WO2017175786A1 - Plaque de guidage de lumière, source de lumière de surface équipée de celle-ci, composition de résine à base de polycarbonate aromatique, article moulé diffusant la lumière - Google Patents
Plaque de guidage de lumière, source de lumière de surface équipée de celle-ci, composition de résine à base de polycarbonate aromatique, article moulé diffusant la lumière Download PDFInfo
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- WO2017175786A1 WO2017175786A1 PCT/JP2017/014198 JP2017014198W WO2017175786A1 WO 2017175786 A1 WO2017175786 A1 WO 2017175786A1 JP 2017014198 W JP2017014198 W JP 2017014198W WO 2017175786 A1 WO2017175786 A1 WO 2017175786A1
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- Prior art keywords
- fluidity improver
- resin composition
- polycarbonate resin
- acid
- aromatic polycarbonate
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- 0 OC1=CCC(*c(cc2)ccc2[O+])C=C1 Chemical compound OC1=CCC(*c(cc2)ccc2[O+])C=C1 0.000 description 2
Classifications
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
Definitions
- the present invention relates to a light guide plate that can be used in a wide range of applications without being restricted in use environment and has excellent transferability, and a surface light source body including the same.
- the present invention also relates to an aromatic polycarbonate resin composition and a light diffusible molded article having improved fluidity during molding without impairing the transparency and light diffusibility of the obtained molded article.
- Backlight devices such as instrument panels, tail lamps, blinkers, etc. for in-vehicle use have light guide plates that emit uniform light.
- liquid crystal display devices used in personal computers, mobile phones, PDAs, etc. are also equipped with a light guide plate to cope with demands for thinning, lightening, power saving, high brightness and high definition. It is.
- a light guide plate constitutes a surface light source body together with a light source or the like and is used in various devices.
- the light guide plate is preferably made of a material with low light attenuation, and polymethyl methacrylate (PMMA), which is lighter in weight and excellent in moldability, has been optimally used.
- PMMA polymethyl methacrylate
- PMMA is inferior in heat resistance, impact resistance, flame retardancy, etc.
- it has a problem that the use environment of the light guide plate is limited.
- an in-vehicle lighting device requires a light guide plate having heat resistance and impact resistance.
- devices such as personal computers, mobile phones, and PDAs tend to increase the heat generated inside them, so materials with higher heat resistance are required, and more recently, especially for mobile phones.
- the light plate is also required to have improved impact resistance.
- polycarbonate resins having excellent mechanical properties such as impact resistance, heat resistance, and electrical properties have recently begun to be used in place of PMMA.
- the polycarbonate resin has such excellent characteristics, but has a high melt viscosity. Therefore, the polycarbonate resin has a drawback of poor fluidity and inferior moldability, and sufficient transferability may not be obtained.
- Patent Document 1 As a method for improving the melt fluidity of the aromatic polycarbonate resin composition, for example, in Patent Document 1, by using a copolyester carbonate resin having an aliphatic segment as a fluidity improver for a polycarbonate resin, It describes that transparency and mechanical strength are maintained.
- Aromatic polycarbonate resins have excellent mechanical and thermal properties, so OA (office automation) equipment, information / communication equipment, electronic / electric equipment, home appliances, automotive components, building materials, etc. Widely used industrially.
- a light diffusible molded product made of a resin composition in which a light diffusing agent such as inorganic fine particles or polymer fine particles is blended with an aromatic polycarbonate resin is more heat resistant and dimension than a light diffusible molded product made of acrylic resin. Because of its excellent stability, it is used in light covers for electric lamp covers, meters, signboards (particularly internally lit), resin window glass, image reading devices or image display devices (for example, backlight modules such as liquid crystal display devices).
- light diffusing films for example, high transmission light diffusing films used for improving the brightness of liquid crystal display devices, etc.
- light diffusive molded products, especially light diffusion plates and light diffusion films used in image display devices are also used.
- Patent Document 2 describes that fluidity is improved by adding a pentaerythritol ester compound and reducing the molecular weight of an aromatic polycarbonate resin by transesterification.
- Patent Document 1 in order to improve fluidity, the total amount of the resin composition obtained by combining the polycarbonate resin and the copolyestercarbonate resin is 100 parts by weight, and the blending amount of the copolyestercarbonate resin is 75 parts by weight. It is necessary to use more.
- the present invention contains a fluidity improver for improving fluidity during molding without impairing the original properties (transparency, impact resistance, high rigidity, mechanical strength, heat resistance, etc.) of the polycarbonate resin.
- An object of the present invention is to provide a light guide plate comprising a highly fluid polycarbonate resin composition, usable in a wide range of applications without being restricted in use environment, and having excellent transferability, and a surface light source body provided with the same.
- Patent Document 2 can improve the fluidity without greatly impairing various properties, but the impact strength is not sufficiently maintained, and there is a concern about yellowing due to transesterification.
- aromatic polycarbonate is also used for aliphatic esters of phthalic acid such as dioctyl phthalate and dibutyl phthalate, which are commonly used as plasticizers, and phosphate esters such as tricresyl phosphate and diphenyl cresyl phosphate. There is a problem of lack of affinity with the base resin and significantly lowering mechanical and thermal properties.
- Another object of the present invention is to provide an aromatic polycarbonate resin composition and a light diffusible molded article having improved fluidity during molding without impairing the transparency and light diffusibility of the resulting molded article. To do.
- the inventors of the present invention are made of a polyester obtained by polycondensing a bisphenol component and an aliphatic dicarboxylic acid component and optionally a biphenol component at a specific ratio in order to improve the fluidity of the polycarbonate resin.
- a fluidity improver and melt-kneading the fluidity improver and the polycarbonate resin the fluidity during molding can be improved without impairing the useful properties (particularly transparency and impact strength) of the polycarbonate resin.
- the present inventors have found that a light guide plate excellent in transferability can be provided, and have completed the present invention. That is, the present invention relates to the inventions shown in the following 1) to 6).
- a resin composition comprising a polycarbonate resin and a fluidity improver,
- the fluidity improver is The following general formula (1)
- X 1 to X 4 may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- X 1 to X 4 may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- X 5 to X 8 may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- Y represents a methylene group, an isopropylidene group, a cyclic group.
- R 1 represents a divalent linear substituent which has 2 to 18 main chain atoms and may be branched.
- the light guide plate is a polycondensation product of the following formula:
- the part corresponding to R 1 of the part consisting of component (C) in the fluidity improver is a straight-chain saturated aliphatic hydrocarbon chain, 1) or 2) Light guide plate.
- the portion corresponding to R 1 of the portion (C) component in the fluidity improver is any one of (CH 2 ) 8 , (CH 2 ) 10 , and (CH 2 ) 12 1) 4.
- the light guide plate according to any one of items 3 to 3.
- a surface light source body comprising: the light guide plate according to any one of 1) to 5); and a light source that emits light toward the light guide plate.
- the present inventors have also studied from a polyester obtained by polycondensing a bisphenol component and an aliphatic dicarboxylic acid component, and optionally a biphenol component at a specific ratio, in order to improve the fluidity of the polycarbonate resin.
- This fluidity improver is melt-kneaded with this fluidity improver, polycarbonate resin, and light diffusing agent, so that the fluidity during molding can be reduced without impairing the transparency and light diffusibility of the resulting molded product.
- the present inventors have found that an improved aromatic polycarbonate resin composition and a light diffusible molded article can be provided, and have completed the present invention. That is, the present invention also relates to the inventions shown in the following 1) to 7).
- a biphenol component (A) represented by 0 to 55 mol%, The following general formula (2)
- X 5 to X 8 are the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- Y represents a methylene group, an isopropylidene group, a cyclic group.
- a resin composition having improved fluidity during resin molding is used without impairing the original properties (transparency, impact resistance, high rigidity, mechanical strength, heat resistance, etc.) of the polycarbonate resin.
- the term “damage” here means that the resin is deteriorated so as not to satisfy the characteristics required for the resin. That is, even when some of the properties of the polycarbonate resin are reduced by adding the fluidity improver in the present invention, the original properties of the polycarbonate resin are as long as the properties required in the application in which the resin is used are satisfied. It was not damaged. Therefore, the description can be rephrased as “without substantially impairing the original properties of the polycarbonate resin”.
- the aromatic polycarbonate resin composition of the present invention has a melt fluidity (moldability) as compared with the conventional one without impairing the excellent properties (transparency, light diffusibility, etc.) of the obtained light diffusible molded product. ).
- the term “damage” here means that the resin is deteriorated so as not to satisfy the characteristics required for the resin. That is, even when some of the properties of the aromatic polycarbonate resin composition are reduced by adding the fluidity improver in the present invention, the application in which the resin composition is used (such as a light diffusing molded article). As long as the characteristics required in the above are satisfied, the original characteristics of the aromatic polycarbonate resin composition are not impaired. Therefore, the description can be rephrased as “without substantially impairing the excellent characteristics of the obtained light diffusible molded article”.
- the light diffusive molded product of the present invention is excellent in transparency and light diffusibility, and can be increased in size, thinned (lightened), complicated in shape, and improved in performance.
- the fluidity improver in the present invention comprises a polyester obtained by polycondensing a bisphenol component, an aliphatic dicarboxylic acid component, and optionally a biphenol component at a specific ratio.
- X 1 to X 4 may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- X 5 to X 8 may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- Y represents a methylene group, an isopropylidene group, a cyclic group.
- R 1 represents a divalent linear substituent which has 2 to 18 main chain atoms and may be branched.
- the fluidity improver in the present invention is a polyester produced by polycondensation of a diol component consisting of a bisphenol component (B) and an optional biphenol component (A) and a dicarboxylic acid component which is a component (C). .
- the fluidity improver is not a low-molecular compound, it is possible to suppress the occurrence of bleed out when molding a polycarbonate resin composition to which the fluidity improver is added.
- the fluidity improver having the molecular structure is highly compatible with the polycarbonate resin, the fluidity of the resin composition obtained by adding the fluidity improver to the polycarbonate resin is efficiently improved. In addition, various properties such as transparency and impact strength inherent to the polycarbonate resin are not impaired.
- the biphenol component (A) contained in the fluidity improver is preferably 0 to 55 mol%, more preferably 10 to 40 mol%, and most preferably 20 to 30 mol%.
- the bisphenol component (B) is preferably contained in an amount of 5 to 60 mol%, more preferably 10 to 50 mol%, and most preferably 20 to 30 mol%.
- the dicarboxylic acid component (C) is preferably contained in an amount of 40 to 60 mol%, more preferably 45 to 55 mol%.
- the molar ratio ((A) / (B)) of the component (A) to the component (B) is preferably 1/9 to 9/1. More preferably, it is 1/7 to 7/1, more preferably 1/5 to 5/1, and most preferably 1/3 to 3/1.
- (A) / (B) is further less than 1/9 and the component (A) is less, the polyester itself becomes completely amorphous and has a low glass transition temperature. May cause fusion of pellets.
- phase separation may occur at the central portion of the thickness during the slow cooling.
- X 1 to X 4 in the general formula (1) may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. It is more preferable that all of X 1 to X 4 are hydrogen atoms in order to improve the handleability such as improving the crystallinity of the fluidity improver itself and preventing fusion during pellet storage.
- X 5 to X 8 in the general formula (2) may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. In order to enhance the compatibility with the polycarbonate resin, it is more preferable that all of X 5 to X 8 are hydrogen atoms.
- Y represents a methylene group, an isopropylidene group, a cyclic alkylidene group, an aryl-substituted alkylidene group, an arylene alkylidene group, —S—, —O—, a carbonyl group or —SO 2 —.
- 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) is particularly preferable in terms of increasing compatibility with the polycarbonate resin.
- dihydric phenols other than bisphenol A include 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-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis ( 4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2- Bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propa Bis (
- Dihydroxydiaryl sulfides dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone, 4,4′- And dihydroxydiaryl sulfones such as dihydroxy-3,3′-dimethyldiphenyl sulfone; and dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl.
- These bisphenol components may be used singly or as a mixture of two or more of them without losing the effect of the present invention.
- the terminal structure of the fluidity improver in the present invention is not particularly limited, but particularly suppresses transesterification with a polycarbonate resin, and suppresses yellowing of the resin composition obtained by adding the fluidity improver to the polycarbonate resin. Therefore, in order to suppress hydrolysis and ensure long-term stability, it is preferably sealed with a monofunctional low molecular compound.
- the sealing rate with respect to all ends of the molecular chain is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and most preferably 90% or more.
- the end-capping rate of the fluidity improver can be determined by the following formula (4) by measuring the number of sealed end functional groups and the number of end functional groups not sealed.
- 1 H-NMR is used to determine the number of each terminal group from the integral value of the characteristic signal corresponding to each terminal group.
- the method of calculating the terminal blocking rate using (4) is preferable in terms of accuracy and simplicity.
- Terminal sealing rate (%) ⁇ [number of sealed terminal functional groups] / ([number of sealed terminal functional groups] + [number of unsealed terminal functional groups]) ⁇ ⁇ 100 (4)
- the monofunctional low molecular compound used for sealing include monohydric phenol, monoamine having 1 to 20 carbon atoms, aliphatic monocarboxylic acid, carbodiimide, epoxy or oxazoline.
- Specific examples of monohydric phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, p-nonylphenol, pt-amylphenol, 4-hydroxybiphenyl, And any mixture thereof.
- pt-butylphenol and p-cumylphenol are preferred because they have a high boiling point and are easy to polymerize.
- aliphatic monocarboxylic acids include fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
- monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and any of these A mixture etc. are mentioned.
- carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di- ⁇ -naphthylcarbodiimide, bis-2,6-diisopropyl Phenylcarbodiimide, poly (2,4,6-triisopropylphenylene-1,3-diisocyanate), 1,5- (diisopropylbenzene) polycarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide and their Arbitrary mixtures etc.
- Examples of epoxies include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, triethylolpropane polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, bisphenol A- Diglycidyl ether, hydrogenated bisphenol A-glycidyl ether, 4,4'-diphenylmethane diglycidyl ether, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, methacrylic acid glycidyl ester, methacrylic acid glycidyl ester polymer, Examples thereof include a sidyl ester polymer-containing compound and an arbitrary mixture thereof.
- Examples of oxazolines include styrene-2
- R 1 therein represents a divalent linear substituent which may have 2 to 18 main chain atoms and may be branched.
- the number of main chain atoms is the number of atoms in the main chain skeleton.
- R 1 is preferably a straight-chain substituent that does not contain a branch, and further, a straight-chain aliphatic hydrocarbon chain that does not contain a branch. Is preferred.
- R 1 may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain.
- R 1 is preferably a straight-chain saturated aliphatic hydrocarbon chain having 2 to 18 carbon atoms from the viewpoint that both the ease of polymerization of the fluidity improver and the improvement of the glass transition point can be achieved. More preferably, it is a straight chain saturated aliphatic hydrocarbon chain having 4 to 16 carbon atoms, more preferably a straight chain saturated aliphatic hydrocarbon chain having 8 to 14 carbon atoms, and a straight chain having 8 carbon atoms. Most preferred is a saturated aliphatic hydrocarbon chain.
- the improvement of the glass transition point of the fluidity improver leads to the improvement of the heat resistance of the resin composition obtained by adding the fluidity improver to the polycarbonate resin.
- the number of main chain atoms of R 1 is preferably an even number in that the melt viscosity of the fluidity improver itself decreases.
- R 1 is particularly preferably one selected from — (CH 2 ) 8 —, — (CH 2 ) 10 —, and — (CH 2 ) 12 —.
- a dicarboxylic acid component may be used independently and may mix 2 or more types in the range which does not lose the effect of this invention.
- the fluidity improver in the present invention may be copolymerized with other monomers to such an extent that the effect is not lost.
- Other monomers include, for example, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids or caprolactams, caprolactones, aliphatic dicarboxylic acids, fatty acids Aromatic diols, aliphatic diamines, alicyclic dicarboxylic acids, and alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols, and aromatic mercaptophenols.
- the content of the other monomer constituting the fluidity improver is less than 50 mol%, preferably less than 30 mol%, more preferably, relative to the total number of moles of the fluidity improver. Less than 10 mol%, most preferably less than 5 mol%.
- the content of the other monomer is 50 mol% or more based on the total number of moles of the fluidity improver, the compatibility of the fluidity improver with the polycarbonate resin is reduced, and the fluidity is reduced. It becomes difficult for the improver to be compatible with the polycarbonate resin.
- aromatic hydroxycarboxylic acid examples include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy -7-naphthoic acid, 2-hydroxy-3-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, and their And alkyl, alkoxy or halogen-substituted products.
- aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl, 4,4 ′′ -dicarboxyterphenyl, bis (4-carboxyphenyl) ether, bis (4-carboxyphenoxy) butane, bis (4-carboxyphenyl) ethane, bis (3-carboxy Phenyl) ether, bis (3-carboxyphenyl) ethane, and alkyl, alkoxy or halogen substituents thereof.
- aromatic diol examples include pyrocatechol, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′- Examples include dihydroxybiphenyl, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenol ether, bis (4-hydroxyphenyl) ethane, 2,2′-dihydroxybinaphthyl, and alkyl, alkoxy or halogen substituents thereof. It is done.
- aromatic hydroxyamine examples include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4′-hydroxybiphenyl, 4-amino-4′-hydroxybiphenyl ether, 4-amino-4′-hydroxybiphenylmethane, 4-amino-4′-hydroxybiphenyl sulfide, 2,2′-diaminobinaphthyl, and their Examples thereof include alkyl, alkoxy, and halogen-substituted products.
- aromatic diamine and aromatic aminocarboxylic acid include 1,4-phenylenediamine, 1,3-phenylenediamine, N-methyl-1,4-phenylenediamine, N, N′-dimethyl-1,4. -Phenylenediamine, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminobiphenylsulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminobiphenoxyethane 4,4′-diaminobiphenylmethane (methylenedianiline), 4,4′-diaminobiphenyl ether (oxydianiline), 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid and their alkyl, alkoxy or halogen substituted products.
- aliphatic dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid Etc.
- aliphatic diamine examples include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1,8-octanediamine, 1,9- Nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine and the like can be mentioned.
- alicyclic dicarboxylic acid examples include hexahydroterephthalic acid, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, and trans-1,4-cyclohexane.
- aromatic mercaptocarboxylic acid, aromatic dithiol and aromatic mercaptophenol include 4-mercaptobenzoic acid, 2-mercapto-6-naphthoic acid, 2-mercapto-7-naphthoic acid, benzene-1,4- Dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, 2,7-naphthalene-dithiol, 4-mercaptophenol, 3-mercaptophenol, 6-mercapto-2-hydroxynaphthalene, 7-mercapto-2 -Hydroxynaphthalene, and reactive derivatives thereof.
- the fluidity improver in the present invention may contain a phosphite antioxidant in advance in that a resin composition having a good color tone can be obtained.
- the fluidity improver containing a phosphite antioxidant in advance means a mixture of a phosphite antioxidant and a fluidity improver.
- This phosphite-based antioxidant functions as an antioxidant even in the resin composition. That is, the simplest production method of the resin composition of the present invention is to mix three components of polycarbonate resin, fluidity improver and phosphite antioxidant at one time, but “polycarbonate resin” and “phosphite”. Mixing the “mixture of the system antioxidant and the fluidity improver” is also included in the embodiment of the present invention.
- the reason for this is to prevent discoloration of the fluidity improver itself, and when the polymerization catalyst used for the polymerization of the fluidity improver is deactivated and the fluidity improver and the polycarbonate resin are mixed. This is considered to be because it is possible to prevent discoloration due to transesterification or hydrolysis reaction between the polyester and the polycarbonate resin contained in the fluidity improver. As a result, a decrease in the molecular weight of the polycarbonate resin can be more effectively suppressed, so that the resin composition containing the fluidity improver can improve only the fluidity without impairing the original properties of the polycarbonate resin. it can.
- the content of the phosphite antioxidant in the fluidity improver is preferably 0.005 to 5% by mass and preferably 0.01 to 2% by mass with respect to the weight of the fluidity improver. More preferably, the content is 0.01 to 1% by mass, and most preferably 0.02 to 0.05% by mass.
- the content of the phosphite antioxidant is less than 0.005% by mass, the content of the phosphite antioxidant is small, and coloring occurs when the fluidity improver is added to the polycarbonate resin. There is.
- there is more content of a phosphite type antioxidant than 5 mass% the impact strength of the resin composition obtained by adding the said fluid improvement agent to polycarbonate resin may be reduced.
- phosphite antioxidants such as “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (pages 235 to 242) published by CMC Publishing, etc. Although not limited to various compounds described in (1).
- phosphite antioxidants include tris (2,4-di-t-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester Phosphoric acid, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-) 4-methylphenyl) pentaerythritol di-phosphite and the like.
- the product names include ADK STAB PEP-36, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8F, ADK STAB PEP-8W, ADK STAB PEP-11C, ADK STAB PEP-24G, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB P, ADK STAB QL, ADK STAB 522A, ADK STAB 329K, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010 (all of which are manufactured by ADEKA CORPORATION), Irgafos 38, Irgafos 126, Irgafos 126 As mentioned above, BASFBAJAPAN LTD.) And the like can be exemplified.
- Adeka Stub PEP-36, Adeka Stub HP-10 are particularly effective in suppressing the transesterification reaction and hydrolysis reaction, and the antioxidant itself has a high melting point and hardly volatilizes from the resin. More preferable are ADK STAB 2112, ADK STAB PEP-24G, Irgafos 126 and the like.
- the fluidity improver in the present invention may contain a hindered phenol antioxidant in advance in that a polycarbonate resin composition having a good color tone can be obtained.
- the content of the hindered phenolic antioxidant in the fluidity improver is preferably 0.005 to 5% by mass, and 0.01 to 2% by mass with respect to the weight of the fluidity improver. Is more preferably 0.01 to 1% by mass, and most preferably 0.02 to 0.5% by mass.
- the content of the hindered phenolic antioxidant is less than 0.005% by mass, the content of the hindered phenolic antioxidant is small, and coloring occurs when the fluidity improver is added to the polycarbonate resin. May occur.
- the content of the hindered phenol antioxidant is more than 5% by mass, the impact strength of the resin composition obtained by adding the above fluidity improver to the polycarbonate resin may be lowered.
- hindered phenol antioxidant examples include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di, or tri) ( ⁇ -methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amyl Hydroquinone, triethylene glycol Bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 2,
- the trade names are Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above) Ouchi Shinsei Chemical Co., Ltd.), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO-80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, ADK STAB AO-330, ADK STAB AO-37 (all of which are manufactured by ADK), IRGANOX-245, IRGANOX-259, IRGANOX-5 5, IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076,
- Adeka Stub AO-60 and Adeka Stub AO-330 are particularly difficult to discolor, and the coloration of the resin can be efficiently suppressed by the combined use with a phosphite antioxidant.
- IRGANOX-1010 is more preferable.
- a monoacrylate phenol-based stabilizer having both an acrylate group and a phenol group can also be used as a phenol-based antioxidant.
- monoacrylate phenol-based stabilizers include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name: Sumilizer GS).
- ADK STAB PEP-36 As a combination of a phosphite antioxidant and a hindered phenol antioxidant, a combination of ADK STAB PEP-36, ADK STAB 2112 and Irgafos 126, ADK STAB AO-60, ADK STAB AO-330 and IRGANOX-1010 is used. It is preferable at the point which can suppress especially coloring.
- the number average molecular weight of the fluidity improver in the present invention refers to a mixed solvent having a volume ratio of p-chlorophenol and toluene of 3: 8 using polystyrene as a standard substance, and the resin in the present invention having a concentration of 0.25 mass. It is a value measured at 80 ° C. by GPC using a solution prepared by dissolving to be%.
- the number average molecular weight of the polyester in the present invention is preferably 2000 to 30000, more preferably 3000 to 20000, and still more preferably 4000 to 15000.
- the fluidity improver may bleed out when a resin composition obtained by adding the fluidity improver to the polycarbonate resin is molded.
- the number average molecular weight of the fluidity improver exceeds 30000, the melt viscosity of the fluidity improver itself increases, and the resin composition obtained by adding the fluidity improver to the polycarbonate resin is processed. Sometimes the fluidity of the time cannot be improved effectively.
- the fluidity improver in the present invention may be produced by any known method.
- the hydroxyl group of the monomer is individually or collectively made into a lower fatty acid ester using a lower fatty acid such as acetic anhydride, and then removed from the carboxylic acid in another reaction vessel or the same reaction vessel.
- the method of making a lower fatty acid polycondensation reaction is mentioned.
- the polycondensation reaction is carried out in the presence of an inert gas such as nitrogen gas in the presence of an inert gas, usually at a temperature of 220 to 330 ° C., preferably 240 to 310 ° C. in the substantial absence of a solvent. It is performed for 0.5 to 5 hours.
- the reaction temperature is lower than 220 ° C., the reaction proceeds slowly, and when it is higher than 330 ° C., side reactions such as decomposition tend to occur.
- the pressure is rapidly reduced to a high degree of vacuum, the dicarboxylic acid monomer and the low molecular weight compound used for end-capping may volatilize, and a resin having a desired composition or molecular weight may not be obtained.
- the ultimate vacuum is preferably 40 Torr or less, more preferably 30 Torr or less, further preferably 20 Torr or less, and particularly preferably 10 Torr or less.
- the polycondensation reaction may employ a multi-stage reaction temperature. If necessary, the reaction product may be withdrawn in a molten state and recovered as soon as the temperature rises or when the maximum temperature is reached.
- the obtained polyester resin may be used as it is, or solid phase polymerization may be further performed for the purpose of removing unreacted raw materials or improving physical properties.
- the obtained polyester resin is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and an inert gas such as nitrogen gas at 100 to 350 ° C. in a solid state.
- the treatment is preferably performed in an atmosphere or under reduced pressure for 1 to 30 hours.
- the particle diameter of the polyester resin particles is larger than 3 mm, the treatment is not sufficient, and problems with physical properties are caused, which is not preferable. It is preferable to select the treatment temperature and the rate of temperature increase during solid-phase polymerization so that the polyester resin particles do not cause fusion.
- Examples of the lower fatty acid anhydride used in the production of the fluidity improver in the present invention include lower fatty acid anhydrides having 2 to 5 carbon atoms such as acetic anhydride, propionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, Examples include trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, and pivalic anhydride.
- acetic anhydride, propionic anhydride, and trichloroacetic anhydride are particularly preferably used.
- the amount of the lower fatty acid anhydride used is 1.01 to 1.5 times equivalent, preferably 1.02 to 1.2 times equivalent to the total of the monomers used and the functional groups such as hydroxyl groups of the terminal blocking agent. It is. When the amount of the lower fatty acid anhydride used is less than 1.01 equivalents, the lower fatty acid anhydride is volatilized, so that the functional group such as a hydroxyl group does not completely react with the lower fatty acid anhydride. In some cases, a low molecular weight resin may be obtained.
- a polymerization catalyst may be used for the production of the fluidity improver in the present invention.
- conventionally known catalysts can be used as polyester polymerization catalysts, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide.
- metal salt catalysts such as metal salt catalysts, organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
- sodium acetate, potassium acetate, and magnesium acetate are more preferable because discoloration of the fluidity improver itself can be prevented and discoloration of the polycarbonate resin composition can be prevented.
- the addition amount of the polymerization catalyst is usually 0 to 100 ⁇ 10 ⁇ 2 mass%, preferably 0.5 ⁇ 10 ⁇ 3 to 50 ⁇ 10 ⁇ 2 mass%, based on the total weight of the polyester resin. is there.
- the shape of the fluidity improver in the present invention is not particularly limited, and examples thereof include pellets, flakes, and powders.
- the particle diameter should just be as small as it can be thrown into the extruder melt-kneaded with polycarbonate resin, and it is preferable that it is 6 mm or less.
- the resin composition obtained by adding the fluidity improver in the present invention to the polycarbonate resin contains 70 to 99.9% by mass of the polycarbonate resin and 0.1 to 30% by mass of the fluidity improver in the present invention. .
- the content of the fluidity improver in the resin composition (100% by mass) is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 3% by mass or more.
- the content of the fluidity improver in the resin composition (100% by mass) is more preferably 30% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.
- the content rate of the fluidity improver in a resin composition (100 mass%) is 0.1 mass% or more, the fluidity
- the content of the fluidity improver in the resin composition (100% by mass) is 30% by mass or less, the heat resistance and mechanical properties of the polycarbonate resin are not significantly impaired.
- the flowability improver in the present invention has a glass transition temperature lower than that of the polycarbonate resin, it lowers the glass transition point of the resin composition obtained by being dissolved in the polycarbonate resin. Therefore, if the fluidity improver in the present invention is contained in excess of 30% by mass, the heat resistance of the resulting resin composition may be lowered.
- the resin composition obtained by adding the fluidity improver in the present invention to the polycarbonate resin is further protected regardless of whether the fluidity improver contains a phosphite antioxidant in advance.
- An agent may be included separately.
- the content of the phosphite antioxidant is 0 with respect to the total mass of the polycarbonate resin and the fluidity improver. 0.005 to 5% by mass, preferably 0.01 to 2% by mass, more preferably 0.01 to 1% by mass, and 0.02 to 0.5% by mass. Most preferably it is.
- a hindered phenolic antioxidant may be additionally contained.
- the content of the hindered phenol antioxidant is based on the total mass of the polycarbonate resin and the fluidity improver. 0.005 to 5% by mass, preferably 0.01 to 2% by mass, more preferably 0.01 to 1% by mass, and 0.02 to 0.5% by mass. % Is most preferred.
- the polycarbonate resin is not particularly limited, and polycarbonate resins having various structural units can be used.
- a polycarbonate resin produced by a method of interfacial polycondensation of divalent phenol and carbonyl halide, a method of melt polymerization (transesterification) of divalent phenol and carbonic acid diester, or the like can be used.
- divalent phenol that is a raw material for the polycarbonate resin
- divalent phenol examples include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ) Ketone, hydroquinone, resorcin, catechol, etc.
- divalent phenols bis (hydroxyphenyl) alkanes are preferred, and divalent phenols mainly composed of 2,2-bis (4-hydroxyphenyl) propane are particularly preferred.
- the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like.
- diaryl carbonates such as dihaloformates of divalent phenols, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate; dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, dia
- aliphatic carbonate compounds such as mil carbonate and dioctyl carbonate.
- the polycarbonate resin may be a resin having a branched structure in addition to a resin in which the molecular structure of the polymer chain is a linear structure.
- a branching agent for introducing such a branched structure 1,1,1-tris (4-hydroxyphenyl) ethane, ⁇ , ⁇ ′, ⁇ ′′ -tris (4-hydroxyphenyl) -1,3, And 5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol), etc.
- molecular weight regulators phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. Can be used.
- the polycarbonate resin used in the present invention is a copolymer having a polycarbonate structural unit and a polyorganosiloxane structural unit in addition to a homopolymer produced using only the above divalent phenol, or a homopolymer thereof.
- a resin composition comprising a copolymer.
- it may be a polyester-polycarbonate resin obtained by conducting a polymerization reaction of a divalent phenol or the like in the presence of an ester precursor such as a bifunctional carboxylic acid such as terephthalic acid or an ester-forming derivative thereof.
- a resin composition obtained by melt-kneading a polycarbonate resin having various structural units can also be used.
- the fluidity improver as a component other than the polycarbonate resin, the fluidity improver, and the antioxidant (phosphite antioxidant, hindered phenol antioxidant), any other depending on the purpose
- Ingredients such as reinforcing agents, thickeners, mold release agents, coupling agents, flame retardants, flame retardants, pigments, colorants, light diffusing agents and other auxiliary agents, or fillers of the present invention. It can be added as long as the effect is not lost.
- the amount of these additives used is preferably in the range of 0 to 100 parts by weight in total with respect to 100 parts by weight of the resin composition obtained by adding a fluidity improver to the polycarbonate resin.
- the amount of the flame retardant used is preferably 7 to 80 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the resin composition obtained by adding a fluidity improver to the polycarbonate resin. Is more preferably 12 to 40 parts by weight.
- Various compounds are known as flame retardants, for example, various compounds described in “Technology and Application of Polymer Flame Retardation” (pages 149 to 221) published by CMC Publishing Co., Ltd. It is not limited. Among these flame retardants, phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants can be preferably used.
- phosphorus-based flame retardants include phosphate esters, halogen-containing phosphate esters, condensed phosphate esters, polyphosphates, and red phosphorus. These phosphorus flame retardants may be used alone or in combination of two or more.
- halogen flame retardant examples include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, deca Examples thereof include bromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, and brominated crosslinked aromatic polymers. Of these, brominated polystyrene and brominated polyphenylene ether are particularly preferred. These halogen flame retardants may be used alone or in combination of two or more. The halogen element content of these halogen flame retardants is preferably 15 to 87%.
- an inorganic filler may be further added in order to improve mechanical strength, dimensional stability, etc., or for the purpose of increasing the amount.
- the inorganic filler examples include zinc sulfate, potassium hydrogen sulfate, aluminum sulfate, antimony sulfate, sulfate ester, potassium sulfate, cobalt sulfate, sodium hydrogen sulfate, iron sulfate, copper sulfate, sodium sulfate, nickel sulfate, barium sulfate, Metal sulfate compounds such as magnesium sulfate and ammonium sulfate; Titanium compounds such as titanium oxide; Carbonate compounds such as potassium carbonate; Metal hydroxide compounds such as aluminum hydroxide and magnesium hydroxide; Silica compounds such as synthetic silica and natural silica; Calcium aluminate, dihydrate gypsum, zinc borate, barium metaborate, borax; nitrate compounds such as sodium nitrate, molybdenum compounds, zirconium compounds, antimony compounds and their modified products; composite fine particles of silicon dioxide and aluminum oxide Etc.
- inorganic fillers include, for example, potassium titanate whiskers, mineral fibers (rock wool, etc.), glass fibers, carbon fibers, metal fibers (stainless fibers, etc.), aluminum borate whiskers, silicon nitride whiskers, boron fibers. , Tetrapotted zinc oxide whisker, talc, clay, kaolin clay, natural mica, synthetic mica, pearl mica, aluminum foil, alumina, glass flakes, glass beads, glass balloon, carbon black, graphite, calcium carbonate, calcium sulfate, silica Examples include calcium acid, titanium oxide, zinc oxide, silica, asbestos, and quartz powder.
- These inorganic fillers may be untreated, or may be subjected to chemical or physical surface treatment in advance.
- the surface treatment agent used for the surface treatment include compounds such as silane coupling agent, higher fatty acid, fatty acid metal salt, unsaturated organic acid, organic titanate, resin acid, and polyethylene glycol. It is done.
- the method for producing the resin composition in the present invention is not particularly limited.
- the resin composition is, for example, a flow improver, a polycarbonate resin, and a necessary resin using a device such as a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roll, a kneader, or a Brabender.
- a device such as a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roll, a kneader, or a Brabender.
- an additive such as a light diffusing agent is blended and melt kneaded.
- the melt kneading temperature is preferably as low as possible for the purpose of suppressing the transesterification reaction between the polyester and the polycarbonate resin contained in the fluidity improver and the yellowing of the resin composition due to thermal degradation of the polycarbonate resin.
- the molded product of the present invention can be molded into shapes such as various irregular extrusion molded products, sheets and films by extrusion molding, for example.
- the various extrusion molding methods include cold runner and hot runner molding methods, as well as injection compression molding, injection press molding, gas assist injection molding, foam molding (including the case of supercritical fluid injection), inserts. Examples thereof include injection molding methods such as molding, in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding.
- an inflation method, a calendar method, a casting method, or the like can be used for forming a sheet or a film.
- it can be formed as a heat-shrinkable tube by applying a specific stretching operation.
- it is also possible to make a hollow molded product by molding the resin composition of the present invention by rotational molding, blow molding or the like.
- the light guide plate of the present invention is manufactured from the above-described resin composition by a known injection molding method.
- a light guide plate having a wedge-shaped cross section in which one surface is an inclined surface having a uniform inclination, and a prism-shaped uneven pattern is applied to the inclined surface to form a diffusely reflecting portion can be formed.
- Such a light guide plate can be manufactured by using an injection mold having a concavo-convex portion formed in a cavity and performing injection molding while transferring the concavo-convex portion.
- a method of providing the uneven portion in the cavity of the injection mold a method of forming the uneven portion in the nest is simple and preferable.
- a mobile phone By providing at least such a light guide plate and a light source that emits light toward the light guide plate, a mobile phone, a mobile terminal, a camera, a watch, a laptop computer, a display, illumination, a signal, a car tail lamp, a head lamp, An edge-type surface light source body used for displaying a thermal power of an electromagnetic cooker can be configured.
- a self-luminous material such as a fluorescent lamp, a cold cathode tube, an LED, or an organic EL can be used.
- the light guide plate of the present invention is made of a resin composition having high fluidity without impairing transparency and mechanical strength, it can be used in a wide range of applications without being restricted in use environment, and has a fine injection mold. Unevenness and the like are sufficiently transferred and molded well. Therefore, by using such a light guide plate, an industrially useful surface light source body can be provided.
- a polycarbonate resin produced by a method of interfacial polycondensation of divalent phenol and carbonyl halide, a method of melt polymerization (transesterification) of divalent phenol and carbonic acid diester, or the like can be used.
- Examples of the divalent phenol that is a raw material of the aromatic polycarbonate resin (I) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl).
- Ethane 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, Bis (4-hydroxyphenyl) ketone, hydroquinone, resorcin, potassium Call, and the like.
- divalent phenols bis (hydroxyphenyl) alkanes are preferred, and divalent phenols mainly composed of 2,2-bis (4-hydroxyphenyl) propane are particularly preferred.
- the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like.
- diaryl carbonates such as dihaloformates of divalent phenols, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate; dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, dia
- aliphatic carbonate compounds such as mil carbonate and dioctyl carbonate.
- the aromatic polycarbonate resin (I) may be a resin having a branched structure in addition to a resin having a linear molecular chain structure.
- a branching agent for introducing such a branched structure 1,1,1-tris (4-hydroxyphenyl) ethane, ⁇ , ⁇ ′, ⁇ ′′ -tris (4-hydroxyphenyl) -1,3, And 5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol), etc.
- molecular weight regulators phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. Can be used.
- the aromatic polycarbonate resin (I) used in the present invention is a copolymer having a polycarbonate structural unit and a polyorganosiloxane structural unit, in addition to a homopolymer produced using only the above divalent phenol.
- the resin composition which consists of these homopolymers and a copolymer may be sufficient.
- it may be a polyester-polycarbonate resin obtained by conducting a polymerization reaction of a divalent phenol or the like in the presence of an ester precursor such as a bifunctional carboxylic acid such as terephthalic acid or an ester-forming derivative thereof.
- the molecular weight of the aromatic polycarbonate-based resin (I) is a viscosity average molecular weight calculated from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent from the viewpoint of obtaining a resin composition having high fluidity, and is 12000. It is preferable to use those having a molecular weight of ⁇ 40000, more preferably 12,000 to 25000, and particularly preferably 12,000 to 18000.
- a resin composition obtained by melt-kneading a polycarbonate resin having various structural units can also be used.
- the resin material containing the aromatic polycarbonate resin (A) an aromatic polycarbonate polymer alloy in which the aromatic polycarbonate resin (A) and another resin or elastomer described later are combined may be used.
- the aromatic polycarbonate resin composition does not impair the excellent transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc. inherent in the aromatic polycarbonate resin (A).
- other resins or elastomers may be blended in the range of 50 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
- PSt polystyrene
- AS resin acrylonitrile-styrene resin
- graft copolymers acrylonitrile-butadiene-
- Styrene resins such as styrene resin (ABS resin), acrylonitrile-ethylene propylene rubber-styrene resin (AES resin), acrylonitrile-acrylate-styrene resin (AAS resin), high impact polystyrene (HIPS), etc .; polyethylene terephthalate (PET) , Polyesters such as polybutylene terephthalate (PBT) and copolymers thereof; acrylic resins such as polymethyl methacrylate (PMMA) and copolymers having methyl methacrylate units; polypropylene (PP) and polyethylene Olefin resins such as ethylene (PE) and ethylene- (meth) acrylic acid copolymers; polyurethanes; silicone resins; syndiotactic PS; polyamides such as 6-nylon and 6,6-nylon; polyarylate; polyphenylene sulfide; Various general-purpose resins or engineering plastics such as polyether ketone; polysulf
- Elastomers include isobutylene-isoprene rubber; polyester elastomer; styrene-butadiene rubber, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-polyisoprene-polystyrene (SIS).
- SBS polystyrene-polybutadiene-polystyrene
- SEBS polystyrene-poly (ethylene-butylene) -polystyrene
- SIS polystyrene-polyisoprene-polystyrene
- Styrene elastomer such as polystyrene-poly (ethylene-propylene) -polystyrene (SEPS); polyolefin elastomer such as ethylene-propylene rubber; polyamide elastomer; acrylic elastomer; diene rubber, acrylic rubber, silicone rubber, etc. Containing methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-styrene resin (MAS tree) ) Impact modifiers such as core-shell type represented by like.
- the fluidity improver (II) in the present invention comprises a polyester obtained by polycondensing a bisphenol component, an aliphatic dicarboxylic acid component, and optionally a biphenol component at a specific ratio.
- the structure of the main chain of the fluidity improver which is one form of the present invention, includes the following general formula (1)
- X 1 to X 4 each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, which may be the same or different.
- X 1 to X 4 each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, which may be the same or different.
- X 5 to X 8 are the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- Y represents a methylene group, an isopropylidene group, a cyclic group.
- R 1 represents a divalent linear substituent having 2 to 18 main chain atoms which may contain a branch.
- the fluidity improver (II) in the present invention is produced by polycondensing a diol component consisting of a bisphenol component (B) and an optional biphenol component (A) and a dicarboxylic acid component which is a component (C). Polyester.
- the fluidity improver is not a low-molecular compound, it is possible to suppress the occurrence of bleed out when molding a polycarbonate resin composition to which the fluidity improver is added.
- the fluidity improver having the molecular structure is highly compatible with the polycarbonate resin, the fluidity of the resin composition obtained by adding the fluidity improver to the polycarbonate resin is efficiently improved. In addition, various properties such as transparency and impact strength inherent to the polycarbonate resin are not impaired.
- the biphenol component (A) contained in the fluidity improver is preferably 0 to 55 mol%, more preferably 10 to 40 mol%, and most preferably 20 to 30 mol%.
- the bisphenol component (B) is preferably contained in an amount of 5 to 60 mol%, more preferably 10 to 50 mol%, and most preferably 20 to 30 mol%.
- the dicarboxylic acid component (C) is preferably contained in an amount of 40 to 60 mol%, more preferably 45 to 55 mol%.
- the molar ratio ((A) / (B)) of the component (A) to the component (B) is preferably 1/9 to 9/1. More preferably, it is 1/7 to 7/1, more preferably 1/5 to 5/1, and most preferably 1/3 to 3/1.
- the polyester itself becomes completely amorphous and has a low glass transition temperature. May cause fusion of pellets.
- (A) / (B) is further less than 9/1, the component (B) is less compatible with the aromatic polycarbonate resin, and a fluidity improver is added to the aromatic polycarbonate resin.
- phase separation may occur at the central portion of the thickness while being gradually cooled.
- X 1 to X 4 in the general formula (1) may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. It is more preferable that all of X 1 to X 4 are hydrogen atoms in order to improve the handleability such as improving the crystallinity of the fluidity improver itself and preventing fusion during pellet storage.
- X 5 to X 8 in the general formula (2) may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. In order to enhance the compatibility with the aromatic polycarbonate resin, it is more preferable that all of X 5 to X 8 are hydrogen atoms.
- Y represents a methylene group, an isopropylidene group, a cyclic alkylidene group, an aryl-substituted alkylidene group, an arylene alkylidene group, —S—, —O—, a carbonyl group or —SO 2 —.
- 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) is preferable in terms of increasing compatibility with the aromatic polycarbonate resin. is there.
- dihydric phenols other than bisphenol A include 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-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis ( 4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2- Bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromopheny
- Dihydroxydiaryl sulfides dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone, 4,4′- And dihydroxydiaryl sulfones such as dihydroxy-3,3′-dimethyldiphenyl sulfone; and dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl.
- These bisphenol components may be used singly or as a mixture of two or more of them without losing the effect of the present invention.
- the terminal structure of the fluidity improver (II) in the present invention is not particularly limited, and is particularly obtained by suppressing transesterification with an aromatic polycarbonate resin and adding the fluidity improver to the aromatic polycarbonate resin.
- it is preferably sealed with a monofunctional low molecular compound.
- the sealing rate with respect to all ends of the molecular chain is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and most preferably 90% or more.
- the end-capping rate of the fluidity improver can be determined by the following formula (4) by measuring the number of sealed end functional groups and the number of end functional groups not sealed.
- 1 H-NMR is used to determine the number of each terminal group from the integral value of the characteristic signal corresponding to each terminal group.
- the method of calculating the terminal blocking rate using (4) is preferable in terms of accuracy and simplicity.
- Terminal sealing rate (%) ⁇ [number of sealed terminal functional groups] / ([number of sealed terminal functional groups] + [number of unsealed terminal functional groups]) ⁇ ⁇ 100 (4)
- the monofunctional low molecular compound used for sealing include monohydric phenol, monoamine having 1 to 20 carbon atoms, aliphatic monocarboxylic acid, carbodiimide, epoxy or oxazoline.
- Specific examples of monohydric phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, p-nonylphenol, pt-amylphenol, 4-hydroxybiphenyl, And any mixture thereof.
- aliphatic monocarboxylic acids include fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
- monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and any of these A mixture etc. are mentioned.
- carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di- ⁇ -naphthylcarbodiimide, bis-2,6-diisopropyl Phenylcarbodiimide, poly (2,4,6-triisopropylphenylene-1,3-diisocyanate), 1,5- (diisopropylbenzene) polycarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide and their Arbitrary mixtures etc.
- Examples of epoxies include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, triethylolpropane polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, bisphenol A- Diglycidyl ether, hydrogenated bisphenol A-glycidyl ether, 4,4'-diphenylmethane diglycidyl ether, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, methacrylic acid glycidyl ester, methacrylic acid glycidyl ester polymer, Examples thereof include a sidyl ester polymer-containing compound and an arbitrary mixture thereof.
- Examples of oxazolines include styrene-2
- R 1 therein represents a divalent linear substituent which may have 2 to 18 main chain atoms and may be branched.
- the number of main chain atoms is the number of atoms in the main chain skeleton.
- R 1 is preferably a straight-chain substituent that does not contain a branch, and further, a straight-chain aliphatic hydrocarbon chain that does not contain a branch. Is preferred.
- R 1 may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain. When the unsaturated bond is included, the fluidity improver may not be sufficiently flexible, and may increase the melt viscosity of the fluidity improver itself.
- R 1 is preferably a straight-chain saturated aliphatic hydrocarbon chain having 2 to 18 carbon atoms from the viewpoint that both the ease of polymerization of the fluidity improver and the improvement of the glass transition point can be achieved. More preferably, it is a straight chain saturated aliphatic hydrocarbon chain having 4 to 16 carbon atoms, more preferably a straight chain saturated aliphatic hydrocarbon chain having 8 to 14 carbon atoms, and a straight chain having 8 carbon atoms.
- R 1 is particularly preferably one selected from — (CH 2 ) 8 —, — (CH 2 ) 10 —, and — (CH 2 ) 12 —.
- a dicarboxylic acid component may be used independently and may mix 2 or more types in the range which does not lose the effect of this invention.
- the fluidity improver (II) in the present invention may be copolymerized with other monomers to such an extent that the effect is not lost.
- Other monomers include, for example, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids or caprolactams, caprolactones, aliphatic dicarboxylic acids, fatty acids Aromatic diols, aliphatic diamines, alicyclic dicarboxylic acids, and alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols, and aromatic mercaptophenols.
- the content of the other monomer constituting the fluidity improver is less than 50 mol%, preferably less than 30 mol%, more preferably, relative to the total number of moles of the fluidity improver. Less than 10 mol%, most preferably less than 5 mol%.
- the content of the other monomer is 50 mol% or more based on the total number of moles of the fluidity improver, the compatibility of the fluidity improver with the aromatic polycarbonate resin decreases. It becomes difficult for the fluidity improver to be compatible with the aromatic polycarbonate resin.
- aromatic hydroxycarboxylic acid examples include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy -7-naphthoic acid, 2-hydroxy-3-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, and their And alkyl, alkoxy or halogen-substituted products.
- aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl, 4,4 ′′ -dicarboxyterphenyl, bis (4-carboxyphenyl) ether, bis (4-carboxyphenoxy) butane, bis (4-carboxyphenyl) ethane, bis (3-carboxy Phenyl) ether, bis (3-carboxyphenyl) ethane, and alkyl, alkoxy or halogen substituents thereof.
- aromatic diol examples include pyrocatechol, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′- Examples include dihydroxybiphenyl, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenol ether, bis (4-hydroxyphenyl) ethane, 2,2′-dihydroxybinaphthyl, and alkyl, alkoxy or halogen substituents thereof. It is done.
- aromatic hydroxyamine examples include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4′-hydroxybiphenyl, 4-amino-4′-hydroxybiphenyl ether, 4-amino-4′-hydroxybiphenylmethane, 4-amino-4′-hydroxybiphenyl sulfide, 2,2′-diaminobinaphthyl, and their Examples thereof include alkyl, alkoxy, and halogen-substituted products.
- aromatic diamine and aromatic aminocarboxylic acid include 1,4-phenylenediamine, 1,3-phenylenediamine, N-methyl-1,4-phenylenediamine, N, N′-dimethyl-1,4. -Phenylenediamine, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminobiphenylsulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminobiphenoxyethane 4,4′-diaminobiphenylmethane (methylenedianiline), 4,4′-diaminobiphenyl ether (oxydianiline), 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid and their alkyl, alkoxy or halogen substituted products.
- aliphatic dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid Etc.
- aliphatic diamine examples include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1,8-octanediamine, 1,9- Nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine and the like can be mentioned.
- alicyclic dicarboxylic acid examples include hexahydroterephthalic acid, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, and trans-1,4-cyclohexane.
- aromatic mercaptocarboxylic acid, aromatic dithiol and aromatic mercaptophenol include 4-mercaptobenzoic acid, 2-mercapto-6-naphthoic acid, 2-mercapto-7-naphthoic acid, benzene-1,4- Dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, 2,7-naphthalene-dithiol, 4-mercaptophenol, 3-mercaptophenol, 6-mercapto-2-hydroxynaphthalene, 7-mercapto-2 -Hydroxynaphthalene, and reactive derivatives thereof.
- the fluidity improver in the present invention may contain a phosphite antioxidant in advance in that a resin composition having a good color tone can be obtained.
- the fluidity improver containing a phosphite antioxidant in advance means a mixture of a phosphite antioxidant and a fluidity improver.
- This phosphite-based antioxidant functions as an antioxidant even in the resin composition. That is, the simplest production method of the resin composition of the present invention is to mix three components of polycarbonate resin, fluidity improver and phosphite antioxidant at one time, but “polycarbonate resin” and “phosphite”. Mixing the “mixture of the system antioxidant and the fluidity improver” is also included in the embodiment of the present invention.
- the reason for this is to prevent discoloration of the fluidity improver itself and to deactivate the polymerization catalyst used for the polymerization of the fluidity improver and mix the fluidity improver and the aromatic polycarbonate resin. This is considered to be because discoloration due to transesterification or hydrolysis reaction between the polyester contained in the fluidity improver and the aromatic polycarbonate resin, which may occur in the fluidity improver, can be prevented. As a result, a decrease in the molecular weight of the aromatic polycarbonate resin can be more effectively suppressed, so that the resin composition containing the fluidity improver is fluid without impairing the original properties of the aromatic polycarbonate resin. Can only improve.
- the content of the phosphite antioxidant in the fluidity improver is preferably 0.005 to 5% by mass and preferably 0.01 to 2% by mass with respect to the weight of the fluidity improver. More preferably, the content is 0.01 to 1% by mass, and most preferably 0.02 to 0.05% by mass.
- the content of the phosphite-based antioxidant is less than 0.005% by mass, the content of the phosphite-based antioxidant is small, and coloring occurs when the fluidity improver is blended with the aromatic polycarbonate-based resin. May occur.
- the content of the phosphite antioxidant is more than 5% by mass, the impact strength of the resin composition obtained by adding the fluidity improver to the aromatic polycarbonate resin may be reduced. is there.
- phosphite antioxidants such as “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (pages 235 to 242) published by CMC Publishing, etc. Although not limited to various compounds described in (1).
- phosphite antioxidants include tris (2,4-di-t-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester Phosphoric acid, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-) 4-methylphenyl) pentaerythritol di-phosphite and the like.
- the product names include ADK STAB PEP-36, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8F, ADK STAB PEP-8W, ADK STAB PEP-11C, ADK STAB PEP-24G, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB P, ADK STAB QL, ADK STAB 522A, ADK STAB 329K, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010 (all of which are manufactured by ADEKA CORPORATION), Irgafos 38, Irgafos 126, Irgafos 126 As mentioned above, BASFBAJAPAN LTD.) And the like can be exemplified.
- Adeka Stub PEP-36, Adeka Stub HP-10 are particularly effective in suppressing the transesterification reaction and hydrolysis reaction, and the antioxidant itself has a high melting point and hardly volatilizes from the resin. More preferable are ADK STAB 2112, ADK STAB PEP-24G, Irgafos 126 and the like.
- the fluidity improver in the present invention may contain a hindered phenol antioxidant in advance in that a polycarbonate resin composition having a good color tone can be obtained.
- the content of the hindered phenolic antioxidant in the fluidity improver is preferably 0.005 to 5% by mass, and 0.01 to 2% by mass with respect to the weight of the fluidity improver. Is more preferably 0.01 to 1% by mass, and most preferably 0.02 to 0.05% by mass.
- the content of the hindered phenolic antioxidant is less than 0.005% by mass, the content of the hindered phenolic antioxidant is small, and the fluidity improver is blended with the aromatic polycarbonate resin. May be colored.
- the content of the hindered phenol antioxidant is more than 5% by mass, the impact strength of the resin composition obtained by adding the fluidity improver to the aromatic polycarbonate resin may be lowered. .
- hindered phenol antioxidant examples include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di, or tri) ( ⁇ -methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amyl Hydroquinone, triethylene glycol Bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 2,
- the trade names are Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above) Ouchi Shinsei Chemical Co., Ltd.), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO-80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, ADK STAB AO330, ADK STAB AO-37 (all of which are manufactured by ADK), IRGANOX-245, IRGANOX-259, IRGANOX-56 , IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076
- ADK STAB AO-60, IRGANOX-1010, and the like since the antioxidant itself is particularly difficult to discolor, and the coloration of the resin can be efficiently suppressed by the combined use with a phosphite antioxidant. Is more preferable.
- a monoacrylate phenol-based stabilizer having both an acrylate group and a phenol group can also be used as a phenol-based antioxidant.
- monoacrylate phenol-based stabilizers include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name: Sumilizer GS).
- a combination of a phosphite antioxidant and a hindered phenol antioxidant particularly suppresses coloring of the resin. It is preferable in that it can be performed.
- the number average molecular weight of the fluidity improver in the present invention refers to a mixed solvent having a volume ratio of p-chlorophenol and toluene of 3: 8 using polystyrene as a standard substance, and the resin in the present invention having a concentration of 0.25 mass. It is a value measured at 80 ° C. by GPC using a solution prepared by dissolving to be%.
- the number average molecular weight of the polyester in the present invention is preferably 2000 to 30000, more preferably 3000 to 25000, and further preferably 4000 to 20000.
- the fluidity improver may bleed out when a resin composition obtained by adding the fluidity improver to the aromatic polycarbonate resin is molded. is there. Further, when the number average molecular weight of the fluidity improver exceeds 30000, the melt viscosity of the fluidity improver itself is increased, and the resin composition obtained by adding the fluidity improver to the aromatic polycarbonate resin. In some cases, the fluidity during the molding process cannot be improved effectively.
- the fluidity improver (II) in the present invention may be produced by any known method.
- the hydroxyl group of the monomer is individually or collectively made into a lower fatty acid ester using a lower fatty acid such as acetic anhydride, and then removed from the carboxylic acid in another reaction vessel or the same reaction vessel.
- the method of making a lower fatty acid polycondensation reaction is mentioned.
- the polycondensation reaction is carried out in the presence of an inert gas such as nitrogen gas in the presence of an inert gas, usually at a temperature of 220 to 330 ° C., preferably 240 to 310 ° C. in the substantial absence of a solvent. It is performed for 0.5 to 5 hours.
- the reaction temperature is lower than 220 ° C., the reaction proceeds slowly, and when it is higher than 330 ° C., side reactions such as decomposition tend to occur.
- the pressure is rapidly reduced to a high degree of vacuum, the dicarboxylic acid monomer and the low molecular weight compound used for end-capping may volatilize, and a resin having a desired composition or molecular weight may not be obtained.
- the ultimate vacuum is preferably 40 Torr or less, more preferably 30 Torr or less, further preferably 20 Torr or less, and particularly preferably 10 Torr or less.
- the polycondensation reaction may employ a multi-stage reaction temperature. If necessary, the reaction product may be withdrawn in a molten state and recovered as soon as the temperature rises or when the maximum temperature is reached.
- the obtained polyester resin may be used as it is, or solid phase polymerization may be further performed for the purpose of removing unreacted raw materials or improving physical properties.
- the obtained polyester resin is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and an inert gas such as nitrogen gas at 100 to 350 ° C. in a solid state.
- the treatment is preferably performed in an atmosphere or under reduced pressure for 1 to 30 hours.
- the particle diameter of the polyester resin particles is larger than 3 mm, the treatment is not sufficient, and problems with physical properties are caused, which is not preferable. It is preferable to select the treatment temperature and the rate of temperature increase during solid-phase polymerization so that the polyester resin particles do not cause fusion.
- Examples of the lower fatty acid anhydride used in the production of the fluidity improver in the present invention include lower fatty acid anhydrides having 2 to 5 carbon atoms such as acetic anhydride, propionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, Examples include trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, and pivalic anhydride.
- acetic anhydride, propionic anhydride, and trichloroacetic anhydride are particularly preferably used.
- the amount of the lower fatty acid anhydride used is 1.01 to 1.5 times equivalent, preferably 1.02 to 1.2 times equivalent to the total of the monomers used and the functional groups such as hydroxyl groups of the terminal blocking agent. It is. When the amount of the lower fatty acid anhydride used is less than 1.01 equivalents, the lower fatty acid anhydride is volatilized, so that the functional group such as a hydroxyl group does not completely react with the lower fatty acid anhydride. In some cases, a low molecular weight resin may be obtained.
- a polymerization catalyst may be used for the production of the fluidity improver in the present invention.
- conventionally known catalysts can be used as polyester polymerization catalysts, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide.
- metal salt catalysts such as metal salt catalysts, organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
- sodium acetate, potassium acetate, and magnesium acetate are more preferable because discoloration of the fluidity improver itself can be prevented and discoloration of the polycarbonate resin composition can be prevented.
- the addition amount of the polymerization catalyst is usually 0 to 100 ⁇ 10 ⁇ 2 mass%, preferably 0.5 ⁇ 10 ⁇ 3 to 50 ⁇ 10 ⁇ 2 mass%, based on the total weight of the polyester resin. is there.
- the light diffusing agent (III) is a fine particle having a light diffusing ability. Examples of such fine particles include inorganic fine particles and polymer fine particles.
- inorganic fine particles examples include glass filler, calcium carbonate, barium sulfate, silica, talc, mica, wollastonite, titanium oxide and the like. Of these, calcium carbonate is preferred.
- the shape of the inorganic fine particles is preferably granular (including indeterminate) or plate-like rather than fibrous.
- a glass filler glass beads, glass balloons, glass milled fibers, glass flakes, ultrathin glass flakes (manufactured by a sol-gel method), amorphous glass and the like can be mentioned.
- other inorganic fine particles having various shapes can be employed.
- the inorganic fine particles may be surface-treated with various silicone compounds such as silane coupling agents and polyorganohydrogensiloxane compounds, fatty acid ester compounds, olefin compounds and the like.
- silicone compounds such as silane coupling agents and polyorganohydrogensiloxane compounds, fatty acid ester compounds, olefin compounds and the like.
- the surface-treated inorganic fine particles are effective in improving thermal stability and hydrolysis resistance.
- the refractive index of the inorganic fine particles is preferably 1.4 to 1.8. When the refractive index of the inorganic fine particles is within this range, both light diffusibility and total light transmittance are good.
- the refractive index of inorganic fine particles is known from various documents, and can be easily measured by a liquid immersion method or the like.
- the polymer fine particles are preferably spherical from the viewpoint of light diffusibility, and the closer to a true spherical shape, the more preferable.
- polymer fine particles organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer; silicone-based crosslinked particles; amorphous heat-resistant polymer particles such as polyethersulfone particles; epoxy resin particles, urethane resin Examples thereof include particles, melamine resin particles, benzoguanamine resin particles, and phenol resin particles.
- amorphous heat-resistant polymer particles the shape of the particles is not impaired when kneading with the aromatic polycarbonate resin (I) while heating, and thus a crosslinkable monomer is not necessarily required.
- organic crosslinked particles are particularly preferred.
- non-crosslinkable monomers used for organic crosslinked particles include non-crosslinkable vinyl monomers such as acrylic monomers, styrene monomers, and acrylonitrile monomers; olefin monomers.
- acrylic monomers examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, Examples include phenyl methacrylate. Of these, methyl methacrylate is particularly preferred.
- styrene monomer examples include alkyl styrene such as styrene, ⁇ -methyl styrene, methyl styrene (vinyl toluene), ethyl styrene, and halogenated styrene such as brominated styrene. Of these, styrene is particularly preferred.
- acrylonitrile monomers examples include acrylonitrile and methacrylonitrile.
- olefin monomer examples include ethylene and various norbornene type compounds.
- Examples of other copolymerizable monomers include glycidyl methacrylate, N-methylmaleimide, maleic anhydride, and the like, and as a result, the organic crosslinked particles may have units such as N-methylglutarimide.
- These monomers may be used alone or in combination of two or more.
- crosslinkable monomer used in the organic crosslinked particles examples include divinylbenzene, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and propylene glycol (meth).
- Examples of the method for producing organic crosslinked particles include an emulsion polymerization method, a suspension polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method.
- a suspension polymerization method a water phase and a monomer phase are individually maintained and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser;
- a method in which the monomer phase is supplied by passing it through a small diameter orifice of several to several tens of ⁇ m or a porous filter in an aqueous liquid having dispersibility to control the particle diameter can also be adopted.
- Silicone-based crosslinked particles are those having a siloxane bond as the main skeleton and an organic substituent on the silicon atom, and those having a high degree of crosslinking represented by polymethylsilsesquioxane and those crosslinked by methylsilicone rubber particles. There is a low degree. In the present invention, those having a high degree of crosslinking represented by polymethylsilsesquioxane are preferred.
- Examples of the organic substituent bonded to the silicon atom of the silicone-based crosslinked particles include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; aryl groups such as phenyl group; aralkyl groups such as benzyl group; carboxyl group, carbonyl Group, ester group, ether group and the like.
- Examples of the method for producing the silicone-based crosslinked particles include a method of forming three-dimensionally crosslinked particles while growing siloxane bonds by hydrolysis and condensation reaction of trifunctional alkoxysilane or the like in water.
- the particle diameter of the silicone-based crosslinked particles can be controlled by the amount of alkali serving as a catalyst, stirring conditions, and the like.
- polymer fine particle production methods include spray drying, submerged curing (coagulation), phase separation (coacervation), solvent evaporation, and reprecipitation. Further, a nozzle vibration method or the like may be combined with these methods.
- polymer fine particles examples include a single-phase structure, a core-shell structure, and an IPN structure in which two or more components are entangled with each other.
- composite particles having inorganic fine particles as a core and organic crosslinked particles as a shell, and composite particles having organic crosslinked particles as a core and epoxy resin, urethane resin or the like as a shell may be used.
- the refractive index of the polymer fine particles is usually about 1.33 to 1.7. When the refractive index of the polymer fine particles is within this range, a sufficient light diffusing function is exhibited in a state of being blended in the resin composition.
- polymer fine particles are preferable to inorganic fine particles. By using the polymer fine particles, it is possible to realize both the light diffusibility and the total light transmittance at a higher level.
- the average particle size of the light diffusing agent (III) is preferably 0.01 to 50 ⁇ m, more preferably 0.1 to 10 ⁇ m, and further preferably 0.1 to 8 ⁇ m.
- the average particle diameter is represented by 50% (D50) of the cumulative distribution of particle sizes obtained by the laser light scattering method.
- the light diffusing agent (III) preferably has a narrow particle size distribution, and more preferably has such a distribution that fine particles in the range of an average particle size of ⁇ 2 ⁇ m are 70% by mass or more of the whole.
- the absolute value of the difference between the refractive index of the light diffusing agent (III) and the refractive index of the aromatic polycarbonate resin (I) is preferably 0.02 to 0.2. When the difference in refractive index is within this range, it is possible to achieve both light diffusibility and total light transmittance at a high level.
- the refractive index of the light diffusing agent (III) is more preferably lower than the refractive index of the aromatic polycarbonate resin (I).
- the compounding amount of the light diffusing agent (III) is 0.1 to 30 with respect to 100 parts by mass in total of the aromatic polycarbonate resin (I), another resin and / or elastomer and the fluidity improver (II). Mass parts are preferred, 0.3 to 20 parts by mass are more preferred, 0.4 to 15 parts by mass are more preferred, and 0.5 to 10 parts by mass are particularly preferred. When the blending amount of the light diffusing agent (III) is within this range, a high light diffusing function is exhibited.
- the resin composition of the present invention contains 70 to 99.9% by mass of the aromatic polycarbonate resin (I) and 0.1 to 30% by mass of the fluidity improver (II).
- the content of the fluidity improver (II) is preferably 0.5% by mass or more, more preferably 1% by mass or more. A mass% or more is particularly preferred.
- the upper limit of the content of the fluidity improver is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. If the content rate of a fluid improvement agent is 0.1 mass% or more, the fluidity
- the fluidity improver in the present invention lowers the glass transition point of the resin composition obtained by being dissolved in the polycarbonate resin. Therefore, if the fluidity improver in the present invention is contained in excess of 30% by mass, the heat resistance of the resulting resin composition may be lowered.
- the resin composition obtained by adding the fluidity improver in the present invention to the aromatic polycarbonate resin is further phosphite regardless of whether the fluidity improver contains a phosphite antioxidant in advance.
- a system antioxidant may be included separately.
- the content of the phosphite antioxidant is based on the total mass of the aromatic polycarbonate resin and the fluidity improver. It is preferably 0.005 to 5% by mass, more preferably 0.01 to 2% by mass, still more preferably 0.01 to 1% by mass, and 0.02 to 0.05% by mass. Most preferably, it is mass%.
- a hindered phenolic antioxidant may be additionally contained.
- the content of the hindered phenol antioxidant is the total mass of the aromatic polycarbonate resin and the fluidity improver. Is preferably 0.005 to 5% by mass, more preferably 0.01 to 2% by mass, still more preferably 0.01 to 1% by mass, and 0.02 to 0%. Most preferably, it is 0.05 mass%.
- the resin composition of the present invention further includes a component other than the aromatic polycarbonate resin, the fluidity improver, the light diffusing agent, and the antioxidant (phosphite antioxidant, hindered phenol antioxidant).
- any other components such as reinforcing agents, thickeners, mold release agents, coupling agents, flame retardants, flame retardants, pigments, colorants, other auxiliaries, or fillers, It can be added as long as the effects of the present invention are not lost.
- the amount of these additives used is preferably in the range of 0 to 100 parts by weight in total with respect to 100 parts by weight of the resin composition obtained by adding a fluidity improver to the polycarbonate resin.
- the amount of the flame retardant used is more preferably 7 to 80 parts by weight with respect to 100 parts by weight of the resin composition obtained by adding a fluidity improver to the aromatic polycarbonate resin. More preferred is 12 to 40 parts by weight.
- Various compounds are known as flame retardants, for example, various compounds described in “Technology and Application of Polymer Flame Retardation” (pages 149 to 221) published by CMC Publishing Co., Ltd. It is not limited. Among these flame retardants, phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants can be preferably used.
- phosphorus-based flame retardants include phosphate esters, halogen-containing phosphate esters, condensed phosphate esters, polyphosphates, and red phosphorus. These phosphorus flame retardants may be used alone or in combination of two or more.
- halogen flame retardant examples include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, deca Examples thereof include bromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, and brominated crosslinked aromatic polymers. Of these, brominated polystyrene and brominated polyphenylene ether are particularly preferred. These halogen flame retardants may be used alone or in combination of two or more. The halogen element content of these halogen flame retardants is preferably 15 to 87%.
- an inorganic filler may be further added in order to improve mechanical strength, dimensional stability, etc., or for the purpose of increasing the amount.
- the inorganic filler examples include zinc sulfate, potassium hydrogen sulfate, aluminum sulfate, antimony sulfate, sulfate ester, potassium sulfate, cobalt sulfate, sodium hydrogen sulfate, iron sulfate, copper sulfate, sodium sulfate, nickel sulfate, barium sulfate, Metal sulfate compounds such as magnesium sulfate and ammonium sulfate; Titanium compounds such as titanium oxide; Carbonate compounds such as potassium carbonate; Metal hydroxide compounds such as aluminum hydroxide and magnesium hydroxide; Silica compounds such as synthetic silica and natural silica; Calcium aluminate, dihydrate gypsum, zinc borate, barium metaborate, borax; nitrate compounds such as sodium nitrate, molybdenum compounds, zirconium compounds, antimony compounds and their modified products; composite fine particles of silicon dioxide and aluminum oxide Etc.
- inorganic fillers include, for example, potassium titanate whiskers, mineral fibers (rock wool, etc.), glass fibers, carbon fibers, metal fibers (stainless fibers, etc.), aluminum borate whiskers, silicon nitride whiskers, boron fibers. , Tetrapotted zinc oxide whisker, talc, clay, kaolin clay, natural mica, synthetic mica, pearl mica, aluminum foil, alumina, glass flakes, glass beads, glass balloon, carbon black, graphite, calcium carbonate, calcium sulfate, silica Examples include calcium acid, titanium oxide, zinc oxide, silica, asbestos, and quartz powder.
- These inorganic fillers may be untreated, or may be subjected to chemical or physical surface treatment in advance.
- the surface treatment agent used for the surface treatment include compounds such as silane coupling agent, higher fatty acid, fatty acid metal salt, unsaturated organic acid, organic titanate, resin acid, and polyethylene glycol. It is done.
- the method for producing the resin composition in the present invention is not particularly limited.
- the resin composition is, for example, an aromatic polycarbonate-based resin, a fluidity improver using an apparatus such as a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two roll, a kneader, or a Brabender. And an additive such as a light diffusing agent and the like, and a known method of melt kneading.
- the melt kneading temperature is as low as possible in order to suppress the transesterification reaction between the polyester contained in the fluidity improver and the aromatic polycarbonate resin, and the yellowing of the resin composition due to thermal degradation of the aromatic polycarbonate resin. It is preferable that
- the molded product of the present invention can be molded into shapes such as various irregular extrusion molded products, sheets and films by extrusion molding, for example.
- the various extrusion molding methods include cold runner and hot runner molding methods, as well as injection compression molding, injection press molding, gas assist injection molding, foam molding (including the case of supercritical fluid injection), inserts. Examples thereof include injection molding methods such as molding, in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding.
- an inflation method, a calendar method, a casting method, or the like can be used for forming a sheet or a film.
- it can be formed as a heat-shrinkable tube by applying a specific stretching operation.
- it is also possible to make a hollow molded product by molding the resin composition of the present invention by rotational molding, blow molding or the like.
- Examples of the light diffusing molded article of the present invention include light diffusing plates, light diffusing films, electronic / electric equipment, OA equipment parts, vehicle parts, machine parts, agricultural materials, fishery materials, transport containers, packaging containers, sundries, etc. Can be mentioned.
- a light diffusing plate for an image display device a light diffusing plate used for a backlight module such as a liquid crystal display device, a light diffusing plate used for a screen of a projection display device such as a projector television
- an image reading device Light diffuser plates, electric light covers, meters, signboards (particularly internally lit), resin window glass, vehicle roofing materials, marine roofing materials, residential roofing materials, solar cell covers, and the like.
- a backlight module such as a liquid crystal display device, various light sources (cold cathode tube, LED, etc.) can be used.
- the aromatic polycarbonate resin composition of the present invention is particularly suitable for producing a large and thin light diffusion plate (particularly a light diffusion plate for an image display device).
- a light diffusion plate having a surface area of 500 to 50000 cm 2 can be obtained.
- the surface area of the light diffusing plate is preferably 1000 to 25000 cm 2 , and the thickness is preferably 0.3 to 3 mm.
- the light diffusing plate may be a single-layer plate having a surface shape such as a Fresnel lens shape or a cylindrical lens shape, and another material having a surface shape such as a Fresnel lens shape or a cylindrical lens shape is laminated on the light diffusing plate.
- a laminated board may be sufficient.
- a single-layer plate having a surface shape such as a Fresnel lens shape or a cylindrical lens shape is formed by molding the aromatic polycarbonate resin composition of the present invention into a desired shape by an injection molding method, a compression molding method, an extrusion molding method, or the like. Can be manufactured.
- a method of forming a Fresnel lens shape (uneven shape) on the surface (i) a method of providing unevenness corresponding to the Fresnel lens shape on the mold cavity surface or the transfer roll surface, and transferring the unevenness to the surface of the molded product; ) Insert another material with irregularities corresponding to the shape of the Fresnel lens into the mold cavity, or laminate it at the time of extrusion to integrate the different material and the molded product, and then remove the other material. And a method of transferring irregularities on the surface of the molded product.
- a concavo-convex shape such as a Fresnel lens shape may be omitted by laminating a layer containing a bright pigment on the light diffusion plate.
- the light diffusing plate for an image display device is formed by forming various light reflection preventing films on the light source side surface (surface opposite to the observer) to prevent reflection of light from the light source. Also good.
- the light diffusive molded article of the present invention can be subjected to surface modification, and as a result, other functions can be imparted.
- Surface modification means a new layer on the surface of light diffusive moldings by vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. It means to provide.
- the surface modification method a known surface modification method employed in ordinary resin molded products can be used.
- Examples of the surface modification method for providing a metal layer or metal oxide layer on the surface of the light diffusive molded article include vapor deposition methods (physical vapor deposition method and chemical vapor deposition method), thermal spraying method, plating method and the like.
- Examples of physical vapor deposition include vacuum vapor deposition, sputtering, ion plating, and the like.
- Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.
- Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method.
- Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method.
- Examples of the electroplating method include laser plating.
- a vapor deposition method or a plating method is preferable.
- a metal oxide layer is provided on the surface of the light diffusible molded article.
- a vapor deposition method is used. Is preferred.
- the vapor deposition method and the plating method may be used in combination. For example, a method of performing electroplating using a metal layer formed by vapor deposition can be employed.
- the polyester contained in the fluidity improver of the present invention is mixed in a mixed solvent having a volume ratio of p-chlorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene of 3: 8 so that the concentration becomes 0.25% by mass.
- a sample solution The standard material was polystyrene, and a similar sample solution was prepared.
- measurement was performed using a high temperature GPC (manufactured by Viscotek: 350 HT-GPC System) under conditions of a column temperature of 80 ° C. and a flow rate of 1.00 mL / min.
- a differential refractometer (RI) was used as a detector.
- the spiral flow (mm) of the resin composition was evaluated using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.).
- the polycarbonate resin composition had a molding temperature of 280 ° C., a mold temperature of 100 ° C., and an injection pressure of 200 MPa.
- the thickness of the molded product was 1 mm and the width was 10 mm.
- IZOD impact strength measurement method In accordance with ASTM D256, a notched test piece of the resin composition was prepared, and the IZOD impact strength (J / m) of this test piece was measured.
- a test piece having a length of 4 cm, a width of 4 cm, and a thickness of 2 mm was prepared by injection molding, and using a haze meter HZ-V3 (manufactured by Suga Test Instruments Co., Ltd.), the total light transmittance (%) and haze ( %).
- Example 2 As monomers, 4,4′-dihydroxybiphenyl, bisphenol A and sebacic acid are charged in a molar ratio of 30:20:50, and p-cumylphenol is used as an end-capping agent with respect to sebacic acid. .2 equivalents, 1.05 equivalents of acetic anhydride was added to the monomer and the phenolic hydroxyl group in the end-capping agent, and the time from the start of pressure reduction to the removal of the fluidity improver was 1.5 hours. A polyester was obtained in the same manner as in Example 1. The number average molecular weight of the obtained polyester was 3,900, and the terminal sealing rate was 90%. The obtained polyester is designated as (C-2).
- Example 2 shows various physical properties of the resin composition.
- Example 3 Polyester was prepared in the same manner as in Example 1 except that bisphenol A and sebacic acid were added as monomers in a molar ratio of 50:50, and the time from the start of decompression to the removal of the fluidity improver was 1 hour. Obtained. The number average molecular weight of the obtained polyester was 11,000. The obtained polyester is designated as (C-3). Further, in the same manner as in Example 1, the resin, the antioxidant and the obtained polyester were blended in the proportions (parts by weight) shown in Table 1 and supplied to the twin-screw extruder, and the resin was melt-kneaded at 260 ° C. A composition was obtained. And the performance of the fluidity improver was evaluated by measuring the physical properties of the resin composition. Table 2 shows various physical properties of the resin composition.
- Example 4 Comparative Example 1
- Resin, antioxidant and polyester were blended in the proportions (parts by weight) shown in Table 1 and supplied to a twin screw extruder, and melt kneaded at 260 ° C. to obtain a resin composition.
- the performance of the fluidity improver was evaluated by measuring the physical properties of the resin composition.
- Table 2 shows various physical properties of the resin composition.
- the fluidity improver (polyester) of the present invention is mixed in a mixed solvent having a volume ratio of p-chlorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene of 3: 8 so that the concentration becomes 0.25% by mass.
- a sample solution was prepared by dissolution.
- the standard material was polystyrene, and a similar sample solution was prepared.
- measurement was performed using a high temperature GPC (manufactured by Viscotek: 350 HT-GPC System) under conditions of a column temperature of 80 ° C. and a flow rate of 1.00 mL / min.
- a differential refractometer (RI) was used as a detector.
- the spiral flow (mm) of the resin composition was evaluated using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.).
- the polycarbonate resin composition had a molding temperature of 280 ° C., a mold temperature of 100 ° C., and an injection pressure of 200 MPa.
- the thickness of the molded product was 1 mm and the width was 10 mm.
- Polyester was prepared in the same manner as in Production Example 1 except that bisphenol A and sebacic acid were added as monomers in a molar ratio of 50:50, and the time from the start of decompression to the removal of the fluidity improver was 1 hour. Obtained. The number average molecular weight of the obtained polyester was 11,000. The obtained polyester is designated as (II-3).
- the aromatic polycarbonate resin compositions obtained in Examples 5 to 7 have significantly improved fluidity, and the light diffusive molded product has a balance between total light transmittance and diffusivity. It was very good.
- the light diffusing aromatic polycarbonate resin composition obtained in Comparative Example 2 did not contain a fluidity improver, and sufficient fluidity could not be obtained.
- the fluidity at the time of molding can be improved without damaging the original properties (transparency, impact resistance, high rigidity, mechanical strength, surface peel resistance, heat resistance, chemical resistance, etc.) of the polycarbonate resin.
- the improved resin composition it is possible to provide a light guide plate that can be used in a wide range of applications without being restricted in use environment and has excellent transferability, and a surface light source body including the same.
- the aromatic polycarbonate resin composition of the present invention has improved melt fluidity (moldability) without impairing the excellent properties (transparency, light diffusibility) of the obtained light diffusible molded article. . Therefore, the light diffusive molded article comprising the aromatic polycarbonate resin composition of the present invention is excellent in transparency, light diffusibility, etc., and is large in size, thinned (light weight), complicated in shape, and high in performance.
- a light diffusing plate for an image display device that is particularly required to be large and thin (for example, a light diffusing plate used in a backlight module such as a liquid crystal display device, a projection type such as a projection television)
- a light diffusing plate used for a screen of a display device As a light diffusing plate used for a screen of a display device), a high-functional light diffusing film surface-treated by printing or the like (for example, a high transmission light diffusing film used for improving the brightness of a liquid crystal display device, etc.) Is preferred.
- the light diffusion molded product of the present invention includes, for example, an electric lamp cover, a meter, a signboard (particularly internally lit), a resin window glass, and an image reading device.
- Light diffusion plate vehicle roofing material, ship roofing material, residential roofing material, solar cell cover, electrical / electronic equipment parts, OA equipment parts, vehicle parts, machine parts, agricultural materials, fishery materials, transport containers, It is useful as a packaging container and miscellaneous goods, and has an extremely high industrial value.
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Abstract
Selon l'invention, un agent améliorant la fluidité qui consiste en un polyester obtenu par polycondesation d'un mélange monomère à base de 0 à 55% en moles d'un composant biphénol, de 5 à 60% en moles d'un composant bisphénol et de 40 à 60% en moles d'un composant acide dicarboxylique (C) (le total des monomères (A) à (C) représentant 100% en moles), est mélangé dans une résine de polycarbonate. Plus précisément, l'invention fournit une composition de résine à base de polycarbonate aromatique et un article moulé diffusant la lumière constitué par moulage de celle-ci. La composition de résine à base de polycarbonate aromatique comprend une résine à base de polycarbonate aromatique (I), l'agent améliorant la fluidité (II) consistant en un polyester de structure spécifique, et un agent de diffusion de lumière (III).
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JP2016076235A JP2017187616A (ja) | 2016-04-06 | 2016-04-06 | 導光板およびこれを備えた面光源体 |
JP2016076236A JP2017186446A (ja) | 2016-04-06 | 2016-04-06 | 芳香族ポリカーボネート系樹脂組成物および光拡散性成形品 |
JP2016-076236 | 2016-04-06 | ||
JP2016-076235 | 2016-04-06 |
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JP7553748B2 (ja) | 2022-07-13 | 2024-09-18 | 住化ポリカーボネート株式会社 | 芳香族ポリカーボネート樹脂組成物および光拡散性成形品 |
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