of the methyl methacrylate of 96.5 mass parts, the methyl acrylate of 2.5 mass parts, the Diisopropyl azodicarboxylate of 0.06 mass parts, the n octylmercaptan of 0.25 mass parts, the water of 250 mass parts, the dispersion agent of 0.09 mass parts and 1.07 mass parts is added in autoclave.
While stir in autoclave, make liquid temperature rise to 70 DEG C from room temperature, keep 120 minutes at 70 DEG C, carry out polyreaction.Make liquid temperature drop to room temperature, polymerization liquid is extracted out from autoclave.Taking out solids component by filtering from polymerization liquid, washing with water, warm air drying 24 hours at 80 DEG C.The solids component of acquisition is supplied to the hopper of twin screw extruder, at barrel temperature 230 DEG C, carries out melting mixing.Then, molten resin is extruded, obtain the granular methacrylic resin [B] of second-order transition temperature 110 DEG C.
< embodiment 1a >
At barrel temperature 230 DEG C, melting mixing is carried out using methacrylic resin [A] 100 mass parts and as the hexadecanol 0.15 mass parts twin screw compounder of lubricant.Then, molten resin is extruded, obtain granular methacrylic resin composition [x1].The composition transitivity of methacrylic resin composition [x1] is shown in table 1.
< embodiment 2a >
Except with the addition of glyceryl monostearate 0.04 mass parts as lubricant further, obtain methacrylic resin composition [x2] by the method identical with embodiment 1a.The composition transitivity of methacrylic resin composition [x2] is shown in table 1.
< embodiment 3a >
Except with the addition of glyceryl monostearate 0.1 mass parts as lubricant further, obtain methacrylic resin composition [x3] by the method identical with embodiment 1a.The composition transitivity of methacrylic resin composition [x3] is shown in table 1.
< embodiment 4a >
Except by except the quantitative change of hexadecanol more 0.3 mass parts, obtain methacrylic resin composition [x4] by the method identical with embodiment 1a.The composition transitivity of methacrylic resin composition [x4] is shown in table 1.
< comparative example 1a >
Except changing to except glyceryl monostearate 0.15 mass parts by hexadecanol 0.15 mass parts, obtain methacrylic resin composition [x5] by the method identical with embodiment 1a.The composition transitivity of methacrylic resin composition [x5] is shown in table 1.
< comparative example 2a >
Except with the addition of hexadecanol 0.15 mass parts as lubricant further, obtain methacrylic resin composition [x6] by the method identical with comparative example 1a.The composition transitivity of methacrylic resin composition [x6] is shown in table 1.
< comparative example 3a >
Except changing to except methacrylic resin [B] by methacrylic resin [A], obtain granular methacrylic resin composition [x7] by the method identical with comparative example 1a.The composition transitivity of methacrylic resin composition [x7] is shown in table 1.
[table 1]
Table 1
As shown in above result, resin combination of the present invention (embodiment 1a ~ 4a) has high glass-transition temperature and low water absorbable.
By the following method the lamination sheets obtained in embodiment 1b ~ 4b and comparative example 1b ~ 4b is evaluated.
< outward appearance >
The methacrylic resin side surface of visual observation lamination sheets, counts foreign matter defect counts.
Will at 1m
2area in defect counts be the situation of less than 1 be recited as ◎, be the situation of 2 be recited as zero, be the situation of 3 be recited as △, be the situation of more than 4 be recited as ×.
< formability >
The methacrylic resin side surface of visual observation lamination sheets, checks with or without the step-like defect (release mark) orthogonal with Extrusion Flow direction.
The situation that cannot confirm step-like defect in the scope along Extrusion Flow direction 30cm is completely recited as ◎, the situation that almost cannot confirm is recited as zero, the situation that can confirm a little be recited as △, the situation that can clearly confirm is recited as ×.
< warpage variable quantity >
Cut out from lamination sheets the rectangle test film that minor face is 30mm, long limit is 150mm according to the mode that the direction vertical with Extrusion Flow direction becomes minor face, the direction parallel with Extrusion Flow direction becomes long limit.The minor face of test film is suspended in midair and places 72 hours among the environment chambers being set as temperature 23 DEG C, relative humidity 50%.Test film is placed cooling at 23 DEG C.Test film is warped into arciform.For the test film that warpage is arciform, this test film is placed on platform according to the mode mode of chevron (namely, be with test film) of ends contact platform, clearance detector is used to measure the ultimate range (usually, maximum near the long limit central part of test film) in the gap of platform and test film.Using this value as initial stage amount of warpage.
Then, be the minor face suspention of arciform test film by warpage, place 24 hours among the environment chambers being set as temperature 85 DEG C, relative humidity 85%.Test film is placed cooling at 23 DEG C.The ultimate range in the gap of platform and test film is measured by method same as described above.The difference of this measured value and initial stage amount of warpage is defined as " warpage variable quantity ".By warpage variable quantity be the situation of below 1mm be recited as ◎, by warpage variable quantity more than the situation of 1mm be recited as ×.
< embodiment 1b >
Polycarbonate (Zhu Hua StyronPloycarbonate Co., Ltd. system " SDPOLYCA (registered trademark) PCX " is dropped into continuously in the single screw extrusion machine [I] of the screw diameter 50mm being set as barrel temperature 280 DEG C, discharge-amount 30kg/ hour.Same below) particle.
The particle of methacrylic resin composition [x1] is dropped into continuously in the single screw extrusion machine [II] of the screw diameter 30mm being set as barrel temperature 220 DEG C, discharge-amount 2kg/ hour.
Polycarbonate and methacrylic resin composition [x1] is side by side extruded from forcing machine [I] and forcing machine [II], import linkage section (ジ ャ Application Network シ ョ Application Block ロ ッ Network), then use the multi-manifold of temperature 250 DEG C by polycarbonate and methacrylic resin composition [x1] co-extrusion modling, form sheet.Make this sheet between 1, No. 2 roller of 4 rollers of transverse direction, carry out lathe shaping (shaping of バ Application Network), with 4 rollers on one side transfer printing minute surfaces cool on one side, obtain by thickness to be the layer comprising methacrylic resin composition [x1] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm.The evaluation result of lamination sheets is shown in table 2.
< embodiment 2b >
Except methacrylic resin composition [x1] is changed to except methacrylic resin composition [x2], obtained by thickness to be the layer comprising methacrylic resin composition [x2] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm by the method identical with embodiment 1b.The evaluation result of lamination sheets is shown in table 2.
< embodiment 3b >
Except methacrylic resin composition [x1] is changed to except methacrylic resin composition [x3], obtained by thickness to be the layer comprising methacrylic resin composition [x3] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm by the method identical with embodiment 1b.The evaluation result of lamination sheets is shown in table 2.
< embodiment 4b >
Except methacrylic resin composition [x1] is changed to except methacrylic resin composition [x4], obtained by thickness to be the layer comprising methacrylic resin composition [x4] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm by the method identical with embodiment 1b.The evaluation result of lamination sheets is shown in table 2.
< comparative example 1b >
Except methacrylic resin composition [x1] is changed to except methacrylic resin composition [x5], obtained by thickness to be the layer comprising methacrylic resin composition [x5] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm by the method identical with embodiment 1b.The evaluation result of lamination sheets is shown in table 2.
< comparative example 2b >
Except methacrylic resin composition [x1] is changed to except methacrylic resin composition [x6], obtained by thickness to be the layer comprising methacrylic resin composition [x6] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm by the method identical with embodiment 1b.The evaluation result of lamination sheets is shown in table 2.
< comparative example 3b >
Except methacrylic resin composition [x1] is changed to except methacrylic resin composition [x7], obtained by thickness to be the layer comprising methacrylic resin composition [x7] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm by the method identical with embodiment 1b.The evaluation result of lamination sheets is shown in table 2.
< comparative example 4b >
Except methacrylic resin composition [x1] is changed to except methacrylic resin [A], obtained by thickness to be the layer of the methacrylic resin [A] of 60 μm and thickness be total thickness that the layer comprising polycarbonate of 940 μm forms the is lamination sheets of 1000 μm by the method identical with embodiment 1b.The evaluation result of lamination sheets is shown in table 2.
[table 2]
Table 2
As shown in above result, the foreign matter defect caused by the gel etc. that may generate during melt molding of duplexer of the present invention (embodiment 1b ~ 4b) is few and release mark is few.And then even if duplexer of the present invention is in hot and humid lower placement, warpage is also few.
Claims (12)
1. a resin combination, contains:
Multipolymer (a) 100 mass parts, described multipolymer (a) comprises from the structural unit of methacrylic acid ester ring type hydrocarbon ester and the structural unit from other monomer;
More than lubricant (x) 0.001 mass parts, below 2 mass parts, be selected from least one in the group be made up of the fatty acid ester that in higher alcohols, hydrocarbon, lipid acid, fatty acid metal salt, aliphatic amide and 1 molecule, not there are more than 2 hydroxyls described lubricant (x) comprising; With
Lubricant (y1) 0 ~ 0.1 mass parts, described lubricant (y1) comprises the direactive glyceride that carbonatoms is the saturated fatty acid of 10 ~ 24.
2. resin combination according to claim 1, wherein, the content of lubricant (y1) is 0 ~ 0.05 mass parts relative to multipolymer (a) 100 mass parts.
3. resin combination according to claim 1, wherein, the content of lubricant (y1) is 0 ~ 0.01 mass parts relative to multipolymer (a) 100 mass parts.
4. a resin combination, contains:
Multipolymer (a) 100 mass parts, described multipolymer (a) comprises from the structural unit of methacrylic acid ester ring type hydrocarbon ester and the structural unit from other monomer;
More than lubricant (x) 0.001 mass parts, below 2 mass parts, be selected from least one in the group be made up of the fatty acid ester that in higher alcohols, hydrocarbon, lipid acid, fatty acid metal salt, aliphatic amide and 1 molecule, not there are more than 2 hydroxyls described lubricant (x) comprising; With
Lubricant (y2) 0 ~ 0.1 mass parts, described lubricant (y2) comprises the fatty acid ester in 1 molecule with more than 2 hydroxyls.
5. resin combination according to claim 4, wherein, the content of lubricant (y2) is 0 ~ 0.05 mass parts relative to multipolymer (a) 100 mass parts.
6. resin combination according to claim 4, wherein, the content of lubricant (y2) is 0 ~ 0.01 mass parts relative to multipolymer (a) 100 mass parts.
7. the resin combination according to any one of claim 1 ~ 6, wherein, lubricant (x) comprise be selected from by carbonatoms be 12 ~ 18 aliphatic monobasic alcohol and carbonatoms be at least one in the group that forms of saturated fatty acid of 16 ~ 24.
8. the resin combination according to any one of claim 1 ~ 7, its second-order transition temperature is more than 115 DEG C and less than 150 DEG C.
9. the resin combination according to any one of claim 1 ~ 8, its saturated water absorption in the water of 23 DEG C is 0.3 ~ 1.8 quality %.
10. a products formed, comprises the resin combination according to any one of claim 1 ~ 9.
11. 1 kinds of duplexers, have: the layer comprising the resin combination according to any one of claim 1 ~ 9, and
Comprise second-order transition temperature and be more than 130 DEG C and the layer of the thermoplastic resin composition of less than 160 DEG C.
12. duplexers according to claim 11, wherein, second-order transition temperature is more than 130 DEG C and the thermoplastic resin composition of less than 160 DEG C is resin combination containing polycarbonate.
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| JP2014-012851 | 2014-01-27 | ||
| PCT/JP2014/074791 WO2015041311A1 (en) | 2013-09-20 | 2014-09-19 | Resin composition and molded article thereof |
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| CN105555863B CN105555863B (en) | 2017-07-18 |
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| CN110494460A (en) * | 2017-02-03 | 2019-11-22 | 卢塞特英国国际有限公司 | Polymer composition |
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| JP6679562B2 (en) * | 2015-02-20 | 2020-04-15 | 株式会社クラレ | Resin composition, molded article and laminate |
| JP6998948B2 (en) * | 2017-05-31 | 2022-01-18 | 株式会社クラレ | Laminated film, laminated molded body, and manufacturing method thereof |
| CN111670105B (en) * | 2018-02-02 | 2022-06-07 | 三菱化学株式会社 | Material for three-dimensional molding, filament for three-dimensional molding, wound body of the filament, and three-dimensional printer cartridge |
| CN112166021A (en) * | 2018-05-22 | 2021-01-01 | 旭化成株式会社 | Two-color injection molded body |
| WO2023120305A1 (en) * | 2021-12-20 | 2023-06-29 | 三菱ケミカル株式会社 | Methacrylic resin composition for injection molding or extrusion molding, resin molded body and method for producing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0453860A (en) * | 1990-06-20 | 1992-02-21 | Asahi Chem Ind Co Ltd | Methacrylate resin composition |
| CN1102420A (en) * | 1993-05-31 | 1995-05-10 | 可乐丽股份有限公司 | Methacrylic resin composition and method for production thereof |
| JP2002332390A (en) * | 2001-05-08 | 2002-11-22 | Hitachi Chem Co Ltd | Nonbirefringent optical resin composition and optical device using the same |
| JP4361393B2 (en) * | 2004-03-03 | 2009-11-11 | 株式会社クラレ | Methacrylic resin composition for optical member and optical member using the same |
| JP2010234640A (en) * | 2009-03-31 | 2010-10-21 | Sumitomo Chemical Co Ltd | Multilayered film |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3312611A1 (en) * | 1983-04-08 | 1984-10-11 | Röhm GmbH, 6100 Darmstadt | METHOD FOR PRODUCING UV-PROTECTED MULTILAYERED PLASTIC MOLDED BODIES |
| DE3333502A1 (en) * | 1983-09-16 | 1985-04-18 | Röhm GmbH, 6100 Darmstadt | THERMOPLASTIC PLASTIC MOLDS CONTAINING UV ABSORBER |
| JPS63184747A (en) * | 1987-01-28 | 1988-07-30 | Matsushita Electric Ind Co Ltd | Photosensitive coloring material |
| JPH083620B2 (en) * | 1987-05-29 | 1996-01-17 | コニカ株式会社 | Photothermographic material having a layer containing a novel blue light absorbing dye |
| JPH01124903A (en) * | 1987-11-10 | 1989-05-17 | Matsushita Electric Ind Co Ltd | Manufacture of thin film solid electrolyte |
| JP2728695B2 (en) * | 1988-10-15 | 1998-03-18 | 株式会社クラレ | Methacrylic resin composition |
| US5487885A (en) * | 1992-12-21 | 1996-01-30 | Biophysica, Inc. | Sunblocking polymers and their formulation |
| JPH06207074A (en) * | 1993-01-13 | 1994-07-26 | Mitsubishi Rayon Co Ltd | Methacrylic resin molding material |
| JPH06240093A (en) * | 1993-02-12 | 1994-08-30 | Sumitomo Chem Co Ltd | Methacrylate resin composition |
| JP3195854B2 (en) * | 1993-04-30 | 2001-08-06 | ダイセル化学工業株式会社 | Near-infrared absorbing polycarbonate resin laminate and molded product thereof |
| JPH10265530A (en) * | 1997-03-26 | 1998-10-06 | Asahi Chem Ind Co Ltd | Acrylic resin for photoconductive plate and resin composition |
| JP3870670B2 (en) * | 2000-06-29 | 2007-01-24 | 日立化成工業株式会社 | Non-birefringent pickup lens resin composition and pickup lens using the same |
| JP2002173572A (en) * | 2000-12-06 | 2002-06-21 | Hitachi Chem Co Ltd | Non-birefringent resin composition for optical use and optical element produced by using the composition |
| JP4047163B2 (en) * | 2002-12-27 | 2008-02-13 | 株式会社クラレ | Methacrylic resin composition for optical member and optical member using the same |
| JP5031598B2 (en) * | 2008-01-28 | 2012-09-19 | 株式会社クラレ | Polycarbonate resin laminate |
| JP2010167659A (en) * | 2009-01-22 | 2010-08-05 | Teijin Chem Ltd | Resin laminate |
| JP5642979B2 (en) * | 2010-02-16 | 2014-12-17 | 旭化成ケミカルズ株式会社 | Methacrylic resin composition |
| JP5514060B2 (en) * | 2010-02-19 | 2014-06-04 | 新日鉄住金化学株式会社 | Adhesive resin composition, cured product, and adhesive film |
| JP2012067240A (en) * | 2010-09-27 | 2012-04-05 | Nippon Steel Chem Co Ltd | Coverlay film and circuit board |
-
2014
- 2014-09-16 TW TW103131841A patent/TWI651333B/en not_active IP Right Cessation
- 2014-09-19 WO PCT/JP2014/074791 patent/WO2015041311A1/en active Application Filing
- 2014-09-19 CN CN201480051845.1A patent/CN105555863B/en not_active Expired - Fee Related
- 2014-09-19 JP JP2015537972A patent/JP6357163B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0453860A (en) * | 1990-06-20 | 1992-02-21 | Asahi Chem Ind Co Ltd | Methacrylate resin composition |
| CN1102420A (en) * | 1993-05-31 | 1995-05-10 | 可乐丽股份有限公司 | Methacrylic resin composition and method for production thereof |
| JP2002332390A (en) * | 2001-05-08 | 2002-11-22 | Hitachi Chem Co Ltd | Nonbirefringent optical resin composition and optical device using the same |
| JP4361393B2 (en) * | 2004-03-03 | 2009-11-11 | 株式会社クラレ | Methacrylic resin composition for optical member and optical member using the same |
| JP2010234640A (en) * | 2009-03-31 | 2010-10-21 | Sumitomo Chemical Co Ltd | Multilayered film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110494460A (en) * | 2017-02-03 | 2019-11-22 | 卢塞特英国国际有限公司 | Polymer composition |
| CN110494460B (en) * | 2017-02-03 | 2022-06-07 | 三菱化学英国有限公司 | Polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015041311A1 (en) | 2017-03-02 |
| TW201514210A (en) | 2015-04-16 |
| TWI651333B (en) | 2019-02-21 |
| JP6357163B2 (en) | 2018-07-11 |
| CN105555863B (en) | 2017-07-18 |
| WO2015041311A1 (en) | 2015-03-26 |
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