JPH0735477B2 - Flame-retardant resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a flame-retardant resin composition, and more specifically, it has a high degree of flame-retardant property and is less likely to undergo dimensional change due to water absorption. The present invention relates to a flame-retardant resin composition which is less likely to be deteriorated by heat, has less deterioration in mechanical strength in spite of mixing various components, and has excellent moldability.

[Problems to be Solved by Conventional Techniques and Inventions] In recent years, many engineering plastics have been developed, and various automobile parts, while making the most of their respective characteristics,
Used for general mechanical parts, electric / electronic parts, etc.

Nylon 46, a type of engineering resin,
Excellent mechanical strength such as tensile strength, bending strength, impact strength,
Furthermore, it has excellent heat resistance and slidability. For example, the melting point of nylon 46 is 295 ° C, the melting point of nylon 6 is 220 ° C,
Since the melting point of nylon 66 is higher than 260 ° C, it can be said that nylon 46 has excellent heat resistance.

However, the flame retardancy and water absorption dimensional stability of this nylon 46 are not sufficient.

In order to improve the flame retardancy of this nylon 46, it is known to blend a halide or antimony trioxide like other nylons. However, when the flame retardant is blended in this way, the melting point of nylon 46 (295 ° C) and the decomposition temperature (320 ° C)
Because of the close proximity to the
(° C) causes a new problem that the resin is deteriorated to cause discoloration and decrease in strength. Moreover, the water absorption dimensional stability of nylon 46 still remains unsolved due to the blending of such a flame retardant.

On the other hand, polyphenylene sulfide, which has been or is about to be used as a heat-resistant engineering plastic in the electric and electronic parts field, is self-extinguishing (1/32 ″ V-0) and has excellent heat resistance. For example, its melting point is 285 ° C., and the polyphenylene fide resin composition reinforced by glass fibers or the like has a high load heat distortion temperature of 260 ° C.

However, since polyphenylene sulfide has a small elongation, even if it is reinforced with glass fiber or the like, satisfactory strength and toughness cannot be obtained and it is fragile. In particular, the welded part of the molded product is fragile. In addition, polyphenylene sulfide is liable to generate gas and burrs during the molding process and needs to be crystallized because the crystallization is required. However, there is a problem that the molding cycle becomes longer and, as a result, the molding cycle becomes longer.

The present invention has been completed under such a technical background.

That is, the object of the present invention is, compared to nylon 46, improved flame retardancy, water absorption dimensional stability, etc., and less deterioration during molding processing, and mechanical properties equivalent to or better than nylon 46. Further, it is an object of the present invention to provide an engineering resin composition having excellent flame retardancy, which is excellent in molding processability as compared with polyphenylene sulfide.

[Means for Solving the Problems] The invention of the present application for solving the problems includes (A) 3 to 25% by weight of polyarylene sulfide, and 50 to
90% by weight nylon 46 and 50-10% by weight nylon 46
Other than the mixture of aliphatic polyamide 10-55% by weight, fibrous filler 3-40% by weight, flame retardant 3-25% by weight, flame retardant auxiliary 1-10% by weight, inorganic filler 3-30 A flame-retardant resin composition comprising 100 parts by weight of a composition of 100% by weight, (B) 0.1 to 5 parts by weight of an epoxy resin, and (C) 0.01 to 2 parts by weight of a heat stabilizer. is there.

-Polyarylene sulfide-The polyarylene sulfide in the present invention has a general formula There is no particular limitation as long as it has a structural unit represented by, and conventionally known polyarylene sulfide can be mentioned.

The polyarylene sulfide used in the present invention may be an uncrosslinked or partially crosslinked polyarylene sulfide and a mixture thereof, or a linear or branched polyarylene sulfide or a mixture thereof. good.

The polyarylene sulfide may be produced by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrosulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. And the self-condensation of p-dichlorothiophenol. Of these, a method of reacting with sodium sulfide p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is preferable. In either case, it is also preferable to add an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide to adjust the degree of polymerization.

The polyarylene sulfide in the present invention may be a copolymer containing a copolymer component in addition to the above structural unit.

Examples of the copolymer component include (However, R in the formula is an alkyl group, a nitro group, a group, an alkoxy group, -COOH, -COOM [M represents a metal atom].
Etc. ) Trifunctional Etc. can be mentioned. The content of these copolymer components in the polyarylene sulfide may be in the range that does not significantly affect the crystallinity, and is usually 30% or less, and particularly 10% or less.

-Polyamide resin mixture-The flame-retardant resin composition of the present invention needs to contain a mixture of nylon 46 and an aliphatic polyamide other than nylon 46 in a specific ratio.

The object of the present invention cannot be achieved by a mixture of a polyamide other than nylon 46 and the aliphatic polyamide. For example, a mixture of Nylon 6 and Nylon 66 will give a resin composition with poor heat resistance, resulting in significant deterioration during molding. On the other hand, in the flame-retardant resin composition of the present application containing a mixture of nylon 46 and other aliphatic polyamide in a specific ratio, nylon 46
Despite being the main component in the mixture, has a good water absorption dimensional stability, and has various excellent advantages as will be illustrated by the examples described later.

Nylon 46 has a concentration of 1g by dissolving nylon 46 in 96% sulfuric acid.
/ dl relative viscosity of sulfuric acid solution adjusted to 1.5-5.5, especially 2.0-
It should be 4.0.

Suitable examples of aliphatic polyamides other than nylon 46 include nylon 6, nylon 66, nylon 6,66, and nylon.
6,10, nylon 6,12, nylon 11, nylon 12, etc. can be mentioned. These may be used in combination of two or more thereof.

The degree of polymerization of aliphatic polyamides other than nylon 46 is not particularly limited, and the relative viscosity of 96% concentrated sulfuric acid solution at 25 ° C is
Any material within the range of 1.5 to 5.0 can be used.

The mutual proportions of nylon 46 and other aliphatic polyamides are such that when the mixture of the two is 100, nylon 4
6 is 50 to 90% by weight (the content of aliphatic polyamide other than nylon 46 is therefore 50 to 10% by weight), preferably
60 to 85% by weight (the content of aliphatic polyamide other than nylon 46 is therefore 40 to 15% by weight). Nylon
When the content of 46 in the mixture is less than 50% by weight, heat resistance is deteriorated, and when the content of nylon 46 exceeds 90% by weight, retention deterioration of the resin composition in the molding machine during molding occurs. It causes the discoloration of the molded product.

—Fibrous Filler— The flame-retardant resin composition of the present invention contains a fibrous filler.

Examples of the fibrous filler include glass fibers (chopped strands, milled fibers), carbon fibers, metal fibers, fibrous potassium titanate, asbestos, and various whiskers such as silicon carbide and silicon nitride. You can Among these, glass fiber is preferable. Of course, the above-mentioned various fibrous fillers can be used alone or in combination of two or more.

When using glass fiber, as the average fiber diameter,
It is usually 20 μm or less, preferably 5 to 14 μm, and its aspect ratio is usually 5 to 500, especially 1
It is preferably 0 to 300.

As the glass fiber, either a glass fiber not surface-treated or a glass fiber treated with a surface treatment agent can be used, but a glass fiber treated with a surface treatment agent is preferable.

The surface treatment agent may be a commonly used surface treatment agent, but an aminosilane-based surface treatment agent, a blocked isocyanate-based treatment agent, an epoxysilane-based treatment agent and the like are preferable.

Further, glass fibers subjected to a converging treatment with a urethane sizing agent and an epoxy sizing agent are also preferable.

—Flame Retardant— The flame retardant resin composition of the present invention contains a flame retardant.

Examples of the flame retardant include a phosphoric acid ester flame retardant, a halogen-containing organic compound flame retardant, an inorganic compound flame retardant, and the like. Among these, halogen-containing organic compound flame retardants are preferable, and bromine-containing resin flame retardants are particularly preferable. As the bromine-containing resin flame retardant, brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene oxide, and brominated epoxy resin are preferable. Of course, the various flame retardants may be used alone or in combination of two or more.

-Flame retardant aid-The flame-retardant resin composition of the present invention contains a flame retardant aid.

Examples of the flame retardant aid include Sb ₂ O ₃ , Na ₂ OSb ₂ O ₅ , Sb ₂ O ₅ , iron oxide, tin oxide, zinc borate, calcium oxide, copper oxide, titanium oxide, aluminum oxide, and the like. it can.
Among these, Sb ₂ O ₃ and Na ₂ OSb ₂ O ₅ are preferable. Of course, the various flame retardant aids may be used alone or in combination of two or more.

-Inorganic filler-The flame-retardant resin composition of the present invention contains an inorganic filler.

Suitable examples of the inorganic filler include calcium carbonate,
Barium sulfate, talc, mica, potassium titanate, feldspar,
Examples thereof include glass beads, wollastonite, zinc white, gypsum, clay and the like. These can be used alone or in combination of two or more.

Further, in the present invention, in addition to the various inorganic fillers, bentonite, sericite, zeolite, ferrite, attapulgite, calcium silicate, magnesium carbonate, dolomite, magnesium oxide, molybdenum disulfide, graphite, quartz, quartz glass, Metal powders such as iron, zinc, copper, aluminum and nickel can also be used.

-Epoxy resin-The flame-retardant resin composition of the present invention contains an epoxy resin.

An epoxy resin having two or more epoxy groups can be preferably used as the epoxy resin.

The epoxy resin may be in liquid or solid form.

Specific examples of the epoxy resin include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4'-dihydroxybiphenyl. ,
1,5-dihydroxynaphthalene, cashew phenol,
Glycidyl ethers of bisphenols such as 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, bisphenol halogens instead of bisphenol, glycidyl ethers such as diglycidyl ether of butanediol, glycidyl phthalic acid glycidyl esters, etc. Glycidyl epoxy resins such as ester type, glycidyl amine type such as N-glycidyl aniline, linear type such as epoxidized polyolefin and epoxidized soybean oil, and cyclic non-glycidyl epoxy such as vinylcyclohexenedioxide and dicyclopentadienedioxide. A resin is exemplified. In addition, novolac type epoxy resins and halogen-substituted products thereof can be used.

Preferred is an epoxy resin containing two or more epoxy groups, such as a novolac type epoxy resin.

The novolac type epoxy resin usually contains two or more epoxy groups and is obtained by reacting a novolac type phenol resin with epichlorohydrin.

Phenol, o-cresol, m-cresol, bisphenol A, resorcinol, p-tert-butylphenol, bisphenol S, bisphenol F, or a mixture thereof is used as the phenols as the raw material.

-Heat-resistant stabilizer-The flame-retardant resin composition of the present invention contains a heat-resistant stabilizer.

Examples of the heat stabilizer include Mg ₆ R ₂ (OH) ₆ CO ₃ .4H ₂
O [wherein R represents Al, Cr or Fe] ] Hydrous carbonate minerals represented by the following can be given, and specific examples thereof include natural products such as hydrotalcite, schititite, and pyrolite, or synthetic products thereof, or mixtures of natural products and synthetic products, or calcined products thereof. be able to.

-Amount of Each Component- The amount of each component in the present invention is as follows.

That is, first, a mixture of polyarylene sulfide, 50 to 90% by weight of nylon 46 and 50 to 10% by weight of an aliphatic polyamide other than nylon, a fibrous filler, a flame retardant, a flame retardant aid and an inorganic filler (these are all May be abbreviated as (A) component), and the amount of polyarylene sulfide compounded is 3 to 25 parts by weight, preferably 5 to 5 parts by weight.
20% by weight, the content of the above polyamide mixture is 10 to 55% by weight, preferably 15 to 50% by weight, the content of the fibrous filler is 3 to 40% by weight, preferably 5 to 35% by weight, a flame retardant. The blending amount of 3 to 25% by weight, preferably 5 to 20% by weight, the blending amount of the flame retardant auxiliary is 1 to 10% by weight, preferably 2 to 8% by weight, and the blending amount of the inorganic filler is 3 to 30% by weight. %, Preferably 5 to 20% by weight.

The compounding amount of the epoxy resin is 0.1 to 5 parts by weight, preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the component (A).

The blending amount of the heat resistance stabilizer is 0.01 to 2 parts by weight, preferably 0.2 to 1 part by weight, relative to 100 parts by weight of the component (A).

The object of the present invention can be achieved only when the blending amount of each component constituting the flame-retardant resin composition of the present invention is within the above range.

On the other hand, when the amount of polyarylene sulfide is less than 3 parts by weight, the flame retardancy is lowered, and the surface of the molded product is not only burned by the heating during molding, but also the surface of the molded product becomes rough, and the water absorption dimensional property is reduced. If the amount exceeds 25 parts by weight, not only the surface of the molded product is burned by heating during molding, but also the surface of the molded product becomes rough and the mold release of the molded product is also deteriorated.

When the blending amount of the mixture such as nylon 46 is less than 10 parts by weight, the low-melting point resin component relatively causes a decrease in heat distortion temperature and the like, and the blending amount of the mixture is 55 parts by weight. If it exceeds the area, the heat distortion temperature will be maintained, but the surface of the molded product will become rough and deterioration due to retention will become noticeable.
Further, it causes a phenomenon that the rate of dimensional change due to water absorption increases.

If the content of the fibrous filler is less than 3% by weight, not only the water absorption dimensional stability and mechanical strength will decrease, but also the heat distortion temperature will decrease. If it is more than 40% by weight, the moldability will increase. And the mechanical strength such as weld strength decreases.

If the blending amount of the flame retardant is less than 3% by weight, the flame retardancy is lowered, and if it exceeds 25% by weight, deterioration due to retention, surface roughening, etc. occur and only defective molded products are obtained.

If the blending amount of the flame retardant aid is less than 1% by weight, the flame retardancy is lowered, and if it exceeds 10% by weight, the moldability is lowered.

If the content of the inorganic filler is less than 3% by weight, the flame retardance is reduced, the deterioration due to retention, the water absorption dimensional property, etc. are reduced.
If it exceeds 30% by weight, the surface of the molded product will be roughened or burnt during molding, and the mechanical strength such as tensile strength will be reduced.

When the compounding amount of the epoxy resin is less than 0.1 parts by weight,
The water absorption dimensional stability of the molded product and the weld tensile strength decrease, and when it exceeds 5 parts by weight, not only the molded product suffers burns and surface roughness but also the weld tensile strength decreases.

If the amount of the heat resistance stabilizer is less than 0.01 part by weight, retention deterioration occurs.

—Preparation of Resin Composition— The flame-retardant resin composition of the present invention can be prepared by various known methods.

When preparing the flame-retardant resin composition, there is no particular restriction on the mixing order of the respective components. In the present invention, not only the component (A) is first prepared and then the remaining components are blended therein, but the components other than the fibrous filler are blended and prepared in any order, and finally the fibrous filler is blended. It is also within the scope of the present invention to blend a filler to prepare the flame-retardant resin composition of the present invention.

The mixing means used for preparing the flame-retardant resin composition of the present invention is not particularly limited as long as a uniform mixture can be obtained, and various mixing methods can be used.

Specific examples thereof include, for example, a ribbon blender, a tumble mixer, a Henschel mixer, an oven roll, a Banbury mixer, a Henschel mixer, a single screw pressing machine, a twin screw extruder, and a single screw reciprocating screw mixer. it can.

The flame-retardant resin composition thus obtained can be molded into various molded articles by various molding methods such as injection molding, compression molding and extrusion molding, and is used as various sealants and coating agents. You can also do it. For example, the flame-retardant resin composition of the present invention is a flat plate, a film,
It is also possible to form a sheet or the like and form a plywood or a laminated body from such a plate-shaped body and another plate-shaped body, or to form a multilayer film or sheet by coextrusion molding.

However, when the flame-retardant resin composition of the present invention is molded by an injection molding method, the effects of the present invention can be exhibited well.

In addition, the flame-retardant resin composition of the present invention is molded by various molding methods in various fields such as fibers, pipes, rods, films, sheets, and bearings in the mechanical field, electrical field, electronic field, and other fields. It can be made into a product. Among them, the flame-retardant resin composition of the present invention is suitable for molding connectors, IC sockets and the like. For example, connectors and IC sockets mounted on burn-in measuring devices have excellent heat resistance, flame retardance,
Where mechanical strength such as dimensional stability, good moldability, and high tensile strength is required, the flame-retardant resin composition of the present invention satisfies these requirements.

[Examples] The present invention will be described more specifically with reference to Examples and Comparative Examples of the present invention.

(Examples 1 to 47, Comparative Examples 1 to 18) Of the components of the types shown in Tables 1 to 4, components other than glass fiber were blended with a Henschel mixer to obtain blended compositions. Twin-screw kneading extruder (PC made by Ikegai Tekko KK, PC
M45II), a flame-retardant resin composition was prepared by adding glass fiber in the middle of an extrusion cylinder while kneading this compounded composition under heating conditions of 290 to 330 ° C. The resin composition was strand-cut to obtain pellets.

The pellets were evaluated as follows. The evaluation results are shown in Tables 1 to 4.

<Moldability> Using the injection molding machine (FS-150) manufactured by NISSEI PLASTIC INDUSTRIES CO., LTD.
0 × 80 × 3.2 mm) was produced.

[Molding conditions] Cylinder temperature; 310 ℃ Mold temperature; 90 ℃ Injection time; 8 seconds Cooling time; 10 seconds Injection pressure; Minimum filling pressure + 100kg ・ f / cm ² Regarding the condition of the obtained test piece, Table 1 ~ The evaluation items shown in Table 4 were visually evaluated. The evaluation items, the symbols indicating the judgment results, and their meanings are shown below.

(1) Surface condition: Good ... The surface is smooth.

× ・ The surface is rough.

(2) Occurrence of burns; ○ ・ ・ No × ・ ・ Yes.

(3) Mold release: ○ ・ ・ Good × ・ ・ Poor <Flame retardancy> Compliant with UL-94 (1/32 inch).

<Dwelling Degradability (Indicated as "Dwelling" in Tables 1 to 4)> Using the same molding machine as described above in <Moldability>, holding time of pellets in the cylinder for 5 minutes, and holding injection Molding was repeated three times, and the color tone of the third test piece was visually judged. The symbols indicating the judgment results and their meanings are shown below. ○: No change.

Δ: There is some discoloration.

X: Discoloration due to deterioration is extremely large.

<Water absorption dimensional stability> A molded shrink plate with a thickness of 80 x 80 x 2 mm is left in a constant temperature and humidity chamber at 40 ° C and 90% RH for 48 hours, and then the dimensional change is corrected by a universal projector (Nikon PROFILE PROJECTOR V- It was measured in 12).

<Tensile strength> According to ASTM D-638.

<Weld Tensile Strength> According to ASTM D-638.

<Heat deformation temperature> (HDT) According to ASTM D-648 (load 18.6 kg / cm ² ).

[Advantages of the Invention] According to the present invention, in addition to having a high degree of flame retardancy, water absorption dimensional change does not easily occur, thermal deterioration during molding is small, and mechanical strength is not deteriorated in spite of the addition of a filler. It was possible to provide a flame-retardant resin composition excellent in molding processability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location // (C08L 77/06 77:00 81:04 63:00) (72) Inventor Yoshio Fukushima Tokyo 277 Calup Kogyo Co., Ltd., 1 Izumicho, Kanda, Chiyoda-ku, Tokyo (72) Inventor Hideo Okawa, 277 Calup Kogyo Co., Ltd., 1 Izumicho, Kanda, Chiyoda-ku, Tokyo (56) Reference JP-A-59-155462 ( JP, A) JP-A-3-76758 (JP, A)

Claims (1)

[Claims] (A) 3 to 25% by weight of (A) polyarylene sulfide, 50 to 90% by weight of nylon 46 and 50 to 10% by weight.
10 to 55% by weight of a mixture of aliphatic polyamides other than nylon 46, 3 to 40% by weight of fibrous filler, 3 to 25% by weight of flame retardant, 1 to 10% by weight of flame retardant aid, and inorganic filler 3 to 30
A flame-retardant resin composition comprising 100 parts by weight of a composition of 100% by weight, (B) an epoxy resin of 0.1 to 5 parts by weight, and (C) a heat stabilizer of 0.01 to 2 parts by weight.