JP4705822B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition having excellent heat resistance, hydrolysis resistance, and thermal stability. The resin composition of the present invention is used in electrical / electronic devices such as office automation equipment, information / communication equipment, and home appliances, in the automobile field, and in the construction field.

Polycarbonate resin is currently an engineering plastic with excellent heat resistance, mechanical strength (especially impact strength), dimensional stability, electrical properties, transparency, hygiene, etc. Electricity, electronics, OA, precision machinery, automobiles, medical care, Widely used in various fields such as security and household goods.
Further, a polycarbonate / polylactic acid alloy is known as a resin composition having a pearly luster and having high fluidity and well-balanced thermal and mechanical properties (see, for example, Patent Document 1). However, this polycarbonate / polylactic acid alloy is required to be further improved in terms of heat resistance, thermal stability and impact resistance. In addition, a resin composition is known in which polycarbonate and polylactic acid are reactively compatibilized with a radical initiator to improve heat resistance (see, for example, Patent Document 2). In Patent Document 2, aliphatic polyester carbonate is used. Therefore, heat resistance and impact resistance are insufficient.
In order to improve the heat resistance of polylactic acid, it has been proposed to add inorganic fillers or vegetable fibers (see, for example, Patent Document 3 and Patent Document 4). However, in these resin compositions, the amount of filler and fiber added inevitably increases in order to increase the crystallinity of polylactic acid depending on the intended use, and therefore there is a problem that fluidity and impact resistance are lowered. is there.

JP-A-7-109413 JP 2002-371172 A JP 2003-128900 A JP 2004-339454 A

  The present invention has been made under such circumstances, and while maintaining the high fluidity and balanced thermal and mechanical properties of polycarbonate / polylactic acid alloy, heat resistance, thermal stability and impact resistance are maintained. An object of the present invention is to provide a polycarbonate resin composition excellent in the above.

  As a result of intensive studies to achieve the above object, the present inventors add a terpene resin and / or a terpene copolymer to an alloy composed of an aromatic polycarbonate / aliphatic polyester (preferably polylactic acid). Therefore, it is possible to obtain a resin composition with improved heat resistance, thermal stability and hydrolysis resistance, and by adding a hydrolysis inhibitor, the balance of mechanical properties, heat resistance and thermal stability can be achieved. As a terpene copolymer, a terpene-phenol copolymer is used as a terpene copolymer, thereby increasing the compatibility between polycarbonate and polylactic acid, further improving thermal stability, and improving impact resistance. It was found that improvement is also possible. The present invention has been completed based on such findings.

That is, the present invention provides the following po-aromatic carbonate resin composition.
(1) (A) 1-100 parts by mass of (B) aliphatic polyester and (C) terpene resin and / or terpene copolymer 1-100 parts by mass with respect to 100 parts by mass of aromatic polycarbonate, Aromatic polycarbonate, wherein the mass ratio [[A] / ([B] + [C])] of component (A) to the total amount of component (B) and component (C) is 1.0 or more Resin composition.
(2) The aromatic polycarbonate resin composition according to (1), further comprising (D) a hydrolysis inhibitor at a ratio of 10 parts by mass or less with respect to 100 parts by mass of (A) aromatic polycarbonate.
(3) The aromatic polycarbonate resin composition according to (1) or (2), wherein the hydrolysis inhibitor comprises at least one compound selected from a carbodiimide compound, an isocyanate compound, an oxazoline compound, and an epoxy compound.
(4) The aromatic polycarbonate resin composition according to any one of (1) to (3), wherein the aliphatic polyester as the component (B) is a copolymer of polylactic acid and / or lactic acid and other hydroxycarboxylic acid. .
(5) The aromatic polycarbonate resin composition according to any one of (1) to (4), wherein the component (C) is a terpene-phenol copolymer.
(6) The aromatic polycarbonate resin composition according to any one of (1) to (5), which is for OA equipment, information / communication equipment, automobile parts, building members, or home appliances.

  According to the present invention, by adding a terpene resin or a terpene copolymer as the component (C) to a component containing (A) an aromatic polycarbonate and (B) an aliphatic polyester (preferably polylactic acid). Thus, a resin composition having improved heat resistance, thermal stability and hydrolysis resistance can be obtained. Furthermore, by adding a hydrolysis inhibitor of component (D), a resin composition that maintains a balance of mechanical properties, heat resistance, and thermal stability can be obtained, and OA equipment, information / communication equipment, It can be suitably used for automobile parts, building members and household appliances.

The present invention is described in detail below.
First, the aromatic polycarbonate which is the component (A) constituting the resin composition of the present invention is not particularly limited and includes various types.

A polymer having a repeating unit having a structure represented by the formula:
In the general formula (1), R ¹ and R ² are each a halogen atom (for example, chlorine, fluorine, bromine, iodine) or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, An isopropyl group, various butyl groups (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups).
m and n are each an integer of 0 to 4, and when m is 2 to 4, R ¹ may be the same or different from each other, and when n is 2 to 4, R ² May be the same as or different from each other.
Z is an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, ethylidene group, isopropylidene group, etc.), A cycloalkylene group having 5 to 15 carbon atoms or a cycloalkylidene group having 5 to 15 carbon atoms (for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group), or a single bond, —SO ₂ -, -SO-, -S-, -O-, -CO- bond, or the following formula (2) or formula (2 ')

The bond represented by is shown.
The polymer is usually represented by the general formula (3)

［式中、Ｒ¹、Ｒ²、Ｚ、ｍ及びｎは、上記一般式（１）と同じである。］

[Wherein, R ¹ , R ² , Z, m and n are the same as those in the general formula (1). ]

It can be easily produced by reacting the represented dihydric phenol with a carbonate precursor such as phosgene.
That is, for example, it can be produced by a reaction of a dihydric phenol and a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight regulator. It can also be produced by a transesterification reaction between a dihydric phenol and a carbonate precursor such as a carbonate compound.
Various things can be mentioned as a dihydric phenol represented by the said General formula (3).
In particular, 2,2-bis (4-hydroxyphenyl) propane [common name, bisphenol A] is preferable.
Examples of dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; bis (1,2-bis (4-hydroxyphenyl) ethane, etc. 4-hydroxyphenyl) alkane, 1,1-bis (4-hydroxyphenyl) cyclohexane; bis (4-hydroxyphenyl) cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclodecane, 4,4′-dihydroxy Examples include diphenyl, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ketone. .
In addition, hydroquinone etc. are mentioned as dihydric phenol.
These dihydric phenols may be used alone or in combination of two or more.
Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The aromatic polycarbonate may be a homopolymer using one of the above dihydric phenols, or may be a copolymer using two or more.
Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.
The polyfunctional aromatic compound is generally called a branching agent, and specifically, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxy Phenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl Benzene, phloroglucin, trimellitic acid, isatin bis (o-cresol) and the like.

  Aromatic polycarbonates having such characteristics are commercially available as aromatic polycarbonate resins such as Taflon FN3000A, FN2500A, FN2200A, FN1900A, FN1700A, and FN1500 [trade name, manufactured by Idemitsu Kosan Co., Ltd.].

The aromatic polycarbonate used in the present invention is not only a homopolymer produced using only the above dihydric phenol, but also a polycarbonate-polyorganosiloxane copolymer (hereinafter abbreviated as PC-POS copolymer). And polycarbonate resin containing a PC-POS copolymer may be mentioned, which is preferable because impact resistance is increased and flame retardancy is also improved. A PC-POS copolymer alone is more preferred.
There are various types of PC-POS copolymers. Preferably, the following general formula (1)

［式中、Ｒ¹、Ｒ²、Ｚ、ｍ及びｎは、上記と同じである。］

[Wherein, R ¹ , R ² , Z, m and n are the same as described above. ]

A polycarbonate part having a repeating unit having a structure represented by the following general formula (4):

［式中、Ｒ³、Ｒ⁴及びＲ⁵は、それぞれ水素原子、炭素数１〜５のアルキル基（例えば、メチル基、エチル基、プロピル基、ｎ−ブチル基、イソブチル基など）又はフェニル基であり、ｐ及びｑは、それぞれ０又は１以上の整数であるが、ｐとｑとの合計は１以上の整数である。］

[Wherein R ³ , R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group) or a phenyl group. P and q are each an integer of 0 or 1 or more, but the sum of p and q is an integer of 1 or more. ]

The polyorganosiloxane part which has a repeating unit of the structure represented by these.
Here, the polymerization degree of the polycarbonate part is preferably 3 to 100, and the polymerization degree of the polyorganosiloxane part is preferably 2 to 500.

The PC-POS copolymer is a block comprising a polycarbonate part having a repeating unit represented by the general formula (1) and a polyorganosiloxane part having a repeating unit represented by the general formula (4). It is a copolymer.
Such a PC-POS copolymer has a reactive group at the terminal which comprises the polycarbonate oligomer (henceforth PC oligomer) which comprises the polycarbonate part manufactured previously, and a polyorganosiloxane part, for example (for example). Polyorganosiloxane (for example, polydimethylsiloxane (PDMS), polydialkylsiloxane such as polydiethylsiloxane or polymethylphenylsiloxane) is dissolved in a solvent such as methylene chloride, chlorobenzene, chloroform, etc., and an aqueous sodium hydroxide solution of bisphenol And triethylamine or trimethylbenzylammonium chloride as a catalyst, and can be produced by interfacial polycondensation reaction.
Further, a PC-POS copolymer produced by the method described in Japanese Patent Publication No. 44-30105 or the method described in Japanese Patent Publication No. 45-20510 can also be used.

Here, the PC oligomer having the repeating unit represented by the general formula (1) is a solvent method, that is, in the presence of a known acid acceptor and molecular weight regulator in a solvent such as methylene chloride. ) And a carbonate precursor such as phosgene or a carbonic acid ester compound can be easily produced.
For example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator, by reaction between a dihydric phenol and a carbonate precursor such as phosgene, or like a dihydric phenol and a carbonate compound. It can be produced by transesterification with a carbonate precursor.
As the carbonic acid ester compound, the same ones as described above can be used, and as the molecular weight regulator, a terminal terminator described later can be used.

In the present invention, the PC oligomer used for the production of the PC-POS copolymer may be a homo-oligomer using one of the above dihydric phenols, or a co-oligomer using two or more. Good.
Further, it may be a thermoplastic random branched carbonate oligomer obtained by using a polyfunctional aromatic compound in combination with the above dihydric phenol.
Furthermore, as an aromatic polycarbonate used for this invention, following General formula (5)

［式中、Ｒ⁶は炭素数１〜３５のアルキル基を示し、ａは０〜５の整数を示す。］
で表わされる末端基を有するポリカーボネートも好適である。

[Wherein R ⁶ represents an alkyl group having 1 to 35 carbon atoms, and a represents an integer of 0 to 5. ]
Also suitable are polycarbonates having end groups represented by

In the general formula (5), R ⁶ is an alkyl group having 1 to 35 carbon atoms, and may be linear or branched.
The bond position may be any of p-position, m-position and o-position, but p-position is preferred.
The polycarbonate having a terminal group represented by the general formula (5) can be easily produced by reacting a dihydric phenol with phosgene or a carbonate compound.

For example, in a solvent such as methylene chloride, by reaction of a dihydric phenol with a carbonate precursor such as phosgene in the presence of a catalyst such as triethylamine and a specific end-stopper, or like dihydric phenol and diphenyl carbonate. It is produced by a transesterification reaction with a carbonate precursor.
Here, the dihydric phenol may be the same as or different from the compound represented by the general formula (3).
Further, it may be a homopolymer using one kind of the above dihydric phenol or a copolymer using two or more kinds.
Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
As the terminal terminator, a phenol compound in which the terminal group represented by the general formula (5) is formed may be used. That is, it is a phenol compound represented by the following general formula (6).

［式中、Ｒ⁶は炭素数１〜３５のアルキル基を示し、ａは０〜５の整数を示す。］

[Wherein R ⁶ represents an alkyl group having 1 to 35 carbon atoms, and a represents an integer of 0 to 5. ]

These alkylphenols include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, docosylphenol, tetracosylphenol, hexacosylphenol, octacosy. Examples include ruphenol, triacontylphenol, dotriacontylphenol, and tetratriacontylphenol. These may be one kind or a mixture of two or more kinds.
In addition, these alkylphenols may be used in combination with other phenolic compounds as long as the effects are not impaired.
In addition, the aromatic polycarbonate manufactured by said method has a terminal group represented by General formula (5) substantially in the one terminal or both terminals of a molecule | numerator.

The viscosity average molecular weight of the aromatic polycarbonate used as the component (A) is preferably 14,000 to 30,000 from the viewpoints of heat resistance and impact resistance, and more preferably from the viewpoint of balance such as mechanical properties. Is 15,000-22,000.
The viscosity average molecular weight (Mv) was determined by measuring the viscosity of the methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] from this, [η] = 1.23 × 10 ⁻ It is a value calculated by the equation of ⁵ Mv ^0.83 .

In the aromatic polycarbonate resin composition of the present invention, the aliphatic polyester as the component (B) is a copolymer of polylactic acid or lactic acid and other hydroxycarboxylic acid (hereinafter referred to as “polycarboxylic acid”) from the viewpoint of mechanical properties and heat resistance. Polylactic acid and its copolymer are sometimes referred to as lactic acid-based resins.), And polylactic acid is particularly preferable.
Polylactic acid is synthesized by ring-opening polymerization from a cyclic dimer of lactic acid, usually called lactide, and its production method is described in US Pat. No. 1,995,970 and US Pat. No. 2,362,511. U.S. Pat. No. 2,683,136 and the like.
A copolymer of lactic acid and other hydroxycarboxylic acid is usually synthesized by ring-opening polymerization from a cyclic ester intermediate of lactide and hydroxycarboxylic acid, and the production method thereof is described in US Pat. No. 3,635,956. U.S. Pat. No. 3,797,499 and the like.
In the case of producing a lactic acid resin by direct dehydration polycondensation without using ring-opening polymerization, lactic acid and, if necessary, other hydroxycarboxylic acid, preferably an organic solvent, particularly a phenyl ether solvent is present. It is suitable for the present invention by polymerizing by a method in which azeotropic dehydration condensation is carried out and water is removed from the solvent distilled off by azeotropic distillation, and the solvent which has been made substantially anhydrous is returned to the reaction system. A lactic acid resin having a polymerization degree is obtained.

As raw lactic acids, any of L- and D-lactic acid, a mixture thereof, or lactide which is a dimer of lactic acid can be used.
Examples of other hydroxycarboxylic acids that can be used in combination with lactic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxycaproic acid. Cyclic ester intermediates of hydroxycarboxylic acid, for example, glycolide, which is a dimer of glycolic acid, and ε-caprolactone, which is a cyclic ester of 6-hydroxycaproic acid, can also be used.
In the production of the lactic acid-based resin, an appropriate molecular weight regulator, a branching agent, other modifiers, and the like can be blended. In addition, lactic acids and hydroxycarboxylic acids as copolymer components can be used alone or in combination of two or more, and two or more of the obtained lactic acid resins can be mixed and used.

The aliphatic polyester (B) used in the present invention preferably has a large molecular weight from the viewpoint of thermal properties and mechanical properties, and preferably has a weight average molecular weight of 30,000 or more.
The aliphatic polyester is preferably a polylactic acid and / or a copolymer of lactic acid and other hydroxycarboxylic acid from the viewpoint of durability, rigidity and biodegradability, and particularly preferably polylactic acid.
The content ratio of the aromatic polycarbonate of component (A) and the aliphatic polyester of component (B) in the present invention is such that the aliphatic polyester of component (B) is 100 parts by mass of aromatic polycarbonate of component (A). It is 1-100 mass parts, Preferably it is the range of 30-50.
By adding the aliphatic polyester (B) to the aromatic polycarbonate (A), the mechanical strength, thermal stability and molding stability are improved.

The terpene resin or terpene copolymer of component (C) used in the aromatic polycarbonate resin composition of the present invention is a terpene monomer alone or a terpene monomer in the presence of a Friedel-Crafts type catalyst in an organic solvent. An aromatic monomer, or a product obtained by copolymerizing a terpene monomer and a phenol. Moreover, the hydrogenation addition terpene resin obtained by hydrogenating the obtained terpene resin may be sufficient. Examples of the terpene monomer include α-pinene, β-pinene, dipentene, and d-limonene, and examples of the aromatic monomer include styrene, α-methylstyrene, and vinyl toluene. Examples of phenols include phenol, cresol, bisphenol A, and the like. The softening point of the component (C) is preferably 100 ° C. or higher, more preferably 125 ° C. or higher.
In the aromatic polycarbonate resin composition of the present invention, by using a terpene-phenol copolymer as the component (C), the compatibility between the polycarbonate and polylactic acid is increased, the thermal stability is further improved, and the impact resistance is improved. Is also possible.

  Examples of the terpene resin and terpene copolymer thus obtained include, for example, “YS resin PX” (terpene resin), “YS resin TO” (aromatic modified terpene resin), “YS resin TR” from Yashara Chemical Co., Ltd. "Aromatically modified terpene resin", "Clearon" (hydrogenated terpene resin), "YS polyster" (terpene phenol resin), "Mighty Ace" (terpene phenol resin) are commercially available and are easily available. .

In the present invention, the content of the (A) component aromatic polycarbonate and the (C) component terpene resin and / or terpene copolymer is (C) with respect to 100 parts by mass of the (A) component aromatic polycarbonate. The component terpene resin and / or terpene copolymer is 1 to 100 parts by mass, preferably 3 to 50 parts by mass.
By adding the terpene resin or terpene copolymer of the component (C) to the aromatic polycarbonate of the component (A), an effect of improving moldability (fluidity) can be obtained.

  The aromatic polycarbonate resin composition of the present invention comprises (B) 1-100 parts by mass of an aliphatic polyester, (C) terpene resin and / or terpene copolymer 1-100 with respect to 100 parts by mass of (A) aromatic polycarbonate. The mass ratio of the component (A) to the total amount of the components (B) and (C) is 1.0 or more [[A] / ([B] + [C]) ≧ 1.0] As a result, a resin composition having an excellent balance of mechanical properties, heat resistance, and thermal stability is obtained. Moreover, it is preferable to make the total amount of (B) component and (C) component with respect to 100 mass parts of (A) component into the range of 1-70 mass parts, More preferably, it is the range of 5-40 mass parts.

The aromatic polycarbonate resin composition of the present invention is further improved in the balance of mechanical properties, heat resistance and thermal stability by adding (D) a hydrolysis inhibitor.
The hydrolysis inhibitor used in the present invention is not particularly limited as long as it is an additive that suppresses hydrolysis of an aliphatic polyester. By containing a hydrolysis inhibitor that suppresses hydrolysis of the aliphatic polyester, the hydrolysis rate of the aliphatic polyester is delayed, and as a result, high mechanical strength, thermal stability, etc. can be maintained over a long period of time. High storage characteristics.
In addition, when adding (D) hydrolysis inhibitor, it is preferable to make the total amount of (B) component and (C) component with respect to 100 mass parts of (A) component into the range of 1-70 mass parts.

Specific examples of the hydrolysis inhibitor include compounds having reactivity with an active hydrogen of an aliphatic polyester. By adding the said compound, the amount of active hydrogen of aliphatic polyester can be reduced, and it can prevent that active hydrogen hydrolyzes an aliphatic polyester chain | strand catalytically. Here, active hydrogen is hydrogen in a bond (N—H bond or O—H bond) of oxygen, nitrogen or the like and hydrogen, and such hydrogen is in a bond of carbon and hydrogen (C—H bond). Reactivity is higher than hydrogen. More specifically, for example, hydrogen in a carboxyl group: —COOH, a hydroxyl group: —OH, an amino group: —NH ₂ , an amide bond: —NHCO— or the like in the aliphatic polyester compound.

  The compound having reactivity with active hydrogen in the aliphatic polyester compound is preferably a carbodiimide compound, an isocyanate compound, an oxazoline compound, or an epoxy compound. It is preferable because hydrolyzability can be further suppressed. Further, when two or more carbodiimide groups, isocyanate groups, oxazoline groups, and epoxy groups are contained in one molecule, the stability of the polycarbonate and polylactic acid increases, which is more preferable.

  Said carbodiimide compound is a compound which has a 1 or more carbodiimide group in a molecule | numerator, and also contains a polycarbodiimide compound. As a method for producing a carbodiimide compound, for example, as a catalyst, for example, O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate, O, O-dimethyl-O- (3-methyl-4- (Methylthio) phenyl) phosphorothioate, organic phosphorus compounds such as O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate, or rhodium complexes, titanium complexes, tungsten complexes, palladium complexes, etc. And a method of producing various polyisocyanate compounds by decarboxylation polycondensation in a solvent-free or inert solvent (for example, hexane, benzene, dioxane, chloroform, etc.) at a temperature of about 70 ° C. or higher. be able to.

  Examples of the monocarbodiimide compound contained in this carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, naphthylcarbodiimide, and among them, particularly industrially available. Easy dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferred.

  Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4′-diphenylmethane diisocyanate. 2,2′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 3,3′-dichloro-4,4 ′ -Biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate Trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane Examples thereof include diisocyanate or 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate.

  The polyisocyanate compound can be easily produced by a known method, and a commercially available product can be appropriately used. Commercially available polyisocyanate compounds include Takenate (manufactured by Mitsui Takeda Chemical; hexamethylene diisocyanate), Coronate (manufactured by Nippon Polyurethane; hydrogenated diphenylmethane diisocyanate), Millionate (manufactured by Nippon Polyurethane; aromatic isocyanate), and the like.

  Examples of the oxazoline-based compound include 2,2′-o-phenylenebis (2-oxazoline), 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis ( 2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-p- Phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2,2′-octamethylenebis (2-oxazoline), 2,2′-ethylenebis ( 4-methyl 2-oxazoline), or 2,2'- diphenylenebis (2-oxazoline). Moreover, an oxazoline group-containing reactive polystyrene can also be used as an oxazoline-based compound.

As said epoxy compound, the compound which has an at least 1 or more epoxy group in a molecule | numerator can be mentioned. Specifically, epoxidized soybean oil, epoxidized linseed oil, epoxy butyl stearate, epoxy octyl stearate, phenyl glycidyl ether, allyl glycidyl ether, p-butylphenyl glycidyl ether, styrene oxide, neohexene oxide, adipine Acid diglycidyl ester, sebacic acid diglycidyl ester, phthalic acid diglycidyl ester, bis-epoxy dicyclopentadienyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, butadiene diepoxide, tetra Phenylethylene epoxide, epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, epoxidized hydrogenated styrene-butadiene Copolymer, bisphenol-A type epoxy compound, bisphenol-S type epoxy compound, phenol novolac type epoxy compound, resorcinol type epoxy compound, 3,4 epoxycyclohexamethyl-3,4-epoxycyclohexylcarboxylate, or 3, Examples include alicyclic epoxy compounds such as 4-epoxycyclohexyl glycidyl ether.
The above hydrolysis inhibitors may be used alone or in combination of two or more.

  The type and blending amount of the component (D) hydrolysis inhibitor are not particularly limited, but the biodegradation rate of the molded product and thus the mechanical strength can be adjusted by appropriately adjusting the type and blending amount of the hydrolysis inhibitor. Since it can be adjusted, it may be determined according to the target product. For example, the hydrolysis inhibitor of the component (D) is preferably 10 parts by mass or less and more preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate of the component (A). preferable.

  The aromatic polycarbonate resin composition of the present invention can contain, if necessary, additive components commonly used in thermoplastic resins, together with the above-described essential components and optional components. Examples of the additive component include an inorganic filler, a flame retardant, a silicone compound, a fluororesin, and a rubber-like elastic body. The compounding amount of the additive component is not particularly limited as long as the characteristics of the aromatic polycarbonate resin composition of the present invention are maintained.

  Next, the manufacturing method of the aromatic polycarbonate resin composition of this invention is demonstrated. In the resin composition of the present invention, the components (A), (B) and (C), and the component (D) used as necessary, are added at the above blending ratios, and other additive components are added. It is obtained by blending at an appropriate ratio and kneading at a temperature of about 200 to 260 ° C. The compounding and kneading at this time are premixed with commonly used equipment such as a ribbon blender and a drum tumbler, and then Henschel mixer, Banbury mixer, single screw extruder, twin screw extruder, multi screw extruder. It can be performed by a method using a machine, a conida or the like. The heating temperature at the time of kneading is usually appropriately selected in the range of 200 to 260 ° C.

  The aromatic polycarbonate resin composition of the present invention uses the above melt-kneaded product or the obtained pellet as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method. Various molded products can be produced by a method, a foam molding method or the like. However, it is particularly suitable for producing a pellet-shaped molding raw material by the melt kneading method and then using this pellet to produce an injection-molded article by injection molding or injection compression molding.

In the aromatic polycarbonate resin composition of the present invention, (C) component terpene resin or terpene copolymer is added to the component in which (A) aromatic polycarbonate and (B) aliphatic polyester (preferably polylactic acid) are blended. By doing so, a resin composition having improved heat resistance, thermal stability and hydrolysis resistance can be obtained. Furthermore, by adding a hydrolysis inhibitor, it becomes a resin composition that maintains a balance of mechanical properties, heat resistance, and thermal stability, and a terpene-phenol copolymer is used as the terpene copolymer. Thus, the compatibility between the polycarbonate and the polylactic acid is increased, the thermal stability is further improved, and the impact resistance can be improved.
Therefore, the aromatic polycarbonate resin composition of the present invention is widely used in fields such as OA equipment, information / communication equipment, automobile parts, building members, and home appliances.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The performance evaluation was performed according to the following measurement method.
(1) Thermal stability: At an internal temperature of the injection molding machine of 300 ° C. and a mold temperature of 80 ° C., it stays for 0 minutes (before residence) and 20 minutes (after residence), and then pulverizes the molded product obtained by injection molding. Each MI was measured under the condition of 260 ° C./21.18N.
(2) Hydrolysis resistance: A molded product injection-molded at an injection molding temperature of 240 ° C. and a mold temperature of 80 ° C. was exposed to steam for 48 hours under a 100 ° C./100% RH condition with a steam tester, and then The MI of the pulverized product was measured under the condition of 260 ° C./21.18N.
(3) Heat resistance: Based on JIS K7191, the heat distortion temperature (HDT) was measured with a load of 1.83 MPa.
(4) Izod impact strength: measured in accordance with ASTM D256 (test conditions, etc .: 23 ° C., wall thickness 1/8 inch (1 / 20.3 cm)).
(5) Drop weight impact strength: Measured at 23 ° C. according to JIS K7211, using a weight of 3.76 kg, a drop speed of 5 m / sec, and a test piece thickness of 2 mm.

Examples 1-12, Comparative Examples 1-4
The components (A) to (D) are blended in the proportions shown in Table 1 [each component is expressed in parts by mass] and supplied to a vent type twin screw extruder (model name TEM35, manufactured by Toshiba Machine Co., Ltd.). The mixture was melt kneaded at 240 ° C. and pelletized. In all Examples and Comparative Examples, phosphorus antioxidant PEP-36 (manufactured by Asahi Denka Kogyo Co., Ltd., trade name) and phenolic antioxidant Irganox 1076 (manufactured by Ciba Specialty Chemicals, Inc.) Each product name was blended in 0.1 parts by mass.
Next, the obtained pellets were dried at 100 ° C. for 5 hours, and then injection molded at a molding temperature of 240 ° C. (mold temperature of 80 ° C.) to obtain test pieces using the resins of the respective examples and comparative examples. . Each performance was evaluated by the above-described various evaluation tests using the obtained test pieces. The performance evaluation results are shown in Table 1.

The materials used for the components (A) to (D) are as follows.
(A) -1: Bisphenol A polycarbonate (FN1700A, manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight: 17,500)
(A) -2: silicone copolymer polycarbonate (viscosity average molecular weight: 17,000, PDMS (polydimethylsiloxane) content: 4.0% by weight, prepared in accordance with Production Example 4 of JP-A No. 2002-12755) .)
(B) -1: Polylactic acid (H-400, manufactured by Mitsui Chemicals, Inc.)
(C) -1: Polyterpene resin (YS resin PX1250, manufactured by Yasuhara Chemical Co., Ltd.)
(C) -2: Phenol-terpene copolymer (YS Polystar T145, manufactured by Yasuhara Chemical Co., Ltd.)
(D) -1: Dicyclohexylcarbodiimide (Carbodilite LA-1, manufactured by Nisshinbo)
(D) -2: Hexamethylene diisocyanate (Takenate 700, manufactured by Mitsui Takeda Chemical Co., Ltd.)
(D) -3: Oxazoline group-containing reactive polystyrene (Epocross RPS-1005, manufactured by Nippon Shokubai Co., Ltd.)

Table 1 shows the following.
(1) As is clear from Examples 1 to 12, heat resistance, hydrolysis resistance, and thermal stability were improved by adding polylactic acid, terpene resin and / or terpene copolymer to aromatic polycarbonate. . Further, by adding a hydrolysis inhibitor, thermal stability and hydrolysis resistance can be further improved.
(2) If the component (C) is not added from Comparative Example 1, the thermal stability is lowered.
(3) From Comparative Examples 2 to 4, the mass ratio of the component (A) to the total amount of the components (B) and (C) [[A] / ([B] + [C])] is less than 1.0. When it exists, heat resistance (HDT) falls remarkably and thermal stability is also low. In addition, even if a stabilizer is added, physical properties and thermal stability are not improved.

Claims (6)

  (A) 1-100 mass parts of (B) aliphatic polyester and (C) terpene resin and / or terpene copolymer 1-100 mass parts with respect to 100 mass parts of aromatic polycarbonate, (B) component An aromatic polycarbonate resin composition, wherein the mass ratio [[A] / ([B] + [C])] of the component (A) to the total amount of the components (C) is 1.0 or more.   The aromatic polycarbonate resin composition according to claim 1, further comprising (D) a hydrolysis inhibitor at a ratio of 10 parts by mass or less with respect to 100 parts by mass of (A) the aromatic polycarbonate.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the hydrolysis inhibitor comprises at least one compound selected from a carbodiimide compound, an isocyanate compound, an oxazoline compound, and an epoxy compound.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the aliphatic polyester (B) is a copolymer of polylactic acid and / or lactic acid and other hydroxycarboxylic acid.   The aromatic polycarbonate resin composition according to claim 1, wherein the component (C) is a terpene-phenol copolymer. The aromatic polycarbonate resin composition according to any one of claims 1 to 5, which is used for OA equipment, information / communication equipment, automobile parts, building members, or home appliances.