WO2015087526A1 - ポリカーボネート樹脂組成物及び光学用成形品 - Google Patents
ポリカーボネート樹脂組成物及び光学用成形品 Download PDFInfo
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- WO2015087526A1 WO2015087526A1 PCT/JP2014/006091 JP2014006091W WO2015087526A1 WO 2015087526 A1 WO2015087526 A1 WO 2015087526A1 JP 2014006091 W JP2014006091 W JP 2014006091W WO 2015087526 A1 WO2015087526 A1 WO 2015087526A1
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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
- 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
-
- 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
- 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
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
- 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
- G02B1/045—Light guides
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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
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present disclosure relates to a polycarbonate resin composition and an optical molded article.
- a planar light source device incorporated in a liquid crystal display device includes a light guide plate.
- PMMA polymethyl methacrylate
- Polycarbonate resin is superior in mechanical properties, thermal properties, and electrical properties to PMMA, but slightly inferior in light transmittance. Therefore, the planar light source device using the light guide plate made of polycarbonate resin has a problem that the luminance is lower than that using the light guide plate made of PMMA.
- Patent Documents 2 to 6 a resin composition using a polycarbonate resin and another material in combination to obtain a light transmittance equal to or higher than that of PMMA and improve the luminance of the light guide plate.
- Various proposals have been made.
- the present disclosure provides a polycarbonate resin composition that does not impair the properties such as heat resistance and mechanical strength inherent in a polycarbonate resin, has high light transmittance, and has excellent light transmittance even when molded at a high temperature. provide.
- the present disclosure also provides an optical molded article that is formed by molding the polycarbonate resin composition, has high brightness, low yellowness, excellent hue, and excellent brightness and hue even when molded at a high temperature.
- the polycarbonate resin composition in the present disclosure is: Polycarbonate resin (A); General formula (1): HO (C 4 H 8 O) m (C 3 H 6 O) n H (1) (Wherein, m and n each independently represents an integer of 4 to 60, and m + n represents an integer of 20 to 90)
- the amount of the tetramethylene glycol derivative (B) is 0.005 to 5.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A)
- the amount of the phosphite compound (C) is 0.005 to 5.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A).
- the optical molded product in the present disclosure is: Polycarbonate resin (A); General formula (1): HO (C 4 H 8 O) m (C 3 H 6 O) n H (1) (Wherein, m and n each independently represents an integer of 4 to 60, and m + n represents an integer of 20 to 90)
- the amount of the tetramethylene glycol derivative (B) is 0.005 to 5.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A)
- the polycarbonate resin composition according to the present disclosure does not impair characteristics such as heat resistance and mechanical strength inherent to the polycarbonate resin, has high light transmittance, and excellent light transmittance even when molded at a high temperature.
- the optical molded article in the present disclosure is formed by molding the polycarbonate resin composition, and has high brightness, small yellowness, excellent hue, and excellent brightness and hue even when molded at a high temperature. . 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 according to Embodiment 1 contains a polycarbonate resin (A), a tetramethylene glycol derivative (B), and a phosphite compound (C).
- the polycarbonate resin (A) is a polymer obtained by a phosgene method in which various dihydroxy diaryl compounds and phosgene are reacted or a transesterification method in which a dihydroxy diaryl compound and a carbonate such as diphenyl carbonate are reacted.
- 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, more preferably 12,000 to 30,000.
- a molecular weight regulator, a catalyst, etc. can be used as needed.
- the tetramethylene glycol derivative (B) has the general formula (1): HO (C 4 H 8 O) m (C 3 H 6 O) n H (1) (Wherein, m and n each independently represents an integer of 4 to 60, and m + n represents an integer of 20 to 90) It is represented by
- the specific tetramethylene glycol derivative (B) represented by the general formula (1) is a bifunctional random copolymer, has high heat resistance, and is represented by the general formula (1).
- a molded article obtained by molding a polycarbonate resin composition containing the specific tetramethylene glycol derivative (B) to be molded at a high temperature has high luminance and light transmittance.
- the tetramethylene glycol derivative (B) represented by the general formula (1) has appropriate lipophilicity, it is excellent in compatibility with the polycarbonate resin (A). Therefore, the tetramethylene glycol derivative (B) ) Improves the transparency of the molded product obtained from the polycarbonate resin composition.
- tetramethylene glycol derivative (B) represented by the general formula (1) it is possible to suppress the generation of unnecessarily shearing heat when molding the polycarbonate resin composition.
- a release agent such as a polyorganosiloxane compound may not be added separately.
- n and n are each independently an integer of 4 to 60
- m + n is an integer of 20 to 90
- m and n are each independently It is preferably an integer of 6 to 40
- m + n is preferably an integer of 20 to 60.
- the weight average molecular weight of the tetramethylene glycol derivative (B) is preferably 1000 to 4000, more preferably 2000 to 3000.
- the weight average molecular weight of the tetramethylene glycol derivative (B) is less than 1000, there is a fear that a sufficient improvement effect of the light transmittance may not be expected.
- the weight average molecular weight exceeds 4000, the light transmittance decreases. As a result, the fogging rate may increase.
- Examples of commercially available tetramethylene glycol derivatives (B) include polyserine DCB-2000 (weight average molecular weight 2000) and polyserine DCB-1000 (weight average molecular weight 1000) manufactured by NOF Corporation (" Polyserine ”is a registered trademark).
- the amount of the tetramethylene glycol derivative (B) is 0.005 to 5.0 parts by weight, 0.1 to 2.0 parts by weight, and further 0.5 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A).
- the amount is preferably 1.5 parts by weight.
- the amount of the tetramethylene glycol derivative (B) is less than 0.005 parts by weight, the effect of improving the light transmittance and hue is insufficient.
- the amount of the tetramethylene glycol derivative (B) exceeds 5.0 parts by weight, the light transmittance is lowered and the clouding rate is increased.
- the polycarbonate resin composition in the present disclosure contains a phosphite compound (C) together with the specific tetramethylene glycol derivative (B) represented by the general formula (1).
- a phosphite compound (C) together with the specific tetramethylene glycol derivative (B) represented by the general formula (1).
- Examples of the phosphite compound (C) include, for example, the general formula (2): (Wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3) Is particularly preferred.
- 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 (2) 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.
- the phosphite compound (C) in addition to the compound represented by the general formula (2), for example, the general formula (3): (Wherein 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 6 carbon atoms.
- 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.
- any 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 8 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 (3) 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-but
- 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.
- the phosphite compound (C) in addition to the compound represented by the general formula (2) and the compound represented by the general formula (3), for example, the general formula (4): (Wherein 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) The compound represented by these is mentioned.
- 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 5.0 parts by weight, 0.01 to 0.5 parts by weight, and further 0.000 to 100 parts by weight of the polycarbonate resin (A).
- the amount is preferably 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 5.0 parts by weight, the effect of improving the light transmittance and hue is insufficient.
- the amount is 0.005 to 1.0 weight with respect to 100 parts by weight of the polycarbonate resin (A). It is preferable that it is a part because the effect of improving light transmittance and hue is greater.
- the amount thereof is 0.05 to 2.0% by weight with respect to 100 parts by weight of the polycarbonate resin (A). It is preferable that it is a part because the effect of improving light transmittance and hue is greater.
- the polycarbonate resin composition according to Embodiment 1 has, for example, a heat stabilizer, an antioxidant, a colorant, a release agent, a softening agent, an antistatic agent, an impact within a range not impairing the effects of the present invention.
- a heat stabilizer for example, an antioxidant, a colorant, a release agent, a softening agent, an antistatic agent, an impact within a range not impairing the effects of the present invention.
- Various additives such as a property improving agent, polymers other than the polycarbonate resin (A), and the like may be appropriately blended.
- the method for producing the polycarbonate resin composition is not particularly limited.
- 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.
- the first embodiment has been described as an example of the technique disclosed in the present application.
- the technology in the present disclosure is not limited to this, and can also be applied to an embodiment in which changes, replacements, additions, omissions, and the like are appropriately performed.
- Embodiment 2 Optical molded product
- the optical molded product according to Embodiment 2 is formed by molding the polycarbonate resin composition according to Embodiment 1 obtained as described above.
- the method for producing the optical molded product there is no particular limitation on the method for producing the optical molded product, and examples thereof include a method of molding a polycarbonate resin composition by a known injection molding method, compression molding method or the like.
- the optical molded product obtained as described above is suitable as, for example, a light guide plate, a surface light emitter material, and a name plate.
- the second embodiment has been described as an example of the technique disclosed in the present application.
- the technology in the present disclosure is not limited to this, and can also be applied to an embodiment in which changes, replacements, additions, omissions, and the like are appropriately performed.
- 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”)
- Tetramethylene glycol derivative (B) Polyoxytetramethylene polyoxypropylene glycol (random type) Polyserine DCB-2000 (Trade name, manufactured by NOF Corporation, weight average molecular weight: 2000, hereinafter referred to as “compound B”)
- 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”)
- KR Polyorganosiloxane compound having phenyl group, methoxy group and vinyl group KR-511 (Product name, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as “KR”)
- test pieces for evaluation were prepared according to the following method and used for evaluation. The results are shown in Table 1.
- Test piece preparation method (I) Pre-dwelling test piece After the obtained pellets were dried at 120 ° C. for 4 hours or more, 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. A multipurpose test piece A type (total length: 168 mm ⁇ thickness: 4 mm) defined in JIS K 7139 “Plastic Test Piece” was prepared. 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).
- test piece after residence After the molten pellet was held at 360 ° C. for 10 minutes in the cylinder of the injection molding machine, a test piece after residence was produced by the same method as the production method of the test piece before residence.
- a spectrophotometer (manufactured by Hitachi, Ltd., U-4100) 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.
- 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 a mask before sample 6.
- 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 compositions of Examples 1-1 to 1-8 were prepared by adding a specific tetramethylene glycol derivative (B) represented by the general formula (1) and a phosphite compound ( C) are blended at specific ratios. Therefore, not only the test piece before residence molded from the polycarbonate resin composition, that is, the test piece molded without being held in the injection molding machine, but also the test piece after residence, ie, in the cylinder of the injection molding machine. Even if it is the test piece shape
- the polycarbonate resin compositions of Examples 1-1 to 1-8 do not impair the heat resistance inherent in the polycarbonate resin (A), have high light transmittance in the visible region, and at high temperatures. Even when molded, the light transmittance is excellent. And the molded article which shape
- the polycarbonate resin composition of Comparative Example 1-1 has a small amount of the specific tetramethylene glycol derivative (B), both the test piece before staying and the test piece after staying have low integrated transmittance, And yellowness is large.
- the polycarbonate resin composition of Comparative Example 1-1 has a low light transmittance in the visible region and a low light transmittance when molded at a high temperature.
- molded such a polycarbonate resin composition is inferior to the hue at the time of shape
- the polycarbonate resin composition of Comparative Example 1-2 Since the polycarbonate resin composition of Comparative Example 1-2 has a large amount of the specific tetramethylene glycol derivative (B), the accumulated transmittance of the test piece before staying is low. In addition, after the residence, the components were decomposed in the test piece, and it was impossible to measure the spectral transmittance. Thus, the polycarbonate resin composition of Comparative Example 1-2 is extremely inferior in heat resistance.
- the pre-retention test piece has a high integrated transmittance and a small yellowness, but the post-retention test.
- the piece has a low integrated transmittance and a high yellowness.
- the polycarbonate resin composition of Comparative Example 1-3 is inferior in heat resistance.
- the polycarbonate resin composition of Comparative Example 1-4 Since the polycarbonate resin composition of Comparative Example 1-4 has a large amount of the phosphite compound (C), the accumulated transmittance of the specimen before residence is low and the yellowness is large. In addition, after the residence, the components were decomposed in the test piece, and it was impossible to measure the spectral transmittance. Thus, the polycarbonate resin composition of Comparative Example 1-4 is extremely inferior in heat resistance.
- the polycarbonate resin composition of Comparative Example 1-5 was blended with polytetramethylene glycol ether / polyoxyethylene glycol random copolymer polyether instead of the specific tetramethylene glycol derivative (B) represented by the general formula (1). Therefore, the test piece before residence has a high integrated transmittance and a small yellowness, but the test piece after residence has a low integrated transmittance and a high yellowness. Thus, the polycarbonate resin composition of Comparative Example 1-5 is inferior in heat resistance.
- the polycarbonate resin composition of Comparative Example 1-6 is obtained by further blending the polycarbonate resin composition of Comparative Example 1-5 with a polyorganosiloxane compound, and the pre-dwelling test piece has a high integrated transmittance, and Yellowness is small.
- the post-residence test piece has a slightly higher integrated transmittance and a lower yellowness than the post-retention test piece of the polycarbonate resin composition of Comparative Example 1-5. There is a big difference.
- the polycarbonate resin composition of Comparative Example 1-6 is inferior in heat resistance.
- Second embodiment Examples 2-1 to 2-3 A pellet of the polycarbonate resin composition was obtained in the same manner as in the first embodiment except that the raw materials were blended in the proportions shown in Table 2.
- test pieces for evaluation were prepared according to the following method and used for evaluation. The results are shown in Table 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, ROBOSHOT S2000i100A) was used at a molding temperature of 360 ° C. and a mold temperature of 80 ° C.
- a spectrophotometer (manufactured by Hitachi, Ltd., U-4100) 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.
- the spectral transmittance of the test piece for every 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 integrated transmittance.
- permeability made 30000 or more favorable (it shows with (circle) in a table
- the polycarbonate resin compositions of Examples 2-1 to 2-3 were obtained by adding a specific tetramethylene glycol derivative (B) represented by the general formula (1) and a phosphite compound ( C) are blended at specific ratios. Therefore, the test piece molded from the polycarbonate resin composition has a high integrated transmittance and a high light transmittance at a wavelength of 450 nm.
- the polycarbonate resin compositions of Examples 2-1 to 2-3 have high light transmittance in the visible region without impairing the heat resistance inherent in the polycarbonate resin (A). And the molded article which shape
- each test specimen for evaluation was prepared in the same manner as in the second embodiment, and subjected to evaluation in the same manner as in the second embodiment. The results are shown in Table 3.
- the integrated transmittance was 28000 or more as good (indicated by ⁇ in the table), and less than 28000 was determined as defective (indicated by x in the table).
- the light transmittance at a wavelength of 450 nm was 55% or more as good (indicated by ⁇ in the table), and less than 55% was defective (indicated by x in the table).
- test piece molded from the polycarbonate resin composition has a high integrated transmittance and a high light transmittance at a wavelength of 450 nm.
- the polycarbonate resin compositions of Examples 3-1 to 3-10 do not impair the heat resistance inherent in the polycarbonate resin (A) and have a high light transmittance in the visible region.
- molded such a polycarbonate resin composition has small yellowness, and is excellent in a hue.
- the polycarbonate resin composition of Comparative Example 3-1 has a low integrated transmittance and a low light transmittance at a wavelength of 450 nm because the amount of the specific tetramethylene glycol derivative (B) is small.
- the polycarbonate resin composition of Comparative Example 3-1 has a low light transmittance in the visible region, and a molded product obtained by molding such a polycarbonate resin composition has a large yellowness and a poor hue.
- the polycarbonate resin composition of Comparative Example 3-2 has a low integrated transmittance and a low light transmittance at a wavelength of 450 nm because the amount of the specific tetramethylene glycol derivative (B) is large.
- the polycarbonate resin composition of Comparative Example 3-2 has a low light transmittance in the visible region, and a molded product obtained by molding such a polycarbonate resin composition has a large yellowness and an inferior hue.
- the polycarbonate resin composition of Comparative Example 3-3 has a low integrated transmittance because the amount of the phosphite compound (C) is small. Thus, the polycarbonate resin composition of Comparative Example 3-3 has a low light transmittance in the visible region.
- the polycarbonate resin composition of Comparative Example 3-4 has a low integrated transmittance and a low light transmittance at a wavelength of 450 nm because of the large amount of the phosphite compound (C). As described above, the polycarbonate resin composition of Comparative Example 3-4 has a low light transmittance in the visible region, and a molded product obtained by molding such a polycarbonate resin composition has a large yellowness and a poor hue.
- each test specimen for evaluation was prepared in the same manner as in the second embodiment, and subjected to evaluation in the same manner as in the second embodiment. The results are shown in Table 4.
- the integrated transmittance was 28000 or more as good (indicated by ⁇ in the table), and less than 28000 was determined as defective (indicated by x in the table).
- the light transmittance at a wavelength of 450 nm was 55% or more as good (indicated by ⁇ in the table), and less than 55% was defective (indicated by x in the table).
- the polycarbonate resin compositions of Examples 4-1 to 4-3 were prepared by adding a specific tetramethylene glycol derivative (B) represented by the general formula (1) and a phosphite compound ( C) are blended at specific ratios. Therefore, the test piece molded from the polycarbonate resin composition has a high integrated transmittance and a high light transmittance at a wavelength of 450 nm.
- the polycarbonate resin compositions of Examples 4-1 to 4-3 have high light transmittance in the visible region without impairing the heat resistance inherent in the polycarbonate resin (A). And the molded article which shape
- the polycarbonate resin compositions of Examples 4-1 to 4-3 are particularly formulated with a compound represented by the general formula (2) as the phosphite compound (C). Due to the synergistic effect of the compound represented by the general formula (2) and the specific tetramethylene glycol derivative (B) represented by the general formula (1), the effect of improving light transmittance and hue in the visible region is greater. .
- the polycarbonate resin composition of Comparative Example 4-1 has a low integrated transmittance because the amount of the phosphite compound (C) is small.
- the polycarbonate resin composition of Comparative Example 4-1 has a low light transmittance in the visible region.
- the polycarbonate resin composition of Comparative Example 4-2 has a low integrated transmittance and a low light transmittance at a wavelength of 450 nm because the amount of the phosphite compound (C) is large.
- the polycarbonate resin composition of Comparative Example 4-2 has a low light transmittance in the visible region, and a molded product obtained by molding such a polycarbonate resin composition has a large yellowness and an inferior hue.
- 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 present disclosure can be suitably used as an optical molded product such as a light guide plate, a surface light emitter material, and a name plate.
Abstract
Description
ポリカーボネート樹脂(A)と、
一般式(1):
HO(C4H8O)m(C3H6O)nH (1)
(式中、m及びnは、それぞれ独立して、4~60の整数を示し、m+nは、20~90の整数を示す)
で表されるテトラメチレングリコール誘導体(B)と、
亜リン酸エステル系化合物(C)とを含有してなり、
前記テトラメチレングリコール誘導体(B)の量が、前記ポリカーボネート樹脂(A)100重量部に対して0.005~5.0重量部であり、
前記亜リン酸エステル系化合物(C)の量が、前記ポリカーボネート樹脂(A)100重量部に対して0.005~5.0重量部である
ものである。
ポリカーボネート樹脂(A)と、
一般式(1):
HO(C4H8O)m(C3H6O)nH (1)
(式中、m及びnは、それぞれ独立して、4~60の整数を示し、m+nは、20~90の整数を示す)
で表されるテトラメチレングリコール誘導体(B)と、
亜リン酸エステル系化合物(C)とを含有してなり、
前記テトラメチレングリコール誘導体(B)の量が、前記ポリカーボネート樹脂(A)100重量部に対して0.005~5.0重量部であり、
前記亜リン酸エステル系化合物(C)の量が、前記ポリカーボネート樹脂(A)100重量部に対して0.005~5.0重量部であるポリカーボネート樹脂組成物
を成形したものである。
実施の形態1に係るポリカーボネート樹脂組成物は、ポリカーボネート樹脂(A)と、テトラメチレングリコール誘導体(B)と、亜リン酸エステル系化合物(C)とを含有したものである。
HO(C4H8O)m(C3H6O)nH (1)
(式中、m及びnは、それぞれ独立して、4~60の整数を示し、m+nは、20~90の整数を示す)
で表される。
で表される化合物が挙げられる。
で表される化合物が挙げられる。
実施の形態2に係る光学用成形品は、前記のごとく得られる実施の形態1に係るポリカーボネート樹脂組成物を成形してなるものである。
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)
ポリオキシテトラメチレンポリオキシプロピレングリコール(ランダムタイプ)
ポリセリンDCB-2000
(商品名、日油(株)製、重量平均分子量:2000、以下「化合物B」という)
(商品名、住友化学(株)製、以下「化合物C2」という)
4-1.ポリテトラメチレングリコールエーテル/ポリオキシエチレングリコールランダム共重合ポリエーテル
ポリセリンDC-3000E
(商品名、日油(株)製、重量平均分子量:3000、以下「化合物B´」という)
KR-511
(商品名、信越化学工業(株)製、以下「KR」という)
実施例1-1~1-8及び比較例1-1~1-6
前記各原料を、表1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。
(I)滞留前試験片
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。
溶融ペレットを前記射出成形機のシリンダ内にて360℃で10分間保持した後、前記滞留前試験片の製造方法と同様の方法にて滞留後試験片を作製した。
分光光度計((株)日立製作所製、U-4100)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、滞留前試験片及び滞留後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。
実施例2-1~2-3
前記各原料を、表2に示す割合にて配合した他は、第1実施態様と同様の方法にてポリカーボネート樹脂組成物のペレットを得た。
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、U-4100)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、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)とした。
波長450nmの可視光線は青色を呈するので、波長450nmの光線透過率が高いほど黄色度が小さく、試験片は色相に優れている。よって、前記積算透過率の評価方法と同様の方法にて試験片の分光透過率を測定し、波長450nmの光線透過率にて色相を評価した。波長450nmの光線透過率が65%以上を良好(表中、○で示す)とした。
実施例3-1~3-10及び比較例3-1~3-4
前記各原料を、表3に示す割合にて配合した他は、第1実施態様と同様の方法にてポリカーボネート樹脂組成物のペレットを得た。
実施例4-1~4-3及び比較例4-1~4-2
前記各原料を、表4に示す割合にて配合した他は、第1実施態様と同様の方法にてポリカーボネート樹脂組成物のペレットを得た。
Claims (11)
- ポリカーボネート樹脂(A)と、
一般式(1):
HO(C4H8O)m(C3H6O)nH (1)
(式中、m及びnは、それぞれ独立して、4~60の整数を示し、m+nは、20~90の整数を示す)
で表されるテトラメチレングリコール誘導体(B)と、
亜リン酸エステル系化合物(C)とを含有してなり、
前記テトラメチレングリコール誘導体(B)の量が、前記ポリカーボネート樹脂(A)100重量部に対して0.005~5.0重量部であり、
前記亜リン酸エステル系化合物(C)の量が、前記ポリカーボネート樹脂(A)100重量部に対して0.005~5.0重量部である、ポリカーボネート樹脂組成物。 - 一般式(2)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2に記載のポリカーボネート樹脂組成物。
- 一般式(2)で表される化合物の量が、ポリカーボネート樹脂(A)100重量部に対して0.005~1.0重量部である、請求項2に記載のポリカーボネート樹脂組成物。
- 亜リン酸エステル系化合物(C)が、少なくとも、一般式(3):
で表される化合物である、請求項1に記載のポリカーボネート樹脂組成物。 - 一般式(3)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に記載のポリカーボネート樹脂組成物。
- 一般式(3)で表される化合物の量が、ポリカーボネート樹脂(A)100重量部に対して0.05~2.0重量部である、請求項5に記載のポリカーボネート樹脂組成物。
- テトラメチレングリコール誘導体(B)の量が、ポリカーボネート樹脂(A)100重量部に対して0.1~2.0重量部であり、亜リン酸エステル系化合物(C)の量が、ポリカーボネート樹脂(A)100重量部に対して0.01~0.5重量部である、請求項1に記載のポリカーボネート樹脂組成物。
- テトラメチレングリコール誘導体(B)の量が、ポリカーボネート樹脂(A)100重量部に対して0.5~1.5重量部であり、亜リン酸エステル系化合物(C)の量が、ポリカーボネート樹脂(A)100重量部に対して0.02~0.1重量部である、請求項1に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1つに記載のポリカーボネート樹脂組成物を成形してなる、光学用成形品。
- 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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KR101715582B1 (ko) | 2017-03-13 |
TWI565753B (zh) | 2017-01-11 |
CN105793357A (zh) | 2016-07-20 |
JP2016020504A (ja) | 2016-02-04 |
US9617418B2 (en) | 2017-04-11 |
JP6987911B2 (ja) | 2022-01-05 |
JPWO2015087526A1 (ja) | 2017-03-16 |
CN107266894B (zh) | 2019-07-19 |
EP3081596A1 (en) | 2016-10-19 |
EP3081596B1 (en) | 2018-07-25 |
JP6271057B2 (ja) | 2018-01-31 |
TW201529717A (zh) | 2015-08-01 |
JP5801516B1 (ja) | 2015-10-28 |
ES2689690T3 (es) | 2018-11-15 |
US20160326365A1 (en) | 2016-11-10 |
CN107266894A (zh) | 2017-10-20 |
TW201809136A (zh) | 2018-03-16 |
JP2017125208A (ja) | 2017-07-20 |
KR20160096631A (ko) | 2016-08-16 |
JP2020094227A (ja) | 2020-06-18 |
KR20160140968A (ko) | 2016-12-07 |
CN107383823B (zh) | 2019-07-12 |
CN107383823A (zh) | 2017-11-24 |
EP3081596A4 (en) | 2017-07-05 |
TW201708384A (zh) | 2017-03-01 |
JP2018053263A (ja) | 2018-04-05 |
JP6677705B2 (ja) | 2020-04-08 |
KR101681879B1 (ko) | 2016-12-01 |
TWI663208B (zh) | 2019-06-21 |
TWI664235B (zh) | 2019-07-01 |
CN105793357B (zh) | 2017-05-31 |
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