WO2016152165A1 - ポリカーボネート樹脂組成物および光学用成形品 - Google Patents
ポリカーボネート樹脂組成物および光学用成形品 Download PDFInfo
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- WO2016152165A1 WO2016152165A1 PCT/JP2016/001711 JP2016001711W WO2016152165A1 WO 2016152165 A1 WO2016152165 A1 WO 2016152165A1 JP 2016001711 W JP2016001711 W JP 2016001711W WO 2016152165 A1 WO2016152165 A1 WO 2016152165A1
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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
- 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
- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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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
- G02B6/0065—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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
Definitions
- the present invention relates to a polycarbonate resin composition and an optical molded article.
- Polycarbonate resins are conventionally used for molded products such as light guide plates, various lenses, and nameplates because they are excellent in impact resistance, heat resistance, transparency, and the like.
- Patent Document 1 discloses an aromatic polycarbonate resin composition for a light guide plate, in which a stabilizer and a release agent are blended with an aromatic polycarbonate resin in which a ratio of a weight average molecular weight to a number average molecular weight is defined in a specific range. Is disclosed.
- Patent Document 2 discloses a polycarbonate resin composition for optical molded articles in which polystyrene and one phosphorus-based antioxidant are blended in a polycarbonate resin.
- Patent Documents 3 to 6 various resin compositions using a polycarbonate resin and other materials in combination are proposed in order to obtain excellent light transmittance and improve the luminance of the optical member. Has been.
- Patent Documents 3 to 6 are required as a recent light guide plate material (particularly, there is no reduction in light transmittance even when molded at a high temperature for thin wall molding). ) Cannot be fully satisfied.
- JP 2007-204737 A Japanese Patent Laid-Open No. 09-020860 JP 2011-133647 A JP-A-11-158364 JP 2001-215336 A JP 2004-051700 A
- the present invention does not impair the heat resistance, mechanical strength, etc. inherent to the polycarbonate resin, has excellent thermal stability, high light transmittance, and excellent light transmittance even when molded at high temperatures.
- a polycarbonate resin composition is provided.
- the present inventors have obtained a polycarbonate resin comprising a polycarbonate resin (A) and a melt viscosity modifier (B) and a phosphite compound (C).
- the ratio of the melt viscosity of the polycarbonate resin composition to the melt viscosity of the polycarbonate resin (A) contained therein satisfies a value within a specific range, thereby reducing the light transmittance even when molded at a high temperature.
- the present inventors have found that a polycarbonate resin composition having no hue and good brightness and brightness can be obtained.
- the present invention relates to 0.005 to 3.0 parts by weight of the melt viscosity modifier (B) and 0.005 to 1.5 parts of the phosphite compound (C) with respect to 100 parts by weight of the polycarbonate resin (A).
- a polycarbonate resin composition comprising 0 part by weight, where the melt viscosity at a measurement temperature of 220 ° C.
- melt viscosity ⁇ 1 of the polycarbonate resin composition and the polycarbonate resin (A) The ratio ⁇ 1 / ⁇ 2 of the melt viscosity ⁇ 2 satisfies 0.45 ⁇ ⁇ 1 / ⁇ 2 ⁇ 0.95, and a polycarbonate resin composition and an optical molded article formed by molding the polycarbonate resin composition are provided. .
- the polycarbonate resin composition of the present invention does not impair the heat resistance, mechanical strength and other properties inherent to the polycarbonate resin, is excellent in thermal stability and weather resistance, and also has a light transmittance even when molded at a high temperature. It is an excellent one. Therefore, even if it is a thin light guide plate with a thickness of about 0.3 mm, for example, the hue changes and the appearance deteriorates, and the resin itself is less likely to deteriorate through high temperature molding. high.
- the polycarbonate resin composition used in the present invention comprises a polycarbonate resin (A), a melt viscosity modifier (B), and a phosphite compound (C).
- A polycarbonate resin
- B melt viscosity modifier
- C phosphite compound
- the polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method obtained by reacting a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate. It is a coalescence.
- a typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
- dihydroxydiaryl compound examples include, in addition to bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy) -3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2- Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3,5-dichlorophenyl) propane; 1 Bis (hydroxyaryl) cycloalkanes such as 1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane
- dihydroxydiaryl compound and, for example, a trivalent or higher valent phenol compound shown below may be mixed and used.
- Examples of the trivalent or higher phenol compound include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6. -Tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2- Bis- [4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.
- the viscosity average molecular weight of the polycarbonate resin (A) is preferably 10,000 to 100,000, and more preferably 12,000 to 30,000.
- a molecular weight regulator, a catalyst, etc. can be used as needed.
- the melt viscosity modifier (B) used in the present invention behaves like a certain type of lubricant when molding a polycarbonate resin composition to reduce the shear viscosity (shear viscosity) of the polycarbonate resin. It means that it is possible to suppress occurrence of shearing heat generation more than necessary, and thus to have an action capable of reducing or suppressing heat generation in the polycarbonate resin.
- the melt viscosity modifier (B), measured temperature 220 ° C., when the melt viscosity at a shear rate of 10 sec -1 was eta, the ratio of the melt viscosity of the melt viscosity of the polycarbonate resin composition .eta.1 and polycarbonate resin (A) ⁇ 2 ⁇ 1 / ⁇ 2 is not particularly limited as long as it can be adjusted to satisfy 0.45 ⁇ ⁇ 1 / ⁇ 2 ⁇ 0.95, but typically, the following general formula (1) And polyether derivatives represented. Other examples include silicone compounds, glycerin compounds, pentaerythritol compounds, and the like.
- Examples of the polyether derivative represented by the general formula (1) include a modified glycol consisting of a tetramethylene glycol unit and a 1-ethylethylene glycol unit (for example, HO— (CH 2 CH 2 CH 2 CH 2 O) 24 (CH 2 CH (C 2 H 5 ) O) 13 -H, etc.), for example, DCD-2000 (weight average molecular weight 2000) manufactured by NOF Corporation is commercially available.
- the weight average molecular weight of the polyether derivative represented by the general formula (1) is preferably 1000 to 4000.
- polyether derivative among the polyether derivatives represented by the general formula (1), a polyether derivative represented by the following general formula (2), general formula (3) or general formula (4) is preferable. It is.
- General formula (2) HO- (CH 2 CH 2 CH 2 CH 2 O) m (CH 2 CH 2 CH (CH 3) CH 2 O) n-H (2) (In the formula, m and n each independently represent an integer of 3 to 60, and m + n represents an integer of 8 to 90.)
- Examples of the polyether derivative represented by the general formula (2) include a modified glycol consisting of a tetramethylene glycol unit and a 2-methyltetramethylene glycol unit (for example, HO— (CH 2 CH 2 CH 2 CH 2 O) 22 (CH 2 CH 2 CH (CH 3 ) CH 2 O) 5 —H), for example, PTG-L1000 (weight average molecular weight 1000), PTG-L2000 (weight average molecular weight 2000) manufactured by Hodogaya Chemical Co., Ltd. ), Or PTG-L3000 (weight average molecular weight 3000) or the like.
- the weight average molecular weight of the polyether derivative represented by the general formula (2) is preferably 1000 to 4000.
- Examples of the polyether derivative represented by the general formula (3) include a modified glycol consisting of an ethylene glycol unit and a propylene glycol unit (for example, C 4 H 9 O— (CH 2 CH 2 O) 21 (CH 2 CH (CH 3 O) 14 -H and C 4 H 9 O— (CH 2 CH 2 O) 30 (CH 2 CH (CH 3 ) O) 30 —H etc.) are preferred, for example, Unilube 60MB-26I (weight average) Molecular weight 1700) and Unilube 50MB-72 (weight average molecular weight 3000) are commercially available.
- the weight average molecular weight of the polyether derivative represented by the general formula (3) is preferably 1000 to 4000.
- Examples of the polyether derivative represented by the general formula (4) include a modified glycol composed of an ethylene glycol unit and a propylene glycol unit (for example, HO— (CH 2 CH 2 O) 17 (CH 2 CH (CH 3 ) O) 17. -H is preferred, and for example, Unilube 50DE-25 (weight average molecular weight 1750) is commercially available, etc.
- the weight average molecular weight of the polyether derivative represented by the general formula (4) is 1000 to 4000. Is preferred.
- the melt viscosity modifier (B) used in the present invention has an appropriate lipophilicity, it is also excellent in compatibility with the polycarbonate resin (A). Therefore, the melt viscosity modifier (B) is used. The transparency of the molded product obtained from the blended polycarbonate resin composition is also improved.
- the weight average molecular weight of the polyether derivative used for such a melt viscosity modifier (B) is preferably 1000 to 4000, more preferably 2000 to 3000. When the weight average molecular weight of the polyether derivative is 1000 to 4000, a sufficient effect of improving the light transmittance can be expected, and the light transmittance does not decrease without increasing the clouding rate.
- the amount of the polyether derivative is 0.005 to 3.0 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.3 to 1. 2 parts by weight is preferred.
- the amount of the polyether derivative is less than 0.005 parts by weight, the effect of improving light transmittance and hue is insufficient.
- the amount of the polyether derivative exceeds 3.0 parts by weight, the clouding rate increases and the light transmittance decreases.
- a phosphite compound (C) is blended together with a melt viscosity modifier (B) such as a specific polyether derivative.
- B melt viscosity modifier
- the melt viscosity modifier (B) and the phosphite compound (C) it is possible to prevent the polycarbonate resin composition from generating shear heat as much as possible, and the polycarbonate resin (A)
- a polycarbonate resin composition having improved light transmittance even when molded at a high temperature can be obtained without impairing the inherent properties such as heat resistance and mechanical strength.
- phosphite compound (C) used in the present invention for example, a compound represented by the following general formula (5) is particularly suitable.
- R 1 represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3)
- R 1 is an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
- Examples of the compound represented by the general formula (5) include triphenyl phosphite, tricresyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and trisnonylphenyl phosphite. It is done. Among these, tris (2,4-di-t-butylphenyl) phosphite is particularly suitable.
- Irgaphos 168 manufactured by BASF (“Irgafoss” is a registered trademark of BSF Societas Europea) is commercially available. Is available.
- Examples of the phosphite compound include compounds represented by the following general formula (6) in addition to the compound represented by the general formula (5).
- R 2 , R 3 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
- Y and Z are either a hydroxyl group or an alcohol having 1 to 8 carbon atoms.
- R 2 , R 3 , R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a carbon number of 6 Represents an alkylcycloalkyl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group.
- examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group.
- Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
- Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl-4-i-propylcyclohexyl group and the like.
- Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group and the like.
- R 2 , R 3 and R 5 are preferably each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkylcycloalkyl group having 6 to 12 carbon atoms.
- R 2 and R 5 are preferably each independently a t-alkyl group such as a t-butyl group, a t-pentyl group, or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.
- R 3 represents the number of carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, t-pentyl, etc.
- An alkyl group of 1 to 5 is preferable, and a methyl group, a t-butyl group, or a t-pentyl group is more preferable.
- R 6 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. Further, an alkyl group having 1 to 5 carbon atoms such as an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group is more preferable.
- R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the description of R 2 , R 3 , R 5 and R 6 .
- R 4 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group.
- X represents a single bond, a sulfur atom or a group represented by the formula: —CHR 7 —.
- R 7 in the formula: —CHR 7 — represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
- Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the alkyl groups and cycloalkyl groups exemplified in the description of R 2 , R 3 , R 5 and R 6 , respectively. It is done.
- X is a single bond, a methylene group, or a methylene group substituted with a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or the like. It is preferably a single bond, and more preferably a single bond.
- A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: * —COR 8 —.
- the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group. And is preferably a propylene group.
- R 8 represents a single bond or an alkylene group having 1 to 8 carbon atoms.
- Examples of the alkylene group having 1 to 8 carbon atoms representing R 8 include the alkylene groups exemplified in the description of A above.
- R 8 is preferably a single bond or an ethylene group.
- * in the formula: * —COR 8 — is a bond on the oxygen side and indicates that the carbonyl group is bonded to the oxygen atom of the phosphite group.
- one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or 1 to carbon atoms.
- 8 represents an alkyl group.
- the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, t-butoxy group, pentyloxy group and the like.
- Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, ⁇ -methylbenzyloxy group, ⁇ , ⁇ -dimethylbenzyloxy group and the like.
- Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the description of R 2 , R 3 , R 5 and R 6 .
- Examples of the compound represented by the general formula (6) include 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl). Propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -2,4,8 , 10-Tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 6- [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy] -4,8-di-t-
- 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4) is particularly useful when the resulting polycarbonate resin composition is used in fields where optical properties are required.
- -Hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine is preferred, for example, Sumitizer GP ("Sumizer" manufactured by Sumitomo Chemical Co., Ltd.). Is commercially available as a registered trademark.
- Examples of the phosphite compound (C) include, in addition to the compound represented by the general formula (5) and the compound represented by the general formula (6), for example, represented by the general formula (7).
- the compound to be used can be preferably used.
- R 9 and R 10 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, and b and c each independently represents 0 Represents an integer of ⁇ 3.
- ADEKA STAB PEP-36 (“ADEKA STAB” is a registered trademark) manufactured by ADEKA Corporation is commercially available.
- the amount of the phosphite compound (C) is 0.005 to 1.0 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate resin (A).
- the amount is preferably 0.02 to 0.1 parts by weight.
- the amount of the phosphite compound (C) is less than 0.005 parts by weight, the light transmittance and hue are not sufficiently improved.
- the amount of the phosphite compound (C) exceeds 1.0 part by weight, the effect of improving light transmittance and hue is insufficient.
- the polycarbonate resin composition according to the embodiment is obtained by molding a polycarbonate resin composition with an ultraviolet absorber that is a component that further improves the weather resistance of the obtained polycarbonate resin composition. It can use suitably according to the use of the molded article.
- an ultraviolet absorber usually blended in a polycarbonate resin such as a benzotriazole-based compound, a triazine-based compound, a benzophenone-based compound, or an oxalic acid anilide-based compound, may be used alone or in combination of two or more. Can be used.
- benzotriazole compounds examples include 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) as benzotriazole compounds.
- 2- (2-hydroxy-5-t-octylphenyl) benzotriazole and the like are particularly suitable.
- TINUVIN 329 (TINUVIN is a registered trademark) manufactured by BASF and Seasorb manufactured by Cypro Kasei Co., Ltd. 709, Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd. and the like are commercially available.
- triazine compounds examples include 2,4-diphenyl-6- (2-hydroxyphenyl-4-hexyloxyphenyl) 1,3,5-triazine, 2- [4,6-bis (2,4-dimethyl). Phenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[( Hexyl) oxy] phenol and the like, for example, TINUVIN 1577 manufactured by BASF is commercially available.
- oxalic acid anilide compound for example, Sanduvor VSU manufactured by Clariant Japan Co., Ltd. is commercially available.
- benzophenone compounds examples include 2,4-dihydroxybenzobenzone and 2-hydroxy-4-n-octoxybenzone.
- the amount of the ultraviolet absorber is 0 to 1.0 part by weight, preferably 0 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin (A).
- the amount of the ultraviolet absorber (D) exceeds 1.0 part by weight, the initial hue of the obtained polycarbonate resin composition may be lowered.
- the quantity of a ultraviolet absorber (D) is 0.1 weight part or more, the effect which improves the weather resistance of a polycarbonate resin composition more is show
- the polycarbonate resin composition according to the embodiment includes, for example, other antioxidants, colorants, mold release agents, softeners, antistatic agents, impact modifiers, as long as the effects of the present invention are not impaired.
- Etc., polymers other than the polycarbonate resin (A), and the like may be appropriately blended.
- the production method of the polycarbonate resin composition is not particularly limited, and the polycarbonate resin (A), the melt viscosity modifier (B), and the phosphite compound (C), and if necessary, the various additives and the polycarbonate resin.
- the type and amount of each component are appropriately adjusted, and these are mixed in a known mixer such as a tumbler or ribbon blender, or melt kneaded in an extruder. Can be mentioned. By these methods, pellets of the polycarbonate resin composition can be easily obtained.
- the shape and size of the pellets of the polycarbonate resin composition obtained as described above examples include an elliptical columnar shape and a cylindrical shape.
- the size of the pellet is preferably about 2 to 8 mm in length, and in the case of an elliptical column, the major axis of the cross-sectional ellipse is preferably about 2 to 8 mm and the minor axis is about 1 to 4 mm.
- the diameter of the cross-sectional circle is preferably about 1 to 6 mm.
- Each of the obtained pellets may be such a size, all the pellets forming the pellet aggregate may be such a size, and the average value of the pellet aggregate is this Such a size may be sufficient, and there is no limitation in particular.
- the polycarbonate resin composition of the present invention is obtained by molding the polycarbonate resin composition obtained as described above.
- the embodiment has been described as an example of the present invention.
- the technology in the present invention is not limited to this, and can also be applied to embodiments in which changes, replacements, additions, omissions, etc. are made as appropriate.
- Polycarbonate resin (A) Polycarbonate resin synthesized from bisphenol A and carbonyl chloride Caliber 200-80 (Trade name, manufactured by Sumika Stylon Polycarbonate Co., Ltd., “Caliver” is a registered trademark of Stylon Europ GmbH, viscosity average molecular weight: 15000, hereinafter referred to as “PC”)
- Melt viscosity modifier (B) (polyether derivative of the following formula): 2-1. Modified glycol (polyether derivative) consisting of a tetramethylene glycol unit and a 2-methyltetramethylene glycol unit: HO— (CH 2 CH 2 CH 2 CH 2 O) 22 (CH 2 CH 2 CH (CH 3 ) CH 2 O) 5 —H PTG-L2000 (Trade name, manufactured by Hodogaya Chemical Co., Ltd., weight average molecular weight: 2000, hereinafter referred to as “compound B1”)
- Modified glycol consisting of tetramethylene glycol unit and 1-ethylethylene glycol unit: HO— (CH 2 CH 2 CH 2 CH 2 O) 24 (CH 2 CH (C 2 H 5 ) O) 13 —H DCD-2000 (Trade name, manufactured by NOF Corporation, weight average molecular weight: 2000, hereinafter referred to as “compound B2”)
- Modified glycol consisting of ethylene glycol unit and propylene glycol unit: C 4 H 9 O— (CH 2 CH 2 O) 30 (CH 2 CH (CH 3 ) O) 30 —H Unilube 50MB-72 (Trade name, manufactured by NOF Corporation, weight average molecular weight: 3000, hereinafter referred to as “compound B3”)
- Modified glycol consisting of ethylene glycol unit and propylene glycol unit: C 4 H 9 O— (CH 2 CH 2 O) 21 (CH 2 CH (CH 3 ) O) 14 —H UNILOVE 60MB-26I (Trade name, manufactured by NOF Corporation, weight average molecular weight: 1700, hereinafter referred to as “compound B4”)
- Modified glycol consisting of ethylene glycol unit and propylene glycol unit: HO— (CH 2 CH 2 O) 17 (CH 2 CH (CH 3 ) O) 17 —H UNILOVE 50DE-25 (Trade name, NOF (made by Co., Ltd., weight average molecular weight: 1750, hereinafter referred to as “compound B5”)
- Phosphite compound (C) 3-1. Tris (2,4-di-t-butylphenyl) phosphite represented by the following formula
- Irgaphos 168 (Trade name, manufactured by BASF, hereinafter referred to as “Compound C1”) 3-2. 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f ] [1, 3, 2] Dioxaphosphepine
- ADK STAB PEP-36 (Trade name, manufactured by ADEKA Corporation, hereinafter referred to as “Compound C3”)
- Examples 1 to 17 and Comparative Examples 1 to 6) The raw materials are collectively put into a tumbler at the ratios shown in Tables 1 and 2 and dry mixed for 10 minutes, and then melted using a twin-screw extruder (manufactured by Nippon Steel Works, TEX30 ⁇ ). Melt kneading was performed at a temperature of 220 ° C. to obtain pellets of a polycarbonate resin composition.
- the pellets obtained in the examples and comparative examples are substantially elliptical cylinders, and the aggregate of 100 pellets has an average length of about 5.1 mm to about 5.4 mm, and an elliptical cross section.
- the average value of the major axis was about 4.1 mm to about 4.3 mm, and the average value of the minor axis was about 2.2 mm to about 2.3 mm.
- test pieces for evaluation were prepared according to the following method and used for evaluation. The results are shown in Tables 1 and 2.
- the obtained pellets and polycarbonate resin (A) pellets were dried at 120 ° C. for 4 hours or longer, and then measured using a capillary rheometer (manufactured by Shimadzu Corporation, Flow Tester CFT-500) at a measurement temperature of 220 ° C. and a shear rate of 1 sec.
- the melt viscosity was measured in the range of -1 to 100 sec -1 .
- the melt viscosity of the polycarbonate resin composition at a shear rate of 10 sec ⁇ 1 was ⁇ 1, and the melt viscosity of the polycarbonate resin (A) was ⁇ 2.
- Test piece preparation method The obtained pellets were dried at 120 ° C. for 4 hours or more, and then an injection molding machine (manufactured by FANUC CORPORATION, ROBOSHOT S2000i100A) was used at a molding temperature of 360 ° C. and a mold temperature of 80 ° C. at JIS K 7139 “Plastics— The multipurpose test piece A type (full length 168 mm ⁇ thickness 4 mm) defined in “Test piece” was produced. The end face of this test piece was cut, and the cut end face was mirror-finished using a resin plate end face mirror machine (Megaro Technica Co., Ltd., Plavity PB-500).
- a spectrophotometer (manufactured by Hitachi, Ltd., UH4150) is equipped with a long optical path measurement accessory device, using a 50 W halogen lamp as a light source, a mask before light source 5.6 mm ⁇ 2.8 mm, a mask before sample 6.0 mm ⁇
- the spectral transmittance of each test piece for each 1 nm in the wavelength region of 380 to 780 nm was measured in the full length direction of the test piece.
- the measured spectral transmittance was integrated and rounded off to the nearest tenth to obtain the total transmittance.
- the integrated transmittance was 30000 or more as good (indicated by ⁇ in the table) and less than 30000 was defective (indicated by x in the table).
- each yellow degree was obtained in a 10 degree visual field using a standard light source D65.
- the yellowness was 20 or less as good (indicated by ⁇ in the table), and when it exceeded 20, it was determined as defective (indicated by x in the table).
- the polycarbonate resin (A) includes a melt viscosity modifier (B) such as a specific polyether derivative and a phosphite compound (C), each having a specific It is blended in proportions. Therefore, the test piece molded from the polycarbonate resin composition has a high integrated transmittance and a low yellowness.
- a melt viscosity modifier such as a specific polyether derivative and a phosphite compound (C)
- the polycarbonate resin compositions of Examples 1 to 18 have the same heat resistance as the polycarbonate resin (A), have high light transmittance in the visible region, and are molded at a high temperature. But it has excellent light transmittance. And the molded article which shape
- the polycarbonate resin composition of Comparative Example 1 has a low integrated transmittance and a high yellowness because the amount of the melt viscosity modifier (compound B1) such as a specific polyether derivative is small.
- molded the polycarbonate resin composition of the comparative example 1 is inferior to a brightness
- the polycarbonate resin composition of Comparative Example 2 has a large amount of the specific melt viscosity modifier (Compound B1), the integrated transmittance is low and the yellowness is large.
- molded the polycarbonate resin composition of the comparative example 2 is inferior to a brightness
- the test piece Since the polycarbonate resin composition of Comparative Example 3 has a small amount of the phosphite compound (C), the test piece has a large yellowness. Thus, the molded article which shape
- the polycarbonate resin composition of Comparative Example 4 has a large amount of the phosphite ester compound (C), so that the integrated transmittance is low and the yellowness is large.
- molded the polycarbonate resin composition of the comparative example 4 is inferior to a brightness
- the polycarbonate resin composition of Comparative Example 5 has a small amount of the specific melt viscosity modifier (compound B5), the integrated transmittance is low and the yellowness is large. Thus, the molded product which shape
- the polycarbonate resin composition of Comparative Example 6 has a large amount of the specific melt viscosity modifier (Compound B5), the integrated transmittance is low and the yellowness is large.
- molded the polycarbonate resin composition of the comparative example 5 is inferior to a brightness
- the components described in the detailed description include not only components essential for solving the problem but also components not essential for solving the problem in order to illustrate the above technique. obtain. Therefore, it should not be immediately recognized that these non-essential components are essential as the non-essential components are described in the detailed description.
- the polycarbonate resin composition of the present invention does not impair the heat resistance, mechanical strength and other properties inherent to the polycarbonate resin, is excellent in thermal stability and weather resistance, and also has a light transmittance even when molded at a high temperature. It is an excellent one. Therefore, even if it is a thin light guide plate with a thickness of about 0.3 mm, for example, the hue changes and the appearance deteriorates, and the resin itself is less likely to deteriorate through high temperature molding. high.
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Abstract
Description
RO-(X-O)m(Y-O)n-R’ (1)
(式中、RおよびR’は、それぞれ独立して水素原子または炭素数1~30のアルキル基を示し、Xは、炭素数2~4のアルキレン基を、Yは、炭素数3~5の分岐アルキレン基を、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。)
一般式(2):
HO-(CH2CH2CH2CH2O)m(CH2CH2CH(CH3)CH2O)n-H (2)
(式中、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。)
C4H9O-(CH2CH2)m(CH2CH(CH3)O)n-H (3)
(式中、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。)
HO-(CH2CH2O)m(CH2CH(CH3)O)n-H (4)
(式中、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。)
1.ポリカーボネート樹脂(A):
ビスフェノールAと塩化カルボニルとから合成されたポリカーボネート樹脂
カリバー200-80
(商品名、住化スタイロンポリカーボネート(株)製、「カリバー」はスタイロン ユーロップ ゲーエムベーハーの登録商標、粘度平均分子量:15000、以下「PC」という)
2-1.テトラメチレングリコールユニットと2-メチルテトラメチレングリコールユニットからなる変性グリコール(ポリエーテル誘導体):
HO-(CH2CH2CH2CH2O)22(CH2CH2CH(CH3)CH2O)5-H
PTG-L2000
(商品名、保土谷化学工業(株)製、重量平均分子量:2000、以下「化合物B1」という)
HO-(CH2CH2CH2CH2O)24(CH2CH(C2H5)O)13-H
DCD-2000
(商品名、日油(株)製、重量平均分子量:2000、以下「化合物B2」という)
C4H9O-(CH2CH2O)30(CH2CH(CH3)O)30-H
ユニルーブ50MB-72
(商品名、日油(株)製、重量平均分子量:3000、以下「化合物B3」という)
C4H9O-(CH2CH2O)21(CH2CH(CH3)O)14-H
ユニルーブ60MB-26I
(商品名、日油(株)製、重量平均分子量:1700、以下「化合物B4」という)
HO-(CH2CH2O)17(CH2CH(CH3)O)17-H
ユニルーブ50DE-25
(商品名、日油((株)製、重量平均分子量:1750、以下「化合物B5」という)
3-1.以下の式で表される、トリス(2,4-ジ-t-ブチルフェニル)フォスファイト
(商品名、BASF社製、以下「化合物C1」という)
3-2.以下の式で表される、2,4,8,10-テトラ-t-ブチル-6-〔3-(3-メチル-4-ヒドロキシ-5-t-ブチルフェニル)プロポキシ〕ジベンゾ〔d,f〕〔1,3,2〕ジオキサホスフェピン
前記各原料を、表1および表2に示す割合にて一括してタンブラーに投入し、10分間乾式混合した後、二軸押出機((株)日本製鋼所製、TEX30α)を用いて、溶融温度220℃にて溶融混練し、ポリカーボネート樹脂組成物のペレットを得た。なお、実施例及び比較例で得られたペレットは、ほぼ楕円柱状であり、ペレット100個からなる集合体は、各々、長さの平均値が約5.1mm~約5.4mm、断面楕円の長径の平均値が約4.1mm~約4.3mm、短径の平均値が約2.2mm~約2.3mmであった。
得られたペレット及びポリカーボネート樹脂(A)のペレットを120℃で4時間以上乾燥した後、キャピラリレオメータ((株)島津製作所製、フローテスタCFT-500)を用い、測定温度220℃、せん断速度1sec-1~100sec-1の範囲で溶融粘度を測定した。せん断速度10sec-1におけるポリカーボネート樹脂組成物の溶融粘度をη1、ポリカーボネート樹脂(A)の溶融粘度をη2とした。
得られたペレットを120℃で4時間以上乾燥した後、射出成形機(ファナック(株)製、ROBOSHOT S2000i100A)を用い、成形温度360℃、金型温度80℃にて、JIS K 7139「プラスチック-試験片」にて規定の多目的試験片A型(全長168mm×厚さ4mm)を作製した。この試験片の端面を切削し、切削端面について、樹脂板端面鏡面機(メガロテクニカ(株)製、プラビューティーPB-500)を用いて鏡面加工した。
分光光度計((株)日立製作所製、UH4150)に長光路測定付属装置を設置し、光源として50Wハロゲンランプを用いて、光源前マスク5.6mm×2.8mm、試料前マスク6.0mm×2.8mmを使用した状態で、波長380~780nmの領域で1nm毎の試験片各々の分光透過率を、試験片の全長方向について測定した。測定した分光透過率を積算し、十の位を四捨五入することにより、各々の積算透過率を求めた。なお、積算透過率が30000以上を良好(表中、○で示す)、30000未満を不良(表中、×で示す)とした。
前記積算透過率の評価方法において測定した分光透過率に基づき、標準光源D65を用い、10度視野にて各々の黄色度を求めた。なお、黄色度が20以下を良好(表中、○で示す)、20を超えると不良(表中、×で示す)とした。
Claims (11)
- ポリカーボネート樹脂(A)100重量部に対して、溶融粘度調整剤(B)0.005~3.0重量部及び亜リン酸エステル系化合物(C)0.005~1.0重量部を配合してなるポリカーボネート樹脂組成物であって、
測定温度220℃、せん断速度10sec-1における溶融粘度をηとしたとき、ポリカーボネート樹脂組成物の溶融粘度η1とポリカーボネート樹脂(A)の溶融粘度η2の比η1/η2が、0.45≦η1/η2≦0.95を満たすことを特徴とする、ポリカーボネート樹脂組成物。 - 前記溶融粘度調整剤(B)が、下記一般式(1)で表されるポリエーテル誘導体であり、該ポリエーテル誘導体の重量平均分子量が1000~4000である、請求項1記載のポリカーボネート樹脂組成物。
一般式(1):
RO-(X-O)m(Y-O)n-R’ (1)
(式中、RおよびR’は、それぞれ独立して水素原子または炭素数1~30のアルキル基を示し、Xは、炭素数2~4のアルキレン基を、Yは、炭素数3~5の分岐アルキレン基を、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。) - 前記一般式(1)で表されるポリエーテル誘導体が、下記一般式(2)で表されるポリエーテル誘導体であり、該ポリエーテル誘導体の重量平均分子量が1000~4000である、請求項1記載のポリカーボネート樹脂組成物。
一般式(2):
HO-(CH2CH2CH2CH2O)m(CH2CH2C(CH3)HCH2O)n-H (2)
(式中、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。) - 前記一般式(1)で表されるポリエーテル誘導体が、下記一般式(3)で表されるポリエーテル誘導体であり、該ポリエーテル誘導体の重量平均分子量が1000~4000である、請求項1記載のポリカーボネート樹脂組成物。
一般式(3):
C4H9O-(CH2CH2)m(CH2C(CH3)HO)n-H (3)
(式中、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。) - 前記一般式(1)で表されるポリエーテル誘導体が、下記一般式(4)で表されるポリエーテル誘導体であり、該ポリエーテル誘導体の重量平均分子量が1000~4000である、請求項1記載のポリカーボネート樹脂組成物。
一般式(4):
HO-(CH2CH2O)m(CH2CH(CH3)O)n-H (4)
(式中、m及びnは、それぞれ独立して、3~60の整数を示し、m+nは、8~90の整数を示す。) - 前記亜リン酸エステル系化合物(C)が、下記一般式(5)、(6)及び(7)で表される化合物から選択された1種以上の化合物である、請求項1記載のポリカーボネート樹脂組成物。
一般式(5):
一般式(6):
一般式(7):
- 前記一般式(5)で表される化合物が、トリス(2,4-ジ-t-ブチルフェニル)フォスファイトである、請求項5記載のポリカーボネート樹脂組成物。
- 前記一般式(6)で表される化合物が、2,4,8,10-テトラ-t-ブチル-6-[3-(3-メチル-4-ヒドロキシ-5-t-ブチルフェニル)プロポキシ]ジベンゾ[d,f][1,3,2]ジオキサホスフェピンである、請求項5記載のポリカーボネート樹脂組成物。
- 前記一般式(7)で表される化合物が、3,9-ビス(2,6-ジ-tert-ブチル-4-メチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ[5,5]ウンデカンであることを特徴とする、請求項5記載のポリカーボネート樹脂組成物。
- 請求項1~9のいずれかに記載のポリカーボネート樹脂組成物を含む、光学用成形品。
- 前記成形品が導光板である、請求項10に記載の光学用成形品。
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CN107207848B (zh) * | 2015-03-26 | 2019-11-05 | 住化Pc有限公司 | 聚碳酸酯树脂组合物及光学用成形品 |
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JP2018119071A (ja) * | 2017-01-26 | 2018-08-02 | 住化ポリカーボネート株式会社 | 車両ランプ用ライトガイド |
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TW201641589A (zh) | 2016-12-01 |
KR20170088943A (ko) | 2017-08-02 |
JP6063101B1 (ja) | 2017-01-18 |
JP6137516B2 (ja) | 2017-05-31 |
KR20170122713A (ko) | 2017-11-06 |
CN107418181A (zh) | 2017-12-01 |
TW201815962A (zh) | 2018-05-01 |
CN107418181B (zh) | 2020-04-21 |
TWI686445B (zh) | 2020-03-01 |
CN107207848B (zh) | 2019-11-05 |
JP2017128742A (ja) | 2017-07-27 |
JPWO2016152165A1 (ja) | 2017-04-27 |
JP2017057408A (ja) | 2017-03-23 |
TWI688605B (zh) | 2020-03-21 |
KR102058330B1 (ko) | 2019-12-20 |
KR20190057156A (ko) | 2019-05-27 |
CN107207848A (zh) | 2017-09-26 |
KR101981561B1 (ko) | 2019-05-23 |
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