CN107148449A - Thin walled optical part poly carbonate resin composition and thin walled optical part - Google Patents
Thin walled optical part poly carbonate resin composition and thin walled optical part Download PDFInfo
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- CN107148449A CN107148449A CN201580061019.XA CN201580061019A CN107148449A CN 107148449 A CN107148449 A CN 107148449A CN 201580061019 A CN201580061019 A CN 201580061019A CN 107148449 A CN107148449 A CN 107148449A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
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Abstract
There is provided：Thin walled optical part poly carbonate resin compositions and thin walled optical part highly transmissive forthright and with good form and aspect.A kind of thin walled optical part poly carbonate resin composition, it is characterized in that, relative to the mass parts of polycarbonate resin (A) 100, contain the mass parts of polytrimethylene glycol (B) 0.1~4, phosphorus system stabilizer (C) 0.005~0.5 mass parts.
Description
Technical field
The present invention relates to thin walled optical part poly carbonate resin composition and thin walled optical part, specifically, relate to
And high-transmission rate and thin walled optical part poly carbonate resin composition with good form and aspect and shaped
Thin walled optical part.
Background technology
Surface light source apparatus is incorporated into the liquid crystal display device such as used in PC, mobile phone, to adapt to
Slimming, lightweight, the demand of Labor-saving and High precision.In addition, incident light evenly and effectively is led into liquid in order to play
Crystalline substance shows the effect of side, and the surface light source apparatus is provided with the light guide plate of writing board shape or has the table of uniform pitch with its one side
The light guide plate in the wedge type section in face.In some cases, relief pattern is also formed in the surface of light guide plate to provide light scattering work(
Energy.
Such light guide plate is obtained by the injection moulding of thermoplastic resin, and foregoing relief pattern is by forming embedding
The transfer for entering the jog on thing surface is assigned.In the past light guide plate by resin material such as polymethyl methacrylate (PMMA) etc. Lai
Shaping；But, caused by the heat produced recently due to the demand of the display device to showing apparent image and near light source
The trend of high temperature in installations, therefore it has been replaced with the higher polycarbonate resin material of heat resistance.
The engineering properties of polycarbonate resin, thermal property, electrical property, have excellent weather resistance, but light transmittance is less than PMMA
Deng therefore, when constituting surface light source unit by the light guide plate and light source of polycarbonate resin, there is the problem of brightness is low.In addition, most
Closely, it is desirable to reduce the light in part and the colour difference of the position away from light in part of light guide plate, but polycarbonate resin and PMMA resins
Compare, the problem of there is easy xanthochromia.
Proposed in patent document 1, improved by adding acrylic resin and ester ring type epoxy light transmittance and
Proposed in the method for brightness, patent document 2, by the way that polycarbonate resin is terminal-modified, improve jog to light guide plate
Transferability, so as to improve the method for brightness, is proposed in patent document 3, by importing the copolyesters carbon with aliphatic segment
Acid esters, the method for improving above-mentioned transferability to improve brightness.
However, the method for patent document 1 is by adding acrylic resin so as to which form and aspect become good, but occur gonorrhoea, because
This can not improve light transmittance and brightness, by adding ester ring type epoxy, have the possibility that transmissivity is improved, but unconfirmed arrive
The improvement of form and aspect.In the case of patent document 2 and patent document 3, mobility, the improvement of transferability can be expected,
But have the shortcomings that heat resistance reduction.
On the other hand, it is known that polyethylene glycol or poly- (2- methyl) second two are compounded in the thermoplastic resins such as polycarbonate resin
Recorded in alcohol etc., patent document 4, the polycarbonate resin of the gamma ray resistant irradiation property containing it, described in patent document 5
, with the thermoplastic resin composition that the antistatic behaviour and appearance for being mixed in PMMA etc. are excellent.
Moreover, being proposed in patent document 6, by with mixing：X-O-[CH(-R)-CH2- O] (R is hydrogen atom or carbon to n-Y
The alkyl of number 1~3) shown in polyethylene glycol or poly- (2- alkyl) ethylene glycol, so as to improve the motion of transmissivity, form and aspect.Pass through
It is compounded polyethylene glycol or poly- (2- alkyl) ethylene glycol, transmissivity, xanthochromia degree (yellowness index：YI) some visible improvement.
It is thin-walled property, large-scale thin in the various mobile terminals such as smart mobile phone, tablet personal computer type terminal however, particularly nearest
Wall with significant speed carry out, since by light guide plate enter light by underface type, carried out using by horizontal lateral edges into light
Peripheral type, as extra-thin light source, gradually require sufficient brightness.In such high-end light guide plate, present situation is with above-mentioned
Transmissivity that prior art is reached, YI levels will not meet and require specification.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 11-158364 publications
Patent document 2：Japanese Unexamined Patent Publication 2001-208917 publications
Patent document 3：Japanese Unexamined Patent Publication 2001-215336 publications
Patent document 4：Japanese Unexamined Patent Publication 1-22959 publications
Patent document 5：Japanese Unexamined Patent Publication 9-227785 publications
Patent document 6：No. 4069364 publications of Japanese Patent No.
The content of the invention
Problems to be solved by the invention
The present invention be in view of above-mentioned actual conditions and make, its object is to there is provided：It is original to polycarbonate resin
Characteristic does not have any destruction, transmissivity and the good thin walled optical part poly carbonate resin composition of form and aspect.
The solution used to solve the problem
The present inventor furthers investigate repeatedly in order to reach above-mentioned problem, as a result finds：By in polycarbonate resin with
Polytrimethylene glycol rather than (2- methyl) second two of the prior art that specific amount compounding methylene is bonded with straight-chain
Alcohol is such to have the material of methyl branch, it is surprising that with the polyethylene glycol described in prior art or poly- (2- alkane
Base) ethylene glycol compares, can also reach more excellent transmissivity and extremely good form and aspect, so far complete the present invention.
The present invention provides following thin walled optical part poly carbonate resin composition, thin walled optical part and thin walled optical
The manufacture method of part.
[1] a kind of thin walled optical part poly carbonate resin composition, it is characterised in that relative to polycarbonate resin
(A) 100 mass parts, contain the mass parts of polytrimethylene glycol (B) 0.1~4, phosphorus system stabilizer (C) 0.005~0.5 mass parts.
[2] the thin walled optical part poly carbonate resin composition according to above-mentioned [1], wherein, relative to poly- carbon
The mass parts of acid ester resin (A) 100, the epoxide (D) further containing 0.0005~0.2 mass parts.
[3] the thin walled optical part poly carbonate resin composition according to above-mentioned [1] or [2], wherein, poly- carbonic acid
The viscosity average molecular weigh (Mv) of ester resin (A) is 10000~15000.
[4] the thin walled optical part poly carbonate resin composition according to any one of above-mentioned [1]~[3], its
The spectral-transmission favtor at wavelength 420nm determined under 300mm optical path lengths is more than 50%.
[5] a kind of thin walled optical part, it is by the polycarbonate resin composition any one of above-mentioned [1]~[4]
Obtained from thing shaping.
[6] the thin walled optical part according to above-mentioned [5], it is the light guide plate of the thickness with below 1mm.
[7] a kind of wall thickness is the manufacture method of below 1mm thin walled optical part, by any one of above-mentioned [1]~[4] institute
The poly carbonate resin composition stated carries out injection moulding at 305~380 DEG C.
The effect of invention
According to the present invention, by containing polytrimethylene glycol (B) with above-mentioned amount, so as to provide to polycarbonate resin
The original characteristic of fat does not have any destruction and then transmissivity and the good thin walled optical part polycarbonate resin composition of form and aspect
There is provided the good thin walled optical part of transmissivity and form and aspect for thing.
Embodiment
Hereinafter, show that the present invention is described in detail for embodiment and example thing etc..
It should be noted that in this specification, in the case that "~" is not particularly illustrated, with comprising described in before and after it
Numerical value is used as the implication of lower limit and higher limit.
[summary]
The thin walled optical part poly carbonate resin composition of the present invention is characterised by, relative to polycarbonate resin
(A) 100 mass parts, contain the mass parts of polytrimethylene glycol (B) 0.1~4, phosphorus system stabilizer (C) 0.005~0.5 mass parts.
Hereinafter, each composition, thin walled optical part of poly carbonate resin composition to constituting the present invention etc. carries out detailed
Explanation.
[polycarbonate resin (A)]
The species of polycarbonate resin to being used in the present invention is not limited, and polycarbonate resin can use a kind
Two or more can be used with arbitrary ratio combine in any combination.
Polycarbonate resin is formula：The polymerization of-[- O-X-O-C (=O) -]-shown basic structure with carbonic acid key
Thing.
In formula, X is generally hydrocarbon, but in order to assign various characteristics, can also use the X for having imported hetero atom, heterodesmic.
In addition, polycarbonate resin can be divided into：Carbon with carbonic acid key Direct Bonding is the fragrant adoption carbon of aromatic series carbon
Acid ester resin and with the aliphatic polycarbonate resin that the carbon of carbonic acid key Direct Bonding is aliphatic carbon, can use.Its
In, from the viewpoints such as heat resistance, mechanical properties, electrical characteristics, optimization aromatic polycarbonate resin.
Specific species to polycarbonate resin is not limited, for example, can enumerate：Make dihydroxy compounds and carbonic ester
The carbonate polymer of precursors reaction.Now, on the basis of dihydroxy compounds and carbonate precursor, it can also make
Polyol etc. reacts.Alternatively, it is also possible to use the method reacted by carbonate precursor of carbon dioxide, with cyclic ether.
In addition, it can also be branched that carbonate polymer, which can be straight-chain,.Further, carbonate polymer can be by 1
Plant the homopolymer that repeat unit is constituted, or the copolymer with two or more repeat unit.Now copolymer can be selected
The various copolymerization forms such as random copolymer, block copolymer.It should be noted that generally, such carbonate polymer into
For thermoplastic resin.
, can when enumerating the example of aromatic dihydroxy compound in monomer as the raw material of aromatic polycarbonate resin
To enumerate：
The dihydroxy benzenes classes such as 1,2- dihydroxy benzenes, 1,3- dihydroxy benzenes (that is, resorcinol), Isosorbide-5-Nitrae-dihydroxy benzenes；
The dihydroxybiphenyl class such as 2,5- dihydroxybiphenyls, 2,2 '-dihydroxybiphenyl, 4,4 '-dihydroxybiphenyl；
2,2 '-dihydroxy -1,1 '-dinaphthalene, 1,2- dihydroxy naphthlenes, 1,3- dihydroxy naphthlenes, 2,3- dihydroxy naphthlenes, 1,6- dihydroxies
The dihydroxy naphthalenes such as base naphthalene, 2,6- dihydroxy naphthlenes, 1,7- dihydroxy naphthlenes, 2,7 dihydroxy naphthalene；
2,2 '-dihydroxy diphenyl ether, 3,3 '-dihydroxy diphenyl ether, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxy -3,
The dihydroxy diaryl ethers such as double (3- hydroxyphenoxies) benzene of 3 '-diformazan yl diphenyl ether, 1,4-, double (4- hydroxyphenoxies) benzene of 1,3-
Class；
2,2- double (4- hydroxy phenyls) propane (that is, bisphenol-A),
Double (4- hydroxy phenyls) propane of 1,1-,
2,2-bis(3-methyl-4-hydroxyphenyl) propane,
Double (3- methoxyl group -4- hydroxy phenyls) propane of 2,2-,
2- (4- hydroxy phenyls) -2- (3- methoxyl group -4- hydroxy phenyls) propane,
Double (3- tert-butyl-hydroxy phenyls) propane of 1,1-,
Double (3,5- dimethyl -4- hydroxy phenyls) propane of 2,2-,
Double (3- cyclohexyl -4- hydroxy phenyls) propane of 2,2-,
2- (4- hydroxy phenyls) -2- (3- cyclohexyl -4- hydroxy phenyls) propane,
α, α '-bis- (4- hydroxy phenyls) -1,4- diisopropyl benzenes,
Double [2- (4- the hydroxy phenyls) -2- propyl group] benzene of 1,3-,
Double (4- hydroxy phenyls) methane,
Double (4- hydroxy phenyls) cyclohexyl-methanes,
Double (4- hydroxy phenyls) phenylmethanes,
Double (4- hydroxy phenyls) (4- acrylic phenyl) methane,
Double (4- hydroxy phenyls) diphenyl methanes,
Double (4- hydroxy phenyls) naphthyl methanes,
Double (4- hydroxy phenyls) ethane of 1,1-,
Double (4- the hydroxy phenyls) -1- diphenylphosphino ethanes of 1,1-,
Double (4- the hydroxy phenyls) -1- naphthylethans of 1,1-,
Double (4- hydroxy phenyls) butane of 1,1-,
Double (4- hydroxy phenyls) butane of 2,2-,
Double (4- hydroxy phenyls) pentanes of 2,2-,
Double (4- hydroxy phenyls) hexanes of 1,1-,
Double (4- hydroxy phenyls) hexanes of 2,2-,
Double (4- hydroxy phenyls) octanes of 1,1-,
Double (4- hydroxy phenyls) octanes of 2,2-,
Double (4- hydroxy phenyls) heptane of 4,4-,
Double (4- hydroxy phenyls) nonanes of 2,2-,
Double (4- hydroxy phenyls) decane of 1,1-,
Double (4- hydroxy phenyls) dodecanes of 1,1-,
Deng double (hydroxyaryl) alkanes；
Double (4- hydroxy phenyls) pentamethylene of 1,1-,
1,1-bis(4-hydroxyphenyl)-cyclohexane,
Double (4- the hydroxy phenyls) -3,3- dimethyl cyclohexanes of 1,1-,
Double (4- the hydroxy phenyls) -3,4- dimethyl cyclohexanes of 1,1-,
Double (4- the hydroxy phenyls) -3,5- dimethyl cyclohexanes of 1,1-,
Double (4- the hydroxy phenyls) -3,3,5- trimethyl-cyclohexanes of 1,1-,
Double (4- hydroxyl -3,5- the 3,5-dimethylphenyls) -3,3,5- trimethyl-cyclohexanes of 1,1-,
Double (4- the hydroxy phenyls) -3- propyl group -5- hexahydrotoluenes of 1,1-, double (4- the hydroxy phenyls) -3- tert-butyl groups-rings of 1,1-
Hexane,
Double (4- the hydroxy phenyls) -4- tert-butyl-cyclos of 1,1-,
Double (4- the hydroxy phenyls) -3- cyclohexylbenzenes of 1,1-,
Double (4- the hydroxy phenyls) -4- cyclohexylbenzenes of 1,1-,
Deng double (hydroxyaryl) naphthenics；
Double (4- hydroxy phenyls) fluorenes of 9,9-,
The bisphenols of the structures containing Cardo such as double (the 4- hydroxy-3-methyls phenyl) fluorenes of 9,9-；
4,4 '-dihydroxydiphenyl thioether,
4,4 '-dihydroxy -3,3 ' the dihydroxy diaryl thioether class such as-dimethyl diphenyl sulfide；
4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxy -3,3 ' dihydroxy diaryl such as-dimethyl diphenyl sulfoxide
Sulfoxide type；
4,4 '-dihydroxy-diphenyl sulfone,
4,4 '-dihydroxy -3,3 ' the dihydroxy diaryl sulfone class such as-dimethyl diphenyl sulfone；
Deng.
In them, preferably double (hydroxyaryl) alkanes, wherein it is preferred that double (4- hydroxy phenyls) alkanes, from impact resistance, resistance to
Hot aspect is set out, double (4- hydroxy phenyls) propane (i.e., bisphenol-A) of particularly preferred 2,2-.
It should be noted that aromatic dihydroxy compound can use a kind can also in any combination with ratio group
Conjunction uses two or more.
In addition, when enumerating the example of the monomer of the raw material as aliphatic polycarbonate resin, can enumerate：
Ethane -1,2- glycol, propane -1,2- glycol, propane -1,3- glycol, 2,2- dimethylpropane -1,3- glycol, 2-
Methyl-2-propyl propane -1,3- glycol, butane -1,4- glycol, pentane -1,5- glycol, hexane -1,6- glycol, decane -1,10-
The alkanediol class such as glycol；
Pentamethylene -1,2- glycol, hexamethylene -1,2- glycol, hexamethylene -1,4- glycol, 1,4 cyclohexane dimethanol, 4-
The cycloalkanes glycols such as (2- hydroxyethyls) cyclohexanol, 2,2,4,4- tetramethyls-cyclobutane -1,3- glycol；
Ethylene glycol, 2, the glycols such as 2 '-oxo diethanol (that is, diethylene glycol), triethylene glycol, propane diols, the spiroglycol；
Double (the 2- '-hydroxyethoxies of 1,2- benzene dimethanols, 1,3- benzene dimethanols, 1,4- benzene dimethanols, 1,4- benzene diethanol, 1,3-
Base) benzene, double (2- hydroxyl-oxethyls) benzene of 1,4-, double (hydroxymethyl) naphthalenes of 2,3-, double (hydroxyl-oxethyl) naphthalenes of 1,6-, 4,4 '-connection
Double (2- hydroxyl-oxethyls) biphenyl of benzene dimethanol, 4,4 '-biphenyl diethanol, 1,4-, bisphenol-A double (2- hydroxyethyls) ether, bisphenol Ss
The aralkyl glycols such as double (2- hydroxyethyls) ethers；
1,2- oxirane (that is, oxirane), 1,2- expoxy propane (that is, expoxy propane), 1,2- cyclopentane epoxides, 1,
2- 7-oxa-bicyclo[4.1.0s, 1,4- 7-oxa-bicyclo[4.1.0s, 1- methyl isophthalic acids, 2- 7-oxa-bicyclo[4.1.0s, 2,3- epoxynorbornanes, 1,3- epoxies third
The ring-type ethers such as alkane；Deng.
In monomer as the raw material of polycarbonate resin, when enumerating the example of carbonate precursor, carboxylic acid halides, carbonic ester are used
Deng.It should be noted that carbonate precursor, which can use a kind, to use two or more with ratio combine in any combination.
As carboxylic acid halides, specifically it can such as enumerate：Phosgene；Bischloroformate body, the dihydroxy of dihydroxy compounds
Haloformates such as the mono-chloroformates body of compound etc..
As carbonic ester, specifically it can such as enumerate：The diaryl carbonates such as diphenyl carbonate, carboxylol ester
Class；The dialkyl carbonates such as dimethyl carbonate, diethyl carbonate；Double manganese ester body, the dihydroxy chemical combination of dihydroxy compounds
Carbonic ester body of the dihydroxy compounds such as monocarbonate body, the cyclic carbonate of thing etc..
The manufacture method of polycarbonate resin
Manufacture method to polycarbonate resin is not particularly limited, and can use any means., can be with when enumerating it
Enumerate：Interfacial polymerization, melt transesterification process, pyridine method, the ring-opening polymerisation method of cyclic carbonate compound, the solid phase of prepolymer
Ester-interchange method etc..
Hereinafter, particularly suitable method in these methods is specifically described.
Interfacial polymerization
First, the situation that polycarbonate resin is manufactured using interfacial polymerization is illustrated.
In interfacial polymerization, in the presence of to reaction for inactive organic solvent and aqueous alkali, generally pH is protected
Hold as more than 9, make dihydroxy compounds and carbonate precursor (being preferably phosgene) reaction, then in the presence of polymerization catalyst
Interfacial polymerization is carried out, so as to obtain polycarbonate resin.It should be noted that in reaction system, there may be as needed point
Son amount conditioning agent (end-capping reagent), it is anti-oxidant for dihydroxy compounds, there can also be antioxidant.
Dihydroxy compounds and carbonate precursor are as described above.It should be noted that in carbonate precursor, preferably using
Phosgene, is especially referred to as phosgenation using method during phosgene.
As being inactive organic solvent to reaction, for example, it can enumerate：Dichloromethane, 1,2- dichloroethanes, chloroform,
Chlorinated hydrocabons such as monochlorobenzene, dichloro-benzenes etc.；The aromatic hydrocarbons such as benzene,toluene,xylene；Deng.It should be noted that organic solvent can be with
Two or more can also be used using a kind with ratio combine in any combination.
As the alkali cpd contained in aqueous alkali, for example, it can enumerate：Sodium hydroxide, potassium hydroxide, lithium hydroxide,
The alkali metal compounds such as sodium acid carbonate, alkaline earth metal compound, wherein it is preferred that sodium hydroxide and potassium hydroxide.Need explanation
It is that alkali cpd, which can use a kind, to use two or more with ratio combine in any combination.
Concentration to the alkali cpd in aqueous alkali is not limited, generally, for the pH in the aqueous alkali by reaction
Control for 10~12, to use with 5~10 mass %.In addition, when being for example blown into phosgene, in order to using the pH of aqueous phase as 10~12, it is excellent
The mode for electing 10~11 as is controlled, it is preferred that the mol ratio of bisphenol compound and alkali cpd is set into usual 1：1.9
Above, wherein 1：More than 2.0, in addition usual 1：Less than 3.2, wherein 1：2.5 it is following.
As polymerization catalyst, for example, it can enumerate：The fat such as trimethylamine, triethylamine, tri-n-butylamine, tripropyl amine (TPA), trihexylamine
Race's tertiary amine；N, N '-dimethyl cyclohexylamine, N, the ester ring type tertiary amine such as N '-diethyl cyclohexylamine；N, N '-dimethyl aniline, N, N '-
The aromatic nitrile bases such as diethylaniline；The quaternary ammonium salts such as trimethyl benzyl ammonia chloride, tetramethyl ammonium chloride, triethyl benzyl ammonia chloride
Deng；Pyridine；Guanine；The salt of guanidine；Deng.It should be noted that polymerization catalyst can use a kind can also be in any combination
Two or more is used with ratio combine.
As molecular weight regulator, for example, it can enumerate：Aromatic series phenol with monovalence phenolic hydroxyl group；Methanol, butanol etc.
Aliphatic alcohol；Mercaptan；Phthalimide etc., wherein optimization aromatic phenol.As such aromatic series phenol, specifically,
It can include：M-methyl phenol, p-methyl phenol, a propylphenol, n-propyl phenol, p-t-butyl phenol, to chain alkyl
The alkyl-substituted phenols such as fortified phenol；Iso-propionyl phenol etc. contains vinyl phenol；Phenol containing epoxy radicals；Septichen, 2- first
The phenol containing carboxyl such as base -6- hydroxyphenyl acetic acids；Deng.It should be noted that molecular weight regulator can use a kind can also with appoint
The combination of meaning and ratio combine use two or more.
The consumption of molecular weight regulator is usually more than 0.5 mole relative to 100 moles of dihydroxy compounds, preferably 1
More than mole, in addition, usually less than 50 moles, preferably less than 30 moles.Should by making the consumption of molecular weight regulator be
Scope, can improve the heat endurance and hydrolytic resistance of resin combination.
During reaction, as long as the order of the mixing such as response matrix, reaction medium, catalyst, additive can be expected
Polycarbonate resin be exactly arbitrary, can arbitrarily set appropriate order.For example, being used as carbonate precursor using phosgene
When, if molecular weight regulator since the reaction of dihydroxy compounds and phosgene (phosgenation) to polymerisation when be
It can just be mixed during only with meaning period in office.
It should be noted that reaction temperature is usually 0~40 DEG C, the reaction time is usually several minutes (for example, 10 minutes)
~a few hours (such as 6 hours).
Melt transesterification process
Then, the situation that polycarbonate resin is manufactured using melt transesterification process is illustrated.
In melt transesterification process, for example, carry out the ester exchange reaction of carbonic diester and dihydroxy compounds.
Dihydroxy compounds is as described above.
On the other hand, as carbonic diester, for example, it can enumerate：Dimethyl carbonate, diethyl carbonate, dimethyl dicarbonate butyl ester
Deng dialkyl carbonate based compound；Diphenyl carbonate；Carbonic acid substituted diphenylamine ester such as carboxylol ester etc..Wherein, preferred carbonic acid two
Phenyl ester and carbonic acid substituted diphenylamine ester, particularly preferred diphenyl carbonate.It should be noted that carbonic diester can use a kind also may be used
To use two or more with ratio combine in any combination.
As long as the ratio of dihydroxy compounds and carbonic diester can obtain desired polycarbonate resin be exactly it is arbitrary,
Relative to 1 mole of dihydroxy compounds, carbonic diester more than equimolar amounts is preferably used, wherein more preferably using 1.01 moles
More than.It should be noted that the upper limit is usually less than 1.30 moles., can be by terminal hydroxyl amount by being set to such scope
Adjust to suitable scope.
In polycarbonate resin, there is its terminal hydroxyl amount has considerable influence to heat endurance, hydrolytic stability, tone etc.
Tendency.It therefore, it can utilize known any means adjustment terminal hydroxyl amount as needed.In ester exchange reaction, generally, lead to
Cross the blending ratio of adjustment carbonic diester and aromatic dihydroxy compound；Degree of decompression during ester exchange reaction etc., so as to
It has been adjusted the polycarbonate resin of terminal hydroxyl amount.It should be noted that by the operation, can generally also adjust and obtain
Polycarbonate resin molecular weight.
The blending ratio of carbonic diester and dihydroxy compounds is adjusted come in the case of adjusting terminal hydroxyl amount, its mixing ratio
Rate is as described above.
In addition, as more positive method of adjustment, can enumerate：The method that end-capping reagent is separately mixed during reaction.It is used as this
When end-capping reagent, can for example enumerate：Unitary phenols, monocarboxylic acid class, carbonic diester class etc..It should be noted that end-capping reagent
1 kind, which can be used, to use two or more with ratio combine in any combination.
When manufacturing polycarbonate resin using melt transesterification process, generally, ester exchange catalyst is used.Ester exchange catalyst
Any catalyst can be used.Wherein, alkali metal compound and/or alkaline earth metal compound are for example preferably used.In addition, auxiliary
The alkalization such as alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound, amine compound can also be applied in combination in ground
Compound.It should be noted that ester exchange catalyst can use a kind can also use 2 kinds with ratio combine in any combination
More than.
In melt transesterification process, reaction temperature is usually 100~320 DEG C.In addition, pressure during reaction is usually 2mmHg
Following reduced pressure., can subject to the foregoing as specific operation, side removes the accessory substances such as aromatic hydroxy compound
Side carries out melt polycondensation reaction.
Melt polycondensation reaction can be carried out using any means in batch (-type), continous way., will be anti-when being carried out with batch (-type)
Desired aromatic polycarbonate resin can be obtained as long as answering the order of the mixing such as matrix, reaction medium, catalyst, additive
It is exactly arbitrary, can arbitrarily sets appropriate order.Wherein, it is considered to during stability of polycarbonate resin etc., melting contracting
Poly- reaction is preferably carried out with continous way.
In melt transesterification process, catalyst deactivators can also be used as needed.It is used as catalyst deactivators, Ke Yiren
Meaning uses the compound for neutralizing ester exchange catalyst.When enumerating it, it can enumerate：The acid compound of sulfur-bearing and its derivative
Deng.It should be noted that catalyst deactivators can use a kind can also be used in any combination with ratio combine 2 kinds with
On.
The alkali metal or alkaline-earth metal that the consumption of catalyst deactivators contains relative to foregoing ester exchange catalyst is usually
More than 0.5 equivalent, more than preferably 1 equivalent, in addition, usually below 10 equivalents, below preferably 5 equivalents.And then, relative to
Polycarbonate resin, usually more than 1ppm, in addition, usually below 100ppm, be preferably below 20ppm.
For polycarbonate resin (A) molecular weight, to be surveyed according to using dichloromethane as solvent, at 25 DEG C of temperature
Viscosity average molecular weigh (Mv) meter of fixed solution viscosity conversion is preferably 10000~15000, is more preferably more than 10500, further
Preferably more than 11000, more than 11500 are particularly preferably, is most preferably more than 12000, more preferably less than 14500.Pass through
Make more than the lower limit that viscosity average molecular weigh is above range, can further improve the poly carbonate resin composition of the present invention
Mechanical strength, by making below the higher limit that viscosity average molecular weigh is above range, can suppress and improve the poly- carbonic acid of the present invention
The mobility reduction of ester resin composition, improves shaping processability, can carry out thin molded handling ease.
It should be noted that the different polycarbonate resin of more than two kinds of viscosity average molecular weigh can also be mixed and used,
In the case of above-mentioned, polycarbonate resin of the viscosity average molecular weigh outside above-mentioned suitable scope can also be mixed.
It should be noted that viscosity average molecular weigh [Mv] refers to, and using dichloromethane as solvent, using Ubbelohde viscometer,
Obtain the inherent viscosity [η] (unit dl/g) at 20 DEG C of temperature, by Schnell viscosity formula, i.e., η=1.23 × 10-4Mv0.83
The value calculated.In addition, inherent viscosity [η] refers to, the specific viscosity [η under each solution concentration [C] (g/dl) is determinedsp], by following
The value that formula is calculated.
The terminal hydroxyl concentration of polycarbonate resin is arbitrary, can suitably select and determine, usually 1000ppm with
Under, be preferably below 800ppm, more preferably below 600ppm.Thus, it is possible to further improve the delay of polycarbonate resin
Heat endurance and tone.In addition, for its lower limit, in the polycarbonate resin manufactured in particular with melt transesterification process, leading to
Often it is more than 10ppm, is preferably more than 30ppm, is more preferably more than 40ppm.Thus, it is possible to suppress the reduction of molecular weight, enter
One step improves the mechanical property of resin combination.
It should be noted that the unit of terminal hydroxyl concentration is to represent the quality of terminal hydroxyl relative to poly- carbonic acid with ppm
The quality of ester resin.Its assay method is the colorimetric assay (Macromol.Chem.88 215 based on titanium tetrachloride/Acetic
(1965) method described in).
Polycarbonate resin can individually (polycarbonate resin be individually not limited to only include a kind with polycarbonate resin
The scheme of polycarbonate resin, for example, with including including monomer composition, molecular weight a variety of polycarbonate resins different from each other
The implication of scheme is used) use, polycarbonate resin can also be combined with the alloy (mixture) of other thermoplastic resins and
Use.Further it can also for example be constituted in the form of the copolymer of following polycarbonate resin：For further carrying
High flame retardant, the purpose of impact resistance, for polycarbonate resin, with being total to for the oligomer with siloxane structure or polymer
Polymers；Thermo oxidative stability, the purpose of anti-flammability are improved for further, with the monomer with phosphorus atoms, oligomer or polymerizeing
The copolymer of thing；For the purpose for improving thermo oxidative stability, with the monomer with dihydroxy-anthracene quinone structure, oligomer or polymerizeing
The copolymer of thing；In order to improve optical property, there is the copolymerization of the oligomer or polymer of alkene architecture with polystyrene etc.
Thing；For the purpose for improving chemical proofing, with polyester resin oligomer or the copolymer of polymer；Deng.
In addition, raising, the raising of mobility of the outward appearance in order to realize formed products, polycarbonate resin can also be containing poly-
Carbonate oligomer.The viscosity average molecular weigh [Mv] of the polycarbonate oligomer is usually more than 1500, is preferably more than 2000, separately
Outside, usually less than 9500, be preferably less than 9000.The polycarbonate oligomer contained is further preferably set to polycarbonate resin
Below the 30 mass % of fat (including polycarbonate oligomer).
Further polycarbonate resin can be not only original raw material, or be regenerated by used product
Polycarbonate resin (so-called raw material recycle polycarbonate resin).
Wherein, the polycarbonate resin of regeneration is preferably below 80 mass %, wherein more preferably in polycarbonate resin
For below 50 mass %.This is because, the polycarbonate resin of regeneration is by heat deterioration, the possibility of the deterioration such as deterioration year in year out
Height, therefore during with more than aforementioned range using such polycarbonate resin, having makes form and aspect, the possibility of mechanical properties reduction
Property.
[polytrimethylene glycol (B)]
The thin walled optical part poly carbonate resin composition of the present invention contains polytrimethylene glycol (B).Poly- Sanya
Methyl glycol (B) is with [- CH2CH2CH2- O-] be construction unit polyethers, industrially, by using acid catalyst, make methylene
Trimethylene (or 1,3- propane diols) polycondensation that base is bonded with straight-chain and manufacture.Polytrimethylene glycol (B) with it is general
The polyethers for being referred to as polypropylene glycol is different.Polypropylene glycol is generally manufactured by the ring-opening polymerisation of expoxy propane, for poly- (2- alkane
Base) ethylene glycol is the polyethers being made up of the construction unit with methyl branch.
Trimethylene such as HOCH2CH2CH2Shown in OH, industrially manufacture by the following method：Utilize oxirane
Hydroformylation obtains 3-HPA, the method hydrogenated；Or by acrolein hydration, by gained 3-HPA Ni
Method that catalyst is hydrogenated etc..In addition, recently, by bioanalysis, make glycerine, glucose, starch etc. and micro-reduction,
Manufacture trimethylene.
The method for manufacturing polytrimethylene glycol by trimethylene is for example recorded in U.S. Patent Application Publication No.
In No. 20020010374 specifications of No. 20020007043 specifications and U.S. Patent Application Publication No., it can be urged by using acid
Agent makes trimethylene polycondensation and manufactured.As acid catalyst, it can enumerate：Sulfuric acid, fluosulfonic acid, phosphoric acid, to toluene sulphur
Acid, benzene sulfonic acid, phosphotungstic acid, phosphomolybdic acid, trifluoromethanesulfonic acid, particularly a preferred catalyst are sulfuric acid.
Polytrimethylene glycol (B) can be homopolymer, or with a kind in addition to trimethylene or 2 kinds
The copolymer of aklylene glycol above.Copolymer can select the various copolymerization forms such as random copolymer, block copolymer.
In addition, for polytrimethylene glycol (B), its end group is preferably hydroxyl.In addition, its single end or two ends
End can be blocked by alkyl ether, aryl ether, aralkyl ethers, fatty acid ester, aryl ester etc., and its performance, which is embodied, not to be influenceed,
Etherate or carboxylate can equally be used.
As the alkyl for constituting alkyl ether, straight-chain or branched can be used, is alkyl, the example of carbon number 1~22
Such as methyl, ethyl, propyl group, butyl, octyl group, lauryl, stearyl, can preferably enumerate polytrimethylene glycol methyl ether,
Ether, butyl ether, bay ether, stearyl ether etc..
It is used as the aryl for constituting aryl ether, it is preferred that preferred carbon number 6~22, more preferably carbon number 6~12, further excellent
The aryl of carbon number 6~10 is selected, for example, can be enumerated：Phenyl, tolyl, naphthyl etc., preferably phenyl, tolyl etc..It is used as aralkyl
Base, it is preferred that preferred carbon number 7~23, more preferably carbon number 7~13, the aralkyl of further preferred carbon number 7~11, for example may be used
To enumerate：Benzyl, phenethyl etc., particularly preferred benzyl.
Straight-chain or branched can be used by constituting the aliphatic acid of fatty acid ester, can be that saturated fatty acid can also
For unrighted acid.
It is the unitary of carbon number 1~22 or the aliphatic acid of binary, such as unitary saturation as the aliphatic acid for constituting fatty acid ester
Aliphatic acid, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, capric acid, laurate, myristic acid, ten
Five alkanoic acids, palmitic acid, Heptadecanoic acide, stearic acid, nonadecylic acid, arachic acid, behenic acids, unitary unrighted acid, such as
For the di-fatty of the unrighted acids such as oleic acid, elaidic acid, linoleic acid, leukotrienes, arachidonic acid, in addition carbon number more than 10
Acid, for example, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tetracosandioic acid, thapsic acid (thapsic acid) and the last of the ten Heavenly stems
Enedioic acid, undecendioic acid, decene dicarboxylic acid.
It is used as the aryl for constituting aryl ester, it is preferred that preferred carbon number 6~22, more preferably carbon number 6~12, further excellent
The aryl of carbon number 6~10 is selected, for example, can be enumerated：Phenyl, tolyl, naphthyl etc., preferably phenyl, tolyl etc..End-capped
Even if group be aralkyl, due to showing good compatibility with makrolon, therefore can also embody same with aryl
Effect, is used as aralkyl, it is preferred that preferred carbon number 7~23, more preferably carbon number 7~13, further preferred carbon number 7~11
Aralkyl, for example, can enumerate：Benzyl, phenethyl etc., particularly preferred benzyl.
In addition, as polytrimethylene glycol (B) number-average molecular weight, preferably 200~5000, more preferably 300 with
Above, more preferably more than 500, more preferably less than 4000, more preferably less than 3000.It is upper more than above range
In limited time, compatibility is reduced, and it is not preferable, and when being less than the lower limit of above range, gas is produced during shaping, it is not preferable.This
The number-average molecular weight of place meaning polytrimethylene glycol is based on the equal molecule of number calculated according to the hydroxyl value that JIS K1577 are determined
Amount.
The content of polytrimethylene glycol (B) is 0.1~4 mass parts relative to the mass parts of polycarbonate resin (A) 100.
It is preferred that content for more than 0.15 mass parts, more than more preferably 0.2 mass parts, below preferably 3.5 mass parts, more preferably
Below 3 mass parts, below more preferably 2.5 mass parts, below particularly preferably 2 mass parts.Content is less than 0.1 mass parts
When, form and aspect, xanthochromia improvement it is insufficient, during more than 4 mass parts, due to polycarbonate resin gonorrhoea and decrease in transmission, and
And when utilizing the melting mixing of extruder, the broken string of strands is multiple, being made for resin combination pellet becomes difficult.
[phosphorus system stabilizer (C)]
The poly carbonate resin composition of the present invention must contain phosphorus system stabilizer.By containing phosphorus system stabilizer, this hair
The form and aspect of bright poly carbonate resin composition become good, and resistance to thermochromism is further improved.
As phosphorus system stabilizer, known arbitrary phosphorus system stabilizer can be used.When enumerating concrete example, it can enumerate：Phosphorus
The oxyacid of the phosphorus such as acid, phosphonic acids, phosphorous acid, phosphinic acids, polyphosphoric acid；Acidic sodium pyrophosphate, acidic potassium pyrophosphate, acid pyrophosphoric acid
The metal acid pyrophosphate salt such as calcium；1st races such as potassium phosphate, sodium phosphate, phosphoric acid caesium, trbasic zinc phosphate or the phosphate of 2B races metal；
Phosphate compound, bi-ester of phosphite, phosphinate compound etc., particularly preferred bi-ester of phosphite.Pass through selection
Bi-ester of phosphite, can obtain the poly carbonate resin composition with higher discoloration-resistant and continuous production.
Bi-ester of phosphite is formula herein：P(OR)3Shown trivalent phosphorous compound, herein, R represent monovalence or two
The organic group of valency.
As such bi-ester of phosphite, for example, it can enumerate：The triphenyl phosphite, (nonyl benzene of phosphorous acid three
Base) ester, phosphorous acid three (one nonyl/dinonyl-phenyl) ester, phosphorous acid three (2,4- di-t-butyls phenyl) ester, phosphorous acid one is pungent
Base diphenyl ester, the phenyl ester of phosphorous acid dioctyl one, the decyl diphenyl ester of phosphorous acid one, the phenyl ester of phosphorous acid didecyl one, the last of the ten Heavenly stems of phosphorous acid three
The stearic alcohol ester (tristearyl phosphite) of ester, trilauryl phosphite, phosphorous acid three, diphosphorous acid distearyl Ji Wusi
Double (the 2,4- di-t-butyl -4- methylbenzenes of alcohol ester (distearyl pentaerythritol diphosphite), diphosphorous acid
Base) pentaerythritol ester, phosphorous acid double (2,6- di-t-butyls phenyl) monooctyl ester, phosphorous acid 2,2- di-2-ethylhexylphosphine oxides (4,6- bis--tertiary fourth
Base phenyl) monooctyl ester, diphosphorous acid four (2,4- di-t-butyls phenyl) -4,4 '-Asia Biphenyl Ester, tetra--tert-butyl groups of 2,4,8,10- -6-
[3- (the 3- tert-butyl groups-hydroxy-5-methyl base phenyl) propoxyl group]-dibenzo [d, f] [1,3,2] dioxaphosphepin cycloheptatriene
(dioxaphosphepine)。
In such bi-ester of phosphite, the aromatic series bi-ester of phosphite shown in following formula (2) or (3) is due to having
Effect ground improves the resistance to thermochromism of the poly carbonate resin composition of the present invention, therefore more preferably.
[in formula (2), R1、R2And R3Can distinguish it is identical can also be different, represent carbon number more than 6 and less than 30 aryl.]
[in formula (3), R4And R5Can distinguish it is identical can also be different, represent carbon number more than 6 and less than 30 aryl.]
As the bi-ester of phosphite shown in above-mentioned formula (2), wherein it is preferred that the triphenyl phosphite, (nonyl of phosphorous acid three
Base phenyl) ester and phosphorous acid three (2,4- di-t-butyl phenyl) ester etc., wherein more preferably (2, the 4- di-t-butyl benzene of phosphorous acid three
Base) ester.As such organophosphite compound, specifically, it can enumerate：ADEKA Corporation's
" Adeka Stab 1178 ", Sumitomo Chemical Co., Ltd. " Sumilizer TNP ", Johoku
Chemical Co., Ltd. " JP-351 ", ADEKA Corporation " Adeka Stab 2112 ", BASF
" Irgafos168 ", Johoku Chemical Co., Ltd. " JP-650 " etc..
As the bi-ester of phosphite shown in above-mentioned formula (3), wherein, double (2, the 4- bis--tertiary fourths of particularly preferred diphosphorous acid
Base -4- aminomethyl phenyls) pentaerythritol ester, double (the 2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol esters of diphosphorous acid and two Asias
Double (2,4- dicumylphenyls) pentaerythritol esters of phosphoric acid are such phosphitylated with pentaerythritol diphosphites structure
Compound.As such organophosphite compound, specifically, for example, can preferably it enumerate：ADEKA Corporation
" Adeka Stab PEP-24G ", " Adeka Stab PEP-36 ", the Dover Chemical Corporation of system
" Doverphos S-9228 " etc..
In bi-ester of phosphite, aromatic series bi-ester of phosphite shown in above-mentioned formula (3) is more excellent due to form and aspect, therefore
More preferably.
It should be noted that phosphorus system stabilizer can contain a kind, can also two or more contain in any combination with ratio
Have.
The content of phosphorus system stabilizer (C) is 0.005~0.5 mass parts relative to the mass parts of polycarbonate resin (A) 100,
More than preferably 0.007 mass parts, more than more preferably 0.008 mass parts, more than particularly preferably 0.01 mass parts, in addition,
Below preferably 0.4 mass parts, below more preferably 0.3 mass parts, below more preferably 0.2 mass parts, specifically for 0.1
Below mass parts.When the content of phosphorus system stabilizer (C) is less than 0.005 mass parts of aforementioned range, form and aspect, resistance to thermochromism become
Insufficient, when the content of phosphorus system stabilizer (C) is more than 0.5 mass parts, not only resistance to thermochromism deteriorates on the contrary but also damp and hot stabilization
Property is also reduced.
[epoxide (D)]
The resin combination of the present invention further preferably contains epoxide (D).By by epoxide (D) and poly- Sanya
Methyl glycol (B) contains together, can further improve resistance to thermochromism.
As epoxide (D), the compound in 1 molecule with more than 1 epoxy radicals is used.Specifically, can be with
It is preferred that enumerating：Phenyl glycidyl ether, allyl glycidyl ether, tert-butyl-phenyl glycidol ether, 3,4- epoxycyclohexyls
Methyl -3 ', 4 '-epoxycyclohexylcarboxylate, 3,4- epoxy -6- methylcyclohexylmethyls -3 ', 4 '-epoxy -6 '-methyl cyclohexane
Yl carboxylic acid ester, 2,3- epoxycyclohexyl-methyls -3 ', 4 '-epoxycyclohexylcarboxylate, 4- (3,4- epoxy -5- methylcyclohexyls)
Butyl -3 ', 4 '-epoxycyclohexylcarboxylate, 3,4- epoxycyclohexyls oxirane, cyclohexyl methyl -3,4- epoxycyclohexyls
Carboxylate, 3,4- epoxy -6- -6 '-methylcyclohexyls of methylcyclohexylmethyl carboxylate, diglycidyl ethers of bisphenol-A
(diglycidyl ether), tetrabromobisphenol A glycidol ether, the diepoxy glyceride (diglycidyl of phthalic acid
Ester), the diepoxy glyceride of hexahydro-phthalic acid, double-epoxy dicyclopentadienyl ether (bis-
Epoxydicyclopentadienyl ether), double-ethylene oxide glycol, double-epoxycyclohexyl adipate ester, butadiene it is bicyclic
Oxygen compound (butadiene diepoxide), tetraphenyl oxirane, the misery ester of epoxy resin (octyl epoxy
Tallate), epoxidized polybutadiene, 3,4- dimethyl -1,2- 7-oxa-bicyclo[4.1.0s, 3,5- dimethyl -1,2- 7-oxa-bicyclo[4.1.0s,
3- methyl -5- the tert-butyl group -1,2- 7-oxa-bicyclo[4.1.0s, octadecyl -2,2- dimethyl -3,4- epoxycyclohexylcarboxylates, positive fourth
Base -2,2- dimethyl -3,4- epoxycyclohexylcarboxylates, cyclohexyl -2- methyl -3,4- epoxycyclohexylcarboxylates, normal-butyl -
2- isopropyl -3,4- epoxy -5- methylcyclohexyls carboxylate, octadecyl -3,4- epoxycyclohexylcarboxylates, 2- ethyl hexyls
Base -3 ', 4 '-epoxycyclohexylcarboxylate, 4,6- dimethyl -2,3- epoxycyclohexyls -3 ', 4 '-epoxycyclohexylcarboxylate, 4,
5- epoxies tetrabydrophthalic anhydride, the 3- tert-butyl group -4,5- epoxies tetrabydrophthalic anhydride, diethyl -4,5- epoxies-suitable
Formula -1,2- cyclohexyl dicarboxylic acids ester, the di-n-butyl 3- tert-butyl group -4,5- epoxies-cis -1,2- cyclohexyl dicarboxylic acids ester, epoxy
Change soybean oil, epoxidation linseed oil etc..
Epoxide can be used alone and can also combine two or more and use.
Wherein, alicyclic epoxide compound, particularly preferred 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxide ring are preferably used
Hexyl carboxylate.
The content of epoxide (D) is 0.0005~0.2 matter preferably with respect to the mass parts of polycarbonate resin (A) 100
Measure more than part, more preferably 0.001 mass parts, be more preferably more than 0.003 mass parts, be particularly preferably 0.005 mass
More than part, in addition, below more preferably 0.15 mass, below more preferably 0.1 mass parts, being particularly preferably 0.05 mass
Below part.When the content of epoxide (D) is less than 0.0005 mass parts, form and aspect, resistance to thermochromism easily become insufficient, surpass
When crossing 0.2 mass parts, not only resistance to thermochromism deteriorates on the contrary, and form and aspect, hydrothermal stability are also easily reduced.
[additive etc.]
The poly carbonate resin composition of the present invention can be for example anti-oxidant containing other additives apart from the above
Agent, releasing agent, ultra-violet absorber, fluorescent whitening agent, pigment, dyestuff, the other polymers in addition to polycarbonate resin, resistance
Fire the additives such as agent, impact resistance modifying agent, antistatic additive, plasticizer, compatilizer.These additives can be compounded one kind or two kinds
More than.
[manufacture method of poly carbonate resin composition]
Manufacture method to the poly carbonate resin composition of the present invention is not limited, can be with widely used known poly- carbon
The manufacture method of acid ester resin composition, can enumerate following method：Use the various mixing such as rotary drum, Henschel mixer
Machine, by polycarbonate resin (A), polytrimethylene glycol (B) and phosphorus system stabilizer (C) and be compounded as needed other into
Divide and be pre-mixed, then with Banbury mixer, roller, Brabender (brabender), single-screw intermixing extruder, twin-screw
The mixers such as mixing extruder, kneader carry out melting mixing.It should be noted that the temperature of melting mixing is not limited especially
Make, usually 240~320 DEG C of scope.
The thin walled optical part of the present invention shows high spectral-transmission favtor with poly carbonate resin composition, can have
The spectral-transmission favtor at wavelength 420nm determined under 300mm optical path lengths is preferably more than 50% so high spectral-transmission favtor.
Spectral-transmission favtor at wavelength 420nm is close to the blue led largely used in the optical components such as light guide plate
Transmissivity in the wavelength domain of wavelength region, in addition, when the transmissivity in the wavelength domain is low, yellow hue increase.
It should be noted that the spectral-transmission favtor at wavelength 420nm is as follows：Shaped using by the long light-path of injection moulding
Product (300mm × 7mm × 4mm), are measured under 300mm optical path lengths, specifically, according to described in aftermentioned embodiment
Method is carried out.
[thin walled optical part]
For the thin walled optical part poly carbonate resin composition of the present invention, by above-mentioned poly carbonate resin composition
Pellet obtained from granulation is formed with various forming processes, can manufacture thin walled optical part.Alternatively, it is also possible to not via grain
Material, and form thin walled optical part by being directly formed by the resin of melting mixing with extruder.
The mobility of the poly carbonate resin composition of the present invention is excellent, when forming the formed products of thin-walled, also without white point
Foreign matter, and formed products excellent appearance, can take into account transmissivity, form and aspect, therefore be suitable for being configured to using injection molding method thin
The optical component of wall.Resin temperature during injection moulding is preferably, should in the injection moulding than general polycarbonate resin
Temperature is to be formed under 260~300 DEG C of high resin temperatures, preferably 305~380 DEG C of resin temperature.Resin temperature
More preferably more than 310 DEG C, more preferably more than 315 DEG C, particularly preferably more than 320 DEG C, in addition, more preferably 370
Below DEG C.During using existing poly carbonate resin composition, resin during shaping is improved to be configured to thin molded article
During temperature, the problem of easily producing white point foreign matter etc there is also the surface of formed products, but by using the resin group of the present invention
Compound, even if being said temperature scope, can also manufacture the thin molded article with good outward appearance.
It should be noted that resin temperature refers to, when being difficult to directly determine in the form of barrel design temperature handle
Hold.
Thin molded article refers in the present invention, is usually below 1mm with wall thickness, is preferably below 0.8mm, more preferably
The formed products of below 0.6mm plate-like portion.Herein, plate-like portion can also form bent plate shape for flat board, can be flat
Surface, can also have bumps etc., in addition, section has inclined plane, or wedge type section etc. on surface.
As thin walled optical part, it can enumerate：LED, organic EL, incandescent lamp bulb, fluorescent lamp, cathode tube etc. directly or
Ground connection can enumerate light guide plate, planar luminous body component etc. as representational example using the part of the machinery equipment of light source
Son.
Light guide plate is the light for being used to import the light sources such as LED in LCD backlight unit, various display devices, lighting device
Device, the light made from the entrance such as side or the back side is generally disposed at the concavo-convex diffusion on surface, sends uniform light.Its shape is led to
It is often can have bumps can also be without bumps on tabular, surface.
The shaping of light guide plate generally preferably passes through injection molding method, ultrahigh speed injection molding method, ejection compress moulding method etc.
Come carry out.
There is no the reduction of gonorrhoea, transmissivity, transmissivity using light guide plate obtained from the resin combination shaping of the present invention
It is extremely good with form and aspect.
The light guide plate of poly carbonate resin composition based on the present invention can be suitable for LCD backlight unit, various aobvious
The field of showing device, lighting device.As the example of such device, it can enumerate：It is mobile phone, mobile notebook, net book, flat
The various mobile terminals such as plate computer, tablet personal computer, smart mobile phone, tablet personal computer type terminal, camera, table, notebook are personal
Computer, various displays, lighting machine etc..
Embodiment
Hereinafter, show that embodiment is further illustrated to the present invention.But, the present invention is not limited to be construed to following
Embodiment.
The raw material and evaluation method used in following embodiment and comparative example is as described below.It should be noted that poly- carbon
The assay method of the viscosity average molecular weigh of acid ester resin (A) is for example foregoing.
[table 1]
(embodiment 1~8, comparative example 1~3)
[manufacture of resin combination pellet]
Above-mentioned each composition is compounded with the ratio (mass parts) shown in table 2, carried out with rotary drum after mixing in 20 minutes, profit
With screw diameter 40mm single screw extrusion machine (Tanabe Plastics Machinery Co., the Ltd. systems with exhaust outlet
" VS-40 "), melting mixing is carried out at 240 DEG C of barrel zone temperature, pellet is obtained by strands cutting.
[form and aspect (YI) and the measure of light transmittance]
After gained pellet is dried 5~7 hours at 120 DEG C using hot air circulation type drying machine, injection machine is utilized
(Toshiba Machinery Co., Ltd.'s system " EC100SX-2A ", be configured at 340 DEG C of resin temperature, 80 DEG C of mold temperature long light-path into
Shape product (300mm × 7mm × 4mm).
For the long light-path formed products, the YI (xanthochromia degree) and wavelength 420mm spectrum carried out under 300mm optical path lengths is saturating
Penetrate rate (unit：Measure %).Measure use long light-path spectral transmission color meter (electricity Se Industrial Co., Ltd of Japan system " ASA 1 ",
Illuminant-C, 2 ° of visuals field).
Evaluation result by more than is shown in following table 2.
[table 2]
[comparative example 4]
In embodiment 1, it is 5 mass parts to make B2 compositions, in addition, the grain using technique study similarly to Example 1
Materialization, but gonorrhoea occurs for resin, it is impossible to obtain transparent resin combination.
Shown by above-mentioned table 2, for the formed products of embodiment, the YI under the 300mm of optical path length length is small, and xanthochromia is few.Enter
Light transmittance under one step 420nm is also high, and the transparency is also excellent.
On the other hand understand, for the formed products of comparative example, 300mm YI is high compared with embodiment.Further light is saturating
Penetrate rate also low.
Thus, it can be known that the present invention, transmissivity and the good thin walled optical part polycarbonate resin group of form and aspect are provided
The purpose of compound is reached first in the case where fully meeting the feature of the present invention.
Industrial applicability
The transmissivity and form and aspect of the poly carbonate resin composition of the present invention are extremely good, therefore can be well suited for thin-walled
Usability in optical component, industry is very high.
Claims (7)
1. a kind of thin walled optical part poly carbonate resin composition, it is characterised in that relative to polycarbonate resin (A)
100 mass parts, contain the mass parts of polytrimethylene glycol (B) 0.1~4, phosphorus system stabilizer (C) 0.005~0.5 mass parts.
2. thin walled optical part poly carbonate resin composition according to claim 1, wherein, relative to makrolon
The mass parts of resin (A) 100, the epoxide (D) further containing 0.0005~0.2 mass parts.
3. thin walled optical part poly carbonate resin composition according to claim 1 or 2, wherein, polycarbonate resin
The viscosity average molecular weigh (Mv) of fat (A) is 10000~15000.
4. according to thin walled optical part poly carbonate resin composition according to any one of claims 1 to 3, its
The spectral-transmission favtor at wavelength 420nm determined under 300mm optical path lengths is more than 50%.
5. a kind of thin walled optical part, it is to shape poly carbonate resin composition according to any one of claims 1 to 4
Obtained from.
6. thin walled optical part according to claim 5, it is the light guide plate of the thickness with below 1mm.
7. a kind of wall thickness is the manufacture method of below 1mm thin walled optical part, will be according to any one of claims 1 to 4
Poly carbonate resin composition carries out injection moulding at 305~380 DEG C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015001756A JP5893774B1 (en) | 2015-01-07 | 2015-01-07 | Polycarbonate resin composition for thin optical parts and thin optical parts |
| JP2015-001756 | 2015-01-07 | ||
| PCT/JP2015/084100 WO2016111101A1 (en) | 2015-01-07 | 2015-12-04 | Polycarbonate resin composition for thin optical components, and thin optical component |
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| Publication Number | Publication Date |
|---|---|
| CN107148449A true CN107148449A (en) | 2017-09-08 |
| CN107148449B CN107148449B (en) | 2018-06-12 |
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| CN201580061019.XA Active CN107148449B (en) | 2015-01-07 | 2015-12-04 | Thin walled optical component poly carbonate resin composition and thin walled optical component |
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| JP (1) | JP5893774B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111936578A (en) * | 2018-03-27 | 2020-11-13 | 三菱工程塑料株式会社 | Polycarbonate resin composition |
| CN113166530A (en) * | 2018-11-29 | 2021-07-23 | 三菱工程塑料株式会社 | Polycarbonate resin composition for optical member |
| CN114466896A (en) * | 2019-09-25 | 2022-05-10 | 三菱工程塑料株式会社 | Polycarbonate resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6720656B2 (en) * | 2016-04-05 | 2020-07-08 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing aromatic polycarbonate resin molded article |
| JP6797657B2 (en) * | 2016-12-13 | 2020-12-09 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for optical components |
| JP6831231B2 (en) * | 2016-12-16 | 2021-02-17 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for optical components |
| JP6446601B1 (en) * | 2017-01-26 | 2018-12-26 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for optical parts and optical parts |
| TW201840708A (en) * | 2017-02-01 | 2018-11-16 | 日本商出光興產股份有限公司 | Polycarbonate resin composition |
| CN110268017A (en) * | 2017-02-01 | 2019-09-20 | 出光兴产株式会社 | Polycarbonate resin composition |
| JP7040267B2 (en) * | 2018-04-27 | 2022-03-23 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition pellets and their molded products |
| JP7309452B2 (en) * | 2019-05-27 | 2023-07-18 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition |
| JP7443739B2 (en) | 2019-12-12 | 2024-03-06 | 三菱瓦斯化学株式会社 | Polycarbonate resin compositions and optical components |
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| KR101715582B1 (en) * | 2013-12-10 | 2017-03-13 | 수미카 스타이론 폴리카보네이트 주식회사 | Polycarbonate resin composition and optical molded article |
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- 2015-01-07 JP JP2015001756A patent/JP5893774B1/en active Active
- 2015-12-04 CN CN201580061019.XA patent/CN107148449B/en active Active
- 2015-12-04 WO PCT/JP2015/084100 patent/WO2016111101A1/en active Application Filing
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| JPH0948911A (en) * | 1995-08-02 | 1997-02-18 | Sumika A B S Latex Kk | Polycarbonate resin composition |
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| CN111936578B (en) * | 2018-03-27 | 2023-03-10 | 三菱工程塑料株式会社 | Polycarbonate resin composition |
| CN113166530A (en) * | 2018-11-29 | 2021-07-23 | 三菱工程塑料株式会社 | Polycarbonate resin composition for optical member |
| CN114466896A (en) * | 2019-09-25 | 2022-05-10 | 三菱工程塑料株式会社 | Polycarbonate resin composition |
| CN114466896B (en) * | 2019-09-25 | 2023-05-30 | 三菱工程塑料株式会社 | Polycarbonate resin composition |
Also Published As
| Publication number | Publication date |
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| JP2016125028A (en) | 2016-07-11 |
| WO2016111101A1 (en) | 2016-07-14 |
| JP5893774B1 (en) | 2016-03-23 |
| CN107148449B (en) | 2018-06-12 |
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