WO2024014465A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2024014465A1 WO2024014465A1 PCT/JP2023/025622 JP2023025622W WO2024014465A1 WO 2024014465 A1 WO2024014465 A1 WO 2024014465A1 JP 2023025622 W JP2023025622 W JP 2023025622W WO 2024014465 A1 WO2024014465 A1 WO 2024014465A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
Definitions
- the present invention relates to an aromatic polycarbonate resin composition and a light-diffusing molded article.
- polycarbonate resin Since polycarbonate resin has excellent impact resistance, heat resistance, transparency, etc., it has conventionally been used for molded products such as light guide plates, various lenses, and nameplates.
- Light-diffusing molded products made of resin compositions containing aromatic polycarbonate resins and light-diffusing agents such as inorganic particles and polymeric particles have better heat resistance and dimensional stability than light-diffusing molded products made of acrylic resin. Because of its excellent performance, it can be used for light covers, meters, signboards (especially internally illuminated type), resin window glass, light diffusion plates for image reading devices or image display devices (for example, light used in backlight modules for liquid crystal display devices, etc.).
- Patent Document 1 describes that fluidity is improved by adding a pentaerythritol-based ester compound and lowering the molecular weight of an aromatic polycarbonate-based resin through transesterification.
- Patent Document 1 meets the requirements of materials in recent years, such as low reduction in transparency and light transmittance even when molded at high temperatures for thin wall molding, and large size. However, it is not possible to fully satisfy the requirements that
- light-diffusing molded products for example, light-diffusing plates for image display devices
- in-vehicle image display devices as thin as about 0.3 mm
- high-temperature conditions such as light irradiation.
- a material with high light diffusivity that does not reduce its transparency and light transmittance even when exposed to the environment for an extremely long period of time.In other words, even if it is large, it does not lose its light transmittance, and yet the light source cannot be seen through it. is now in demand.
- the present invention does not impair the inherent properties of polycarbonate resin such as heat resistance and mechanical strength, has excellent thermal stability, and has high transparency, light transmittance, and light diffusivity. .Even if a large molded product with a thickness of about 3 mm (for example, a light diffusion plate for an image display device) is exposed to high temperature conditions such as light irradiation for an extremely long period of time, the transparency and light transmittance will not deteriorate.
- An object of the present invention is to provide an aromatic polycarbonate resin composition that does not easily cause clouding or coloring, that is, has high light diffusivity without reducing light transmittance even when it is large, and yet does not allow the light source to be seen through it. purpose.
- an aromatic polycarbonate resin containing a predetermined amount of a linear aromatic polycarbonate resin, a polyether derivative (B), and a light diffusing agent (C).
- the composition has excellent thermal stability and high light transmittance without impairing the inherent properties of polycarbonate resin such as heat resistance and mechanical strength, and is molded into a thin molded product of about 0.3 mm.
- the present invention has been completed based on the discovery that even when the light guide plate is exposed to high temperature conditions such as by irradiation with a light source for a long period of time, there is little decrease in transparency and permeability (hard to cause clouding or coloration).
- the present invention provides a linear aromatic polycarbonate resin (A), a polyether derivative (B), a light diffusing agent (C), a phosphorus antioxidant (D), and an aromatic compound represented by the following formula (1).
- the polycarbonate resin composition of the present invention does not impair the inherent properties of polycarbonate resin such as heat resistance and mechanical strength, has excellent thermal stability, and has high transparency, light transmittance, and light diffusivity. Even when the resulting molded product is exposed for a long period of time to high-temperature conditions such as the blazing sun and/or irradiation with a light source, its transparency and permeability are unlikely to decrease (it is unlikely to become cloudy or colored). Therefore, even if it is a thin molded product (diffusion plate) with a thickness of about 0.3 mm, for example, it is unlikely that the hue will change and the appearance will deteriorate (deterioration), and it can be used under high temperature conditions caused by the external environment or light source.
- a polycarbonate resin composition that does not easily reduce transparency (does not easily become cloudy or colored) even when exposed to water for a long period of time, that is, has a high light diffusing property that does not reduce light transmittance and does not allow the light source to be seen through. It can provide products and has extremely high industrial value.
- the aromatic polycarbonate resin composition of the embodiment of the present invention comprises a linear aromatic polycarbonate resin (A), a polyether derivative (B), a light diffusing agent (C), and, if necessary, a phosphorus antioxidant. (D) and/or a specific aromatic compound (E).
- the aromatic polycarbonate resin composition according to the embodiment can further contain an epoxy compound and/or other components, etc., if necessary.
- the "linear aromatic polycarbonate resin (A)" is a polycarbonate resin based on an aromatic compound, and as long as the aromatic polycarbonate resin composition targeted by the present invention can be obtained.
- branched aromatic polycarbonates are excluded from the scope of the present invention as much as possible because they reduce transparency and light transmittance.
- linear aromatic polycarbonate resins include polymers obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate. can.
- Representative examples include polycarbonate resins made from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).
- examples of the dihydroxydiaryl compound include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2 , 2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-hydroxy- 3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis Bis(hydroxyaryl)alkanes such as (4-hydroxy-3,5-dichlorophenyl)propane; 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexan
- Bis(hydroxyaryl)cycloalkanes dihydroxydiarylethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiaryl such as 4,4'-dihydroxydiphenyl sulfide Sulfides; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy- Examples include dihydroxydiarylsulfones such as 3,3'-dimethyldiphenylsulfone. These can be used alone or in combination. In addition to these, piperazine, dipiperidyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc. can be used in combination.
- the viscosity average molecular weight of the linear aromatic polycarbonate resin (A) is preferably 10,000 to 100,000, more preferably 12,000 to 30,000.
- a molecular weight regulator, a catalyst, etc. can be used as necessary.
- the polyether derivative (B) is a derivative of a polyether compound, and is not particularly limited as long as the aromatic polycarbonate resin composition targeted by the present invention can be obtained. do not have.
- Such polyether derivatives include, as a typical example, a polyether derivative represented by the following formula (2).
- Formula (2) RO-(X-O)m(Y-O)n-R' (In the formula, R and R' each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, X is a straight chain alkylene group or a branched alkylene group having 2 to 4 carbon atoms, and Y is Represents a linear alkylene group or branched alkylene group having 2 to 5 carbon atoms, X and Y may be the same or different, m and n each independently represent 3 to 60, and m+n is 6 to 120)
- the weight average molecular weight of the polyether derivative represented by formula (2) is preferably 500 to 8,000, more preferably 1,000 to 4,000.
- a commercially available product can be used as the polyether derivative represented by formula (2).
- the polyether derivative represented by formula (2) may be a compound represented by formula (2-1) below.
- the weight average molecular weight of the polyether derivative represented by formula (2-1) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- the polyether derivative represented by formula (2) may be a compound represented by formula (2-2) below.
- the weight average molecular weight of the polyether derivative represented by formula (2-2) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- the polyether derivative represented by formula (2-2) commercially available products can be used.
- the polyether derivative represented by formula (2) may be a compound represented by formula (2-3) below.
- the weight average molecular weight of the polyether derivative represented by formula (2-3) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- polyether derivative represented by formula (2-3) commercially available products can be used.
- the polyether derivative represented by the formula (2) includes a polyether derivative represented by the following formula (3), a polyether derivative represented by the formula (4), a polyether derivative represented by the formula (5), A polyether derivative represented by formula (6), a polyether derivative represented by formula (7), a polyether derivative represented by formula (8), a polyether derivative represented by formula (9), a polyether derivative represented by formula ( It is preferable that at least one selected from the group including the polyether derivative represented by formula (10) and the polyether derivative represented by formula (11) is included.
- the polyether derivative represented by the formula (2-1) is a polyether derivative represented by the following formula (3), a polyether derivative represented by the formula (4), or a polyether derivative represented by the formula (5). It is preferable that at least one selected from the group consisting of derivatives, polyether derivatives represented by formula (6), and polyether derivatives represented by formula (7) is included.
- the polyether derivative represented by formula (2-2) contains at least one selected from the group including the polyether derivative represented by formula (8) and the polyether derivative represented by formula (9). It is preferable.
- the polyether derivative represented by formula (2-3) contains at least one selected from the group including the polyether derivative represented by formula (10) and the polyether derivative represented by formula (11). It is preferable.
- Formula (3) HO-( CH2CH2CH2CH2O ) m (CH( CH3 ) CH2O ) n - H (In the formula, m and n each independently represent 3 to 60, and m+n represents 8 to 90.)
- polyether derivative represented by formula (3) a modified glycol containing a tetramethylene glycol unit and a propylene glycol unit is suitable.
- Commercial products can be used as such polyether derivatives, such as Polyserine DCB-1000 (weight average molecular weight 1000), Polyserine DCB-2000 (weight average molecular weight 2000), and Polyserine DCB manufactured by NOF Corporation. -4000 (weight average molecular weight 4000), etc. can be used.
- the weight average molecular weight of the polyether derivative represented by formula (3) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- Formula (4) HO- ( CH2CH2CH2CH2O ) m ( CH2CH2CH ( CH3 ) CH2O )n- H (In the formula, m and n each independently represent 3 to 60, and m+n represents 8 to 90.)
- polyether derivative represented by formula (4) a modified glycol containing a tetramethylene glycol unit and a 2-methyltetramethylene glycol unit is preferable.
- Commercial products can be used as such polyether derivatives, such as PTG-L1000 (weight average molecular weight 1000), PTG-L2000 (weight average molecular weight 2000) manufactured by Hodogaya Chemical Industry Co., Ltd. -L3000 (weight average molecular weight 3000) etc. can be used.
- the weight average molecular weight of the polyether derivative represented by formula (4) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- polyether derivative represented by formula (5) a modified glycol containing an ethylene glycol unit and a propylene glycol unit is preferred.
- Commercially available products can be used as such polyether derivatives, such as Unilube 50DE-25 (weight average molecular weight 1750) and Unilube 75DE-25 (weight average molecular weight 1400) manufactured by NOF Corporation. can.
- the weight average molecular weight of the polyether derivative represented by formula (5) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- Formula (6) RO-( CH2CH2CH2CH2O )m(CH( CH3 ) CH2O ) n - H (In the formula, R represents an alkyl group having 1 to 30 carbon atoms, m and n each independently represent 3 to 60, and m+n represents 8 to 90.)
- polyether derivative represented by formula (6) a modified glycol containing a tetramethylene glycol unit and a propylene glycol unit and having a butyl group at one end or a stearyl group at one end is suitable.
- Commercial products can be used as such polyether derivatives, such as Polyserine BC-1000 (butyl group at one end, weight average molecular weight 1000), Polyserine SC-1000 (stearyl group at one end), manufactured by NOF Corporation. group, weight average molecular weight 1000), etc. can be used.
- the weight average molecular weight of the polyether derivative represented by formula (6) is preferably 500 to 8,000, more preferably 1,000 to 4,000.
- Formula (7) RO-( CH2CH2O )m(CH( CH3 ) CH2O ) n -H (In the formula, R represents an alkyl group having 1 to 30 carbon atoms, m and n each independently represent 3 to 60, and m+n represents 8 to 90.)
- polyether derivative represented by formula (7) a modified glycol containing an ethylene glycol unit and a propylene glycol unit and having a butyl group at one end or a stearyl group at one end is suitable.
- Commercially available products can be used as such polyether derivatives, such as Unilube 50MB-11 (butyl group at one end, weight average molecular weight 1000), Unilube 50MB-26 (butyl group at one end, manufactured by NOF Corporation), Unilube 50MB-72 (butyl group at one end, weight average molecular weight 3000), Unilube 10MS-250KB (stearyl group at one end, weight average molecular weight 2000), etc. can be used.
- the weight average molecular weight of the polyether derivative represented by formula (7) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- Formula (8) HO-( CH2CH2CH2CH2O ) m ( CH2CH2O ) n - H (In the formula, m and n each independently represent 3 to 60, and m+n represents 8 to 90.)
- polyether derivative represented by formula (8) a modified glycol containing a tetramethylene glycol unit and an ethylene glycol unit is preferable.
- Commercially available products can be used as such polyether derivatives, such as Polyserine DC3000E (weight average molecular weight 3000) and Polyserine DC1800E (weight average molecular weight 1800) manufactured by NOF Corporation.
- the weight average molecular weight of the polyether derivative represented by formula (8) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- polytetramethylene glycol is preferred.
- Commercial products can be used as such polyether derivatives, such as PTG-650SN (weight average molecular weight 650), PTG-850SN (weight average molecular weight 850), and PTG- manufactured by Hodogaya Chemical Industry Co., Ltd. 1000SN (weight average molecular weight 1000), PTG-1400SN (weight average molecular weight 1400), PTG-2000SN (weight average molecular weight 2000), or PTG-2900 (weight average molecular weight 2900) can be used.
- the weight average molecular weight of the polyether derivative (polytetramethylene glycol) represented by formula (9) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- Formula (10) Formula: HO-(CH( CH3 ) CH2O )q-H (In the formula, q represents 7 to 120.)
- polypropylene glycol is preferred.
- Commercial products can be used as such polyether derivatives, such as Polyglycol P2000P (weight average molecular weight 2000) manufactured by Dow Chemical, Uniol D-1000 (weight average molecular weight 1000) manufactured by NOF Corporation, Uniol D-2000 (weight average molecular weight 2000), Uniol D-4000 (weight average molecular weight 4000), etc. can be used.
- the weight average molecular weight of the polyether derivative (polypropylene glycol) represented by formula (10) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- polybutylene glycol is preferable.
- Commercial products can be used as such polyether derivatives, such as Uniol PB-500 (weight average molecular weight 500), Uniol PB-1000 (weight average molecular weight 1000), and Uniol PB manufactured by NOF Corporation. -2000 (weight average molecular weight 2000), etc. can be used.
- the weight average molecular weight of the polyether derivative (polybutylene glycol) represented by formula (11) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- the polyether derivative represented by the general formula (2) generally has high heat resistance, and a molded article obtained by molding an aromatic polycarbonate resin composition containing the polyether derivative at a high temperature has high brightness and light transmittance.
- Each of the polyether derivatives represented by the formulas (2) to (11) above can be used as long as the aromatic polycarbonate resin composition and optical molded article targeted by the present invention can be obtained. It can contain repeating units other than repeating units. Examples of such repeating units include repeating units based on impurities that may be included in the starting materials of polyether derivatives, repeating units based on initiators (polymerization initiators) used during polymerization, etc. can.
- examples of the polymerization initiator include the following compounds. Examples include hydrogenated bisphenol A, bisphenol A, isosorbide, glycerin, pentaerythritol, sorbitol, and glucose.
- polyserine 60DB-2000H (manufactured by NOF Corporation) represented by the following formula (3') can also be used (formula 3 -2)).
- the weight average molecular weight of the polyether derivative represented by formula (3-2) is preferably from 500 to 8,000, more preferably from 1,000 to 4,000.
- the polyether derivative (B) used in the present invention has appropriate lipophilicity, it also has excellent compatibility with the aromatic polycarbonate resin (A). Transparency can be maintained without reducing the transparency of a molded article obtained from the blended aromatic polycarbonate resin composition.
- the weight average molecular weight of such polyether derivative (B) is preferably 500 to 8,000, more preferably 1,000 to 4,000.
- the CPR (unit: dimensionless) (Controlled Polymerization Rate: index indicating the amount of basic substance in the polyether derivative: according to JIS K1557-4) of the polyether derivative (B) used in the present invention ) is preferably 2.0 or less, more preferably 1.0 or less.
- the polyether derivative (B) has excellent compatibility with the polycarbonate resin, suppresses decomposition and deterioration, has excellent storage stability, and improves the hue of the resulting polycarbonate resin composition. less likely to have a negative impact on
- the CPR of polyserine DCB-2000 which corresponds to the polyether derivative (B) represented by the above formula (3), is less than 1.0.
- the CPR of Polyserine 60DB-2000H (manufactured by NOF Corporation), which corresponds to B), is less than 1.0
- PTG-1000SN manufactured by NOF Corporation
- polyether derivative (B) represented by the above formula (9) has a CPR of less than 1.0
- (manufactured by Hodogaya Chemical Industry Co., Ltd.) has a CPR of less than 1.0.
- the pH of the polyether derivative (B) used in the present invention is preferably 5.0 or more and less than 7.5, and 6. More preferably, it is 0 or more and less than 7.0.
- the pH of the polyether derivative (B) is 5.0 or more and less than 7.5, decomposition and deterioration are suppressed, the storage stability is excellent, and the hue of the obtained polycarbonate resin composition is unlikely to be adversely affected.
- the pH of polyserine DCB-2000 which corresponds to the polyether derivative (B) represented by the above formula (3), is 6.7.
- the pH of Polyserine 60DB-2000H (manufactured by NOF Corporation) corresponding to (manufactured by Kagaku Kogyo Co., Ltd.) has a pH of 6.7.
- the temperature at which the weight of the polyether derivative (B) used in the present invention reaches 90% is: The temperature is preferably 300°C or higher, more preferably 330°C or higher.
- the temperature at which the polyether derivative (B) reaches 90% weight is 300° C. or higher, decomposition and deterioration are suppressed, the storage stability is excellent, and the hue of the resulting polycarbonate resin composition is unlikely to be adversely affected.
- the temperature at which 90% weight of polyserine DCB-2000, which corresponds to the polyether derivative (B) represented by the above formula (3), is 330°C;
- the temperature at which 90% weight of polyserine 60DB-2000H (manufactured by NOF Corporation), which corresponds to the ether derivative (B), reaches 90% is 400°C.
- the amount of the polyether derivative is 0.1 to 2.0 parts by weight, preferably 0.3 to 1.8 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin (A). If the amount of the polyether derivative is less than 0.1 parts by weight, the effect of improving light transmittance and hue may be insufficient. Conversely, if the amount of the polyether derivative exceeds 2.0 parts by weight, the haze rate may increase and the light transmittance may decrease.
- the light diffusing agent (C) is not particularly limited as long as it can scatter light inside the polycarbonate resin composition, and there are particular restrictions on the chemical composition such as polymeric and inorganic types. There isn't.
- the light diffusing agent (C) is added to the linear polycarbonate resin (A) and dispersed by a known method such as melt mixing using an extruder, it is not compatible with the matrix phase or is difficult to be compatible with the matrix phase. It is necessary to exist as particles.
- fine particles having light diffusing ability are preferable.
- Such fine particles include inorganic fine particles and polymer fine particles.
- the inorganic fine particles include glass fillers, calcium carbonate, barium sulfate, silica, talc, mica, wollastonite, titanium oxide, and the like. Among these, calcium carbonate is preferred.
- the shape of the inorganic fine particles is preferably granular (including amorphous) or plate rather than fibrous. For example, in the case of glass fillers, glass beads, glass balloons, glass milled fibers, glass flakes, ultra-thin glass flakes (manufactured by a sol-gel method), amorphous glass, etc. may be used. Similarly, various shapes of other inorganic fine particles can be employed.
- the fine polymer particles are preferably spherical from the viewpoint of light diffusivity, and the closer the shape is to a perfect sphere, the more preferable they are.
- Commercially available products can be used as the light diffusing agent.
- Tospearl (registered trademark) 120S” manufactured by Momentive Performance Materials Japan is used as a silicone light diffusing agent
- Gelz Pearl (registered trademark) GM-0449S” and “Gantz Pearl GM-0205S” manufactured by Aica Kogyo Co., Ltd., and "Chemisnow (registered trademark) KMR-3TA” manufactured by Soken Chemical Co., Ltd. can be used.
- the light diffusing agent (C) fine particles obtained by copolymerizing a styrene monomer, a methyl methacrylate monomer, and a crosslinking agent (styrene-methyl methacrylate copolymerized crosslinked fine particles) can also be suitably used. It can be obtained using general emulsion polymerization methods, solution polymerization methods, dispersion polymerization methods, suspension polymerization methods, bulk polymerization methods, soap-free polymerization methods, seed polymerization methods, and the like. Among these polymerization methods, emulsion polymerization, dispersion polymerization, and suspension polymerization are preferred, and emulsion polymerization and dispersion polymerization are particularly preferred from the viewpoint of physical properties of the light diffusing plate.
- the crosslinking agent used in the crosslinked styrene-methyl methacrylate copolymer particles may be any radically polymerizable monomer containing two or more vinyl groups or (meth)acryloyl groups.
- Such specific examples include, for example, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythol tetraacrylate, pentaerythol tetramethacrylate.
- These crosslinking agents may be used alone or in combination of two or more.
- the average particle diameter of the crosslinked styrene-methyl methacrylate copolymer particles is 5 to 30 ⁇ m. A more preferable average particle diameter is in the range of 8 to 20 ⁇ m. If the average particle size is less than 5 ⁇ m, the surface state of the resulting light diffusing plate will maintain smoothness, resulting in insufficient light scattering and poor light diffusivity; if the average particle size exceeds 30 ⁇ m, the resulting light diffusing plate may Since the surface condition approaches smoothness, light travels straight and passes through the surface, resulting in a decrease in light scattering and poor light diffusivity and light source transmission prevention properties, which is not preferable. Common methods for measuring the average particle diameter of fine particles include the Coulter method, dynamic light scattering method, centrifugal sedimentation method, and the like.
- the refractive index of the crosslinked styrene-methyl methacrylate copolymer particles is in the range of 1.54 to 1.57. A more preferable range is 1.55 to 1.57. If the refractive index is less than 1.54, haze may occur and light transmittance may decrease. Moreover, when it exceeds 1.57, light diffusivity may decrease.
- the refractive index can be changed by adjusting the polymerization ratio of each monomer of styrene and methyl methacrylate when copolymerizing the fine particles.
- styrene-methyl methacrylate copolymer crosslinked fine particles for example, SMX-12R (average particle size 12.3 ⁇ m, refractive index 1.56) manufactured by Sekisui Plastics Co., Ltd., or GMS-6121 (average particle size manufactured by Guide Win Special Chemicals) A diameter of 11.3 ⁇ m and a refractive index of 1.56) are commercially available.
- SMX-12R average particle size 12.3 ⁇ m, refractive index 1.56 manufactured by Sekisui Plastics Co., Ltd.
- GMS-6121 average particle size manufactured by Guide Win Special Chemicals
- a common method for measuring the refractive index of crosslinked styrene-methyl methacrylate copolymer particles includes the Becke method. Resin particles are placed on a slide glass, and a refractive liquid (manufactured by CARGILLE: Cargill standard refractive liquid) is dropped. Mix the resin particles and refractive liquid thoroughly, irradiate them with a sodium lamp from below, and observe the outline of the particles from above. If the outline cannot be seen, it is assumed that the refractive index of the refractive liquid and the resin particles are equal.
- the absolute value of the difference between the refractive index of the light diffusing agent and the refractive index of the aromatic polycarbonate resin is preferably 0.02 to 0.2.
- the refractive index of the light diffusing agent is lower than the refractive index of the aromatic polycarbonate resin.
- the average particle size of the diffusing agent is preferably 0.1 to 50 ⁇ m, more preferably 0.5 to 10 ⁇ m, and particularly preferably 1 to 5 ⁇ m. If the average particle size of the light diffusing agent is too small, a sufficient light-dispersing effect cannot be obtained, and if it is too large, the surface of the molded article may become rough or the mechanical strength of the molded article may decrease.
- the average particle size of the light diffusing agent is the volume average particle size measured by the Coulter counter method. In the call counter method, an electrolyte in which sample particles are suspended is passed through a pore (aperture), and the particle size is determined by reading the change in the voltage pulse that is generated in proportion to the volume of the particles. Furthermore, by measuring the voltage pulse height one by one, a volume distribution histogram of sample particles can be obtained. Particle size or particle size distribution measurement using such a coal counter method is the most frequently used particle size distribution measuring device.
- the light diffusing agent (C) preferably has a refractive index difference ( ⁇ n) of 0.01 or more with respect to the polycarbonate resin (A).
- ⁇ n refractive index difference
- a light diffuser is also used.
- the difference in refractive index from the polycarbonate resin is more preferably 0.05 or more, particularly preferably 0.07 or more.
- the mass average particle diameter of the light diffusing agent (C) is usually 0.5 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, and usually 30 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. , more preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less. If the mass average particle size is too small, the resulting polycarbonate resin composition will have poor light diffusivity, and when used as a diffuser plate, etc., the light source will tend to show through or have poor visibility; If it is too high, the diffusion effect on the content may become low.
- the light diffusing agent (C) may be used alone or in combination of two or more in any combination and ratio. It is preferable to use a silicone light diffusing agent and another light diffusing agent together.
- An inorganic light diffusing agent may be used in combination with any one of a silicone light diffusing agent, an acrylic light diffusing agent, and styrene-methyl methacrylate copolymer crosslinked fine particles.
- a silicone light diffusing agent an acrylic light diffusing agent, or a styrene-methyl methacrylate copolymer crosslinked fine particle
- the amount of silicone or organic diffusing agent can be reduced. The same light diffusivity as before can be obtained.
- titanium oxide white pigment
- TIPAQUE registered trademark
- PC-3 manufactured by Ishihara Sangyo Co., Ltd.
- CP-K manufactured by Resino Color Industries, Ltd.
- KRONOS registered trademark 2233 manufactured by Kronos, etc.
- the blending amount of the light diffusing agent (C) is preferably 0.1 to 6.0 parts by weight, and more preferably 1.0 to 5.0 parts by weight, based on 100 parts by weight of the linear aromatic polycarbonate resin (A). preferable. If it is less than 0.1 part by weight, light will not be sufficiently scattered and the effect of preventing the visibility of the light source will be poor, and if it exceeds 6.0 parts by weight, the transmittance may decrease significantly.
- the aromatic polycarbonate resin composition of the embodiment of the present invention may contain a phosphorus antioxidant (D), if necessary.
- a phosphorus antioxidant D
- the aromatic polycarbonate resin composition simultaneously contains the polyether derivative (B), the diffusing agent (C), and the phosphorus antioxidant (D)
- the phosphorus antioxidant (D) is not particularly limited as long as it can obtain the aromatic polycarbonate resin composition targeted by the present invention, but includes phosphite compounds having the following phosphite structure. It is preferable.
- the phosphorus antioxidant (D) is a phosphite compound represented by the following formula (12), a phosphite compound represented by the following formula (13), It is preferable to contain at least one compound selected from a phosphoric acid ester compound, a phosphorous acid ester compound represented by the following formula (14), and a phosphite compound represented by the following formula (15).
- the phosphorus antioxidant (D) contains, for example, a compound represented by the following formula (12).
- R 1 represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3.
- R 1 is an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
- Examples of the compound represented by formula (12) include triphenyl phosphite, tricresyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, trisnonylphenyl phosphite, etc. .
- tris(2,4-di-t-butylphenyl) phosphite is particularly suitable; for example, it is commercially available as Irgafos 168 manufactured by BASF ("Irgafos" is a registered trademark of BFA Societas Europe). available at.
- the phosphorus antioxidant (D) contains, for example, a compound represented by the following formula (13).
- R 2 , R 3 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a cycloalkyl group having 6 to 12 carbon atoms.
- R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- X represents a single bond, a sulfur atom, or the formula: -CHR 7 - (Here, R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.)
- A represents a group represented by a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 1 to 8 carbon atoms Alkylene group or formula: *-COR 8 - (where R 8 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side)
- One of Y and Z represents a hydroxyl group, an alkoxy group having
- R 2 , R 3 , R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 6 to 8 carbon atoms.
- examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, group, t-pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group and the like.
- examples of the cycloalkyl group having 5 to 8 carbon atoms include cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.
- alkylcycloalkyl group having 6 to 12 carbon atoms examples include 1-methylcyclopentyl group, 1-methylcyclohexyl group, and 1-methyl-4-i-propylcyclohexyl group.
- aralkyl group having 7 to 12 carbon atoms examples include benzyl group, ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group, and the like.
- R 2 , R 3 and R 5 are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms.
- R 2 and R 5 are preferably each independently a t-alkyl group such as a t-butyl group, a t-pentyl group, or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.
- R 3 is a carbon number such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, etc. It is preferably an alkyl group of 1 to 5, and more preferably a methyl group, t-butyl group or t-pentyl group.
- the R 6 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, and is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group. More preferably, it is an alkyl group having 1 to 5 carbon atoms such as , n-butyl group, i-butyl group, sec-butyl group, t-butyl group, or t-pentyl group.
- R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the explanation of R 2 , R 3 , R 5 and R 6 above.
- R 4 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
- X represents a single bond, a sulfur atom, or a group represented by the formula: -CHR 7 -.
- R 7 in the formula: -CHR 7 - represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
- Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the alkyl groups and cycloalkyl groups exemplified in the explanation of R 2 , R 3 , R 5 and R 6 above, respectively. It will be done.
- X is a single bond, a methylene group, or a methylene group substituted with a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, etc.
- it is a single bond, and more preferably a single bond.
- A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: *-COR 8 -.
- alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1,3-propylene group, etc. are mentioned, preferably a propylene group.
- R 8 in the formula: *-COR 8 - represents a single bond or an alkylene group having 1 to 8 carbon atoms. Examples of the alkylene group having 1 to 8 carbon atoms representing R 8 include the alkylene groups exemplified in the explanation of A above.
- R 8 is preferably a single bond or an ethylene group. Further, * in the formula: *-COR 8 - is a bond on the oxygen base paper side, and indicates that the carbonyl group is bonded to the oxygen atom of the phosphite group.
- one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or a carbon number 1 to 8 represents an alkyl group.
- the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, t-butoxy group, and pentyloxy group.
- Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, ⁇ -methylbenzyloxy group, ⁇ , ⁇ -dimethylbenzyloxy group, and the like.
- Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the explanation of R 2 , R 3 , R 5 and R 6 above.
- Examples of the compound represented by formula (13) include 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy [dibenzo[d,f][1,3,2]dioxaphosphepine, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-2,4,8, 10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]- 4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 6-[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionyloxy]-4,8-di-t-butyl
- 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl -4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine is suitable, for example, Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) Sumilizer" is commercially available as a registered trademark).
- the phosphorus antioxidant (D) contains, for example, a compound represented by the following formula (14).
- R 9 and R 10 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, and b and c each independently represent 0 Indicates an integer between ⁇ 3.
- Examples of the compound represented by formula (14) include bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, and the like.
- Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is commercially available under the trade name "ADEKA STAB PEP-24G" manufactured by ADEKA.
- ADEKA STAB PEP-36 (“ADEKA STAB” is a registered trademark) manufactured by ADEKA Corporation is commercially available.
- the phosphorus antioxidant (D) contains, for example, a compound represented by the following formula (15).
- R 11 to R 18 each independently represent an alkyl group or an alkenyl group having 1 to 3 carbon atoms.
- R 11 and R 12 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 may combine with each other to form a ring.
- R 19 to R 22 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- d to g each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. is an integer from 0 to 5.
- X 1 to X 4 each independently represent a single bond or a carbon atom. When X 1 to X 4 are single bonds, among R 11 to R 22 , The functional group connected to the single bond is excluded from general formula (15).
- a specific example of the compound represented by formula (15) includes bis(2,4-dicumylphenyl)pentaerythritol diphosphite. This is manufactured by Dover Chemical Company, product name “Doverphos (registered trademark) S-9228", manufactured by ADEKA Company, product name “ADEKASTAB PEP-45” (bis(2,4-dicumylphenyl) pentaerythritol diphosphite) It is commercially available as .
- the above-mentioned aromatic polycarbonate resin composition that satisfies at least one selected from the following is preferred:
- the phosphite compound represented by the formula (12) contains tris(2,4-di-t-butylphenyl)phosphite;
- the phosphite compound represented by the formula (13) is 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl) ) propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine;
- the phosphite compound represented by the formula (14) is 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3, 9-diphosphaspiro[5,5]undecane; and the phosphite compound represented by formula (15) contains bis(2,4-dicumylphenyl)
- the amount of the phosphorus antioxidant (D) is preferably 0.5 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin (A). .
- the aromatic polycarbonate resin composition of the embodiment of the present invention includes a polyether derivative (B), a light diffusing agent (C), a phosphorus antioxidant (D), and an aromatic polycarbonate represented by the following formula (1). It is more preferable that the compound (E) is included. In this way, by using the polyether derivative (B), the light diffusing agent (C), the phosphorous antioxidant (D), and the aromatic compound (E), the excellent properties required for light diffusing molded products can be achieved. While maintaining optical properties, it is possible to prevent deterioration such as aging deterioration in addition to deterioration caused by usage conditions of a molded article made of the obtained aromatic polycarbonate resin composition.
- thermal deterioration caused by long-term irradiation of an optical molded article made from an aromatic polycarbonate resin composition with a light source (such as an LED light source) is effectively prevented.
- a light-diffusion molded product is exposed to harsh conditions such as under the scorching sun and/or continues to receive light irradiation for a long time, the temperature of the surface of the molded product may rise.
- Thermal deterioration of the aromatic polycarbonate resin (A) may progress little by little.
- the polyether derivative (B) in the resin composition may be modified, impairing the transparency (brightness or light transmittance) expected of aromatic polycarbonate resin compositions used in ordinary light-diffusing molded products, and making molding difficult. Clouding or coloring (light to dark coloring) may occur on the surface of the product.
- the specific aromatic compound (E) of the following formula (1) is particularly effective as a compound that inhibits deterioration such as modification of the polyether derivative (B).
- the polyether in the molded article can be It has been found that the deterioration of the derivative (B) can be suppressed to reduce or alleviate the phenomenon of cloudiness or coloration (light to deep coloration).
- the amount of the aromatic compound (E) used in the embodiment of the present invention is preferably 0.003 parts by weight or less based on 100 parts by weight of the aromatic polycarbonate resin (A).
- the amount of the aromatic compound (E) should be 0.0001 parts by weight per 100 parts by weight of the aromatic polycarbonate resin (A). Parts by weight or more.
- the amount of the aromatic compound (E) is more preferably 0.0005 parts by weight or more and 0.003 parts by weight or less based on 100 parts by weight of the aromatic polycarbonate resin (A). If the amount of the aromatic compound (C) is less than 0.0001 part by weight, the effect of inhibiting clouding or coloring will be insufficient. On the other hand, if the amount of the aromatic compound (C) exceeds 0.003 parts by weight, it is not desirable because it may not be possible to achieve the high level of light transmittance and hue required for an optical molded article.
- the aromatic polycarbonate resin composition according to the embodiment includes, for example, an ultraviolet absorber, which is a component that further improves the weather resistance of the resulting aromatic polycarbonate resin composition. It can be used as appropriate depending on the purpose of the molded product obtained by molding the product.
- ultraviolet absorber for example, ultraviolet absorbers that are usually blended into polycarbonate resin, such as benzotriazole compounds, triazine compounds, benzophenone compounds, and oxalic acid anilide compounds, may be used alone or in combination of two or more. Can be used.
- benzotriazole compounds include 2-(2-hydroxy-5-t-octylphenyl)benzotriazole and 2-(3-tert-butyl-2-hydroxy-5-methylphenyl). -5-chloro-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4- methyl-6-( 3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylph enyl)-2H-benzotriazole, 2-[2 '-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-Methylenbis[6-(2H-benzotriazol-2-
- 2-(2-hydroxy-5-t-octylphenyl)benzotriazole and the like are particularly suitable, such as TINUVIN 329 manufactured by BASF (TINUVIN is a registered trademark) and Seasorb manufactured by Cipro Kasei Co., Ltd. 709, Chemisorb 79 manufactured by ChemiPro Kasei Co., Ltd., and the like are commercially available.
- triazine compounds examples include 2,4-diphenyl-6-(2-hydroxyphenyl-4-hexyloxyphenyl)1,3,5-triazine, 2-[4,6-bis(2,4-dimethyl) phenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[( hexyl)oxy]phenol, etc., and for example, TINUVIN 1577 manufactured by BASF is commercially available.
- oxalic acid anilide compound for example, Sanduvor VSU manufactured by Clariant Japan Co., Ltd. is commercially available.
- benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and the like.
- the amount of the ultraviolet absorber is 0 to 1.0 parts by weight, preferably 0 to 0.5 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin (A). If the amount of the ultraviolet absorber exceeds 1.0 parts by weight, the initial hue of the resulting aromatic polycarbonate resin composition may be reduced. Moreover, when the amount of the ultraviolet absorber is 0.1 part by weight or more, the effect of further improving the weather resistance of the aromatic polycarbonate resin composition is particularly exhibited.
- the aromatic polycarbonate resin composition of the embodiment of the present invention can contain an epoxy compound (F).
- an epoxy compound (F) in this way, when the aromatic polycarbonate resin composition contains the polyether derivative (B), the aromatic compound (E), and the epoxy compound (F) at the same time, it is possible to obtain the excellent optical properties required for a light-diffusing molded article. While maintaining and improving, it is possible to prevent deterioration such as deterioration due to usage conditions and aging deterioration without deteriorating the initial optical properties of the molded product made of the resulting aromatic polycarbonate resin composition.
- the epoxy compound (F) is not particularly limited as long as it has at least one epoxy group in its molecule and can provide the aromatic polycarbonate resin composition targeted by the present invention.
- the epoxy compound (F) is, for example, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, epoxidized soybean oil, ⁇ -caprolactone modified 3',4'-epoxycyclohexylmethyl 3,4- It can include epoxycyclohexane carboxylate, epoxy group-containing acrylic/styrene polymer, 2,2-bis(4-hydroxycyclohexyl)propane-diglycidyl ether, and the like.
- the epoxy compound (F) contains 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
- the aromatic polycarbonate resin composition of the embodiment of the present invention preferably contains 0.001 to 0.2 parts by weight of the epoxy compound (F) based on 100 parts by weight of the linear aromatic polycarbonate resin, and preferably contains 0.001 to 0.2 parts by weight of the epoxy compound (F). It is more preferable to contain 0.002 to 0.1 part by weight, and particularly preferably 0.005 to 0.05 part by weight.
- the aromatic polycarbonate resin composition of the embodiment of the present invention contains 0.001 to 0.2 parts by weight of the epoxy compound (E) with respect to 100 parts by weight of the linear aromatic polycarbonate resin, the composition has light diffusing properties.
- the aromatic polycarbonate resin composition according to the embodiment may contain, for example, a heat stabilizer, other antioxidant, coloring agent, mold release agent, softener, antistatic agent, within the range that does not impair the effects of the present invention.
- a heat stabilizer other antioxidant, coloring agent, mold release agent, softener, antistatic agent
- additives such as additives, impact modifiers, polymers other than the linear aromatic polycarbonate resin, etc. may be appropriately blended.
- the aromatic polycarbonate resin composition of the embodiment of the present invention is prepared by mixing a linear aromatic polycarbonate resin, a polyether derivative (B), and a light diffusing agent (C), and optionally adding a phosphorus antioxidant ( D), an aromatic compound (E), an epoxy compound (F), the above-mentioned various additives, a polymer other than the linear aromatic polycarbonate resin, etc. can be exemplified.
- the manufacturing method is not particularly limited, and the types and amounts of each component can be adjusted as appropriate.
- the method of mixing the components is not particularly limited, and examples include a method of mixing with a known mixer such as a tumbler and a ribbon blender, and a method of melt-kneading with an extruder. By these methods, pellets of aromatic polycarbonate resin compositions can be easily obtained.
- the aromatic compound (E) may be mixed before melt-kneading, or may be added to or mixed with the polyether derivative (B) in advance.
- the shape and size of the aromatic polycarbonate resin composition pellets obtained as described above are not particularly limited, and may be any shape and size that common resin pellets have.
- the shape of the pellet includes an elliptical cylinder shape, a cylindrical shape, and the like.
- the size of the pellet it is preferable that the length is about 2 to 8 mm, and in the case of an elliptical columnar shape, it is preferable that the long axis of the ellipse in cross section is about 2 to 8 mm, and the short axis of about 1 to 4 mm.
- the diameter of the circular cross section is about 1 to 6 mm.
- each pellet obtained may have such a size, or all pellets forming a pellet aggregate may have such a size, and the average value of the pellet aggregate may be this size.
- the size may be similar, and there is no particular limitation.
- the light-diffusing molded article of the embodiment of the present invention can be obtained by molding the above-mentioned aromatic polycarbonate resin composition.
- a large and thin light diffusing plate (particularly a light diffusing plate for an image display device), a light diffusing plate having a surface area of 500 to 50,000 cm 2 can be obtained.
- the surface area of the light diffusing plate is preferably 1,000 to 25,000 cm 2 and the thickness is preferably 0.3 to 3 mm.
- the aromatic polycarbonate resin composition of the present invention it is possible to produce a light diffusing plate that is large in size, has high dimensional stability, and is thin (lightweight).
- the manufacturing method of the light-diffusing molded product is not particularly limited.
- the aromatic Examples include a method of molding a polycarbonate resin composition.
- the light-diffusing molded product according to the present invention includes, for example, a light-diffusing plate, a light-diffusing film, electronic/electrical equipment, parts of OA equipment, vehicle parts, mechanical parts, agricultural materials, fishing materials, transportation containers, packaging containers, and miscellaneous goods. etc.
- a light diffusing plate for image display devices a light diffusing plate used in a backlight module of a liquid crystal display device, etc., a light diffusing plate used in a screen of a projection type display device such as a projector television, etc.
- Various light sources can be used as backlight modules for liquid crystal display devices and the like.
- Linear aromatic polycarbonate resin Polycarbonate resin synthesized from bisphenol A and carbonyl chloride, viscosity average molecular weight: 15,000, SD Polycarbonate 200-80 (trade name) manufactured by Sumika Polycarbonate Co., Ltd., "SD Polycarbonate” is a registered trademark of Sumika Polycarbonate Co., Ltd. , hereinafter also referred to as (A1).
- Tris(2,4-di-t-butylphenyl)phosphite represented by the following formula: Irgafos 168 (trade name) manufactured by BASF, hereinafter also referred to as (D1).
- Epoxy compound (F) 3',4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate Celoxide 2021P (trade name) manufactured by Daicel Chemical Industries, Ltd., hereinafter also referred to as (F1).
- Examples 1 to 14 and Comparative Examples 1 and 2 The above raw materials were put into a tumbler at once in the proportions shown in Table 1, and after dry mixing for 10 minutes, the melting temperature was adjusted to 230°C using a twin-screw extruder (TEX30 ⁇ , manufactured by Japan Steel Works, Ltd.). The mixture was melt-kneaded to obtain pellets of the aromatic polycarbonate resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2.
- the pellets obtained in Examples and Comparative Examples are both approximately elliptical cylinder-shaped, and each aggregate of 100 pellets has an average length of about 5.1 mm to about 5.4 mm and an elliptical cross section.
- the average value of the long axis was about 4.1 mm to about 4.3 mm, and the average value of the short axis was about 2.2 mm to about 2.3 mm.
- each evaluation test piece was prepared and subjected to evaluation according to the following method. The results are shown in Table 1.
- Method for preparing test piece After drying the obtained pellets at 120°C for 4 hours or more, they were molded into 50mm width x 90mm length using an injection molding machine (ROBOSHOT S2000i100A, manufactured by Fanuc Corporation) at a molding temperature of 290°C and a mold temperature of 80°C. A three-stage plate-shaped test piece (3 mm thick part: 35 mm in length / 2 mm thick part: 30 mm in length / 1 mm thick part: 25 mm in length) was created.
- ROBOSHOT S2000i100A injection molding machine
- Total light transmittance (%): The total light transmittance was measured using a 1 mm portion of the obtained three-tiered plate-shaped test piece in accordance with JIS K7361. The larger the numerical value, the better the light transmittance of the molded article. A molded article with a thickness of 1 mm and a total light transmittance value of 40% or more was evaluated as good, and other cases were evaluated as poor.
- Light diffusivity (degrees) Light diffusivity (D50) was determined using a 1 mm portion of the three-tiered plate-shaped test piece used in 1 above using an automatic variable angle photometer (Goniophotometer GP-1R manufactured by Murakami Color Research Institute). The detailed measurement method is as follows. The larger this value is, the better the light diffusivity of the molded article is. A straight light beam from the light source of an automatic variable angle photometer is applied to the test piece from the normal direction, the intensity of the transmitted light is measured with a movable receiver, and the transmittance is plotted against the angle from the normal direction. The angle (D50) at which the transmittance becomes 50% of the straight light transmittance was determined. The unit is "degrees", and light diffusivity (D50) of 30 degrees or more was considered good.
- Light source transparency prevention (visual judgment): A rectangular hole of 3 cm x 5 cm was made in the center of a 20W straight tube LED lamp manufactured by Philips, and an injection molded plate of 3 cm x 5 cm x 1 mm was placed in the hole at a height of approximately 1.5 cm from the LED light source. . The ability to prevent the light source from seeing through was visually determined from a height of about 20 cm above the injection molded plate installed on the LED lamp. If sufficient light diffusivity was provided and the outline of the LED light source disappeared, it was judged to be extremely good. A case where the outline of the LED light source was slightly visible was judged as good, and a case where the outline of the LED light source was clearly visible due to poor light diffusivity was judged as poor.
- Tables 1 to 3 also show the raw materials, blending ratios, and evaluation results of each example and comparative example.
- the aromatic polycarbonate resin compositions of Examples 1 to 14 contain a linear aromatic polycarbonate resin, a polyether derivative (B), and a light diffusing agent (C), and optionally a phosphorus antioxidant (D). ), an aromatic compound (E), an epoxy compound (F), etc., in specific proportions. Therefore, the test piece molded from the aromatic polycarbonate resin composition has the required high total light transmittance, light diffusivity, and light source visibility resistance, has a low degree of yellowness, and shows almost no deterioration after the heating test. None.
- a molded article made from such an aromatic polycarbonate resin composition has a low degree of yellowness and excellent hue, and also shows almost no deterioration after a heating test.
- the aromatic polycarbonate resin composition of Comparative Example 1 contained a small amount of light diffusing agent, so the degree of light diffusion was low and the property of preventing light source transmission was poor. Further, the aromatic polycarbonate resin composition of Comparative Example 2 had a low total light transmittance because the amount of the light diffusing agent was large.
- the components described in the detailed description include not only components that are essential for solving the problem, but also components that are not essential for solving the problem in order to exemplify the above technology. obtain. Therefore, just because these non-essential components are described in the detailed description, it should not be immediately determined that those non-essential components are essential.
- the aromatic polycarbonate resin composition of the present invention does not impair the inherent properties of the polycarbonate resin, such as heat resistance and mechanical strength, and has excellent thermal stability and weather resistance. Even when a molded article containing the composition is heated, it has excellent appearance and optical properties. Therefore, even when used in applications where the surface of the diffuser plate is continuously heated by long-term irradiation of a thin diffused light source with a thickness of about 0.3 mm, the hue of the obtained diffuser plate may change and the appearance may change. There is no deterioration in optical properties, and the value of industrial use is extremely high.
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Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2024503793A JP7553748B2 (ja) | 2022-07-13 | 2023-07-11 | 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 |
| CN202380032124.5A CN118974167A (zh) | 2022-07-13 | 2023-07-11 | 芳香族聚碳酸酯树脂组合物及光扩散性成形品 |
| KR1020267003805A KR20260028875A (ko) | 2022-07-13 | 2023-07-11 | 방향족 폴리카르보네이트 수지 조성물 및 광확산성 성형품 |
| KR1020247032204A KR20240148445A (ko) | 2022-07-13 | 2023-07-11 | 방향족 폴리카르보네이트 수지 조성물 및 광확산성 성형품 |
| JP2024152792A JP7755018B2 (ja) | 2022-07-13 | 2024-09-05 | 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 |
| JP2025166073A JP2026004462A (ja) | 2022-07-13 | 2025-10-02 | 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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| JP2007063361A (ja) * | 2005-08-30 | 2007-03-15 | Teijin Chem Ltd | 帯電防止性ポリカーボネート樹脂組成物 |
| JP2009221472A (ja) * | 2008-02-22 | 2009-10-01 | Toray Ind Inc | 熱可塑性樹脂組成物 |
| JP2020045391A (ja) * | 2018-09-14 | 2020-03-26 | 出光興産株式会社 | ポリカーボネート系樹脂組成物 |
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| JP3916477B2 (ja) | 2002-02-14 | 2007-05-16 | 帝人化成株式会社 | ポリカーボネート樹脂製高透過光拡散フィルム |
| JP4721317B2 (ja) * | 2004-08-05 | 2011-07-13 | 株式会社Adeka | 光拡散性ポリカーボネート樹脂組成物及び透光性成形品 |
| JP4890766B2 (ja) | 2005-01-28 | 2012-03-07 | 帝人化成株式会社 | 光拡散性芳香族ポリカーボネート樹脂組成物 |
| JP2008189804A (ja) * | 2007-02-05 | 2008-08-21 | Mitsubishi Engineering Plastics Corp | ポリカーボネート樹脂組成物およびこれを成形してなる導光板、並びに光拡散性部材 |
| JP5206909B1 (ja) | 2011-07-21 | 2013-06-12 | Dic株式会社 | ポリカーボネート樹脂組成物及びその樹脂成形品 |
| JP5879124B2 (ja) | 2011-12-28 | 2016-03-08 | 出光興産株式会社 | ポリカーボネート樹脂組成物ペレットの製造方法 |
| JP6875127B2 (ja) | 2014-10-24 | 2021-05-19 | 三菱瓦斯化学株式会社 | 光拡散フィルム |
| WO2017175786A1 (ja) * | 2016-04-06 | 2017-10-12 | 株式会社カネカ | 導光板、これを備えた面光源体、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 |
| JP7055108B2 (ja) * | 2017-02-07 | 2022-04-15 | 株式会社クラレ | アクリル系樹脂二軸延伸フィルムおよびその製造方法 |
| CN111630108B (zh) * | 2018-01-26 | 2022-12-27 | 住化Pc有限公司 | 芳香族聚碳酸酯树脂组合物和光学用成型品 |
| 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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- 2023-07-11 TW TW112125754A patent/TWI910442B/zh active
- 2023-07-11 KR KR1020267003805A patent/KR20260028875A/ko active Pending
- 2023-07-11 WO PCT/JP2023/025622 patent/WO2024014465A1/ja not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007063361A (ja) * | 2005-08-30 | 2007-03-15 | Teijin Chem Ltd | 帯電防止性ポリカーボネート樹脂組成物 |
| JP2009221472A (ja) * | 2008-02-22 | 2009-10-01 | Toray Ind Inc | 熱可塑性樹脂組成物 |
| JP2020045391A (ja) * | 2018-09-14 | 2020-03-26 | 出光興産株式会社 | ポリカーボネート系樹脂組成物 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7620137B1 (ja) * | 2024-03-18 | 2025-01-22 | 出光興産株式会社 | ポリカーボネート樹脂組成物および成形体 |
| WO2025197265A1 (ja) * | 2024-03-18 | 2025-09-25 | 出光興産株式会社 | ポリカーボネート樹脂組成物および成形体 |
Also Published As
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|---|---|
| JP7553748B2 (ja) | 2024-09-18 |
| KR20240148445A (ko) | 2024-10-11 |
| TWI910442B (zh) | 2026-01-01 |
| CN118974167A (zh) | 2024-11-15 |
| TW202411346A (zh) | 2024-03-16 |
| JP2024178208A (ja) | 2024-12-24 |
| JPWO2024014465A1 (https=) | 2024-01-18 |
| JP2026004462A (ja) | 2026-01-14 |
| KR20260028875A (ko) | 2026-03-04 |
| JP7755018B2 (ja) | 2025-10-15 |
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