KR101752013B1 - Polycarbonate resin composition, and molded article produced from the resin composition - Google Patents
Polycarbonate resin composition, and molded article produced from the resin composition Download PDFInfo
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- KR101752013B1 KR101752013B1 KR1020117028305A KR20117028305A KR101752013B1 KR 101752013 B1 KR101752013 B1 KR 101752013B1 KR 1020117028305 A KR1020117028305 A KR 1020117028305A KR 20117028305 A KR20117028305 A KR 20117028305A KR 101752013 B1 KR101752013 B1 KR 101752013B1
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- 0 CC(*)(c1ccccc1)c1c(C)ccc(C(*)(*)c2ccccc2)c1 Chemical compound CC(*)(c1ccccc1)c1c(C)ccc(C(*)(*)c2ccccc2)c1 0.000 description 2
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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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
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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Abstract
0.01 to 0.15 parts by mass of a phosphorous acid ester represented by the following general formula (I) or the like and 0.01 to 0.15 parts by mass of an organopolysiloxane compound having a phenyl group, a methoxy group, and a vinyl group, based on 100 parts by mass of the polycarbonate A polycarbonate resin composition which is formed by molding the resin composition and is excellent in mold releasability by reducing yellow mold and silver generation and mold adhesion of a polycarbonate resin composition by a molded article such as a light guide plate, film or sheet, A molded article comprising the resin composition is provided.
[Chemical Formula 1]
(Wherein R 1 represents an aryl group or an alkyl group, which may be the same or different)
Description
The present invention relates to a polycarbonate resin composition and a molded article made of the resin composition. More particularly, the present invention relates to a polycarbonate resin composition which is free from yellowing or silver occurrence in a resin composition even in high temperature molding, A carbonate resin composition, and a molded article comprising the resin composition.
2. Description of the Related Art In recent years, thinner liquid crystal displays have been developed, and injection molded light guide plates having a thickness of 0.25 mm have been developed. However, since the flowability of the polycarbonate is insufficient, it is very difficult to injection-mold the thin light guide plate, and thus molding can not be performed at 280 to 320 ° C, which is the general recommended molding condition of polycarbonate. For this reason, there are cases where molding at 360 to 380 ° C other than the normal condition is carried out, and there is a case in which a trace of air on the surface of the molded article called silver or yellowing of the polycarbonate is generated and light emitted from the backlight unit is yellowish , The transmittance is lowered, and the function can not be attained even in the form of a light guide plate.
For example, a resin composition for a light guide plate having excellent light transmittance, thermal stability, and moldability has been proposed by adding an antioxidant and a releasing agent to a polycarbonate resin having a molecular weight of 13000 to 15000 (Patent Document 1). Further, by adding a polyorganosiloxane having at least a phenyl group on its side chain and a branched siloxane structure and a dynamic viscosity of 1 to 200 cSt at 25 DEG C to the polycarbonate resin, , And a color tone is excellent (Patent Document 2).
However, the addition of an antioxidant and a releasing agent to the polycarbonate resin described in Patent Document 1 causes a problem that a large amount of silver, which is one of the defective appearance, is generated at a molding condition of 360 ° C or higher, and does not function as, for example, a light guide plate there was. Patent Document 1 also discloses that the content of the low molecular weight aromatic polycarbonate polymer having a molecular weight of less than 1,000 is 2% by mass or less, thereby preventing mold adhesion and deterioration of appearance. However, , There is a problem in that the molding of the light guide plate can not prevent the attachment of the mold even if only the component having a molecular weight of 1,000 or less is taken into consideration.
In addition, the resin composition of Patent Document 2 has a problem that the generation of gas under high-temperature molding conditions of 340 ° C or higher and the mold attachment are not sufficient.
In addition, if silver occurs in a molded article, it can not be shipped as a product, and if a mold is adhered to the molded article, there is a problem of sticking to the molded article so that it can not be shipped as a product but needs to be stopped and cleaned Occurs. In particular, since the light-guiding metal plate type has fine prisms or lenses, if the number of times of cleaning increases, there is a risk of causing scratches on the microstructure, and therefore, it is necessary to avoid this.
The present invention relates to a polycarbonate resin composition which solves the above problems in the polycarbonate resin composition and which is excellent in mold releasability with reduced yellowing and silver generation and mold adhesion of the resin composition and a molded article made of the resin composition And to provide the above objects.
In order to achieve the above object, the inventors of the present invention have extensively studied the components contained in the polycarbonate resin composition, additives, and the like, and as a result, have found a polycarbonate resin composition capable of achieving the above object. The present invention has been completed based on this finding.
That is, the present invention is directed to the following.
(1) 0.01 to 0.15 parts by mass of a phosphorous acid ester represented by the following general formula (I) and / or (II) and 0.01 to 0.15 parts by mass of an organopolysiloxane compound having a phenyl group, a methoxy group and a vinyl group, based on 100 parts by mass of the polycarbonate By mass of the polycarbonate resin composition.
[Chemical Formula 1]
(In the formula (I), R 1 represents an aryl group or an alkyl group, and may be the same or different)
(2)
Wherein R 9 is an alkyl group having 1 to 20 carbon atoms and R 10 to R 14 are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, which may be the same or different,
2. The polycarbonate resin composition according to 1 above, wherein the content of the phosphorous ester and the organopolysiloxane compound is 0.03 to 0.1 part by mass, respectively.
3. The polycarbonate resin composition according to 1 or 2 above, wherein the acetone-soluble fraction of the polycarbonate is 9 mass% or less.
4. A molded article obtained by molding the polycarbonate resin composition according to any one of 1 to 3 above.
5. A light guide plate, film or sheet formed by molding the polycarbonate resin composition according to any one of 1 to 3 above.
It is possible to provide a polycarbonate resin composition excellent in mold releasability with reduced yellowing and generation of silver and mold adhesion of the polycarbonate resin composition and a molded article comprising the resin composition.
Hereinafter, the present invention will be described in detail.
The present invention relates to a polycarbonate composition comprising 0.01 to 0.15 parts by mass of a phosphorous acid ester represented by the following general formula (I) and / or (II) and 100 to 200 parts by mass of an organopolysiloxane compound having a phenyl group, a methoxy group, 0.15 parts by mass of a polycarbonate resin composition.
(3)
[In the formula (I), R 1 represents an aryl group or an alkyl group, which may be the same or different]
[Chemical Formula 4]
Wherein R 9 is an alkyl group having 1 to 20 carbon atoms and R 10 to R 14 are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, which may be the same or different,
Of the phosphorous acid esters represented by the general formula (I) and / or (II), the phosphorous acid ester represented by the formula (I) is particularly preferable.
In the present invention, a polycarbonate resin in which a predetermined amount of the polycarbonate is mixed with a predetermined amount of a phosphorous ester represented by the general formula (I) and / or (II) and an organopolysiloxane compound having a phenyl group, a methoxy group, By the composition, a remarkable synergistic effect for solving the problems of the present invention is obtained.
The polycarbonate resin to be used in the present invention is not particularly limited and those produced by various conventionally known methods can be used. For example, it is possible to use a solution prepared by a solution method (interfacial polycondensation method) or a melting method (ester exchange method) of a divalent phenol and a carbonate precursor, that is, in the presence of an end stopper, A polycondensation method, or a method of transesterifying with divalent phenol, diphenyl carbonate or the like in the presence of an end terminator.
As the dihydric phenol, various ones can be mentioned, and 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) is particularly preferable. Bisphenols other than bisphenol A include, for example, bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane; Bis (4-hydroxyphenyl) naphthylmethane; 1,1-bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-tetramethylphenyl) propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane; 2,2-bis (4-hydroxy-3,5-tetrachlorophenyl) propane; Bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-tetrabromophenyl) propane, and 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 4,4'-dihydroxyphenyl ether; Dihydroxyaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyl phenyl ether, and 4,4'-dihydroxydiphenyl sulfide; Dihydroxy diaryl sulfide such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide; Dihydroxy diaryl sulfoxide such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone; Dihydroxydiarylsulfone such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, and dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl and the like . These divalent phenols may be used alone or in combination of two or more.
On the other hand, examples of the carbonate precursor include carbonyl halide, carbonyl ester, or haloformate, and specifically, phosgene, dihaloformate of divalent phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.
The general PC resin may have a branched structure. The branched branch may be 1,1,1-tris (4-hydroxyphenyl) ethane,?,? ',? "-Tris (4-hydroxyphenyl) 1,3,5-triisopropylbenzene, fluoroglycine, trimellitic acid, and 1,3-bis (o-cresol).
As the terminal terminating agent, a monovalent carboxylic acid and its derivative or a monovalent phenol may be used. (Perfluoronylphenyl) phenol, p- (perfluorooxylphenyl) phenol, p-phenylphenol, p-cumylphenol, p- Phenol, p-tert-perfluorobutylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) 3,3,3-hexafluoropropyl] phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p-hydroxybenzoic acid perfluorododecyl, p- (1H, 2-hexyloxy) phenol, 2H, 2H, 9H-perfluorononanic acid, and 1,1,1,3,3,3-tetrafluoro-2-propanol.
In addition, a branching agent may be contained, for example, 1,1,1-tris (4-hydroxyphenyl) ethane; α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; A compound having three or more functional groups such as fluoroglycine, trimellitic acid, and 1,3-bis (o-cresol) may be used.
In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin is usually 10,000 to 50,000, preferably 13,000 to 35,000, and more preferably 14,000 to 20,000.
The viscosity average molecular weight (Mv) is determined by measuring the viscosity of a methylene chloride solution at 20 占 폚 using an Ubbelohde type viscometer, and calculating the intrinsic viscosity [?]
[?] = 1.23 x 10 -5 Mv 0.83
Next, phosphorous acid esters are used in the present invention. As the phosphorous acid ester, the following formula (I) and / or (II) may be mentioned, and especially (I) is preferable.
[Chemical Formula 5]
[In the formula (I), R 1 represents an aryl group or an alkyl group, which may be the same or different]
In the general formula (I), when R 1 is an aryl group, R 1 is preferably an aryl group represented by the following general formula (a), (b) or (c)
[Chemical Formula 6]
[In the formula (a), R 2 represents an alkyl group having 1 to 10 carbon atoms]
(7)
[In the formula (b), R 3 represents an alkyl group having 1 to 10 carbon atoms]
[Chemical Formula 8]
As the phosphorous acid ester represented by the general formula (I), Adekastab PEP36 (trade name, available from Asahi Denka Co., Ltd.), which is a commercially available product, can be used in the present invention, but it is not limited to PEP36.
[Chemical Formula 9]
Wherein R 9 is an alkyl group having 1 to 20 carbon atoms and R 10 to R 14 are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, which may be the same or different,
As the phosphite ester represented by the general formula (II), adecastab C (trade name, manufactured by Asahi Denka Co., Ltd.), which is a commercially available product, can be used in the present invention, but not limited to adecastab C alone.
The phosphorous acid ester represented by the general formula (I) and / or (II) is added in an amount of about 0.01 to about 0.15 parts by mass, preferably 0.03 to 0.1 part by mass, and more preferably 0.03 to 0.07 part by mass per 100 parts by mass of the polycarbonate do.
When the addition amount of the phosphorous acid ester represented by the general formula (I) and / or the general formula (II) is in the range of 0.01 to 0.15 parts by mass based on 100 parts by mass of the polycarbonate, Even if the molding conditions are as high as described above, the effect of gas generation, yellowing, and mold adhesion is greatly reduced.
On the other hand, if the addition amount is less than 0.01 part by mass, sufficient effect can not be exhibited. If the addition amount exceeds 0.15 parts by mass, there is a risk that the mold adhesion increases and the heat resistance of the resin composition deteriorates.
On the other hand, it is essential that the organopolysiloxane compound has a phenyl group, a methoxy group, and a vinyl group, and any desired effect can not be obtained even if the organopolysiloxane compound is dropped. For example, Japanese Patent Application Laid-Open No. 2004-250557 discloses the use of methylphenylsiloxane or the like, but the organopolysiloxane compound of the present invention is structurally different from this compound.
The organopolysiloxane compound may be any one having a phenyl group, a methoxy group and a vinyl group, and preferably has a kinematic viscosity at 25 DEG C of about 1 to 500 cSt.
The organopolysiloxane compound having a phenyl group, a methoxy group and a vinyl group is used in an amount of about 0.01 to 0.15 parts by mass, preferably 0.03 to 0.1 part by mass, more preferably 0.03 to 0.07 parts by mass, per 100 parts by mass of the polycarbonate .
When the added amount is in the range of 0.01 to 0.15 parts by mass based on 100 parts by mass of the polycarbonate, the occurrence of silver occurs even under the molding conditions of a high temperature of 340 占 폚 or more, However, the effect of greatly reducing the mold attachment is exhibited.
On the other hand, when the addition amount is less than 0.01 part by mass, a sufficient effect is not exhibited. When the addition amount exceeds 0.15 parts by mass, there is a risk that the adhesion of the mold increases or the resin becomes cloudy.
In the present invention, a commercially available organopolysiloxane compound having a phenyl group, a methoxy group and a vinyl group may be KR-511 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), but is not limited to KR-511.
Since the polycarbonate resin composition of the present invention contains the above components, the polycarbonate resin composition having excellent releasability can be obtained with reduced yellowing of the molded article, occurrence of silver, and mold adhesion even under high temperature molding conditions. It is preferable to adjust the acetone soluble fraction of polycarbonate to 9 mass% or less, because the mold adhesion is further suppressed.
That is, as a result of examining a decomposable low-molecular component that causes mold adhesion at the time of high-temperature molding of the polycarbonate resin composition, it has been found that if only conventionally proposed low-molecular components having a molecular weight of less than 1000 are contained in an amount of 2% It has been found that the adhesion of the mold can not be prevented.
Therefore, in the present invention, the molecular weight of the low molecular weight component in the polycarbonate which is easily decomposed at the time of molding is about 5000 or less. An acetone-soluble fraction was employed as a method for detecting components having a molecular weight of 5,000 or less. That is, in the present invention, when the oligomer is synthesized and polymerized, polymerization of the catalyst, terminal stopper and the like, optimization of the timing, and purification process of the solvent are studied. When the acetone soluble fraction is 9 mass% or less , It is found that mold attachment is more remarkably suppressed.
By making the acetone soluble fraction of the polycarbonate 9 mass% or less, adhesion of a sufficient mold can be prevented even in the molding of the light guide plate having various molding conditions and molding methods.
The method for producing the polycarbonate resin composition of the present invention is not particularly limited. The polycarbonate and the above components are mixed and subjected to melt kneading. The melt-kneading can be carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a cone . The heating temperature at the time of melt kneading is suitably selected in the range of usually about 220 to 280 deg.
An example of a specific manufacturing method is described below.
That is, 0.01 to 0.15 parts by mass of an organopolysiloxane compound having a phenyl group, a methoxy group and a vinyl group is first added to 100 parts by mass of a polycarbonate, and a known mixer such as a ribbon blender, Banbury mixer, drum tumbler, Henschel mixer, , 0.01 to 0.15 parts by mass of a phosphorous acid ester represented by the general formula (1) is further added, and the mixture is sufficiently mixed with the mixer. The blend thus obtained is melted and kneaded by heating at a cylinder temperature of 240 to 280 DEG C using a single screw extruder, a twin screw extruder, a coneizer, a multiaxial screw extruder and the like. Thereafter, the mixture is pelletized using a pelletizer or the like to obtain the polycarbonate resin composition of the present invention.
Further, the phosphorous ester represented by the above general formula (1) and / or (II) and the organopolysiloxane compound having a phenyl group, a methoxy group and a vinyl group may be added to polycarbonate at the same time and mixed.
The polycarbonate resin composition of the present invention can be produced by using the above melt-kneaded product or the obtained resin pellets as raw materials by a known molding method such as a blow molding method, an injection molding method, an injection compression molding method, an extrusion molding method, a vacuum molding method, , A press molding method, an air-blow molding method, a foam molding method, a thermal bending molding method, a compression molding method, a calender molding method, and a rotary molding method.
In the present invention, a light guide plate, a lens, and a film can be exemplified as such a molded article.
Of these, the light guide plate is not particularly limited, and a flat plate having a thickness of about 3 mm may be formed. In addition, the shape is not necessarily limited to a flat plate shape, but may be a curved plate having a lens effect, and may be suitably selected according to purposes and applications. For example, the light guide plate may have a wedge-shaped cross section that gradually becomes thinner as the thickness of the light guide plate is away from the light source. Alternatively, a structure may be employed in which a display portion formed of a separate member is integrally formed on the front surface of the planar light-emitting body.
In order to obtain uniform surface light emission, it is necessary to form a light-scattering layer rich on the back surface of the light guide plate as it moves away from the light source. To this end, A printing process for forming a dense pattern such as a dot shape or a slit shape may be performed using a paint. Further, instead of the dot printing, a prism transfer method in which a prism cut is simultaneously formed at the time of injection molding in the production of a light guide plate may be used.
In forming the light scattering layer on the light guide plate, the light guide plate is not limited to the entire surface of the light guide plate, but may be formed on a part thereof.
In the light guide plate, lens or film, which is a molded article of the present invention, yellowing and silver which are likely to occur during high-temperature molding are suppressed, and a product having excellent transparency can be provided. In addition, since the mold attachment is reduced and the molded article including the polycarbonate resin excellent in releasability is obtained, the molding efficiency is greatly improved.
In the present invention, in addition to the above-mentioned components, various additives can be added to the extent that the performance is not impaired. Examples of the additives include antioxidants such as hindered phenol-based compounds, arylphosphine-based compounds and ester-based compounds other than the phosphorous acid esters, light stabilizers such as UV absorbers and hindered amine-based UV absorbers, , A colorant, an antistatic agent, an anti-blocking agent, a release agent, a releasing agent other than the organopolysiloxane, a plasticizer, and a lubricant.
Among them, the antioxidant includes, for example, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, Tricyclohexylphosphite, tricresylphosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (ethylphenyl) phosphite, tris Monoalkyldiarylphosphite such as 2-ethylhexyldiphenylphosphite and the like, trialkylphosphite such as trimethylphosphate, triethylphosphate, tributylphosphate, trioctylphosphate, tridecylphosphate, trioctadecylphosphate, etc. Tricycloalkyl phosphates such as trialkylphosphate and tricyclohexylphosphate, tri (P-tolyl) phosphine, tris (p-nonylphenyl) phosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris , And tris (naphthyl) phosphine, and the like.
Examples of commercially available products of hindered phenol-based antioxidants include "Irganox 1076" (trade name, manufactured by Chiba Gijutsu), "Irganox 1010" (trade name, (Trade name, manufactured by Ethyl Company) and "SUMILINER GM" (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the light diffusing agent include any one or a combination of two or more selected from crosslinked polymethacrylate resin particles, silicone resin particles, silica particles, quartz particles, silica fibers, quartz fibers and glass fibers .
The ultraviolet absorber is preferably selected from malonic acid ester compounds, oxalylarnide compounds, and benzotriazole compounds. These may be used singly or in combination of two or more.
Examples of the malonic ester compound include benzylidene bisdiethyl malonate and 4-methoxyphenyl-methylene-dimethyl ester. As the oxalylarnide-based compound, an oxalylarnide compound having a hydrocarbon group having 1 to 12 carbon atoms may, for example, be mentioned. As the benzotriazole-based compound, an acrylic polymer having a side chain having a benzotriazole-based skeleton is preferable.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.
Example
[Examples 1 to 8, Comparative Examples 1 to 8]
Each component was mixed in the ratios shown in Table 1, and then kneaded in a single-shaft kneading extruder (diameter 40 mmφ) at 280 ° C, screw rotation speed of 100 rpm, and discharge rate of 15 kg / hr to pelletize. In Table 1, numerical values representing the addition ratios of the respective components represent the parts by mass relative to 100 parts by mass of the polycarbonate resin.
Next, the pellets obtained in the above process were dried by hot air at 120 ° C for 5 hours, and then molded at a molding temperature of 380 ° C and a mold temperature of 80 ° C using a molding machine (Sumitomo Nestel N515 / 150 manufactured by Sumitomo Heavy Industries, Ltd.) , The molding cycle was fixed, and 20 shots were formed so that the residence time in the cylinder became constant, and sampling was started. By adjusting the cooling time, the total light transmittance, the yellowness index (YI), and the plate for appearance evaluation of 40 mm x 80 mm x 3.0 mm with a retention time of 5 minutes and 20 minutes in the molding machine were manufactured.
The total light transmittance and yellowness of each of the samples obtained by injection molding were measured by a tester manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7105.
The appearance (presence / absence of silver generation) of the obtained sample with a retention time of 20 minutes in the molding machine was visually evaluated in accordance with the following evaluation criteria.
◎ · Silver is not observed.
○ · Although a little silver is observed, it may be allowed depending on the type of product.
× · · Silver is often observed and is not allowed as a product.
×× · · Silver is very much observed and is not allowed as a product.
The obtained pellets were each subjected to hot-air drying at 120 ° C for 5 hours, and then dried at a molding temperature of 340 ° C and a mold temperature of 80 ° C using SG100M-HP manufactured by Sumitomo Heavy Industries Co., Ltd. for a sample of 40 mm x 80 mm x 2.0 mm Was continuously formed in 1500 shots. After 1500-shot continuous molding, mold particles were taken out, and the mold adhesion was visually evaluated in accordance with the following evaluation criteria.
◎ Attachment is not observed.
Appearance is slightly observed.
X · · Attachment is observed a lot.
XX · · · Attachment is very much observed.
The types of the materials used in this example and the comparative example are as follows.
(A) Polycarbonate
PC-1: bisphenol A polycarbonate manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight: 15,000, acetone soluble fraction: 8.5% by mass)
PC-2: bisphenol A polycarbonate manufactured by Idemitsu Kosan Co., viscosity average molecular weight 14000, acetone soluble fraction: 8.7% by mass)
PC-3: Bisphenol A polycarbonate manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight: 17000, acetone soluble fraction: 8.5% by mass)
PC-4: Bisphenol A polycarbonate manufactured by Idemitsu Kosan Co., viscosity average molecular weight 15,000, acetone soluble fraction: 11.7% by mass)
PC-5: bisphenol A polycarbonate, viscosity average molecular weight 17000, acetone soluble fraction: 10.1% by mass, manufactured by Idemitsu Kosan Co., Ltd.)
In the above, the method of measuring the acetone-soluble fraction is as follows.
20 g of the sample was extracted with acetone solvent at 80 ° C for 3 hours, filtered and dried using an evaporator, and then the acetone extraction amount was calculated.
The production method of the polycarbonate PC-1 to PC-5 is as follows.
Production Example 1 (Production of polycarbonate PC-1)
(1) Polycarbonate oligomer synthesis process
0.2% by mass sodium aditonate (Na 2 S 2 O 4 ) was added to a later-dissolved bisphenol A (BPA) in a 5.6% by mass aqueous solution of sodium hydroxide to prepare BPA Was dissolved to prepare an aqueous solution of sodium hydroxide of BPA. A tubular reactor having an inner diameter of 6 mm and a tube length of 30 m was continuously passed an aqueous solution of sodium hydroxide of BPA at a flow rate of 40 l / hr and methylene chloride at a flow rate of 15 l / hr, and a flow rate of 4.0 kg / hr of phosgene ≪ / RTI > The tubular reactor had a jacket portion, and cooling water was passed through the jacket to maintain the temperature of the reaction liquid at 40 캜 or lower. The reaction liquid sent out from the tubular reactor was continuously introduced into a molding reactor equipped with an internal volume of 40 L of a bucket equipped with a retreating blade and further an aqueous solution of sodium hydroxide of BPA at 2.8 L / hr, 25 mass% The reaction was carried out at 29 to 32 占 폚 with 0.07 l / hr of sodium aqueous solution, 17 l / hr of water and 1 mass% of triethylamine aqueous solution at a flow rate of 0.64 l / hr. The reaction liquid was continuously withdrawn from the molding reactor, and the water phase was separated and removed by stopping it, and a methylene chloride phase was collected. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 338 g / l and a chloroformate group concentration of 0.71 mol / l.
(2) Polymerization process of polycarbonate
15.0 L of the oligomer solution, 10.0 L of methylene chloride, 182 g of p-tert-butylphenol (PTBP) and 1.5 mL of triethylamine were charged into a plastic reactor having an internal volume of 50 L equipped with a stirrer, To this was added an aqueous solution of sodium hydroxide of bisphenol A (BPA) (obtained by dissolving 1.1 kg of bisphenol A (BPA) in an aqueous solution obtained by dissolving 642 g of sodium hydroxide and 2.2 g of sodium aditioate in 9.4 L of water) Time polymerization reaction was carried out. To dilute, 10.0 L of methylene chloride was added, and the mixture was allowed to stand still to separate the organic phase containing polycarbonate and the aqueous phase containing excess bisphenol A (BPA) and sodium hydroxide, and the organic phase was isolated.
(3) Cleaning process
The methylene chloride solution of the polycarbonate obtained in the above step (2) was sequentially washed with a 15 vol% aqueous solution of 0.03 mol / l sodium hydroxide and 0.2 mol / l hydrochloric acid, and then the electrical conductivity Washing with pure water was repeated until it became 0.05 ㎲ / m or less.
(4) Flaking process
The methylene chloride solution of the polycarbonate obtained in the above step (3) was concentrated and pulverized to obtain a polycarbonate flake (PC-1). The obtained flakes were dried under reduced pressure at 120 DEG C for 12 hours. The obtained polycarbonate had a viscosity average molecular weight of 15000 and an acetone-soluble fraction of 8.5%.
Production Example 2 (Production of polycarbonate PC-2)
(2) Production of PC-1 was carried out except that the amount of p-tert-butylphenol (PTBP) in the polycarbonate polymerization step was changed to 199 g. The viscosity average molecular weight was 14000 and the acetone soluble fraction was 8.7%.
Production Example 3 (Production of polycarbonate PC-3)
(2) The same procedure as in the production of PC-1 was conducted except that the amount of p-tert-butylphenol (PTBP) in the polycarbonate polymerization step was changed to 154 g. The viscosity average molecular weight was 17000 and the acetone soluble fraction was 8.5%.
Production Example 4 (Production of polycarbonate PC-4)
(1) Polycarbonate oligomer synthesis process
0.2% by mass sodium aditonate (Na 2 S 2 O 4 ) was added to a later-dissolved bisphenol A (BPA) in a 5.6% by mass aqueous solution of sodium hydroxide to prepare BPA Was dissolved to prepare an aqueous solution of sodium hydroxide of BPA. A tubular reactor having an inner diameter of 6 mm and a tube length of 30 m was continuously passed an aqueous solution of sodium hydroxide of BPA at a flow rate of 40 l / hr and methylene chloride at a flow rate of 15 l / hr, and a flow rate of 4.0 kg / hr of phosgene ≪ / RTI > The tubular reactor had a jacket portion, and cooling water was passed through the jacket to keep the temperature of the reaction liquid at 40 캜 or lower.
The reaction liquid sent out from the tubular reactor was continuously taken out, and the water phase was separated and removed by stopping it, and a methylene chloride phase was collected. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 280 g / l and a chloroformate group concentration of 1.02 mol / l.
(2) Polymerization process of polycarbonate
12.5 L of the oligomer solution, 10.8 L of methylene chloride, 166 g of p-tert-butylphenol (PTBP) and 1.8 mL of triethylamine were introduced into a plastic reactor having an internal volume of 50 L equipped with a stirrer, To this was added an aqueous solution of sodium hydroxide of bisphenol A (BPA) (obtained by dissolving 1.3 kg of bisphenol A (BPA) in an aqueous solution obtained by dissolving 765 g of sodium hydroxide and 2.7 g of sodium aditioate in 11.2 L of water) Time polymerization reaction was carried out. To dilute, 10.0 L of methylene chloride was added, and the mixture was allowed to stand still to separate the organic phase containing polycarbonate and the aqueous phase containing excess bisphenol A (BPA) and sodium hydroxide, and the organic phase was isolated.
(3) Cleaning process
The methylene chloride solution of the polycarbonate obtained in the above step (2) was sequentially washed with a 15 vol% aqueous solution of 0.03 mol / l sodium hydroxide and 0.2 mol / l hydrochloric acid, and then the electrical conductivity Washing with pure water was repeated until it became 0.05 ㎲ / m or less.
(4) Flaking process
A polycarbonate flake (PC-4) was obtained by concentrating and pulverizing the methylene chloride solution of the polycarbonate obtained in the above step (3). The obtained flakes were dried under reduced pressure at 120 DEG C for 12 hours. The resulting polycarbonate had a viscosity average molecular weight of 15,000 and an acetone-soluble fraction of 11.7%.
Production Example 5 (Production of polycarbonate PC-5)
(2) Production of PC-4 was carried out except that the PTBP of the polycarbonate polymerization process was changed to 141 g. The viscosity average molecular weight was 17000 and the acetone soluble fraction was 10.1%.
(B) Antioxidants
Antioxidant 1: Adekastab PEP36 (trade name, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, manufactured by Asahi Denka Co.,
Antioxidant-2: Irg (Irgafos) 168 (trade name, tris (2,4-di-tert-butylphenyl) phosphite, manufactured by Chiba Specialty Chemicals Co.,
(2,4-tert-butyl-6-methylphenyl) ethylphosphite, manufactured by Chiba Specialty Chemicals Co.,
(2,4-di-tert-butylphenyl) -4,4'-biphenylene-diphosphite] manufactured by Chiba Specialty Chemicals Co.,
(C) an organopolysiloxane compound
Organosiloxane-1: KR-511 (trade name, an organopolysiloxane compound having a phenyl group, a methoxy group and a vinyl group, manufactured by Shin-Etsu Chemical Co., Ltd.)
· Organosiloxane-2: SH556 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd., polymethylphenylsiloxane (branched type))
The results of the examples are shown in Table 1, and the results of the comparative examples are shown in Table 2, respectively.
From Table 1, it can be seen that good results can be obtained in the molded articles molded from the polycarbonate resin composition of the present invention.
On the other hand, the following can be seen from Table 2 which shows a comparative example.
Comparative Example 1 in which no organosiloxane was added showed that the generation of silver which is the same as YI and the light transmittance but the appearance defective was not suppressed and the adhesion of the mold was further increased as compared with Example 1 .
As compared with Comparative Example 2 in which the addition amount of the antioxidant is more than 0.15 parts by mass, which is the upper limit of the present invention, it is understood that the adhesion of the mold is not suppressed because the antioxidant is excessively large as compared with Example 4. [
Comparative Example 3 using organosiloxane-2 with a polycarbonate having a high molecular weight showed a deterioration in YI at the time of staying for 20 minutes as compared with Example 3. In addition, since the siloxane paper is different, it can be seen that there are considerably many silver or metal molds with poor appearance.
Compared with Comparative Example 4 using organosiloxane-2, compared with Example 3, YI deteriorated at the time of staying for 5 minutes and 20 minutes. In addition, there are many silver defects in appearance, and it can be seen that many metal molds are attached.
Comparative Example 6 using the antioxidant-3 showed a deterioration in YI during the 20 minute retention especially when compared with Example 3. In addition, it can be seen that there are a lot of silver or mold attaching which is defective in appearance.
Comparative Example 7 using the antioxidant-4 showed a deterioration in the YI during the 20 minute retention especially when compared with the Example 3. Also, it can be seen that there is much mold adhesion.
Compared with Examples 3 and 8 using PC-5 having a low molecular weight and Comparative Example 8 using the antioxidant-1 and organosiloxane-1, silver was slightly generated , And mold adhesion occurred.
From the above, it has been found that in the polycarbonate resin composition in which a predetermined amount of the polycarbonate is combined with the phosphorous acid ester represented by the general formula (I) and / or (II) and the organopolysiloxane compound having a phenyl group, , A remarkable synergistic effect can be obtained.
Industrial availability
The polycarbonate resin composition of the present invention is a polycarbonate resin composition excellent in releasability and reduced in yellowing and silver generation and mold adhesion even in molding under high temperature conditions and is excellent in electric and electronic parts, optical members, architectural parts, OA equipment , Electric / electronic devices, and information / communication devices, light guide plates, films, and sheets.
Claims (5)
[Chemical Formula 1]
[In the formula (I), R 1 represents an aryl group or an alkyl group, which may be the same or different]
(2)
(In the formula (II), R 9 is an alkyl group having 1 to 20 carbon atoms, and R 10 to R 14 are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, which may be the same or different)
Wherein the content of the phosphorous ester and the organopolysiloxane compound is 0.03 to 0.1 part by mass, respectively.
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| JP2009131303A JP5593040B2 (en) | 2009-05-29 | 2009-05-29 | Polycarbonate resin composition and molded product comprising said resin composition |
| JPJP-P-2009-131303 | 2009-05-29 | ||
| PCT/JP2010/058882 WO2010137611A1 (en) | 2009-05-29 | 2010-05-26 | Polycarbonate resin composition, and molded article produced from the resin composition |
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| KR (1) | KR101752013B1 (en) |
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| JP5879124B2 (en) | 2011-12-28 | 2016-03-08 | 出光興産株式会社 | Method for producing polycarbonate resin composition pellets |
| JP6408760B2 (en) * | 2013-11-11 | 2018-10-17 | 出光興産株式会社 | Polycarbonate resin composition |
| JP6828954B2 (en) * | 2013-11-11 | 2021-02-10 | 出光興産株式会社 | Polycarbonate resin molding material |
| CN109971147B (en) * | 2014-02-28 | 2022-06-28 | 出光兴产株式会社 | Polycarbonate resin and polycarbonate resin composition |
| CN106062034A (en) * | 2014-02-28 | 2016-10-26 | 出光兴产株式会社 | Polycarbonate resin and polycarbonate resin composition |
| JP6929838B2 (en) | 2015-10-14 | 2021-09-01 | コンバテック・テクノロジーズ・インコーポレイテッドＣｏｎｖａｔｅｃ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｉｎｃ | Medical device with an opening system |
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| JP2005096421A (en) | 2003-09-02 | 2005-04-14 | Mitsubishi Engineering Plastics Corp | Aromatic polycarbonate resin pellet for light guide plate, light guide plate, method for manufacturing light guide plate and surface illuminant |
| JP2007204737A (en) | 2006-01-06 | 2007-08-16 | Mitsubishi Engineering Plastics Corp | Aromatic polycarbonate resin composition for lightguide plate, and lightguide plate |
| JP2007284540A (en) | 2006-04-14 | 2007-11-01 | Idemitsu Kosan Co Ltd | Polycarbonate resin composition and its molded plate |
| JP2007302793A (en) * | 2006-05-11 | 2007-11-22 | Idemitsu Kosan Co Ltd | Light-diffusing resin composition and light-diffusing plate obtained using the same |
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| US20080114103A1 (en) * | 2006-11-13 | 2008-05-15 | General Electric Company | Thermoplastic Polycarbonate Compositions With Improved Static Resistance |
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| JP2005096421A (en) | 2003-09-02 | 2005-04-14 | Mitsubishi Engineering Plastics Corp | Aromatic polycarbonate resin pellet for light guide plate, light guide plate, method for manufacturing light guide plate and surface illuminant |
| JP2007204737A (en) | 2006-01-06 | 2007-08-16 | Mitsubishi Engineering Plastics Corp | Aromatic polycarbonate resin composition for lightguide plate, and lightguide plate |
| JP2007284540A (en) | 2006-04-14 | 2007-11-01 | Idemitsu Kosan Co Ltd | Polycarbonate resin composition and its molded plate |
| JP2007302793A (en) * | 2006-05-11 | 2007-11-22 | Idemitsu Kosan Co Ltd | Light-diffusing resin composition and light-diffusing plate obtained using the same |
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| JP5593040B2 (en) | 2014-09-17 |
| JP2010275484A (en) | 2010-12-09 |
| KR20120024664A (en) | 2012-03-14 |
| CN102449067B (en) | 2015-05-06 |
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| CN104212149A (en) | 2014-12-17 |
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