JPH03182550A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in the resistance to heat and oil, impact strength, mechanical strengths, etc., by compounding a compsn. comprising a polyamide and a polyarylene sulfide with a specified amt. of a specific phosphorus compd. CONSTITUTION:100 pts.wt. compsn. comprising 2-90wt.% polyamide (e.g. nylon 46) and 98-10wt.% polyarylene sulfide (e.g. polyphenylene sulfide) is compounded with 5-40 pts.wt. at least one phosphorus compd. selected from the group consisting of compds. of formula I (wherein R1 to R3 are each a hydrocarbon group; R4 to R7 are each H or R1; and n is 1-20) and formula II [wherein R8 to R10 are each a (halogenated) hydrocarbon group].

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a flame-retardant resin composition having excellent heat resistance, impact resistance, oil resistance and mechanical strength.

b. Conventional technology In recent years, many engineering plastics have been developed, each taking advantage of its characteristics and being used for applications such as automobile parts, electrical/electronic parts, and mechanical parts.

Polystyrene sulfide (PPS resin), one of these engineering plastics, has heat resistance,
It has excellent flame retardancy and oil resistance, and is known to exhibit even better mechanical properties when combined with various additives and inorganic fillers.

However, the disadvantage of PPS resin is that its brittleness against impact cannot be sufficiently improved.

Therefore, in order to improve the impact resistance of PPS resin,
Compositions in which a polyamide polymer is added to S resin are disclosed in JP-A-53-69255, JP-A-53-155462, and JP-A-6.
1-126170, etc.

However, the problems to be solved by the C0 invention are as follows:
Although compositions such as No. 155462 and No. 61-126170 have improved impact resistance, they have the problem of significantly lower flame retardancy.

60 Means for Solving the Problems In view of the above-mentioned problems, the present inventors have conducted intensive studies to develop a resin composition with excellent heat resistance, impact resistance, oil resistance, mechanical properties, and flame retardance. As a result, (A) 2 to 90% by weight of polyamide polymer (hereinafter referred to as r (A) a component) (B) 98 to 10% by weight of polyarylene sulfide (hereinafter referred to as ``component (B)'') (C) a compound represented by the following general formula (I) (hereinafter referred to as "
At least one phosphorus compound selected from the following (hereinafter referred to as "compound (■)") and a compound represented by the following general formula (II) (hereinafter referred to as "compound (■)") (hereinafter collectively referred to as "(C)") A flame-retardant resin composition, characterized in that it contains 5 to 40 parts by weight of a compound (referred to as "acid").

General formula (I) (wherein R1, R2, R3 represent the same or different hydrocarbon groups, R4, R5, R6, R7 represent hydrogen or hydrocarbon groups. R4, R5, R6, R7 are the same (N is 1 to 20.) General formula (II) R, -0\ Re-0-P=O R1o -0' (In the formula, R8, R9 and RIO are the same or different. may represent a hydrocarbon group or a halogenated hydrocarbon group.

) It provides:

The present invention will be explained in detail below.

In the present invention, as component (A), polyamide obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam, 6-aminocaproic acid,
11-aminoundecanoic acid, 12-aminododecanoic acid,
Polyamides derived from amino acids such as para-aminomethylbenzoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2.2.4-/2.4°4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylenediamine, 1.3-/1.4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-
3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-
aliphatic such as aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine,
Alicyclic and aromatic diamines and adipic acid, speric acid, sebacic acid, azelaic acid, dodecanniic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium Examples include polyamide resins derived from aliphatic, alicyclic, and aromatic dicarboxylic acids such as sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid, as well as copolymerized polyamide resins and mixed polyamide resins thereof. It will be done.

Preferred among these are polycaproamide (nylon 6) and polyundecamide (nylon 11).
, polydodecanamide (nylon 12), polyhexamethylene adipamide (nylon 6.6), nylon 4,6
, and copolyamide-based polymers containing these as main components.

The preferred relative viscosity of the above component (A) (1 g of polymer is 9
(measured in 100 ml of 8% H2SOa at 23°C) is 2-6.

The content of component (A) in the resin composition of the present invention is 2 to 90
% by weight, preferably 5 to 85% by weight, more preferably 10 to 80% by weight.

(A) If the tc content is less than 2% by weight, the impact resistance will be too low, and if it exceeds 90% by weight, the flame retardance will not be achieved.

Component (B) of the present invention has the general formula as its structural unit: %formula% (In the formula, Ar represents an aromatic group having 6 or more carbon atoms.

) is the main component. Examples of aromatic groups include p-phenylene, m-phenylene, 2.6-naphthalene, 4.
Representative examples include 4'-biphenylene, p,p'-bibenzyl, and nuclear substituted products thereof. Poly-p-phenylene sulfide having an unsubstituted p-phenylene nucleus, that is, a structural unit represented by the general formula: is preferred from the viewpoint of moldability.

Here, the main component means containing at least 70 mol% or more of the above structural units. This main component is 70
If the amount is less than mol%, undesirable results will occur, such as decreased crystallinity of the resulting polymer, low transition temperature, and poor physical properties of the molded product. If it is less than 30 mol%, an aromatic group having a bond of trivalent or higher valence, for example 1.2
．． It may contain a 4-bonded phenylene nucleus, an aliphatic group, a heteroatom-containing group, etc.

The method for producing the above component (B) includes a condensation reaction between a dihalogenated aromatic compound and a dithiol aromatic compound or a monohalogenated aromatic thiol, or a dihalogenated aromatic compound and an alkali sulfide, an alkali hydrosulfide, and an alkali. Examples include, but are not limited to, a method using a desalting condensation reaction from a mixture of hydrogen sulfide and an alkali compound, or a mixture of hydrogen sulfide and an alkali compound.

The content of component (B) in the resin composition of the present invention is 10 to 9
8% by weight, preferably 15-95% by weight, more preferably 20-90% by weight. When the content of component (B) is 10% by weight or less, the flame retardant level is low, and when it exceeds 90% by weight, the impact resistance is low.

In the present invention, in addition to the components (A) and (B), other polymers may be added as necessary. Other polymers include copolymers of α,β-unsaturated dicarboxylic acid anhydrides and olefin compounds, modified polyolefins such as aminosilane-modified polyolefins, epoxy group-containing polyolefins, and grafts of vinyl monomers of these; polypropylene, polyethylene, pvc,
Examples include polycarbonate, PBT, PET, epoxy resin, polyvinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer, and PEEK. Among these, modified polyolefin is used as component (A) and component (B).
Usually 2 to 10% by weight of the total amount of components and other polymers
By using it, the impact resistance of the composition can be further improved.

In the compound I used in the present invention, the general formula (I)
In R+% R2 and R3 are preferably hydrocarbon groups, and R4, R5, R6 and R7 are preferably hydrogen atoms. n is 1-20, preferably 1-20
It is 10. Compound (1) can be used alone or in combination of two or more.

Compound I may be a commercially available product, such as CR-733 (manufactured by Daihe Kagaku Kogyo Co., Ltd.) and CR-755 (manufactured by Daihe Kagaku Kogyo Co., Ltd.).

In the compound H used in the present invention, the general formula (II
), the hydrocarbon groups for R7, R8, and R9 include alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, and cyclohexyl, phenyl, and xylenyl. The halogenated hydrocarbon group includes an aromatic group having 6 to 12 carbon atoms such as a chloroethyl group, a tolyl group, a chloroethyl group, a dichloroethyl group, a bromoethyl group, a dibromoethyl group, a dibromobutyl group, a chlorobromopropyl group, etc. 6 to 1 carbon atoms, such as a halogenated alkyl group of number 1 to 8, chlorophenyl group, dichlorophenyl group, bromophenyl group, tribromophenyl group, etc.
Examples include the halogenated aromatic group of No.2.

Specific examples of these include the following.

Trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate,
Tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris-(chloroethyl)-phosphate, tris-(dichloroethyl)-phosphate, tris-(bromoethyl)-phosphate, tris-(dibromoethyl)- phosphate, tris-(dibromopropyl)-phosphate, tris-(chlorobromopropyl)-phosphate, tris-(dibromobutyl)-phosphate, tris(chlorobromobutyl)-phosphate, tris-(chlorophenyl)-phosphate, tris-( dichlorophenyl)-phosphate, tris-(
bromophenyl)-phosphate, tris-(dibromophenyl)-phosphate, tris-(tribromophenyl)-phosphate, dimethylethyl phosphate,
Methyl dibutyl phosphate, ethyl dipropyl phosphate, 4-chlorophenyl diphenyl phosphate, phenyl dibromophenyl phosphate, etc., preferably trimethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, tris- (
chloroethyl)-phosphate, etc.

Compound (II) can be used alone or in combination of two or more.

In the present invention, it is preferable to use compound (1) and compound (2) together as component (C) because the surface appearance of the molded product is further excellent, and the ratio of their combined use is usually 1 to 501.
50 to 99 (weight ratio, compound I/compound ■).

The amount of component (C) used is 5 to 40 parts by weight, preferably 7 to 3 parts by weight, based on the total weight of components (A) and (B).
It is blended in an amount of 5 parts by weight, more preferably 10 to 30 parts by weight. If the proportion of component (C) is less than 5 parts by weight, flame retardancy will be low, and if it exceeds 40 parts by weight, heat resistance will decrease.

Furthermore, in the present invention, as an antioxidant, for example, 2.6-
Di-t-butyl-4-methylphenol, 2-(l-methylcyclohexyl)-4,6-dimethylphenol,
2,2-methylene-bis-(4-ethyl-6-tert-butylphenol), tris(di-nonylphenyl)phosphite; UV absorbers such as pt-butylphenyl salicylate, 2,2'-dihydroxy- 4-Methoxybenzophenone, 2-(2'-hydroxy-4'
-m-octoxyphenyl)benzotriazole; lubricants such as paraffin wax, stearic acid, hydrogenated oils,
Stearamide, methylene bisstearamide, m-butyl stearate, ketone wax, octyl alcohol, hydroxystearic acid triglyceride; flame retardant,
For example, antimony oxide, aluminum hydroxide, zinc oxalate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agents, such as stearamidopropyldimethyl-β-hydroxyethyl, ammonium drate; coloring agents such as titanium oxide, carbon black; fillers such as calcium oxide, clay, silica, glass fibers, glass spheres,
Carbon fiber; pigment, etc. can be added as necessary.

Components (A) to (C) of the composition of the present invention can be mixed by a conventional method using, for example, a single-screw or twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, or the like. For example, after mixing each component with a mixer, use an extruder to
What is necessary is just to melt-knead and granulate at 350 degreeC. Furthermore, each component can be simply melt-kneaded and molded directly in a molding machine.

e. Examples The present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 11 and Comparative Examples 1 to 5 Each component was kneaded at 310°C using a 50 m/m extruder according to the blending ratio shown in Table 1.
And compositions of Comparative Examples 1 to 5 were obtained. Each of the obtained compositions was made into pellets, and each test piece was produced at 310° C. using an injection molding machine (Toshiba 1580A), and each test was conducted as follows. The results are shown in Table-1.

Heat resistance: heat distortion temperature (HDT) ASTM D646
1/2'', 4.6 kg/cJ.

Impact resistance: Izod impact strength (Izod Imp,
) to ASTM D256 1/8', notched 23
Measured by °.

Oil resistance: 160 in ASTM No. 1 dumbbell and gear oil
℃ for 1000 hours, measure the tensile strength, calculate the rate of change from the initial value W = (T/To) x 100% (T: tensile strength after aging, TO: tensile strength before aging), and calculate this value. was used as an index of oil resistance.

Tensile strength: Measured according to ASTM D638 (ASTMI dumbbell).

Combustion test: Measured according to UL-941/16'.

Margin below In addition, each component in Table-1 is as follows.

(A) Component PA46: Nylon 46 (manufactured by JSR, KS300) PA6: Nylon 6 (manufactured by Toshi Side, Amiran CM1017) PA66: Nylon 66 (manufactured by Toshi Side, Amilan CM167) (B) Component pps: Polyphenylene sulfide (Kureha Chemical■
Using a 40 m/m extruder, 2 parts by weight of maleic anhydride and 2 parts by weight of peroxide (hexyl peroxide) were added to 100 parts of polyethylene (E791, manufactured by Nippon Oil Corporation) at a temperature of 200°C using a 40 m/m extruder. Oxide) 0.4 parts by weight was mixed and made into pellets.

(C) Component C-1=In general formula (I), R1, R2 and R3
is a phenyl group, R4, R5, R6 and R7 are hydrogen atoms, and n is a mixture of 1 to 10, and contains 5.8% by weight of triphenyl phosphate.

C-2:) Riphenyl phosphate f0 Effects of the invention The composition of the invention has excellent heat resistance, impact resistance, oil resistance, mechanical strength, and flame retardancy, and furthermore, has low water absorption and has low molded product dimensions. Changes are also small; for example, automotive parts,
A molded product suitable as a part for electric/electronic equipment can be provided.

Claims (1)

[Claims] (1) (A) 2 to 90% by weight of polyamide polymer (B)
(C) At least one compound selected from a compound represented by the following general formula (I) and a compound represented by the following general formula (II), based on 100 parts by weight of a composition consisting of 98 to 10% by weight of polyarylene sulfide. A flame-retardant resin composition comprising 5 to 40 parts by weight of a phosphorus compound. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3 represent the same or different hydrocarbon groups, R_4, R_5, R_6, R_7 represent hydrogen or hydrocarbon groups. .R_4, R_5, R_6
, R_7 may be the same or different. n is 1 to 20
It is. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_8, R_9 and R_1_0 may be the same or different and represent a hydrocarbon group or a halogenated hydrocarbon group.)