CN103998514A - Styrene-based optical resin composition - Google Patents

Styrene-based optical resin composition Download PDF

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Publication number
CN103998514A
CN103998514A CN201280061401.7A CN201280061401A CN103998514A CN 103998514 A CN103998514 A CN 103998514A CN 201280061401 A CN201280061401 A CN 201280061401A CN 103998514 A CN103998514 A CN 103998514A
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quality
styrene resin
resin composite
polyoxyethylene
content
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CN103998514B (en
Inventor
西野广平
藤松秀隆
塚田雅史
佐藤诚
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Toyo Styrene Co Ltd
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Toyo Styrene Co Ltd
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Priority to CN201710197060.0A priority Critical patent/CN106947177B/en
Priority to CN201710197076.1A priority patent/CN106947178B/en
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08K5/15—Heterocyclic compounds having oxygen in the ring
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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    • 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
    • C08K5/49—Phosphorus-containing compounds
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    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0013—Means for improving the coupling-in of light from the light source into the light guide
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
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Abstract

The present invention addresses the problem of providing a transparent styrene-based optical resin composition that minimizes a shortcoming of styrene-based resins, namely that environmental changes such as changes in temperature or humidity, or immersion in water cause the clouding (bleaching) of molded products thereof. The present invention provides a styrene-based optical resin composition that contains a styrene-based resin having a weight-average molecular weight of 150,000-700,000 and a hydrophilic additive, and is characterized in that the hydrophilic additive: is at least one substance selected from among polyoxyethylene surfactants having an average added mole number of ethylene oxide of 3-150 and/or polyethylene glycols having an average molecular weight of 200-10,000; has an HLB value of 5-20; and composes 0.4-2.0 mass% of the 100 mass% of the styrene-based resin composition.

Description

Optics styrene resin composite
Technical field
The present invention relates to suppress the transparent styrene resin composite of the albinism that causes because of environmental change.
Background technology
For phenylethylene resin series, there is the characteristics such as the excellent transparency, rigidity, low water absorbable, dimensional stability, and forming process is excellent, therefore by various forming methods such as injection molding, extrusion moulding, blow moldings, can be widely used as electric equipment products and various Industrial materials, food container, groceries etc.In addition, as the transparent purposes of performance, also can be used for the opticses such as light guiding plate.
As the backlight of liquid-crystal display, exist marginal ray (Light edge) the type backlight that light source is disposed to the positive type backlight just below of display unit and light source is disposed to side.Assembling light guiding plate is on edge light type backlight, photoconduction from side is played a role to liquid crystal panel, can in the extensive uses such as the indicating meter of TV, desktop personal computer, subnotebook PC, mobile phone, auto navigation (car navigation), use.Light guiding plate is used always take the acrylic resin that PMMA (polymethylmethacrylate) is representative, but water-absorbent is high, therefore has the situation that problem that products formed bends or size change.
For this reason, propose to use the MS resin of the multipolymer as vinylbenzene and (methyl) methyl acrylate that has improved these characteristics.The improving technologies such as variable color reduction when patent documentation 1 has proposed the water-absorbent of MS resin and moulding.
Yet, following and the light guiding plate of oligopolymer amount below 2% of the weight-average molecular weight (Mw) 6～170,000, residual monomer amount 3000ppm of vinylbenzene-(methyl) acrylic acid polymer resin disclosed in patent documentation 1, but its water-absorbent is high, and dimensional stability is not as take the tendency of the phenylethylene resin series that styrenic monomers is raw material.
On the other hand, though the water-absorbent of the phenylethylene resin series that the styrenic monomers of take is raw material is low, but there is the problem (albinism) that makes products formed generation gonorrhoea because of environmental changes such as temperature and humidity, warm water immersions (non-patent literature 1) in phenylethylene resin series, as the transparency of advantage according to the difference of purposes and damaged.Particularly, products formed is exposed to from hot and humid environment and is changed to room temperature environment, or, from room temperature environment, be changed to the situation of low temperature environment, thereby the moisture evenly existing in phenylethylene resin series becomes unstable and is separated and generates discoid defect, its result, there is the phenomenon of gonorrhoea in products formed inside.In addition, after the products formed of phenylethylene resin series is flooded more than the specified time in hot water, while taking out products formed, albefaction can occur, this is also the phenomenon because producing as aforementioned mechanism.
If products formed generation gonorrhoea in the situation of optical path length, exists and significantly reduces because scattering of light makes transmissivity, the problem that the brightness of indicating meter declines as light guiding plate.
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2003-075648 communique
[non-patent literature]
[non-patent literature 1] fiber association magazine, 34 volumes, No. 6,245～253 pages, 1978
Summary of the invention
[inventing problem to be solved]
Problem of the present invention is to provide the transparent styrene resin composite that has suppressed the albinism that causes because of environmental change.
[technique means of dealing with problems]
According to the present invention, a kind of optics styrene resin composite is provided, it contains weight-average molecular weight is 150,000～700,000 phenylethylene resin series and hydrophilic additive, wherein, described hydrophilic additive is for being selected from least a kind in the polyoxyethylene glycol that polyoxyethylene-type surfactant that the average addition mole number of oxyethane (ethylene oxide) is 3～150 and molecular-weight average are 200～10000, HLB value is 5～20, and the content in described styrene resin composite 100 quality % is 0.4～2.0 quality %.
The present inventor etc. further investigate because of the albinism that environmental change causes in order to suppress, and first recognize that interpolation hydrophilic additive is effective to the inhibition of albinism., further study and find that only adding wetting ability can not effectively suppress albinism.Therefore, further study, result is known: the individual formation of (1) hydrophilic additive tool, (2) this HLB value is the value in specified range, and during the amount that (3) this content is specified range, the inhibition that can maintain the stable on heating while albinism of styrene resin composite becomes high, and does not also damage the transparency of phenylethylene resin series.The action effect that can obtain this effect is still not clear, but only from can effectively bringing into play the situation of above-mentioned 3 conditions simultaneously, thinks the effect that multiplies each other causing due to these 3 conditions.
Below, illustration various embodiments of the present invention.
Preferably, described hydrophilic additive is the polyoxyethylene-type surfactant that the average addition mole number of oxyethane is 10～60, and the content in described styrene resin composite 100 quality % is 0.6～1.4 quality %.
Preferably, described hydrophilic additive is the polyoxyethylene-type surfactant that the average addition mole number of oxyethane is 13～35, and the content in described styrene resin composite 100 quality % is 0.6～0.9 quality %.
Preferably, the HLB value of described hydrophilic additive is 10～18.
Preferably, described polyoxyethylene-type surfactant is polyoxyethylene-type nonionic surfactant.
Preferably, polyoxyethylene-type nonionic surfactant be selected from the Voranol EP 2001 that following general formula (1) represents and/or in the polyoxyethylene fatty acid ester representing with following general formula (2) more than a kind.
(in formula, R represents the alkyl of carbonatoms 8～20.In addition, can be to there is multivalence Voranol EP 2001 till 6 valencys of a plurality of Voranol EP 2001 skeletons, there is the multivalence polyoxyethylene fatty acid ester till 6 valencys of a plurality of polyoxyethylene fatty acid ester skeletons.N is the addition mole number of integer and representative ring oxirane unit.)
Preferably, described hydrophilic additive is that molecular-weight average is 200～10000 polyoxyethylene glycol, and the content in described styrene resin composite 100 quality % is 0.6～1.4 quality %.
Preferably, described hydrophilic additive is that molecular-weight average is 200～1800 polyoxyethylene glycol.
Preferably, the content of described hydrophilic additive in described styrene resin composite 100 quality % is 0.6～0.9 quality %.
In addition, described phenylethylene resin series be by styrenic monomers and (methyl) acrylic acid copolymer and vinylbenzene-(methyl) acrylic copolymeric resin, the content of the styrenic monomers unit of phenylethylene resin series is that the content of 90.0～99.9 quality %, (methyl) acrylic acid units is 0.1～10.0 quality %.Wherein, using the total of the content of the styrenic monomers unit of phenylethylene resin series and (methyl) acrylic acid units as 100 quality %.
In addition, described phenylethylene resin series be by styrenic monomers and (methyl) acrylic acid copolymer and vinylbenzene-(methyl) acrylic copolymeric resin, the content of the styrenic monomers unit of phenylethylene resin series is that the content of 40.0～99.0 quality %, (methyl) acrylic acid units is 1.0～60.0 quality %.Wherein, using the total of the content of the styrenic monomers unit of phenylethylene resin series and (methyl) acrylic acid units as 100 quality %.
In addition, also contain 6-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-)-2,4,8,10-, tetra--tertiary butyl benzo (d, f) (1,3,2) dioxy phosphorus heterocycle heptane (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]-2,4,8,10-tetra-tert-butyl-dibenzo[d, f] [1,3,2] dioxaphosphepin).
In addition, containing phosphorous antioxidant and/or hindered phenol (hindered phenol) is antioxidant.
In addition, a kind of products formed, consists of with styrene resin composite above-mentioned optics.
In addition, a kind of light guiding plate, consists of above-mentioned products formed.
[invention effect]
Styrene resin composite of the present invention is compared to PMMA or MS resin, its water-absorbent is low and cheap, do not produce the albinism causing because of environmental change as the shortcoming of phenylethylene resin series, water white transparency is excellent, so can be applicable to bring into play the transparent purposes of phenylethylene resin series itself.
Embodiment
Below, embodiments of the present invention are elaborated.
< < phenylethylene resin series > >
Phenylethylene resin series polymerizable styrenic monomers of the present invention and obtaining.Styrenic monomers refers to, as the independent or mixture of more than two kinds of the vinylbenzene of aromatic vinyl base system monomer, alpha-methyl styrene, o-methyl styrene, p-methylstyrene etc., preferably vinylbenzene.In addition, in the scope that does not affect feature of the present invention, can carry out copolymerization with styrenic monomers, can enumerate the Acrylic Acid Monomers such as vinylformic acid, methacrylic acid, the vinyl cyanide such as vinyl cyanide, methacrylonitrile base monomer, the α such as the acrylic monomers such as butyl acrylate, ethyl propenoate, methyl acrylate, methyl methacrylate or maleic anhydride, fumaric acid, β-ethylene unsaturated carboxylic acid class, the imide series monomer classes such as phenyl maleimide, N-cyclohexylmaleimide.
Styrene resin composite is configured to good by phenylethylene resin series and various additive, the ratio of the phenylethylene resin series in styrene resin composite 100 quality % can be 90～99.6 quality %, is preferably 95～99.6 quality %.As the ratio of phenylethylene resin series, particularly, for example, be 90,91,92,93,94,95,96,97,98,99,99.6 quality %, also can be within any 2 numerical ranges in this illustrated numerical value.
As phenylethylene resin series, by styrenic monomers and (methyl) acrylic acid copolymer and vinylbenzene-(methyl) acrylic copolymeric resin time, the content of the styrenic monomers unit of phenylethylene resin series is 90.0～99.9 quality %, and the content of (methyl) acrylic acid units is that 0.1～10.0 quality % is good.Wherein, using the total of the content of styrenic monomers unit and (methyl) acrylic acid units as 100 quality %.(methyl) vinylformic acid refers to, vinylformic acid, methacrylic acid etc., be preferably methacrylic acid at this.
The mensuration of (methyl) acrylic acid units content in phenylethylene resin series is at room temperature to implement.Weigh the phenylethylene resin series of 0.5g, and be dissolved in after the mixing solutions of toluene/ethanol=8/2 (volume ratio), with the potassium hydroxide-ethanol solution of 0.1mol/L, carry out neutralization titration, endpoint detection, according to the usage quantity of potassium hydroxide-ethanol solution, calculate the content of the quality criteria of (methyl) acrylic acid units.At this, can use potential difference automatic titration device, utilize the AT-510 processed of capital of a country electronic industry Co., Ltd. to measure.Raw material styrenic monomers when the content of (methyl) acrylic acid units in phenylethylene resin series can be by phenylethylene resin series polymerization and the ratio of components of (methyl) Acrylic Acid Monomer are adjusted, but the phenylethylene resin series that also can mix the phenylethylene resin series that contains (methyl) acrylic acid units in the scope mixing and not contain (methyl) acrylic acid units is adjusted.
As phenylethylene resin series, by styrenic monomers and (methyl) acrylic ester copolymer and vinylbenzene-(methyl) acrylic copolymer resin time, the content of the styrenic monomers unit of preferred phenylethylene resin series is 40.0～99.0 quality %, and the content of (methyl) acrylic ester unit is 1.0～60.0 quality %.Wherein, using the total of the content of styrenic monomers unit and (methyl) acrylic ester unit as 100 quality %.(methyl) acrylate is, the methacrylic esters such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, the acrylate of methyl acrylate, ethyl propenoate etc. etc.
The content of (methyl) acrylic ester unit in phenylethylene resin series can utilize thermal cracking gas chromatography instrument to measure by following condition.
Pyrolysis oven: PYR-2A (Shimadzu Scisakusho Ltd's system)
Pyrolysis oven Temperature Setting: 525 ℃
Gas chromatograph: GC-14A (Shimadzu Scisakusho Ltd's system)
Post: glass 3mm footpath * 3m processed
Weighting agent: FFAP Chromsorb WAW10%
Injection, detector temperature: 250 ℃
Column temperature: 120 ℃
Carrier gas: nitrogen
As the polymerization process of phenylethylene resin series, can enumerate the known styrene polymerization methods such as block polymerization, solution polymerization process, suspension polymerization, emulsion polymerization method.Consider quality and productivity, mass polymerization, solution polymerization process are good, preferably successive polymerization.As solvent such as using the alkyl benzenes such as benzene, toluene, ethylbenzene and dimethylbenzene, the ketones such as acetone, methyl ethyl ketone, the aliphatic hydrocarbons such as hexane, hexanaphthene etc.
During phenylethylene resin series polymerization, can use as required polymerization starter, chain-transfer agent.As polymerization starter, radical polymerization initiator is good, can enumerate known habitual material, for example, 1, 1-bis-(t-butylperoxy) hexanaphthene (1, 1-di (t-butylperoxy) cyclohexane), 2, 2-bis-(t-butylperoxy) butane (2, 2-di (t-butylperoxy) butane), 2, 2-bis-(4, 4-bis--t-butylperoxy cyclohexyl) propane (2, 2-di (4, 4-di-t-butyl peroxy cyclohexyl) propane), 1, 1-bis-(tert-pentyl peroxy) hexanaphthene (1, 1-di (t-amyl peroxy) cyclohexane) the peroxy ketal class such as, hydrogen phosphide cumene (Cumene hydroperoxide), hydroperoxide (Hydroperoxide) classes such as tertbutanol peroxide (t-butyl hydroperoxide), tert-butyl peroxy acetate (t-Butyl peroxyacetate), alkyl peroxide (Alkyl peroxide) classes such as the different pelargonate of tert-pentyl peroxy (t-amyl (peroxy isononanoate)), tert-butyl peroxide isopropyl benzene (t-butyl cumyl peroxide), peroxidation di tert butyl carbonate (Di-t-butyl peroxide), dicumyl peroxide (Dicumyl peroxide), the dialkyl ester classes such as the tertiary own ester of peroxidation two (Di-t-hexyl peroxide), tert-butyl peroxy acetate (t-butylperoxy acetate), t-butyl peroxy benzoic ether (t-butyl peroxybenzoate), the peroxy esters classes such as t-butyl peroxy sec.-propyl monocarbonate (t-butyl peroxyisopropylmonocarbonate), BPIC (t butyl peroxy isopropyl carbonate) (t-butylperoxy isopropyl carbonate), the peroxy carbonates classes such as polyethers four (t-butylperoxy carbonic ether) (Polyether tetrakis (t-butyl peroxy carbonate)), N, two (hexanaphthene-1-formonitrile HCN) (N of N '-azo, N'-azobis (cyclohexane-1-carbonitrile)), N, two (2-the methylbutyronitrile) (N of N '-azo, N'-azobis (2-methyl butyronitrile)), N, N '-azo two (2, 4-methyl pentane nitrile) (N, N'-azobis (2, 4-dimethyl valeronitrile)), N, two [2-(hydroxymethyl) the propionitrile] (N of N '-azo, N'-azobis[2-(hydroxymethyl) propionitrile]) etc., can use a kind in these or combine two or more use.As chain-transfer agent, can enumerate aliphatics mercaptan, aromatic mercaptans, pentaphenylethane, alpha-methyl styrene dimer and terpinolene (Terpinolene) etc.
While carrying out successive polymerization, first with polymerization process, adopt known grooved steel basin or the tower reactor etc. of mixing completely, in order to reach target molecular weight, molecular weight distribution, reaction conversion ratio by regulating polymerization temperature etc. to control polyreaction.The polymeric solution containing through the polymkeric substance of polymerization process is transferred to devolatilization operation, removes unreacted monomer and polymer solvent.Devolatilization operation forms by the vacuum volatilization groove with having heaters with devolatilization forcing machine of venting hole etc.The polymkeric substance of the molten state through devolatilization operation is transferred to granulating working procedure.In granulating working procedure, by porous dies, molten resin is extruded into rope strand shape, by thermal cutting mode in cold cut mode, aerial thermal cutting mode, water, is processed into particle shape.
The weight-average molecular weight of phenylethylene resin series of the present invention is 150,000～700,000, and 180,000～500,000 is good.If be less than 150,000, the intensity of products formed becomes not enough, if surpass 700,000, formability significantly reduces.The kind of the solvent of using when the kind of temperature of reaction, the residence time that the weight-average molecular weight of phenylethylene resin series can be by polymerization process, the kind of polymerization starter and addition, chain-transfer agent and addition, polymerization and amount etc. are controlled.
As for weight-average molecular weight (Mw) and Z molecular-weight average (Mz), number molecular-weight average (Mn), use gel permeation chromatography (GPC) and measure by following condition.
GPC instrument kind: the Shodex GPC-101 processed of Showa Denko K. K
Post: the PLgel10 μ processed m MIXED-B of polymkeric substance laboratory company
Mobile phase: tetrahydrofuran (THF)
Sample solution concentration: 0.2 quality %
Temperature: 40 ℃ of furnace temperature, 35 ℃ of inlets, 35 ℃ of detectors
Detector: differential refractometer
Molecular weight of the present invention be the stripping curve based on monodisperse polystyrene calculate the molecular weight of each elution time and as calculating with the molecular weight of polystyrene conversion value.
< < hydrophilic additive > >
Hydrophilic additive refers to, have can with the compound of the hydrophilic radical of water mutual effect (hydrogen bond).Hydrophilic radical is preferably polyether chain.Polyether chain is the skeleton structure that ehter bond is connected and forms, such as enumerating synthetic polyoxyethylene chain, polyoxypropylene chains, the polyoxy butylene chain by the addition reaction of the epoxy alkane such as oxyethane (being sometimes recited as below EO), propylene oxide, butylene oxide ring, or by the synthetic polyglycerol chains such as dehydrating condensation of glycerine, polyoxyethylene chain is good.Polyether chain can have 1 group in 1 molecule, also can have many groups.
Among various hydrophilic additives like this, in the present invention, add at least a kind in the polyoxyethylene glycol be selected from polyoxyethylene-type surfactant that the average addition mole number of oxyethane is 3～150 and molecular-weight average 200～10000.In order to improve the inhibition of albinism, find must use in test the hydrophilic additive of so specific formation.
In addition, the HLB value of hydrophilic additive is 5～20.In order to improve the inhibition of albinism, find in test must use such hydrophilic additive with specific HLB value.HLB value is preferably 8～20, and more preferably 10～20, most preferably be 10～18.HLB (Hydrophilic-lipophilic blance) value means the hydrophilic value of additive, HLB value is 8～10 stable dispersion in water if, if surpass 10, from having the dispersion state of transparent feel, become and are consoluet state pellucidly.In thering is the nonionic surfactant of polyether chain, utilize HLB value=(molecular weight of hydrophilic radical part)/(molecular weight of additive) * 20 to calculate, such hydrophilic additive HLB value=0 of alkane of not containing hydrophilic radical, for the polyoxyethylene glycol only with hydrophilic radical, HLB value=20 are between 0～20 for nonionic surfactant HLB value.
Hydrophilic additive so that the mode that the content in styrene resin composite 100 quality % is 0.4～2.0 quality % add.In order to maintain the thermotolerance of styrene resin composite, improve the inhibition of albinism, discovery laboratory need to be added to become the mode of such content simultaneously.The content of the hydrophilic additive in styrene resin composite 100 quality % is preferably 0.7～1.6 quality % or 0.6～1.4 quality %, more preferably 0.6～0.9 quality %.
The loss on heating under 200 ℃ of temperature, nitrogen environment of hydrophilic additive is for good below 10 quality %.Loss on heating under 200 ℃ of temperature, nitrogen environment gas can utilize thermogravimetric analysis (TGA) to try to achieve, and the heat-up rate heating with 10 ℃/min from room temperature state under nitrogen environment is tried to achieve by the weight loss amount at 200 ℃ of temperature.Loss on heating under 200 ℃ of temperature, nitrogen environment surpasses the additive of 10 quality %, and volatility is high, when the forming process of phenylethylene resin series, produce gas, likely makes metal pattern, roller be polluted.
As the addition means of hydrophilic additive, can enumerate and utilize polymerization process, devolatilization operation, the granulating working procedure of phenylethylene resin series to add the method for mixing; Forcing machines while utilizing forming process etc. add the method for mixing; The phenylethylene resin series adding by nothing is mixed into the resin combination dilution that is adjusted into the hydrophilic additive of high density the method for target content etc., is not particularly limited.
For example can enumerate by the styrene resin composite of the hydrophilic additive that contains 0.5～50.0 quality % with without the phenylethylene resin series adding utilizes forcing machine or injection moulding forming machine and mix, obtain styrene resin composite, the products formed of aimed concn, the method for light guiding plate.
< polyoxyethylene-type surfactant >
As polyoxyethylene-type surfactant, can enumerate polyoxyethylene-type nonionic surfactant, polyoxyethylene-type anionic surfactant, polyoxyethylene-type cationic surfactant, polyoxyethylene-type amphoterics etc., polyoxyethylene-type nonionic surfactant is good.
Polyoxyethylene-type nonionic surfactant can enumerate the Voranol EP 2001 of following general formula (1) expression or polyoxyethylene fatty acid ester, the polyoxyethylene of following general formula (2) expression solidify Viscotrol C, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, but be selected from Voranol EP 2001 and/or polyoxyethylene fatty acid ester a kind above for good.In addition, even if use the multivalence polyoxyethylene fatty acid ester there is the multivalence Voranol EP 2001 of a plurality of Voranol EP 2001 skeletons or there are a plurality of polyoxyethylene fatty acid ester skeletons in a part in a part also can realize object of the present invention.The valence mumber of Voranol EP 2001, polyoxyethylene fatty acid ester refers to, the Voranol EP 2001 skeleton existing in a part or the quantity of polyoxyethylene fatty acid ester skeleton.
(in formula, R represents the alkyl of carbonatoms 8～20.In addition, can be the multivalence Voranol EP 2001 with the Voranol EP 2001 skeleton till a plurality of 6 valencys, can be also the multivalence polyoxyethylene fatty acid ester with the polyoxyethylene fatty acid ester skeleton till a plurality of 6 valencys.N is the addition mole number of integer and representative ring oxirane unit.)
Voranol EP 2001 is make oxyethane and alcohol addition and obtain, and polyoxyethylene fatty acid ester is to make oxyethane and lipid acid addition or make lipid acid and polyoxyethylene glycol direct esterification and obtaining, and the average addition mole number of oxyethane is 3～150.In order to improve the inhibition of albinism, from the known needs of experimental result, make average addition mole number in such specified range.Average addition mole number is preferably 7～100, and more preferably 10～60, more preferably 10～50, most preferably be 13～35.
As polyoxyethylene-type surfactant of the present invention, particularly for example can enumerate, alkylpolyoxyethylene, ceteth, octadecyl Soxylat A 25-7, octyl group alkylpolyoxyethylene, tetradecyl Soxylat A 25-7, the alkyl polyoxyethylene ethers such as 2-ethylhexyl Soxylat A 25-7, Tween-20, the polyoxyethylene sorbitan fatty acid ester of polyoxyethylene sorbitol acid anhydride three stearic acid etc., the polyoxyethylene sorbitol fatty acid ester of polyoxyethylene sorbitol four oleic acid esters etc., polyethylene glycol monolaurate, polyethylene glycol mono stearate, polyglycol distearate, the polyoxyethylene fatty acid ester of polyethylene glycol monooleate etc., polyoxyethylene solidifies Viscotrol C, polyoxyethylene monomethyl ether, polyoxyethylene dimethyl ether, polyoxyethylene glycerol ether, polyoxyethylene four oleic acid esters, polyoxyethylene three isostearates, polyoxyethylene coconut fatty acid glyceryl ester etc.
< polyoxyethylene glycol >
The molecular-weight average of the polyoxyethylene glycol using in the present invention is 200～10000.200～4000 is good, and 200～1800 for better, and 300～1000 is best.If the molecular-weight average of polyoxyethylene glycol is less than 200, when forming process, produce gas, pollute metal pattern or roller, thereby not preferred.In addition, if be greater than 10000, prevent that the effect of albinism from having the trend of reduction, and reduce with the intermiscibility of phenylethylene resin series, styrene resin composite, its products formed produce gonorrhoea.Molecular-weight average is the value calculating according to the concentration (based on JISK1557) of the hydroxyl that utilizes Tetra hydro Phthalic anhydride pyridine method to measure.
< < additive antioxidants > >
Styrene resin composite of the present invention can contain mineral oil in the scope that does not affect water white transparency of the present invention.In addition, also can contain internal lubricant, the hindered phenols such as stearic acid, ethylenebis stearic amide is that antioxidant, phosphorous antioxidant, sulphur are that antioxidant, lactone are that antioxidant, hindered amine are the additive of stablizer, UV light absorber, antistatic agent etc.In addition, as exterior lubricant, ethylenebis stearic amide is good, and in resin combination, content is that 30～200ppm is good.
For styrene resin composite of the present invention, because the deterioration of the optical characteristics such as the transmissivity of the feature as phenylethylene resin series, tone, the transparency is little, for example, so can, in the transparent field of performance, preferably use at optical applications with material as optics.As optical applications, can enumerate lens, light guiding plate, film, optical fiber, optical waveguides etc.
By add (c) 6-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-)-2 in styrene resin composite of the present invention, 4, 8, 10-tetra--tertiary butyl dibenzo (d, f) (1, 3, 2) dioxy phosphorus heterocycle heptane (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]-2, 4, 8, 10-tetra-tert-butyl-dibenzo[d, f] [1, 3, 2] dioxaphosphepin) (call " compounds X " in the following text), (d) phosphorous antioxidant, (e) hindered phenol is at least one in antioxidant, thereby can give long-term thermostability.The field of using between for a long time as optical applications, long-term thermal stability is one of key property.Long-term thermal stability shows the variation of the color harmony transmissivity causing because of heat of long-term chien shih used time, and the variation of the color harmony transmissivity of the styrene resin composite of excellent heat stability is little.For long-term thermal stability, can pass through accelerated test, at the lower keeping of high-temperature condition (60～90 ℃) products formed of the indeformable degree of resin, with color harmony transmissivity rheological parameters' change with time, evaluate.
Compounds X is in same molecular, to have the processing stabilizers that hindered phenol is the skeleton of antioxidant and the skeleton of phosphorous antioxidant.
As compounds X, the content in styrene resin composite 100 quality % is that 0.02～0.40 quality % is good, and 0.05～0.20 quality % is for better.If the content of compounds X is less than 0.02 quality %, long-term thermal stability is poor, and initial stage color harmony transmissivity is variation also.In addition, even if surpass 0.40 quality %, long-term thermostability also worsens.Long-term thermostability shows the variation of the color harmony transmissivity causing because of heat of long-term chien shih used time, and the variation of the color harmony transmissivity of the styrene resin composite of excellent heat stability is little.Long thermostability can be passed through accelerated test, at the lower keeping products formed of high-temperature condition (60～90 ℃) of the indeformable degree of resin, with the rheological parameters' change with time of color harmony transmissivity, evaluates.The content of the compounds X in styrene resin composite 100 quality %, being for example particularly 0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.10,0.15,0.20,0.25,0.30,0.35,0.40 quality %, can be also the value within the scope of any 2 in illustrative numerical value here.
By add compounds X in styrene resin composite of the present invention, thereby can give long-term thermal stability, even and if to add phosphorous antioxidant and/or hindered phenol be antioxidant, also can give long-term thermal stability.
Phosphorous antioxidant preferably contains 0.02～0.50 quality % in styrene resin composite 100 quality %, more preferably contains 0.05～0.40 quality %, further preferably contains 0.05～0.30 quality %.If be less than 0.02 quality %, long-term poor heat stability, initial stage color harmony transmissivity is also poor.Even if surpass 0.50 quality %, long-term thermostability also worsens.The content of the phosphorous antioxidant in styrene resin composite 100 quality %, being for example particularly 0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.10,0.15,0.20,0.25,0.30,0.35,0.40,0.45,0.50 quality %, can be also the value within the scope of any 2 in illustrative numerical value here.
Hindered phenol is that antioxidant preferably contains 0.02～0.50 quality % in styrene resin composite 100 quality %, more preferably contains 0.02～0.30 quality %, further preferably contains 0.05～0.30 quality %.If be less than 0.02 quality %, long-term poor heat stability, initial stage color harmony transmissivity is also poor.Even if surpass 0.50 quality %, long-term thermal stability also worsens.Hindered phenol in styrene resin composite 100 quality % is the content of antioxidant, being for example particularly 0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.10,0.15,0.20,0.25,0.30,0.35,0.40,0.45,0.50 quality %, can be also the value within the scope of any 2 in illustrative numerical value here.
Phosphorous antioxidant refers to the phosphorous acid esters of the phosphorus compound of trivalent.Phosphorous antioxidant, for example can enumerate, three (2, 4-bis--tert-butyl-phenyl) phosphorous acid ester, 2, 2 '-methylene-bis (4, 6-bis--tertiary butyl-1-phenyl oxygen) (2-ethylhexyl oxygen base) phosphorus, two (2, 4-dicumylphenyl) pentaerythritol diphosphites, 4, 4 '-xenyl di 2 ethylhexyl phosphonic acid four (2, 4-bis--tert-butyl-phenyl), 3, 9-two (2, 6-bis--tertiary butyl-4-methylphenoxy)-2, 4, 8, 10-tetra-oxa--3, 9-bis-phospha spiral shell (5.5) undecanes, ring neopentane four bases two (2, 4-bis--tert-butyl-phenyl phosphorous acid ester), two octadecyl pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, two-[2-methyl-4, 6-two-(1, 1-dimethyl ethyl) phenyl] ethide phosphite ester, 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, four (2, 4-bis--tertiary butyl-5-aminomethyl phenyl)-4, 4 '-xenyl, two phosphinates etc.As phosphorous antioxidant, the phosphorous antioxidant of hydrolytic resistance excellence is good, preferably three (2,4-bis--tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4,6-, bis--tertiary butyl-1-phenyl oxygen) (2-ethylhexyl oxygen) phosphorus, two (2,4-dicumylphenyl) pentaerythritol diphosphites, 3,9-two (2,6-bis--tertiary butyl-4-methylphenoxy)-2,4,8,10-tetra-oxa--3,9-bis-phospha spiral shell (5.5) undecanes.Be particularly preferably three (2,4-, bis--tert-butyl-phenyl) phosphorous acid ester.Phosphorous antioxidant can be used separately and also can be used together more than two kinds.
Hindered phenol is that antioxidant refers to, has the antioxidant of phenol hydroxyl at basic framework.Hindered phenol is antioxidant, for example, can enumerate octadecyl-3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester, two [2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1, the 1-dimethyl ethyls]-2,4,8 of 3,9-, 10-tetra-oxaspiros [5.5] undecane, ethylenebis (oxygen base ethylidene) two (3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters), two (octylsulfo the methyl)-ortho-cresols of 4,6-, two ((dodecyl sulfo-) the methyl)-ortho-cresols of 4,6-, 2,4-dimethyl-6-(1-methyl pentadecyl) phenol, four (methylene radical-3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester) methane, DL-alpha-tocopherol, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2-(1-(2-hydroxyl-3,5-bis--tert-pentyl phenyl) ethyl)-4,6-bis--tert-pentyl phenyl acrylate, 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), two-[3,3-pair-(4 '-hydroxyl-3 '-tert-butyl-phenyl)-butyric acid]-glycol ester etc.Be preferably octadecyl-3-(3,5-bis--tert-butyl-hydroxy phenyl) propionic ester, 3, two [the 2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1 of 9-, 1-dimethyl ethyl]-2,4,8,10-, tetra-oxaspiros [5.5] undecane, ethylenebis (oxygen base ethylidene) two (3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters).Hindered phenol is that antioxidant can be used separately and also can be used together more than two kinds.
As compounds X, phosphorous antioxidant and hindered phenol, be the addition means of antioxidant, can enumerate and utilize polymerization process, devolatilization operation, the granulating working procedure of phenylethylene resin series to add the method for mixing; Forcing machine during by forming process, injection moulding forming machine etc. add the method for mixing; The phenylethylene resin series adding by nothing is mixed into the resin combination dilution that is adjusted into these additives of high density the method for target content etc., is not particularly limited.
UV light absorber is to have the UV light absorber suppressing because of UV-induced deteriorated or painted function, such as enumerating the UV light absorber such as benzophenone series, benzotriazole system, triazine system, benzoic ether system, salicylate system, cyanoacrylate system, oxalic acid aniline system, malonic ester system, carbonamidine system.They can be used alone or in combination of two or more kinds, and also can be used together the photostabilizers such as hindered amine.
< < styrene resin composite > >
Styrene resin composite of the present invention can utilize injection-molded moulding, extrusion moulding, blow molding, compressed moulding etc. to obtain products formed according to the various forming methods of object.The shape of products formed can be the shape forming according to object, does not limit.For example tabular products formed if, can be used as light guiding plate.As the method that forms light guiding plate, the known reflection graphic patterns such as the back side (penetrating the opposition side of the face of light) set-point pattern that have at tabular products formed.While being processed into light guiding plate with resin board, the whole face of the end face of the plane of incidence of light or resin board is carried out milled processed and forms minute surface is good.In addition, in order to improve radiative homogeneity, and can be on the surface of tabular products formed (can radiative face) prism pattern is set.The surface of tabular products formed or the pattern at the back side can form when the moulding of tabular products formed, for example, if injection-molded moulding is metal pattern shape, if extrusion moulding forms pattern by roller transfer etc.
It is good that the vicat softening temperature of styrene resin composite of the present invention is 95～104 ℃, and 97～104 ℃ for better.If vicat softening temperature is less than 95 ℃, thermotolerance is not enough, has the possibility that makes products formed distortion according to environment for use.
For the mist degree of styrene resin composite of the present invention, form the products formed of 4mm thickness, be below 5%, to be good, be for better below 1%.
[embodiment]
Below, enumerate embodiment and illustrate the present invention, but the present invention is not limited to these embodiment.
< < tests 1 > >
(manufacture of phenylethylene resin series A-1～A-3)
Using the 1st reactor as complete mixed type steel basin and the 2nd reactor and as the 3rd reactor of the plug flow type reactor with static mixer, in the mode of series connection, be connected to form polymerization process, according to the manufacture of the condition enforcement phenylethylene resin series shown in table 1.The capacity of each reactor is respectively: the 1st reactor is that 39 liters, the 2nd reactor are that 39 liters, the 3rd reactor are 16 liters.The raw material of recording with table 1 forms raw materials solution, the continuous base feed solution of flow of recording with table 1 to the 1st reactor.At the entrance of the 1st reactor, to become the mode of the interpolation concentration (quality criteria is with respect to the concentration of total metering of benzene feedstock ethene and methacrylic acid) of table 1 record, to material solution, add polymerization starter, and evenly mix.The polymerization starter that table 1 is recorded is as follows:
Polymerization starter-1:2,2-bis-(4,4-t-butylperoxy cyclohexyl) propane (is used the PATORA A processed of Japan Oil Co.)
Polymerization starter-2:1,1-bis-(t-butylperoxy) hexanaphthene (is used the PERHEXA C processed of Japan Oil Co.)
At this, in the 3rd reactor, so that produce thermograde along flow direction, in middle portion, exit portion, to become the mode of the temperature of table 1, adjust.
Then; by the solution that contains polymkeric substance that utilizes the 3rd reactor to take out is continuously imported to by 2 sections that connect form with giving in the vacuum volatilization groove of hot device; to become the mode adjustment of the resin temperature of table 1 record, give the temperature of hot device; and the pressure of recording by table 1 is adjusted; thereby after unreacted benzene ethene is separated with ethylbenzene; utilize porous dies to extrude as rope strand shape, utilize the cooling and cut-out by rope strand of cold cut mode, carry out granulating.
[table 1]
* the concentration of 1 quality criteria with respect to vinylbenzene+methacrylic acid, vinylbenzene+methyl methacrylate
(embodiment 1-1～1-33, comparative example 1-1～1-9)
With the content shown in table 2, use the single axle extruding machine that screw diameter is 40mm, the melting mixing under 230 ℃ of barrel temperatures, screw speed 100rpm by phenylethylene resin series A-1～A-3 and additive, obtains particle.The additive using in table 2 is as follows.
B-1: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=25 (EMULGEN123P processed of Kao Corp)
B-2: the average addition of vinyl octadecyl Soxylat A 25-7 oxyethane mole number=12 (EMULGEN320P processed of Kao Corp)
B-3: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=9 (EMULGEN109P processed of Kao Corp)
B-4: the average addition of vinyl ceteth oxyethane mole number=7 (EMULGEN210P processed of Kao Corp)
B-5: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=30 (EMULGEN130K processed of Kao Corp)
B-6: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=47 (EMULGEN150 processed of Kao Corp)
B-7: the average addition of vinyl tetradecyl Soxylat A 25-7 oxyethane mole number=85 (EMULGEN4085 processed of Kao Corp)
B-8: the average addition of polyethylene glycol monolaurate oxyethane mole number=12 (EMANON1112 processed of Kao Corp)
B-9: the average addition of vinyl octadecyl Soxylat A 25-7 oxyethane mole number=6 (EMULGEN306P processed of Kao Corp)
B-10: polyoxyethylene solidifies Viscotrol C (the EMANON CH-40 processed of Kao Corp)
B-11: the polyoxyethylene glycol that molecular-weight average is 400 (PEG#400 processed of Japan Oil Co)
B-12: the polyoxyethylene glycol that molecular-weight average is 300 (PEG#300 processed of Japan Oil Co)
B-13: the polyoxyethylene glycol that molecular-weight average is 600 (PEG#600 processed of Japan Oil Co)
B-14: the polyoxyethylene glycol that molecular-weight average is 1000 (PEG#1000 processed of Japan Oil Co)
B-15: the polyoxyethylene glycol that molecular-weight average is 2000 (PEG#2000 processed of Japan Oil Co)
B-16: the polyoxyethylene glycol that molecular-weight average is 3100 (PEG#4000 processed of Japan Oil Co)
B-17: the polyoxyethylene glycol of molecular-weight average 8800 (PEG#6000 processed of Japan Oil Co)
B-18: polyoxyethylene monomethyl ether (the UNIOX M-550 processed of Japan Oil Co)
B-19: polyoxyethylene three Unimac 5680s (the UNIOX GT-20IS processed of Japan Oil Co)
B-20: octyl group alkylpolyoxyethylene (EMULGEN2025G processed of Kao Corp)
B-21: polyoxyethylene glycerol ether (the UNIOX G-750 processed of Japan Oil Co)
B-22: polyoxyethylene four oleic acid (the UNIOX ST-30E processed of Japan Oil Co)
B-23: stearyl alcohol (KALCOL8098 processed of Kao Corp)
B-24: glyceryl monostearate (the EXCEL S-95 processed of Kao Corp)
B-25: the polyoxyethylene glycol that molecular-weight average is 60000 (the ALKOX L-6 processed of Ming Cheng chemical industry Co., Ltd.)
B-26: the Polyglycerine that molecular-weight average is 500 (the Polyglycerine #500 processed of Ban Ben pharmaceutical industries Co., Ltd.)
The particle that use obtains carries out injection-molded moulding under 230 ℃ of barrel temperatures, metal pattern temperature 50 C, makes the tabular products formed moulding of 127 * 127 * 3mm thickness.
In addition, embodiment 1-33 be use screw diameter 40mm single axle extruding machine by phenylethylene resin series A-1 and additive B-1 melting mixing under 230 ℃ of barrel temperatures, screw speed 100rpm, once obtain after the particle of concentration 20 quality % of additive B-1, so that becoming the mode of the ratio of 1:24, this particle and phenylethylene resin series A-1 mix, and injection-molded moulding and the products formed that obtains.
＜MFR＞
The MFR of styrene resin composite (melt mass flow rate) is under 200 ℃, the condition of 49N load, based on JIS K7210, measures.
< initial stage tone is evaluated >
The test film that cuts out 115 * 85 * 3mm thickness from resulting tabular products formed, is ground end face is ground by polishing, obtains the tabular products formed that end face has minute surface.For the tabular products formed obtaining, use the visual spectrophotometer V-670 of ultraviolet ray of Japan Spectroscopy Corporation's system, under the incident light of size 20 * 1.6mm, 0 ° of angle of diffusion, measure the spectral transmission of the wavelength 350nm～800nm under optical path length 115mm, according to JIS K7105, calculate the YI value under 2 °, the visual angle of illuminant-C.The value obtaining is table 2 " YI115mm ".In addition, " the transmissivity 115mm " shown in table 2 represents the average transmittance of wavelength 380nm～780nm.
And then, " mist degree 4mm " in table 2 obtains as follows, , use the particle obtaining in above-mentioned operation, 220 ℃ of barrel temperatures, at 40 ℃ of metal pattern temperature, carry out injection-molded moulding, make the tabular products formed moulding of 55 * 50 * 4mm thickness, use the test film obtaining thus, utilize NDH5000 (Japanese electricity Se Industrial Co., Ltd system), based on JIS K-7105, measure and be worth, " YI4mm " of table 2 used this test film, adopt colour examining colour-difference-metre NDJ4000 (Japanese electricity Se Industrial Co., Ltd system), with reflection method, measure and the value that obtains.
< albefaction inhibition >
In addition, for the albinism of confirming to produce based on environmental change, by the tabular products formed at end face with minute surface 60 ℃, the environmental exposure of 90% relative humidity 150 hours, at 23 ℃, the environment of 50% relative humidity, take out test film, observation, in the inner albinism producing of products formed, is judged as follows as albefaction inhibition.
◎: do not produce albefaction completely
Zero: take out slightly albefaction after 1 hour, but disappear after 24 hours
△: take out albefaction after 1 hour, but almost disappear after 24 hours
*: take out significantly albefaction after 1 hour, even if also do not disappear through 24 hours
Softening (Vicat Softening) the temperature > of < dimension card
For vicat softening temperature, according to JIS K-7206, with 50 ℃/hr of heat-up rate, trial load 50N, try to achieve.
< comprehensive evaluation >
According to following benchmark, carry out comprehensive evaluation.
S: albefaction inhibition is that ◎ and vicat softening temperature are more than 100 ℃
A: can not fully meet the condition of S, albefaction inhibition is that ◎ and vicat softening temperature are more than 98 ℃, or albefaction inhibition be zero and vicat softening temperature be more than 100 ℃
B: can not fully meet the condition of A, albefaction inhibition is that ◎ and vicat softening temperature are more than 95 ℃, or albefaction inhibition be zero and vicat softening temperature be more than 98 ℃, or albefaction inhibition is that △ and vicat softening temperature are more than 100 ℃
C: can not fully meet above-mentioned arbitrary condition
The characteristic and the evaluation result that in table 2, show each resin combination.
[table 2]
The albefaction inhibition of the products formed that embodiment is relevant is excellent, and transmissivity and YI value all do not worsen and also excellence of the transparency and tone.In not adding hydrophilic additive or addition very few comparative example 1-1,1-2,1-4, the inhibition of albefaction present situation is insufficient.In the comparative example 1-3 and 1-5 of the excessive interpolation of hydrophilic additive, thermotolerance excessively reduces.In addition, in comparative example 1-6 and 1-7, the stearyl alcohol, the glyceryl monostearate that add respectively as hydrophilic additive are tested, but albefaction inhibition is insufficient.In addition, in comparative example 1-8 and 1-9, add large polyoxyethylene glycol, the Polyglycerine of molecular weight and test, but hydrophilic additive do not mix with phenylethylene resin series, products formed generation gonorrhoea.
From above result, in order to maintain thermotolerance, the transparency of styrene resin composite and to suppress albinism, must meet following 3 conditions: (1) hydrophilic additive has characteristic and forms, (2) its HLB value is the value in specific scope, and (3) its content amount that is specified range.Known with reference to embodiment 1-20～1-21, at phenylethylene resin series, also can access identical result while being styrenic monomers with the multipolymer of (methyl) vinylformic acid or (methyl) acrylate.
< < tests 2 > >
(embodiment 2-1～2-46)
Using the 1st reactor as complete mixed type steel basin and the 2nd reactor and as the 3rd reactor of the plug flow type reactor with static mixer, in the mode of series connection, be connected to form polymerization process, according to the manufacture of the condition enforcement phenylethylene resin series shown in table 1.The capacity of each reactor is respectively: the 1st reactor is that 39 liters, the 2nd reactor are that 39 liters, the 3rd reactor are 16 liters.The raw material of recording with table 1 forms raw materials solution, the continuous base feed solution of flow of recording with table 1 to the 1st reactor.
In addition, at the entrance of the 3rd reactor, the hydrophilic additive with polyether chain is added to become the mode of the kind shown in table 3 and content.The additive using and the kind of polyoxyethylene glycol are as follows.
B-1: the polyoxyethylene glycol that molecular-weight average is 400 (PEG#400 processed of Japan Oil Co)
B-2: the polyoxyethylene glycol that molecular-weight average is 1000 (PEG#1000 processed of Japan Oil Co)
B-3: the polyoxyethylene glycol that molecular-weight average is 2000 (PEG#2000 processed of Japan Oil Co)
B-4: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=25 (EMULGEN123P processed of Kao Corp)
B-5: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=12 (EMULGEN320P processed of Kao Corp)
B-6: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=9 (EMULGEN109P processed of Kao Corp)
B-7: the average addition of vinyl alkylpolyoxyethylene oxyethane mole number=30 (EMULGEN130K processed of Kao Corp)
B-8: the average addition of polyethylene glycol monolaurate oxyethane mole number=12 (EMANON1112 processed of Kao Corp)
Then, by the solution that contains polymkeric substance that is taken out to continuously the 3rd reactor import to by 2 sections that connect form with giving in the vacuum volatilization groove of hot device, after unreacted benzene ethene is separated with ethylbenzene, extrude into rope strand shape and cooling after, cut off granulation.At this, the resin temperature settings in the devolatilization groove in the 1st stage is 160 ℃, and the pressure of vacuum volatilization groove is 65kPa, and the resin temperature settings in the devolatilization layer in the 2nd stage is 235 ℃, and the pressure of vacuum volatilization groove is 0.8kPa.
Next, to become the content shown in table 3, the single axle extruding machine that uses screw diameter 40mm, obtains the particle of phenylethylene resin series and obtains particle as chasing after additivated compounds X, additive D and additive E melting mixing under 230 ℃ of barrel temperatures, screw speed 100rpm above-mentioned.The compounds X, D and the E that in table 3, use are shown in below.At this, compounds X represents 6-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-)-2,4,8,10-tetra--tertiary butyl dibenzo (d, f) (1,3,2) dioxy phosphorus heterocycle heptane, additive D represents phosphorous antioxidant, additive E represents that hindered phenol is antioxidant.
Compounds X: 6-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-)-2,4,8,10-tetra--tertiary butyl dibenzo (d, f) (1,3,2) dioxy phosphorus heterocycle heptane (the SUMILIZER GP processed of Sumitomo Chemical Co)
D-1: three (2,4-, bis--tert-butyl-phenyl) phosphorous acid ester (Irgafos168 processed of BASF Japan Co., Ltd.)
D-2:2,2 '-methylene-bis (4,6-, bis--tertiary butyl-1-phenyl oxygen) (2-ethylhexyl oxygen) phosphorus (the ADKSTAB HP-10 processed of Asahi Denka Co., Ltd.)
D-3: two (2,4-dicumylphenyl) pentaerythritol diphosphites (Dover Chemical Corporation Doverphos S-9228 processed)
D-4:3, two (2,6-, the bis--tertiary butyl-4-methylphenoxy)-2,4,8 of 9-, 10-tetra-oxa--3,9-bis-phospha spiral shell (5.5) undecanes (the ADKSTAB PEP-36 processed of Asahi Denka Co., Ltd.)
E-1: octadecyl-3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester (Irganox1076 processed of BASF Japan Co., Ltd.)
E-2:3, two [2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1, the 1-dimethyl ethyls]-2,4,8 of 9-, 10-tetra-oxaspiros [5.5] undecane (ADKSTABAO-80 processed of Asahi Denka Co., Ltd.)
E-3: ethylenebis (oxygen ethene) two (3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic ester) (Irganox245 processed of BASF Japan Co., Ltd.)
In addition, melt mass flow rate (MFR) is according to JIS K7210, under 200 ℃, the condition of 49N load, measures, and vicat softening temperature is according to JIS K7206, under 50 ℃/hr of heat-up rate, trial load 50N, measures.
In addition, use the particle obtaining, under 230 ℃ of barrel temperatures, metal pattern temperature 50 C, carry out injection-molded moulding, make the tabular products formed moulding of 127 * 127 * 3mm thickness.In order to evaluate long-term thermostability, and the products formed obtaining is taken care of 1000 hours in the furnace temperature of 80 ℃.In order to evaluate initial stage products formed before keeping and the products formed optical characteristics after keeping, and from tabular products formed, cut out the test film of 115 * 85 * 3mm thickness, grinds end face is ground by polishing, preparation has the tabular products formed of minute surface at end face.For the tabular products formed after grinding, use the visual spectrophotometer V-670 of ultraviolet ray of Japan Spectroscopy Corporation's system, under the incident light of size 20 * 1.6mm, 0 ° of angle of diffusion, measure the spectral transmission of the wavelength 350nm～800nm under optical path length 115mm, according to JIS K7105, calculate the YI value under 2 °, the visual angle of illuminant-C.Transmissivity shown in table 3 means the average transmittance of wavelength 380nm～780nm.
Next, based on following formula, calculate Δ YI poor.
Δ YI is poor=(have the YI compared to the initial stage chasing after in additivated embodiment poor)-(YI compared to the initial stage not chasing after in additivated embodiment is poor)
In an example, in chasing after additivated embodiment 2-2, the value poor compared to the YI at initial stage is 1.1, and not chasing after the YI difference compared to the initial stage in additivated embodiment 2-1 is 5.1, so the Δ YI of embodiment 2-2 is poor for-4.0.This value representation has by the raising effect of appending the long-term thermostability that additive (compounds X, phosphorus are that D, hindered phenol are E) causes, is worth littlely, represents that long-term thermostability improves effect larger.
In addition, for the albinism of confirming to produce because of environmental change, by the tabular products formed at end face with minute surface 60 ℃, the environmental exposure of 90% relative humidity 150 hours, at 23 ℃, the environment of 50% relative humidity, take out test film, observation, in the inner albinism producing of products formed, is judged as follows as albefaction inhibition.
◎: do not produce albefaction completely
Zero: take out slightly albefaction after 1 hour, but disappear after 24 hours
△: take out albefaction after 1 hour, but almost disappear after 24 hours
*: take out significantly albefaction after 1 hour, even if also do not disappear through 24 hours
< comprehensive evaluation >
According to following benchmark, by albefaction inhibition, Δ YI, poor, vicat softening temperature evaluation result quantizes.
Fractional value (◎ → 3 of albefaction inhibition; Zero → 2; △ → 1; * → 0)
The fractional value that Δ YI is poor (below 4.0 → 4;-below 3.5 → 3;-below 2.5 → 2;-below 1.5 → 1; In addition → 0)
The fractional value of vicat softening temperature (99 ℃ of above → 3; 97 ℃ of above → 2; 95 ℃ of above → 1; In addition → 0)
For the total of the fractional value obtaining according to said reference, according to following benchmark, carry out comprehensive evaluation.
S:10; A:9; B:8; C:7; Below D:6
Table 3 shows characteristic and the evaluation result of each resin combination.In embodiment 2-1～2-42, the phenylethylene resin series A-1 that use is made according to condition 1, in embodiment 2-43～2-44, use the phenylethylene resin series A-2 making according to condition 2, in embodiment 2-45～2-46, use the phenylethylene resin series A-3 making according to condition 3.
[table 3]
Known with reference to table 3, all the albefaction inhibition of embodiment is all excellent.In addition, comparing embodiment 2-1～2-35 and embodiment 2-36～2-42 are known, and when the content of compounds X is 0.02～0.40 quality %, long-term thermostability is excellent especially.In addition, known with reference to embodiment 2-43～2-46, when being styrenic monomers with the multipolymer of (methyl) vinylformic acid or (methyl) acrylate, phenylethylene resin series also can access same result.
< < tests 3 > >
(embodiment 3-1～3-36)
In test 3, do not add compounds X, adopt the method same with test 2 to evaluate.In embodiment 3-1～3-32, the phenylethylene resin series A-1 that use is made according to condition 1, in embodiment 3-33～3-34, use the phenylethylene resin series A-2 making according to condition 2, in embodiment 3-35～3-36, use the phenylethylene resin series A-3 making according to condition 3.
The results are shown in table 4.
[table 4]
Known with reference to table 4, all the albefaction inhibition of embodiment is all excellent.In addition, comparing embodiment 3-1～3-24 and embodiment 3-25～3-32 are known, and phosphorus is that the content of D is that 0.05～0.40 quality % and phenol are the content of E while being 0.02～0.30 quality %, and long-term thermal stability is excellent especially.In addition, known with reference to embodiment 3-33～3-36, phenylethylene resin series also can access same result while being the multipolymer of styrenic monomers and (methyl) vinylformic acid or (methyl) acrylate.
[utilizability in industry]
Styrene resin composite of the present invention can prevent the albinism causing because of environmental change, and the transparency and tone are excellent, so also can maintain the transparency as the advantage of phenylethylene resin series in the purposes that produces albinism because of environmental change, can preferably use all the time.
And, because the tonal variation of the styrene resin composite of long-term thermal stability excellence is little, so compared with the past, can in the situation that keeping the long-term transparency and tone, use.
For example, can be applicable to the light guiding plate such as indicating meter, subnotebook PC, mobile phone, auto navigation etc. of televisor, desktop personal computer.

Claims (15)

1. an optics styrene resin composite, it contains weight-average molecular weight is 150,000～700,000 phenylethylene resin series and hydrophilic additive, this optics is characterised in that with styrene resin composite, described hydrophilic additive is at least a kind that is selected from the polyoxyethylene glycol that polyoxyethylene-type surfactant that the average addition mole number of oxyethane is 3～150 and molecular-weight average are 200～10000, HLB value is 5～20, and the content in described styrene resin composite 100 quality % is 0.4～2.0 quality %.
2. optics styrene resin composite as claimed in claim 1, wherein, described hydrophilic additive is the polyoxyethylene-type surfactant that the average addition mole number of oxyethane is 10～60, and the content in described styrene resin composite 100 quality % is 0.6～1.4 quality %.
3. optics styrene resin composite as claimed in claim 1 or 2, wherein, described hydrophilic additive is the polyoxyethylene-type surfactant that the average addition mole number of oxyethane is 13～35, and the content in described styrene resin composite 100 quality % is 0.6～0.9 quality %.
4. optics styrene resin composite as claimed in claim 3, wherein, the HLB value of described hydrophilic additive is 10～18.
5. the optics styrene resin composite as described in any one in claim 1～4, wherein, described polyoxyethylene-type surfactant is polyoxyethylene-type nonionic surfactant.
6. the optics styrene resin composite as described in any one in claim 1～5, it is characterized in that, in the polyoxyethylene fatty acid ester that polyoxyethylene-type nonionic surfactant represents for the Voranol EP 2001 that is selected from following general formula (1) and represents and/or following general formula (2) more than a kind
In formula, R represents the alkyl of carbonatoms 8～20; And, can be to have multivalence Voranol EP 2001 till 6 valencys of a plurality of Voranol EP 2001 skeletons, have the multivalence polyoxyethylene fatty acid ester till 6 valencys of a plurality of polyoxyethylene fatty acid ester skeletons, n be the addition mole number of integer and representative ring oxirane unit.
7. optics styrene resin composite as claimed in claim 1, wherein, described hydrophilic additive is the polyoxyethylene glycol of molecular-weight average 200～10000, and the content in described styrene resin composite 100 quality % is 0.6～1.4 quality %.
8. optics styrene resin composite as claimed in claim 7, wherein, described hydrophilic additive is the polyoxyethylene glycol of molecular-weight average 200～1800.
9. optics styrene resin composite as claimed in claim 8, wherein, the content of described hydrophilic additive in described styrene resin composite 100 quality % is 0.6～0.9 quality %.
10. the optics styrene resin composite as described in any one in claim 1～9, it is characterized in that, described phenylethylene resin series be by styrenic monomers and (methyl) acrylic acid copolymer and vinylbenzene-(methyl) acrylic copolymeric resin, the content of the styrenic monomers unit of phenylethylene resin series is 90.0～99.9 quality %, the content of (methyl) acrylic acid units is 0.1～10.0 quality %, wherein, using the total of the content of the styrenic monomers unit of phenylethylene resin series and (methyl) acrylic acid units as 100 quality %.
11. optics styrene resin composites as described in any one in claim 1～9, it is characterized in that, described phenylethylene resin series be by styrenic monomers and (methyl) acrylic ester copolymer and vinylbenzene-(methyl) acrylic copolymer resin, the content of the styrenic monomers unit of phenylethylene resin series is 40.0～99.0 quality %, the content of (methyl) acrylic ester unit is 1.0～60.0 quality %, wherein, using the total of the content of the styrenic monomers unit of phenylethylene resin series and (methyl) acrylic ester unit as 100 quality %.
12. optics styrene resin composites as described in any one in claim 1～11, it is characterized in that, also contain 6-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-)-2,4,8,10-, tetra--tertiary butyl dibenzo (d, f) (1,3,2) dioxy phosphorus heterocycle heptane.
13. optics styrene resin composites as described in any one in claim 1～12, is characterized in that, containing phosphorous antioxidant and/or hindered phenol is antioxidant.
14. 1 kinds of products formeds, is characterized in that, the optics described in any one in claim 1～claim 13 forms with styrene resin composite.
15. 1 kinds of light guiding plates, is characterized in that, the products formed described in claim 14, consist of.
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