JPH11181265A - Polycarbonate-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate based resin composition by improving a wet heat resistance which is a defect of the polycarbonate-based resin composition made as fire retardant by using an alkali (alkaline earth) metal salt of a perfluoroalkane sulfonic acid. SOLUTION: This polycarbonate-based resin composition consists of (A) 100 pts.wt. polycarbonate based resin, (B) 0.001-3 pt.wt. alkali metal salt of a perfluoroalkane sulfonic acid or alkaline earth metal salt of the perfluoroalkane sulfonic acid, and (C) 2-50 pt.wt. polyester-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polycarbonate resin having improved heat and moisture resistance by flame retarding a polycarbonate resin with an alkali (earth) metal salt of perfluoroalkanesulfonic acid and using a polyester resin in combination. Composition.

[0002]

2. Description of the Related Art Polycarbonate resin has mechanical strength,
It has excellent heat resistance and transparency, and is widely used as a material for electric and electronic parts, a material for automobile parts, a material for construction, a material for sheets, a material for food containers, and the like.

[0003] In applications requiring flame retardancy, various flame retardants are added and used.

Metal salts of organic acids such as metal salts of organic sulfonic acids such as metal salts of aliphatic sulfonic acids and aromatic sulfonic acids, metal salts of inorganic acids such as sodium chloride, and inorganic salts such as ammonium salts. It is known that a salt-based flame retardant gives high flame retardancy by adding a very small amount to a polycarbonate resin. For example, JP-A-48-43751 discloses a method using an alkali salt of an organic sulfonic acid.
No. 45, JP-A-49-88943, a method using an alkali metal salt of perfluoroalkanesulfonic acid, JP-A-50-98545, and JP-A-50-98.
No. 546 discloses a technique such as a method using an alkali metal salt or an alkaline earth metal salt of a monomeric or polymeric aromatic sulfonic acid.

[0005]

However, when an alkali (earth) metal salt of perfluoroalkanesulfonic acid is added to a polycarbonate resin, high flame retardancy can be obtained with a small amount of addition, but high temperature and high humidity can be obtained. When exposed to the lower side, mechanical strength such as tensile strength and bending strength is reduced, that is, wet heat resistance is poor. Accordingly, the use of the material for electric and electronic parts, the material for automobile parts, and the like, in which the flame retardancy and the heat and humidity resistance are required, are greatly restricted.

An object of the present invention is to provide a polycarbonate resin composition which is flame-retardant using an alkali (earth) metal salt of perfluoroalkanesulfonic acid and has good wet heat resistance.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have proposed a flame-retardant polycarbonate resin which is flame-retardant using an alkali (earth) metal salt of perfluoroalkanesulfonic acid and has good wet heat resistance. As a result of diligent studies on obtaining a composition, they have found that the above object can be achieved by further using a polyester resin in combination with a polycarbonate resin composition containing an alkali (earth) metal salt of perfluoroalkanesulfonic acid. Thus, the present invention has been completed.

It is well known that polyester resins are generally susceptible to hydrolysis and have poor wet heat resistance.
It is well known that the hydrolysis reaction is further accelerated when an organic acid or a metal salt of an inorganic acid is present. However, surprisingly, when a polyester resin is used in combination with a polycarbonate resin composition using an alkali (earth) metal salt of perfluoroalkanesulfonic acid, the moist heat resistance of the polycarbonate resin composition is greatly increased. It was found to improve.

That is, the present invention relates to (A) 100 parts (parts by weight, hereinafter the same) of a polycarbonate resin, (B) an alkali metal perfluoroalkanesulfonate and / or an alkaline earth metal perfluoroalkanesulfonate. 0.001 to 3 parts, and (C) 2 to 50 parts of a polyester-based resin (Claim 1). The polycarbonate-based resin composition according to Claim 1, further comprising (D) a fluorine-based resin or (E) a polycarbonate-based resin composition comprising 0.01 to 3 parts of silicone (Claim 2); the polycarbonate-based resin composition according to Claim 1; and (D) a fluorine-based resin and (E) silicone 0 And 0.1 to 3 parts of the polycarbonate-based resin composition (Claim 3), The polycarbonate according to Claim 1, 2 or 3. Over preparative based resin composition, further (F) made by adding 0.1 to 10 parts olefin polymer polycarbonate resin composition (claim 4), (B)
The polycarbonate resin composition according to claim 1, wherein the perfluoroalkanesulfonic acid alkali metal salt and / or the perfluoroalkanesulfonic acid alkaline earth metal salt is potassium perfluorobutanesulfonic acid. Regarding item 5).

[0010]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate resin composition of the present invention comprises 100 parts of a polycarbonate resin (A), an alkali metal salt of perfluoroalkanesulfonic acid and / or an alkaline earth metal salt of perfluoroalkanesulfonic acid (B). ) A composition comprising 0.001 to 3 parts and polyester resin (C) 2 to 50 parts.

The polycarbonate resin (A) used in the present invention is obtained by reacting a phenol compound having a valency of 2 or more with phosgene or a carbonic acid diester such as diphenyl carbonate.

The dihydric or higher phenol compound is a dihydric phenol, for example, 2,2-bis (4
-Hydroxyphenyl) propane [commonly known as bisphenol A], bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4
-Hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) ) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4
-Hydroxyphenyl) ethane, 2-methyl-1,1-
Bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4
-Hydroxyphenyl) propane, 2,2-bis (3,
5-dibromo-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4
-Hydroxyphenyl) propane, 1,1-bis (4-
(Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4-methyl-2, 2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) nonane, 1,10-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,
2-bis (4-hydroxyphenyl) -1,1,1,
Dihydroxydiarylalkanes such as 3,3,3-hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-
Dichloro-4-hydroxyphenyl) cyclohexane,
Dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane, bis (4-hydroxyphenyl) sulfone, bis (3,5-
Dihydroxydiaryl sulfones such as dimethyl-4-hydroxyphenyl) sulfone and bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether, bis (3,5-dimethyl-)
Dihydroxydiaryl ethers such as 4-hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetramethyl-4,
Dihydroxydiaryl ketones such as 4'-dihydroxybenzophenone, bis (4-hydroxyphenyl)
Dihydroxydiaryl sulfides such as sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, and dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide And dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl and dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to the dihydric phenols, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene are also included. Among these, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (3,5-dimethyl-4-hydroxyphenyl) methane , 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) sulfone,
4,4'-dihydroxybenzophenone is the polycarbonate resin composition of the present invention, the moldability, mechanical strength,
Preferred from the viewpoint of flame retardancy. These dihydric phenols and the like may be used alone or in combination of two or more.

As the carbonic acid diester compound, diaryl carbonate such as diphenyl carbonate,
Examples include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The polycarbonate resin (A) may use a branching agent for producing a branch, if necessary. Examples of the branching agent include phloroglucin, melitic acid, trimellitic acid, trimellitic chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β -Resorcinic acid, resorcinaldehyde, trimethyl chloride, isatin bis (o-cresol), trimethyl trichloride, 4-chloroformylphthalic anhydride, benzophenonetetracarboxylic acid, 2,4,4'-trihydroxybenzophenone, 2,2 '2,4,4'-tetrahydroxybenzophenone,2,4,4'-trihydroxyphenyl ether, 2,2 ', 4,4'-tetrahydroxyphenyl ether, 2,4,4'-trihydroxydiphenyl-2- Propane, 2,2'-bis (2,4-di Hydroxyphenyl) propane, 2,2 ', 4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxydiphenylmethane, 1- [α-methyl-α-
(4'-dihydroxyphenyl) ethyl] -3-
[Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 "-Hydroxyphenyl) ethyl] benzene, α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
3,5-triisopropylbenzene, 2,6-bis (2
-Hydroxy-5'-methylbenzyl) -4-methylphenol, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene, 4,6
-Dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptane, 1,3,5-tris (4'-
Hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis [4,4-bis (4′-hydroxyphenyl) cyclohexyl] propane, 2,6-bis (2 ′ -Hydroxy-
5'-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2 '-Hydroxy-5'-isopropylbenzyl) -5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2', 4 ', 7-trihydroxyflavan, ,
4,4-trimethyl-2 ', 4', 7-trihydroxyflavan, 1,3-bis (2 ', 4'-dihydroxyphenylisopropyl) benzene, tris (4'-hydroxyphenyl) -amyl-s-triazine And so on.

As the terminal terminator at the time of polymerization of the polycarbonate resin (A), various known terminating agents can be used. Specifically, monohydric phenols such as phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, bromophenol, tribromophenol,
Nonylphenol and the like can be mentioned.

As the polycarbonate resin (A),
In order to further enhance flame retardancy, a copolymer with a phosphorus compound, or a polycarbonate resin end-capped with a phosphorus compound or a polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate portion and a polyorganosiloxane portion is used. You may.

The content of the copolymer component from the phosphorus compound and the polyorganosiloxane must be 50% or less in the polycarbonate resin (A).

Further, in order to enhance the weather resistance, a copolymer with a dihydric phenol having a benzotriazole group, a polycarbonate resin end-blocked with a monohydric phenol having a benzotriazole group, or the like can be used.

As the polycarbonate resin (A), 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (3,5-dimethyl) -4-hydroxyphenyl) methane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) sulfone, Molding a polycarbonate resin or a polycarbonate-polyorganosiloxane copolymer obtained by reacting at least one phenolic compound selected from 4,4'-dihydroxybenzophenone with phosgene or a carbonic acid diester; It is preferably used in view of the properties and the mechanical strength of the obtained molded article.

The viscosity average molecular weight of the polycarbonate resin (A) used in the present invention is preferably 10,000 to 10,000.
60000, more preferably 15000-4500
0, particularly preferably 18,000 to 35,000.
When the viscosity average molecular weight is less than 10,000, the flame retardancy of the obtained resin composition and the strength of the molded article obtained from the resin composition become insufficient, and when it exceeds 60000, there is a tendency that there is a problem in molding fluidity. is there.

The polycarbonate resin (A) may be used alone or in combination of two or more. 2
When used in combination of more than one kind, there is no particular limitation on how to combine. For example, those having different copolymer components, different copolymer molar ratios, different molecular weights, and the like may be used in any combination.

In the present invention, an alkali metal perfluoroalkanesulfonate and / or an alkaline earth metal perfluoroalkanesulfonate (B) is used for imparting flame retardancy.

Specific examples of the perfluoroalkanesulfonic acid in the component (B) include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoropentanesulfonic acid, Examples include perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, and perfluoromethylbutanesulfonic acid. Of these, perfluorobutanesulfonic acid is preferred from the viewpoint of compatibility with the polycarbonate resin (A) and the effect of imparting flame retardancy to the polycarbonate resin composition of the present invention.

Specific examples of the alkali (earth) metal in the component (B) include lithium, sodium, potassium and cesium as the alkali metal, and magnesium, calcium, strontium and barium as the alkaline earth metal. Can be Of these, alkali metals are preferred from the viewpoint of compatibility with the polycarbonate resin (A) and the effect of imparting flame retardancy to the polycarbonate resin composition of the present invention.
Particularly, potassium is preferable from the above-mentioned point.

Specific examples of the alkali metal perfluoroalkanesulfonic acid compound and / or the alkaline earth metal perfluoroalkanesulfonic acid compound (B) include, for example, a compound represented by the following general formula (I): (C _n F _{2n + 1} SO ₃ ) _m M (I) (n is an integer of from 1 to 10, M is an alkali (earth) metal, m
Represents a valence of M), for example, potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, potassium perfluoromethanesulfonate, potassium perfluoroethanesulfonate,
Examples thereof include potassium perfluorooctanesulfonate and calcium perfluorobutanesulfonate.

Among the alkali metal perfluoroalkanesulfonate and / or the alkaline earth metal perfluoroalkanesulfonate (B), potassium perfluorobutanesulfonate has a high compatibility with the polycarbonate resin (A). It is preferable from the viewpoint of the effect of imparting flame retardancy to the polycarbonate resin composition of the present invention.

These may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination is not particularly limited. For example, those having different perfluoroalkane units and those having different alkali (earth) metals can be used in any combination.

The content of the alkali metal perfluoroalkanesulfonic acid compound and / or the alkaline earth metal perfluoroalkanesulfonic acid compound (B) is as follows:
0.0 to 100 parts of polycarbonate resin (A)
01 to 3 parts, preferably 0.005 to 2.5 parts.
Parts, more preferably 0.01 to 2 parts. 0.00
If less than 1 part, the flame retardant effect is not seen, and if more than 3 parts, the moist heat resistance decreases.

In the present invention, the polycarbonate resin (A)
The polyester resin (C) is used to improve the wet heat resistance of a composition comprising the above compound and a perfluoroalkanesulfonic acid alkali metal salt compound and / or a perfluoroalkanesulfonic acid alkaline earth metal salt compound (B).

The polyester resin (C) comprises a divalent or higher carboxylic acid component, a divalent or higher alcohol, and / or
It is a thermoplastic polyester resin obtained by polycondensing a phenol component with a known method.

The divalent or higher carboxylic acid component includes
Divalent or higher valent aromatic carboxylic acid having 8 to 22 carbon atoms, divalent or higher carboxylic acid having 3 to 12 carbon atoms, 8 to 1 carbon atom
Carboxylic acids such as divalent or higher valent alicyclic carboxylic acids of 5 and ester-forming derivatives thereof are exemplified. Specific examples thereof include a divalent or higher valent aromatic carboxylic acid having 8 to 22 carbon atoms and ester-forming derivatives thereof such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and bis (p-carboxylate). Phenyl) methane, anthracenedicarboxylic acid, 4,4 ′
Carboxylic acids such as -diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid; and their ester-forming ability. Derivatives such as alkyl esters, alkali metal salts, halides, etc .; and C3 to C12 divalent or higher aliphatic carboxylic acids;
Examples of the divalent or higher alicyclic carboxylic acid having a valence of 15 to 15 and ester-forming derivatives thereof include succinic acid, adipic acid,
Examples thereof include carboxylic acids such as sebacic acid, decanedicarboxylic acid, azelaic acid, dodecanedioic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid, and derivatives having ester-forming ability thereof. These may be used alone or in combination of two or more. Of these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferably used in view of the moldability of the polycarbonate resin composition of the present invention, the wet heat resistance, and the mechanical strength of the obtained molded article.

Examples of the dihydric or higher alcohol and / or phenol component include aliphatic compounds having 2 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and 6 to 4 carbon atoms.
0 aromatic compounds having two or more hydroxyl groups in the molecule, and ester-forming derivatives thereof. Specific examples thereof include those having 2 to 2 carbon atoms.
15 aliphatic compounds having two or more hydroxyl groups in the molecule, for example, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, glycerin, pentaerythritol and the like are compounds having 6 to 20 carbon atoms and an alicyclic compound having two or more hydroxyl groups in the molecule, Compounds such as cyclohexanedimethanol, cyclohexanediol, and 2,2'-bis (4-hydroxycyclohexyl) propane, which are aromatic compounds having 6 to 40 carbon atoms and having two or more hydroxyl groups in the molecule; 2,2'-bis (4-hydroxyphenyl) propane, hydroquinone and the like. Further, as these ester-forming derivatives, for example, alkali metal salt alkoxides, alkyl esters and the like are also used. These may be used alone or in combination of two or more. Among these, ethylene glycol, cyclohexane dimethanol, butanediol,
2,2'-bis (4-hydroxyphenyl) propane is preferably used in view of the dispersibility of the polyester resin in the polycarbonate resin composition of the present invention and the compatibility with the polycarbonate resin.

The polyester resin (C) may contain, in addition to the above components, known copolymerizable components as long as the polycarbonate resin composition of the present invention does not impair the properties such as flame retardancy and wet heat resistance. It may be copolymerized. Examples of the copolymerizable component include oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid, and ester-forming derivatives thereof, such as alkyl esters at both ends, and cyclic esters such as ε-caprolactone. It can be used as a copolymer component.

Further, as the polyether compound, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, poly (ethylene oxide / tetrahydrofuran) block and / or random copolymer Polymer, poly (ethylene oxide / propylene oxide / tetrahydrofuran) block and / or random copolymer, ethylene oxide addition polymer of bisphenol A,
Propylene oxide addition polymer of bisphenol A, tetrahydrofuran addition polymer of bisphenol A, (ethylene oxide / propylene oxide) addition polymer of bisphenol A, ethylene oxide addition polymer of bisphenol S, propylene oxide addition polymer of bisphenol S, and bisphenol S Bisphenols such as tetrahydrofuran addition polymers and bisphenol S (ethylene oxide / propylene oxide) addition polymers, and ethylene oxide, propylene oxide, and alkylene oxide addition polymers such as tetrahydrofuran are also examples of copolymerizable components. Further, as polylactone, ε-caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, trimethyl-ε-
Examples of the copolymer component include polymers of cyclic lactones such as caprolactone, β-propiolactone, hivalolactone, γ-valerolactone, enantholactone, and caprylolactone.

The polyether compound and / or
Polylactones may be used alone or in combination of two or more different and / or different molecular weights.

The polyether compound and / or
The copolymerization ratio of polylactone is 40% or less, and moreover 35%.
% Or less is preferable. If the copolymerization ratio exceeds 40%, the wet heat resistance tends to decrease.

Specific examples of the polyester resin (C) include aromatic polyesters such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate and polybutylene naphthalate. And aliphatic polyesters such as polyethylene adipate. Further, copolymers of these aromatic polyesters with aliphatic or alicyclic polyesters may be used. These may be used alone or in combination of two or more. Among these, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyarylate are compatible with the polycarbonate resin (A) and have flame retardancy, moldability, wet heat resistance. It is preferably used from the point of view.

In a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent of the polyester resin (C),
The intrinsic viscosity (IV) measured at 25 ° C is preferably from 0.30 to 2.00 dl / g, more preferably from 0.4 to dl / g.
0 to 1.80 dl / g, particularly preferably 0.50 to
1.60 dl / g. 0.30 dl / g intrinsic viscosity
When the value is less than the above, there are many cases where the mechanical strength of the molded product is insufficient, and when it exceeds 2.00 dl / g, there is a tendency that there is a problem in the formability.

The content of the polyester resin (C) is 2 to 50 parts per 100 parts of the polycarbonate resin (A).
Parts, preferably 5 to 45 parts, more preferably 10 to
40 parts. If it is less than 2 parts, the effect of improving the wet heat resistance is small, and if it exceeds 50 parts, the flame retardancy is reduced.

In the present invention, a fluororesin (D) and / or silicone (E) can be used for the purpose of further improving flame retardancy and wet heat resistance.

The fluororesin (D) is a resin containing 20% or more (% by weight, hereinafter the same) of fluorine atoms in the resin, preferably 40% or more.
% Or more. Specific examples include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, a monomer copolymerizable with a monomer used in the production of the fluororesin (D), such as ethylene, may be used as long as the physical properties such as flame retardancy of the obtained molded article are not impaired. A copolymer obtained by polymerization in combination may be used. Among them, polytetrafluoroethylene is preferably used in terms of flame retardancy and wet heat resistance. These fluororesins (D) may be used alone or in combination of two or more.

The average molecular weight of the fluororesin (D) is 10
It is preferably from 100,000 to 20,000,000, more preferably from 2,000,000 to 10,000,000. If the amount is less than 1,000,000, it becomes difficult to handle due to adhesiveness. If the amount exceeds 20,000,000, dispersion tends to be poor in the composition, and the mechanical strength of the composition tends to decrease.

The silicone (E) is an organosiloxane, which is a siloxane compound such as dimethylsiloxane and phenylmethylsiloxane, and polydimethylsiloxane, polyphenylmethylsiloxane, dimethylsiloxane and phenylmethylsiloxane obtained by polymerizing these. And organopolysiloxanes such as copolymers of In the case of an organopolysiloxane, a modified silicone having a molecular terminal substituted by a substituent having an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, an ether bond or the like is also useful. Among them, polymethylsiloxane, polyphenylmethylsiloxane, a copolymer of methylsiloxane and phenylmethylsiloxane or an epoxy group-containing polymer thereof is preferably used because of its good compatibility with the polycarbonate resin. .

The number average molecular weight of the silicone (E) is preferably from 200 to 10,000,000, and more preferably from 1,000 to 5,000,000 from the viewpoint that the flame retardancy can be further improved. When the number average molecular weight is less than 200, the mechanical strength of the composition tends to decrease, and when it exceeds 10,000,000, the compatibility with the polycarbonate resin tends to decrease.

The shape of the silicone (E) is not particularly limited, and any shape such as oil, gum, varnish, powder, and pellet may be used.

The content of the fluororesin (D) and / or the silicone (E) is 0.01 to 3 parts with respect to 100 parts of the polycarbonate resin (A).
It is preferably from 2.5 to 2.5 parts, more preferably from 0.05 to 2 parts. When the addition amount is less than 0.01 part, the effect of improving the flame retardancy and wet heat resistance is small, and when the addition amount exceeds 3 parts, the moldability of the fluororesin (D) is increased, and the flame retardancy of the silicone (E) is decreased. Is undesirably reduced.

When the fluororesin (D) and the silicone (E) are used in combination, the flame retardancy and wet heat resistance can be further improved as compared with the case where they are added alone.

When the fluororesin (D) and the silicone (E) are used in combination, the use ratio ((D) / (E)) is 99/1 to 1/99, and more preferably 95/5 to 5/95. It is preferred that When the use ratio is less than 99/1 or more than 1/99, there is a tendency that the synergistic effect of using both together is not observed.

The moist heat resistance of the polycarbonate resin composition of the present invention can be further improved by using the olefin polymer (F).

The olefin polymer (F) is used in a broad sense including polyolefin in a narrow sense, a mixture of a polyolefin and a polydiene, and a copolymer of an olefin monomer and a diene monomer. Ethylene, propylene, 1-
Butene, 1-pentene, 1-isobutene, butadiene,
Isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3
-Cyclohexadiene, 1,4-cyclohexadiene,
1 from the group of monomers such as 1,5-cyclooctadiene, 1,3-cyclooctadiene, α, ω-non-conjugated dienes;
Examples thereof include a homopolymer or a copolymer of monomers selected from a combination of two or more species, and a mixture of two or more polymers selected from a homopolymer and a copolymer thereof.

Further, the olefin polymer (F) may be a polymer obtained by copolymerizing another copolymerizable vinyl monomer in the above polymer. Examples of the other copolymerizable vinyl monomers include, for example, styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, and aromatic vinyl compounds.
Vinyl toluene and divinyl benzene, etc., methyl methacrylate as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate, etc. And alkyl acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate and stearyl acrylate, and glycidyl (meth) acrylate As esters, glycidyl methacrylate, glycidyl acrylate, and the like,
As vinyl alkyl ethers, vinyl methyl ether, vinyl ethyl ether, vinyl i-propyl ether, vinyl n-propyl ether, vinyl i-butyl ether, vinyl n-amyl ether, vinyl i-amyl ether, vinyl 2-ethylhexyl ether and vinyl octadecyl Ethers and the like, unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile,
Acrylamide, methacrylamide and the like as unsaturated amino compounds, and maleic acid di-n-propyl ester and maleic acid di-alkyl ester as maleic acid di-alkyl esters.
i-butyl ester, maleic acid dimethyl ester, maleic acid di-n-propyl ester, maleic acid di-octyl ester, maleic acid di-nonyl ester and the like, and allyl alkyl ethers such as allyl ethyl ether and allyl n-octyl ether. And acrylic acid, methacrylic acid, maleic acid, maleic anhydride, vinyl acetate, N-phenylmaleimide and the like. These may be used alone or in combination of two or more.

The content of the other copolymerizable vinyl monomer is preferably 60% or less, more preferably 50% or less, of all the monomers constituting the olefin polymer. If it exceeds 60%, the effect of improving the wet heat resistance of the composition tends to decrease.

Melt index (MI) of the olefin polymer (F) (200 ° C., 2 kg load, JIS K
(According to 6730) is preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less. If the MI exceeds 500 g / 10 minutes, the thermal stability of the composition tends to decrease. Further, the M
The lower limit of I is 0.1 g / 10 from the viewpoint of moldability and dispersibility.
Min, and further 0.3 g / 10 min.

Specific examples of the olefin polymer (F) include polyethylene, (linear) high-density polyethylene,
(Linear) Low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer and other ethylene or α-olefins and (meth) acrylates Copolymers, copolymers of ethylene or α-olefin with glycidyl (meth) acrylate such as ethylene-glycidyl methacrylate copolymer, ethylene or α-olefin with (meth) acrylate and glycidyl (meth) acrylate A copolymer with
Copolymers of ethylene or α-olefin with carbon monoxide and (meth) acrylic acid ester can be used. Among these, copolymers of ethylene or α-olefin and (meth) acrylate, specifically, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid Butyl copolymers and the like are preferred from the viewpoint of the balance between compatibility with the polycarbonate resin and the effect of improving wet heat resistance. In the copolymer, the copolymerization ratio of the (meth) acrylic acid ester is determined based on the compatibility with the polycarbonate resin (A) and the polyester resin (C) and the effect of improving the wet heat resistance of the polycarbonate resin composition of the present invention. From 5 to 60%, more preferably 10 to 50%, especially 1
Preferably it is 5-45%. If it is less than 5%, the compatibility with the polycarbonate resin tends to decrease, and if it exceeds 60%, the wet heat resistance of the composition tends to decrease.

The olefin polymer (F) may be used alone or in combination of two or more. When two or more kinds are used in combination, the way of combination is not particularly limited. For example, those having different types, copolymer components and molar ratios, and / or those having different viscosities may be used in any combination.

The amount of the olefin polymer (F) added is
0.1 parts with respect to 100 parts of the polycarbonate resin (A).
The amount is 1 to 10 parts, preferably 0.3 to 8 parts, more preferably 0.5 to 7 parts. When the amount is less than 0.1 part, the effect of improving the moist heat resistance is not seen. When the amount exceeds 10 parts, the flame retardancy is reduced, and the peeling on the surface of the molded article tends to be seen.

In order to further improve the flame retardancy, the polycarbonate resin composition of the present invention may contain other flame retardants such as phosphate ester, red phosphorus, ammonium phosphate,
Phosphorus compounds such as melamine phosphate, nitrogen compounds such as melamine and melamine cyanurate, boric acid compounds such as zinc borate, guanidine compounds, and metal hydroxides can be added.

Further, by adding a reinforcing filler to the polycarbonate resin composition of the present invention, the heat resistance and the like can be further improved. Specific examples of reinforcing fillers include, for example, fibrous fillers such as glass fiber, carbon fiber, and potassium titanate fiber, glass beads, glass flakes, talc, mica, kaolin, wollastonite, smectite, diatomaceous earth, and carbonic acid. Calcium, calcium sulfate, barium sulfate and the like can be mentioned.

Among the reinforcing fillers, silicate compounds and / or fibrous reinforcing agents are preferred.

The silicate compound has a chemical composition of S
A compound having a shape such as powder, granules, needles, and plates containing iO ₂ units, for example, magnesium silicate,
Examples thereof include aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin, diatomaceous earth, and smectite, which may be natural or synthesized. Among them, talc, mica, kaolin and smectite are preferred, and mica and talc are more preferred.

The average diameter of the silicate compound [particle diameter when converted to a circle determined by image processing of a micrograph] is not particularly limited, but a preferable average diameter is 0.01 to 100 μm. And more preferably 0.1 to 50 μm, and particularly preferably 0.3 to 40 μm.
μm. If the average particle size is less than 0.01 μm, the effect of improving the strength is not sufficient, and if it exceeds 100 μm, the toughness tends to decrease.

Further, the silicate compound may be treated with a surface treating agent such as a silane coupling agent or a titanate coupling agent. Examples of the silane coupling agent include epoxy silane, amino silane, and vinyl silane. Examples of the titanate coupling agent include monoalkoxy type, chelate type, and coordinate type. .

The method of treating the silicate compound with a surface treating agent is not particularly limited, and can be carried out by a usual method. For example, the surface treatment agent can be added to the layered silicate and stirred or mixed in a solution or while heating.

As the fibrous reinforcing agent, glass fiber,
And carbon fiber. When a fibrous reinforcing agent is used, it is preferable to use chopped strand glass fibers treated with a sizing agent from the viewpoint of workability. Further, in order to enhance the adhesiveness between the resin and the fibrous reinforcing agent, it is preferable that the surface of the fibrous reinforcing agent is treated with a coupling agent, and a material using a binder may be used. Examples of the coupling agent include the same compounds as described above.

When glass fibers are used as the reinforcing filler, those having a diameter of about 1 to 20 μm and a length of about 0.01 to 50 mm are preferable. If the fiber length is too short, the effect of reinforcement is not sufficient, and if it is too long, the surface properties, extrusion processability, and moldability of the molded product are undesirably deteriorated.

The reinforcing fillers may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation on the combination, but a preferable combination is two or more kinds of reinforcing fillers selected from mica, talc and glass fiber.

Further, as long as the properties of the polycarbonate resin composition of the present invention are not impaired, any other thermoplastic or thermosetting resin such as polyamide resin, polystyrene resin, polyphenylene sulfide resin, A polyphenylene ether-based resin, polyacetal-based resin, polysulfone-based resin, rubber-like elastic material, or the like may be used alone or in combination of two or more.

In order to improve the performance of the polycarbonate resin composition of the present invention, an antioxidant such as a phenolic antioxidant and a thioether antioxidant, and a heat stabilizer such as a phosphorus-based stabilizer are used. Etc. alone or 2
It is preferable to use a combination of two or more types. Further, if necessary, usually well-known stabilizers, lubricants, release agents, plasticizers, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizers And additives such as antibacterial agents may be used alone or in combination of two or more.

The method for molding the polycarbonate resin composition obtained in the present invention is not particularly limited.
Molding methods generally used for thermoplastic resins, for example, injection molding, blow molding, extrusion molding, vacuum molding, press molding, calender molding and the like can be applied.

The polycarbonate resin composition of the present invention is preferably used for applications such as electric and electronic parts such as OA equipment, housing materials, and automobile parts.

[0071]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

The polycarbonate resin composition was evaluated by the following method.

Evaluation method The obtained polycarbonate resin composition was heated at 120 ° C. for 4 hours.
After drying for more than an hour, bars (12 mm wide, 1 mm long) of 1/12 inch, 1/8 inch and 1/4 inch thickness were taken with an 80t injection molding machine (IS-80 manufactured by Toshiba Machine Co., Ltd.).
27 mm) and evaluated by the following method.

Evaluation of Flame Retardancy: Flame retardancy was evaluated according to the UL94 vertical flammability test using 1/12 inch and 1/8 inch bars. In addition, "x" in flame retardancy is UL.
94 Represents out of vertical combustion test standard (not V). Moisture / heat resistance: A 1/4 inch bar was held at 121 ° C. under saturated pressurized steam for 60 hours to perform a heat and moisture resistance treatment. The bar before and after the wet heat resistance treatment was subjected to a bending test according to ASTM D-790 to determine the maximum strength. The bending strength retention was determined from the bending strength before and after the wet heat resistance treatment according to the following equation. Bending strength retention = ｛(Bending strength after wet heat resistance treatment) /
(Bending strength before wet heat resistance treatment)｝ × 100 (%)

The raw materials used are shown below.

PC-1: a bisphenol A type polycarbonate resin having a viscosity average molecular weight of 22,000 PC-2: a bisphenol A type polycarbonate resin having a viscosity average molecular weight of 30,000 PET: polyethylene terephthalate (intrinsic viscosity 0.75) PBT: polybutylene terephthalate ( Intrinsic viscosity 0.85) PFBSK: potassium perfluorobutanesulfonate (MegaFac F-114 manufactured by Dainippon Ink and Chemicals, Inc.) PFBSNa: sodium perfluorobutanesulfonate PFOSK: potassium perfluorooctanesulfonate PFBSCa: perfluoro Calcium butanesulfonate Silicone-1: Dow Corning Silicone Toray Silicon Powder Silicone Silicone-2: Dow Corning Toray Silicone Silicone BY-27 (ultra high molecular weight polydimethylsiloxane) PTFE: polytetrafluoroethylene (Polyflon F-104, manufactured by Daikin Industries, Ltd.) EEA-1: ethylene ethyl acrylate (Evaflex A, manufactured by DuPont Mitsui Polychemicals, Inc.) -709, ethyl acrylate content 35%) EEA-2: ethylene ethyl acrylate (Evaflex A-701, manufactured by DuPont Mitsui Polychemicals, Inc., ethyl acrylate content 9%) LLDPE: linear low density polyethylene (Idemitsu Petrochemical) Moirec 0168N manufactured by Co., Ltd.)

Example 1 100 parts of polycarbonate resin (PC-1), potassium perfluorobutanesulfonate (PFBSK) 0.00
After dry blending 7 parts and 10 parts of polyethylene terephthalate (PET), the cylinder temperature is set to 280 ° C. using a co-directional twin screw extruder (PCM-30 manufactured by Ikegai Iron Works).
To carry out extrusion kneading to obtain a resin composition. The obtained resin composition was evaluated according to the above evaluation method.

Table 1 shows the results.

Examples 2 to 13 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the compositions shown in Table 1 were used.

Table 1 shows the results.

[0081]

[Table 1]

Example 14 100 parts of polycarbonate resin (PC-1), 0.2 part of potassium perfluorobutanesulfonate (PFBSK)
Parts, 10 parts of polyethylene terephthalate (PET), and 0.3 parts of polytetrafluoroethylene (PTFE), and then kneading with a co-axial twin-screw extruder at a cylinder temperature of 280 ° C to obtain a resin composition I got something. The obtained resin composition was evaluated according to the above evaluation method.

Table 2 shows the results.

Examples 15 to 26 Resin compositions were obtained and evaluated in the same manner as in Example 14 except that the compositions shown in Table 2 were used.

Table 2 shows the results.

[0086]

[Table 2]

Example 27 100 parts of polycarbonate resin (PC-1), 0.2 part of potassium perfluorobutanesulfonate (PFBSK)
Parts, 10 parts of polyethylene terephthalate (PET) and 3 parts of ethylene ethyl acrylate (EEA-1) are dry-blended, and then extruded and kneaded at a cylinder temperature of 280 ° C. using a co-axial twin screw extruder to obtain a resin composition. I got The obtained resin composition was evaluated according to the above evaluation method.

Table 3 shows the results.

Examples 28 to 42 Resin compositions were obtained and evaluated in the same manner as in Example 27, except that the compositions shown in Table 3 were used.

Table 3 shows the results.

[0091]

[Table 3]

Comparative Examples 1 to 16 Resin compositions were obtained and evaluated in the same manner as in Examples 1 to 42 except that the compositions shown in Table 4 were used.

Table 4 shows the results.

[0094]

[Table 4]

Examples 1 to 13 (Table 1) and Comparative Examples 1 to 8
Comparison with Nos. 15 and 16 (Table 4) shows that Examples 1 to 13 of the polycarbonate resin composition of the present invention are excellent in both flame retardancy and wet heat resistance. Also,
Examples 2 to 5 show that among the alkali (earth) metal salts of perfluoroalkanesulfonic acid, potassium perfluorobutanesulfonic acid is excellent in flame retardancy and wet heat resistance.

Further, when Examples 14 to 26 (Table 2) are compared with Examples 1 to 13 and Comparative Examples 9 and 12, the use of a fluorine-based resin and / or silicone further increases the flame retardancy and wet heat resistance. It can be seen that a polycarbonate resin composition was obtained.

Further, it can be seen that a flame-retardant polycarbonate resin composition having more excellent wet heat resistance is obtained by using an olefin polymer together with the polycarbonate resin composition of the present invention.

[0098]

According to the present invention, a polyester resin is used in combination with a polycarbonate resin composition made flame-retardant using an alkali (earth) metal salt of perfluoroalkanesulfonic acid, so that in addition to flame retardancy, moisture and heat resistance can be obtained. Thus, it is possible to provide an excellent polycarbonate resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 83:04 23:02)

Claims (5)

[Claims] (A) 100 parts by weight of a polycarbonate resin; (B) 0.001 to 3 parts by weight of an alkali metal perfluoroalkanesulfonate and / or an alkaline earth metal perfluoroalkanesulfonate; C) A polycarbonate resin composition comprising 2 to 50 parts by weight of a polyester resin. 2. A polycarbonate resin composition comprising the polycarbonate resin composition according to claim 1 and 0.01 to 3 parts by weight of (D) a fluorine resin or (E) silicone. 3. A polycarbonate resin composition obtained by further adding (D) a fluorine resin and (E) 0.01 to 3 parts by weight of silicone to the polycarbonate resin composition according to claim 1. 4. A polycarbonate resin composition obtained by further adding (F) 0.1 to 10 parts by weight of an olefin polymer to the polycarbonate resin composition according to claim 1, 2 or 3. 5. The method according to claim 1, wherein (B) the alkali metal perfluoroalkanesulfonate and / or the alkaline earth metal perfluoroalkanesulfonate is potassium perfluorobutanesulfonate. Polycarbonate resin composition.