JP2608936B2 - Resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition having excellent thermal stability and chemical resistance.

[Prior Art] Polycarbonate resins are excellent in heat resistance and impact resistance, and are widely used for various mechanical parts such as daily life goods, office equipment, electric and electronic parts, and the like. However, polycarbonate resins have a disadvantage that they have poor chemical resistance and are liable to crack when they come into contact with certain solvents under the presence of stress.

Attempts to improve the chemical resistance of polycarbonate resin by melting and mixing polyamide resin with polycarbonate resin,
JP-A-59-68368 discloses that this binary resin composition exhibits improved chemical resistance. However, when the polycarbonate resin and the polyamide resin are melted and mixed, the polycarbonate resin is decomposed, and the molding itself 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. However, this binary resin composition was not completely usable.

Japanese Patent Application Laid-Open No.
No. 257960 discloses that the decomposition of a polycarbonate resin can be suppressed by blending a compound having at least one -COX group (X is a halogen atom) directly bonded to an aromatic ring into a blend of a polycarbonate resin and a polyamide resin. Is disclosed. However, the thermal stability of the resin composition according to this proposal is not always sufficient, and a practical resin composition has not been obtained.

[Object of the Invention] An object of the present invention is to provide a resin composition having excellent thermal stability and chemical resistance.

The present inventors have conducted intensive studies to improve the heat resistance of the above-mentioned binary resin composition, and as a result, by blending a specific amount of chlorinated butyl rubber with this binary resin composition, its thermal stability has been improved. Was found to be dramatically improved. As a result of further study based on this finding, the present inventors have reached the present invention.

[Constitution of the Invention] The present invention relates to (A) 25 to 90% by weight of a polycarbonate resin and (B) 75 to 10% by weight of a polyamide resin. At least one compound selected from the group consisting of polyolefins
The present invention relates to a resin composition containing parts by weight.

Polycarbonate resin (A) used in the present invention
Is an average molecular weight of 10,000- derived from dihydric phenol
It is a polycarbonate of 100,000, preferably 15,000 to 60,000, and is usually produced by a solution method or a melt method of a dihydric phenol and a carbonate precursor. A typical example of dihydric phenol is bisphenol A [2,2-bis (4
-Hydroxyphenyl) propane], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4- (Hydroxy-3-methylphenyl) propane. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkane compounds, especially bisphenol A. 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 producing the polycarbonate resin, an appropriate molecular weight regulator, a branching agent, a catalyst and the like can be used.

Further, the polyamide resin (B) used in the present invention
Is a lactam having three or more rings, a polymerizable ε-amino acid,
It is produced by polycondensation of dibasic acid and diamine. Specific examples include ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone,
Polymers such as α-piperidone, and diamines such as hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and metaxylylenediamine, and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane Examples include a polymer or copolymer obtained by polycondensing a dicarboxylic acid such as a basic acid or 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 / 6T, 6I / 6T etc.

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

The component (C) used in the present invention is a halogen-containing rubber or a halogenated polyolefin, and specific examples of the halogen-containing rubber include halogenated rubbers such as chlorinated butyl rubber, brominated butyl rubber, and chlorosulfonated polyethylene. Thing, chloroprene rubber, chloroprene
Halogen-containing substances are already used as raw material components such as isoprene copolymer, chloroprene-styrene copolymer, chloroprene-acrylonitrile copolymer, vinylidene fluoride / chlorinated ethylene copolymer, and epichlorohydrin rubber Things can be given.

These halogen-containing rubbers may be solid or liquid.

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-1.
And polymers and copolymers of olefin compounds such as These halogen-containing rubbers or halogenated polyolefins may be used alone or in combination of two or more. Among the halogen-containing rubbers and halogenated polyolefins, halogenated butyl rubber and chlorinated polyethylene are particularly preferred.

The mixing ratio of the component (C) is 0.1 to 15 parts by weight, preferably 1 to 10 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 is not sufficient, and silver stripes are formed on the molded product or the molded product is discolored. If the amount exceeds 15 parts by weight, the mechanical strength and the thermal characteristics (particularly, the deflection temperature under load) will decrease.

Further, to the composition of the present invention, the following components can be added, and by adding these components in an appropriate amount, impact resistance, particularly a decrease in impact resistance after melt retention can be greatly improved, is preferable. That is.

(A) Modified block copolymer, modified olefin polymerization resistance; 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. Here, the vinyl aromatic compound polymer block is a polymer block having a form in which one or more vinyl compounds selected from styrene, α-methylstyrene, vinyltoluene and the like are polymerized or copolymerized. The olefin compound polymer block includes monoolefins such as ethylene, propylene, 1-butene and isobutylene, conjugated diolefins such as butadiene, isoprene and 1,3-pentadiene, 1,4-hexadiene,
It is a polymer block having a form in which one or more olefin compounds selected from non-conjugated diolefins such as norbornene and norbornene derivatives are polymerized or copolymerized. The block copolymer serving as a substrate is modified by an addition reaction with an unsaturated carboxylic acid or a derivative thereof, and the modified block copolymer used here is synthesized. Further, the block copolymer serving as the base may be a random copolymer of an unsaturated carboxylic acid or a derivative thereof.

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 acids and the like, acid anhydrides of these dicarboxylic acids,
Examples include esters, imides, etc., acrylic acid, methacrylic acid, etc., and esters and amides of these monocarboxylic acids. These can be used alone or in combination of two or more. Of these, unsaturated dicarboxylic acids or derivatives thereof are preferred, and maleic anhydride is particularly preferred.

The modified olefin polymer is a modified olefin polymer in which a molecular unit containing a carboxylic acid group or a derivative thereof is bonded to an olefin compound polymer. Here, the olefin compound polymer is a monoolefin such as ethylene, propylene, 1-butene and isobutylene; a conjugated diolefin such as butadiene, isoprene and 1,3-pentadiene;
A polymer having a form in which at least one olefin compound selected from non-conjugated diolefins such as hexadiene, norbornene and norbornene derivative is polymerized or copolymerized. The olefin compound polymer is modified by an addition reaction with an unsaturated carboxylic acid or a derivative thereof, and a modified olefin polymer used in the present invention is synthesized. Further, the olefin compound polymer may be one obtained by randomly copolymerizing an unsaturated carboxylic acid or a derivative thereof.

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] -5,2,3-dicarboxylic acid and the like, and acid anhydrides, esters, and the like of these dicarboxylic acids
Examples include amides, imides, etc., acrylic acid, methacrylic acid, etc., and esters and amides of these monocarboxylic acids. These can be used alone or in combination of two or more. Of these, unsaturated dicarboxylic acids or derivatives thereof are preferred, and maleic anhydride is particularly preferred.

The amount of the modified block copolymer and / or modified flefin polymer is preferably in the range of 0.1 to 15 parts by weight based on 100 parts by weight of the composition comprising the (A) polycarbonate resin and (B) the polyamide resin. It is.

(B) Hydroxyl group-containing polymer; The hydroxyl group-containing polymer is preferably any polymer containing a hydroxyl group having a proton donating property in its structure. Examples of suitable polymers include polycondensates composed of aliphatic or aromatic diols or polyhydric alcohols and epihalogen hydrins, polyvinyl alcohols, olefin compounds / vinyl alcohol copolymers, and polyolefin / polyvinyl alcohol block copolymers. In addition to polymers and copolymers already containing hydroxyl groups in the main chain of polymers, polymers based on polyolefins, polystyrene and rubber elastomers can be used with suitable comonomers or with functionalized hydroxyl groups. A graft polymer obtained by grafting is also preferable. These hydroxyl group-containing polymers include bisenol A
And a polycondensate composed of epichlorohydrin.

The suitable amount of the hydroxyl group-containing polymer is in the range of 1 to 10 parts by weight based on 100 parts by weight of the composition comprising the (A) polycarbonate resin and the (B) polyamide resin.

(C) Epoxy group-containing polymer; As the epoxy group-containing polymer, a copolymer of an α-olefin and glycidyl methacrylate and / or glycidyl acrylate is preferable. This copolymer may be any of a random copolymer and a graft copolymer. α-olefins include ethylene, propylene,
Butene-1, isobutylene, pentene-1, octene-1, dodecene-1,4-methylpentene-1 and the like. Of these, particularly preferred are ethylene and propylene. This copolymer may contain other vinyl compounds as a copolymer component in addition to α-olefin, glycidyl methacrylate, and glycidyl acrylate. Other vinyl compounds include styrene, vinyl acetate, methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl chloride, α-methyl styrene,
Examples include divinylbenzene and acrylic acid.

The compounding amount of the epoxy group-containing polymer is as described in the above (A).
The range of 1 to 10 parts by weight is appropriate for 100 parts by weight of the composition comprising the polycarbonate resin and the polyamide resin (B).

(D) Impact modifier: The impact modifier comprises a vinyl cyanide compound, a methacrylate ester, an acrylate ester and an aromatic vinyl compound in the presence of a rubber containing a repeating unit derived from butadiene. An elastic polymer obtained by copolymerizing two or more monomers selected from the group can be exemplified. Examples of the rubber containing a repeating unit derived from butadiene include polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, and butadiene / acrylate copolymer. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of methacrylates and acrylates include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, and the like. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, P
-Methylstyrene, alkoxystyrene, halogenated styrene and the like. These elastic copolymers may be produced by any polymerization method such as bulk polymerization, solution polymerization and emulsion polymerization, and the copolymerization method may be a single-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer of only a graft component produced as a by-product at the time of production, or may be a mixture of two or more kinds of elastic copolymers.

The compounding amount of the impact modifier is the composition 10 comprising the above (A) polycarbonate resin and (B) polyamide resin.
The range of 1 to 25 parts by weight relative to 0 parts by weight is appropriate.

One or more of the compounds shown in the above (A) to (D) can be selected and used as needed, and (A) to (D)
All may be used. When two or more groups (a), (b) and (c) are used, the mechanical strength and thermal properties (particularly the deflection temperature under load) will decrease if the amount is too large. It is preferable that the total amount is not more than 20 parts by weight based on 100 parts by weight of the composition comprising the (A) polycarbonate resin and the (B) polyamide resin.

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

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 composition of the present invention can be applied to any molding method, for example, injection molding, extrusion molding, compression molding, rotational molding, etc., and the heat stability at the time of molding and the chemical resistance of the obtained molded product are extremely good. .

[Examples] Next, the present invention will be described in detail with reference to examples. In addition,
The evaluation in the examples was based on the following method.

(1) Evaluation of appearance of molded product The first shot and the fifteenth shot of a sample plate molded by an injection molding machine
The shot eyes were compared visually. The evaluation was performed by the following method.

(2) Chemical resistance test The basic plate was thinner (T-80 manufactured by Nippon Bee Chemical Co., Ltd.).
0) was immersed at 23 ° C. for 3 minutes, and compared with an unimmersed sample plate. The evaluation was performed in two stages.

(3) Impact resistance test (with IZOD notch) The test was performed according to ASTM D-256.

Examples 1 to 14 and Comparative Examples 1 to 9 The polycarbonate resin was dried at 120 ° C. for 5 hours or more, and the polyamide resin was dried at 105 ° C. for 5 hours or more, and then mixed with the halogen-containing rubber at the compounding ratio shown in Table 1, Using a 30 mmφ vent type extruder (Nakatani Co., Ltd., VSK-30), pelletization was performed at a cylinder temperature of 250 to 260 ° C. After drying the pellets at 105 ° C for 5 hours or more, they were molded using an injection molding machine (J-120SA, Japan Steel Works, Ltd.) under the following molding conditions, and a physical property test piece and a sample plate (50 mm x 80 mm) × 2 mm). An impact test and a chemical resistance test were performed using the obtained test piece and a sample plate. The results are shown in Table 1.

Molding conditions Examples 1 to 12 and Comparative examples 2 to 5: Cylinder temperature 250 ° C Examples 13, 14 and Comparative examples 6 to 9: Cylinder temperature 260 ° C Comparative example 1: Cylinder temperature 280 ° C Mold temperature is 70 ° C

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 11:00 15:02)

Claims (1)

(57) [Claims] (1) 25-90% by weight of a polycarbonate resin (A)
And (B) 75 to 10% by weight of a polyamide resin, and 100 parts by weight of at least one compound selected from the group consisting of (C) a halogen-containing rubber and a halogenated polyolefin.
A resin composition containing parts by weight.