JP2018095812A - Polycarbonate resin composition for optical components - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition for optical components having an excellent hue and moist heat resistance.SOLUTION: A polycarbonate resin composition for optical components contains, relative to a polycarbonate resin (A) 100 pts.mass, a polyalkylene glycol (B) containing no epoxy group at its terminal of 0.1-4 pts.mass, a polyalkylene glycol (C) containing an epoxy group at its terminal of 0.005-2 pts.mass, and a phosphorous stabilizer (D) of 0.005-0.5 pts.mass.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition for optical parts, and more particularly, to a polycarbonate resin composition for optical parts having a good hue and improved heat and humidity resistance.

  A surface light source device is incorporated in a liquid crystal display device used for a personal computer, a cellular phone and the like in order to meet demands for thinning, lightening, labor saving, and high definition. The planar light source device includes a flat light guide plate for the purpose of uniformly and efficiently guiding incident light to the liquid crystal display side.

  Such a light guide plate is obtained by injection molding of a thermoplastic resin. Conventionally, the light guide plate has been molded from a resin material such as polymethylmethacrylate (PMMA). Recently, however, a display device that displays a clearer image has been demanded, and the temperature inside the device is increased by heat generated near the light source. Therefore, it is being replaced with a polycarbonate resin material having higher heat resistance.

  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. When configured, there is a problem that the luminance is low. Recently, it has been demanded to reduce the difference in chromaticity between the light incident portion of the light guide plate and a location away from the light incident portion, but there is a problem that the polycarbonate resin is more easily yellowed than the PMMA resin.

Patent Document 1 discloses a method for improving light transmittance and luminance by adding an acrylic resin and an alicyclic epoxy, and Patent Document 2 describes a transfer property of a concavo-convex portion to a light guide plate by modifying a polycarbonate resin terminal. 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.
However, although the method of Patent Document 1 improves the hue by adding an acrylic resin, it cannot be increased in light transmittance and brightness due to white turbidity, and the transmittance is improved by adding an alicyclic epoxy. Although there is a possibility, the effect of improving the hue is not recognized. In the case of Patent Document 2 and Patent Document 3, although an improvement effect of fluidity and transferability can be expected, there is a disadvantage that heat resistance is lowered.

On the other hand, it is known in Patent Document 4, Patent Document 5, and the like that polyethylene glycol or poly (2-methyl) ethylene glycol is blended with a thermoplastic resin such as a polycarbonate resin. And in this patent document, the present applicant has the formula: X—O— [CH (—R) —CH ₂ —O] _n —Y (wherein R is a hydrogen atom or an alkyl having 1 to 3 carbon atoms). The proposal which improves the transmittance | permeability and a hue was carried out by mix | blending the polyethyleneglycol or poly (2-alkyl) ethyleneglycol represented by group.

  However, in recent years, various types of mobile terminals such as smartphones and tablet terminals have been made increasingly thin and large-sized, and the required specifications for such high-end light guide plates are increasing. Sophisticated.

JP-A-11-158364 JP 2001-208917 A JP 2001-215336 A JP-A-1-22959 JP-A-9-227785 Japanese Patent No. 4069364

However, it has been found that the polycarbonate resin composition containing the polyalkylene glycol as described above has a problem in moisture and heat resistance particularly when a thin molded product such as a light guide plate for a high end is formed.
The subject (object) of this invention is providing the polycarbonate resin composition for optical components which has a favorable hue and was excellent in heat-and-moisture resistance.

As a result of intensive investigations to achieve the above-mentioned problems, the present inventor has blended polyalkylene glycol with polyalkylene glycol having an epoxy group at the terminal, and a phosphorous stabilizer. However, it has been found that it has excellent heat and humidity resistance while having an excellent hue, and has completed the present invention.
The present invention relates to the following polycarbonate resin composition for optical parts.

[1] 0.1 to 4 parts by mass of polyalkylene glycol (B) having no epoxy group at the terminal and polyalkylene glycol (C) having an epoxy group at the terminal to 100 parts by mass of the polycarbonate resin (A) A polycarbonate resin composition for optical parts, containing 0.005 to 2 parts by mass and 0.005 to 0.5 parts by mass of a phosphorus stabilizer (D).
[2] The polycarbonate resin composition for optical parts according to the above [1], wherein the alkylene group of the polyalkylene glycol (C) having an epoxy group at the terminal has 3 or more carbon atoms.
[3] The above-mentioned [1], wherein the mass ratio of the content of the polyalkylene glycol (B) having no epoxy group at the terminal and the polyalkylene glycol (C) having an epoxy group at the terminal is 30:70 to 99: 1. ] Or the polycarbonate resin composition for optical components according to [2].
[4] The polycarbonate resin composition for optical components according to any one of the above [1] to [3], wherein the epoxy equivalent of the polyalkylene glycol (C) having an epoxy group at the terminal is 200 to 1000 g / eq.
[5] The total content of the polyalkylene glycol (B) having no epoxy group at the terminal and the polyalkylene glycol (C) having an epoxy group at the terminal is 0.1% relative to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition for optical components according to any one of the above [1] to [4], which is 2 to 3 parts by mass.
[6] An optical component comprising the polycarbonate resin composition for optical components according to any one of [1] to [5].

  The polycarbonate resin composition for optical parts of the present invention has a good hue, excellent heat and humidity resistance, excellent fluidity and high light transmittance.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples.
In the present specification, “to” is used in the sense of including the numerical values described before and after the lower and upper limits unless otherwise specified.

The polycarbonate resin composition for optical parts of the present invention is 0.1 to 4 parts by mass of a polyalkylene glycol (B) having no epoxy group at the terminal and 100 epoxy parts at the terminal with respect to 100 parts by mass of the polycarbonate resin (A). It contains 0.005 to 2 parts by mass of a polyalkylene glycol (C) having a content of 0.005 to 0.5 parts by mass of a phosphorus stabilizer (D).
Hereafter, each component etc. which comprise the polycarbonate resin composition for optical components of this invention are demonstrated in detail.

[Polycarbonate resin (A)]
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C (═O) —] —. In the formula, 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 carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, 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. Further, 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. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:
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, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

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,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

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-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardio structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (especially from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferred.
In addition, 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.

In addition, when an example of a monomer that is a raw material of the aliphatic polycarbonate resin is given,
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;

  Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

  Glycols such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;

  1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  Among the monomers used as the raw material for the polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester 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 method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. 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.

The molecular weight of the polycarbonate resin (A) is preferably a viscosity average molecular weight (Mv) of 10000 to 18000, more preferably 10500 or more, further preferably 11000 or more, particularly preferably 11500 or more, and most preferably 12000 or more. More preferably 17500 or less, further preferably 17000 or less, and particularly preferably 16500 or less. By making the viscosity average molecular weight more than the lower limit of the above range, 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.
The polycarbonate resin (A) may be used by mixing two or more kinds of polycarbonate resins having different viscosity average molecular weights. In this case, the polycarbonate resin having a viscosity average molecular weight outside the above preferred range is mixed. May be.

In the present invention, the viscosity average molecular weight Mv of the polycarbonate resin is determined by using methylene chloride as a solvent and obtaining an intrinsic viscosity η (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. It means the value calculated from the formula.
η = 1.23 × 10 ⁻⁴ Mv ^0.83
The intrinsic viscosity η is a value calculated from the following equation by measuring the specific viscosity η _sp at each solution concentration [C] (g / dl).

  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. Further, for example, for the purpose of further improving flame retardancy and impact resistance, 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 A monomer, oligomer or polymer having a copolymer; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; Copolymers with oligomers or polymers having an olefinic structure; copolymers with polyester resin oligomers or polymers for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, 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. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, 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).
However, 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.

[Polyalkylene glycol compound having no epoxy group at the terminal (B)]
The polycarbonate resin composition for optical components of the present invention contains 0.1 to 4 parts by mass of polyalkylene glycol (B) having no epoxy group at the terminal with respect to 100 parts by mass of the polycarbonate resin (A).

  As polyalkylene glycol (B) having no epoxy group at the terminal, various polyalkylene glycols can be used. For example, branched polyalkylene glycol represented by the following general formula (1) or the following general formula (2) The linear polyalkylene glycol represented by these is mentioned as a preferable thing. The branched polyalkylene glycol represented by the following general formula (1) or the linear polyalkylene glycol represented by the following general formula (2) may be a copolymer with another copolymer component. Although it is good, it is preferably a homopolymer.

Wherein R represents an alkyl group having 1 to 3 carbon atoms, and X and Y are each independently a hydrogen atom, an aliphatic acyl group having 1 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, carbon An aryl group having 6 to 22 carbon atoms or an aralkyl group having 7 to 23 carbon atoms, and m represents an integer of 10 to 400.
The branched polyalkylene glycol represented by the general formula (1) may be a homopolymer composed of one kind of R or a copolymer composed of different Rs.

(In the formula, X and Y are each independently a hydrogen atom, an aliphatic acyl group having 2 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, an aryl group having 6 to 22 carbon atoms, or 7 to 23 carbon atoms. (Wherein p represents an integer of 2 to 6 and r represents an integer of 6 to 100).
The linear polyalkylene glycol represented by the general formula (2) may be a homopolymer composed of a single p or a copolymer composed of a different p.

  As the branched polyalkylene glycol, in the general formula (1), (2-methyl) ethylene glycol in which X and Y are hydrogen atoms and R is a methyl group or (2-ethyl) ethylene glycol in which an ethyl group is preferable is preferable. .

  As the linear polyalkylene glycol, in general formula (2), X and Y are hydrogen atoms, p is 2, polyethylene glycol, p is 3, polytrimethylene glycol, and p is 4, polytetramethylene. Preferable examples include glycol, polypentamethylene glycol having p of 5, and polyhexamethylene glycol having p of 6, more preferably polytrimethylene glycol and polytetramethylene glycol.

  The polyalkylene glycol (B) is selected from linear alkylene ether units (P1) represented by the following general formula (3) and units represented by the following general formulas (4-1) to (4-4). A polyalkylene glycol copolymer having a branched alkylene ether unit (P2) is also preferred.

(In formula (3), p represents an integer of 2 to 6)
As a linear alkylene ether unit represented by General formula (3), the single unit which consists of 1 type of p, or the several unit which consists of different p may mix.

(In formulas (4-1) to (4-4), R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each of formulas (4-1) to (4- In 4), at least one of R ^{1 to} R ¹⁰ is an alkyl group having 1 to 3 carbon atoms.)

  As the linear alkylene ether unit (P1) represented by the general formula (3), when describing it as glycol, ethylene glycol in which p is 2, trimethylene glycol in which p is 3, and tetra in which p is 4 Examples thereof include methylene glycol, pentamethylene glycol having p of 5, and hexamethylene glycol having p of 6, which may be mixed, preferably trimethylene glycol and tetramethylene glycol, and tetramethylene glycol is particularly preferable.

  Trimethylene glycol is industrially obtained by hydroformylating ethylene oxide to obtain 3-hydroxypropionaldehyde and hydrogenating it or hydrogenating 3-hydroxypropionaldehyde obtained by hydrating acrolein with a Ni catalyst. Manufactured by the method. Recently, trimethylene glycol is also produced by reducing glycerin, glucose, starch and the like to microorganisms by a bio method.

  As the branched alkylene ether unit represented by the general formula (4-1), when this is described as glycol, (2-methyl) ethylene glycol, (2-ethyl) ethylene glycol, (2,2-dimethyl) ethylene glycol, etc. These may be mixed, and (2-methyl) ethylene glycol and (2-ethyl) ethylene glycol are preferred.

  As a branched alkylene ether unit represented by the above general formula (4-2), when described as glycol, (2-methyl) trimethylene glycol, (3-methyl) trimethylene glycol, (2-ethyl) trimethylene glycol , (3-ethyl) triethylene glycol, (2,2-dimethyl) trimethylene glycol, (2,2-methylethyl) trimethylene glycol, (2,2-diethyl) trimethylene glycol (ie neopentyl glycol) , (3,3-dimethyl) trimethylene glycol, (3,3-methylethyl) trimethylene glycol, (3,3-diethyl) trimethylene glycol and the like, and these may be mixed.

  As a branched alkylene ether unit represented by the above general formula (4-3), when this is described as glycol, (3-methyl) tetramethylene glycol, (4-methyl) tetramethylene glycol, (3-ethyl) tetramethylene glycol , (4-ethyl) tetramethylene glycol, (3,3-dimethyl) tetramethylene glycol, (3,3-methylethyl) tetramethylene glycol, (3,3-diethyl) tetramethylene glycol, (4,4-dimethyl) ) Tetramethylene glycol, (4,4-methylethyl) tetramethylene glycol, (4,4-diethyl) tetramethylene glycol, and the like. These may be mixed, and (3-methyl) tetramethylene glycol is preferable.

  As a branched alkylene ether unit represented by the above general formula (4-4), when described as glycol, (3-methyl) pentamethylene glycol, (4-methyl) pentamethylene glycol, (5-methyl) pentamethylene glycol , (3-ethyl) pentamethylene glycol, (4-ethyl) pentamethylene glycol, (5-ethyl) pentamethylene glycol, (3,3-dimethyl) pentamethylene glycol, (3,3-methylethyl) pentamethylene glycol (3,3-diethyl) pentamethylene glycol, (4,4-dimethyl) pentamethylene glycol, (4,4-methylethyl) pentamethylene glycol, (4,4-diethyl) pentamethylene glycol, (5,5 -Dimethyl) pentamethylene glycol (5,5-methylethyl) pentamethylene glycol, (5,5-diethyl) such as pentamethylene glycol, and the like, it may also be these mixtures.

  As described above, the units represented by the general formulas (4-1) to (4-4) constituting the branched alkylene ether unit have been described with glycol as an example for convenience. However, the present invention is not limited to these glycols, and these alkylene oxides. Alternatively, these polyether-forming derivatives may be used.

  Preferable examples of the polyalkylene glycol copolymer include a copolymer composed of a tetramethylene ether unit and a unit represented by the general formula (4-3), particularly a tetramethylene ether unit and 3-methyltetramethylene. A copolymer comprising an ether unit is more preferable. Further, a copolymer comprising a tetramethylene ether unit and a unit represented by the general formula (4-1) is also preferable, in particular, a copolymer comprising a tetramethylene ether unit and a 2-methylethylene ether unit, and tetramethylene ether. A copolymer composed of units and 2-ethylethylene ether units is more preferred. Furthermore, a copolymer composed of a tetramethylene ether unit and the above general formula (4-2) is also preferable, and a copolymer composed of a 2,2-dimethyltrimethylene ether unit, that is, a neopentyl glycol ether unit is also preferable.

  The polyalkylene glycol copolymer may be a random copolymer or a block copolymer.

The linear alkylene ether unit (P1) represented by the general formula (3) and the branched alkylene ether unit (P2) represented by the general formulas (4-1) to (4-4) of the polyalkylene glycol copolymer. ) Is a molar ratio of (P1) / (P2), preferably 95/5 to 5/95, more preferably 93/7 to 40/60, and still more preferably 90/10. It is more preferable that the linear alkylene ether unit (P1) is rich.
The mole fraction is measured using a ¹ H-NMR measuring apparatus and deuterated chloroform as a solvent.

  Among the above-mentioned, particularly preferable polyalkylene glycol (B) includes homopolymers such as polytrimethylene glycol, poly (2-methyl) ethylene glycol, poly (2-ethyl) ethylene glycol, polytetramethylene glycol, and polytetramethylene glycol. Methylene glycol-polyethylene glycol, polytetramethylene glycol-polytrimethylene glycol, polytetramethylene glycol-poly (2-methyl) ethylene glycol, polytetramethylene glycol-poly (3-methyl) tetramethylene glycol, polytetramethylene glycol- Poly (2-ethyl) ethylene glycol, polytetramethylene glycol-polyneopentyl glycol, polyethylene glycol-polytrimethylene glycol, polyethylene glycol Le - poly (2-methyl) copolymers such as ethylene glycol.

  Further, as polyalkylene glycol (B), even if one or both ends thereof are blocked with carboxylic acid or alcohol, there is no effect on the performance expression, and esterified products or etherified products can be used in the same manner. Therefore, X and / or Y in the general formulas (1) and (2) is an aliphatic acyl group having 2 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, an aryl group having 6 to 22 carbon atoms, or the number of carbon atoms. It may be a 7-23 aralkyl group.

Examples of the esterified product include fatty acid esters, and either linear or branched fatty acid esters can be used. 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 23 carbon atoms, such as a monovalent saturated fatty acid, specifically formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid. , Enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and monovalent unsaturated fatty acids, specifically, Unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid and arachidonic acid, and divalent fatty acids having 10 or more carbon atoms, specifically sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid , Tapsia and decenedioic acid, undecenedioic acid, dodecenedioic acid.
These fatty acids can be used alone or in combination. The fatty acid also includes a fatty acid having one or more hydroxyl groups in the molecule.

  Preferable specific examples of the fatty acid ester of polyalkylene glycol include polypropylene glycol stearate in which R is a methyl group, X and Y are aliphatic acyl groups having 18 carbon atoms in general formula (1), R is a methyl group, X And polypropylene glycol behenate in which Y is an aliphatic acyl group having 22 carbon atoms. Preferable specific examples of fatty acid esters of linear polyalkylene glycol include polyalkylene glycol monopalmitate, polyalkylene glycol dipalmitate, polyalkylene glycol monostearate, polyalkylene glycol distearate, polyalkylene glycol (Monopalmitic acid / monostearic acid) ester, polyalkylene glycol behenate and the like.

  The alkyl group constituting the alkyl ether of the polyalkylene glycol may be either linear or branched, for example, carbon number such as methyl group, ethyl group, propyl group, butyl group, octyl group, lauryl group, stearyl group, etc. Examples of such a polyalkylene glycol include alkylmethyl ether, ethyl ether, butyl ether, lauryl ether, stearyl ether and the like of polyalkylene glycol.

  The aryl group constituting the aryl ether of the polyalkylene glycol is preferably an aryl group having 6 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 carbon atoms, such as a phenyl group or tolyl. Group, naphthyl group and the like, and phenyl group, tolyl group and the like are preferable. In addition, even if the end-capping group is an aralkyl group, it exhibits good compatibility with polycarbonate, so that it can exhibit the same action as an aryl group. The aralkyl group preferably has 7 to 23 carbon atoms. An aralkyl group having 7 to 13 carbon atoms, more preferably 7 to 11 carbon atoms is preferable, and examples thereof include a benzyl group and a phenethyl group, and a benzyl group is particularly preferable.

The number average molecular weight of the polyalkylene glycol (B) is preferably 500 to 5000, more preferably 600 or more, further preferably 700 or more, more preferably 4000 or less, still more preferably 3000 or less, particularly preferably. 2000 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 easily generated during molding, which is not preferable.
The number average molecular weight of the polyalkylene glycol is a number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K1577.

  Polyalkylene glycol (B) may be used individually by 1 type, or may use 2 or more types together.

  The content of the polyalkylene glycol (B) is 0.1 to 4 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A) as described above, preferably 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, more preferably 0.25 parts by mass or more, preferably 3.5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2.5 parts by mass or less, especially 2 parts by mass. Hereinafter, it is particularly preferably 1.5 parts by mass or less, and particularly preferably 1 part by mass or less.

[Polyalkylene glycol (C) having an epoxy group at the terminal]
The polycarbonate resin composition for optical parts of the present invention contains a polyalkylene glycol (C) having an epoxy group at the terminal in addition to the polyalkylene glycol (B) having no epoxy group at the terminal. And
The polyalkylene glycol (C) having an epoxy group at the terminal is not limited as long as it is a polyalkylene glycol having an epoxy group at the terminal, and is exemplified as the polyalkylene glycol (B) having no epoxy group at the terminal. Preference is given to polyalkylene glycols in which part or all of the hydroxyl groups present at the ends of the polyalkylene glycol, preferably both ends are substituted with other epoxy groups.

The polyalkylene glycol of the polyalkylene glycol (C) having an epoxy group at the terminal is preferably one having an alkylene ether unit having 3 or more carbon atoms in the alkylene group.
Preferable specific examples of the polyalkylene glycol (C) having an epoxy group at the terminal include mono- or diglycidylated products such as polytrimethylene glycol and polytetramethylene glycol, polytetramethylene glycol-polyethylene glycol, polytetramethylene glycol-polytri Methylene glycol, polytetramethylene glycol-poly (2-methyl) ethylene glycol, polytetramethylene glycol-poly (3-methyl) tetramethylene glycol, polytetramethylene glycol-polyneopentyl glycol, polyethylene glycol-polytrimethylene glycol, Examples thereof include mono- or diglycidylated products such as polyethylene glycol-poly (2-methyl) ethylene glycol.

The epoxy equivalent of the polyalkylene glycol (C) having an epoxy group at the terminal is preferably 200 to 1000 g / eq, more preferably 220 to 600 g / eq, and further preferably 250 to 550 g / eq. preferable.
Here, the epoxy equivalent of the polyalkylene glycol (C) having an epoxy group at the terminal is measured by a technique based on JIS K7236.

  The content of the polyalkylene glycol (C) having an epoxy group at the terminal is 0.005 to 2 parts by mass, preferably 0.01 parts by mass or more, more preferably 100 parts by mass of the polycarbonate resin (A). The amount is 0.015 parts by mass or more, preferably 1.5 parts by mass or less, more preferably 1.2 parts by mass or less, further preferably 1 part by mass or less, and particularly preferably 0.8 parts by mass or less. When the content of the polyalkylene glycol (C) is less than 0.005 parts by mass, the heat and moisture resistance is deteriorated, and when it exceeds 2 parts by mass, the heat and moisture resistance is deteriorated.

Moreover, the sum total of content of the polyalkylene glycol (B) which does not have an epoxy group at the terminal, and the polyalkylene glycol (C) which has an epoxy group at the terminal is 0.2 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is preferable that it is -3 mass parts, and it is more preferable that it is 0.2-3 mass parts.
Furthermore, the mass ratio of the content of the polyalkylene glycol (B) having no epoxy group at the terminal and the polyalkylene glycol (C) having an epoxy group at the terminal is preferably 30:70 to 99: 1. More preferably, it is 50:50 to 99: 1, and still more preferably 60:40 to 99: 1. When the content of the polyalkylene glycol (B) is less than 30%, gas is easily generated during extrusion and molding.

[Phosphorus stabilizer (D)]
The polycarbonate resin composition for optical parts of the present invention further contains a phosphorus stabilizer. By containing a combination of a polyalkylene glycol (B) having no epoxy group at the terminal, a polyalkylene glycol (C) having an epoxy group at the terminal, and a phosphorus stabilizer, the hue of the polycarbonate resin composition of the present invention can be changed. Further, it becomes better, and the heat discoloration is further improved.
Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, 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 can be mentioned, and phosphite compounds are particularly preferred. By selecting a phosphite compound, a polycarbonate resin composition having higher discoloration resistance and continuous productivity can be obtained.

Here, 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. Phyto, monooctyl diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, Bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butylphenyl) octyl phosphite, 2,2-methylene (4,6-di-tert-butylphenyl) octyl phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-diphosphite, 6- [3- (3-tert- Butyl-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] -dioxaphosphine.

  Among such phosphite compounds, an aromatic phosphite compound represented by the following formula (5) or (6) is more preferable because the heat discoloration of the polycarbonate resin composition of the present invention is effectively enhanced.

(In the formula, 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.)

(In the formula, R ⁴ and R ⁵ may be the same or different and each represents an aryl group having 6 to 30 carbon atoms.)

  As the phosphite compound represented by the above formula (5), triphenyl phosphite, tris (monononylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like are preferable. Tris (2,4-di-tert-butylphenyl) phosphite is more preferred. Specific examples of such 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., “ADEKA STAB manufactured by ADEKA 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 (6) include bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl). Those having a pentaerythritol diphosphite structure such as -4-methylphenyl) pentaerythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are particularly preferred. Specific examples of such an organic phosphite compound include “Adeka Stub PEP-24G”, “Adeka Stub PEP-36” manufactured by Adeka, “Doverphos S-9228” manufactured by Doverchemical, and the like.

Among the phosphite compounds, the aromatic phosphite compound represented by the above formula (6) is more preferable because the hue is more excellent.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  Content of a phosphorus stabilizer (D) is 0.005-0.5 mass part with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 0.007 mass part or more, More preferably, it is 0.00. 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. When the content of the phosphorus stabilizer (D) is less than 0.005 parts by mass, the hue and the heat discoloration are insufficient, and when it exceeds 0.5 parts by mass, the heat discoloration is only deteriorated. In addition, the wet heat stability is also reduced.

[Additives, etc.]
The polycarbonate resin composition for optical parts of the present invention is made of other additives other than those described above, such as mold release agents, antioxidants, ultraviolet absorbers, fluorescent brighteners, pigments, dyes, and polycarbonate resins. It can contain additives such as polymers, flame retardants, impact modifiers, antistatic agents, plasticizers, compatibilizers and the like. These additives may be used alone or in combination of two or more.

[Production Method of Polycarbonate Resin Composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition for optical components of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, polycarbonate resin (A), polyalkylene glycol (B), (C), and phosphorus The system stabilizer (D) and other components to be blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, Brabender, single screw kneading extrusion And a melt kneading method using a mixer such as a machine, a twin-screw kneading extruder, or a kneader. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

  The polycarbonate resin composition of the present invention can produce various molded articles 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 molded product without going through the pellets.

The polycarbonate resin composition of the present invention is excellent in hue and heat-and-moisture resistance, has excellent fluidity and exhibits high light transmittance, and thus is suitably used for molding optical parts, particularly thin-walled optical parts by injection molding. It is done. 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 the injection molding of polycarbonate resin, particularly in the case of a thin molded product. A resin temperature of ˜400 ° C. is preferred. The resin temperature is preferably 310 ° C. or higher, more preferably 315 ° C. or higher, particularly preferably 320 ° C. or higher, and more preferably 390 ° C. or lower. When the conventional polycarbonate resin composition is used, there is a problem that when the resin temperature at the time of molding is increased in order to mold a thin molded product, the molded product is likely to be yellowed. By using the composition, it becomes possible to produce a molded product having a good hue, particularly a thin-walled optical component, even in the above temperature range. In addition, reducing the molecular weight of the polycarbonate resin in order to form a thin molded product has been conventionally performed, but the polycarbonate resin composition of the present invention has good fluidity, so that it can be molded without reducing the molecular weight. Thus, a molded product having higher strength can be obtained.
The resin temperature is grasped as the barrel set temperature when it is difficult to directly measure the resin temperature.

  Here, the thin-walled molded article refers to a molded article having a plate-like portion with a thickness of usually 1 mm or less, preferably 0.8 mm or less, more preferably 0.6 mm or less. Here, 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.

Examples of the optical parts include parts of devices and instruments that directly or indirectly use light sources such as LEDs, organic EL, incandescent bulbs, fluorescent lamps, and cathode tubes.
Optical parts using the polycarbonate resin composition for optical parts 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.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
The raw materials and evaluation methods used in the following examples and comparative examples are as follows.

(Examples 1-11, Comparative Examples 1-3)
[Production of resin composition pellets]
Each component described in Table 1 was blended in the proportions (parts by mass) shown in Table 2 below, mixed for 20 minutes with a tumbler, and then a single screw extruder with a vent with a screw diameter of 40 mm (manufactured by Tanabe Plastic Machinery Co., Ltd.). “VS-40”) was melt-kneaded at a cylinder temperature of 240 ° C., and pellets were obtained by strand cutting.

[Measurement of Hue (YI)]
The obtained pellets were dried at 120 ° C. for 5 to 7 hours with a hot air circulating dryer, and then with an injection molding machine (“EC100SX-2A” manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 340 ° C. and a mold temperature of 80 ° C. A long optical path molded product (300 mm × 7 mm × 4 mm) was molded.
About this long optical path molded product, YI (yellowing degree) was measured at an optical path length of 300 mm. For the measurement, a long optical path spectral transmission color meter (“ASA 1” manufactured by Nippon Denshoku Industries Co., Ltd., C light source, 2 ° visual field) was used.

[Evaluation of Humidity and Heat Resistance: Measurement of Hue (YI)]
The long optical path molded product was held in a thermostatic chamber at 65 ° C. and a humidity of 85% for 500 hours, and a moisture and heat resistance test was performed. The YI of the long optical path molded product after the test was measured, and the change in hue (ΔYI) before and after the test was determined.
The above evaluation results are shown in Table 2 below.

  Since the polycarbonate resin composition for optical parts of the present invention is a polycarbonate resin material having a good hue and excellent moisture and heat resistance, it can be suitably used for various optical parts and the like.

Claims (6)

  0.1 to 4 parts by mass of polyalkylene glycol (B) having no epoxy group at the terminal and 0.005 of polyalkylene glycol (C) having an epoxy group at the terminal to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition for optical parts, which comprises ˜2 parts by mass and 0.005 to 0.5 parts by mass of a phosphorus stabilizer (D).   The polycarbonate resin composition for optical components according to claim 1, wherein the alkylene group of the polyalkylene glycol (C) having an epoxy group at the terminal has 3 or more carbon atoms.   The mass ratio of the content of the polyalkylene glycol (B) having no epoxy group at the terminal and the polyalkylene glycol (C) having an epoxy group at the terminal is 30:70 to 99: 1. The polycarbonate resin composition for optical components as described.   The polycarbonate resin composition for optical components according to any one of claims 1 to 3, wherein an epoxy equivalent of the polyalkylene glycol (C) having an epoxy group at the terminal is 200 to 1000 g / eq.   The total content of the polyalkylene glycol (B) having no epoxy group at the terminal and the polyalkylene glycol (C) having an epoxy group at the terminal is 0.2 to 3 with respect to 100 parts by mass of the polycarbonate resin (A). It is a mass part, The polycarbonate resin composition for optical components in any one of Claims 1-4.   An optical component comprising the polycarbonate resin composition for an optical component according to claim 1.