JP2898367B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition having excellent heat stability and chemical resistance.

<Conventional Technology> Polycarbonate resins are widely used for various parts such as daily necessities and office equipment, electric and electronic parts, etc. because of their excellent properties. However, polycarbonate resins have a drawback that they have poor chemical resistance and are liable to crack when exposed to a certain solvent under the presence of stress.

In order to remedy this drawback, JP-A-59-68368 discloses an attempt to melt-mix a polycarbonate resin with a polyamide resin, stating that the binary resin composition exhibits improved chemical resistance. Have been. However, when the polycarbonate resin and the polyamide resin are melt-mixed, the polycarbonate resin is decomposed and molding is extremely difficult. Even if a molded product is obtained, the molded product may be discolored or silver stripes may be generated on the molded product. Therefore, this binary resin composition was not completely usable.

<Object of the Invention> An object of the present invention is to provide a resin composition having excellent heat stability and chemical resistance during molding.

The present inventor has conducted intensive studies to improve the thermal stability of the binary resin composition, and as a result, the modified polyester resin containing a metal salt of sulfonic acid is blended with the binary resin composition to thereby improve the thermal stability. I found that the thermal stability was dramatically improved. As a result of further study based on this finding, the present inventors have reached the present invention.

<Structure of the Invention> The present invention relates to a modified polyester comprising (A) 25 to 90% by weight of a polycarbonate resin, (B) 100 to 100 parts by weight of a resin composition comprising a polyamide resin and (C) a metal sulfonate base. resin
The present invention relates to a resin composition containing 0.1 to 20 parts by weight.

Conventionally, it has been proposed to blend a small amount of a polymer containing a metal sulfonate group into a polycarbonate resin to make the polycarbonate resin flame-retardant. However,
A resin composition in which a polyamide resin is blended with a polycarbonate resin in an amount of 10% by weight or more has a combustion behavior greatly different from that of the polycarbonate resin.The composition of the present invention is obtained by blending a modified polyester resin containing a metal sulfonate group. As shown in the following table, the flammability is promoted.

The polycarbonate in the table has a viscosity average molecular weight of 24,9
Bisphenol A polycarbonate resin of No. 00 (manufactured by Teijin Chemicals Ltd .: Panlite L-1250), polyamide is intrinsic viscosity of 1.5 with m-cresol, NH ₂ group 40 eq / t, COOH group 40 eq / t
Nylon-6, modified polyester is terephthalic acid 58.5
It is a modified polyester resin having an intrinsic viscosity of 0.60, comprising an acid component composed of 40 mol% of isophthalic acid, 1.5 mol% of sodium 5-sulfoisophthalate, and a diol component composed of 50 mol% of ethylene glycol and neopentyl glycol 50 mol%. .

As is clear from the above table, the incorporation of the modified polyester resin containing the metal sulfonate group improves the flame retardancy when only the polycarbonate resin is used (Experiment Nos. 2 and 3). However, in the case of a resin composition of a polycarbonate resin and a polyamide resin, combustion becomes easier (in the case of Experiment Nos. 5 and 6 and Experiment No. 4, dripping is severe and the fire goes out immediately). That is, the modified polyester resin containing the sulfonic acid metal base does not act as a flame retardant at all with respect to the resin composition of the polycarbonate resin and the polyamide resin targeted by the present invention.

The (A) polycarbonate resin used in the present invention is a polycarbonate resin derived from dihydric phenol, and has a polymerization degree of usually 15,000 to 100,00 in terms of viscosity average molecular weight.
0, preferably 18,000 to 60,000. Such a polycarbonate resin is usually produced from a dihydric phenol and a carbonate precursor by a solution method or a melting method. Representative examples of dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-
Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and the like. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkane compounds, especially bisphenol A. The dihydric phenols can be used alone or in combination of two or more. Examples of the carbonate precursor include carbonyl halide, carbonate and haloformate. Representative examples include phosgene, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof. In the production of polycarbonate resin, a suitable molecular weight regulator, branching agent, if necessary,
A catalyst or the like can also be used.

Further, the polyamide resin (B) used in the present invention is a polymer composed of aminocarboxylic acid alone or a dicarboxylic acid and a diamine, or a polymer obtained by ring-opening polymerization of α, ω-caprolactam. To give a concrete example, ε
-Caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid,
9-aminononanoic acid, α-pyrrolidone, polymers such as α-piperidone, further diamines such as hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, meta-xylylenediamine and terephthalic acid, isophthalic acid, Polymers or copolymers obtained by polycondensation with dicarboxylic acids such as adipic acid, sebacic acid, dodecane dibasic acid and glutaric acid. For example, nylon 4, 6, 7, 8, 11, 12, 6.6,
6.9,6,10,6,11,6,12,6 / 6,6,6 / 12,6 / 6
T, 6I / 6T and the like.

The mixing ratio of the (A) polycarbonate resin and the (B) polyamide resin is preferably 25 to 90% by weight of the component (A), more preferably
Component (B) is 75 to 10% by weight, preferably 70 to 20% by weight, based on 30 to 80% by weight. (B) The mixing ratio of the component is 10
If it is less than 75% by weight, the effect of improving chemical resistance is not sufficient, and if it exceeds 75% by weight, dimensional stability is deteriorated due to moisture absorption of the polyamide resin.

The component (C) used in the present invention is a modified polyester resin containing a sulfonic acid metal base. The polyester resin referred to here is a polymer or copolymer obtained by subjecting a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof to a condensation reaction as main raw materials. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, oxalic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and the like. Examples of the diol component include an alkylene glycol having 2 to 10 carbon atoms and an alicyclic diol having 6 to 15 carbon atoms. Specific examples include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, 3-methylpentanediol, 2-methylpentanediol, 2-ethylhexanediol, cyclohexanedimethanol, and the like. . Further, a polyalkylene glycol can be used as the diol component. Specifically, poly (alkylene oxide) -α, ω-diol such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or random or block of ethylene oxide and 1,2-propylene oxide Copolymers and the like can be mentioned.

The method for modifying the polyester resin to contain a sulfonic acid metal base is optional.However, a dicarboxylic acid component to which a sulfonic acid metal base is previously bonded, such as sodium 5-sulfoisophthalate or an ester-forming derivative thereof, is used as the polyester resin. A method of forming an addition copolymer at the time of polymerization is generally used. The amount of the sulfonic acid metal base-containing dicarboxylic acid component used at this time is usually 0.5 to 20 mol%, preferably 0.5 to 20 mol%, based on all the acid components constituting the modified polyester resin.
1.0 to 15 mol%. The metal forming the sulfonic acid metal base is preferably an alkali metal, particularly preferably sodium or potassium.

The compounding ratio of the modified polyester resin as the component (C) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the composition comprising the (A) polycarbonate resin and the (B) polyamide resin.
Preferably it is 1 to 15 parts by weight. When the compounding ratio of the component (C) is less than 0.1 part by weight, the effect of improving the thermal stability at the time of molding is not sufficient, and silver stripes are formed on the molded product or the molded product is discolored. If the amount exceeds 20 parts by weight, the effect is saturated and does not improve much.

The composition of the present invention can further improve the thermal stability at the time of molding by adding an appropriate amount of the following components, and this is also preferable.

Halogen-containing rubber, halogenated polyolefin: -1 Specific examples of the halogen-containing rubber include halogenated rubbers such as chlorinated butyl rubber, brominated butyl rubber, and chlorosulfonated polyethylene, chloroprene rubber, chloroprene-isoprene copolymer, and chloroprene. -Examples of raw materials which already contain halogens, such as styrene copolymers, chloroprene-acrylonitrile copolymers, vinylidene fluoride-chlorinated ethylene copolymers and epichlorohydrin rubber, etc. be able to. These halogen-containing rubbers may be solid or liquid.

-2 The halogenated polyolefin is produced from the polyolefin by an arbitrary method such as an aqueous suspension chlorination method, and the polyolefin used in this case is ethylene, propylene, butene-1,4-methylpentene-. Polymers and copolymers of the olefin compound as described in 1.

These halogen-containing rubbers and halogenated polyolefins may be used alone or in combination of two or more. Among these halogen-containing rubbers and halogenated polyolefins, halogenated butyl rubber and chlorinated polyethylene are particularly preferred.

The amount of the halogen-containing rubber and halogenated polyolefin is from 1 to 1 based on 100 parts by weight of the composition comprising the (A) polycarbonate resin and the (B) polyamide resin.
A range of 0 parts by weight is appropriate.

Epoxy resin, phenoxy resin: Epoxy resins include bisphenol-type epoxy resins obtained by polycondensation of bisphenols and epichlorohydrin, halogenated bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, phenol novolak and O-cresol novolak. A glycidyl etherified novolak type epoxy resin can be used.

These epoxy resins and phenoxy resins may be used alone or in combination of two or more.
The range of 0.1 to 15 parts by weight is appropriate for 100 parts by weight of the composition comprising (A) the polycarbonate resin and (B) the polyamide resin.

Modified block copolymer, modified olefin polymer, elastic copolymer: -1 The modified block copolymer is a block copolymer composed of at least one vinyl aromatic compound polymer block and at least one olefin compound polymer block. Coalescing (hereafter referred to as the base block copolymer)
Is a modified block copolymer in which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded.

The vinyl aromatic compound polymer block referred to herein is a polymer block obtained by polymerizing or copolymerizing one or more vinyl compounds selected from styrene, α-methylstyrene, vinyltoluene, and the like, and an olefin compound polymer block. Monoolefins such as ethylene, propylene, 1-butene and isobutylene, butadiene, isoprene, 1,3-
One or more olefin compounds selected from conjugated diolefins such as pentadiene and non-conjugated diolefins such as 1,4-hexadiene, norbornene and norbornene derivatives are polymerized or copolymerized polymer blocks. When a conjugated diolefin is used as the olefin compound, the polymer block may be hydrogenated.

The block copolymer serving as a substrate is modified by an addition reaction with an unsaturated carboxylic acid or a derivative thereof to form a modified block copolymer. Further, the block copolymer serving as a base may be a copolymer obtained by random copolymerization of an unsaturated carboxylic acid or a derivative thereof.

Specific examples of the unsaturated carboxylic acid or derivative thereof used herein include maleic acid, fumaric acid, itaconic acid, maleic halide, cis-4-cyclohexene-1,2-
Dicarboxylic acid, endo-cis-bicyclo [2,2,1] -5
-Pentene-2,3-dicarboxylic acid and the like; acid anhydrides, esters and imides of these dicarboxylic acids; acrylic acid and methacrylic acid; and esters and amides of these monocarboxylic acids. These may be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or derivatives thereof are preferred, and maleic anhydride is particularly preferred.

-2 Modified olefin polymer is a modified olefin polymer in which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to the olefin polymer.

The olefin polymer referred to here includes monoolefins such as ethylene, propylene, 1-butene and isobutylene, conjugated diolefins such as butadiene, isoprene and 1,3-pentadiene, and non-olefins such as 1,4-hexadiene, norbornene and norbornene derivatives. One or more olefin compounds selected from conjugated diolefins are polymerized or copolymerized.

The olefin polymer is modified by an addition reaction with an unsaturated carboxylic acid or a derivative thereof to form a modified olefin polymer. Further, the olefin polymer may be one obtained by randomly copolymerizing an unsaturated carboxylic acid or a derivative thereof.

As the unsaturated carboxylic acid or derivative thereof used herein, the unsaturated carboxylic acid or derivative thereof described in the section of -1 modified block copolymer is similarly used.

-3 elastic copolymer, in the presence of a rubber containing a repeating unit derived from butadiene, two or more kinds selected from the group consisting of vinyl cyanide compounds, methacrylic esters, acrylic esters and aromatic vinyl compounds A monomer;
It is an elastic copolymer obtained by copolymerizing an unsaturated carboxylic acid or a derivative thereof, and preferably has a rubber component content of 50% by weight or more.

Examples of the rubber containing a repeating unit derived from butadiene referred to herein include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylate copolymer, and the like.

Examples of the vinyl cyanide compound used herein include acrylonitrile, methacrylonitrile, and the like.Methacrylic acid esters and acrylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, and acryl. Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, and octyl acrylate.Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. it can.

Examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2,2 , 1] -5-pentene-2,3-dicarboxylic acid and the like, acid anhydrides, esters and imides of these dicarboxylic acids.

The vinyl cyanide compound, methacrylic acid ester,
Two or more monomers selected from the group consisting of acrylic esters and aromatic vinyl compounds, and unsaturated carboxylic acids or derivatives thereof in the presence of the above rubber component are subjected to bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The elastic copolymer can be obtained by polymerization by any polymerization method.

These modified block copolymers, modified olefin polymers and elastic copolymers may be used alone or in combination of two or more. Further, the compounding amount is suitably from 1 to 20 parts by weight based on 100 parts by weight of the composition comprising (A) the polycarbonate resin and (B) the polyamide resin.

The compounds shown in the above, can be used by selecting one or two or more as necessary,
All may be used together. , Are more effective in improving the thermal stability when they are used in combination with each other in small amounts than in large amounts.

Further, the composition of the present invention contains a polyolefin or α
-A copolymer of olefin and glycidyl methacrylate and / or glycidyl acrylate may be added. By adding these, even better chemical resistance can be obtained.

The copolymer of α-olefin and glycidyl methacrylate and / or glycidyl acrylate may be any of a random copolymer and a graft copolymer. Examples of the α-olefin used in the copolymer include ethylene, propylene, butene-1, isobutylene, pentene-1, octene-1, dodecene-1, 4-methylpentene-1, and the like. Particularly preferred are ethylene and propylene. This copolymer may contain a vinyl compound other than α-olefin, glycidyl methacrylate, and glycidyl acrylate as a copolymer component. Other vinyl compounds include styrene,
Examples include vinyl acetate, methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl chloride, α-methylsultin, divinylbenzene, acrylic acid and the like.

Such a copolymer of polyolefin and α-olefin and glycidyl methacrylate and / or glycidyl acrylate may be used alone or in combination of two or more, and the total amount thereof is (A) polycarbonate resin. It is preferable that the amount is not more than 10 parts by weight based on 100 parts by weight of the composition composed of (B) and the polyamide resin.

In addition, the composition of the present invention can further improve the impact resistance by blending other impact modifiers in addition to the compounds described above, and the blending amount is (A) The content is preferably 25 parts by weight or less based on 100 parts by weight of the resin composition comprising the polycarbonate resin and the polyamide resin (B).

Further, the composition of the present invention may contain, for example, an antioxidant, a flame retardant, an antistatic agent, an ultraviolet absorber, and the like, in addition to the above-mentioned components, as long as the properties of the resin composition are not impaired.

The resin composition of the present invention can be produced by mixing the components with a mixer such as a tumbler, a blender, a Nauter mixer, a Banbury mixer, a kneading roll, and an extruder.

<Effect of the Invention> The composition of the present invention has excellent thermal stability during molding and can be applied to any molding method, for example, injection molding, extrusion molding, compression molding, and the like. <Example> Next, the present invention will be further described with reference to examples. In addition, the evaluation in an Example is based on the following method.

(I) Appearance of molded article: A sample plate was continuously molded from the first shot to the fifteenth shot under the conditions described in the examples and comparative examples.
It was continuously formed until a shot. The sample plate of the 15th shot is visually compared with the sample plate of the first shot, and the state of the change is set to “before staying”. The sample plate of the 19th shot is visually compared with the sample plate of the first shot. In comparison, the state of the change was defined as “after staying” and evaluated as follows.

◎ No discoloration, no silver streaks ○ Slight discoloration, no silver streaks △ Discoloration, no silver streaks × Discoloration, silver streaks occurred ×× Unformable (ii) Impact resistance: according to ASTM D-256 The Izod / notched impact strength (kgf · cm / cm) of the 1/8 ″ test specimen was measured. (I) A test specimen was prepared in the same manner as in the evaluation of the appearance of the molded article, and “before residence”. And "after the stay" were indicated by the average value of four measured values.

(Iii) Chemical resistance: ASTM D-638 (plate) Type III, thickness 1/8 ″
After immersing the specimen in Esso-regular gasoline at 30 ° C for 10 minutes with a strain of 1.0% using the tensile test specimen shown in Fig. 1, the presence or absence of cracks in the specimen and the fracture before and after gasoline immersion Elongation was measured according to ASTM D-638.

Examples 1 to 16 and Comparative Examples 1 to 7 After drying the polycarbonate resin at 120 ° C. for 5 hours and the polyamide resin at 105 ° C. for 5 hours, the polycarbonate resin, the polyamide resin and the various additives described in Table 1 were added to the first resin. The mixture was mixed at the blending amounts (parts by weight) shown in the table, and pelletized at a cylinder temperature of 250 to 260 ° C. using a 30 mmφ vent type extruder (VSK-30, manufactured by Nakatani Corporation). This pellet
After drying at 105 ° C for 5 hours, it was molded at a cylinder temperature of 250 ° C using an injection molding machine (manufactured by Nippon Steel Works Co., Ltd .: J-120SA) to prepare a sample plate (50 mm x 80 mm x 2 mm) and a physical property test piece. did. The appearance, impact resistance and chemical resistance of the molded product were evaluated using the obtained sample plate and test piece. The results are shown in Table 1.

In addition, the symbol which shows a polycarbonate resin, a polyamide resin, and various additives in a table | surface is as follows.

PC: bisphenol A polycarbonate resin (viscosity average molecular weight 24,900, manufactured by Teijin Chemicals Ltd .: Panlite L-125)
0) PA: polyamide resin (nylon-6, intrinsic viscosity 1.5 with m-cresol, NH ₂ group 40 eq / t, COOH group 40 eq / t) A: 98.5 mol% of terephthalic acid and 1.5 mol% of sodium 5-sulfoisophthalate Modified polyester resin consisting of an acid component and ethylene glycol (intrinsic viscosity 0.55) B: 58.5 mol% of terephthalic acid, 40 mol% of isophthalic acid and 5
A modified polyester resin comprising an acid component comprising 1.5 mol% of sodium sulfoisophthalate and a diol component comprising 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol (intrinsic viscosity 0.60) C: polyethylene terephthalate resin (intrinsic viscosity 0.64) D : Chlorinated polyethylene (chlorine content 30%, manufactured by Showa Denko KK: Eraslen 301A) E: Bisphenol A type epoxy resin (epoxy equivalent 3800)
~ 5000 g / eq, manufactured by Toto Kasei Co., Ltd .: Epototo YO-7020) F: Modified olefin polymer obtained by modifying an ethylene-propylene copolymer with maleic anhydride (manufactured by Mitsui Petrochemical Co., Ltd .:
Tuffmer M90610) G: Ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd .: Bond First E) H: MBS resin (Kanebuchi Chemical Industry Co., Ltd .: Kaneace B-56)

[Brief description of the drawings]

FIG. 1 shows a strain imparting device used for a chemical resistance test.
In the figure, 1 is a test piece, 2, 3 and 4 are columns.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI (C08L 77/00 69:00 67:02) (56) References JP-A-59-113049 (JP, A) JP-A-63 −273659 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 69/00 C08L 77/00

Claims (1)

(57) [Claims] 1. A modified polyester resin comprising (A) 25 to 90% by weight of a polycarbonate resin, (B) 10 to 75% by weight of a polyamide resin, 100 parts by weight of a resin composition, and (C) a metal sulfonate base.
A resin composition containing 0.1 to 20 parts by weight.