CN106947178A - Optics styrene resin composite - Google Patents
Optics styrene resin composite Download PDFInfo
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- CN106947178A CN106947178A CN201710197076.1A CN201710197076A CN106947178A CN 106947178 A CN106947178 A CN 106947178A CN 201710197076 A CN201710197076 A CN 201710197076A CN 106947178 A CN106947178 A CN 106947178A
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
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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
- C08K5/49—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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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- 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
- G02B6/0065—Manufacturing aspects; Material aspects
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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
- C08K5/49—Phosphorus-containing compounds
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The present invention provides a kind of transparent styrene resin composite of (albinism) the problem of producing products formed gonorrhoea because of environmental changes such as temperature, humidity, warm water immersions for suppressing the shortcoming as phenylethylene resin series.The optics styrene resin composite of the present invention, it contains the phenylethylene resin series and hydrophilic additive that weight average molecular weight is 150,000~700,000, the styrene resin composite is characterised by, average addition molal quantity of the above-mentioned hydrophilic additive selected from oxirane is at least one kind of in 3~150 polyoxyethylene-type surfactant and the polyethylene glycol of mean molecule quantity 200~10000, and HLB value is 5~20 and the content in the above-mentioned mass % of styrene resin composite 100 is 0.4~2.0 mass %.
Description
The application is the divisional application of application publication number CN103998514A original application, and the applying date of original application is 2012 12
The moon 19, Application No. 201280061401.7, entitled " optics styrene resin composite ".
Technical field
The present invention relates to the transparent styrene resin composite that can suppress the albinism caused by environmental change.
Background technology
For phenylethylene resin series, with characteristics such as the excellent transparency, rigidity, low water absorbable, dimensional stabilitys,
And molding processibility is excellent, therefore by the various forming methods such as injection moulding, extrusion molding, blow molding, it is widely used as
Electric equipment products and various industrial materials, food container, groceries etc..In addition, being used as the purposes for playing the transparency, it can also be used to
The optical components such as light guide plate.
As the backlight of liquid crystal display, the positive just following type backlight that light source is configured to display device is there is
Lamp and marginal ray (Light edge) type backlight that light source is configured to side.Assembling light guiding plate is incited somebody to action on edge light type backlight
Light guide from side plays a role to liquid crystal panel, can be personal in TV, the display of desktop personal computer, notebook type
Used in the extensive uses such as computer, mobile phone, auto navigation (car navigation).Light guide plate is used with PMMA (poly- first always
Base methyl acrylate) be representative allyl resin, but water imbibition is high, therefore the problem of bent with products formed or size hair
The situation for changing.
Therefore, propose use improve these characteristics as styrene and the MS of the copolymer of (methyl) methyl acrylate
Resin.The improving technologies such as discoloration reduction when patent document 1 proposes water imbibition and the shaping of MS resins.
However, Patent Document 1 discloses the weight average molecular weight (Mw) of styrene-(methyl) acrylic acid series polymeric compounds resin
6~170,000, the light guide plate of below residual monomer amount 3000ppm and oligomer amount below 2%, but its water imbibition is high, and size
Stability is not as the tendency using styrenic monomers as the phenylethylene resin series of raw material.
On the other hand, though, polystyrene tree low using styrenic monomers as the water imbibition of the phenylethylene resin series of raw material
Fat is present makes the problem of gonorrhoea occurs for products formed (white because of environmental changes such as temperature and humidity, warm water immersions (non-patent literature 1)
Change phenomenon), it is damaged as the transparency of advantage according to the difference of purposes.Specifically, products formed is exposed to high from high temperature
Wet environment, which becomes, turns to room temperature environment, or, become from room temperature environment in the case of turning to low temperature environment, in phenylethylene resin series
The moisture of even presence becomes unstable and occurs to be separated to generate discoid defect, as a result, occurring inside products formed
The phenomenon of gonorrhoea.In addition, after the products formed of phenylethylene resin series impregnated into more than the stipulated time in the hot water, taking out products formed
When can occur albefaction, this is also the phenomenon because being produced such as foregoing mechanism.
If in the case that gonorrhoea, the optical path length as light guide plate occur for products formed, exist makes transmission because of light scattering
Rate is greatly reduced, the problem of brightness of display declines.
【Prior art literature】
【Patent document】
【Patent document 1】Japanese Unexamined Patent Publication 2003-075648 publications
【Non-patent literature】
【Non-patent literature 1】Fiber association magazine, volume 34, No. 6, page 245~253,1978
The content of the invention
【Invent problem to be solved】
The problem of the present invention is to provide the transparent polystyrene tree for inhibiting the albinism caused by environmental change
Oil/fat composition.
【The technological means solved the problems, such as】
According to the present invention there is provided a kind of optics styrene resin composite, its contain weight average molecular weight for 150,000~
700000 phenylethylene resin series and hydrophilic additive, wherein, the hydrophilic additive is selected from oxirane (ethylene
Oxide the polyoxyethylene-type surfactant and mean molecule quantity that average addition molal quantity) is 3~150 are 200~10000
Polyethylene glycol in it is at least one kind of, HLB value is 5~20, and containing in the mass % of styrene resin composite 100
Measure as 0.4~2.0 mass %.
The present inventor etc. are furtherd investigate to suppress the albinism caused by environmental change, first
The suppression for solving addition hydrophilic additive whitening phenomenon is effective.But, further carry out research and find only to add hydrophily
Albinism can not effectively be suppressed.Therefore, further studied, as a result understood：(1) hydrophilic additive tool is individual
Constitute, (2) HLB value be particular range in value, and (3) content be particular range amount when, be able to maintain that polystyrene
The inhibition of albinism becomes high while the heat resistance of resin combination, and does not also damage phenylethylene resin series
The transparency.The action effect that this effect can be obtained is still not clear, but only from can simultaneously effectively play above-mentioned 3 conditions
Situation set out, it is believed that be due to multiplication effect caused by this 3 conditions.
Hereinafter, the various embodiments of the present invention are illustrated.
It is preferred that, the hydrophilic additive is that the average addition molal quantity of oxirane is 10~60 polyoxyethylene-type surface
Activating agent, and content in the mass % of styrene resin composite 100 is 0.6~1.4 mass %.
It is preferred that, the hydrophilic additive is that the average addition molal quantity of oxirane is 13~35 polyoxyethylene-type surface
Activating agent, and content in the mass % of styrene resin composite 100 is 0.6~0.9 mass %.
It is preferred that, the HLB value of the hydrophilic additive is 10~18.
It is preferred that, the polyoxyethylene-type surfactant is polyoxyethylene-type nonionic surfactant.
It is preferred that, polyoxyethylene-type nonionic surfactant is the polyoxyethylene alkyl ether represented selected from following formulas (1)
And/or more than a kind in the polyoxyethylene fatty acid ester represented with following formulas (2).
(in formula, R represents the alkyl of carbon number 8~20.Furthermore it is possible to be 6 valencys with multiple polyoxyethylene alkyl ether skeletons
Untill multivalence polyoxyethylene alkyl ether, the multivalence polyoxyethylene untill 6 valencys with multiple polyoxyethylene fatty acid ester skeletons
Fatty acid ester.N is integer and represents the addition molal quantity of ethylene oxide unit.)
It is preferred that, the hydrophilic additive is the polyethylene glycol that mean molecule quantity is 200~10000, and in the styrene
Content in the mass % of based resin composition 100 is 0.6~1.4 mass %.
It is preferred that, the hydrophilic additive is the polyethylene glycol that mean molecule quantity is 200~1800.
It is preferred that, content of the hydrophilic additive in the mass % of styrene resin composite 100 be 0.6~
0.9 mass %.
In addition, the phenylethylene resin series are by styrenic monomers and styrene-(first obtained by (methyl) acrylic acid copolymer
Base) acrylic copolymeric resin, the content of the styrenic monomer unit of phenylethylene resin series is 90.0~99.9 mass %, (first
Base) acrylic acid units content be 0.1~10.0 mass %.Wherein, by the styrenic monomer unit of phenylethylene resin series and
The total of the content of (methyl) acrylic acid units is used as 100 mass %.
In addition, the phenylethylene resin series are by styrenic monomers and styrene-(first obtained by (methyl) acrylic acid copolymer
Base) acrylic copolymeric resin, the content of the styrenic monomer unit of phenylethylene resin series is 40.0~99.0 mass %, (first
Base) acrylic acid units content be 1.0~60.0 mass %.Wherein, by the styrenic monomer unit of phenylethylene resin series and
The total of the content of (methyl) acrylic acid units is used as 100 mass %.
In addition, also containing 6- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propoxyl group) -2,4,8,10- tetra--tert-butyl benzenes
And (d, f) (1,3,2) dioxy phospha cycloheptane (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, being antioxidant containing phosphorous antioxidant and/or hindered phenol (hindered phenol).
In addition, a kind of products formed, is made up of above-mentioned optics with styrene resin composite.
In addition, a kind of light guide plate, is made up of above-mentioned products formed.
【Invention effect】
The styrene resin composite of the present invention is compared to PMMA or MS resins, and its water imbibition is low and cheap, does not produce
As the albinism because of caused by environmental change of the shortcoming of phenylethylene resin series, colorless transparency is excellent, so can fit
For playing the transparent purposes of phenylethylene resin series in itself.
Embodiment
Hereinafter, embodiments of the present invention are described in detail.
《Phenylethylene resin series》
The present invention the polymerizable styrenic monomers of phenylethylene resin series and obtain.Styrenic monomers refer to, are used as aromatic series
Styrene, α-methylstyrene, o-methyl styrene, the p-methylstyrene of vinyl monomer etc. independent or two or more
Mixture, preferably styrene.In addition, can be total in the range of feature of present invention is not influenceed with styrenic monomers
It is poly-, the acrylic monomers such as acrylic acid, methacrylic acid can be enumerated, the cyanided vinyl monomer, propylene such as acrylonitrile, methacrylonitrile
The acrylic monomers such as acid butyl ester, ethyl acrylate, methyl acrylate, methyl methacrylate or maleic anhydride, fumaric acid etc.
α, β-ethylene unsaturated carboxylic acid's class, the imide series monomer class such as phenyl maleimide, N-cyclohexylmaleimide.
Styrene resin composite is made up of phenylethylene resin series and various additives and is preferred, in styrene resin composite
The ratio of phenylethylene resin series in 100 mass % can be 90~99.6 mass %, preferably 95~99.6 mass %.As
The ratio of phenylethylene resin series, specifically, for example, 90,91,92,93,94,95,96,97,98,99,99.6 mass %,
Can be within the scope of any 2 numerical value in illustrated numerical value herein.
As phenylethylene resin series, by styrenic monomers and styrene-(methyl) obtained by (methyl) acrylic acid copolymer
During acrylic copolymeric resin, the content of the styrenic monomer unit of phenylethylene resin series is 90.0~99.9 mass %, (first
Base) contents of acrylic acid units is preferred for 0.1~10.0 mass %.Wherein, by styrenic monomer unit and (methyl) propylene
The total of the content of acid unit is used as 100 mass %.(methyl) acrylic acid refers to, acrylic acid, methacrylic acid etc., herein preferably
For methacrylic acid.
The measure of (methyl) acrylic acid units content in phenylethylene resin series is to implement at room temperature.Weigh 0.5g benzene
Vinylite, and be dissolved in after the mixed solution of toluene/ethanol=8/2 (volume ratio), with 0.1mol/L potassium hydroxide second
Alcoholic solution carries out acid-base titration, detects terminal, according to the usage amount of potassium hydroxide-ethanol solution, calculates (methyl) acrylic acid units
Quality criteria content.Here, potential difference automatic titration device can be used, capital of a country electronics industry Co. Ltd. system AT- is utilized
510 are measured.When the content of (methyl) acrylic acid units in phenylethylene resin series can be polymerize by phenylethylene resin series
Raw material is that styrenic monomers and the ratio of components of (methyl) acrylic monomers are adjusted, but it is also possible to mixed in the range of mixing
Close the phenylethylene resin series containing (methyl) acrylic acid units and come with the phenylethylene resin series for not containing (methyl) acrylic acid units
It is adjusted.
As phenylethylene resin series, by styrenic monomers and styrene-(first obtained by (methyl) acrylic ester copolymer
Base) acrylic copolymer resin when, the content of the styrenic monomer unit of phenylethylene resin series preferably is 40.0~99.0
Quality %, the content of (methyl) acrylic ester unit is 1.0~60.0 mass %.Wherein, by styrenic monomer unit and (first
Base) total of content of acrylic ester unit is used as 100 mass %.(methyl) acrylate is, methyl methacrylate, methyl
The methacrylates such as ethyl acrylate, acrylate of methyl acrylate, ethyl acrylate etc. etc..
The content of (methyl) acrylic ester unit in phenylethylene resin series can be using thermal cracking gas chromatography instrument by following
Condition is measured.
Pyrolysis oven：PYR-2A (Shimadzu Scisakusho Ltd's system)
It is pyrolyzed furnace temperature setting：525℃
Gas chromatograph：GC-14A (Shimadzu Scisakusho Ltd's system)
Post：Glass system 3mm footpaths × 3m
Filler：FFAP Chromsorb WAW 10%
Injection, detector temperature：250℃
Column temperature：120℃
Carrier gas：Nitrogen
As the polymerization of phenylethylene resin series, block polymerization, solution polymerization process, suspension polymerization, breast can be enumerated
Change styrene polymerization method known to polymerization etc..In view of quality and productivity ratio, mass polymerization, solution polymerization process are preferred,
It is preferred that continuous polymerization.It is used as solvent alkyl benzene, acetone, Methylethyl such as usable benzene, toluene, ethylbenzene and dimethylbenzene
The ketones such as ketone, the aliphatic hydrocarbon such as hexane, hexamethylene etc..
When phenylethylene resin series polymerize, polymerization initiator, chain-transferring agent can be used as needed.As polymerization initiator,
Radical polymerization initiator is preferred, and can enumerate known usual material, for example, 1,1- bis- (t-butylperoxy) hexamethylene (1,
1-di (t-butylperoxy) cyclohexane), 2,2- bis- (t-butylperoxy) butane (2,2-di (t-
Butylperoxy) butane), 2,2- bis- (4,4- di-t-butyl peroxides butylcyclohexyl) propane (2,2-di (4,4-di-t-
Butyl peroxy cyclohexyl) propane), 1,1- bis- (t-amyl peroxy) hexamethylene (1,1-di (t-amyl
Peroxy) cyclohexane) etc. peroxy ketal class, cumyl hydroperoxide (Cumene hydroperoxide), peroxidating
Tert-butyl alcohol (t-butyl hydroperoxide) etc. hydroperoxides (Hydroperoxide) class, tert-butyl peroxy acetate (t-
Butyl peroxyacetate), the alkyl such as t-amyl peroxy isononoate (t-amyl (peroxy isononanoate))
Peroxide (Alkyl peroxide) class, t-butylcumylperoxide (t-butyl cumyl peroxide), peroxidating
Di tert butyl carbonate (Di-t-butyl peroxide), cumyl peroxide (Dicumyl peroxide), the tertiary own ester of peroxidating two
Dialkyl esters such as (Di-t-hexyl peroxide), tert-butyl peroxy acetate (t-butylperoxy
Acetate), t-butyl peroxybenzoate (t-butyl peroxybenzoate), tert-butylperoxyiso-propyl monocarbonate
Peroxide esters such as (t-butyl peroxyisopropylmonocarbonate), BPIC t butyl peroxy isopropyl carbonate (t-
Butylperoxy isopropyl carbonate), polyethers four (t-butylperoxy carbonic ester) (Polyether
Tetrakis (t-butyl peroxy carbonate)) etc. peroxycarbonic acid esters, N, N '-azo is double (hexamethylene -1- formonitrile HCNs)
(N, N'-azobis (cyclohexane-1-carbonitrile)), N, double (2- methylbutyronitriles) (N, the N'-azobis of N '-azo
(2-methyl butyronitrile)), N, double (2,4- methyl pentane nitrile) (N, the N'-azobis (2,4- of N '-azo
Dimethyl valeronitrile)), N, double [2- (hydroxymethyl) propionitrile] (N, the N'-azobis [2- of N '-azo
(hydroxymethyl) propionitrile]) etc., it can be used 1 in these kind or combine two or more and use.Turn as chain
Moving agent can enumerate, aliphatic mercaptan, aromatic mercaptans, pentaphenylethane, α-methylstyrene dimer and terpinolene
(Terpinolene) etc..
When carrying out continuous polymerization, groove profile tank diameter or tower reactor are thoroughly mixed known to polymerization process first
Deng, in order to reach target molecular weight, molecular weight distribution, reaction conversion ratio and by adjust polymerization temperature etc. control polymerisation.
The polymeric solution of polymer containing aggregated process is transferred to devolatilization process, unreacted monomer and polymer solvent is removed.
Devolatilization process is made up of the vacuum volatilization groove with having heaters and devolatilization extruder with steam vent etc..By through devolatilization process
The polymer of molten condition is transferred to granulating working procedure.In granulating working procedure, molten resin is extruded into rope strand shape by porous dies, led to
Cross thermal cutting mode in cold cut mode, aerial thermal cutting mode, water and be processed into grain shape.
The weight average molecular weight of the phenylethylene resin series of the present invention is preferred for 150,000~700,000,180,000~500,000.If less than
150000, then the intensity of products formed become not enough, if it exceeds 700,000 mouldabilities are significantly reduced.Phenylethylene resin series are again divided equally
Son amount can pass through the reaction temperature of polymerization process, holdup time, the species of polymerization initiator and addition, the kind of chain-transferring agent
Species and amount of the solvent used when class and addition, polymerization etc. are controlled.
As for weight average molecular weight (Mw) and Z mean molecule quantities (Mz), number mean molecule quantity (Mn), gel permeation chromatography is used
(GPC) and by following condition determine.
GPC instrument species：Showa Denko K. K Shodex GPC-101
Post：10 μm of MIXED-B of Polymer Laboratory company system PLgel
Mobile phase：Tetrahydrofuran
Sample solution concentration：0.2 mass %
Temperature：40 DEG C of furnace temperature, 35 DEG C of inlet, 35 DEG C of detector
Detector：Differential refractometer
The molecular weight of the present invention is molecular weight and the conduct that the stripping curve based on monodisperse polystyrene calculates each elution time
Calculated value is come with the molecular weight that polystyrene converts.
《Hydrophilic additive》
Hydrophilic additive refers to, with compound that can be with the hydrophilic radical of aqueous phase interaction (hydrogen bond).Hydrophilic radical is excellent
Elect polyether chain as.Polyether chain is the connected skeleton structure of ehter bond, for example, can enumerate and (be recorded sometimes below by oxirane
For EO), expoxy propane, the addition reaction of the epoxyalkane such as epoxy butane synthesize polyoxyethylene chain, polyoxypropylene chains, polyoxy
Butylene chain, or the synthesis such as the dehydrating condensation for passing through glycerine polyglycerol chain, polyoxyethylene chain is preferred.Polyether chain is in 1 molecule
In can have 1 group, it is possibility to have it is multigroup.
Among such various hydrophilic additives, in the present invention, average addition mole of the addition selected from oxirane
Number is at least one kind of in 3~150 polyoxyethylene-type surfactant and the polyethylene glycol of mean molecule quantity 200~10000.
In order to improve the inhibition of albinism, find in test use the hydrophilic additive of such specific composition.
In addition, the HLB value of hydrophilic additive is 5~20.In order to improve the inhibition of albinism, find in experiment
In must use such hydrophilic additive with specific HLB value.HLB value is preferably 8~20, and more preferably 10~20,
Most preferably 10~18.HLB (Hydrophilic-lipophilic blance) value is the hydrophilic value for representing additive,
HLB value is if 8~10 stable dispersions in water, if it exceeds 10 are changed into transparent from the dispersity with transparent feel
The state that ground is completely dissolved.HLB value=(hydrophilic radical part is utilized in the nonionic surfactant with polyether chain
Molecular weight)/(molecular weight of additive) × 20 are calculated, and do not contain hydrophilic additive as the alkane of hydrophilic radical
HLB value=0, for only having the polyethylene glycol of hydrophilic radical, HLB value=20 are for nonionic surfactant HLB value
Between 0~20.
Hydrophilic additive is so that the content in the mass % of styrene resin composite 100 is 0.4~2.0 mass %
Mode add.In order to maintain the heat resistance of styrene resin composite while improving the inhibition of albinism, find
Laboratory needs to be added in the way of as such content.Parent in the mass % of styrene resin composite 100
The content of aqueous additive is preferably 0.7~1.6 mass % or 0.6~1.4 mass %, more preferably 0.6~0.9 matter
Measure %.
The loss on heating under 200 DEG C of temperature, nitrogen environment of hydrophilic additive is preferred for below 10 mass %.In temperature
Loss on heating under 200 DEG C of degree, nitrogen environment gas can be tried to achieve using thermogravimetry (TGA), in a nitrogen environment from room temperature shape
State is heated with 10 DEG C/min of programming rate, is tried to achieve by the weight loss amount at 200 DEG C of temperature.In 200 DEG C of temperature, nitrogen ring
Additive of the loss on heating more than 10 mass % under border, volatility is high, produce gas in the processing and forming of phenylethylene resin series
Body, it is possible to be contaminated metal pattern, roller.
As the adding method of hydrophilic additive, can enumerate using the polymerization process of phenylethylene resin series, devolatilization process,
The method of granulating working procedure addition mixing；The method that mixing is added using extruder during processing and forming etc.；Pass through no added benzene
The resin combination dilution that vinylite will be adjusted to the hydrophilic additive of high concentration is mixed into method of target content etc.,
It is not particularly limited.
It can such as enumerate the styrene resin composite and nothing of the hydrophilic additive containing 0.5~50.0 mass %
The phenylethylene resin series of addition are mixed using extruder or injection moulding forming machine, obtain the phenylethylene resin series of aimed concn
Composition, products formed, the method for light guide plate.
＜ polyoxyethylene-type surfactants ＞
As polyoxyethylene-type surfactant, polyoxyethylene-type nonionic surfactant, polyoxyethylene-type can be enumerated cloudy
Ionic surfactant, polyoxyethylene-type cationic surfactant, polyoxyethylene-type amphoteric surfactant etc., polyoxy
Ethylene type nonionic surfactant is preferred.
Polyoxyethylene-type nonionic surfactant can enumerate following formulas (1) expression polyoxyethylene alkyl ether or under
State polyoxyethylene fatty acid ester, the polyoxyethylene solidification castor oil, polyoxyethylene sorbitol acid anhydride aliphatic acid of formula (2) expression
Ester, polyoxyethylene sorbitol fatty acid ester, but a kind in polyoxyethylene alkyl ether and/or polyoxyethylene fatty acid ester
It is preferred above.In addition, polyxyethylated even with having the multivalence of multiple polyoxyethylene alkyl ether skeletons in a molecule
Ether or the multivalence polyoxyethylene fatty acid ester in a molecule with multiple polyoxyethylene fatty acid ester skeletons can also realize this
The purpose of invention.Polyoxyethylene alkyl ether, the valence mumber of polyoxyethylene fatty acid ester refer to, the polyoxyethylene present in a molecule
The quantity of alkyl ether skeleton or polyoxyethylene fatty acid ester skeleton.
(in formula, R represents the alkyl of carbon number 8~20.Furthermore it is possible to be with multiple 6 valencys untill polyoxyethylene alkyl ether
The multivalence polyoxyethylene alkyl ether of skeleton or with multiple 6 valencys untill polyoxyethylene fatty acid ester skeleton multivalence
Polyoxyethylene fatty acid ester.N is integer and represents the addition molal quantity of ethylene oxide unit.)
Polyoxyethylene alkyl ether is to make oxirane and alcohol addition and obtain, polyoxyethylene fatty acid ester be make oxirane and
Aliphatic acid addition makes aliphatic acid and polyethylene glycol direct esterification and obtained, and the average addition molal quantity of oxirane is 3~150.
In order to improve the inhibition of albinism, understand to need to make average addition molal quantity in such particular range from experimental result
It is interior.Average addition molal quantity is preferably 7~100, more preferably 10~60, more preferably 10~50, most preferably 13~
35。
As the polyoxyethylene-type surfactant of the present invention, specifically it can such as enumerate, dodecyl polyoxyethylene
Ether, ceteth, Steareth, octyldodecyl APEO, myristyl polyoxy
The alkyl polyoxyethylene ethers, polyoxyethylene sorbitan monolaurate, polyoxy such as vinethene, 2- ethylhexyl APEOs
The polyoxyethylene sorbitan fatty acid ester of the stearic acid of ethene sorbitan three etc., the oleate of polyoxyethylene sorbitol four
Deng polyoxyethylene sorbitol fatty acid ester, polyethylene glycol monolaurate, polyethylene glycol mono stearate, polyethylene glycol two
The polyoxyethylene fatty acid ester of stearate, polyethylene glycol monooleate etc., polyoxyethylene solidification castor oil, polyoxyethylene list first
It is base ether, polyoxyethylene dimethyl ether, polyoxyethylene glycerol ether, the oleate of polyoxyethylene four, the isostearate of polyoxyethylene three, poly-
Oxygen ethene coconut fatty acid ester etc..
＜ polyethylene glycol ＞
The mean molecule quantity of the polyethylene glycol used in the present invention is 200~10000.200~4000 are preferred, and 200~1800 are
More preferably, 300~1000 be optimal.If the mean molecule quantity of polyethylene glycol is less than 200, gas is produced in processing and forming,
Metal pattern or roller are polluted, thus it is not preferred.In addition, if more than 10000, then preventing the effect of albinism has becoming for reduction
Gesture, and reduced with the intermiscibility of phenylethylene resin series, styrene resin composite, its products formed produce gonorrhoea.Average mark
Son amount is calculated and obtained according to the concentration (being based on JIS K1557) of the hydroxyl determined using phthalic anhydride pyridine method
Value.
《Additive antioxidants》
The styrene resin composite of the present invention can contain mineral in the range of the colorless transparency of the present invention is not influenceed
Oil.Alternatively, it is also possible to contain the internal lubricants such as stearic acid, ethylenebis stearic amide, hindered phenol series antioxidant, phosphorus system
Antioxidant, sulphur system antioxidant, lactone system antioxidant, amine system of being obstructed stabilizer, ultra-violet absorber, antistatic agent etc.
Additive.In addition, as exterior lubricant, ethylenebis stearic amide is preferred, in resin combination content be 30~
200ppm is preferred.
For the styrene resin composite of the present invention, due to the transmission of the feature as phenylethylene resin series
The deterioration of the optical characteristics such as rate, tone, the transparency is small, so the field of the transparency can played, such as optics material
Preferably used in optical applications.As optical applications, lens, light guide plate, film, optical fiber, fiber waveguide etc. can be enumerated.
By adding (c) 6- (3- (3- tertiary butyl-4-hydroxy -5- methyl in the styrene resin composite of the present invention
Phenyl) propoxyl group) -2,4,8,10- tetra--tert-butyl group dibenzo (d, f) (1,3,2) dioxy phospha cycloheptane (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 in the following text " compound X "), (d) phosphorous antioxidant, (e) hindered phenol series antioxidant
In at least one, so as to assign long-term heat endurance.The field used as optical applications during length, for a long time
Heat endurance is one of key property.When being used during long-term thermal stability display is long because of thermally-induced tone and transmissivity
Change, the tone of the styrene resin composite of excellent heat stability and the change of transmissivity are small.For long-term thermal stability,
Products formed can be taken care of, with tone under the high-temperature condition (60~90 DEG C) of the indeformable degree of resin by accelerated test
Evaluated with transmissivity rheological parameters' change with time.
Compound X is the skeleton for the skeleton and phosphorous antioxidant for having hindered phenol series antioxidant in identical intramolecular
Processing stabilizers.
As compound X, the content in the mass % of styrene resin composite 100 is that 0.02~0.40 mass % is
Good, 0.05~0.20 mass % is more preferably.If compound X content is less than 0.02 mass %, long-term thermal stability is poor, just
Phase tone and transmissivity are also deteriorated.In addition, even more than 0.40 mass %, long-term heat endurance also deteriorates.Long-term heat is steady
When being used during qualitative display is long because of the change of thermally-induced tone and transmissivity, the phenylethylene resin series of excellent heat stability
The tone of composition and the change of transmissivity are small.Long heat endurance can be by accelerated test, in the indeformable degree of resin
Products formed is taken care of under high-temperature condition (60~90 DEG C), is evaluated with tone and the rheological parameters' change with time of transmissivity.Polystyrene
The content of compound X in the mass % of resin combination 100, specifically for example, 0.02,0.03,0.04,0.05,0.06,
0.07th, 0.08,0.09,0.10,0.15,0.20,0.25,0.30,0.35,0.40 mass %, or illustrate herein
The value within the scope of any 2 in numerical value.
By adding compound X in the styrene resin composite of the present invention, so as to assign long-term thermal stability
Property, even and if add phosphorous antioxidant and/or hindered phenol series antioxidant, it can also assign long-term thermal stability.
Phosphorous antioxidant contains 0.02~0.50 mass % preferably in the mass % of styrene resin composite 100,
Further preferably 0.05~0.40 mass %, further preferably 0.05~0.30 mass %.If less than 0.02 mass %,
Then long-term heat endurance is poor, initial stage tone and transmissivity it is also poor.Even if more than 0.50 mass %, long-term heat endurance is also disliked
Change.The content of phosphorous antioxidant in the mass % of styrene resin composite 100, specifically for example, 0.02,0.03,
0.04th, 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 matter
Measure %, or the value within the scope of any 2 in the numerical value illustrated herein.
Hindered phenol series antioxidant contains 0.02~0.50 matter preferably in the mass % of styrene resin composite 100
Measure %, further preferably further preferably 0.02~0.30 mass %, 0.05~0.30 mass %.If less than 0.02 matter
Measure %, then long-term heat endurance is poor, initial stage tone and transmissivity it is also poor.Even if more than 0.50 mass %, long-term thermal stability
Also deteriorate.The content of hindered phenol series antioxidant in the mass % of styrene resin composite 100, be, for example, specifically
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、
0.45th, 0.50 mass %, or the value within the scope of any 2 in the numerical value illustrated herein.
Phosphorous antioxidant refers to the phosphorous acid esters of the phosphorus compound of trivalent.Phosphorous antioxidant, for example, can enumerate, three
(2,4- di-t-butyls phenyl) phosphite ester, 2,2 '-di-2-ethylhexylphosphine oxide (4,6- di-t-butyl -1- phenyl oxygen) (2- ethylhexyls
Epoxide) phosphorus, double (2,4- dicumylphenyls) pentaerythritol diphosphites, (the 2,4- bis--tertiary fourth of 4,4 '-xenyl di 2 ethylhexyl phosphonic acid four
Base phenyl), the double phospha spiral shells (5.5) of (2,6- di-t-butyl -4- methylphenoxies) four oxa- -3,9- of -2,4,8,10- two of 3,9-
Hendecane, the base of ring neopentane four double (2,4- di-t-butyls phenyl phosphites), double octadecyl pentaerythrite diphosphorous acids
Ester, double (nonyl phenyl) pentaerythritol diphosphites, double-[- 4,6- pairs-(1,1- dimethyl ethyls) phenyl of 2- methyl] ethyl
Phosphite ester, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, four (2,4- di-t-butyl -5- aminomethyl phenyls) -4,
Phosphinate of 4 '-xenyl two etc..As phosphorous antioxidant, the excellent phosphorous antioxidant of hydrolytic resistance is preferred, and preferably three
(2,4- di-t-butyls phenyl) phosphite ester, 2,2 '-di-2-ethylhexylphosphine oxide (4,6- di-t-butyl -1- phenyl oxygen) (2- ethylhexyls
Oxygen) phosphorus, double (2,4- dicumylphenyls) pentaerythritol diphosphites, double (the 2,6- di-t-butyl -4- methylenedioxy phenoxies of 3,9-
Base) four oxa- -3,9- of -2,4,8,10- two phospha spiral shell (5.5) hendecane.Particularly preferably three (2,4- di-t-butyls phenyl) are sub-
Phosphate.Phosphorous antioxidant can be used alone can also and with more than two kinds.
Hindered phenol series antioxidant refers to there is the antioxidant of phenolic hydroxyl group in basic framework.Hindered phenol series are anti-oxidant
Agent, for example, can enumerate, double [2- (3- (the tertiary fourths of 3- of octadecyl -3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester, 3,9-
Base -4- hydroxy-5-methyl bases phenyl) propionyloxy) -1,1- dimethyl ethyls] -2,4,8,10- four oxaspiro [5.5] hendecane,
Double (the octylsulfo first of ethylenebis (epoxide ethylidene) double (3- (a 5- tertiary butyl-4-hydroxies-tolyl) propionic esters), 4,6-
Base)-orthoresol, 4,6- double ((dodecyl is thio) methyl)-orthoresol, 2,4- dimethyl -6- (1- methyl pentadecyl) benzene
Phenol, four (methylene -3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester) methane, DL- alpha-tocopherols, the 2- tert-butyl groups -6-
(the 3- tert-butyl group -2- hydroxy-5-methyl bases benzyl) -4- aminomethyl phenyls acrylate, 2- (1- (2- hydroxyl two-tert-amyl benzenes of -3,5-
Base) ethyl) two-tertiary pentyls of -4,6- phenyl acrylate, 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols), 1,1,3- tri-
(2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), double-[3,3-
Double-(4 '-hydroxyl -3 '-tert-butyl-phenyl)-butyric acid]-glycol ester etc..Preferably octadecyl -3- (3,5- di-t-butyl -s
4- hydroxy phenyls) propionic ester, double [2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) the propionyloxy) -1,1- diformazans of 3,9-
Base ethyl] -2,4,8,10- four oxaspiro [5.5] hendecane, the double (3- (the 5- tert-butyl group -4- hydroxyls of ethylenebis (epoxide ethylidene)
A base-tolyl) propionic ester).Hindered phenol series antioxidant can be used alone can also and with more than two kinds.
As compound X, phosphorous antioxidant and hindered phenol series antioxidant adding method, it can enumerate and utilize benzene second
The polymerization process of alkene system resin, devolatilization process, the method for granulating working procedure addition mixing；With extruder during processing and forming, injection
The method of the addition mixing such as molding forming machine；High concentration these additives will be adjusted to by no added phenylethylene resin series
Resin combination dilution is mixed into method of target content etc., is not particularly limited.
Ultra-violet absorber is with the ultra-violet absorber for suppressing the function because of UV-induced deterioration or coloring, example
Benzophenone series, enumerate BTA system, triazine system, benzoic ether system, salicylate system, cyanoacrylate system, grass can such as be enumerated
The ultra-violet absorbers such as sour aniline system, malonate system, carbonamidine system.They can be used alone or in combination of two or more kinds,
The light stabilizers such as hindered amine can be used together.
《Styrene resin composite》
The styrene resin composite of the present invention can utilize injection molding shaping, extrusion molding, blow molding, compression forming
Products formed is obtained Deng the various forming methods according to purpose.The shape of products formed can be the shape according to formed by purpose,
Do not limit.For example if tabular products formed, then it can be used as light guide plate.It is used as the method for forming light guide plate, it is known to
The back side (the opposite side for projecting the face of light) of tabular products formed sets the reflection graphic patterns such as dot pattern.Light guide plate is processed into resin plate
When, the whole face of end face of the plane of incidence or resin plate to light is ground processing and forms minute surface and be preferred.In addition, in order to improve transmitting
The uniformity of light, and prism pattern can be set on the surface (face that can launch light) of tabular products formed.Tabular products formed
The pattern at surface or the back side can be formed in the shaping of tabular products formed, such as if injection molding shaping is then metal pattern
Shape, if extrusion molding then forms pattern by roller transfer etc..
The vicat softening temperature of the styrene resin composite of the present invention is 95~104 DEG C and is preferred that 97~104 DEG C is more
It is good.If vicat softening temperature is less than 95 DEG C, heat resistance is not enough, there is the possibility for deforming products formed according to use environment.
For the mist degree of the styrene resin composite of the present invention, the products formed of 4mm thickness is formed, is less than 5% to be
It is good, it is less than 1% for more preferably.
【Embodiment】
Hereinafter, enumerate embodiment and illustrate the present invention, but the present invention is not limited to these embodiments.
《Experiment 1》
(phenylethylene resin series A-1~A-3 manufacture)
Using as the 1st reactor and the 2nd reactor for being thoroughly mixed type tank diameter and be used as carry static mixer piston
3rd reactor of formula flow-type reactor is connected in series to constitute polymerization process, implements according to the condition shown in table 1
The manufacture of phenylethylene resin series.The capacity of each reactor is respectively：1st reactor is 39 liters, the 2nd reactor is 39 liters, the 3rd anti-
It is 16 liters to answer device.The raw material recorded with table 1 constitutes preparing raw material solution, and the flow recorded to the 1st reactor with table 1 is continuously supplied
Material solution.In the entrance of the 1st reactor, with recorded as table 1 addition concentration (quality criteria relative to Materials Styrene and
The concentration of the total amount of methacrylic acid) mode add polymerization initiator to material solution, and uniformly mix.What table 1 was recorded
Polymerization initiator is as follows：
Polymerization initiator -1：2,2- bis- (4,4- t-butyl peroxies butylcyclohexyl) propane (uses Japan Oil Co PATORA
A。)
Polymerization initiator -2：1,1- bis- (t-butylperoxy) hexamethylene (uses Japan Oil Co PERHEXA C.)
Here, in the 3rd reactor, so as to produce thermograde along flow direction, center section, exit portion with as
The mode of the temperature of table 1 is adjusted.
Then, by the way that the solution containing polymer being continuously withdrawn using the 3rd reactor is imported into what is constituted by 2 sections connected
With giving in the vacuum volatilization groove of hot device, the temperature for giving hot device is adjusted in the way of the resin temperature recorded as table 1, and by table
1 pressure recorded is adjusted, so that by after unreacted benzene ethene and ethylo benzene separation, rope strand is extruded as using porous dies
Shape, rope strand is cooled down and cut off using cold cut mode, granulated.
【Table 1】
* 1 relative to styrene+methacrylic acid, the quality criteria of styrene+methyl methacrylate concentration
(embodiment 1-1~1-33, comparative example 1-1~1-9)
With the content shown in table 2, using the single axle extruding machine that screw diameter is 40mm, by phenylethylene resin series A-1~A-3 and add
Plus agent melting mixing under 230 DEG C of barrel temperature, screw speed 100rpm, obtain particle.The following institute of additive used in table 2
Show.
B-1：Average addition molal quantity=25 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 123P)
B-2：Average addition molal quantity=12 (the Kao Corp's system of vinyl octadecyl APEO oxirane
EMULGEN 320P)
B-3：Average addition molal quantity=9 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 109P)
B-4：Average addition molal quantity=7 (the Kao Corp's system of vinyl ceteth oxirane
EMULGEN 210P)
B-5：Average addition molal quantity=30 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 130K)
B-6：Average addition molal quantity=47 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 150)
B-7：Average addition molal quantity=85 (the Kao Corp's system of vinyl myristyl APEO oxirane
EMULGEN 4085)
B-8：Average addition molal quantity=12 (the Kao Corp EMANON of polyethylene glycol monolaurate oxirane
1112)
B-9：Average addition molal quantity=6 (the Kao Corp's system of vinyl octadecyl APEO oxirane
EMULGEN 306P)
B-10：Polyoxyethylene solidification castor oil (Kao Corp EMANON CH-40)
B-11：Mean molecule quantity is 400 polyethylene glycol (Japan Oil Co PEG#400)
B-12：Mean molecule quantity is 300 polyethylene glycol (Japan Oil Co PEG#300)
B-13：Mean molecule quantity is 600 polyethylene glycol (Japan Oil Co PEG#600)
B-14：Mean molecule quantity is 1000 polyethylene glycol (Japan Oil Co PEG#1000)
B-15：Mean molecule quantity is 2000 polyethylene glycol (Japan Oil Co PEG#2000)
B-16：Mean molecule quantity is 3100 polyethylene glycol (Japan Oil Co PEG#4000)
B-17：The polyethylene glycol (Japan Oil Co PEG#6000) of mean molecule quantity 8800
B-18：Polyoxyethylene monomethyl ether (Japan Oil Co UNIOX M-550)
B-19：The isostearic acid of polyoxyethylene three (Japan Oil Co UNIOX GT-20IS)
B-20：Octyldodecyl APEO (Kao Corp EMULGEN2025G)
B-21：Polyoxyethylene glycerol ether (Japan Oil Co UNIOX G-750)
B-22：The oleic acid of polyoxyethylene four (Japan Oil Co UNIOX ST-30E)
B-23：Stearyl alcohol (Kao Corp KALCOL 8098)
B-24：Glyceryl monostearate (Kao Corp EXCEL S-95)
B-25：Mean molecule quantity is 60000 polyethylene glycol (bright into chemical industry Co. Ltd. system ALKOX L-6)
B-26：Mean molecule quantity is 500 polyglycereol (slope this pharmaceutical industries Co. Ltd. system polyglycereol #500)
Using obtained particle, injection molding shaping is carried out under 230 DEG C of barrel temperature, metal pattern temperature 50 C, makes 127
The tabular products formed shaping of × 127 × 3mm thickness.
In addition, embodiment 1-33 is the single axle extruding machine using screw diameter 40mm by phenylethylene resin series A-1 and additive B -1
The melting mixing under 230 DEG C of barrel temperature, screw speed 100rpm, once obtains the mass % of concentration 20 of additive B -1
After grain, so that the particle and phenylethylene resin series A-1 turn into 1：The mode of 24 ratio is mixed, and injection molding shaping and
Obtained products formed.
＜ MFR ＞
The MFR (melt mass flow rate) of styrene resin composite is under conditions of 200 DEG C, 49N loads, to be based on
What JIS K 7210 were measured.
＜ hue evaluations at initial stage ＞
The test film of 115 × 85 × 3mm thickness is cut out from resulting tabular products formed, end face is carried out by polishing grinding
Grinding, obtaining end face has the tabular products formed of minute surface.For obtained tabular products formed, Japan Spectroscopy Corporation's system is used
Ultraviolet visible spectrophotometer V-670, under 20 × 1.6mm of size, the incident light of 0 ° of diffusion angle, determine optical path length
The spectral transmission of wavelength 350nm~800nm under 115mm, the YI values under 2 ° of the visual angle of illuminant-C are calculated according to JIS K7105.
Obtained value is " the YI 115mm " of table 2.In addition, shown in table 2 " transmissivity 115mm " represents that wavelength 380nm~780nm's is flat
Equal transmissivity.
And then, in table 2 " mist degree 4mm " is obtained as follows, i.e. using the particle obtained in above-mentioned operation, in barrel temperature
Injection molding shaping is carried out at 220 DEG C of degree, 40 DEG C of metal pattern temperature, the tabular products formed of 55 × 50 × 4mm thickness is molded, makes
Thus obtained test film is used, using NDH5000 (electricity Se Industrial Co., Ltd of Japan system), is measured based on JIS K-7105
And be worth, table 2 " YI 4mm " are to use the test film, using colour examining colour-difference-metre NDJ4000 (the industrial strain formula meetings of Japan's electricity color
Society's system), value obtained from being measured with bounce technique.
＜ albefaction inhibitions ＞
In addition, in order to confirm the albinism produced based on environmental change, the tabular products formed in end face with minute surface is existed
60 DEG C, the environmental exposure of 90% relative humidity 150 hours, take out test film, observation exists in the environment of 23 DEG C, 50% relative humidity
The albinism produced inside products formed, judgement is carried out as follows as albefaction inhibition.
◎：Albefaction is not produced completely
○：Disappeared after taking out 1 hour after slightly albefaction, but 24 hours
△：Almost disappeared after albefaction, but 24 hours after taking out 1 hour
×：Significantly albefaction after taking out 1 hour, even if also not disappeared by 24 hours
＜ dimension card softenings (Vicat Softening) temperature ＞
For vicat softening temperature, according to JIS K-7206, tried to achieve with 50 DEG C/hr of programming rate, test load 50N.
＜ overall merits ＞
According to following benchmark, overall merit is carried out.
S：Albefaction inhibition is ◎ and vicat softening temperature is more than 100 DEG C
A：S condition can not be fully met, albefaction inhibition is ◎ and vicat softening temperature is more than 98 DEG C, or albefaction suppression
Effect processed is zero and vicat softening temperature is more than 100 DEG C
B：A condition can not be fully met, albefaction inhibition is ◎ and vicat softening temperature is more than 95 DEG C, or albefaction suppression
Effect processed is zero and vicat softening temperature is more than 98 DEG C, or albefaction inhibition is △ and vicat softening temperature is 100 DEG C
More than
C：Any of the above-described condition can not fully be met
The characteristic and evaluation result of each resin combination are shown in table 2.
【Table 2】
EO... oxirane PEG... polyethylene glycol*The mean molecule quantity of polyglycerol ester
The albefaction inhibition of the related products formed of embodiment is excellent, and transmissivity and YI values do not deteriorate and the transparency and color
Adjust also excellent.The suppression of albefaction present situation in comparative example 1-1,1-2, the 1-4 very few without hydrophilic additive or addition
System is insufficient.In the comparative example 1-3 and 1-5 that hydrophilic additive is excessively added, heat resistance is excessively reduced.In addition, comparative example
In 1-6 and 1-7, the stearyl alcohol as hydrophilic additive, glyceryl monostearate are added respectively and is tested, but albefaction
Inhibition is insufficient.In addition, in comparative example 1-8 and 1-9, the big polyethylene glycol of addition molecular weight, polyglycereol are tested, but
Hydrophilic additive does not mix with phenylethylene resin series, and gonorrhoea occurs for products formed.
From result above, in order to maintain the heat resistance of styrene resin composite, the transparency and suppress albinism,
It must is fulfilled for following 3 conditions：(1) hydrophilic additive has characteristic composition, and (2) its HLB value is the value in specific scope,
And (3) its content is the amount of particular range.It is polystyrene in phenylethylene resin series it can be seen from embodiment 1-20~1-21
Identical result can be also obtained during the copolymer of monomer and (methyl) acrylic acid or (methyl) acrylate.
《Experiment 2》
(embodiment 2-1~2-46)
Using as the 1st reactor and the 2nd reactor for being thoroughly mixed type tank diameter and be used as carry static mixer piston
3rd reactor of formula flow-type reactor is connected in series to constitute polymerization process, implements according to the condition shown in table 1
The manufacture of phenylethylene resin series.The capacity of each reactor is respectively：1st reactor is 39 liters, the 2nd reactor is 39 liters, the 3rd anti-
It is 16 liters to answer device.The raw material recorded with table 1 constitutes preparing raw material solution, and the flow recorded to the 1st reactor with table 1 is continuously supplied
Material solution.
In addition, in the entrance of the 3rd reactor, by the hydrophilic additive with polyether chain with as the species shown in table 3
Added with the mode of content.The additive and the species of polyethylene glycol used is as follows.
B-1：Mean molecule quantity is 400 polyethylene glycol (Japan Oil Co PEG#400)
B-2：Mean molecule quantity is 1000 polyethylene glycol (Japan Oil Co PEG#1000)
B-3：Mean molecule quantity is 2000 polyethylene glycol (Japan Oil Co PEG#2000)
B-4：Average addition molal quantity=25 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 123P)
B-5：Average addition molal quantity=12 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 320P)
B-6：Average addition molal quantity=9 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 109P)
B-7：Average addition molal quantity=30 (the Kao Corp's system of vinyl alkylpolyoxyethylene oxirane
EMULGEN 130K)
B-8：Average addition molal quantity=12 (the Kao Corp EMANON of polyethylene glycol monolaurate oxirane
1112)
Then, it will be continuously withdrawn to the solution containing polymer of the 3rd reactor and imported into by 2 sections the connected bands constituted
Have in the vacuum volatilization groove for giving hot device, after unreacted benzene ethene and ethylo benzene separation, after being extruded as rope strand shape and cooling down, carry out
Cut off that particle is made.Here, the resin temperature settings in the devolatilization groove in the 1st stage are 160 DEG C, the pressure of vacuum volatilization groove is
Resin temperature settings in 65kPa, the devolatilization layer in the 2nd stage are 235 DEG C, and the pressure of vacuum volatilization groove is 0.8kPa.
Next, so that as the content shown in table 3, using screw diameter 40mm single axle extruding machine, benzene is obtained by above-mentioned
The particle of vinylite and as chase after additivated compound X, additive D and additive E 230 DEG C of barrel temperature,
Melting mixing obtains particle under screw speed 100rpm.Compound X, D and E that are used in table 3 are shown in hereafter.Here,
Compound X represents 6- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propoxyl group) -2,4,8,10- four-tert-butyl group dibenzo
(d, f) (1,3,2) dioxy phospha cycloheptane, additive D represents phosphorous antioxidant, and additive E represents that hindered phenol series are anti-oxidant
Agent.
Compound X：6- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propoxyl group) -2,4,8,10- four-tert-butyl group dibenzo
(d, f) (1,3,2) dioxy phospha cycloheptane (Sumitomo Chemical Co SUMILIZER GP)
D-1：Three (2,4- di-t-butyls phenyl) phosphite esters (BASF Japan Co. Ltd. systems Irgafos 168)
D-2：2,2 '-di-2-ethylhexylphosphine oxide (4,6- di-t-butyl -1- phenyl oxygen) (2- ethylhexyls oxygen) phosphorus (Asahi Denka Co., Ltd.'s system
ADKSTAB HP-10)
D-3：Double (2,4- dicumylphenyls) pentaerythritol diphosphites (Dover Chemical Corporation systems
Doverphos S-9228)
D-4：The double phospha spiral shells (5.5) of (2,6- di-t-butyl -4- methylphenoxies) four oxa- -3,9- of -2,4,8,10- two of 3,9-
Hendecane (Asahi Denka Co., Ltd. ADKSTAB PEP-36)
E-1：Octadecyl -3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester (BASF Japan Co. Ltd. systems
Irganox 1076)
E-2：Double [2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) the propionyloxy) -1,1- dimethyl ethyls] -2 of 3,9-,
The oxaspiros of 4,8,10- tetra- [5.5] hendecane (Asahi Denka Co., Ltd. ADKSTABAO-80)
E-3：Double (3- (a 5- tertiary butyl-4-hydroxies-tolyl) propionic ester) (the Japan plants of formulas of BASF of ethylenebis (oxygen ethene)
Commercial firm Irganox 245)
In addition, melt mass flow rate (MFR) is according to JIS K 7210, enter under conditions of 200 DEG C, 49N loads
Row is determined, and vicat softening temperature is, according to JIS K 7206, to be measured under 50 DEG C/hr of programming rate, test load 50N.
In addition, using obtained particle, injection molding shaping is carried out under 230 DEG C of barrel temperature, metal pattern temperature 50 C,
It is molded the tabular products formed of 127 × 127 × 3mm thickness.In order to evaluate long-term heat endurance, and obtained products formed is existed
Keeping 1000 hours in 80 DEG C of furnace temperature.In order to evaluate keeping before initial stage products formed and keeping after products formed optical characteristics,
And the test film of 115 × 85 × 3mm thickness is cut out from tabular products formed, end face is ground by polishing grinding, prepared
End face has the tabular products formed of minute surface.For the tabular products formed after grinding, the ultraviolet of Japan Spectroscopy Corporation is used
The visual spectrophotometer V-670 of line, under 20 × 1.6mm of size, the incident light of 0 ° of diffusion angle, is determined under optical path length 115mm
Wavelength 350nm~800nm spectral transmission, according to JIS K7105 calculate illuminant-C 2 ° of visual angle under YI values.Shown in table 3
Transmissivity be the average transmittance for representing wavelength 380nm~780nm.
Next, it is poor to calculate Δ YI based on following formula.
Δ YI is poor=(have the YI compared to initial stage chased after in additivated embodiment poor)-(does not chase after additivated implementation
The YI compared to initial stage in example is poor)
In one example, in additivated embodiment 2-2 is chased after, the value poor compared to the YI at initial stage is 1.1, and not addition adds
Plus poor compared to the YI at initial stage in the embodiment 2-1 of agent is 5.1, so embodiment 2-2 Δ YI differences are -4.0.The value is indicated
The raising effect of long-term heat endurance, is worth smaller, table as caused by additional additive (compound X, phosphorus system D, hindered phenol series E)
Show that long-term heat endurance improves effect bigger.
In addition, in order to confirm the albinism produced by environmental change, will there is the tabular products formed of minute surface in end face
In 60 DEG C, the environmental exposure of 90% relative humidity 150 hours, test film, observation are taken out in the environment of 23 DEG C, 50% relative humidity
The albinism produced inside products formed, judgement is carried out as follows as albefaction inhibition.
◎：Albefaction is not produced completely
○：Disappeared after taking out 1 hour after slightly albefaction, but 24 hours
△：Almost disappeared after albefaction, but 24 hours after taking out 1 hour
×：Significantly albefaction after taking out 1 hour, even if also not disappeared by 24 hours
＜ overall merits ＞
According to following benchmark, by albefaction inhibition, Δ YI be poor, vicat softening temperature evaluation result is quantized.
Fractional value (◎ → 3 of albefaction inhibition；○→2；△→1；×→0)
Δ YI difference fractional value (below -4.0 → 4；- below 3.5 → 3；- below 2.5 → 2；- below 1.5 → 1；In addition →
0)
The fractional value (more than 99 DEG C → 3 of vicat softening temperature；More than 97 DEG C → 2；More than 95 DEG C → 1；In addition → 0)
For the total of the fractional value according to obtained by said reference, overall merit is carried out according to following benchmark.
S：10；A：9；B：8；C：7；D：Less than 6
Table 3 shows the characteristic and evaluation result of each resin combination.In embodiment 2-1~2-42, made using according to condition 1
Into phenylethylene resin series A-1, the phenylethylene resin series A-2 being made according to condition 2 is used in embodiment 2-43~2-44, is implemented
The phenylethylene resin series A-3 being made according to condition 3 is used in example 2-45~2-46.
【Table 3】
It can be seen from table 3, the albefaction inhibition of whole embodiments is excellent.In addition, comparing embodiment 2-1~2-35 and
Embodiment 2-36~2-42 understands that when compound X content is 0.02~0.40 mass %, long-term heat endurance is especially excellent
It is different.In addition, it can be seen from embodiment 2-43~2-46, phenylethylene resin series be styrenic monomers with (methyl) acrylic acid or
Same result can be also obtained during the copolymer of (methyl) acrylate.
《Experiment 3》
(embodiment 3-1~3-36)
In addition in experiment 3 without compound X, evaluated using with 2 same methods of experiment.Embodiment 3-1~3-32
In, using the phenylethylene resin series A-1 being made according to condition 1, the benzene being made according to condition 2 is used in embodiment 3-33~3-34
The phenylethylene resin series A-3 being made according to condition 3 is used in vinylite A-2, embodiment 3-35~3-36.
It the results are shown in table 4.
【Table 4】
It can be seen from table 4, the albefaction inhibition of whole embodiments is excellent.In addition, comparing embodiment 3-1~3-24 and
Embodiment 3-25~3-32 understands that phosphorus system D content is 0.05~0.40 mass % and phenol system E content is 0.02~0.30
During quality %, long-term thermal stability is especially excellent.In addition, it can be seen from embodiment 3-33~3-36, phenylethylene resin series are benzene
Same result can be also obtained during the copolymer of vinyl monomer and (methyl) acrylic acid or (methyl) acrylate.
【Industrial applicability】
The styrene resin composite of the present invention is prevented from the albinism caused by environmental change, and the transparency
And excellent hue, so being also able to maintain that as styrene in the purposes for producing albinism because of environmental change all the time
It is the transparency of the advantage of resin, can preferably uses.
Also, because the tone variations of the excellent styrene resin composite of long-term thermal stability are small, so compared with the past
It can be used in the case where keeping the long-term transparency and tone.
For example, can be applied to television set, the display of desktop personal computer, subnotebook PC, mobile phone, auto navigation etc.
Light guide plate etc..
Claims (15)
1. a kind of optics styrene resin composite, it contains the phenylethylene resin series that weight average molecular weight is 150,000~700,000
And hydrophilic additive, the optics styrene resin composite is characterised by, the hydrophilic additive is to be selected from ring
The polyoxyethylene-type surfactant and mean molecule quantity that the average addition molal quantity of oxidative ethane is 10~150 are 200~10000
Polyethylene glycol in it is at least one kind of, HLB value is 5~20, and containing in the mass % of styrene resin composite 100
Measure as 0.6~2.0 mass %.
2. optics styrene resin composite as claimed in claim 1, wherein, the hydrophilic additive is epoxy second
The average addition molal quantity of alkane is 10~60 polyoxyethylene-type surfactant, and in the styrene resin composite
Content in 100 mass % is 0.6~1.4 mass %.
3. optics styrene resin composite as claimed in claim 1, wherein, the hydrophilic additive is epoxy second
The average addition molal quantity of alkane is 13~35 polyoxyethylene-type surfactant, and in the styrene resin composite
Content in 100 mass % is 0.6~0.9 mass %.
4. optics styrene resin composite as claimed in claim 3, wherein, the HLB value of the hydrophilic additive
For 10~18.
5. optics styrene resin composite as claimed in claim 1, wherein, the polyoxyethylene-type surfactant
For polyoxyethylene-type nonionic surfactant.
6. optics styrene resin composite as claimed in claim 5, wherein, polyoxyethylene-type non-ionic surface lives
Property agent be selected from following formulas (1) represent polyoxyethylene alkyl ether and/or following formulas (2) represent polyoxyethylene fatty acid
More than a kind in ester,
In formula, R represents the alkyl of carbon number 8~20；And it is possible to be 6 valencys with multiple polyoxyethylene alkyl ether skeletons
Untill multivalence polyoxyethylene alkyl ether, the multivalence polyoxyethylene untill 6 valencys with multiple polyoxyethylene fatty acid ester skeletons
Fatty acid ester, n is integer and represents the addition molal quantity of ethylene oxide unit.
7. optics styrene resin composite as claimed in claim 1, wherein, the hydrophilic additive is average mark
The polyethylene glycol of son amount 200~10000, and content in the mass % of styrene resin composite 100 for 0.6~
1.4 mass %.
8. optics styrene resin composite as claimed in claim 7, wherein, the hydrophilic additive is average mark
The polyethylene glycol of son amount 200~1800.
9. optics styrene resin composite as claimed in claim 8, wherein, the hydrophilic additive is in the benzene
Content in the mass % of vinylite composition 100 is 0.6~0.9 mass %.
10. optics styrene resin composite as claimed in claim 1, wherein, the phenylethylene resin series are by benzene
Vinyl monomer and styrene obtained by (methyl) acrylic acid copolymer-(methyl) acrylic copolymeric resin, phenylethylene resin series
The content of styrenic monomer unit is 90.0~99.9 mass %, and the content of (methyl) acrylic acid units is 0.1~10.0 matter
Measure %, wherein, using the total of the styrenic monomer unit of phenylethylene resin series and the content of (methyl) acrylic acid units as
100 mass %.
11. optics styrene resin composite as claimed in claim 1, wherein, the phenylethylene resin series are by benzene
Vinyl monomer and styrene obtained by (methyl) acrylic ester copolymer-(methyl) acrylic copolymer resin, polystyrene tree
The content of the styrenic monomer unit of fat is 40.0~99.0 mass %, the content of (methyl) acrylic ester unit for 1.0~
60.0 mass %, wherein, by the content of the styrenic monomer unit of phenylethylene resin series and (methyl) acrylic ester unit
Total is used as 100 mass %.
12. optics styrene resin composite as claimed in claim 1, wherein, also containing 6- (3- (the 3- tert-butyl groups -4-
Hydroxy-5-methyl base phenyl) propoxyl group) -2,4,8,10- tetra--tert-butyl group dibenzo (d, f) (1,3,2) dioxy phospha cycloheptane.
13. optics styrene resin composite as claimed in claim 1, wherein, containing phosphorous antioxidant and/or by
Hinder phenol antioxidant.
14. a kind of products formed, it is characterised in that used as the optics described in any one in 1~claim 13 of claim
Styrene resin composite is constituted.
15. a kind of light guide plate, it is characterised in that be made up of the products formed described in claim 14.
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| JP2011-279021 | 2011-12-20 | ||
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| JP2012157742 | 2012-07-13 | ||
| CN201280061401.7A CN103998514B (en) | 2011-12-20 | 2012-12-19 | Styrene-based optical resin composition |
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| CN103998514B (en) * | 2011-12-20 | 2017-04-26 | 东洋苯乙烯股份有限公司 | Styrene-based optical resin composition |
| JP6310219B2 (en) * | 2013-09-27 | 2018-04-11 | 東洋スチレン株式会社 | Styrenic resin composition for optics |
| JP6262004B2 (en) * | 2014-02-05 | 2018-01-17 | Ｐｓジャパン株式会社 | Light guide plate |
| JP2017211399A (en) * | 2014-10-09 | 2017-11-30 | コニカミノルタ株式会社 | Infrared-shielding coating and infrared-shielding film |
| KR102341902B1 (en) * | 2016-09-09 | 2021-12-21 | 카오카부시키가이샤 | Dicarboxylic acid crystal and method for producing same |
| JP7064827B2 (en) * | 2017-03-06 | 2022-05-11 | 東洋スチレン株式会社 | Optical styrene resin composition, molded product and light guide |
| JP6585742B2 (en) * | 2018-01-10 | 2019-10-02 | 東洋スチレン株式会社 | Styrenic resin composition for optics |
| JP7247200B2 (en) * | 2018-08-09 | 2023-03-28 | 株式会社カネカ | Expandable resin particles, method for producing the same, and expanded molded article |
| CN113661207A (en) * | 2019-04-23 | 2021-11-16 | 电化株式会社 | Styrene resin composition, molded article, and light guide plate |
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| JP2017061697A (en) | 2017-03-30 |
| JP6248169B2 (en) | 2017-12-13 |
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| WO2013094641A1 (en) | 2013-06-27 |
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| JP2017078172A (en) | 2017-04-27 |
| TW201716488A (en) | 2017-05-16 |
| KR20190085556A (en) | 2019-07-18 |
| KR20140107474A (en) | 2014-09-04 |
| TWI605086B (en) | 2017-11-11 |
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| CN103998514A (en) | 2014-08-20 |
| TWI570179B (en) | 2017-02-11 |
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| TW201345967A (en) | 2013-11-16 |
| KR101998748B1 (en) | 2019-10-01 |
| CN103998514B (en) | 2017-04-26 |
| JPWO2013094641A1 (en) | 2015-04-27 |
| JP2018090813A (en) | 2018-06-14 |
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| CN106947177A (en) | 2017-07-14 |
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