WO2015011994A1 - 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 - Google Patents
薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 Download PDFInfo
- Publication number
- WO2015011994A1 WO2015011994A1 PCT/JP2014/064717 JP2014064717W WO2015011994A1 WO 2015011994 A1 WO2015011994 A1 WO 2015011994A1 JP 2014064717 W JP2014064717 W JP 2014064717W WO 2015011994 A1 WO2015011994 A1 WO 2015011994A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polycarbonate resin
- thin
- resin composition
- pellet
- mass
- Prior art date
Links
- 0 CC**(C)(*)N=O Chemical compound CC**(C)(*)N=O 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Definitions
- the present invention relates to a polycarbonate resin composition for thin optical parts and a thin optical part, and more specifically, a polycarbonate resin composition for thin optical parts having high transmittance and good hue, a thin optical part formed by molding the same, and a thin optical part
- the present invention relates to a method for manufacturing an optical component, a polycarbonate resin pellet for a thin optical component, and a method for manufacturing a polycarbonate resin pellet for a thin optical component.
- a liquid crystal display device used in personal computers, mobile phones, and the like has a surface light source device incorporated in order to meet the demands for thinning, lightening, labor saving, and high definition.
- the surface light source device has a wedge-shaped cross-section light guide plate or a flat plate shape with a uniform inclined surface for the purpose of uniformly and efficiently guiding incident light to the liquid crystal display side.
- a light guide plate is provided. In some cases, an uneven pattern is formed on the surface of the light guide plate to provide a light scattering function.
- Such a light guide plate is obtained by injection molding of a thermoplastic resin, and the above concavo-convex pattern is imparted by transferring the concavo-convex portion formed on the surface of the nest.
- the light guide plate has been molded from a resin material such as polymethylmethacrylate (PMMA).
- PMMA polymethylmethacrylate
- Polycarbonate resin is excellent in mechanical properties, thermal properties, electrical properties, and weather resistance, but its light transmittance is lower than that of PMMA, etc., so that a surface light source body is formed from a light guide plate made of polycarbonate resin and a light source.
- a surface light source body is formed from a light guide plate made of polycarbonate resin and a light source.
- the luminance is low.
- Patent Document 1 describes a method for improving light transmittance and luminance by adding an acrylic resin and an alicyclic epoxy.
- Patent Document 2 describes a method for modifying the end of the polycarbonate resin to transfer the uneven portion to the light guide plate.
- a method for improving the brightness by increasing the brightness, and Patent Document 3 propose a method for improving the brightness by introducing a copolyester carbonate having an aliphatic segment to improve the transferability.
- Patent Document 1 improves the hue by adding an acrylic resin
- the light transmittance and luminance cannot be increased due to white turbidity
- the transmittance is improved by adding an alicyclic epoxy.
- the effect of improving the hue is not recognized.
- Patent Document 2 and Patent Document 3 although improvement of fluidity and transferability can be expected, there is a drawback that heat resistance is lowered.
- Patent Document 4 discloses a ⁇ -irradiation-resistant polycarbonate containing the same.
- Patent Document 5 describes a thermoplastic resin composition excellent in antistatic property and surface appearance in which the resin is blended with PMMA or the like.
- Patent Document 6 polyethylene ether glycol represented by the formula: X—O— [CH (—R) —CH 2 —O] n—Y (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) or
- R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- the polycarbonate resin for the light guide is thin-molded at a temperature higher than the molding temperature of normal polycarbonate resin, so even if the mechanical strength is sacrificed, the viscosity average molecular weight is lowered and the fluidity is increased. Is required.
- the polycarbonate resin for thin optical components typified by the light guide is a material having a low mechanical strength compared to the conventional polycarbonate resin, so when producing pellets with an extruder, The extruded polycarbonate resin strands are easily broken during cooling, and there is a problem that stable production is difficult.
- the average length of the pellets is in the range of 2.5 to 3.5 mm, and more than 70% of the average length length is plus or minus 0.
- a polycarbonate resin pellet for optical discs in the range of 1 mm has been proposed.
- the pellet aggregate with such a small amount of fine powder does not involve air entrainment during plasticization, and an optical disk substrate free from silver streak is obtained.
- the shape of the pellet is described. It has not been.
- the average value of the pellet length is 2.5 to 3.5 mm
- the average value of the major axis of the cross-sectional ellipse is 2.60 to 3.2 mm
- a polycarbonate molding material for an optical disk substrate has been proposed in which 70% or more of the pellets are contained in an average length ⁇ 0.08 mm and an average long diameter ⁇ 0.12 mm.
- a balanced three-dimensional shape with a ratio of the major axis to the major axis of about 0.7 to 1.5 is obtained, and the distribution is a narrow range.
- Patent Document 8 is also characterized in that the pellet aggregate has a uniform shape, but there is no description of the details of the elliptical shape of the individual pellets, and the specific manufacturing method of the pellets is simply a strand. It only describes that it is cut and manufactured.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a polycarbonate resin composition for a thin-walled optical component having good transmittance and hue without impairing the original properties of the polycarbonate resin. .
- the present invention can process a low molecular weight polycarbonate resin with low mechanical strength into a shape that generates a relatively small amount of fine powder even when the pellets contact each other, and can be used to form a light guide. Accordingly, it is an object of the present invention to provide a polycarbonate resin pellet for a thin-walled optical component in which yellowing of a molded product and optical fluctuation are unlikely to occur. Moreover, it is providing the method of manufacturing such a pellet stably.
- the present inventor contains a specific amount of a polyalkylene ether glycol in a polycarbonate resin and a specific amount of a phosphorus stabilizer. It has been found that better transmission, good hue and very good heat discoloration can be achieved. Moreover, when producing pellets of such a polycarbonate resin composition, the strand cross-sectional shape at the time of extrusion is flattened to give the strands elasticity and to prevent cracking during cooling, so that the pellets for thin optical components Can be manufactured stably.
- the present invention provides the following polycarbonate resin composition for thin optical parts, thin optical parts, methods for producing thin optical parts, polycarbonate resin pellets for thin optical parts, and methods for producing polycarbonate resin pellets for thin optical parts.
- a polycarbonate resin composition for thin optical parts characterized by containing 0.005 to 0.5 parts by mass.
- X and Y represent a hydrogen atom, an aliphatic acyl group or an alkyl group having 1 to 22 carbon atoms, X and Y may be different from each other, m is an integer of 3 to 6, and n is Represents an integer of 6 to 100.
- a thin-walled optical component obtained by molding the polycarbonate resin composition according to any one of [1] to [7] above.
- the thin optical component according to [8] which is a light guide plate having a thickness of 1 mm or less.
- An elliptical columnar pellet made of the polycarbonate resin composition according to any one of [1] to [7] above, having a length of 2.0 to 5.0 mm and having an elliptical cross section A polycarbonate resin pellet for a thin-walled optical component, wherein the ratio of major axis / minor axis is 1.5 to 4 and the minor axis is 1.0 to 3.0 mm.
- the polycarbonate resin pellet is fixed in a 50 liter tumbler, which is stored in a 2 liter polyethylene sealed container having an outer diameter of 125 mm and a total height of 233 mm containing 500 g of the polycarbonate resin pellet.
- a thin wall characterized by being extruded as a strand from a discharge nozzle having an elliptical die hole provided in a cross section with the major axis of the elliptical section in a substantially horizontal state, cooled and solidified in a cooling water tank, and cut with a strand cutter A method for producing polycarbonate resin pellets for optical parts.
- the polycarbonate resin composition for thin optical components having good transmittance and hue and good heat discoloration and thin wall having good transmittance and hue are obtained without impairing the original properties of the polycarbonate resin.
- An optical component can be provided, and can be particularly suitably used for a thin optical component represented by a light guide plate.
- the polycarbonate resin pellets of the present invention have a low viscosity average molecular weight of 10,000 to 15,500, they are difficult to be pulverized by contact between the pellets, resulting in yellowing of the molded product and optical fluctuations. It is extremely excellent as a pellet for thin optical parts such as difficult light guides.
- it is possible to stably produce pellets for thin-walled optical components by flattening the cross-sectional shape of the strand at the time of extrusion, thereby giving elasticity to the strand and making it difficult to break during cooling. it can.
- FIG. 1 is a schematic diagram of a polycarbonate resin pellet for a thin-walled optical component according to the present invention.
- FIG. 2 is a conceptual diagram of a process for producing a polycarbonate resin pellet by extruding a strand from an extruder and a method for evaluating the limit strength.
- FIG. 3 is a conceptual diagram showing details of the limit strength evaluation method.
- the polycarbonate resin composition for thin optical components of the present invention is 0.1 to 2 parts by mass of the polyalkylene ether glycol compound (B) represented by the general formula (1) with respect to 100 parts by mass of the polycarbonate resin (A). And 0.005 to 0.5 parts by mass of the phosphorus stabilizer (C).
- B polyalkylene ether glycol compound represented by the general formula (1)
- C phosphorus stabilizer
- Polycarbonate resin (A) There is no restriction
- the polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C ( ⁇ O) —] —.
- X is generally a hydrocarbon, but for imparting various properties, X into which a hetero atom or a hetero bond is introduced may be used.
- the polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon, and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, either of which can be used.
- aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.
- the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned.
- a polyhydroxy compound or the like may be reacted.
- a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used.
- the polycarbonate polymer may be linear or branched.
- the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units.
- the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer.
- such a polycarbonate polymer is a thermoplastic resin.
- aromatic dihydroxy compounds among monomers used as raw materials for aromatic polycarbonate resins are:
- Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
- Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;
- 2,2′-dihydroxy-1,1′-binaphthyl 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;
- 2,2-bis (4-hydroxyphenyl) propane ie, bisphenol A
- 1,1-bis (4-hydroxyphenyl) propane 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane, ⁇ , ⁇ '-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, Bis (4-hydroxyphenyl) methane, Bis (4-hydroxyphenyl)
- 1,1-bis (4-hydroxyphenyl) cyclopentane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexan
- Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;
- bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (particularly from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferred.
- 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.
- Ethane-1,2-diol propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;
- Glycols such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;
- 1,2-epoxyethane ie ethylene oxide
- 1,2-epoxypropane ie propylene oxide
- 1,2-epoxycyclopentane 1,2-epoxycyclohexane
- 1,4-epoxycyclohexane 1,4-epoxycyclohexane
- 1-methyl -1,2-epoxycyclohexane 2,3-epoxynorbornane
- cyclic ethers such as 1,3-epoxypropane; and the like.
- carbonyl halides, carbonate esters and the like are used as examples of carbonate precursors.
- 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.
- carbonyl halide examples include phosgene; haloformates such as a bischloroformate of a dihydroxy compound and a monochloroformate of a dihydroxy compound.
- carbonate ester examples include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as
- the manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
- Arbitrary methods include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
- a polycarbonate resin is manufactured by the interfacial polymerization method.
- a dihydroxy compound and a carbonate precursor preferably phosgene
- an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher.
- Polycarbonate resin is obtained by interfacial polymerization in the presence.
- a molecular weight adjusting agent may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.
- the dihydroxy compound and the carbonate precursor are as described above.
- phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.
- organic solvent inert to the reaction examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done.
- 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.
- alkali compound contained in the alkaline aqueous solution examples include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred.
- 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.
- the concentration of the alkali compound in the alkaline aqueous solution is not limited, but it is usually used at 5 to 10% by mass in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12.
- the molar ratio of the bisphenol compound to the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11.
- the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.
- polymerization catalyst examples include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like.
- 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.
- the molecular weight regulator examples include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like, among which aromatic phenols are preferred.
- aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol.
- a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
- the amount used of the molecular weight regulator is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the dihydroxy compound.
- the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set.
- the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
- the reaction temperature is usually 0 to 40 ° C.
- the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).
- melt transesterification method for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.
- the dihydroxy compound is as described above.
- examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable.
- carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
- the ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and above all, 1.01 mol or more is used. It is more preferable.
- the upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.
- the amount of terminal hydroxyl groups tends to have a large effect on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method.
- a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like.
- the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.
- the mixing ratio is as described above.
- a more aggressive adjustment method there may be mentioned a method in which a terminal terminator is mixed separately during the reaction.
- the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like.
- 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.
- a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.
- the reaction temperature is usually 100 to 320 ° C.
- the pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less.
- a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.
- the melt polycondensation reaction can be performed by either a batch method or a continuous method.
- the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily.
- the melt polycondensation reaction is preferably carried out continuously.
- a catalyst deactivator may be used as necessary.
- a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof.
- 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.
- the amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.
- the molecular weight of the polycarbonate resin (A) is preferably 10,000 to 15,000 in terms of viscosity average molecular weight (Mv) converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.
- Mv viscosity average molecular weight
- it is 10,500 or more, More preferably, it is 11,000 or more, Especially, 11,500 or more, Most preferably, it is 12,000 or more, More preferably, it is 14,500 or less.
- the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by making the viscosity average molecular weight not more than the upper limit of the above range, The fluidity of the polycarbonate resin composition of the invention can be suppressed and improved, and the molding processability can be improved and the thin-wall molding process can be easily performed.
- Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.
- the intrinsic viscosity [ ⁇ ] is a value calculated from the following equation by measuring the specific viscosity [ ⁇ sp ] at each solution concentration [C] (g / dl).
- the terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of polycarbonate resin can be improved more.
- the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a resin composition can be improved more.
- the unit of the terminal hydroxyl group concentration represents the mass of the terminal hydroxyl group with respect to the mass of the polycarbonate resin in ppm.
- the measuring method is a colorimetric determination by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88 215 (1965)).
- the polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination.
- a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy
- the polycarbonate resin may contain a polycarbonate oligomer.
- the viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less.
- the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).
- the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin).
- the regenerated polycarbonate resin is preferably 80% by mass or less of the polycarbonate resin, and more preferably 50% by mass or less.
- Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.
- the polycarbonate resin composition for thin optical parts of the present invention contains a polyalkylene ether glycol compound (B) represented by the following general formula (1).
- X and Y represent a hydrogen atom, an aliphatic acyl group or an alkyl group having 1 to 22 carbon atoms, X and Y may be different from each other, m is an integer of 3 to 6, and n is Represents an integer of 6 to 100.
- n degree of polymerization
- a polymerization degree n of less than 6 is not preferable because gas is generated during molding.
- the polymerization degree n exceeds 100, the compatibility is lowered, which is not preferable.
- the polyalkylene ether glycol compound (B) may be a copolymer with another copolymer component, but a polyalkylene ether glycol homopolymer is preferred.
- polypentamethylene ether glycol is m
- polyalkylene ether glycol compound (B) even if one or both ends thereof are blocked with a fatty acid or alcohol, there is no influence on the performance expression, and a fatty acid ester or ether can be used in the same manner. It may be an aliphatic acyl group or an alkyl group having X and / or 1 to 22 carbon atoms in 1).
- the fatty acid ester product either a linear or branched fatty acid ester can be used, and the fatty acid constituting the fatty acid ester may be a saturated fatty acid or an unsaturated fatty acid. Also, those in which some hydrogen atoms are substituted with a substituent such as a hydroxyl group can be used.
- the fatty acid constituting the fatty acid ester is a monovalent or divalent fatty acid having 1 to 22 carbon atoms, for example, a monovalent saturated fatty acid, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid.
- the fatty acid also includes a fatty acid having one or more hydroxyl groups in the molecule.
- polyalkylene ether glycol fatty acid ester examples include polyalkylene ether glycol monopalmitate, polyalkylene ether glycol dipalmitate, polyalkylene ether glycol monostearate, polyalkylene ether glycol distearate, polyalkylene Examples include ether glycol (monopalmitic acid / monostearic acid) ester, polyalkylene ether glycol behenate, and the like.
- alkyl group constituting the alkyl ether either linear or branched can be used, and an alkyl group having 1 to 22 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a lauryl group
- Preferred examples include stearyl groups such as alkyl methyl ether, ethyl ether, butyl ether, lauryl ether and stearyl ether of polyalkylene ether glycol.
- the number average molecular weight of the polyalkylene ether glycol compound (B) is preferably 200 to 5,000, more preferably 300 or more, still more preferably 500 or more, more preferably 4,000 or less, More preferably, it is 3,000 or less. Exceeding the upper limit of the above range is not preferable because the compatibility is lowered, and if it is lower than the lower limit of the above range, gas is generated during molding, which is not preferable.
- the number average molecular weight of a polyalkylene ether glycol compound here is the number average molecular weight computed based on the hydroxyl value measured based on JISK1577.
- the content of the polyalkylene ether glycol compound (B) is 0.1 to 2 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A).
- the preferred content is 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, preferably 1.9 parts by mass or less, more preferably 1.7 parts by mass or less, and further preferably 1.6 parts by mass. It is as follows. When the content is less than 0.1 part by mass, the hue and yellowing are not sufficiently improved. When the content exceeds 2 parts by mass, strand breakage frequently occurs during melt kneading by an extruder, and the resin composition pellets It becomes difficult to create.
- the polycarbonate resin composition of the present invention needs to contain a phosphorus stabilizer.
- a phosphorus stabilizer By containing a phosphorus stabilizer, the hue of the polycarbonate resin composition of the present invention is improved, and the heat discoloration is further improved. Any known phosphorous stabilizer can be used.
- phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid
- acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate
- phosphoric acid Phosphates of Group 1 or Group 2B metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate
- phosphate compounds, phosphite compounds, phosphonite compounds and the like are mentioned, and phosphite compounds are particularly preferred.
- the phosphite compound is a trivalent phosphorus compound represented by the general formula: P (OR) 3 , and R represents a monovalent or divalent organic group.
- Examples of such phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphine.
- an aromatic phosphite compound represented by the following formula (2) or (3) is more preferable because the heat discoloration of the polycarbonate resin composition of the present invention is effectively enhanced. .
- R 1 , R 2 and R 3 may be the same or different and each represents an aryl group having 6 to 30 carbon atoms. ]
- R 4 and R 5 may be the same or different and each represents an aryl group having 6 to 30 carbon atoms. ]
- phosphite compound represented by the above formula (2) triphenyl phosphite, tris (monononylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like are preferable. Of these, tris (2,4-di-tert-butylphenyl) phosphite is more preferable.
- organic phosphite compounds include, for example, “ADEKA STAB 1178” manufactured by ADEKA, “SUMILIZER TNP” manufactured by Sumitomo Chemical Co., Ltd., “JP-351” manufactured by Johoku Chemical Industry Co., Ltd. 2112 ",” Irgaphos 168 “manufactured by BASF,” JP-650 “manufactured by Johoku Chemical Industry Co., Ltd., and the like.
- Examples of the phosphite compound represented by the above formula (3) include bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert- Those having a pentaerythritol diphosphite structure such as butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are particularly preferred.
- Specific examples of such organic phosphite compounds include “ADEKA STAB PEP-24G”, “ADEKA STAB PEP-36” manufactured by ADEKA, “Doverphos S-9228” manufactured by Doverchemical, and the like.
- 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and ratios.
- the content of the phosphorus stabilizer (C) is 0.005 to 0.5 parts by mass, preferably 0.007 parts by mass or more, more preferably 0.005 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). 008 parts by mass or more, particularly preferably 0.01 parts by mass or more, preferably 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, still more preferably 0.2 parts by mass or less, particularly 0 .1 part by mass or less.
- the content of the phosphorus stabilizer (C) is less than 0.005 parts by mass of the above range, the hue and heat discoloration are insufficient, and the content of the phosphorus stabilizer (C) is 0.5 parts by mass. If it exceeds 1, not only the heat discoloration is deteriorated, but also the wet heat stability is lowered.
- the polycarbonate resin composition of the present invention preferably further contains an epoxy compound (D).
- an epoxy compound By containing an epoxy compound, the hue of the polycarbonate resin composition of the present invention becomes better, and the heat discoloration is further improved.
- epoxy compound (D) a compound having one or more epoxy groups in one molecule is used. Specifically, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl -3 ', 4'-epoxy-6'-methylcyclohexyl carboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexyl carboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) Butyl-3 ′, 4′-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarbox
- the content of the epoxy compound (D) is preferably 0.0005 to 0.2 parts by mass, more preferably 0.001 parts by mass or more, and still more preferably 0 with respect to 100 parts by mass of the polycarbonate resin (A). 0.003 parts by mass or more, particularly preferably 0.005 parts by mass or more, more preferably 0.15 parts by mass or less, still more preferably 0.1 parts by mass or less, particularly preferably 0.05 parts by mass or less. .
- the content of the epoxy compound (D) is less than 0.0005 parts by mass, the hue and the heat discoloration tend to be insufficient, and when it exceeds 0.2 parts by mass, the heat discoloration is not only deteriorated. Also, hue and wet heat stability are likely to decrease.
- the ratio of the content of the phosphorus stabilizer (C) and the epoxy compound (D) in the polycarbonate resin composition is a mass ratio of (C) / (D).
- a range of 0.5 to 10 is preferable.
- the mass ratio of (C) / (D) is more preferably 0.7 or more, further preferably 0.8 or more, more preferably 8 or less, still more preferably 7 or less, and particularly preferably 8 It is as follows.
- the polycarbonate resin composition of the present invention includes other additives other than those described above, for example, antioxidants, mold release agents, ultraviolet absorbers, fluorescent brighteners, pigments, dyes, other polymers other than polycarbonate resins, Additives such as a flame retardant, an impact resistance improver, an antistatic agent, a plasticizer, and a compatibilizing agent can be contained. These additives may be used alone or in combination of two or more.
- the manufacturing method of a well-known polycarbonate resin composition can be employ
- the temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.
- the polycarbonate resin composition for thin optical components of the present invention exhibits high spectral transmittance, and the spectral transmittance measured at an optical path length of 300 mm at a wavelength of 420 nm is preferably 55% or more, more preferably 56% or more, and further Preferably, it can have a high spectral transmittance of 57% or more.
- the spectral transmittance at a wavelength of 420 nm is a transmittance in a wavelength region close to the wavelength region of a blue LED often used in optical components such as a light guide plate, and if the transmittance in this wavelength region is low, yellowishness Will increase.
- the spectral transmittance at a wavelength of 420 nm is measured with an optical path length of 300 mm using an injection molded long optical path molded product (300 mm ⁇ 7 mm ⁇ 4 mm), and is specifically performed according to the method described in the examples described later. .
- the polycarbonate resin composition for thin optical parts of the present invention is usually formed into pellets by melting and kneading each component as described above.
- the polycarbonate resin pellet is preferably a pellet having an elliptical columnar shape.
- FIG. 1 is a schematic diagram of the polycarbonate resin pellet for thin-walled optical components.
- a preferred polycarbonate resin pellet has a length L in the range of 2.0 to 5.0 mm, and a ratio of the major axis d to the minor axis a (d / a) in the elliptical cross section of the pellet is in the range of 1.5 to 4.
- the minor axis a is in the range of 1.0 to 3.0 mm.
- the pellets are easily crushed and the amount of fine powder generated tends to increase. If the ratio of the major axis d to the minor axis a (d / a) deviates from the range of 1.5 to 4, the strength of the resin strands tends to decrease, the production of pellets by extrusion becomes unstable, and the elliptical minor axis a If it is not within the range of 1.0 to 3.0 mm, the pellets are easily crushed and the amount of fine powder generated tends to increase.
- the ratio of the major axis d to the minor axis a is preferably 1.6 or more, more preferably 1.7 or more, still more preferably 1.8 or more, and preferably 3.5 or less. Yes, more preferably 3.0 or less.
- Such a polycarbonate resin pellet has such a shape that the pellet is accommodated in a paper bag, a flexible container, or the like, and it is difficult to generate fine powder even when subjected to vibration or load when transporting and delivering it. Have. Since the major axis direction of the elliptical cross section of the pellet becomes horizontal and receives the load, it is considered that it is difficult to pulverize.
- the amount of fine powder generation of such polycarbonate resin pellets is as follows: 500 g of resin pellets are housed in a 2 liter polyethylene sealed container having an outer diameter of 125 mm and a total height of 233 mm, and placed in a 50 liter tumbler and fixed.
- the amount of fine powder having a particle diameter of 1 mm or less that is generated after rotating at a rotational speed for 20 minutes is preferably 50 ppm or less.
- the polycarbonate resin is stored in a raw material supply machine, and from there, is fed to the extruder by a feeder (quantitative feeder) from a hopper installed on the extruder.
- the polycarbonate resin may be in the form of pellets or powder.
- Other components other than the polycarbonate resin can be blended at any stage before being charged into the extruder. For example, after all components are blended by a tumbler, a Henschel mixer, and a blender, they may be fed into a hopper chute via a feeder and supplied to an extruder as necessary.
- As the extruder a single screw extruder, a twin screw extruder or the like can be used. Moreover, you may supply to a hopper chute
- the extruder may be a single screw extruder or a twin screw extruder, but a twin screw extruder is preferred.
- the L / D of the screw of the extruder is preferably 10 to 80, more preferably 15 to 70, and still more preferably 20 to 60. If the screw is too short, deaeration tends to be insufficient, and if it is too long, the color tone tends to deteriorate.
- the polycarbonate resin composition is extruded in a strand shape from the discharge nozzle at the tip of the extruder, and it is preferable to use a die having an elliptical die hole as the die of the discharge nozzle.
- a die having an elliptical die hole As the die of the discharge nozzle, the flatness of the pellet can be changed.
- the dies of the discharge nozzle are preferably extruded by attaching the major axis of the elliptical die hole in a substantially horizontal state, and attaching the strand having an elliptical cross section to be extruded so that the major axis is substantially horizontal.
- the temperature of the polycarbonate resin immediately after being extruded is usually about 300 ° C.
- the strand having an elliptical cross-section has a major axis that is substantially horizontal and is taken up by a take-up roller, and is cooled by being transported through the water stored in the cooling water tank. In order to reduce the deterioration of the resin, it is better that the time from when the strand is pushed out of the die until entering the water is shorter. Normally, it is better to enter the water within 1 second after being pushed out of the die.
- the cooled strand is sent to a pelletizer by a take-up roller, cut to a pellet length of 2.0 to 5.0 mm, and made into a pellet.
- FIG. 2 is a conceptual diagram showing a process for producing a polycarbonate resin pellet by extruding a strand from an extruder
- FIG. 3 is a conceptual diagram showing details of a limit strength evaluation method.
- an interval (X mm, hereinafter also referred to as “limit interval”) defined as an interval between the support C and the support A where the strand is not broken by continuous operation is 300 mm or less.
- the polycarbonate resin composition for thin optical components of the present invention can be produced by molding pellets obtained by pelletizing the above-described polycarbonate resin composition by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a thin optical component without going through the pellets.
- the polycarbonate resin composition of the present invention has excellent fluidity, and even when it is a thin molded product, it has excellent appearance of a molded product without white spot foreign matter, and can achieve both transmittance and hue. It is suitably used for molding optical components.
- the resin temperature at the time of injection molding is preferably molded at a resin temperature higher than 260 to 300 ° C., which is a temperature generally applied to injection molding of polycarbonate resin, and a resin temperature of 305 to 380 ° C. is preferable.
- the resin temperature is more preferably 310 ° C or higher, further preferably 315 ° C or higher, particularly preferably 320 ° C or higher, and more preferably 370 ° C or lower.
- the thin-walled molded article refers to a molded article having a plate-like portion having a thickness of usually 1 mm or less, preferably 0.8 mm or less, more preferably 0.6 mm or less.
- the plate-like portion may be a flat plate or a curved plate, may be a flat surface, may have irregularities on the surface, and the cross section has an inclined surface. Or a wedge-shaped cross section.
- Thin-walled optical parts include parts of equipment and instruments that directly or indirectly use light sources such as LEDs, organic EL, incandescent bulbs, fluorescent lamps, cathode tubes, etc., and typical examples include light guide plates and surface light emitter parts. It is illustrated as a thing.
- the light guide plate is used to guide light from a light source such as an LED in a liquid crystal backlight unit, various display devices, and lighting devices. It diffuses by the unevenness and emits uniform light.
- the shape is usually flat, and the surface may or may not have irregularities.
- the light guide plate is usually formed preferably by an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, or the like.
- the light guide plate molded using the resin composition of the present invention does not have white turbidity or a decrease in transmittance, and has a very good transmittance and hue.
- the light guide plate made of the polycarbonate resin composition of the present invention can be suitably used in the fields of liquid crystal backlight units, various display devices, and lighting devices.
- Examples of such devices include mobile phones, mobile notebooks, netbooks, slate PCs, tablet PCs, smartphones, tablet terminals, and other portable terminals, cameras, watches, notebook computers, various displays, lighting devices, and the like. It is done.
- Example 1 Comparative Examples 1 to 5
- the raw materials used are as shown in Table 1 below.
- Example 5 In Example 1, except that the B1 component was changed to 4 parts by mass, pelletization was examined in the same manner as in Example 1. However, strand breakage occurred frequently during melt-kneading by an extruder, and the resin composition pellets Creation was difficult.
- the molded product of the example has a small YI at 300 mm with a long optical path length, and shows little yellowing. Furthermore, the light transmittance at 420 nm is high and the transparency is excellent. On the other hand, in the comparative example of Table 3, it can be seen that YI of 300 mm is worse than that of the example. Furthermore, the light transmittance is also low.
- Example 8 to 14 Comparative Examples 6 to 7, Reference Examples 1 to 3
- the raw materials used are as shown in Table 4 below.
- ASA 1 manufactured by Nippon Denshoku Industries Co., Ltd., C light source, 2 ° visual field
- ASA 1 manufactured by Nippon Denshoku Industries Co., Ltd., C light source, 2 ° visual field
- the thin-walled molded product of the example containing the epoxy compound (D) has a small initial YI at 300 mm having a long optical path length and an excellent hue. Further, it can be seen that the increase in YI value after the heat treatment is small and the heat discoloration is excellent.
- Example 15 Each component described in Table 1 above was blended in the proportions (parts by mass) described in Example 5 of Table 2 above, mixed for 20 minutes with a tumbler, and then vented twin screw extruder (manufactured by Nippon Steel Works). “TEX44 ⁇ II”) is continuously supplied to the extruder from the hopper, melted and mixed in the extruder, and the major axis is 6.5 mm under the extrusion conditions of a cylinder temperature of 240 ° C., a discharge rate of 150 kg / h, and a screw speed of 250 rpm.
- a die having an elliptical die hole with a diameter of 3.5 mm is extruded from an extrusion nozzle provided with its major axis horizontal, in a strand shape with the major axis of the elliptical cross section approximately horizontal, introduced into a cooling water tank, and a strand
- the pellet was cut with a pelletizer at a take-up speed of 40 m / min and a cutter blade rotation speed of 600 rpm to obtain polycarbonate resin pellets.
- (1) Major axis / minor axis ratio of pellet elliptical cross section The major axis, minor axis, and length of the obtained pellet were measured, and an average value of 100 was shown for each.
- the ratio of the average value of the major axis / minor axis was defined as the pellet flatness.
- the major axis of the pellet was 2.9 mm
- the minor axis was 1.5 mm
- the pellet length was 2.9 mm
- the ratio of major axis / minor axis was 1.9.
- the limit strength of the strand was evaluated by the following method. As shown in FIG. 2, the resin strand obtained by extruding the obtained polycarbonate resin pellets from the extruder is sent to the pelletizer while being supported by the support C to the support B and the support A. As shown in detail in FIG. 3, the critical strength of the resin strand is that the strand take-up speed (Vx) is 100 mm / sec, and the height difference between the support C and A and the support B at the same height supporting the strand is 290 mm. At the time, it was evaluated as an interval (X mm) between the support C and the support A at the same height where the strands were not broken by continuous operation for 1 hour or more. The support spacing was 260 mm.
- the particle size of the fine powder in this measurement is 1 mm or less.
- the amount of fine powder generated was 35 ppm by mass.
- Example 16 Each component described in Table 1 above was blended in the proportions (parts by mass) described in Example 7 in Table 2 above, mixed for 20 minutes with a tumbler, and then vented twin screw extruder (manufactured by Nippon Steel Works). “TEX44 ⁇ II”) is continuously supplied to the extruder from the hopper, melted and mixed in the extruder, and the major axis is 6.5 mm under the extrusion conditions of a cylinder temperature of 240 ° C., a discharge rate of 150 kg / h, and a screw speed of 250 rpm.
- a die having an elliptical die hole with a diameter of 2.9 mm was extruded from an extrusion nozzle provided with the major axis horizontal, in a strand shape with the major axis of the elliptical section approximately horizontal, introduced into a water tank, and the strand
- the pellet was cut by a pelletizer at a take-up speed of 40 m / min and a cutter blade rotation speed of 600 rpm to obtain polycarbonate resin pellets.
- the major axis of the pellet was 2.9 mm
- the minor axis was 1.2 mm
- the length of the pellet was 3.2 mm
- the ratio of major axis / minor axis was 2.4.
- the number of strand breaks was 0, and the support support interval was 270 mm.
- the amount of fine powder generated was 34 ppm by mass, the number of white spot defects was zero, and the number of pellets with vacuum voids was zero.
- Example 17 Each component described in Table 4 above was blended in (parts by mass) in the proportions described in Example 9 in Table 5 above, mixed for 20 minutes with a tumbler, and then vented twin-screw extruder (Nippon Steel Works) Manufactured continuously from a hopper made of “TEX44 ⁇ II”), melted and mixed in the extruder, under a cylinder temperature of 240 ° C., a discharge amount of 150 kg / h, and an extrusion condition of a screw rotation speed of 250 rpm, a major axis of 6.5 mm, A die having an elliptical die hole with a short diameter of 3.5 mm is extruded from an extrusion nozzle provided with the major axis horizontal, in a strand shape with the major axis of the elliptical section approximately horizontal, and introduced into a water tank. The pellet was cut with a pelletizer at a take-up speed of 40 m / min and a cutter blade rotation speed
- the major axis of the pellet was 2.9 mm
- the minor axis was 1.5 mm
- the pellet length was 2.9 mm
- the ratio of major axis / minor axis was 1.9.
- the number of strand breaks was 0, and the support support interval was 260 mm.
- the amount of fine powder generated was 35 ppm by mass, the number of white spot defects was zero, and the number of pellets with vacuum voids was zero.
- the polycarbonate resin composition of the present invention has very good transmittance and hue and is excellent in heat discoloration. Therefore, the polycarbonate resin composition can be used suitably for thin-walled optical components and has very high industrial applicability.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
そして、特許文献6では、式:X-О-[CH(-R)-CH2-O]n-Y (Rは水素原子または炭素数1~3のアルキル基)で表わされるポリエチレンエーテルグリコールまたはポリ(2-アルキル)エチレンエーテルグリコールを配合することにより、透過率や色相を改良する提案がなされている。ポリエチレンエーテルグリコールまたはポリ(2-アルキル)エチレンエーテルグリコールを配合することで透過率や黄変度(イェローインデックス:YI)は若干の改善が見られる。
また、工場で製造されたペレットを配送のため紙袋やフレキシブルコンテナ等に入れ、輸送しただけでも、ペレット同士の接触により一部が微粉化してしまう。このような微粉が混入したペレットを用いて、導光体等を成形すると、成形物の黄変や光学的ゆらぎが発生しやすいといった問題点がある。
微粉による問題を解決する手段としては、成形する際に微粉除去機を経由して微粉を取り除くことで解消できるが、工程が一つ余計に入り異物混入の恐れがあることから、できれば経由したくないといった要望がある。
また、本発明は、機械的強度が弱い低分子量のポリカーボネート樹脂から、ペレット同士が接触しても比較的微粉発生量が少ない形状に加工し、これを用いて導光体を成形することを可能とすることで、成形物の黄変、光学的ゆらぎが発生し難い薄肉光学部品用のポリカーボネート樹脂ペレットを提供することにある。また、このようなペレットを安定して製造する方法を提供することである。
また、このようなポリカーボネート樹脂組成物のペレットを製造する際、押出時のストランド断面形状を扁平化させることにより、ストランドに弾性を持たせ、冷却時に割れにくくすることで、薄肉光学部品用のペレットを安定して製造することを可能とした。そして、ペレタイズ後のペレット形状を特定の扁平形状とすることで、ペレット同士の接触でも微粉化しにくいことを見出し、結果として、成形物の黄変、光学的ゆらぎが発生し難い導光体等の薄肉光学部品用のペレットとして極めて優れていることを見出した。
[3]ポリカーボネート樹脂(A)の粘度平均分子量(Mv)が10,000~15,000である上記[1]又は[2]に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
[4]ポリカーボネート樹脂(A)の粘度平均分子量(Mv)が11,000~14,500である上記[1]~[3]のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
[5]ポリアルキレンエーテルグリコール化合物(B)がポリテトラメチレンエーテルグリコールである上記[1]~[4]のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
[6]リン系安定剤(C)がペンタエリスリトールジホスファイト構造を有する安定剤である上記[1]~[5]のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
[7]300mmの光路長で測定した波長420nmでの分光透過率が55%以上である上記[1]~[6]のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
[9]1mm以下の厚みを有する導光板である上記[8]に記載の薄肉光学部品。
[11]上記[1]~[7]のいずれか1項に記載のポリカーボネート樹脂組成物からなる楕円柱状のペレットであって、長さが2.0~5.0mmであり、その楕円断面の長径/短径の比が1.5~4、短径が1.0~3.0mmであることを特徴とする薄肉光学部品用ポリカーボネート樹脂ペレット。
[12]前記ポリカーボネート樹脂ペレットは、ポリカーボネート樹脂ペレット500gを収納した外径125mm、全高233mmの容量2リットルのポリエチレン製密閉容器に収納したものを50リットルのタンブラーに入れて固定し、30rpmの回転数で20分間回転させた後に発生する粒径1mm以下の微粉の量が50ppm以下である上記[11]に記載の薄肉光学部品用ポリカーボネート樹脂ペレット。
[13]ペレットの断面楕円の長径/短径の比が1.8~4である上記[11]又は[12]に記載の薄肉光学部品用ポリカーボネート樹脂ペレット。
[15]ストランドの引取速度が100mm/secにおけるストランドを支えるサポートの高低差が290mmであるとき、1時間以上の連続運転でストランドが折れない、同じ高さのサポートの間隔が300mm以下である上記[14]に記載の薄肉光学部品用ポリカーボネート樹脂ペレットの製造方法。
なお、本願明細書において、「~」とは、特に断りがない場合、その前後に記載される数値を下限値及び上限値として含む意味で使用される。
本発明の薄肉光学部品用ポリカーボネート樹脂組成物は、ポリカーボネート樹脂(A)100質量部に対し、前記一般式(1)で表されるポリアルキレンエーテルグリコール化合物(B)を0.1~2質量部、リン系安定剤(C)を0.005~0.5質量部含有することを特徴とする。
以下、本発明のポリカーボネート樹脂組成物を構成する各成分等につき、詳細に説明する。
本発明において使用するポリカーボネート樹脂の種類に制限はなく、ポリカーボネート樹脂は、1種類を用いてもよく、2種類以上を任意の組み合わせ及び任意の比率で併用してもよい。
式中、Xは一般には炭化水素であるが、種々の特性付与のためヘテロ原子、ヘテロ結合の導入されたXを用いてもよい。
2,5-ジヒドロキシビフェニル、2,2’-ジヒドロキシビフェニル、4,4’-ジヒドロキシビフェニル等のジヒドロキシビフェニル類;
1,1-ビス(4-ヒドロキシフェニル)プロパン、
2,2-ビス(3-メチル-4-ヒドロキシフェニル)プロパン、
2,2-ビス(3-メトキシ-4-ヒドロキシフェニル)プロパン、
2-(4-ヒドロキシフェニル)-2-(3-メトキシ-4-ヒドロキシフェニル)プロパン、
1,1-ビス(3-tert-ブチル-4-ヒドロキシフェニル)プロパン、
2,2-ビス(3,5-ジメチル-4-ヒドロキシフェニル)プロパン、
2,2-ビス(3-シクロヘキシル-4-ヒドロキシフェニル)プロパン、
2-(4-ヒドロキシフェニル)-2-(3-シクロヘキシル-4-ヒドロキシフェニル)プロパン、
α,α’-ビス(4-ヒドロキシフェニル)-1,4-ジイソプロピルベンゼン、
1,3-ビス[2-(4-ヒドロキシフェニル)-2-プロピル]ベンゼン、
ビス(4-ヒドロキシフェニル)メタン、
ビス(4-ヒドロキシフェニル)シクロヘキシルメタン、
ビス(4-ヒドロキシフェニル)フェニルメタン、
ビス(4-ヒドロキシフェニル)(4-プロペニルフェニル)メタン、
ビス(4-ヒドロキシフェニル)ジフェニルメタン、
ビス(4-ヒドロキシフェニル)ナフチルメタン、
1,1-ビス(4-ヒドロキシフェニル)エタン、
1,1-ビス(4-ヒドロキシフェニル)-1-フェニルエタン、
1,1-ビス(4-ヒドロキシフェニル)-1-ナフチルエタン、
1,1-ビス(4-ヒドロキシフェニル)ブタン、
2,2-ビス(4-ヒドロキシフェニル)ブタン、
2,2-ビス(4-ヒドロキシフェニル)ペンタン、
1,1-ビス(4-ヒドロキシフェニル)ヘキサン、
2,2-ビス(4-ヒドロキシフェニル)ヘキサン、
1,1-ビス(4-ヒドロキシフェニル)オクタン、
2,2-ビス(4-ヒドロキシフェニル)オクタン、
1,1-ビス(4-ヒドロキシフェニル)ヘキサン、
2,2-ビス(4-ヒドロキシフェニル)ヘキサン、
4,4-ビス(4-ヒドロキシフェニル)ヘプタン、
2,2-ビス(4-ヒドロキシフェニル)ノナン、
1,1-ビス(4-ヒドロキシフェニル)デカン、
1,1-ビス(4-ヒドロキシフェニル)ドデカン、
等のビス(ヒドロキシアリール)アルカン類;
1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-3,3-ジメチルシクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-3,4-ジメチルシクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-3,5-ジメチルシクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-3,3,5-トリメチルシクロヘキサン、
1,1-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)-3,3,5-トリメチルシクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-3-プロピル-5-メチルシクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-3-tert-ブチル-シクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-4-tert-ブチル-シクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-3-フェニルシクロヘキサン、
1,1-ビス(4-ヒドロキシフェニル)-4-フェニルシクロヘキサン、
等のビス(ヒドロキシアリール)シクロアルカン類;
9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン等のカルド構造含有ビスフェノール類;
4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルフィド等のジヒドロキシジアリールスルフィド類;
4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルホン等のジヒドロキシジアリールスルホン類;
等が挙げられる。
なお、芳香族ジヒドロキシ化合物は、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
エタン-1,2-ジオール、プロパン-1,2-ジオール、プロパン-1,3-ジオール、2,2-ジメチルプロパン-1,3-ジオール、2-メチル-2-プロピルプロパン-1,3-ジオール、ブタン-1,4-ジオール、ペンタン-1,5-ジオール、ヘキサン-1,6-ジオール、デカン-1,10-ジオール等のアルカンジオール類;
ポリカーボネート樹脂の製造方法は、特に限定されるものではなく、任意の方法を採用できる。その例を挙げると、界面重合法、溶融エステル交換法、ピリジン法、環状カーボネート化合物の開環重合法、プレポリマーの固相エステル交換法などを挙げることができる。
以下、これらの方法のうち、特に好適なものについて具体的に説明する。
まず、ポリカーボネート樹脂を界面重合法で製造する場合について説明する。
界面重合法では、反応に不活性な有機溶媒及びアルカリ水溶液の存在下で、通常pHを9以上に保ち、ジヒドロキシ化合物とカーボネート前駆体(好ましくは、ホスゲン)とを反応させた後、重合触媒の存在下で界面重合を行うことによってポリカーボネート樹脂を得る。なお、反応系には、必要に応じて分子量調整剤(末端停止剤)を存在させるようにしてもよく、ジヒドロキシ化合物の酸化防止のために酸化防止剤を存在させるようにしてもよい。
なお、反応温度は通常0~40℃であり、反応時間は通常は数分(例えば、10分)~数時間(例えば、6時間)である。
次に、ポリカーボネート樹脂を溶融エステル交換法で製造する場合について説明する。
溶融エステル交換法では、例えば、炭酸ジエステルとジヒドロキシ化合物とのエステル交換反応を行う。
一方、炭酸ジエステルとしては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジ-tert-ブチルカーボネート等の炭酸ジアルキル化合物;ジフェニルカーボネート;ジトリルカーボネート等の置換ジフェニルカーボネートなどが挙げられる。中でも、ジフェニルカーボネート及び置換ジフェニルカーボネートが好ましく、特にジフェニルカーボネートがより好ましい。なお、炭酸ジエステルは1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
また、より積極的な調整方法としては、反応時に別途、末端停止剤を混合する方法が挙げられる。この際の末端停止剤としては、例えば、一価フェノール類、一価カルボン酸類、炭酸ジエステル類などが挙げられる。なお、末端停止剤は、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
なお、粘度平均分子量の異なる2種類以上のポリカーボネート樹脂を混合して用いてもよく、この場合には、粘度平均分子量が上記の好適な範囲外であるポリカーボネート樹脂を混合してもよい。
ただし、再生されたポリカーボネート樹脂は、ポリカーボネート樹脂のうち、80質量%以下であることが好ましく、中でも50質量%以下であることがより好ましい。再生されたポリカーボネート樹脂は、熱劣化や経年劣化等の劣化を受けている可能性が高いため、このようなポリカーボネート樹脂を前記の範囲よりも多く用いた場合、色相や機械的物性を低下させる可能性があるためである。
本発明の薄肉光学部品用ポリカーボネート樹脂組成物は、下記一般式(1)で表されるポリアルキレンエーテルグリコール化合物(B)を含有する。
ポリアルキレンエーテルグリコール化合物(B)としては、他の共重合成分との共重合体であってもよいが、ポリアルキレンエーテルグリコール単独重合体が好ましい。
脂肪酸エステルを構成する脂肪酸としては、炭素数1~22の1価又は2価の脂肪酸、例えば、1価の飽和脂肪酸、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキジン酸、ベヘン酸や、1価の不飽和脂肪酸、例えば、オレイン酸、エライジン酸、リノール酸、リノレン酸、アラキドン酸などの不飽和脂肪酸、また炭素数10以上の二価の脂肪酸、例えば、セバシン酸、ウンデカン二酸、ドデカン二酸、テトラデカン二酸、タプシア酸及びデセン二酸、ウンデセン二酸、ドデセン二酸である。
これらの脂肪酸は一種又は二種以上組み合せて使用できる。前記脂肪酸には、1つ又は複数のヒドロキシル基を分子内に有する脂肪酸も含まれる。
ここでいうポリアルキレンエーテルグリコール化合物の数平均分子量はJIS K1577に準拠して測定した水酸基価に基づいて算出した数平均分子量である。
本発明のポリカーボネート樹脂組成物は、リン系安定剤を含有することを必要とする。リン系安定剤を含有することで、本発明のポリカーボネート樹脂組成物の色相が良好なものとなり、さらに耐熱変色性が向上する。
リン系安定剤としては、公知の任意のものを使用できる。具体例を挙げると、リン酸、ホスホン酸、亜燐酸、ホスフィン酸、ポリリン酸などのリンのオキソ酸;酸性ピロリン酸ナトリウム、酸性ピロリン酸カリウム、酸性ピロリン酸カルシウムなどの酸性ピロリン酸金属塩;リン酸カリウム、リン酸ナトリウム、リン酸セシウム、リン酸亜鉛など第1族または第2B族金属のリン酸塩;ホスフェート化合物、ホスファイト化合物、ホスホナイト化合物などが挙げられるが、ホスファイト化合物が特に好ましい。ホスファイト化合物を選択することで、より高い耐変色性と連続生産性を有するポリカーボネート樹脂組成物が得られる。
このようなホスファイト化合物としては、例えば、トリフェニルホスファイト、トリス(モノノニルフェニル)ホスファイト、トリス(モノノニル/ジノニル・フェニル)ホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、モノオクチルジフェニルホスファイト、ジオクチルモノフェニルホスファイト、モノデシルジフェニルホスファイト、ジデシルモノフェニルホスファイト、トリデシルホスファイト、トリラウリルホスファイト、トリステアリルホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールホスファイト、ビス(2,6-ジ-tert-ブチルフェニル)オクチルホスファイト、2,2-メチレンビス(4,6-ジ-tert-ブチルフェニル)オクチルホスファイト、テトラキス(2,4-ジ-tert-ブチルフェニル)-4,4’-ビフェニレン-ジホスファイト、6-[3-(3-tert-ブチル-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]-ジオキサホスフェピン等が挙げられる。
本発明のポリカーボネート樹脂組成物は、さらにエポキシ化合物(D)を含有することが好ましい。エポキシ化合物を含有することで、本発明のポリカーボネート樹脂組成物の色相がより良好なものとなり、さらに耐熱変色性がより向上する。
エポキシ化合物は、単独で用いても2種以上組み合わせて用いてもよい。
エポキシ化合物(D)を含有する場合には、ポリカーボネート樹脂組成物中の、リン系安定剤(C)とエポキシ化合物(D)の含有量の比は、(C)/(D)の質量比で0.5~10の範囲にあることが好ましい。(C)/(D)の質量比が0.5を下回ると色相、特に初期YI値が悪くなりやすく、10を超えると耐熱変色性が悪くなりやすい。(C)/(D)の質量比は、より好ましくは0.7以上であり、さらに好ましくは0.8以上であり、また、より好ましくは8以下、さらに好ましくは7以下、特に好ましくは8以下である。
本発明のポリカーボネート樹脂組成物は、上記した以外のその他の添加剤、例えば、酸化防止剤、離型剤、紫外線吸収剤、蛍光増白剤、顔料、染料、ポリカーボネート樹脂以外の他のポリマー、難燃剤、耐衝撃改良剤、帯電防止剤、可塑剤、相溶化剤などの添加剤を含有することができる。これらの添加剤は一種または二種以上を配合してもよい。
本発明のポリカーボネート樹脂組成物の製造方法に制限はなく、公知のポリカーボネート樹脂組成物の製造方法を広く採用でき、ポリカーボネート樹脂(A)、ポリアルキレンエーテルグリコール(B)及びリン系安定剤(C)、並びに、必要に応じて配合されるその他の成分を、例えばタンブラーやヘンシェルミキサーなどの各種混合機を用い予め混合した後、バンバリーミキサー、ロール、ブラベンダー、単軸混練押出機、二軸混練押出機、ニーダーなどの混合機で溶融混練する方法が挙げられる。なお、溶融混練の温度は特に制限されないが、通常240~320℃の範囲である。
波長420nmでの分光透過率は、導光板等の光学部品でも多用される青色LEDの波長領域に近接する波長域での透過率であり、またこの波長域での透過率が低いと黄色味が増加することになる。
なお、波長420nmでの分光透過率は、射出成形された長光路成形品(300mm×7mm×4mm)を用い300mmの光路長で測定され、具体的には後記実施例に記載の方法に従って行われる。
本発明の薄肉光学部品用ポリカーボネート樹脂組成物は、上記したように各成分を溶融混練して、通常はペレットとされる。ポリカーボネート樹脂ペレットとしては、楕円柱状の形状を有するペレットとすることが好ましい。
図1は、その薄肉光学部品用ポリカーボネート樹脂ペレットの摸式図である。
好ましいポリカーボネート樹脂ペレットは、長さLが2.0~5.0mmの範囲にあり、ペレットの楕円断面の長径dと短径aの比(d/a)が1.5~4の範囲にあり、かつ短径aが1.0~3.0mmの範囲にあることを特徴とする。
長径dと短径aの比(d/a)は、好ましくは1.6以上であり、より好ましくは1.7以上、さらに好ましくは1.8以上であり、また好ましくは3.5以下であり、より好ましくは3.0以下である。
このようなポリカーボネート樹脂ペレットの微粉発生の量は、樹脂ペレット500gを外径125mm、全高233mmの容量2リットルのポリエチレン製密閉容器に収納し、それを50リットルのタンブラーに入れて固定し、30rpmの回転数で20分間回転させた後に発生する粒径1mm以下の微粉の量は、好ましくは50ppm以下である。
上記ポリカーボネート樹脂ペレットを製造する方法としては、各種の方法が適用可能であるが、以下にその好適な態様を説明する。
ポリカーボネート樹脂以外の他の成分は、押出機に投入される前の任意の段階で配合することができる。例えば、タンブラー、ヘンシェルミキサー、ブレンダーによって全成分を配合したのち、必要に応じてフィーダーを介してホッパーシュートに投入し、押出機に供給してもよい。押出機には一軸押出機、二軸押出機などが使用出来る。また、ポリカーボネート樹脂とは別経路でホッパーシュートに供給してもよい。
楕円断面状のストランドは、その長径を略水平にして引き取りローラーによって引き取られ、冷却水槽に溜められた水中を搬送されるようにして、冷却される。樹脂の劣化を少なくするために、ストランドがダイから押し出されてから水に入るまでの時間は短い方が良い。通常は、ダイから押し出されてから1秒以内に水中に入るのが良い。
ポリカーボネート樹脂ペレットを押出機の吐出ノズル2から押出されたストランド1は、冷却水槽3に導入して冷却された後、引き取りローラーのサポートC、B、Aに順に支持されながら引き取られ、ペレタイザー4に送られる。この際、ストランドの引取速度(Vx)が100mm/secで、ストランド1を支える同じ高さにあるサポートC及びAとC-A間にあるサポートBの高低差が290mmであるとき、1時間以上の連続運転でストランドが折れないサポートCとサポートAの間隔として定義される間隔(Xmm、以下「限界間隔」ともいう。)が、300mm以下であることが好ましい。
本発明の薄肉光学部品用ポリカーボネート樹脂組成物は、上記したポリカーボネート樹脂組成物をペレタイズしたペレットを各種の成形法で成形して薄肉光学部品を製造することができる。またペレットを経由せずに、押出機で溶融混練された樹脂を直接、成形して薄肉光学部品にすることもできる。
なお、樹脂温度とは、直接測定することが困難な場合はバレル設定温度として把握される。
導光板は、液晶バックライトユニットや各種の表示装置、照明装置の中で、LED等の光源の光を導光するためのものであり、側面または裏面等から入れた光を、通常表面に設けられた凹凸により拡散させ、均一の光を出す。その形状は、通常平板状であり、表面には凹凸を有していても有していなくてもよい。
導光板の成形は、通常、好ましくは射出成形法、超高速射出成形法、射出圧縮成形法などにより行われる。
本発明の樹脂組成物を用いて成形した導光板は、白濁や透過率の低下がなく、透過率および色相が極めて良好である。
使用した原料は以下の表1の通りである。
なお、ポリカーボネート樹脂(A)の粘度平均分子量は、ウベローデ粘度計を用いて塩化メチレン中20℃の極限粘度[η]を測定し、以下の式より求めた。
[η]=1.23×10-4×(Mv)0.83
上記した各成分を、表2及び表3に記した割合(質量部)で配合し、タンブラーにて20分混合した後、スクリュー径40mmのベント付単軸押出機(田辺プラスチック機械社製「VS-40」)により、シリンダー温度240℃で溶融混練し、ストランドカットによりペレットを得た。
得られたペレットを120℃で5~7時間、熱風循環式乾燥機により乾燥した後、射出成形機(東芝機械社製「EC100SX-2A」)により、樹脂温度340℃、金型温度80℃で長光路成形品(300mm×7mm×4mm)を成形した。
この長光路成形品について、300mmの光路長でYI(黄変度)と波長420nmの分光透過率(単位:%)の測定を行った。測定には長光路分光透過色計(日本電色工業社製「ASA 1」、C光源、2°視野)を使用した。
以上の評価結果を以下の表2および表3に示す。
実施例1において、B1成分を4質量部にした以外は実施例1と同様の方法でペレット化を検討したが、押出機による溶融混練の際のストランドの断線が多発し、樹脂組成物ペレットの作成が困難であった。
一方、表3の比較例のものは300mmのYIが実施例のものに較べて、悪いことが分かる。さらに光線透過率も低い。
使用した原料は以下の表4の通りである。
上記した各成分を、表5及び表6に記した割合(質量部)で配合し、タンブラーにて20分混合した後、スクリュー径40mmのベント付単軸押出機(田辺プラスチック機械社製「VS-40」)により、シリンダー温度240℃で溶融混練し、ストランドカットによりペレットを得た。
得られたペレットを120℃で5~7時間、熱風循環式乾燥機により乾燥した後、射出成形機(東芝機械社製「EC100SX-2A」)により、樹脂温度340℃、金型温度80℃で長光路成形品(300mm×7mm×4mm)を成形した。
この長光路成形品について、300mmの光路長でYI(黄変度)(以下、「初期YI」)と波長420nmの分光透過率(単位:%)の測定を行った。測定には長光路分光透過色計(日本電色工業社製「ASA 1」、C光源、2°視野)を使用した。
さらに、長光路成形品を、85℃で800時間保持した後、300mm光路長でYIを測定(処理後YI)し、YI値の差(ΔYI=処理後YI-初期YI)を求めた。
以上の評価結果を以下の表5及び表6に示す。
前記表1に記載した各成分を、前記表2の実施例5に記した割合(質量部)で配合し、タンブラーにて20分混合した後、ベント式二軸押出機(日本製鋼所社製「TEX44αII」)のホッパーから押出機に連続的に供給し、押出機内で溶融混合し、シリンダー温度240℃、吐出量150kg/h、スクリュー回転数250rpmの押出条件にて、長径6.5mm、短径3.5mmの楕円状のダイス穴を有するダイスを、その長径を水平にして設けた押出ノズルから、ストランド状にその楕円断面の長径を略水平にして押出し、冷却水槽に導入して、ストランドの引取速度40m/min、カッター刃の回転速度600rpmで、ペレタイザーで切断してポリカーボネート樹脂のペレットを得た。
得られたペレットの長径と短径、長さを測定し、それぞれ100個の平均値を示した。長径/短径の平均値の比をペレット扁平率とした。
ペレットの長径は2.9mm、短径は1.5mm、ペレットの長さは2.9mm、長径/短径の比は1.9であった。
ダイスから出てくるストランドは、押出の方向が定まらずに蛇行することを防ぐため、ストランドにサポートを押し付けて一定の負荷をかけることにより、ストランドが真直ぐに押出されるようにしている。
この状態で、1時間当たりのストランドが切れた回数をカウントし、押出の安定性を評価した。
ストランド切れ回数は0回であった。
また、ストランドの限界強度を以下の方法で評価した。
図2に示すように、得られたポリカーボネート樹脂ペレットを押出機から押出された樹脂ストランドは、サポートCからサポートB、サポートAに支えながらペレタイザーに送られる。樹脂ストランドの限界強度は、図3に詳細に示すとおり、ストランドの引取速度(Vx)が100mm/secで、ストランドを支える同じ高さにあるサポートC及びAとサポートBの高低差が290mmであるとき、1時間以上の連続運転でストランドが折れない同じ高さのサポートCとサポートAの間隔(Xmm)として評価した。
サポートの限界間隔は260mmであった。
得られたポリカーボネート樹脂ペレット500gを外径125mm、全高233mmの容量2リットルのポリエチレン製密閉容器に収納し、それを50リットルのタンブラー(誠和鉄工所社製「SKD-50」)に入れて固定し、30rpmの回転数で20分間回転させ、ペレット同士が擦れて微粉が発生する状況にした。
微粉量の測定は、水とエチルアルコールを1:1で混合した液体1リットル中に振動試験後のペレット500gを入れて充分に撹拌した後、濾紙を用いてペレットの微粉を含む上澄み液を濾過した後の濾紙を120℃のオーブンで2時間乾燥した後の質量を測定し、濾紙質量の純増量から付着微粉量(質量ppm)を算出し、それを微粉発生量とした。本測定における微粉の粒径は1mm以下である。
微粉発生量は35質量ppmであった。
得られたポリカーボネート樹脂ペレットを用い、射出成形機(東芝機械社製「EC100SX-2A」)により、340℃の温度で、100mm×100mm×0.4mm厚の薄肉平板を成形し、10枚当たりの白点不良を生じた個数(枚数)をカウントした。
白点不良は0個であった。
得られたポリカーボネート樹脂ペレット100個について、目視観察を行い、真空ボイドが存在するペレットの数をカウントした。
真空ボイドが存在したペレットの個数は0個であった。
前記表1に記載した各成分を、前記表2の実施例7に記した割合(質量部)で配合し、タンブラーにて20分混合した後、ベント式二軸押出機(日本製鋼所社製「TEX44αII」)のホッパーから押出機に連続的に供給し、押出機内で溶融混合し、シリンダー温度240℃、吐出量150kg/h、スクリュー回転数250rpmの押出条件にて、長径6.5mm、短径2.9mmの楕円状のダイス穴を有するダイスを、その長径を水平にして設けた押出ノズルから、ストランド状にその楕円断面の長径を略水平にして押出し、水槽に導入して、ストランドの引取速度40m/min、カッター刃の回転速度600rpmで、ペレタイザーで切断してポリカーボネート樹脂のペレットを得た。
ストランド切れ回数は0回であり、サポートの限界間隔は270mmであった。微粉発生量は34質量ppm、白点不良は0個、真空ボイドが存在したペレットの個数は0個であった。
前記表4に記載した各成分を、前記表5の実施例9に記した割合で(質量部)で配合し、タンブラーにて20分混合した後、ベント式二軸押出機(日本製鋼所社製「TEX44αII」)のホッパーから押出機に連続的に供給し、押出機内で溶融混合し、シリンダー温度240℃、吐出量150kg/h、スクリュー回転数250rpmの押出条件にて、長径6.5mm、短径3.5mmの楕円状のダイス穴を有するダイスを、その長径を水平にして設けた押出ノズルから、ストランド状にその楕円断面の長径を略水平にして押出し、水槽に導入して、ストランドの引取速度40m/min、カッター刃の回転速度600rpmで、ペレタイザーで切断してポリカーボネート樹脂のペレットを得た。
ストランド切れ回数は0回であり、サポートの限界間隔は260mmであった。微粉発生量は35質量ppm、白点不良は0個、真空ボイドが存在したペレットの個数は0個であった。
Claims (15)
- さらに、エポキシ化合物(D)を0.0005~0.2質量部含有し、リン系安定剤(C)とエポキシ化合物(D)の含有量の質量比(C)/(D)が0.5~10である請求項1に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
- ポリカーボネート樹脂(A)の粘度平均分子量(Mv)が10,000~15,000である請求項1又は2に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
- ポリカーボネート樹脂(A)の粘度平均分子量(Mv)が11,000~14,500である請求項1~3のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
- ポリアルキレンエーテルグリコール化合物(B)がポリテトラメチレンエーテルグリコールである請求項1~4のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
- リン系安定剤(C)がペンタエリスリトールジホスファイト構造を有する安定剤である請求項1~5のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
- 300mmの光路長で測定した波長420nmでの分光透過率が55%以上である請求項1~6のいずれか1項に記載の薄肉光学部品用ポリカーボネート樹脂組成物。
- 請求項1~7のいずれか1項に記載のポリカーボネート樹脂組成物を成形した薄肉光学部品。
- 1mm以下の厚みを有する導光板である請求項8に記載の薄肉光学部品。
- 請求項1~7のいずれか1項に記載のポリカーボネート樹脂組成物を305~380℃で射出成形することを特徴とする肉厚が1mm以下の薄肉光学部品の製造方法。
- 請求項1~7のいずれか1項に記載のポリカーボネート樹脂組成物からなる楕円柱状のペレットであって、長さが2.0~5.0mmであり、その楕円断面の長径/短径の比が1.5~4、短径が1.0~3.0mmであることを特徴とする薄肉光学部品用ポリカーボネート樹脂ペレット。
- 前記ポリカーボネート樹脂ペレットは、ポリカーボネート樹脂ペレット500gを収納した外径125mm、全高233mmの容量2リットルのポリエチレン製密閉容器に収納したものを50リットルのタンブラーに入れて固定し、30rpmの回転数で20分間回転させた後に発生する粒径1mm以下の微粉の量が50ppm以下である請求項11に記載の薄肉光学部品用ポリカーボネート樹脂ペレット。
- ペレットの断面楕円の長径/短径の比が1.8~4である請求項11又は12に記載の薄肉光学部品用ポリカーボネート樹脂ペレット。
- 請求項11~13のいずれか1項に記載の樹脂ペレットを製造する方法であって、粘度平均分子量が10,000~15,000のポリカーボネート樹脂を、押出機の先端部に設けた楕円状のダイス穴を有する吐出ノズルから、断面楕円の長径部を略水平状態にしてストランドとして押出し、これを冷却水槽中で冷却固化し、ストランドカッターによってカットすることを特徴とする薄肉光学部品用ポリカーボネート樹脂ペレットの製造方法。
- ストランドの引取速度が100mm/secにおけるストランドを支えるサポートの高低差が290mmであるとき、1時間以上の連続運転でストランドが折れない、同じ高さのサポートの間隔が300mm以下である請求項14に記載の薄肉光学部品用ポリカーボネート樹脂ペレットの製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167001809A KR102121093B1 (ko) | 2013-07-26 | 2014-06-03 | 박육 광학 부품용 폴리카르보네이트 수지 조성물 및 박육 광학 부품 |
US14/894,671 US9701835B2 (en) | 2013-07-26 | 2014-06-03 | Polycarbonate resin composition for thin optical component, and thin optical component |
CN201480042499.0A CN105431488B (zh) | 2013-07-26 | 2014-06-03 | 薄壁光学构件用聚碳酸酯树脂组合物及薄壁光学构件 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-155539 | 2013-07-26 | ||
JP2013155539A JP5699188B2 (ja) | 2013-07-26 | 2013-07-26 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
JP2014043838 | 2014-03-06 | ||
JP2014-043838 | 2014-03-06 | ||
JP2014-081958 | 2014-04-11 | ||
JP2014081958A JP5699240B1 (ja) | 2014-03-06 | 2014-04-11 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015011994A1 true WO2015011994A1 (ja) | 2015-01-29 |
Family
ID=52393047
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/064717 WO2015011994A1 (ja) | 2013-07-26 | 2014-06-03 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2015011994A1 (ja) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016111117A1 (ja) * | 2015-01-07 | 2016-07-14 | 三菱エンジニアリングプラスチックス株式会社 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
WO2016111101A1 (ja) * | 2015-01-07 | 2016-07-14 | 三菱エンジニアリングプラスチックス株式会社 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
WO2016194749A1 (ja) | 2015-05-29 | 2016-12-08 | 出光興産株式会社 | ポリカーボネート樹脂組成物及びその成形品 |
JP2016222860A (ja) * | 2015-06-03 | 2016-12-28 | 住化スタイロンポリカーボネート株式会社 | ポリカーボネート樹脂組成物およびそれからなる光学用成形品 |
EP3070124A4 (en) * | 2013-11-11 | 2017-07-12 | Idemitsu Kosan Co., Ltd. | Polycarbonate resin composition |
CN107109046A (zh) * | 2015-02-03 | 2017-08-29 | 三菱工程塑胶株式会社 | 芳香族聚碳酸酯树脂组合物及其成型品 |
JP2017197704A (ja) * | 2016-04-20 | 2017-11-02 | 住化ポリカーボネート株式会社 | ポリカーボネート樹脂組成物及び光学用成形品 |
CN107949604A (zh) * | 2015-11-27 | 2018-04-20 | 三菱工程塑胶株式会社 | 芳香族聚碳酸酯树脂组合物及其成型品 |
JP2019035098A (ja) * | 2017-02-01 | 2019-03-07 | 出光興産株式会社 | ポリカーボネート樹脂組成物 |
US10472477B2 (en) | 2015-01-07 | 2019-11-12 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition for thin optical component, and thin optical component |
CN110546204A (zh) * | 2017-04-18 | 2019-12-06 | 三菱工程塑料株式会社 | 光学部件用聚碳酸酯树脂组合物和光学部件 |
JPWO2019026784A1 (ja) * | 2017-07-31 | 2020-05-28 | 出光興産株式会社 | 芳香族ポリカーボネート樹脂組成物及び光学成形品 |
JP2020193253A (ja) * | 2019-05-27 | 2020-12-03 | 三菱エンジニアリングプラスチックス株式会社 | ポリカーボネート樹脂組成物 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1135692A (ja) * | 1997-07-23 | 1999-02-09 | Mitsubishi Eng Plast Kk | 光ディスク基板用ポリカーボネート成形材料 |
JP2000234052A (ja) * | 1999-02-16 | 2000-08-29 | Mitsubishi Engineering Plastics Corp | 光ディスク基板用ポリカーボネート成形材料 |
WO2011083635A1 (ja) * | 2010-01-07 | 2011-07-14 | 出光興産株式会社 | 芳香族ポリカーボネート樹脂組成物及びそれを用いた光学成形品 |
JP2013000913A (ja) * | 2011-06-13 | 2013-01-07 | Asahi Kasei Chemicals Corp | 押出機およびそれを用いた溶融混練方法 |
JP2013139097A (ja) * | 2011-12-28 | 2013-07-18 | Idemitsu Kosan Co Ltd | ポリカーボネート樹脂組成物ペレット及びその製造方法 |
JP2013231899A (ja) * | 2012-05-01 | 2013-11-14 | Mitsubishi Engineering Plastics Corp | 導光板用ポリカーボネート樹脂組成物および導光板 |
-
2014
- 2014-06-03 WO PCT/JP2014/064717 patent/WO2015011994A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1135692A (ja) * | 1997-07-23 | 1999-02-09 | Mitsubishi Eng Plast Kk | 光ディスク基板用ポリカーボネート成形材料 |
JP2000234052A (ja) * | 1999-02-16 | 2000-08-29 | Mitsubishi Engineering Plastics Corp | 光ディスク基板用ポリカーボネート成形材料 |
WO2011083635A1 (ja) * | 2010-01-07 | 2011-07-14 | 出光興産株式会社 | 芳香族ポリカーボネート樹脂組成物及びそれを用いた光学成形品 |
JP2013000913A (ja) * | 2011-06-13 | 2013-01-07 | Asahi Kasei Chemicals Corp | 押出機およびそれを用いた溶融混練方法 |
JP2013139097A (ja) * | 2011-12-28 | 2013-07-18 | Idemitsu Kosan Co Ltd | ポリカーボネート樹脂組成物ペレット及びその製造方法 |
JP2013231899A (ja) * | 2012-05-01 | 2013-11-14 | Mitsubishi Engineering Plastics Corp | 導光板用ポリカーボネート樹脂組成物および導光板 |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3070124A4 (en) * | 2013-11-11 | 2017-07-12 | Idemitsu Kosan Co., Ltd. | Polycarbonate resin composition |
US9783674B2 (en) | 2013-11-11 | 2017-10-10 | Idemitsu Kosan Co., Ltd. | Polycarbonate resin composition |
US10472477B2 (en) | 2015-01-07 | 2019-11-12 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition for thin optical component, and thin optical component |
WO2016111101A1 (ja) * | 2015-01-07 | 2016-07-14 | 三菱エンジニアリングプラスチックス株式会社 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
WO2016111117A1 (ja) * | 2015-01-07 | 2016-07-14 | 三菱エンジニアリングプラスチックス株式会社 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
CN107109046A (zh) * | 2015-02-03 | 2017-08-29 | 三菱工程塑胶株式会社 | 芳香族聚碳酸酯树脂组合物及其成型品 |
WO2016194749A1 (ja) | 2015-05-29 | 2016-12-08 | 出光興産株式会社 | ポリカーボネート樹脂組成物及びその成形品 |
JP7271860B2 (ja) | 2015-05-29 | 2023-05-12 | 出光興産株式会社 | ポリカーボネート樹脂組成物及びその成形品 |
JPWO2016194749A1 (ja) * | 2015-05-29 | 2018-03-15 | 出光興産株式会社 | ポリカーボネート樹脂組成物及びその成形品 |
US11034834B2 (en) | 2015-05-29 | 2021-06-15 | Idemitsu Kosan Co., Ltd. | Polycarbonate resin composition and molded article of same |
JP2016222860A (ja) * | 2015-06-03 | 2016-12-28 | 住化スタイロンポリカーボネート株式会社 | ポリカーボネート樹脂組成物およびそれからなる光学用成形品 |
CN107949604B (zh) * | 2015-11-27 | 2020-10-09 | 三菱工程塑胶株式会社 | 芳香族聚碳酸酯树脂组合物及其成型品 |
US10767043B2 (en) | 2015-11-27 | 2020-09-08 | Mitsubishi Enigineering-Plastics Corporation | Aromatic polycarbonate resin composition and molded article of the same |
CN107949604A (zh) * | 2015-11-27 | 2018-04-20 | 三菱工程塑胶株式会社 | 芳香族聚碳酸酯树脂组合物及其成型品 |
JP2017197704A (ja) * | 2016-04-20 | 2017-11-02 | 住化ポリカーボネート株式会社 | ポリカーボネート樹脂組成物及び光学用成形品 |
JP2019035098A (ja) * | 2017-02-01 | 2019-03-07 | 出光興産株式会社 | ポリカーボネート樹脂組成物 |
EP3578608A4 (en) * | 2017-02-01 | 2020-10-14 | Idemitsu Kosan Co.,Ltd. | POLYCARBONATE RESIN COMPOSITION |
JP7033051B2 (ja) | 2017-02-01 | 2022-03-09 | 出光興産株式会社 | ポリカーボネート樹脂組成物 |
CN110546204A (zh) * | 2017-04-18 | 2019-12-06 | 三菱工程塑料株式会社 | 光学部件用聚碳酸酯树脂组合物和光学部件 |
CN110546204B (zh) * | 2017-04-18 | 2021-08-17 | 三菱工程塑料株式会社 | 光学部件用聚碳酸酯树脂组合物和光学部件 |
JPWO2019026784A1 (ja) * | 2017-07-31 | 2020-05-28 | 出光興産株式会社 | 芳香族ポリカーボネート樹脂組成物及び光学成形品 |
US11525056B2 (en) | 2017-07-31 | 2022-12-13 | Idemitsu Kosan Co., Ltd. | Aromatic polycarbonate resin composition and optical molded article |
JP2020193253A (ja) * | 2019-05-27 | 2020-12-03 | 三菱エンジニアリングプラスチックス株式会社 | ポリカーボネート樹脂組成物 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6101856B1 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
KR102121093B1 (ko) | 박육 광학 부품용 폴리카르보네이트 수지 조성물 및 박육 광학 부품 | |
WO2015011994A1 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
JP5699240B1 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
JP5699188B2 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
JP5893774B1 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
JP2018028025A (ja) | 光学部材用ポリカーボネート樹脂組成物 | |
JP6587948B2 (ja) | 光学部品用ポリカーボネート樹脂組成物および光学部品 | |
JP6893340B2 (ja) | 光学部品用ポリカーボネート樹脂組成物および光学部品 | |
JP6416423B1 (ja) | 光学部品用ポリカーボネート樹脂組成物および光学部品 | |
JP6645886B2 (ja) | ポリカーボネート樹脂組成物 | |
JP6522818B2 (ja) | 光学部品用ポリカーボネート樹脂組成物及び光学部品 | |
JP6526871B2 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
WO2016111117A1 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
JP6490490B2 (ja) | ポリカーボネート樹脂組成物および薄肉光学部品 | |
JP6522493B2 (ja) | 光学部品用ポリカーボネート樹脂組成物および光学部品 | |
JP6396792B2 (ja) | 導光部材用ポリカーボネート樹脂組成物及び導光部材 | |
JP6446601B1 (ja) | 光学部品用ポリカーボネート樹脂組成物及び光学部品 | |
WO2018193702A1 (ja) | 光学部品用ポリカーボネート樹脂組成物及び光学部品 | |
JP6422734B2 (ja) | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 | |
JP2019214744A (ja) | ポリカーボネート樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480042499.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14830289 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14894671 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20167001809 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14830289 Country of ref document: EP Kind code of ref document: A1 |