JP2007077208A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is colored little and excellent in transparency and also excellent in hydrolysis resistance and chemical resistance. <P>SOLUTION: The resin composition contains (A) an aromatic polycarbonate resin, (B) a cycloaliphatic polyester resin, and (C) at least one phosphate metal salt selected from among chain or cyclic phosphate alkaline earth metal salts, zinc salts, and aluminum salts. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition containing an aromatic polycarbonate resin and an alicyclic polyester resin, and particularly to a resin composition from which a molded product with little coloring and excellent hydrolysis resistance can be obtained.

  Aromatic polycarbonate resin is a resin with excellent mechanical strength such as transparency, heat resistance, impact strength, and dimensional stability, so it contains building materials such as carport roofing materials and inorganic fillers such as glass fibers. It is widely used for electrical equipment such as chassis and gears for OA equipment, medical equipment such as dialyzer.

  Aromatic polycarbonate resins are generally considered to have poor chemical resistance, and attempts have been made to improve chemical resistance by blending aromatic polyester resins such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET). It has been broken. Although these resins have high compatibility with each other, they are not compatible with each other. Therefore, the compatibility is improved by using an ester exchange reaction at the time of blending. However, if the reaction is over, the heat resistance is lowered, and if the reaction is not sufficient, the transparency is lowered and sufficient mechanical strength cannot be obtained.

  On the other hand, a poly (1,4-cyclohexanedimethanol-1,4-cyclohexanedicarboxylate) resin (hereinafter abbreviated as PCC resin) and an aromatic polycarbonate resin are compatible with each other. Are known to exhibit high transparency. However, when a PCC resin and an aromatic polycarbonate resin are made into a composition by melt-kneading or the like, a transesterification reaction is caused, and a transparent but yellow-colored product is obtained. Therefore, a transesterification inhibitor is used to prevent coloring. (See Non-Patent Document 1).

  Examples of the transesterification inhibitor between an aromatic polycarbonate resin and a certain aromatic polyester resin or alicyclic polyester resin include, for example, acidic phosphates, specific phosphites, Group IB or IIB metals. Phosphate, phosphorus oxoacid, and acid pyrophosphate metal salts are known (see Patent Documents 1 and 2).

On the other hand, a resin composition containing a certain type of organophosphate metal salt has been proposed, and a composition comprising an alkyl group or alkenyl group phosphate zinc salt having 10 to 20 carbon atoms and a polyvinyl chloride resin, Good processability, such as reduced adhesion to heating rolls (Patent Document 3), and a resin composition containing a polyarylene sulfide resin or a thermoplastic polyester resin and an organophosphate metal salt has a high crystallization rate. , Shortening of the molding cycle (Patent Document 4), polycarbonate and / or polyester carbonate, specific graft polymer represented by ABS having a glass transition temperature of less than 10 ° C., alkyl group having 1 to 24 carbon atoms, carbon Phosphoric acid of a cycloalkyl group having 5 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms Resin composition comprising ester metal salt, it is excellent in impact strength and heat stability are shown. (Patent Document 5)
J.Phys.:Condens. Matter 8 (1996) p3811-3827 US Patent 5,441,997 WO99 / 63002 Japanese Patent Publication No.54-19422 JP-A-11-35807 Japanese translation of PCT publication No. 2002-509174

In recent years, a sterilization method using an autoclave at 120 ° C. is often used for sterilization of medical instruments, but according to our study, in the composition using the transesterification inhibitor described in Patent Documents 1 and 2, It has been found that the hydrolysis resistance of the resin is not sufficient in an environment at the time of sterilization, and there is a problem that the molecular weight is lowered. If the hydrolysis resistance is poor, the medical device may be cracked, cracked and eventually damaged.
Patent Documents 3, 4 and 5 disclose a composition in which an organic phosphate metal salt is blended with a certain type of resin, but a resin composition containing an aromatic polyester resin and an alicyclic polyester resin. It is not known that an organophosphate metal salt is added to the resin, thereby suppressing the transesterification reaction, suppressing coloring, and improving hydrolysis resistance.
That is, an object of the present invention is to provide a resin composition which is less colored and excellent in transparency, and excellent in hydrolysis resistance and chemical resistance.

（式中、Ｒ¹〜Ｒ¹⁴は、それぞれ独立に炭素数１〜５０のアルキル基を示し、Ｍは、アルカリ土類金属、亜鉛およびアルミニウムからなる群より選ばれる金属を示す。） As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are a resin composition containing an aromatic polycarbonate resin and an alicyclic polyester resin, wherein the resin composition containing a specific phosphate metal salt is The present inventors have found that the problems can be solved and have reached the present invention. That is, the gist of the present invention is (A) an aromatic polycarbonate resin, (B) an alicyclic polyester resin, and (C) at least 1 represented by the following formula (1), (2), (3) or (4). The present invention resides in a resin composition containing a phosphoric acid ester metal salt.

(In the formula, R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 50 carbon atoms, and M represents a metal selected from the group consisting of alkaline earth metals, zinc and aluminum.)

  Since the resin composition of the present invention is less colored and highly transparent, it is useful as a resin composition for producing optical parts, and also has excellent hydrolysis resistance and chemical resistance. It is useful as a medical device requiring sterilization and a resin composition for manufacturing parts.

Hereinafter, the present invention will be described in detail. However, the description of the constituent elements (embodiments) described below is a representative example of the embodiments of the present invention, and the present invention is not limited to these descriptions. .
The (A) aromatic polycarbonate resin in the resin composition of the present invention is a polycarbonate having an aromatic ring, and is usually obtained by reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester. The phosgene method, the transesterification method and the like are not particularly limited.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A) Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl) Phenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4) Hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) Bis (hydroxyaryl) alkanes exemplified by -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, etc .; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy) Bis (hydroxyaryl) cycloalkanes exemplified by phenyl) -3,3-5-trimethylcyclohexane, etc .; 4-4′-dihydroxyphenyl ether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether, etc. Dihydroxydiaryl ethers, as exemplified by: 4,4′-di Dihydroxydiaryl sulfides exemplified by droxyphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethylphenyl sulfide and the like; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3 ′ -Dihydroxy diaryl sulfoxides exemplified by dimethyldiphenyl sulfoxide and the like; dihydroxy diaryl sulfones exemplified by 4,4'-dihydroxydiphenyl sulfone and the like; hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like.

（式中、Ａ’は、炭素数１〜１８の置換されていてもよい脂肪族又は芳香族炭化水素基であり、２つのＡ’は同一であっても異なっていてもよい。）
上記式（５）で表される炭酸ジエステルとしては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジ−ｔ−ブチルカーボネート等のジアルキルカーボネート；ジフェニルカーボネート、ジトリルカーボネート等のジアリールカーボネート等が例示される。これらの炭酸ジエステルは、単独で使用してもよく、２種以上を組み合わせて使用してもよいが、これらの中では、ジフェニルカーボネート、置換ジフェニルカーボネートが好ましく、特にジフェニルカーボネートを用いるのが好ましい。 These aromatic dihydroxy compounds may be used as a mixture of two or more if necessary. Among these, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) is particularly preferably used.
Examples of the carbonic acid diester include a compound represented by the following formula (5).

(In the formula, A ′ is an optionally substituted aliphatic or aromatic hydrocarbon group having 1 to 18 carbon atoms, and two A ′ may be the same or different.)
Examples of the carbonic acid diester represented by the above formula (5) include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate; and diaryl carbonates such as diphenyl carbonate and ditolyl carbonate. These carbonic acid diesters may be used alone or in combination of two or more. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.

In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 4,6-dimethyl-2,4,6 -Tris (4-hydroxyphenyl) -2-heptene, 1,3,5-tris (2-hydroxyphenyl) benzol, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,6-bis (2 -Hydroxy-5-methylbenzyl) -4-methylphenol, [alpha], [alpha] ', [alpha] "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, etc. , 3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin Scan phenol, it may be used in an amount corresponding to the branch of 5-bromo isatin bisphenol or the like.

In the case of a phosgene polycarbonate, a terminal terminator or a molecular weight modifier may be used.
As the terminal terminator or the molecular weight modifier, a compound having a monovalent phenolic hydroxyl group can be used, and as the compound having a monovalent phenolic hydroxyl group, ordinary phenol, pt-butylphenol, tribromo can be used. Phenol, long chain alkyl phenol, alkyl ether phenol, hydroxybenzoic acid alkyl ester and the like can be mentioned.
In addition to compounds having a monovalent phenolic hydroxyl group, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, aromatic carboxylic acids, and the like can also be used.
In the case of the polycarbonate resin used in the present invention, the end terminator or the molecular weight modifier may be used in combination of two or more as required.

The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is calculated as [η] = 1.23 × 10 ⁻⁴ × M ^0.83 from the intrinsic viscosity [η] measured at 20 ° C. in a methylene chloride solvent. The average molecular weight M is usually 10,000 to 100,000, preferably 13,000 to 50,000.
1 g of polycarbonate is dissolved in 100 ml of methylene chloride, and its specific viscosity (ηsp) is measured with an Ostwald viscometer. Furthermore, the concentration (c) was changed, the specific viscosity was measured in the same manner, and each concentration (c) and the specific viscosity / concentration ratio (ηsp / c) measured at the concentration were plotted in a graph.
Intrinsic viscosity [η] = limηsp / c
c → O
Ask for.

The (B) alicyclic polyester resin used in the resin composition according to the present invention is mainly obtained from a dicarboxylic acid component and a diol component, and the dicarboxylic acid component includes an alicyclic dicarboxylic acid and / or an ester forming property thereof. It can be obtained by using a derivative as a main component and a diol component having an alicyclic diol as a main component, subjecting both components to esterification or transesterification, and then polycondensation.
In addition, it shall mean that it is 80 mol% or more with respect to a dicarboxylic acid component and a diol component here, respectively as a main component. (B) The alicyclic polyester resin can contain components other than the above-mentioned dicarboxylic acid component and diol component in the raw material used unless the performance is impaired. It is about 10 mol% or less with respect to the total number of moles of the dicarboxylic acid component and the diol component.

The alicyclic dicarboxylic acid and / or ester-forming derivative thereof is not particularly limited as long as two carboxyl groups are bonded to the alicyclic structure. For example, 1,2-cyclohexanedicarboxylic acid 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, 2,7 -Decahydronaphthalenedicarboxylic acid, its ester-forming derivative, etc. are mentioned. Among these, 1,4-cyclohexanedicarboxylic acid and / or an ester-forming derivative thereof is preferable because the molding temperature of the obtained polyester resin is close to the molding temperature of a conventional polyester resin and is easily available industrially. In particular, 1,4-cyclohexanedicarboxylic acid is most preferable in terms of hydrolysis resistance compared to its ester-forming derivative.
The ratio of the trans isomer to the cis isomer of 1,4-cyclohexanedicarboxylic acid and / or its ester-forming derivative (trans isomer: cis isomer) is usually in the range of 80:20 to 100: 0. 85: 15-100: 0 is preferable from the heat resistant point of the alicyclic polyester resin obtained, More preferably, it is 90: 10-100: 0.

  As the dicarboxylic acid component in the present invention, the alicyclic dicarboxylic acid or the ester-forming derivative thereof as described above is usually 80 mol% or more, preferably 90 mol% or more based on the total dicarboxylic acid component, Other aromatic dicarboxylic acids, aliphatic dicarboxylic acids and the like may be contained. Specifically, terephthalic acid, phthalic acid, isophthalic acid, phenylenedioxycarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-diphenylketone dicarboxylic acid, 4,4 Aromatic dicarboxylic acids such as' -diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and succinic acid, glutanic acid, adipic acid, pimelic acid, suberic acid, azelain Examples thereof include acids, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, (di) alkyl esters in which each alkyl group has about 1 to 4 carbon atoms, and halides.

The alicyclic diol component is not particularly limited as long as two hydroxyl groups are bonded to the alicyclic structure, but since the heat resistance of the obtained polyester resin can be increased, It is preferably a diol having a 5-membered ring or a 6-membered ring and having two hydroxyl groups.
Examples of such alicyclic diols include 5-membered members such as 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, and bis (hydroxymethyl) tricyclo [5.2.1.0] decane. Ring-containing diol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2 , 2-membered ring-containing diols such as 2-bis (4-hydroxycyclohexyl) -propane, and the like. Of these, diols having two hydroxyl groups bonded to a 6-membered ring, specifically 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol are preferred. 4-cyclohexanedimethanol is preferred. 1,4-Cyclohexanedimethanol has high reactivity because the methylol group is located at the 1st and 4th positions, a polyester having a high glass transition temperature can be obtained, and a polyester resin having a high glass transition temperature can be obtained. This is because it has the advantage of being a product and easy to obtain.
The ratio of trans and cis isomers of 1,4-cyclohexanedimethanol (trans: cis) is in the range of 60:40 to 100: 0 in terms of the glass transition temperature of the resulting alicyclic polyester resin. It is preferable.

  In the present invention, the diol component contains an alicyclic diol as described above in an amount of 80 mol% or more, preferably 90 mol% or more based on the total diol component. If it is less than 80 mol%, the compatibility with polycarbonate tends to be poor, and the heat resistance tends to be poor.

  Other diol components used in the present invention include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, and xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis. And aromatic diols such as (4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and bis (4-β-hydroxyethoxyphenyl) sulfonic acid.

Furthermore, as a small amount copolymerization component other than the diol component and the dicarboxylic acid component, for example, hydroxycarboxylic acid such as glycolic acid, p-hydroxybenzoic acid, p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acid, and stearyl alcohol Monofunctional components such as benzyl alcohol, stearic acid, behenic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid Trifunctional or higher functional components such as acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, sugar ester, and the like may be used.
In addition, as (B) alicyclic polyester resin, an alicyclic ring obtained from a dicarboxylic acid component having 1,4-cyclohexanedicarboxylic acid as a main component and a diol component having 1,4-cyclohexanedimethanol as a main component. A polyester resin is preferable in view of compatibility with the (A) aromatic polycarbonate resin.

  As a use ratio of each component in the esterification reaction or transesterification reaction of the dicarboxylic acid component and the diol component, the total of the diol components is preferably 1 to 2 moles relative to the total of the dicarboxylic acid components. In particular, when the main component is a diol component having a high boiling point such as 1,4-cyclohexanedimethanol, the molar ratio is preferably 1 to 1.2 moles.

  In the esterification or transesterification reaction and polycondensation reaction for producing the alicyclic polyester, it is preferable to use a catalyst in order to obtain a sufficient reaction rate. Such a catalyst is not particularly limited as long as it is a catalyst usually used for esterification or transesterification, and examples thereof include a titanium compound, a germanium compound, an antimony compound, and a tin compound. Of these, titanium compounds are preferred because of their high activity in both esterification or transesterification and subsequent polycondensation reactions. Specifically, tetra-n-propyl titanate, tetra-i-propyl titanate are preferred. , Tetra-n-butyl titanate or a hydrolyzate of these organic titanates, etc., and one kind may be used or two or more kinds may be used in combination. Moreover, you may combine with a magnesium compound, a phosphorus compound, etc. as needed. The usage-amount at the time of using a catalyst is in the range of 1-2000 ppm normally with respect to the polyester resin to produce | generate, Preferably it is the range of 10-1000 ppm.

  The intrinsic viscosity of the alicyclic polyester resin used in the present invention is preferably 0.4 to 1.6 dl / g, more preferably 0.6 to 1.5 dl / g. If the intrinsic viscosity is less than 0.4 dl / g, the mechanical strength is insufficient, and if it is greater than 1.6 dl / g, the fluidity is lowered and the moldability is poor. The polyester resin used in the above may be one obtained by performing solid phase polymerization as necessary to increase the intrinsic viscosity.

  The terminal carboxylic acid concentration of the alicyclic polyester resin used in the present invention is usually 50 equivalents / ton or less, preferably 30 equivalents / tons or less, and more preferably 20 equivalents / tons or less. When the terminal carboxylic acid concentration is too high, the hydrolysis resistance of the alicyclic polyester resin itself decreases, and the hydrolysis resistance tends to decrease even in the resin composition mixed with the aromatic polycarbonate resin.

  The melting point of the alicyclic polyester resin used in the present invention is usually 200 ° C. or higher, preferably 210 ° C. or higher, and the upper limit is usually about 260 ° C. Among them, as a preferable alicyclic polyester resin, in the case of an alicyclic polyester resin mainly composed of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid component and 1,4-cyclohexanedimethanol as a diol component, Is 200 to 250 ° C, preferably 210 to 230 ° C, particularly preferably 215 to 230 ° C.

The (C) phosphate ester metal salt in the resin composition according to the present invention is represented by the following formula (1), (2), (3) or (4). In the formula, R ^{1 to} R ¹⁴ each independently represent an independently selected alkyl group having 1 to 50 carbon atoms, and the lower limit of the carbon number is preferably 10, more preferably 16, and the preferable upper limit is 30, Preferably 24. Such alkyl groups include n-octyl, isooctyl, 2-ethylhexyl, tert-octyl, n-decyl, isononyl, isodecyl, n-dodecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso Examples include octadecyl, n-eicosyl, n-docosyl, n-tricosyl, n-tetracosyl, hexacosyl, and triacontyl. R ^{1 to} R ¹⁴ are preferably the same group from the viewpoint of availability. M represents a metal selected from the group consisting of an alkaline earth metal and zinc, and examples of the alkaline earth metal include magnesium and calcium. (C) The phosphoric acid ester metal salt is preferably a zinc or aluminum salt, more preferably a zinc salt, from the viewpoint of the color tone of the resin composition obtained (low yellowness). Preferred phosphoric acid ester metal salts include zinc salt of monostearyl phosphate, zinc salt of distearyl phosphate and mixtures thereof, aluminum salt of monostearyl phosphate, aluminum salt of distearyl phosphate and mixtures thereof It is done.

  In the resin composition of the present invention, the weight ratio [(A) :( B)] of (A) aromatic polycarbonate resin and (B) alicyclic polyester resin is preferably 90:10 to 10:90, and 90: 10:30:70 is more preferable, 90: 10-25: 75 is still more preferable, and 90: 10-60: 40 is particularly preferable. (A) If the ratio of the aromatic polycarbonate resin is too small, for example, when the alicyclic polyester resin is crystalline, the resin composition may be crystallized by heat treatment during sterilization treatment, and may become cloudy and impair transparency. . Also, the heat resistance tends to be inferior. On the other hand, if the proportion of the polycarbonate resin is too large, the effect of improving the chemical resistance may be small. The content of (C) phosphate ester metal salt is usually 0.01 to 5 parts by weight with respect to 100 parts by weight of the total of (A) aromatic polycarbonate resin and (B) resin of alicyclic polyester resin. The lower limit is preferably 0.05 parts by weight and the upper limit is 3 parts by weight. Further, when the resin composition contains titanium derived from a catalyst or the like at the time of resin production, the moles of the titanium atom in the resin composition and the phosphorus atom in the resin composition derived from the phosphate metal salt The ratio (hereinafter abbreviated as P / Ti) is preferably 3 to 25, particularly preferably 5 to 20. If P / Ti is less than 3, the resin composition tends to be colored, and if P / Ti is greater than 25, the hydrolysis resistance tends to be inferior.

The resin composition of the present invention has other polymers, flame retardants, impact resistance improvers, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, and plasticizers that impart desired properties depending on the purpose. , Release agents, lubricants, compatibilizers, foaming agents, glass fibers, glass beads, glass flakes, carbon fibers, fibrous magnesium, potassium titanate whiskers, ceramic whiskers, mica, talc and other reinforcing materials, fillers, face wash You may contain 1 type, such as quantity, or 2 or more types.

  Examples of the method of blending each component include a method using a tumbler, a Henschel mixer, and the like, and a method of quantitatively feeding to an extruder hopper with a feeder and mixing. Examples of the kneading method include a method using a single screw extruder, a twin screw extruder or the like. The kneading temperature is not particularly limited as long as the thermal stability of the (A) aromatic polycarbonate resin and (B) alicyclic polyester resin can be maintained, but the resin temperature in the kneader is 230 to 350 ° C. A range is preferred. In order to achieve such a resin temperature, for example, when a biaxial kneader having a screw diameter of 100 mm or less is used as the kneader, it is usually achieved by setting the barrel set temperature in the range of 230 to 350 ° C.

In the present invention, when (A) the aromatic polycarbonate resin and (B) the alicyclic polyester resin are melt-kneaded, it is preferable to remove moisture, gas, and the like. As this method, for example, a method using a kneader with a vent device is simple. A kneader in which venting devices are installed at two or more locations can also be used.
The resin composition of the present invention obtained as described above has an intrinsic viscosity retention of 70% or more after being exposed to a steam atmosphere of 120 ° C. and 0.11 MPa in a pressure cooker test machine for 24 hours. The nesting index is preferably 10 or less. The measurement conditions are as described in Examples described later. A low intrinsic viscosity retention means poor water resistance, and a high yellowness index (YI) means yellowish coloration and poor transparency. It is not preferred for applications that require sterilization. The resin composition having the intrinsic viscosity retention ratio and the yellowness index (YI) is a metal component of the component (C) among the resin compositions of the present invention containing the components (A), (B) and (C). Preferably, it can be obtained by selecting zinc or aluminum as a preferable range.

  The resin composition of the present invention can be formed into a desired molded article according to a conventional molding method such as injection molding or blow molding. The molding temperature is not particularly limited as long as the thermal stability of the resin composition can be maintained, but the barrel temperature is preferably in the range of 230 to 350 ° C. The molded article of the resin composition of the present invention can be suitably used for applications requiring high-temperature sterilization treatment such as medical instruments.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.
The raw materials and evaluation methods used in the following examples are as follows.
Moreover, the physical properties of the resin composition and the molded product were evaluated by the methods described below for the items described below.

Component of resin composition (A) Aromatic polycarbonate resin (A-1) Iupilon (registered trademark) S-3000F manufactured by Mitsubishi Engineering Plastics Co., Ltd.
(B) Cycloaliphatic polyester resin (B-1): Cycloaliphatic polyester resin described in Production Example 1 below Intrinsic viscosity = 1.143 dl / g, terminal carboxylic acid concentration = 13.2 equivalent / ton, YI (pellet ) = 8.9, melting point 217.3 ° C.
(B-2): Cycloaliphatic polyester resin described in Production Example 2 below Intrinsic viscosity = 0.841 dl / g, terminal carboxylic acid concentration = 2.7 equivalent / ton, YI (pellet) = 13.8, melting point 219 .6 ° C
(C) Phosphate ester metal salt (C-1) Phosphate ester zinc salt: LBT-1830 manufactured by Sakai Chemical Industry Co., Ltd.
Mixture of zinc salt of monostearyl phosphate and zinc salt of distearyl phosphate (C-2) Phosphate aluminum salt: LBT-1813 manufactured by Sakai Chemical Industry Co., Ltd.
Mixture of aluminum salt of monostearyl phosphate and aluminum salt of distearyl phosphate (C-3) Phosphate ester calcium salt: LBT-1820 manufactured by Sakai Chemical Industry Co., Ltd.
Mixture of calcium salt of monostearyl phosphate and calcium salt of distearyl phosphate (D) Phosphorus compounds other than phosphate ester metal salts (D-1) Phosphorous acid: Wako Pure Chemical Industries, Ltd. (D-2) Polyphosphoric acid : Wako Pure Chemical Industries

Various physical property measurement methods and analysis methods

<Method for measuring intrinsic viscosity>
About 0.25 g of a sample was dissolved in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1) so that the concentration was about 1.00 g / dL, and the concentration C ( g / dL). This solution was cooled to 30 ° C. and held, and with a fully automatic solution viscometer (“2CH type DJ504” manufactured by Sentec Co., Ltd.), the sample solution dropped seconds (t) and the solvent only dropped seconds (t ₀ ) Was measured and calculated by the following formula.
IV = ((1 + 4KHηsp) 0.5-1) / (2KHC)
Here, ηsp = t / t ₀ −1, η is the sample solution dropping time, η0 is the solvent dropping time, C is the sample solution concentration (g / dL), and KH is the Huggins constant. . KH adopted 0.33.

<Method for Measuring Terminal Carboxylic Acid Concentration (AV)>
0.4 g of pellets are collected in a test tube, added to 25 ml of benzyl alcohol, and heated and dissolved in an oil bath set at 195 ± 3 ° C. for 7 to 9 minutes. The obtained dissolved solution was allowed to cool to room temperature, 2 ml of ethyl alcohol was added, and 0.01 N hydroxylation was performed using an automatic titration apparatus (manufactured by Toa Decay Co., Ltd., model: AUT-501) using a composite pH electrode. Titrated with sodium benzyl alcohol solution.
A 0.01 N sodium hydroxide / benzyl alcohol solution was prepared and standardized according to JIS K8006, and the factor was calculated. Obtain the titration amount from the inflection point of the obtained titration curve,
Terminal carboxylic acid concentration (AV) = {(AB) × 0.01N × F} / W
Based on the above, AV was calculated.
In this formula, A is a measurement titer (ml), B is a blank titer (ml), F is a 0.01 N sodium hydroxide / benzyl alcohol solution titer, and W is a pellet weight.

<Yellowness Index (YI)>
In accordance with JISK7103, using a photoelectric colorimeter (ND-300 manufactured by Nippon Denshoku Industries Co., Ltd.), a sample pellet was filled into a cylindrical quartz cell having a diameter of 30 mm and a height of 18 mm, and averaged four times while rotating about 90 degrees. The tristimulus values X, Y, and Z were measured and the yellowness Y1 was calculated by the following equation.
YI = 100 (1.28X-1.06Z) / Y
<Measuring method of melting point>
According to JIS K 7121, it measured as follows using the differential scanning calorimeter (DSC220 by Seiko Instruments Inc.).
About 10 mg is cut out from the pelletized sample with a cutter knife, sealed in an aluminum pan, heated from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min, held at 300 ° C. for 3 minutes, and then a temperature falling rate of 20 ° C. / It was cooled from 300 ° C. to 25 ° C. in minutes, and further heated up to 300 ° C. at a rate of temperature increase of 20 ° C./min. As the melting point, the value at the time of the second temperature increase was adopted, and the temperature was the maximum part of the heat of fusion peak.

<Hydrolysis resistance>
The pellets were placed in a saturated pressure cooker tester (manufactured by Hirayama Seisakusho, model: PC-242) and treated at 120 ° C. and a water vapor pressure of 0.11 MPa for 24 hours.
Hydrolysis resistance was indicated by the retention rate (%) of the intrinsic viscosity (IVI) after treatment relative to the intrinsic viscosity (IVO) before treatment.

<Production Example 1 (B-1)>
A stainless steel reactor having a capacity of 100 liters equipped with a stirrer, a distilling tube, a heating device, a pressure gauge, a thermometer, and a decompression device was charged with 1,4-cyclohexanedicarboxylic acid (trans isomer: cis cis ratio is 96: 4). 101.5 parts by weight, 87 parts by weight of 1,4-cyclohexanedimethanol (trans isomer: cis isomer ratio of 69:31) and 0.005 part by weight of a 6% by weight butanol solution of tetra-n-butyl titanate were charged, The inside of the reactor was replaced with nitrogen gas. While sealing the inside of the reactor with nitrogen gas, the internal temperature was raised to 150 ° C. in 30 minutes, and further raised from 150 ° C. to 200 ° C. over 1 hour. Next, the esterification reaction was performed by maintaining at 200 ° C. for 1 hour, and then the polycondensation reaction was performed while gradually increasing the pressure in the reactor from 200 ° C. to 250 ° C. over 45 minutes. The polycondensation reaction was carried out for 3.7 hours while maintaining the reactor internal pressure at an absolute pressure of 0.1 kPa and the reaction temperature at 250 ° C. After completion of the polycondensation reaction, the obtained resin was extracted in a strand shape into water, cut and pelletized. Intrinsic viscosity and terminal carboxylic acid concentration are 1.143 dl / g, 13.2 equivalent / ton, YI (pellet) = 8, respectively.
. 9. The melting point was 217.3 ° C.

<Production Example 2 (B-2)>
The same procedure as in Production Example 1 was conducted, except that the amount of 1,4-cyclohexanedimethanol in Production Example 1 was changed to 87.9 parts by weight and the polycondensation reaction time was changed from 3.7 hours to 4.5 hours. It was. The intrinsic viscosity and the terminal carboxylic acid concentration were 0.841 dl / g, 2.7 equivalent / ton, YI (pellet) = 13.8, and melting point 219.6 ° C., respectively.

<Example 1>
70 parts by weight of the aromatic polycarbonate resin (A-1), 30 parts by weight of the alicyclic polyester resin (B-1) and 0.1 parts by weight of the phosphoric acid ester metal salt (C-1) are weighed. Then, the mixture was uniformly mixed with a tumbler mixer to obtain a mixture. The obtained mixture was supplied to a hopper of a twin-screw kneader equipped with a degassing device (TEX30-42W manufactured by Nippon Steel Works). The biaxial kneader was melt-kneaded under conditions of a cylinder set temperature of 280 ° C., a screw rotation speed of 150 rpm, and a discharge rate of 15 kg / hr, extruded into a strand, and pelletized with a cutter.
Using the obtained pellets, the hydrolysis resistance test and YI were measured, and the results are shown in Table 1.
<Examples 2-6 and Comparative Examples 1-4>
In the kneading conditions of Example 1, pellets were similarly obtained according to the formulation described in Table 1.
The obtained hydrolysis resistance test and YI were measured using the obtained pellets, and the results are shown in Table 1.

  As is clear from the above results, in Comparative Example 4 in which the resin composition containing (A) the aromatic polycarbonate resin and (B) the alicyclic polyester resin does not contain a phosphorus compound, the hydrolysis resistance is good. YI is remarkably inferior, and in Comparative Examples 1 to 3 containing phosphorous acid or polyphosphoric acid, YI is good, but hydrolysis resistance is remarkably inferior. On the other hand, in Examples 1 to 6 containing the phosphoric acid ester metal salt of the present invention, both YI and hydrolysis resistance are good in good balance.

  The resin composition of the present invention is particularly useful as a resin composition for the field of molded products such as medical devices that require high-temperature sterilization because the yellowness index is relatively small, coloring is small, and hydrolysis resistance is excellent. .

Claims (6)

(A) an aromatic polycarbonate resin, (B) an alicyclic polyester resin, and (C) at least one phosphate metal salt represented by the following formula (1), (2), (3) or (4): A resin composition characterized by containing.

(In the formula, R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 50 carbon atoms, and M represents a metal selected from the group consisting of alkaline earth metals and zinc.) (B) an alicyclic polyester resin is a dicarboxylic acid component whose main component is 1,4-cyclohexanedicarboxylic acid and / or an ester-forming derivative thereof, and a diol component whose main component is 1,4-cyclohexanedimethanol The resin composition according to claim 1, which is an alicyclic polyester resin obtained from the following. The weight ratio [(A) :( B)] of (A) aromatic polycarbonate resin and (B) alicyclic polyester resin is 90:10 to 10:90, and (A) and (B) The resin composition according to claim 1 or 2, wherein the content of (C) per 100 parts by weight in total is 0.01 to 5 parts by weight. The resin composition according to any one of claims 1 to 3, wherein the (B) alicyclic polyester resin is an alicyclic polyester resin having a melting point of 210 ° C or higher and a terminal carboxylic acid concentration of 30 equivalents / ton or less. The ratio of the trans isomer to the cis isomer of 1,4-cyclohexanedicarboxylic acid and / or its ester-forming derivative (trans isomer: cis isomer) is 85:15 to 100: 0, and the trans of 1,4-cyclohexanedimethanol The resin composition according to any one of claims 2 to 4, wherein a ratio of the isomer to the cis isomer (trans isomer: cis isomer) is 60:40 to 100: 0. 6. The intrinsic viscosity retention after exposure to a steam atmosphere of 120 ° C. and 0.11 MPa in a pressure cooker tester for 24 hours is 70% or more and the yellowness index is 10 or less. The resin composition according to item.