JP2003119378A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a polyamide resin composition having excellent flame retardancy, chemical and blister resistances and surface beautifulness and a molded product composed of the same. SOLUTION: This polyamide resin composition comprises 100 pts.wt. of a polyamide resin (A) composed of a dicarboxylic acid unit (a) containing 60-100 mol% of a terephthalic acid unit and a diamine unit (b) containing 60-100 mol% of a 6-18C aliphatic alkylenediamine unit and 1-100 pts.wt. of a brominated polystyrene (B). In the composition, 0.5-100 wt.% of the brominated polystyrene (B) is a brominated polystyrene having epoxy groups.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamide resin composition and a molded article made of the same. The polyamide resin composition of the present invention is excellent in flame retardancy, chemical resistance, surface beauty and blister resistance, and is therefore flame retardant for industrial materials, industrial materials, household products, electric / electronic parts, automobile parts, etc. It can be suitably used for applications requiring high properties and excellent mechanical properties.

[0002]

2. Description of the Related Art Aliphatic polyamides represented by nylon 6 and nylon 66 are excellent in heat resistance, chemical resistance, rigidity, abrasion resistance, moldability and the like, and have been used in many applications as engineering plastics. . In the electric / electronic field, since high flame retardancy based on UL-94 standard is required, many flame retardant methods using various flame retardants have been proposed and put into practical use. However, these aliphatic polyamides have large water absorption, and there have been problems such as dimensional change of molded products and deterioration of physical properties. More recently,
In the electrical and electronic fields where flame retardancy is required, a method called surface mount method (SMT) is rapidly spreading,
Along with this, conventional polyamide resins are no longer able to support heat resistance.

Therefore, a highly heat-resistant semi-aromatic polyamide containing a polyamide composed of an aliphatic alkylenediamine and terephthalic acid as a main component has come to be used in electric and electronic fields requiring flame retardancy. For example, JP-A-3-239755, JP-A-4-96970, JP-A-5-320503, and JP-A-6-263.
Japanese Patent Publication 985 proposes a polyamide resin composition in which brominated polystyrene is blended with a semi-aromatic polyamide as a flame retardant.

However, simply in the semi-aromatic polyamide resin composition blended with brominated polystyrene,
The compatibility between the semi-aromatic polyamide and the brominated polystyrene is poor, and the dispersion state of the flame retardant is poor, so that a molded article produced by using the polyamide resin composition has a reduced chemical resistance and the surface of the molded article is peeled off. The surface is rough, and the colored product has a problem in appearance such as whitening of the rough surface.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is, therefore, to provide a polyamide resin composition excellent in flame retardancy, chemical resistance, surface beauty and blister resistance, and a molded article comprising the same. .

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that it is difficult to blend a brominated polystyrene having an epoxy group in the molecule into a semi-aromatic polyamide. The present invention has been completed by finding that a polyamide resin composition excellent in flame resistance, chemical resistance, surface beauty and blister resistance can be obtained.

That is, the present invention provides a dicarboxylic acid unit (a) containing 60 to 100 mol% of a terephthalic acid unit.
And 1 to 100 parts by weight of brominated polystyrene (B) with respect to 100 parts by weight of a polyamide resin (A) composed of a diamine unit (b) containing 60 to 100 mol% of an aliphatic alkylenediamine unit having 6 to 18 carbon atoms. A polyamide resin composition containing 1 part, wherein 0.5 to 100% by weight of the brominated polystyrene (B) is a brominated polystyrene having an epoxy group, and the polyamide resin composition. The present invention relates to a molded product made of a material.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The dicarboxylic acid unit (a) constituting the polyamide resin (A) used in the present invention has 60 terephthalic acid units.
The content of the terephthalic acid unit is preferably in the range of 75 to 100 mol%,
The range of 90 to 100 mol% is more preferable. When the content of the terephthalic acid unit is less than 60 mol%, the heat resistance of the obtained polyamide resin composition decreases.

The above-mentioned dicarboxylic acid unit (a) may contain other dicarboxylic acid units other than the terephthalic acid unit as long as it is 40 mol% or less. As the other dicarboxylic acid unit, malonic acid, Dimethyl malonic acid, succinic acid,
Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; 1,3
Alicyclic dicarboxylic acids such as cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid,
1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid,
Diphenyl sulfone-4,4'-dicarboxylic acid, 4,
A unit derived from an aromatic dicarboxylic acid such as 4′-biphenyldicarboxylic acid can be mentioned, and one or more of these can be used. Of these, units derived from aromatic dicarboxylic acids are preferred. As the content of these other dicarboxylic acid units,
It is preferably 25 mol% or less, and more preferably 10 mol% or less. Furthermore, a unit derived from a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, or pyromellitic acid may be contained within the range where melt molding is possible.

Polyamide resin (A) used in the present invention
The diamine unit (b) constituting the compound contains 60 to 100 mol% of an aliphatic alkylenediamine unit having 6 to 18 carbon atoms, and the content of the aliphatic alkylenediamine unit having 6 to 18 carbon atoms is 75. To 100 mol% is preferable, and 90 to 100 mol% is more preferable. When the content of the aliphatic alkylenediamine unit having 6 to 18 carbon atoms is less than 60 mol%, various properties such as heat resistance, low water absorption and chemical resistance of the obtained polyamide resin composition are deteriorated. Examples of the aliphatic alkylenediamine unit having 6 to 18 carbon atoms include 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, Linear aliphatic alkylenediamines such as 1,11-undecanediamine and 1,12-dodecanediamine; 1
-Butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3 -Dimethyl-1,4-butanediamine, 1,
4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-
Pentanediamine, 3-methyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine,
2,4-dimethyl-1,6-hexanediamine, 3,3
-Dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6- Hexanediamine, 2,4-diethyl-
1,6-hexanediamine, 2,2-dimethyl-1,7
-Heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 2-methyl-1,8 -Octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-
Octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine,
3,4-dimethyl-1,8-octanediamine, 4,5
-Dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-
1,8-octanediamine, 4,4-dimethyl-1,8
Examples thereof include units derived from branched-chain aliphatic alkylenediamines such as -octanediamine and 5-methyl-1,9-nonanediamine, and one or more of these can be used.

Among the above aliphatic alkylenediamine units, 1,6-hexanediamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,
9-nonanediamine, 1,10-decanediamine, 1,
A unit derived from 11-undecanediamine or 1,12-dodecanediamine is preferable, and a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit is more preferable. When the 1,9-nonanediamine unit and the 2-methyl-1,8-octanediamine unit are used in combination, the molar ratio of the 1,9-nonanediamine unit: 2-methyl-1,8-octanediamine unit is Is preferably 99: 1 to 1:99, and 95:
More preferably, it is 5 to 40:60, and 90:10.
More preferably, it is 80:20. When the polyamide resin containing the 1,9-nonanediamine unit and / or the 2-methyl-1,8-octanediamine unit in the above proportions is used, heat resistance, moldability, low water absorption, and surface beauty are more excellent. A polyamide resin composition is obtained.

The above diamine unit (b) is 40 mol%
If it is the following, you may contain diamine units other than the C6-C18 aliphatic alkylenediamine unit,
Examples of the other diamine units include aliphatic diamines such as ethylenediamine, propanediamine, and 1,4-butanediamine; alicyclic rings such as cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, norbornanedimethylamine, and tricyclodecanedimethylamine. Formula diamine; p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane,
Examples thereof include units derived from aromatic diamines such as 4,4′-diaminodiphenyl sulfone and 4,4′-diaminodiphenyl ether, and one or more of these can be used. The content of these other diamine units is preferably 25 mol% or less, more preferably 10 mol% or less.

Polyamide resin (A) used in the present invention
It is preferable that 10% or more of the terminal groups of the molecular chain are blocked with a terminal blocking agent. The rate at which the terminal group of the molecular chain is blocked by the terminal blocking agent (terminal blocking rate) is more preferably 40% or more, and further preferably 70% or more. The use of a polyamide resin having a terminal sealing rate of 10% or more provides more excellent physical properties such as melt moldability and surface beauty.

The end-capping ratio of the polyamide resin (A) is determined by measuring the number of carboxyl-group ends, amino-group ends and end-groups capped by the end-capping agent present in the polyamide resin. It can be obtained by 1). The number of each end group is ¹ H-NMR, and the accuracy is obtained from the integral value of the characteristic signal corresponding to each end group,
It is preferable in terms of simplicity.

End capping rate (%) = [(X−Y) / X] × 100 (1) [wherein, X is the total number of molecular chain end groups (this is usually equal to twice the number of polyamide molecules). ), And Y represents the total number of carboxyl group terminals and amino group terminals. ]

The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the polyamide terminal, but is not limited in terms of reactivity and stability of the terminal. Therefore, a monocarboxylic acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can also be used.

The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid,
Aliphatic monocarboxylic acids such as pivalic acid and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid And other aromatic monocarboxylic acids; any mixture thereof, and the like. Among these,
In terms of reactivity, stability of sealed ends, price, etc., acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid and benzoic acid are preferred.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine,
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; cycloaliphatic amines such as cyclohexylamine, dicyclohexylamine;
Aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine and the like; and arbitrary mixtures thereof can be mentioned. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, high boiling point, stability of capped terminal and cost.

Polyamide resin (A) used in the present invention
Can be produced using any method known as a method for producing a crystalline polyamide. For example,
It can be produced by a method such as a solution polymerization method using an acid chloride and a diamine as raw materials or an interfacial polymerization method, a melt polymerization method using a dicarboxylic acid and a diamine as raw materials, a solid phase polymerization method, and a melt extruder polymerization method.

For the polyamide resin (A), for example, a diamine, a dicarboxylic acid, a catalyst and, if necessary, an end-capping agent are added all at once to produce a nylon salt, and then 2
Polymerization by heating at a temperature of 00 to 250 ° C.
It can be produced by prepolymer having an intrinsic viscosity [η] at 0 ° C. of 0.1 to 0.6 dl / g and further solid phase polymerization or polymerization using a melt extruder. Intrinsic viscosity [η] of prepolymer is 0.1-0.6d
When the ratio is within the range of 1 / g, a polyamide resin having a small deviation in the molar balance between the carboxyl group and the amino group and a decrease in the polymerization rate in the post-polymerization stage, a small molecular weight distribution, and excellent physical properties and moldability can be obtained. can get. When the final stage of polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or under an inert gas flow, and the polymerization temperature is 200-28.
Within the range of 0 ° C, the polymerization rate is high, the productivity is excellent, and coloring and gelation can be effectively suppressed. When the final stage of the polymerization is carried out by a melt extruder, the polymerization temperature is preferably 370 ° C. or lower. When the polymerization is carried out under such conditions, the polyamide resin is hardly decomposed and a polyamide resin having no deterioration is obtained.

In producing the polyamide resin (A), phosphoric acid, phosphorous acid, hypophosphorous acid, or salts or esters thereof, for example, may be added as a catalyst in addition to the above-mentioned end capping agent. it can. As the above-mentioned salt or ester, phosphoric acid, phosphorous acid or hypophosphorous acid and a metal such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony Salts; ammonium salts of phosphoric acid, phosphorous acid or hypophosphorous acid; ethyl esters, isopropyl esters, butyl esters, hexyl esters, isodecyl esters, octadecyl esters, decyl esters of phosphoric acid, phosphorous acid or hypophosphorous acid , Stearyl ester, phenyl ester and the like.

Polyamide resin (A) used in the present invention
Has an intrinsic viscosity [η] of 0.4 measured in concentrated sulfuric acid at 30 ° C.
~ 3.0 dl / g is preferred, 0.5-2.0
dl / g is more preferable, and 0.6 to 1.5 dl
More preferably, it is / g. If the intrinsic viscosity [η] is within the above range, a molded product excellent in mechanical properties, heat resistance and the like can be obtained.

The polyamide resin composition of the present invention contains brominated polystyrene (B) as a constituent component other than the above polyamide resin (A), and the brominated polystyrene (B) is contained.
0.5 to 100% by weight is brominated polystyrene having an epoxy group (hereinafter, this may be referred to as "epoxy group-containing brominated polystyrene"). The brominated polystyrene referred to in the present invention includes those obtained by polymerizing a styrene monomer to produce polystyrene, and then brominating this polystyrene, and those obtained by polymerizing a brominated styrene monomer.

The brominated polystyrene having an epoxy group is preferably a brominated polystyrene containing a monomer unit having an epoxy group, and examples of the monomer unit include glycidyl acrylate, glycidyl methacrylate and itaconic acid. Glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-3- Methyl-1-pentene,
Examples thereof include units derived from 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p-glycidylstyrene, and the like. Among these, units derived from glycidyl acrylate and glycidyl methacrylate are preferable. Moreover, these monomer units may use only 1 type and may use 2 or more types.

The content of the above-mentioned monomer unit having an epoxy group is preferably in the range of 0.05 to 20 mol% with respect to the total structural units of the epoxy group-containing brominated polystyrene, and 0.1 Is more preferably in the range of 20 to 20 mol%, and even more preferably in the range of 0.5 to 20 mol%. When the content of the monomer unit having an epoxy group is less than 0.05 mol%, the compatibility with the polyamide resin (A) becomes insufficient, resulting in deterioration of mechanical properties of the obtained polyamide resin composition and molding. Poor appearance may occur. On the other hand, when the content of the monomer unit having an epoxy group exceeds 20 mol%, the polyamide resin (A)
When mixed with, the melt viscosity tends to increase.

The above-mentioned brominated polystyrene containing a monomer unit having an epoxy group can be prepared, for example, by polymerizing a styrene monomer to produce polystyrene, then brominating this polystyrene, and then preparing a unit having an epoxy group. A method of adding a monomer to polystyrene, a method of polymerizing a styrene monomer to produce polystyrene, a method of adding a monomer having an epoxy group to polystyrene, and then brominating the polymer, a styrene monomer And a monomer having an epoxy group are copolymerized and then the polymer is brominated, a brominated styrene monomer is polymerized to produce a brominated styrene polymer, and then an epoxy group is added to the polymer. It can be produced by a method of adding a monomer having a group, a method of copolymerizing a brominated styrene monomer and a monomer having an epoxy group, or the like. In the case of copolymerization, the copolymerization may be performed in any form such as random copolymerization, block copolymerization and alternating copolymerization. Among these, as the epoxy group-containing brominated polystyrene, from the viewpoint of thermal stability, those obtained by the above-mentioned production methods are preferable, and those obtained by the above production method are more preferable.

The proportion of the epoxy group-containing brominated polystyrene in the brominated polystyrene (B) is in the range of 0.5 to 100% by weight, based on the total weight of the brominated polystyrene (B), and 5 to 100% by weight. It is preferably within the range. By using the brominated polystyrene containing the epoxy group-containing brominated polystyrene in the above proportion, a polyamide resin composition having excellent chemical resistance and surface beauty can be obtained.

The molecular weight of the brominated polystyrene (B) is preferably in the range of 5,000 to 500,000,
The range of 10,000 to 400,000 is more preferable. When the molecular weight is less than 5,000, the heat resistance of the obtained polyamide resin composition tends to decrease, and when the molecular weight is more than 500,000, the melt viscosity tends to increase.

The bromine content of the brominated polystyrene (B) is preferably in the range of 50 to 80% by weight, and 55 to 55%.
A range of 75% by weight is more preferable. Bromine content is 50
If it is less than wt%, in order to impart high flame retardancy to the polyamide resin composition, a large amount must be added,
Mechanical properties may be impaired, and if the bromine content is more than 80% by weight, heat resistance may decrease.

The polyamide resin composition of the present invention contains 1 to 100 parts by weight of the brominated polystyrene (B) with respect to 100 parts by weight of the polyamide resin (A), and 10 to 80 parts by weight. It is preferable to contain it in a ratio of. When the content ratio of the brominated polystyrene (B) is less than 1 part by weight, the flame retardancy of the obtained polyamide resin composition decreases, and the content ratio of the brominated polystyrene (B) is 100.
When it exceeds the weight part, the chemical resistance, mechanical properties and thermal properties of the obtained polyamide resin composition deteriorate.

In the polyamide resin composition of the present invention, the brominated polystyrene (B) is preferably present in the continuous phase of the polyamide resin as a dispersed phase having an average dispersed particle size of 3 μm or less. As the average dispersed particle size,
It is preferably 2 μm or less, and the polyamide resin phase and the brominated polystyrene phase may be completely compatible with each other to form a uniform phase. By setting the average dispersed particle diameter of the dispersed phase within the above range, it is possible to suppress the surface roughness of the molded article obtained by a molding method such as injection molding and the whitening of the colored article.

If necessary, the polyamide resin composition of the present invention may further contain a flame retardant aid (C) and / or a filler (D).

Examples of the flame retardant aid (C) include antimony trioxide, antimony pentoxide, sodium antimonate, sodium oxide, tin oxide, zinc stannate, zinc oxide, iron oxide, magnesium hydroxide, calcium hydroxide. , Zinc borate, kaolin clay, calcium carbonate and the like, and one or more of them can be used. These flame retardant aids (C) may be treated with a silane coupler, a titanium coupler or the like. Of these, zinc borate and zinc stannate are preferably used. The content of the flame retardant aid (C) is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polyamide resin (A). By blending these flame retardant aids, a polyamide resin composition having excellent flame retardancy can be obtained with a small amount of flame retardant.

If necessary, the polyamide resin composition of the present invention may further contain a filler (D) having various forms such as fibrous form, powder form and cloth form.

Examples of the fibrous filler include polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, diaminodiphenyl ether and terephthalic acid or isophthalic acid. Organic fibrous fillers such as wholly aromatic polyamide fibers such as fibers obtained from condensates, wholly aromatic liquid crystal polyester fibers; inorganic fibrous fillers such as glass fibers, carbon fibers, boron fibers and the like. To be When such a fibrous filler is blended, not only the mechanical strength of the obtained molded product is improved, but also dimensional stability, low water absorption, etc. are further improved. The average length of the fibrous filler is preferably in the range of 0.05 to 50 mm,
From the viewpoint of further improving the moldability of the polyamide resin composition and further improving the sliding properties, heat resistance, and mechanical properties of the resulting molded product, it is more preferably within the range of 1 to 10 mm. These fibrous fillers may be secondarily processed into a cloth shape or the like.

As the powdery filler, for example, silica, silica-alumina, alumina, titanium oxide, zinc oxide, boron nitride, talc, mica, potassium titanate,
Calcium silicate, magnesium sulfate, aluminum borate, asbestos, glass beads, carbon black,
Examples include graphite, molybdenum disulfide, polytetrafluoroethylene, and the like. The average particle size of these powdery fillers is preferably in the range of 0.1 to 200 μm, more preferably in the range of 1 to 100 μm. When these powdered fillers are blended, the dimensional stability, mechanical properties, heat resistance properties, chemical / physical properties, sliding properties and the like of the obtained molded product are further improved.

The filler (D) can be used alone or in combination of two or more. The content of these fillers (D) is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the polyamide resin (A),
More preferably 0.1 to 150 parts by weight, 0.5
More preferably, it is from about 100 parts by weight. When the content of the filler is within the above range, a polyamide resin composition having excellent moldability and mechanical properties can be obtained. Further, the surface of these fillers is surface-treated with a silane coupling agent, a titanium coupling agent, or other high molecular weight or low molecular weight surface treating agent for the purpose of improving dispersibility in the polyamide resin. Is preferred.

In the polyamide resin composition of the present invention, if necessary, an acid catcher such as hydrotalcite; other polymer such as polyphenylene sulfide, polyolefin, polyester, aliphatic polyamide, polyphenylene oxide, liquid crystal polymer; coloring agent UV absorber; light stabilizer; hindered phenol type, thio type, phosphorus type,
An amine-based antioxidant, an antistatic agent, a crystal nucleating agent, a plasticizer, a release agent, a lubricant, etc. can also be added.

By blending the polyamide resin (A) with the brominated polystyrene (B) and, if necessary, the flame retardant aid (C), the filler (D) and the above-mentioned various additives. The polyamide resin composition of the present invention can be manufactured. As a compounding method, for example, a method of adding a component such as brominated polystyrene (B) during the polycondensation reaction of the polyamide resin (A), the polyamide resin (A)
Examples of the method include a method of dry-blending the ingredients such as brominated polystyrene (B) and a method of melt-kneading using an extruder. Among these, in view of easiness of operation, usually melting is performed using an extruder. The method of kneading is advantageous. The extruder used at this time is preferably a twin-screw extruder, and the melt-kneading temperature is preferably in the range of 280 to 340 ° C.

The polyamide resin composition of the present invention is molded by a molding method generally used for thermoplastic resin compositions, such as injection molding, extrusion molding, press molding, blow molding, calender molding and cast molding. By
Molded articles having various shapes can be manufactured. For example, the polyamide resin composition of the present invention is melted in a cylinder of an injection molding machine in which the cylinder temperature is adjusted within the range of the melting point of the polyamide resin to 350 ° C. and is introduced into a mold having a predetermined shape (injection). By doing so, a molded product having a predetermined shape can be manufactured. Further, by melting the polyamide resin composition in an extruder in which the cylinder temperature is adjusted within the above range, and spinning it out from a die nozzle,
Fibrous molded articles can be manufactured. Furthermore, a polyamide resin composition is melted in an extruder whose cylinder temperature is adjusted within the above range and extruded from a T die, whereby a film or sheet-shaped molded article can be manufactured. Further, it is also possible to use it in a form in which a coating layer made of a paint, a metal, another kind of polymer or the like is formed on the surface of the molded product manufactured by such a method.

[0041]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. The average dispersed particle size, flammability, chemical resistance and blister resistance of the flame retardant in the examples were evaluated by the following methods.

Average dispersed particle diameter of organic halogen compound: A frozen fractured surface of a molded article was etched in chloroform under the condition of 80 ° C. × 1 hr, and observed by a scanning electron microscope.
From the obtained photograph, the dispersed particle diameter d and the number of particles n were determined, and the average particle diameter of the dispersed phase was calculated by the following formula. Average particle size = (Σd ⁴ · n) / (Σd ³ · n)

Flammability: The flammability was determined according to the UL-94 standard. The upper end of a 1 mm-thick injection-molded product is clamped to vertically fix the test piece, and a predetermined flame is applied to the lower end for 10 seconds to separate the test piece, and the burning time (first time) of the test piece is measured. Immediately after extinguishing, apply flame to the bottom edge again and release,
The burning time (second time) of the test piece is measured. The same measurement is repeated for five pieces, and a total of 10 pieces of data, that is, 5 pieces of data of the first burning time and 5 pieces of data of the second burning time, are obtained. Let T be the total of 10 data and M be the maximum value of the 10 data. If T is 50 seconds or less and M is 10 seconds or less, it does not burn up to the clamp, melted with flame does not fall and ignites cotton under 12 inches, "V-0", T is 250 seconds or less, If M is 30 seconds or less and the other conditions satisfy the same conditions as V-0, "V-1", T is 2
If V is 50 seconds or less and M is 30 seconds or less, it does not burn up to the clamp, and the melted material with flame falls and ignites the cotton 12 inches below, resulting in "V-2".

Chemical resistance (mechanical properties): JIS No. 2 test pieces obtained by injection molding were immersed in methylene chloride for 168 hours, and the tensile strength was measured by the tensile test method of ASTM D638.

Chemical resistance (appearance): JIS No. 2 test piece obtained by injection molding is immersed in methylene chloride for 168 hours, and the appearance of the molded article is visually observed. When the surface was whitened, it was evaluated as "x".

Appearance of molded product: An injection molded product having a length of 10 cm, a width of 4 cm, and a thickness of 1 mm was prepared, and the appearance (color tone and surface condition) of the molded product was visually observed to find that it was not whitened and had a surface. When the condition was smooth and good, it was evaluated as "good", and when it was white or when the surface condition was not smooth, it was evaluated as "poor".

Evaluation of blister resistance: A test piece having a thickness of 0.5 mm, a width of 10 mm and a length of 30 mm formed by injection molding was conditioned for 72 hours at a temperature of 40 ° C. and a relative humidity of 50%. The reflow process of the temperature profile shown in FIG. 1 was performed using an infrared heating furnace (SMT scope manufactured by Sanyo Seiko). A temperature sensor was installed on the molded product and the profile was measured. The measured peak temperature in Figure 1 is from 240 ℃ to 2
The test was conducted at intervals of 5 ° C. up to 70 ° C. After passing through the process, the appearance of the test piece was observed. The limit temperature at which the test piece did not melt and blisters did not occur was defined as the blister resistance temperature. Blister is a phenomenon in which a blister-like swelling occurs on the surface of a molded product. When there was a change below 250 ° C., it was judged as “X”, when there was a change within the range of 250 to 260 ° C., it was judged as “Δ”, and the others were judged as “◯”.

In the following Examples, Comparative Examples and Reference Examples,
The following polyamide resins were used. PA9MT: a terephthalic acid unit as a dicarboxylic acid unit, a 1,9-nonanediamine unit and 2-methyl-
The 1,8-octanediamine unit is replaced with the diamine unit (1,9
-Molar ratio of nonanediamine unit: 2-methyl-1,8-octanediamine unit is 85:15), and intrinsic viscosity
[η] 1.00 dl / g, melting point 308 ° C, terminal sealing rate 90
% (End-capping agent: benzoic acid) polyamide resin. PA6IT: terephthalic acid unit and isophthalic acid unit are dicarboxylic acid units (terephthalic acid unit: isophthalic acid unit molar ratio is 60:40), 1,6-hexanediamine unit is diamine unit, melting point 312 ° C., intrinsic viscosity A polyamide resin having [η] of 1.02 dl / g and a terminal sealing rate of 91% (terminal sealing agent: benzoic acid).

<Examples 1 to 5> Brominated polystyrene obtained by adding 2.0 mol% of glycidyl methacrylate to the above polyamide resin (hereinafter referred to as "GMA-PB").
abbreviated as "rS"), brominated polystyrene ("PBS-64" manufactured by Great Lakes Chemical Co., Ltd .; hereinafter referred to as "PB").
abbreviated as "rS"), zinc borate ("Firebreak 415" manufactured by Borax), a mixture of sodium oxide and antimony pentoxide ("Sun Epoch NA-1070L" manufactured by Nissan Chemical Industries, Ltd.), zinc stannate (Nippon Light Metal) "FLAMTARD-S" manufactured by Co., Ltd.) and glass fibers ("CS-3J-256S" manufactured by Nitto Boseki Co., Ltd.) were premixed at the ratios shown in Table 1 below. This is supplied to a twin-screw extruder (“TEX44C” manufactured by Nippon Steel Co., Ltd.), melt-kneaded and extruded under the condition of a cylinder temperature of 320 ° C., cooled and cut to form pellets of a polyamide resin composition. Obtained. Table 1 shows the results of evaluation of the molded product obtained by injection molding (cylinder temperature 330 ° C., mold temperature 150 ° C.) of this pellet by the above method.

<Comparative Examples 1 and 2> A polyamide resin composition was prepared in the same manner as in Examples 1 to 5, except that GMA-PBrS was not used and the other components were blended in the proportions shown in Table 1 below. Of pellets were obtained. Table 1 shows the results of evaluation of the molded product obtained by injection molding (cylinder temperature 330 ° C., mold temperature 150 ° C.) of this pellet by the above method.

Comparative Example 3 PA66 (“Leona 1300S” manufactured by Asahi Kasei) was mixed with GMA-PBrS, a mixture of sodium oxide and antimony pentoxide (Nissan Chemical Industry Co., Ltd.).
"San Epoch NA-1070L") and glass fibers ("CS-3J-256S" manufactured by Nitto Boseki Co., Ltd.) were premixed in the proportions shown in Table 1 below. This is supplied to a twin-screw extruder (“TEX44C” manufactured by Nippon Steel Co., Ltd.), melt-kneaded and extruded under the condition of a cylinder temperature of 280 ° C., cooled and cut to form a pellet of polyamide resin composition. Obtained. This pellet is injection molded (cylinder temperature 2
Table 1 shows the results of evaluation by the above-described method for the molded product obtained by heating at 80 ° C. and mold temperature of 80 ° C.).

[0052]

[Table 1]

From the results shown in Table 1 above, the polyamide resin compositions of Examples 1 to 5 containing the semi-aromatic polyamide resin and the epoxy group-containing brominated polystyrene in the proportions defined in the present invention were epoxy group-containing. It can be seen that, as compared with the polyamide resin compositions of Comparative Examples 1 and 2 which do not contain brominated polystyrene, the average dispersed particle size is smaller, and the chemical resistance and surface beauty are extremely excellent. In addition, Example 1
The polyamide resin compositions of Nos. 5 to 5 have extremely excellent chemical resistance and blister resistance as compared with the polyamide resin composition of Comparative Example 3 containing an aliphatic polyamide resin in place of the semi-aromatic polyamide resin. Recognize.

[0054]

EFFECTS OF THE INVENTION According to the present invention, a polyamide resin composition excellent in flame retardancy, chemical resistance, surface beauty and blister resistance, and a molded article comprising the same are provided.

[Brief description of drawings]

[Figure 1] Temperature profile of test piece when passing through infrared furnace

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA22 AA55 AA56 AB18 AB27                       AB28 AD01 AE07 AE17 AF02                       AF47 AF53 AH07 AH12 AH19                       BA01 BB05                 4J002 BC11X BD15Y CF16Y CL00W                       CL03Y CL06Y DA017 DA027                       DA037 DE056 DE096 DE107                       DE126 DE137 DE147 DE186                       DE187 DE236 DG027 DG047                       DJ017 DJ027 DJ036 DJ047                       DJ057 DK007 DL007 FA04Y                       FA047 FA08Y FA087 FB096                       FB166 FD01Y FD017 FD136                       GC00 GN00 GQ00

Claims (5)

[Claims] 1. A terephthalic acid unit of 60 to 100 mol%.
Bromination with respect to 100 parts by weight of a polyamide resin (A) composed of a dicarboxylic acid unit (a) contained and a diamine unit (b) containing 60 to 100 mol% of an aliphatic alkylenediamine unit having 6 to 18 carbon atoms. Polystyrene (B)
A polyamide resin composition containing 1 to 100 parts by weight, wherein 0.5 to 100% by weight of the brominated polystyrene (B) is a brominated polystyrene having an epoxy group. 2. The polyamide resin composition according to claim 1, wherein the aliphatic alkylenediamine unit having 6 to 18 carbon atoms is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. 3. The polyamide resin (A) has an intrinsic viscosity of 0.
The polyamide resin composition according to claim 1 or 2, which has a content of 4 to 3.0 dl / g. 4. A flame-retardant auxiliary (C) in an amount of 0.1 to 50 parts by weight and / or a filler (D) in an amount of 0.1 to 200 parts by weight, based on 100 parts by weight of the polyamide resin (A). The polyamide resin composition according to any one of claims 1 to 3, wherein 5. A molded article made of the polyamide resin composition according to claim 1.