CN101490169B - Styrene resin composition and molded body - Google Patents
Styrene resin composition and molded body Download PDFInfo
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- CN101490169B CN101490169B CN2007800273914A CN200780027391A CN101490169B CN 101490169 B CN101490169 B CN 101490169B CN 2007800273914 A CN2007800273914 A CN 2007800273914A CN 200780027391 A CN200780027391 A CN 200780027391A CN 101490169 B CN101490169 B CN 101490169B
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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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
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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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
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/02—Simple or compound lenses with non-spherical faces
- G02B3/08—Simple or compound lenses with non-spherical faces with discontinuous faces, e.g. Fresnel lens
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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
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
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Abstract
Disclosed is a resin composition which enables to obtain a molded body excellent in dimensional stability, light resistance, optical characteristics and thermal stability. Also disclosed is a molded body of such a resin composition. Specifically disclosed is a styrene resin composition containing, per 100 parts by mass of a styrene copolymer composed of 90-99% by mass of a styrene monomer unit and 10-1% by mass of a (meth)acrylic acid monomer unit, 1-10 parts by mass of an unmelted compound having a refractive index difference of 0.05-0.15 from the styrene copolymer and an average particle diameter of 2-10 mum or 0.5-2.5 parts by mass of polyorganosiloxane crosslinked beads having an average particle diameter of 1-10 mum, 0.1-2 parts by mass of a hindered amine compound, and 0.1-2 parts by mass of a benzotriazole compound.
Description
Technical field
The present invention relates to the formed body of styrene resin composite and its moulding of use.
Background technology
Projectable and display image on the screen lens of the rear projection screen that uses in the projection TV etc.Owing to wish that these screen lens become clear and the visual angle is wide when the viewer observes, the therefore general formation that adopts the combination of lens formed bodys such as biconvex lens, Fresnel lens.In these lens formed bodys, be extensive use of excellent methacrylic resin such as the transparency, photostabilization, scoring resistance, forming process, these formed bodys generally wait moulding by extrusion forming, extrusion moulding, flow casting molding, injection molding.
The methacrylic resin that uses in such screen lens is owing to the water-intake rate height, and therefore the size by its formed body that forms changes because of suction easily.In order to address this problem, following method is disclosed, promptly, use makes the resin that carries out polymerization in the molten mixture that has aromatic vinyl monomer, (methyl) acrylic ester monomer and a multi-functional unsaturated monomer of vinylbenzene-diene interpolymer and obtain, and obtains Fresnel lens (with reference to patent documentation 1).
In addition, the formed material of the diffuser plate of liquid crystal TV also uses methacrylic resin, but also there is same problem in this technology.
Patent documentation 1: the spy opens flat 5-341101 communique
Summary of the invention
Problem of the present invention is to provide the resin combination of the formed body that can obtain dimensional stability, photostabilization, optical characteristics, thermostability and briliancy excellence and the formed body of this resin combination.
The inventor etc. have carried out conscientiously research in order to solve above-mentioned problem, found that, by containing with styrenic monomers unit and methacrylic acid monomer unit is the styrene resin composite injection molding or the extrusion moulding of the multipolymer of main component, specific not melting compound or the crosslinked pearl of organopolysiloxane and specific photostabilizer, can obtain the formed body of dimensional stability, photostabilization, light diffusing, excellent heat stability, thereby finish the present invention.
That is, the present invention has following main points.
1. styrene resin composite, with respect to styrene based copolymer 100 mass parts that contain styrenic monomers unit 90～99 quality % and (methyl) acrylic monomer unit 10～1 quality %, contain refringence with this styrene based copolymer and be 0.05～0.15 and median size be that not melting compound 1～10 mass parts of 2～10 μ m or crosslinked pearl 0.5～2.5 mass parts of organopolysiloxane, hindered amine based compound 0.1～2 mass parts and benzotriazole based compound 0.1～2 mass parts that median size is 1～10 μ m form.
2. as above-mentioned 1 described styrene resin composite, wherein, melting compound is not to contain the monomeric cross-linking copolymer of (methyl) acrylic ester as monomeric unit.
3. as above-mentioned 1 described styrene resin composite, wherein, melting compound is not the cross-linked polymer that contains methyl methacrylate and n-butyl acrylate as monomeric unit.
4. each described styrene resin composite as in above-mentioned 1～3, wherein, the hindered amine based compound is two (2,2,6,6-tetramethyl--4-piperidyl) sebates.
As above-mentioned 1～4 in each described styrene resin composite, wherein, the benzotriazole based compound is 2-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol.
As above-mentioned 1～5 in each described styrene resin composite, wherein,, also contain benzoxazole based compound 0.0005～0.5 mass parts with respect to styrene based copolymer 100 mass parts.
7. as above-mentioned 6 described styrene resin composites, wherein, the benzoxazole based compound is 2,5-thiophene two bases (the 5-tertiary butyl-1,3-benzoxazole).
As above-mentioned 1～7 in each described styrene resin composite, wherein, with respect to styrene based copolymer 100 mass parts, it is that tensio-active agent or negatively charged ion are that tensio-active agent and non-amine nonionic are tensio-active agent 0.1～3 mass parts that styrene resin composite also contains amine.
9. as above-mentioned 8 described styrene resin composites, wherein, amine is that tensio-active agent is N-hydroxyethyl-N-(2-hydroxyalkyl) amine.
10. as above-mentioned 8 described styrene resin composites, wherein, negatively charged ion is that the proportioning that tensio-active agent and non-amine nonionic are tensio-active agent is that negatively charged ion is that tensio-active agent/non-amine nonionic is tensio-active agent=0.5/99.5～15/85 (mass ratio).
11. as above-mentioned 8 or 10 described styrene resin composites, wherein, negatively charged ion is that tensio-active agent is the metal organic sulfonate of carbonatoms 10～14, non-amine nonionic is that tensio-active agent is a glycerin fatty acid ester.
12. a formed body is the formed body that is formed by each described styrene resin composite in above-mentioned 1～11, its thickness is 1～7mm.
13. as above-mentioned 12 described formed bodys, wherein, formed body is an injection molded article.
14. as above-mentioned 12 described formed bodys, wherein, formed body is the extrusion moulding body.
15. a light diffusing sheet uses each described formed body in above-mentioned 12～14.
Light diffusing, dimensional stability, photostabilization, thermostability, the briliancy excellence of the formed body that forms by styrene resin composite of the present invention.
Embodiment
Below, describe the present invention in detail.
As the styrenic monomers of using among the present invention, for example can enumerate vinylbenzene, alpha-methyl styrene, p-methylstyrene, to t-butyl styrene etc., be preferably vinylbenzene.
As (methyl) acrylic monomer that uses among the present invention, can enumerate for example vinylformic acid, methacrylic acid, ethylacrylic acid etc., preferable methyl vinylformic acid.
Styrene based copolymer contains styrenic monomers unit 90～99 quality %, preferred 91～97 quality % and (methyl) acrylic monomer unit 10～1 quality %, preferred 9～3 quality %.If the styrenic monomers unit surpasses 99 quality %, the thermostability of the formed body that then obtains sometimes descends, if less than 90 quality %, then deforms owing to moisture absorption makes formed body sometimes.
Styrene based copolymer, except above-mentioned styrenic monomers and (methyl) acrylic monomer, also can contain can with the ethene base system monomer of their copolymerization, its amount is measured 100 mass parts with respect to the total of styrenic monomers and methacrylate monomer, is preferably below 10 mass parts.
As this can copolymerization ethene base system monomer, can enumerate for example vinyl cyanide monomer such as vinyl cyanide or methacrylonitrile; Unsaturated carboxylic acid monomers such as vinylformic acid, maleic anhydride, toxilic acid, methylene-succinic acid, itaconic anhydride; Maleimide monomers such as maleimide, N-methyl maleimide, N-phenylmaleimide etc.They can use separately or will also use more than 2 kinds.
With respect to styrene based copolymer 100 mass parts, styrene resin composite of the present invention must contain 1～10 mass parts, the following not melting compound of preferred 2～9 mass parts.If the content of melting compound is not less than 1 mass parts, then turbidity, diffusivity reduce and light diffusing decline, if surpass 10 mass parts, then full light transmittance can descend.
Be not particularly limited as melting compound not, can enumerate and contain the cross-linking copolymer of (methyl) acrylic ester monomer as monomeric unit.Particularly, contain monomeric cross-linking copolymers such as methyl methacrylate, Jia Jibingxisuanyizhi, methyl acrylate, n-butyl acrylate, preferably contain the cross-linking copolymer of methyl methacrylate or contain methyl methacrylate and the cross-linking copolymer of n-butyl acrylate.
Melting compound does not preferably show the fusing point more than 200 ℃ or the compound of softening temperature under 1 atmospheric atmosphere.If fusing point or softening temperature be less than 200 ℃, then with the styrenic melt kneading time or when the extrusion moulding of styrene resin composite, injection molding, the easy fusion of this compound can not keep excellent optical sometimes.The refringence between melting compound and the styrene based copolymer is not 0.05～0.15, and is preferred 0.07～0.13, and median size is 2～10 μ m, is preferably 3～9 μ m.Light diffusing descends if the turbidity of the formed body that refringence less than 0.05, then obtains, diffusivity reduce, if surpass 0.15, then full light transmittance descends.In addition, if median size less than 2 μ m, the full light transmittance of the formed body that then obtains descends, if surpass 10 μ m, then turbidity and light diffusivity descend.
In addition, styrene resin composite of the present invention with respect to styrene based copolymer 100 mass parts, contains crosslinked pearl 0.5～2.5 mass parts of organopolysiloxane, preferred 0.8～2.2 mass parts.The content of the crosslinked pearl of organopolysiloxane is during less than 0.5 mass parts, and turbidity, diffusivity reduce and light diffusing descends, if surpass 2.5 mass parts, then full light transmittance descends.
In addition, the median size of melting compound and the crosslinked pearl of organopolysiloxane the value that is to use CoulterMultisizer (Beckman Coulter corporate system) to record not.Mensuration is undertaken by the laser diffraction light scattering method, solvent makes water, use homogenizer test portion to be disperseed 1 minute with the power of 200W, PIDS (Polarization Intensity Differential Scattering) concentration is adjusted to 45～55%, with the specific refractory power of water is 1.33 to measure, and the value that will be calculated by volume distributed median is as median size.
Styrene resin composite of the present invention, with respect to styrene based copolymer 100 mass parts, must contain hindered amine based compound 0.1～2 mass parts, preferred 0.2～1.2 mass parts and benzotriazole based compound 0.1～2 mass parts, preferred 0.2～1.2 mass parts.
Hindered amine based compound, benzotriazole based compound are during less than 0.1 mass parts, and photostabilization is insufficient, and when surpassing 2 mass parts, the yellow chromaticity of the light diffusing sheet that obtains strengthens and not preferred.
The hindered amine based compound is that amine is the light stability rising agent, can enumerate for example sebacic acid two (2,2,6,6-tetramethyl--1 (octyloxy)-4-piperidyl) ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) [[3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-] methyl] butyl malonic acid ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, methyl 1,2,2,6,6-pentamethyl--4-piperidyl sebate, two (2,2,6,6-tetramethyl--4-piperidyl) sebate etc.They can use separately or will also use more than 2 kinds.
In addition, the benzotriazole based compound is a UV light absorber, can enumerate for example 2-(2H-benzotriazole-2-yl)-p-cresol, two (1-methyl isophthalic acid-phenylethyl) phenol of 2-(2H-benzotriazole-2-yl)-4-6-, 2-[5-chlorine (2H)-benzotriazole-2-yl]-the 4-methyl]-6-(tertiary butyl) phenol, 2,4-di-t-butyl-6-(5-chlorobenzotriazole-2-yl) phenol, 2-(2H-benzotriazole-2-yl)-4, the 6-di-tert-pentyl phenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol etc., they can use separately or will more than 2 kinds and use.
Among the present invention, with respect to styrene based copolymer 100 mass parts, preferably further containing in resin combination as tinting material is benzoxazole based compound 0.0005～0.5 mass parts of so-called white dyes, more preferably 0.0008～0.2 mass parts, and this is comparatively ideal.Benzoxazole based compound content is 0.0005 mass parts when above, compares with less than 0.0005 mass parts the time, and the yellow chromaticity of the sheet that obtains reduces, and outward appearance further improves, and the full light transmittance of the sheet that obtains has the trend of raising, thereby is preferred.Be 0.5 mass parts when following, compare when surpassing 0.5 mass parts that the photostabilization of the multilayer tablet that obtains further improves, thereby is preferred.
As the benzoxazole based compound, for example can enumerate 2,5-thiophene two bases (the 5-tertiary butyl-1, the 3-benzoxazole), 2,5-thiophene two bases (the 5-tertiary butyl-1, the 3-benzoxazole) 10% with the mixture, 4 of dicyclohexyl phthalate 90%, 4 '-two (benzoxazoles-2-yl) Stilbene etc., they can use separately or with them and use.
Desire is given when being used for the dust-proof antistatic performance of the present invention, with respect to styrene based copolymer 100 mass parts, preferably further containing amine is that tensio-active agent or negatively charged ion are tensio-active agent and non-amine nonionic surfactant 0.1～3 mass parts, more preferably contains 0.1～2.5 mass parts.If amine is tensio-active agent or negatively charged ion be tensio-active agent and non-amine nonionic be tensio-active agent more than 0.1 mass parts, then compare with less than 0.1 mass parts the time, can obtain sufficient anti-static effect.If surpass 3 mass parts, and when 3 mass parts are following, to compare, the sheet of gained may variable color.
As amine is tensio-active agent, can enumerate for example alkyl diethanolamine, polyoxyethylene alkyl amine, alkyl diglycollic amide, polyoxyethylene alkylamide, N-hydroxyethyl-N-(2-hydroxyalkyl) amine etc., they can use separately or will also use more than 2 kinds.
As negatively charged ion is tensio-active agent, can enumerate metal organic sulfonate, specifically, and for example alkyl sodium sulfonate, alkylsulphonic acid lithium, sodium alkyl benzene sulfonate, alkyl benzene sulphonate (ABS) lithium etc.Wherein preferably use alkyl sodium sulfonate.More preferably carbonatoms is 10～14 alkyl sodium sulfonate.They can use separately or will also use more than 2 kinds.
As non-amine nonionic is tensio-active agent, can enumerate for example Voranol EP 2001, polyoxyethylene fatty acid ester, glycerin fatty acid ester.Wherein, preferably use glycerin fatty acid ester.They can use separately or will also use more than 2 kinds.
With above-mentioned negatively charged ion is that tensio-active agent and non-amine nonionic are tensio-active agent and time spent, if with negatively charged ion is that tensio-active agent/non-amine nonionic is that tensio-active agent is the ratio use of 0.5/99.5～15/85 (mass ratio), preferred 5/95～12/88 (mass ratio), then can obtain excellent antistatic performance.
There is no particular limitation for the manufacture method of styrene based copolymer of the present invention, can preferably adopt mass polymerization, suspension polymerization, solution polymerization process, emulsion polymerization.
There is no particular limitation for the fitting method of not melting compound or the crosslinked pearl of organopolysiloxane, for example can enumerate before the styrene based copolymer polymerization, in the polymerization, the method that cooperates after the polymerization; By mix method that cooperates etc. with styrene based copolymer.
After with the styrene based copolymer granulating; when it is carried out melting mixing with melting compound not or the crosslinked pearl of organopolysiloxane; also there is no particular limitation for its blending means; for example can be by carrying out with known mixing devices such as Henschel mixer, drum mixers after the pre-mixing; re-use forcing machines such as single shaft forcing machine or biaxial extruder and carry out melt kneading, thus uniform mixing.
In addition, the material of following manufacturing can also be used for raw material, promptly, prepared beforehand the styrene based copolymer middle and high concentration be mixed with the high concentration mixture of melting compound not or the crosslinked pearl of organopolysiloxane, when injection/extrusion moulding, this high concentration mixture and styrene based copolymer done mix, making the content of melting compound not or the crosslinked pearl of organopolysiloxane is normality.
As required, can in styrene resin composite of the present invention, cooperate additive.For example, in order to improve flowability, release property, can cooperate softening agent, lubricant, silicone oil etc.In addition, in order further to improve thermostability, can cooperate thermo-stabilizer.
The thickness of formed body of the present invention is 1～7mm, is preferably 1.3～4mm.If, then can not obtain excellent light diffusing sometimes less than 1mm or above 7mm.
Embodiment
Below, specify the present invention by embodiment, but should be interpreted as the invention is not restricted to these embodiment.
The manufacturing of styrene based copolymer
The used following formation of groove in the manufacturing: the 1st complete tempering tank of the about 5L of volume the 2nd complete tempering tank with about 15L is connected in series, the 1st of preheater groove and the 2nd 2 of the grooves that volatilize that volatilize will be installed again be connected in series.In monomer solution 100 mass parts that constitute by the vinylbenzene 85 quality % that contain 4-tert-butyl catechol 0.1ppm, methacrylic acid 15 quality % that in reference example, obtain, mix ethylbenzene 15 mass parts, tert-butyl hydroperoxide sec.-propyl monocarbonate 0.01 mass parts, 2,4-phenylbenzene-4-methyl-1-pentene 0.2 mass parts is made material solution.This material solution is supplied in the 1st complete tempering tank that is controlled at 135 ℃ with the speed of 6.0kg per hour.Transformation efficiency in the 1st complete tempering tank exit is 28 quality %.From the 1st complete tempering tank, take out continuously afterwards, be supplied in the 2nd complete tempering tank that is controlled at 135 ℃.Transformation efficiency in the 2nd complete tempering tank exit is 63 quality %.Then from the 2nd complete tempering tank, take out continuously,, be directed into and be controlled at 67kPa, 160 ℃ the 1st volatilize in the groove with the preheater heating.From the 1st volatilization groove, take out continuously again,, be directed into and be controlled in 1.3kPa, 230 ℃ the 2nd volatilization groove, remove monomer with the preheater heating.Be extruded into strip and cut-out, thereby obtain granular styrene based copolymer (A-1).
Except using the monomer solution that constitutes by vinylbenzene 92 quality %, methacrylic acid 8 quality %, adopt the method identical to carry out with (A-1), obtain styrene based copolymer (A-2).
Except using the monomer solution that constitutes by vinylbenzene 96 quality %, methacrylic acid 4 quality %, adopt the method identical to carry out with (A-1), obtain styrene based copolymer (A-3).
Except using the monomer solution that constitutes by vinylbenzene 99.5 quality %, methacrylic acid 0.5 quality %, adopt the method identical to carry out with (A-1), obtain styrene based copolymer (A-4).
As the crosslinked pearl of organopolysiloxane (B) of melting compound not
As the crosslinked pearl of organopolysiloxane of melting compound not, use organic silica bead Tospearl 120 (median size 2 μ m of GE-TOSHIBASILICONE corporate system, specific refractory power 1.420) (B-1), Tospearl 2000B (median size 6 μ m, specific refractory power 1.420) (B-2), Tospearl3120 (median size 12 μ m, specific refractory power 1.420) (B-3).
As the not manufacturing of the MMA-nBA crosslinking copolymerization pearl (C) of melting compound
In the autoclave that has agitator, add methyl methacrylate 20 mass parts, n-butyl acrylate 80 mass parts, as Vinylstyrene 5 mass parts of linking agent, as benzoyl peroxide 0.2 mass parts of polymerization starter, as Sodium dodecylbenzene sulfonate 0.001 mass parts of suspension stabilizer and tricalcium phosphate 0.5 mass parts, pure water 200 mass parts, 95 ℃ of following polymerizations of temperature 6 hours, again in 130 ℃ of following polymerizations of temperature 2 hours.After reaction finishes, wash, dewater, drying, obtain crosslinked pearl (C).The median size of crosslinked pearl (C) is 4 μ m, and specific refractory power is 1.460.
As the not manufacturing of the crosslinked pearl of vinylbenzene-MMA (D) of melting compound
In the autoclave that has agitator, add vinylbenzene 60 mass parts, methyl methacrylate 40 mass parts, as Vinylstyrene 5 mass parts of linking agent, as benzoyl peroxide 0.2 mass parts of polymerization starter, as Sodium dodecylbenzene sulfonate 0.001 mass parts of suspension stabilizer and tricalcium phosphate 0.5 mass parts, pure water 200 mass parts, 95 ℃ of following polymerizations of temperature 6 hours, again in 130 ℃ of following polymerizations of temperature 2 hours.After reaction finishes, wash, dewater, drying, obtain crosslinked pearl (D).The median size of crosslinked pearl (D) is 8 μ m, and specific refractory power is 1.555.
As the not manufacturing of the crosslinked pearl of PMMA (E) of melting compound
In the autoclave that has agitator, add methyl methacrylate 100 mass parts, as Vinylstyrene 5 mass parts of linking agent, as benzoyl peroxide 0.2 mass parts of polymerization starter, as Sodium dodecylbenzene sulfonate 0.001 mass parts of suspension stabilizer and tricalcium phosphate 0.5 mass parts, pure water 200 mass parts, 95 ℃ of following polymerizations of temperature 6 hours, again in 130 ℃ of following polymerizations of temperature 2 hours.After reaction finishes, wash, dewater, drying, obtain crosslinked pearl (E-1).The median size of crosslinked pearl is 8 μ m, and specific refractory power is 1.494.
Except using tricalcium phosphate 1.5 mass parts, be that 1 μ m, specific refractory power are 1.494 crosslinked pearl (E-2) by obtaining median size with the same method for making of E-1.
In addition, except using tricalcium phosphate 1.0 mass parts, be that 3 μ m, specific refractory power are 1.494 crosslinked pearl (E-3) by obtaining median size with the same method for making of E-1.
And then, except using tricalcium phosphate 0.2 mass parts, be that 13 μ m, specific refractory power are 1.494 crosslinked pearl (E-4) by obtaining median size with the same method for making of E-1.
Tinting material (F)
As tinting material, use white dyes 2,5-thiophene two bases (the 5-tertiary butyl-1,3-benzoxazole) (Ciba corporate system UVITEX OB) (F-1), as the anthraquinone of coloring resin agent be derived prods (the system Diaresin BLUE J of Mitsubishi Chemical Ind) (F-2).
Tensio-active agent (G)
As amine is tensio-active agent, and (MIYOSHI grease corporate system Duspar125B) uses as (G-1) with N-hydroxyethyl-N-(2-hydroxyalkyl) amine.As negatively charged ion is that tensio-active agent uses sodium laurylsulfonate (G-2), is that nonionic is that tensio-active agent uses distearin (G-3) as non-amine.
According to (A-1)～(A-4) of the proportioning mixing shown in table 1-2～1-3 as styrene based copolymer; As not crosslinked pearl B-2, C, D, (E-1)～(E-4) of melting compound; Two (2,2,6,6-tetramethyl--4-piperidyl) sebates as the hindered amine based compound; As the 2-(2H-benzotriazole-2-yl)-4 of benzotriazole based compound, 6-di-tert-pentyl phenol; (F-1), (F-2) as tinting material; As amine is N-hydroxyethyl-N-(2-hydroxyalkyl) amine (G-1) of tensio-active agent; single shaft forcing machine with the 40mm diameter; in temperature is that 240 ℃, screw rod revolution are to mediate under the condition of 100rpm; carry out granulating, obtain showing the particle of the styrene resin composite 1-1～1-23 shown in 1-2～1-3.
Embodiment 1-1～1-10, comparative example 1-1～1-15
Use styrene resin composite 1-1～1-23, utilize 2 ounces of reciprocating type injection moulding machines of screw rod (society of Nigata ironworker institute system), in 230 ℃ of following injection moldings of barrel temperature, obtain the formed body that size 300mm * 300mm * 0.5mm is thick, 300mm * 300mm * 2mm is thick, 300mm * 300mm * 10mm is thick.
Estimate optical characteristics, photostabilization, dimensional stability (moisture absorption warpage), static electricity resistance (surface resistivity), the thermostability of gained formed body, be shown in table 1-4～1-6.
In addition, according to (A-1)～(A-4) of the proportioning mixing shown in table 2-2～2-3 as styrene based copolymer; As not crosslinked pearl (B-1)～(B-3), C, the D of melting compound; Two (2,2,6,6-tetramethyl--4-piperidyl) sebates as the hindered amine based compound; As the 2-(2H-benzotriazole-2-yl)-4 of benzotriazole based compound, 6-di-tert-pentyl phenol; (F-1), (F-2) as tinting material; (G-1)～(G-3) as tensio-active agent; single shaft forcing machine with the 40mm diameter; in temperature is that 240 ℃, screw rod revolution are to mediate under the condition of 100rpm, carries out granulating, obtains showing the particle of the styrene resin composite 2-1～2-23 shown in the 2-2.
Embodiment 2-1～2-10, comparative example 2-1～2-15
Use styrene resin composite 2-1～2-23, utilize the reciprocating type injection moulding machine of screw rod (society of Nigata ironworker institute system), in 230 ℃ of following injection moldings of barrel temperature, obtain the formed body that size 300mm * 300mm * 0.5mm is thick, 300mm * 300mm * 2mm is thick, 300mm * 300mm * 10mm is thick.
Estimate optical characteristics, photostabilization, dimensional stability (moisture absorption warpage), static electricity resistance (surface resistivity), the thermostability of gained formed body, be shown in table 2-3～2-5.
When turbidity more than 99%, full light transmittance more than 65%, diffusivity more than 17%, the b value below 1.0, briliancy is at 3500cm/m
2When above, can judge that optical characteristics is good.And to show excellent photostabilization, then aberration Δ E must will show excellent size stability less than 1, the moisture absorption warpage must will show excellent thermostability below 1mm, adding thermal distortion must be less than 1mm, show excellent static electricity resistance, the surface resistivity value is necessary for 10
12Below the Ω.
Embodiment 1-11,2-11
Use styrene resin composite 1-1,2-1, utilize the forcing machine of T mould mode to make sheet.In addition, use the full flight screw single shaft forcing machine of 65mm φ.When carrying out the moulding of sheet material, the operating temperature of each barrel is 230 ℃.The data of the optical characteristics of the extrudate piece of gained, photostabilization, moisture absorption warpage, thermostability, surface resistivity are shown in table 1-4, table 2-3.
[table 1-1]
Table 1-1
| Resin is formed (quality %) styrene/methacrylic acid | Specific refractory power | |
| Styrene based copolymer A-1 | 85.3/14.7 | 1.570 |
| Styrene based copolymer A-2 | 92.1/7.9 | 1.581 |
| Styrene based copolymer A-3 | 96.0/4.0 | 1.588 |
| Styrene based copolymer A-4 | 99.6/0.4 | 1.595 |
[table 1-2]
[table 1-3]
[table 1-4]
[table 1-5]
[table 1-6]
[table 2-2]
[table 2-3]
[table 2-4]
[table 2-5]
Each measuring method of the light diffusing sheet that obtains is as follows.
(1) full light transmittance, turbidity:, use Japanese electric look industrial's system HAZE determinator (NDH-2000) to measure according to ASTM D-1003.
(2) diffusivity: use Japanese electric look industrial system goniophotometer (GC5000L), measure the transmittance I of 0 ° of acceptance angle
0, 70 ° of acceptance angles transmittance I
70, calculate by following formula.
Diffusivity (%)=(I
70/ I
0) * 100
(3) photostabilization: use the smart mechanism of Japan to make the weather-proof instrument ATLAS of society of institute system xenon lamp CI65A, measure the aberration Δ E of irradiation after 400 hours.
(4) dimensional stability (moisture absorption warpage): the light diffusing sheet that will cut into 180mm * 180mm size, under 50 ℃, the atmosphere of humidity 80%, placed 7 days, before measure placing with vernier callipers and place the deflection of four jiaos of backs, with the value of its mean value, with the yardstick of this value as dimensional stability as the moisture absorption warpage.
(5) yellow chromaticity, aberration: use Japanese electric look corporate system colour-difference meter (∑-80), measure L, a and b, as the yardstick of yellow chromaticity with the b value representation.And the aberration Δ E of photostabilization evaluation is obtained by following formula.
ΔE＝((L-L′)
2+(a-a′)
2+(b-b′)
2)
1/2
Wherein, L, a and b are the form and aspect before photostabilization is estimated, and L ', a ' and b ' are the form and aspect of (behind the irradiation 400Hr) after the photostabilization evaluation.
(6) add thermal distortion: the light diffusing sheet that will cut into 300mm * 300mm size was placed 7 days under 80 ℃ atmosphere, measure to place the deflection of four jiaos of backs with vernier callipers, and its mean value as the value that adds thermal distortion, is worth yardstick as thermostability with this.
(7) static electricity resistance: use the surface resistivity of KAWAGUCHI corporate system to measure machine (R503), mensuration is according to the surface resistivity value of JIS K-6911 damping formed body after 24 hours under 23 ℃ of temperature, humidity 50%RH, with the yardstick of this value as static electricity resistance.
(8) briliancy: 9 of cold-cathode tubes that on reflector plate, are spaced diameter 5mm, length 200mm with 20mm, the 5mm place is provided with and cuts into the light diffusing sheet of 180mm * 180mm size above cold-cathode tube, and then loads diffusion barrier, prismatic lens, briliancy raising film thereon.Light cold-cathode tube in the darkroom,, use TOPCON corporate system brightness photometer (BM-7),, obtain its mean value with 30mm measuring space 36 points in the position of distance light diffusing sheet 1000mm.
Following the carrying out of evaluation beyond the light diffusing sheet.
(9) specific refractory power:, use Abb under wavelength 589nm, 23 ℃ atmosphere, to measure for melting compound not.In addition,, use digital index meter (ATAGO corporate system RX-2000), use the potassiumiodide saturated aqueous solution, under 25 ℃ of temperature, measure as contact liquid for styrene based copolymer.
(10) the methacrylic acid monomer unit Determination on content in the styrene based copolymer:
I. the mensuration of the total amount of methacrylic acid monomer unit in the styrene based copolymer and remaining methacrylic acid
1) add chloroform in styrene based copolymer 2g: alcohol mixed solution (2: 1) 100ml makes it dissolving.2) carry out titration to the 0.5% phenolphthalein ethanolic soln that wherein adds as indicator, and then with the 0.1N potassium hydroxide-ethanol solution.When the color of indicator was not disappeared in 30 seconds as terminal point.3), get chloroform as no-load (no load) test: alcohol mixed solution (2: 1) 100ml, carry out and 2) same operation.4) obtain methacrylic acid content in the styrene based copolymer by following formula.
Methacrylic acid content (%)=[(A-B) * M}/(S * 1000)] * 100
A:1) titer that needs in (ml)
B:3) titer that needs in (ml)
S: the quality of styrene based copolymer (g)
M: with the quality (8.6 (mg)) of the methacrylic acid of 0.1N potassium hydroxide-ethanol solution 1ml equivalent
II. the mensuration of remaining methacrylic acid amount in the styrene based copolymer
Styrene based copolymer 0.5g is dissolved among the chloroform 10ml, and with N, dinethylformamide is measured as interior mark, measures under following GC condition determination.
Device name: the corporate system GC14B of Shimadzu Seisakusho Ltd. fid detector
Post: glass column φ 3mm * 3m
Weighting agent: diethylene glycol succinate
Carrier gas: nitrogen
Temperature: 110 ℃ on post, 180 ℃ of inlets
III. obtain in the total amount of methacrylic acid monomer unit in the styrene based copolymer that from I, records and remaining methacrylic acid, the value that deducts the remaining methacrylic acid amount in the styrene based copolymer that records among the II and get is as the methacrylic acid monomer unit content in the styrene based copolymer.Wherein, for the measured value of the remaining methacrylic acid in the styrene based copolymer situation, remaining methacrylic acid amount as 0 quality %, is obtained the unitary content of methacrylic acid monomer in the styrene based copolymer less than 0.1 quality %.
(11) resin of styrene based copolymer is formed: styrol copolymer is dissolved in makes 2% solution in the deuterochloroform as measuring sample, carry out with FT-NMR (NEC corporate system FX-90Q type)
13C-NMR measures, and is calculated by the peak area of vinylbenzene and methyl methacrylate.
Utilizability on the industry
Multilayer tablet size temperature of the present invention, light resistance, light diffusing, static electricity resistance, briliancy excellence, particularly useful as the screen lens of rear projection screen of the picture of projection TV etc. etc.
In addition, quote the full content of Japanese patent application 2006-196516 number of filing an application on July 19th, 2006 and Japanese patent application 2006-209984 number specification sheets, claims and the summary of filing an application on August 1st, 2006 at this, as the disclosure of specification sheets of the present invention and introduce.
Claims (15)
1. styrene resin composite, with respect to styrene based copolymer 100 mass parts that contain styrenic monomers unit 91～97 quality % and (methyl) acrylic monomer unit 9～3 quality %, contain refringence with this styrene based copolymer and be 0.05～0.15 and median size be that not melting compound 1～10 mass parts of 2～10 μ m or crosslinked pearl 0.5～2.5 mass parts of organopolysiloxane, hindered amine based compound 0.1～2 mass parts and benzotriazole based compound 0.1～2 mass parts that median size is 1～10 μ m form.
2. styrene resin composite according to claim 1, wherein, melting compound is not to contain the monomeric cross-linking copolymer of (methyl) acrylic ester as monomeric unit.
3. styrene resin composite according to claim 1, wherein, melting compound is not the cross-linked polymer that contains methyl methacrylate and n-butyl acrylate as monomeric unit.
4. according to each described styrene resin composite in the claim 1～3, wherein, the hindered amine based compound is two (2,2,6,6-tetramethyl--4-piperidyl) sebates.
5. according to each described styrene resin composite in the claim 1～4, wherein, the benzotriazole based compound is 2-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol.
6. according to each described styrene resin composite in the claim 1～5, wherein,, also contain benzo with respect to styrene based copolymer 100 mass parts
Azole compounds 0.0005～0.5 mass parts.
7. styrene resin composite according to claim 6, wherein, benzo
Azole compounds is 2,5-thiophene two bases (the 5-tertiary butyl-1,3-benzo
Azoles).
8. according to each described styrene resin composite in the claim 1～7, wherein, with respect to styrene based copolymer 100 mass parts, it is that tensio-active agent or negatively charged ion are that tensio-active agent and non-amine nonionic are tensio-active agent 0.1～3 mass parts that styrene resin composite also contains amine.
9. styrene resin composite according to claim 8, wherein, amine is that tensio-active agent is N-hydroxyethyl-N-(2-hydroxyalkyl) amine.
10. styrene resin composite according to claim 8, wherein, negatively charged ion is the proportioning that tensio-active agent and non-amine nonionic are tensio-active agent, by quality ratio, is that negatively charged ion is that tensio-active agent/non-amine nonionic is tensio-active agent=0.5/99.5～15/85.
11. according to Claim 8 or 10 described styrene resin composites, wherein, negatively charged ion is that tensio-active agent is the metal organic sulfonate of carbonatoms 10～14, and non-amine nonionic is that tensio-active agent is a glycerin fatty acid ester.
12. a formed body is the formed body that is formed by each described styrene resin composite in the claim 1～11, its thickness is 1～7mm.
13. formed body according to claim 12, wherein, formed body is an injection molded article.
14. formed body according to claim 12, wherein, formed body is the extrusion moulding body.
15. a light diffusing sheet uses each described formed body in the claim 12～14.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006196516 | 2006-07-19 | ||
| JP196516/2006 | 2006-07-19 | ||
| JP2006209984 | 2006-08-01 | ||
| JP209984/2006 | 2006-08-01 | ||
| PCT/JP2007/064272 WO2008010553A1 (en) | 2006-07-19 | 2007-07-19 | Styrene resin composition and molded body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101490169A CN101490169A (en) | 2009-07-22 |
| CN101490169B true CN101490169B (en) | 2011-06-29 |
Family
ID=38956885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800273914A Expired - Fee Related CN101490169B (en) | 2006-07-19 | 2007-07-19 | Styrene resin composition and molded body |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2008010553A1 (en) |
| KR (1) | KR20090040293A (en) |
| CN (1) | CN101490169B (en) |
| TW (1) | TWI458774B (en) |
| WO (1) | WO2008010553A1 (en) |
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| JP5736182B2 (en) * | 2011-02-07 | 2015-06-17 | 東洋スチレン株式会社 | Styrene- (meth) acrylic acid copolymer composition |
| JP7097221B2 (en) * | 2018-04-19 | 2022-07-07 | Ｐｓジャパン株式会社 | Flame-retardant styrene resin composition and molded product |
| TW202346381A (en) * | 2022-05-13 | 2023-12-01 | 日商電化股份有限公司 | Optical styrene-based resin composition, light guide plate, edge-light system flat-surface light source unit, light diffusion plate, and direct under-light system flat-surface light source unit |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006124522A (en) * | 2004-10-29 | 2006-05-18 | Denki Kagaku Kogyo Kk | Styrene-based resin composition and molded product of the same |
| WO2006057355A1 (en) * | 2004-11-26 | 2006-06-01 | Denki Kagaku Kogyo Kabushiki Kaisha | Multilayer sheet and light diffusion sheet |
| WO2006062171A1 (en) * | 2004-12-09 | 2006-06-15 | Denki Kagaku Kogyo Kabushiki Kaisha | Styrene resin composition and sheet thereof |
| WO2006068198A1 (en) * | 2004-12-22 | 2006-06-29 | Denki Kagaku Kogyo Kabushiki Kaisha | Styrene resin composition, molded body thereof, and diffusion plate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3243577B2 (en) * | 1992-06-08 | 2002-01-07 | 住友化学工業株式会社 | Impact resistant Fresnel lens |
| JP2001329431A (en) * | 2000-05-18 | 2001-11-27 | Kuraray Co Ltd | Conjugate fiber |
| JP3934489B2 (en) * | 2002-06-12 | 2007-06-20 | 株式会社日本触媒 | Method and apparatus for producing (meth) acrylic acid polymer |
| JP3912546B2 (en) * | 2004-10-28 | 2007-05-09 | ライオン株式会社 | Shampoo composition |
-
2007
- 2007-07-19 JP JP2008525903A patent/JPWO2008010553A1/en active Pending
- 2007-07-19 TW TW096126417A patent/TWI458774B/en not_active IP Right Cessation
- 2007-07-19 CN CN2007800273914A patent/CN101490169B/en not_active Expired - Fee Related
- 2007-07-19 WO PCT/JP2007/064272 patent/WO2008010553A1/en active Application Filing
- 2007-07-19 KR KR1020097000997A patent/KR20090040293A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006124522A (en) * | 2004-10-29 | 2006-05-18 | Denki Kagaku Kogyo Kk | Styrene-based resin composition and molded product of the same |
| WO2006057355A1 (en) * | 2004-11-26 | 2006-06-01 | Denki Kagaku Kogyo Kabushiki Kaisha | Multilayer sheet and light diffusion sheet |
| WO2006062171A1 (en) * | 2004-12-09 | 2006-06-15 | Denki Kagaku Kogyo Kabushiki Kaisha | Styrene resin composition and sheet thereof |
| WO2006068198A1 (en) * | 2004-12-22 | 2006-06-29 | Denki Kagaku Kogyo Kabushiki Kaisha | Styrene resin composition, molded body thereof, and diffusion plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008010553A1 (en) | 2009-12-17 |
| CN101490169A (en) | 2009-07-22 |
| TWI458774B (en) | 2014-11-01 |
| TW200811233A (en) | 2008-03-01 |
| WO2008010553A1 (en) | 2008-01-24 |
| KR20090040293A (en) | 2009-04-23 |
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