TW201936783A - Polycarbonate resin additive, polycarbonate resin composition containing same and molded body thereof - Google Patents

Abstract

Provided are: a polycarbonate resin additive capable of enhancing the fluidity, mold releasability, and heat resistance of a polycarbonate resin; and a polycarbonate resin composition containing the same, and a molded body thereof. The polycarbonate resin additive contains a compound represented by general formula (1). In general formula (1), R represents an alkyl group having 1-20 carbon atoms, which may have a substituent, and m represents a number which is 2 to 100. R in general formula (1) is preferably a secondary alkyl group having 3-20 carbon atoms.

Description

Additive for polycarbonate resin, polycarbonate resin composition containing the same, and molded body thereof

The present invention relates to an additive for a polycarbonate resin, a polycarbonate resin composition containing the same, and a molded article thereof, and more particularly to a polycarbonate which can provide fluidity, mold release property and heat resistance of a polycarbonate resin. An additive for an ester resin, a polycarbonate resin composition containing the same, and a molded body thereof.

Polycarbonate resins are widely used as molding materials in OA (office automation) equipment, electric and electronic equipment, optical equipment, automatic vehicle parts, and building materials because of their excellent impact resistance, electrical properties, and optical properties. However, the polycarbonate resin has a problem that the fluidity of the resin is inferior to other general-purpose resins, and it is necessary to have a high molding processing temperature, and it is inferior in mold formability, and has a problem of heat resistance such as coloring.

In addition, the polycarbonate resin is molded into various molded articles by injection molding, but when the shape is complicated in the case of a component such as an OA machine such as a photocopier or a facsimile machine, an electric or electronic device, or the like, the shape is complicated. Concavities and convexities such as ribs or bosses are formed on the molded article. Therefore, it is difficult to mold the molded article from the mold, and it is impossible to remove the mold and open the hole in the molded article, and even if the mold can be removed, deformation, whitening or distortion may occur, resulting in the size of the molded article. There are problems such as accuracy, strength, and appearance reduction, so it is necessary to improve the mold release property of the polycarbonate resin.

In general, dioctyl phthalate or trimethyl phenol phosphate, which is a plasticizer used in a vinyl chloride resin or the like, can improve the fluidity of the polycarbonate resin, but these are similar to the polycarbonate resin. The compatibility is poor, and there is a problem that the physical properties or heat resistance of the resin are remarkably lowered. In view of such a situation, Patent Document 1 proposes an aromatic fatty acid ester in which a polycarbonate resin is blended with a specific diol. Further, Patent Documents 2 and 3 propose a soft acid ester slip agent in which a polycarbonate resin is blended with pentaerythritol.
[Previous Technical Literature]
[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2004-137423.

[Problems to be solved by the invention]

However, as in Patent Document 1, even if a specific fatty acid ester of a specific diol is blended with a polycarbonate resin, the improvement of the fluidity of the polycarbonate resin is insufficient, and the improvement of the mold release property is not focused. And no review has been conducted. Further, as in Patent Documents 2 and 3, even if a palmitic acid ester slipper of pentaerythritol is added to the polycarbonate resin, fluidity and mold release property are not sufficient. Therefore, the additive for polycarbonate resin in the past is difficult to improve the fluidity, mold release property, and heat resistance at the time of processing the polycarbonate resin composition, and therefore, the present situation is expected to be further improved.

Therefore, an object of the present invention is to provide an additive for a polycarbonate resin which can improve fluidity, mold release property and heat resistance of a polycarbonate resin, a polycarbonate resin composition containing the same, and a molded article thereof.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors have found that a compound having a specific structure can impart excellent fluidity, mold release property, and heat resistance to a polycarbonate resin, and the present invention has been successfully completed.

That is, the additive for a polycarbonate resin of the present invention is characterized by containing a compound represented by the following general formula (1);

In the general formula (1), R represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and m represents a number of 2 to 100.

In the additive for a polycarbonate resin of the present invention, R in the above general formula (1) is preferably a second-order alkyl group having 3 to 20 carbon atoms.

The polycarbonate resin composition of the present invention is characterized by comprising (a) a polycarbonate resin and (b) an additive for a polycarbonate resin, and (b) an additive for a polycarbonate resin is a polycarbonate resin of the present invention Additives.

In the polycarbonate resin composition of the present invention, the content of the (b) polycarbonate resin additive is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the (a) polycarbonate resin.

The molded article of the present invention is characterized by being obtained from the polycarbonate resin composition of the present invention.

[Effects of the Invention]

According to the present invention, there is provided an additive for a polycarbonate resin which can improve fluidity, mold release property and heat resistance of a polycarbonate resin, a polycarbonate resin composition containing the same, and a molded article thereof.

Hereinafter, embodiments of the present invention will be described in detail.
First, an additive for a polycarbonate resin of the present invention will be described. The additive for a polycarbonate resin of the present invention contains a compound represented by the following general formula (1). Here, in the general formula (1), R represents an alkyl group having 1 to 20 carbon atoms, and m represents a number of 2 to 100.

In the general formula (1), the alkyl group having 1 to 20 carbon atoms represented by R may, for example, be a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group or an isobutyl group. Base, sec-butyl, tert-butyl, n-pentyl, isopentyl, pentan-2-yl, pent-3-yl, neopentyl, tert-pentyl, 1,2-dimethylpropane Base, n-hexyl, cyclohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, hex-2-yl, hex-3-yl, n -heptyl, hept-2-yl, hept-3-yl, hept-4-yl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl, tert-octyl, 2-ethylhexyl, 2-methylhexyl, 2-propylhexyl, oct-2-yl, oct-3- , oct-4-yl, n-fluorenyl, isodecyl, indol-2-yl, indol-3-yl, n-fluorenyl, isodecyl, indol-2-yl, n-undecyl, Isopentyl, n-dodecyl, isododecyl, n-tridecanyl, isotridecyl, n-tetradecyl, isotetradecyl, n-pentadecayl, isopentadepyl, n -hexadecyl, isohexadecyl, n-heptadecyl, isoheptadethyl, n-octadecyl, isooctyl, n-n-19, iso-n 19, n- twenty-s, Twenty base .

In the general formula (1), from the viewpoints of fluidity, mold release property and heat resistance of the polycarbonate resin, the alkyl group represented by R is preferably a second-order alkyl group having 3 to 20 carbon atoms, and carbon is preferably used. The second alkyl group having 5 to 9 atomic atoms is preferred, and the hept-3-yl group is most preferred.

The second-stage alkyl group may, for example, be 2-propyl, sec-butyl, pent-2-yl, pent-3-yl, 1,2-dimethylpropyl or 1,3-dimethyl Butyl, 1-isopropylpropyl, 1,2-dimethylbutyl, hex-2-yl, hex-3-yl, hept-2-yl, hept-3-yl, hept-4- Base, 1,4-dimethylpentyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, oct-2-yl, oct-3-yl, octyl 4-yl, indol-2-yl, indol-3-yl, indol-2-yl and the like.

Further, in the general formula (1), the alkyl group having 1 to 20 carbon atoms represented by R may have a substituent. The substituent may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group or an isopentyl group. , tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, dicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, Tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, decyl, isodecyl, fluorenyl, etc.; methoxy, ethoxy, propoxy , isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy , heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, etc. Alkoxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio Tert-pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio Alkylthio group such as tert-octylthio, 2-ethylhexylthio; vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl , 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, dicyclohexenyl, heptenyl, octenyl Alkenyl groups such as decenyl, pentacenyl, behenyl, and behenyl; benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl An arylalkyl group; an aryl group such as a phenyl group or a naphthyl group; an aryloxy group such as a phenoxy group or a naphthyloxy group; an arylthio group such as a phenylthio group or a naphthylthio group; a pyridyl group, a pyrimidinyl group or an anthracene group; Azinyl, piperidinyl, piperidyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furyl, benzene And furyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, anthracene Mercapto, 2-pyrrolidone-1-yl, 2-piperidin-1-yl, 2,4-dioxyimidazol-3-yl a heterocyclic group such as 2,4-dioxyoxazolidin-3-yl; a halogen atom such as fluorine, chlorine, bromine or iodine; an ethyl group, a 2-chloroethyl group, a propyl group, a decyl group, and a propylene group; Sulfhydryl, methacryl fluorenyl, phenylcarbonyl (benzylidene), phthalic acid, 4-trifluoromethylbenzylidene, trimethylethenyl, sulfonyl, oxalate, stearic acid a mercapto group such as an anthracenyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, an n-octadecyloxycarbonyl group or an amine formazan group; an oxime group such as an ethoxy group or a benzyloxy group; Amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, Chlorophenylamino, toluidine, aminoanisole, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, Phenoxycarbonylamino, acetamidoamine, benzhydrylamine, methionylamino, trimethylethenylamine, laurylamine, aminecarboxamido, N,N - dimethylaminocarbonylamino group, N,N-diethylaminocarbonylamino group, morpholinylcarbonylamino group, Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonyl, N-methyl-methoxycarbonylamino, phenoxycarbonylamine Substituents such as sulfonylamino group, N,N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, etc. An amine group; a sulfonylamino group, a sulfonyl group, a carboxyl group, a cyano group, a sulfonic acid group, a hydroxyl group, a nitro group, a decyl group, a quinone group, an amine group, a sulfonyl group, etc., and these groups may also be used. More replaced. Further, a carboxyl group and a sulfonic acid group may form a salt. Further, when the alkyl group having 1 to 20 carbon atoms has a substituent having a carbon atom, the number of carbon atoms including the carbon atom contained in the substituent is in the range of 1 to 20.

In the general formula (1), m represents a number of from 2 to 100, and from the viewpoints of fluidity, mold release property, and heat resistance of the polycarbonate resin, m is preferably 4 to 45, and more preferably 8 to 35. It is more preferably 10 to 20, and particularly preferably 10 to 15.

The compound represented by the formula (1) is an aliphatic carboxylic acid having 2 to 21 carbon atoms represented by the following general formula (2), an alkyl ester thereof, an acid anhydride thereof, an alkali metal salt thereof, Or a carboxylic acid halide (also referred to as an acid halide) obtained by esterification reaction with polyethylene glycol represented by the following general formula (3). A catalyst for promoting the esterification reaction can also be used in the reaction. As the catalyst, conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.

In the general formula (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms.

In the general formula (3), n represents a number from 2 to 100.

R ¹ of the general formula (2) corresponds to R of the alkyl group of the general formula (1). The aliphatic carboxylic acid having 2 to 21 carbon atoms represented by the general formula (2) may, for example, be acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid or 2-methylbutyric acid (hydroangelic acid). ), hexanoic acid, 2-methylpentanoic acid, heptanoic acid, 2-methylheptanoic acid, n-octanoic acid, isooctanoic acid, 2-ethylhexanoic acid, citric acid, citric acid, lauric acid, myristic acid, ten Pentaolic acid, palmitic acid, heptadecanoic acid, stearic acid, and the like. From the viewpoint of fluidity, mold release property, and heat resistance of the polycarbonate resin, the aliphatic carboxylic acid having 2 to 21 carbon atoms represented by the general formula (2) has R ¹ as a carbon number of 3 to 20 The carboxylic acid of the second-stage alkyl group is preferred, and the carboxylic acid of the second-order alkyl group having 5 to 9 carbon atoms of R ¹ is preferred, and 2-ethylhexanoic acid is preferred. Further, n of the general formula (3) corresponds to m of the general formula (1).

From the viewpoint of fluidity, mold release property and heat resistance of the polycarbonate resin, the polyethylene glycol of the general formula (3) is preferably a polyethylene glycol having a number average molecular weight of 200 to 2,000, and a number average molecular weight of 350 to ～. Polyethylene glycol of 1500 is preferred, and polyethylene glycol having a number average molecular weight of 500 to 900 is more preferable, and polyethylene glycol having a number average molecular weight of 500 to 700 is particularly preferable. Further, the number average molecular weight of the polyethylene glycol of the general formula (3) is a value obtained by the following method for measuring the average molecular weight.

<Number average molecular weight measurement method>
The hydroxyl value was measured by a hydroxyl value measuring method, and the number average molecular weight (hereinafter also referred to as "Mn") was determined by the following formula.
Number average molecular weight = (56110 × 2) / hydroxyl value

<hydroxy value measurement method>
・Pharmaceutical A (acetylation agent)
(1) Triethyl phosphate 1560mL
(2) Anhydrous acetic acid 193mL
(3) Perchloric acid (60%) 16g
Mix the above reagents according to (1) → (2) → (3).
・Pharmaceutical B
The pyridine and pure water were mixed in a volume ratio to 3:1.
・Try drug C
Two to three drops of phenolphthalein solution were added to 500 mL of isopropyl alcohol, and neutralized with a 1 N-KOH aqueous solution.

First, 2 g of a sample was placed in a 200 mL Erlenmeyer flask, and 10 mL of xylene was added thereto and dissolved by heating. Add 15 mL of reagent A, and violently shake after embolization. Add 20 mL of reagent B, and violently shake after embolization. Add reagent C 50mL. The titration was carried out using a 1 N-KOH aqueous solution, and the calculation was carried out by the following formula.

Hydroxyl value [mgKOH/g] = 56.11 × f × (TB) / S
f: factor of 1N-KOH aqueous solution (factor)
B: empty test titration [mL]
T: the titer of this test [mL]
S: sample amount [g]

The compound represented by the general formula (1) of the present invention may, for example, be a compound represented by the following chemical formulas No. 1 to No. 7.

Compound No.1

The additive for a polycarbonate resin of the present invention may be a single type of the compound represented by the general formula (1), or a mixture of two or more types. Further, the additive for a polycarbonate resin of the present invention may contain, in addition to the compound represented by the general formula (1), a component which produces an unreacted raw material, a by-product or the like of the compound. The additive for a polycarbonate resin of the present invention preferably contains 90% by mass or more of the compound represented by the general formula (1), and preferably contains 95, from the viewpoint of fluidity, mold release property and heat resistance of the polycarbonate resin. More than % by mass.

The additive for a polycarbonate resin of the present invention can be used by blending a polycarbonate resin with a polycarbonate resin composition.

Next, the polycarbonate resin composition of the present invention will be described. The polycarbonate resin composition of the present invention contains (a) a polycarbonate resin (hereinafter, simply referred to as "(a) component)"), and (b) an additive for a polycarbonate resin (hereinafter, a single The polycarbonate resin composition referred to as "(b) component)"), and (b) the additive for polycarbonate resin is the additive for polycarbonate resin of this invention.

As the polycarbonate resin, a conventionally known or commercially available one may be used, but an aromatic polycarbonate produced by a reaction of a divalent phenol and a carbonate precursor is preferred. The reaction between the divalent phenol and the carbonate precursor is, for example, a solution method or a melting method, and specific examples thereof include a reaction between a divalent phenol and phosgene, a transesterification reaction between a divalent phenol and a diphenyl carbonate, and the like. .

Examples of the divalent phenol include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, and 1,1-bis(4-hydroxyphenyl). Ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, oxidized double 4-hydroxyphenyl), bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxyphenyl)ether, double (4-hydroxyphenyl) ketone and the like. In addition, examples of the divalent phenol include hydroquinone, resorcin, and catechol. These divalent phenols may be used singly or in combination of two or more. Particularly preferred divalent phenols such as bis(hydroxyphenyl)alkanes are, in particular, bisphenol A as the main raw material.

In addition, examples of the carbonate precursor include a carbonyl halide, a carbonyl ester, and a haloformate, and specific examples thereof include phosgene, a dihaloformate of divalent phenol, and diphenyl carbonate. Dimethyl carbonate, diethyl carbonate, and the like.

Further, the polycarbonate resin may have a branched structure, and examples of the branching agent include 1,1,1-paraxyl (4-hydroxyphenyl)ethane, α,α',α"-parameter (4). -hydroxyphenyl)-1,3,5-triisopropylbenzene, fluoroglycine, trimellitic acid, isatinbis (o-cresol), etc. In order to adjust the molecular weight, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol or the like can also be used.

Further, as the polycarbonate resin, a copolymer having a polycarbonate portion and a polyorganosiloxane portion or a polycarbonate resin containing the copolymer may be used. Further, the copolymer may be a polyester obtained by subjecting a polycarbonate to polymerization in the presence of an ester precursor such as a bifunctional carboxylic acid such as citric acid or an ester thereof to form a derivative or the like. Polycarbonate resin. Further, various polycarbonate resins may be suitably used in combination.

Further, the polycarbonate resin may be not only a resin having a polycarbonate content of 100%, but also a so-called polymer alloy in which a polycarbonate and another resin are mixed. Examples of such a polymer alloy include polycarbonate/ABS resin, polycarbonate/AS resin, polycarbonate/rubber-based polymer compound, polycarbonate/ABS resin/rubber-based polymer compound, and polycondensation. Carbonate/polyethylene terephthalate, polycarbonate/polybutylene terephthalate, polycarbonate/ASA resin, polycarbonate/AES resin, and the like.

In the polycarbonate resin composition of the present invention, the content ratio of the component (b) in 100 parts by mass of the component (a) is 0.1 part by mass from the viewpoints of fluidity, mold release property, heat resistance and the like at the time of processing. It is preferably from 10 parts by mass to 0.3 parts by mass, more preferably from 0.5 part by mass to 5.0 parts by mass, even more preferably from 1.0 to 5.0 parts by weight.

In the polycarbonate resin composition of the present invention, various additives such as a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, and a hindered amine-based light stabilizer may be added as needed. Further, the polycarbonate resin composition of the present invention can be stabilized. Various additives such as these antioxidants may be blended in advance with the additive for polycarbonate resin of the present invention before being blended into the polycarbonate resin.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecylphenol, and distearylthiol (3, 5-di-t-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-t-butyl-4-hydroxyphenyl)propanoate] , 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2' -methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylenebis(6-tert-butyl-m-cresol), 2,2'-ethylene Bis(4,6-di-t-butylphenol), 2,2'-ethylenebis(4-secondbutyl-6-tert-butylphenol), 1,1,3-parade (2- Methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-gin (2,6-dimethyl-3-hydroxy-4-tributylbenzyl) Polycyanate, 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)isocyanate, 1,3,5-para (3,5-di Tributyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-propenyloxy-3-t-butyl -5-methylbenzyl)phenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl)propionate, 肆[3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionic acid methyl] Alkane, thiodiethylene glycol bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-third) 4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid]diol ester, bis[2-t-butyl 4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]p-nonanoate, 1,3,5-para [[3,5-di Tributyl-4-hydroxyphenyl)propoxycarbonylethyl]isocyanate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4) -hydroxy-5-methylphenyl)propenyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol bis[(3- Tributyl-4-hydroxy-5-methylphenyl)propionate] and the like. The amount of the phenolic antioxidant to be added is preferably 0.001 to 10 parts by mass, and preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the polycarbonate resin.

Examples of the phosphorus-based antioxidant include decyl phenyl phosphite and ginseng [2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio). )-5-methylphenyl]phosphite, tridecyl phosphite, octyl diphenyl phosphite, bis(indenyl)monophenylphosphite, di(tridecyl)pentaerythritol di Phosphate, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4- Methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-diisopropylphenylphenyl)pentaerythritol di Phosphate, tetrakis(trisyl)isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylene bis(2-tert-butyl-5-methylphenol Diphosphite, hexakis(tridecyl)-1,1,3-glycol(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, bismuth (2,4) -di-tert-butylphenyl)-biphenyldiphosphinate, 9,10-dihydro-9-oxa-10-phosphinophen-10-oxide, 2,2'-methylene double (4,6-t-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-t-butylphenyl)-octadecyl phosphite, 2,2'-ethylenebis(4,6-di-t-butylphenyl) Fluorophosphite, ginseng (2-[(2,4,8,10-indole-t-butyldibenzo[d,f][1,3,2]dioxaphospholene-6-) Alkyloxy]ethyl)amine, 2-ethyl-2-butylpropanediol, and a phosphite of 2,4,6-tri-t-butylphenol. The amount of the phosphorus-based antioxidant to be added is preferably 0.001 to 10 parts by mass, and preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the polycarbonate resin.

Examples of the thioether-based antioxidant include dialkylthiodipropionate such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate. Classes, and pentaerythritol tetrakis (β-alkyl thiopropionic acid) esters. The amount of the thioether-based antioxidant added is preferably 0.001 to 10 parts by mass, and preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the polycarbonate resin.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 5 2-hydroxybenzophenone such as 5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl) Benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-third -5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-trioctylphenyl)benzotriazole, 2-(2'-hydroxy- 3',5'-diisopropylphenylphenyl)benzotriazole, 2,2'-methylenebis(4-th-octyl-6-(benzotriazolyl)phenol), 2- 2-(2'-hydroxyphenyl)benzotriazoles such as (2'-hydroxy-3'-t-butyl-5'-carboxyphenyl)benzotriazole; Hydroquinone monobenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-pentylphenyl a benzoate such as -3,5-di-t-butyl-4-hydroxybenzoate or hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; 2-B Base-2'-ethoxyoxalin aniline, 2 - oxanilides such as ethoxy-4'-dodelosylanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano a cyanoacrylate such as 3-methyl-3-(p-methoxyphenyl)acrylate; 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis (2) ,4-di-t-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2 Triaryltriazines such as -hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-t-butylphenyl)-s-triazine. The amount of the ultraviolet absorber added is preferably 0.001 to 30 parts by mass, and preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the polycarbonate resin.

The hindered amine light stabilizer may, for example, be 2,2,6,6-tetramethyl-4-piperidinyl stearate or 1,2,2,6,6-pentamethyl-4. - piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl Azelaic acid ester, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetra Methyl-4-piperidinyl) sebacate, bismuth (2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate,肆(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl Benzyl-4-piperidinyl) bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidin Pyridyl) bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2 -butyl-2-(3,5-di-t-butyl-4-hydroxybenzyl)malonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylic acid Ester, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 -tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl)imido}], 1,2,3 , 4-butanecarboxylic acid/2,2-bis(hydroxyl Methyl)-1,3-propanediol/3-hydroxy-2,2-dimethylpropanal/1,2,2,6,6-pentamethyl-4-piperidyl ester polycondensate, double (1 ,2,2,6,6-pentamethyl-4-piperidinyl)=sebacate/methyl=1,2,2,6,6-pentamethyl-4-piperidinyl=癸二Acid ester mixture, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- Piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinyl) hexane/dibromoethane polycondensate, 1 ,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexane/2,4-dichloro-6-morpholinyl-s-triazine polycondensate, 1, 6-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexane/2,4-dichloro-6-t-octylamino-s-triazine polycondensate, 1,5,8,12-anthracene [2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine -6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-fluorene [2,4-bis(N-butyl-N-(1,2,2) ,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11- Reference [2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-ylamino] Mono-, 1,6,11-para [2,4-bis(N-butyl-N-(1,2,2,6,6-five) 4-piperidinyl)amino)-s-triazin-6-ylamino]undecane, 3,9-bis[1,1-dimethyl-2-{ gin (2,2, 6,6-tetramethyl-4-piperidinyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9- Bis[1,1-dimethyl-2-{((1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)butylcarbonyloxy}ethyl]-2, 4,8,10-tetraoxaspiro[5.5]undecane, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2 A hindered amine compound such as 6,6-tetramethyl-4-piperidyl hexadecanate or 2,2,6,6-tetramethyl-4-piperidyl octadecanoate. The amount of the hindered amine light stabilizer to be added is preferably 0.001 to 30 parts by mass, and preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the polycarbonate resin.

In the polycarbonate resin composition of the present invention, an aromatic carboxylic acid metal salt, an alicyclic alkyl carboxylic acid metal salt, or a p-t-butyl group may be added as necessary in order not to impair the effects of the present invention. A nucleating agent such as aluminum benzoate, an aromatic phosphate metal salt, a dibenzylidene sorbitol, a metal soap, a hydrotalcite, a triazine ring-containing compound, a metal hydroxide, a phosphate-based flame retardant, and a condensed phosphoric acid Ester-based flame retardant, phosphate-based flame retardant, inorganic phosphorus-based flame retardant, (poly)phosphate-based flame retardant, halogen-based flame retardant, antimony-based flame retardant, antimony trioxide, etc. Other inorganic flame retardant auxiliaries, other organic flame retardant auxiliaries, fillers, antistatic agents, pigments, slip agents, foaming agents, etc. as other additives.

The triazine ring-containing compound may, for example, be melamine, 2,4-diamino-6-hydroxy-1,3,5-triazine, benzoguanamine, acetamide or phthalocyanine. Phthadiaguanamine, melamine cyanurate, melamine melamine, butyl decylamine, norbornene diamine, methylene dimethylamine, ethyl melamine, trimethylene double Melamine, tetramethylene bis melamine, hexamethylene bis melamine, 1,3-extension bis melamine, and the like.

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kisuma 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.).

Examples of the phosphate-based flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, chloroethyl phosphate, and dichloroethylene. Propyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, xylyl phosphate, octyl diphenyl phosphate, xylyl diphenyl phosphate, Isopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, ginseng- T-butylphenyl)phosphate, isopropylphenyldiphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, cis-(isopropylphenyl)phosphate, and the like.

Examples of the condensed phosphate-based flame retardant include 1,3-phenylphenylbis(diphenylphosphate), 1,3-phenylenebis(dixylenyl phosphate), and bisphenol. A bis(diphenyl phosphate) or the like.

Examples of the (poly)phosphate-based flame retardant include ammonium (poly)phosphate such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrroline, piperazine pyrrolizonate or the like. Amine salt.

Examples of other inorganic flame retardant auxiliary agents include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, and montmorillonite, and surface-treated products thereof. For example, TIPAQUER-680 can be used. (titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.), Kyowamag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: Kyowa Chemical Industry Co., Ltd.), Alcamizer 4 (zinc denatured hydrotalcite) : Various commercial products such as Concord Chemical Industry Co., Ltd.). Further, examples of other organic flame retardant aids include pentaerythritol.

In addition, in the polycarbonate resin composition of the present invention, additives which are generally used for synthetic resins, such as a crosslinking agent and an anti-blocking agent, may be blended in the effect range of the present invention as necessary within the range of the effect of the present invention. Spray, plate-out preventing agent, surface treatment agent, plasticizer, slip agent, flame retardant, fluorescent agent, mold inhibitor, fungicide, antibacterial agent, foaming agent, metal inert agent , release agent, pigment, processing aid, antioxidant, light stabilizer, catalyst deactivation agent during polymerization.

Further, in the polycarbonate resin composition of the present invention, a thermoplastic resin other than the above polycarbonate resin may be blended as necessary insofar as the effect of the present invention is not impaired.

Examples of the thermoplastic resin include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, polybutene-1, poly- A-olefin polymer such as 3-methylpentene or poly-4-methylpentene or a polyolefin-based copolymer such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer or ethylene-propylene copolymer Resin and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride, polychloropropene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer , vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-ring Halogen-containing resin such as hexylmalanimide copolymer; petroleum resin, couma resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and/or α-methylstyrene and other monomers ( For example, anhydrous maleic acid, phenyl maleimide, methyl methacrylate Copolymer of butadiene, acrylonitrile, etc. (for example, AS resin, ABS (acrylonitrile butadiene styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat resistant ABS resin, etc.); polymethacrylic acid Methyl ester, polyvinyl alcohol, polyethylene formaldehyde, polyvinyl butyral; poly(ethylene terephthalate), polybutylene terephthalate, polycyclohexane dimethylene terephthalate Aromatic polyester such as alkyl terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc., and polytetramethylene p-benzoate Linear polyester such as diformate; polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydextrin a decomposable aliphatic polyester such as an alkane or a poly(2-oxetanone); a polydecene amine such as polyphenylene oxide, polycaprolactam or polyhexamethylene hexamethyleneamine; Polyacetal, polyphenylene sulfide, polyurethane, cellulose resin, polyimine resin, polyfluorene, polyphenylene ether
Thermoplastic resins such as polyphenylene ether, polyether ketone, polyether ether ketone, liquid crystal polymer, and the like. Further, the thermoplastic resin may be an isoprene rubber, a butadiene rubber, an acrylonitrile-butadiene copolymer rubber, a styrene-butadiene copolymer rubber, a fluororubber, a polyoxyethylene rubber, or an olefin elastomer. Elastomer such as a body, a styrene elastomer, a polyester elastomer, a nitrile elastomer, a nylon elastomer, a vinyl chloride elastomer, a polyamide elastomer, or a polyurethane elastomer . In the polycarbonate resin composition of the present invention, these thermoplastic resins may be used singly or in combination of two or more. Further, the thermoplastic resin can also be alloyed.

The thermoplastic resin is a molecular weight, a degree of polymerization, a density, a softening point, a ratio of insoluble matter to a solvent, a degree of stereoregularity, presence or absence of a catalyst residue, a kind or a compounding ratio of a monomer as a raw material, and a polymerization touch. The type of media (for example, Ziegler catalyst, metallocene catalyst, etc.) can be used.

The polycarbonate resin composition of the present invention is obtained by blending the components (a) and (b) in an appropriate ratio, and kneading with other additives as necessary. At this time, the mixing and kneading system can use the commonly used machines, such as a ribbon blender, a drum tumblers, etc., and then use the Henrich mixer and the closed mixing. It is carried out by a method such as a refiner, a single-axis screw extruder, a twin-screw extruder, a multi-axis screw extruder, and a co-kneader. The heating temperature during the kneading is usually suitably selected within the range of 240 to 300 °C. In addition, the component component other than the component (a) may be added as a masterbatch which is melted and kneaded in advance with the component (a).

The polycarbonate resin composition of the present invention is produced as a pellet obtained by the above-described melt kneading molding method, or the pellet is used as a raw material by an injection molding method, an injection compression molding method, or extrusion molding. A variety of molded articles are produced by a method, a blow molding method, a press molding method, a vacuum molding method, a foam molding method, or the like. In particular, it is preferable to produce a pellet-shaped molding material by a melt-kneading molding method, and to use the pellet in the next step, which is particularly suitable for the production of an injection-molded article obtained by injection molding and injection compression molding. use. Further, as the injection molding method, a gas injection molding method may be employed in order to prevent shrinkage of the appearance or to reduce the weight.

Next, the molded body of the present invention will be described. The molding system of the present invention is obtained from the polycarbonate resin composition of the present invention. The molded article of the present invention is obtained by molding a polycarbonate resin composition by the above method.

The polycarbonate resin composition of the present invention and a molded article thereof (including an injection molded article and an injection molded article) can be used in a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), and a telephone. , photocopiers, fax machines, ECR (electronic money registration machines), electronic calculators, electronic notes, cards, fixtures, stationery, etc., OA machines, washing machines, refrigerators, sweepers, microwave ovens, lighting fixtures, game consoles Home appliances such as irons, ovens, televisions, radios, video decks, video cameras, radio cassettes, tape recoders, mini-discs, CD players, amplifiers, AV equipment such as liquid crystal displays, electrical and electronic equipment enclosures, electrical and electronic components, automotive interior and exterior materials, automotive parts, vehicles, ships, aircraft parts, residential and building materials, glasses, lenses, optical equipment, optical parts, and , boxes, eye masks, snowboards, rackets, musical instruments, various containers and other daily necessities, sporting goods, and other uses.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited.

<Examples 1 to 3>
The polyethylene glycol having a number average molecular weight of 600 is esterified with 2-ethylhexanoic acid to obtain the additive-1 for polycarbonate resin of the present invention represented by Chemical Formula No. 1 (hereinafter referred to as additive-1). .

Using the obtained additive-1, the polycarbonate resin composition of the present invention was obtained by the blending (parts by mass) described in the following Table 1. The polycarbonate resin composition is further blended with 0.2 parts by mass of a phenol-based antioxidant (Adekastab AO-50, manufactured by ADEKA) and a phosphorus-based antioxidant (Adekastab C, (share)), based on 100 parts by mass of the polycarbonate resin. Made by ADEKA) 0.1 parts by mass. The polycarbonate resin composition obtained was supplied to an extruder (Labo Plastomill 2-axis extruder, manufactured by Toyo Seiki Co., Ltd.), and kneaded at 260 ° C by melt-kneading. The obtained pellets were dried at 80 ° C for 12 hours, and the spiral flow length was evaluated by the following test method. The results are shown in Table 1.

Further, in place of the above test piece, a mold release evaluation test die of 80 mm × 100 mm × 40 mm (depth), a wall thickness of 3 mm, and a draft of a draft of 0 was used as a molded product mold, and molding was carried out under the same molding conditions. The release property and heat resistance were evaluated. The results are shown in Table 1.

<Example 4>
The polyethylene glycol having a number average molecular weight of 600 and an n-octanoic acid are subjected to an esterification reaction to obtain an additive-2 for a polycarbonate resin of the present invention (hereinafter referred to as an additive-2) represented by Chemical Formula No. 2. Using the obtained additive-2, the polycarbonate resin composition of the present invention was prepared by the blending (parts by mass) described in Table 1 below. After the antioxidant was added in the same manner as in Example 1, the spiral flow length, the mold release property, and the heat resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 5>
The polyethylene glycol having a number average molecular weight of 600 and an isooctanoic acid are subjected to an esterification reaction to obtain an additive-3 for a polycarbonate resin of the present invention (hereinafter referred to as an additive-3) represented by Chemical Formula No. 3. Using the obtained additive-3, the polycarbonate resin composition of the present invention was prepared by the blending (parts by mass) described in Table 1 below. After the antioxidant was added in the same manner as in Example 1, the same procedure as in Example 1 was carried out, and the spiral flow length, mold release property, and heat resistance were evaluated. The results are shown in Table 1.

<Example 6>
The polyethylene glycol having a number average molecular weight of 600 is subjected to an esterification reaction with n-butyric acid to obtain the additive-4 for a polycarbonate resin of the present invention represented by Chemical Formula No. 4 (hereinafter referred to as "Additive-4"). Using the obtained additive-4, the polycarbonate resin composition of the present invention was prepared by the blending (parts by mass) described in Table 1 below. After the antioxidant was added in the same manner as in Example 1, the spiral flow length, the mold release property, and the heat resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 7>
The polyethylene glycol having a number average molecular weight of 600 is subjected to an esterification reaction with n-decanoic acid to obtain an additive-5 for a polycarbonate resin of the present invention (hereinafter referred to as an additive-5) represented by Chemical Formula No. 5. Using the obtained additive-5, the polycarbonate resin composition of the present invention was prepared by the blending (parts by mass) described in Table 1 below. After the antioxidant was added in the same manner as in Example 1, the spiral flow length, the mold release property, and the heat resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 1>
The spiral flow length, mold release property, and heat resistance were evaluated in the same manner as in Example 1 except that the additive-1 for polycarbonate resin was not used. The results are shown in Table 1.

<Comparative Example 2>
The spiral flow length and mold release property were evaluated in the same manner as in Example 1 except that bis(2-ethylhexyl phthalate) of the synthetic resin plasticizer was used instead of the additive-1 as the comparative additive-1. Heat resistance. The results are shown in Table 1.

<Spiral Flow Length (SFL) Test Method>
The measurement was carried out under the conditions of a molding temperature of 280 ° C, a mold temperature of 80 ° C, a wall thickness of 2 mm, a width of 10 mm, and an injection pressure of 110 MPa. The unit is cm. The longer the value, the more excellent the fluidity during processing.

<Releasability test method>
The pressure of the extrusion pin was measured. The maximum pressure is 2.9 MPa, and the smaller the value, the better the mold release property.

<Heat resistance test method>
The molded article obtained by the mold release test was used as a test piece and the yellowness (YI value) was measured. The smaller the value of the yellowness is, the smaller the coloring is, and the heat resistance is excellent.

*1: Bisphenol A type polycarbonate resin (melt volume flow rate: 19 cm ³ / 10 minutes (300 ° C, 1.2 kg load)

From the results shown in Table 1, it is understood that the additive for a polycarbonate resin of the present invention can improve the fluidity, mold release property, and heat resistance of the polycarbonate resin.

Claims (5)

An additive for polycarbonate resin characterized by containing a compound represented by the following general formula (1); In the general formula (1), R represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and m is a number of 2 to 100. The additive for polycarbonate resin according to claim 1, wherein R in the above general formula (1) is a second-order alkyl group having 3 to 20 carbon atoms. A polycarbonate resin composition comprising (a) a polycarbonate resin and (b) an additive for a polycarbonate resin, and (b) an additive for a polycarbonate resin is a polycarbonate according to claim 1 or 2. An additive for ester resins. The polycarbonate resin composition of claim 3, wherein the content of the (b) polycarbonate resin additive is 0.1 to 10 parts by mass based on 100 parts by mass of the (a) polycarbonate resin. A shaped body characterized by being obtained from the polycarbonate resin composition of claim 3 or 4.