WO1994009070A1

WO1994009070A1 - Resin composition and molded article

Info

Publication number: WO1994009070A1
Application number: PCT/JP1993/001508
Authority: WO
Inventors: Katsuhiko Okada; Kiyoaki Nishijima
Original assignee: Teijin Limited
Priority date: 1992-10-21
Filing date: 1993-10-20
Publication date: 1994-04-28

Abstract

A resin composition comprising substantially: (a) 30-70 wt. % of a polyamide resin (component A); (b) 5-40 wt. % of a powdery inorganic filler (component B) mainly comprising a silicate; (c) 10-40 wt. % of a halogen compound (component C); (d) 2-10 wt. % of a pentavalent antimony compound (compound D); and (e) 0-40 wt. % of a filler (component E) other than the component B, a molded article made therefrom, and a product of plating of the article. The molded article not only has an excellent flame retardancy but also can well be plated on its surface.

Description

Specification

1. Title of invention

Resin composition and molded article

2. Detailed Description of the Invention

Industrial applications

TECHNICAL FIELD The present invention relates to a resin composition containing a polyamide resin as a main resin component, and a molded article formed therefrom. More specifically, the present invention relates to a molded article having excellent metal plating properties and flame retardancy, and a resin composition therefor.

Conventional technology

Conventionally, molded products made of ABS resin with metal plating have been used in automobile parts, home appliances, toys, and electric and electronic parts due to demands for weight reduction. However, ABS resin molded products are not satisfactory in heat resistance, rigidity and the like, and therefore have been mainly used mainly for decorative purposes.

On the other hand, polyamide resins are useful engineering plastics because they have excellent heat resistance, mechanical properties such as tensile strength and flexural strength, and flow properties. Numerous proposals have been made regarding the metal plating of polyamide resin molded products as a representative of resins. For example, the inventions described in JP-A-59-174634, 62-223261 and 63-150348 are examples thereof, and polyamide resins such as nylon 6, nylon 66, nylon 46, and MXD 6 nylon. In addition, an inorganic filler typified by calcium gayate is blended with the mixture to provide a molded article of a polyamide resin having good metal plating properties. In recent years, in the electrical and electronic fields such as home appliances and OA equipment, flame retardancy has been demanded.However, all of these proposals relate only to non-flame retardant compositions. A composition capable of metal plating has not yet been found.

Halogenated compounds are one method of flame retarding polyamide resins. Further, a composition in which a metal oxide is added to impart flame retardancy has been proposed. In short, the flame-retardant polyamide resin, as described above, is given a satisfactory finish using the plating method known for conventional ABS resin molded products and polyamide resin molded products. I couldn't. Therefore, if good flame resistance can be imparted to a flame-retarded polyamide resin molded product, its utility value is expected to greatly expand.

Problems to be solved by the invention

Therefore, a first object of the present invention is to provide a polyamide resin molded article having excellent mechanical properties and excellent heat resistance, a good metal plating on its surface, and a flame retardant property. It is an object of the present invention to provide a polyamide resin molded article imparted with properties and a resin composition therefor. A second object of the present invention is to provide a polyamide resin molded article having excellent flame retardancy, a good metal plating surface, and a metal plating surface having high adhesion.

A third object of the present invention is to provide a molded article excellent in flame retardancy and having a value that is useful as various home appliances, automobile parts or electric / electronic parts, and a resin composition therefor.

Means for solving the problem

The present inventors have conducted intensive studies to improve the plating property of a flame-retarded polyimide resin molded article in order to achieve the object of the present invention. It has been found that a composition in which a powdered inorganic filler, a halogenated compound, and a pentavalent antimony compound are combined and blended in a specific amount meets the above-mentioned object. The present invention has been achieved based on the above-mentioned new findings, and (a) a polyamide resin (A component) in an amount of 30 to 70% by weight.

(b) Powdered inorganic filler mainly composed of gaylate (component B)

5 ~ 40% by weight

(c) Halogenated compound (Component C) 10 to 40% by weight

(d) Pentavalent antimony compound (D component) 2 to 10% by weight and

(e) Fillers other than the B component (E component) 0 to 40%

It is a more substantial resin composition, and a molded article formed from this resin composition.

Hereinafter, the present invention will be described in more detail.

Examples of the polyamide resin as the component A used in the present invention include a ring-opening polymer of a cyclic lactam, a self-polycondensate of an aminocarboxylic acid, and a polycondensate of a dibasic acid and diamine. Aliphatic polyamides such as Nylon 6, Nylon 66, Nylon 46, Nylon 610, Nylon 612, Nylon 11 and Nylon 12; Poly (meta-xylene adipamide), Poly ( Aliphatic monoaromatic polyamides such as xamethylene terephthalamide), poly (hexamethylene isophthalamide) and poly (tetramethylene isophthalamide), and copolymers and mixtures thereof. . The polymerization method of the polyamide resin (component A) used in the resin composition of the present invention is not particularly limited, and may be a melt polymerization, an interfacial polymerization, a solution polymerization, a bulk polymerization, a solid-phase polymerization, or a method combining these methods. Can be used.

The molecular weight of the polyamide resin is not particularly limited, but a number average molecular weight in the range of about 100,000 to about 500,000 is particularly preferable. If the molecular weight is less than this range, the mechanical properties (particularly impact strength) of the molded article are poor, and if the molecular weight exceeds the above range, the moldability tends to decrease and the surface properties of the molded article tend to deteriorate. .

As the component A of the present invention, a commercially available polyamide resin can be used as it is. Preferred are the aliphatic polyamides. More preferred polyamides are nylon 6, nylon 46 and nylon 6 6 is exemplified. Most preferred is nylon 46.

In the resin composition of the present invention, the content of the component A is 30 to 70% by weight, It is preferably from 35 to 65% by weight. Here, the content of the component A is a value determined based on the total weight (100% by weight) of the resin composition including the components A to E. Hereinafter, the content (% by weight) of each component is determined in the same manner as that of the component A.

Examples of the powdery inorganic filler mainly composed of the maleic acid salt of the component B used in the resin composition of the present invention include alkali metals of gay acid or aluminogeiic acid, Mg, Ca, Fe, M Examples thereof include metal salts such as n, and specific examples thereof include calcined kaolin or talc, wollastonite, and my strength. Of these, calcined kaolin or talc is preferable. Further, it is preferable that these powdery fillers have been surface-treated with a coupling agent mainly comprising a silane compound such as aminosilane.

These fillers may be in the form of a powder that is generally used as a filler for a resin, and generally has an average particle size of 50 / zm or less, preferably 30 m or less. is there. If these particles having a large particle diameter are used, it is difficult to uniformly disperse the particles in the resin composition. Particularly preferred are those having an average particle size in the range of about 0.5-1 Q μm.

The compounding amount of the powdered filler (component B) mainly composed of a gaylate is 5 to 40% by weight, preferably 8 to 35% by weight, more preferably 10 to 30% by weight. preferable. If the amount of the component B is less than 5% by weight, the metal adhesion is extremely poor. On the other hand, if it exceeds 40% by weight, the fluidity of the composition in the molten state is remarkably poor, and not only the appearance of the obtained molded product is deteriorated, but also the mechanical strength is lowered.

As the halogenated compound of the component C used in the resin composition of the present invention, those generally used as flame retardants for resins are used, and as the halogen, bromine and chlorine are preferable.

Specific examples of the halogenated compound include, for example, brominated polystyrene, brominated polyphenylene ether, brominated epoxy, brominated bisphenol A-diglycidyl ether and its oligomer, brominated bisphenol-A. Polycarbonate manufactured as raw material Typical examples thereof include a net oligomer, a brominated pipenyl ether, a brominated diphthalimide compound, and a dimer of a chlorinated hexapentadiene. Among them, brominated polystyrene is particularly preferable. Brominated polystyrene is produced by polymerizing brominated styrene or by brominating polystyrene. Brominated polystyrene can be used even if another vinyl compound is copolymerized. In this case, examples of the vinyl compound include styrene and α-methylstyrene. The degree of polymerization of the brominated polystyrene is not particularly limited, but those having a weight-average molecular weight of about 10,000,000 to about 1,000,000,000 are preferably used. The bromine-containing ratio in the brominated polystyrene is suitably in the range of 60 to 80% by weight.

The compounding amount of the halogenated compound (component C) is 10 to 40% by weight, preferably 15 to 35% by weight, and more preferably 20 to 30% by weight. If the amount is less than 10% by weight, the flame retardant effect of the polyamide resin molded product is not sufficient, and if it exceeds 40% by weight, the mechanical and thermal properties characteristic of the polyamide resin molded product are impaired. Not so desirable.

As the pentavalent antimony compound of the D component used in the present invention, typically, antimony pentoxide, sodium antimonate or a mixture of both is preferably used, but other pentavalent antimony compounds are preferably used. It may be. According to the study of the present inventors, when antimony trioxide, which is a commonly used flame retardant, is used in place of pentavalent antimony, the effect of inhibiting the plating property is large, and a good molded article is obtained. It has been found that the amount of addition is limited to a very small amount in order to form a surface. In this case, the flame retardancy is naturally inferior, so further measures are required to obtain normal flame retardancy. When a pentavalent antimony compound is used as the D component in the resin composition of the present invention, the plating properties are not impaired at all, so that a desired amount can be added, and the molded article has flame retardancy. And the formation of a good plating surface can be achieved. These D components may be used alone or in combination of two or more compounds.

The compounding amount of the pentavalent antimony compound (component D) is 2 to 10% by weight, preferably 5 to 8% by weight. When the blending amount is less than 2% by weight, the blending effect is small. When the blending amount is more than 10% by weight, the effect is not expected to be increased by further blending. It is not preferable because the moldability such as the moldability is inferior. The more preferable compounding amount of the component D is such that the ratio of the antimony metal atom 1 to the halogen atoms 2 to 5 of the halogen compound of the component C is one.

The resin composition of the present invention may further contain a filler (component E) other than the component B in addition to the components A to D. The E component is added, for example, for the purpose of reinforcing a resin molded product, modifying the surface, or modifying electrical or thermal properties. In addition, component E is added to improve moldability and chemical properties. The E component is added in an amount of 0 to 40% by weight, preferably 3 to 30% by weight based on the resin composition.

Specific examples of the E component include, for example, fibrous materials such as glass fiber, aramide fiber, carbon fiber, steel fiber, ceramic fiber, potassium titanate, boron whisker, and the like. Examples include powdered, granular or plate-like inorganic fillers such as calcium, barium sulfate, glass beads, and glass flex. Also, copper compounds such as copper iodide, hindered funinol for the purpose of improving heat resistance. It is also possible to add an antioxidant or a heat stabilizer such as a compound, an aromatic amine compound, an organic phosphorus compound, a sulfur compound, etc. In addition, for the purpose of improving the melt viscosity stability and hydrolysis resistance, etc. And various epoxy compounds, oxazoline compounds, etc. Examples of the epoxy compound include a reaction of bisphenol-A with epichlorohydrin. Bisufue Nord one A-type epoxy compounds obtained Te, aliphatic Dali glycidyl ethers obtained from the reaction of various glycol Ya glycerol and E Pikuroruhi Dorin, Novolak type epoxy compounds, aromatic or aliphatic carboxylic acid type epoxy compounds, alicyclic compound type epoxy compounds, and the like are preferable. As the oxazoline compound, aromatic or aliphatic bisoxazoline, particularly 2, 2, 1-bis (2 —2,1′-m-phenylenebis (2-year-old oxazoline) is preferred.

For example, stabilizers, coloring agents, lubricants, ultraviolet absorbers, and antistatic agents commonly used as additives for other resins can also be added.

Further, the resin composition of the present invention may contain a small amount of other thermoplastic resin, for example, polyester resin, polyphenylene sulfide resin, polyphenylene ether resin, polycarbonate resin, phenyloxy resin, polyethylene and copolymers thereof. Copolymer, polypropylene and its copolymer, polystyrene and its copolymer, acrylic resin and acryl-based copolymer, polyamide elastomer, polyester elastomer, etc .; thermosetting resin, for example, fuynol resin, melamine Resins, unsaturated polyester resins, silicone resins and the like may be blended.

In order to obtain the resin composition of the present invention, a predetermined amount of each component may be mixed by an arbitrary compounding method.

Generally, it is preferable to mix the components more uniformly and densely. A method of mixing and homogenizing all or a part of the components simultaneously or separately with a mixer such as a blender, kneader, roll, extruder, or the like, Can be mixed simultaneously or separately with a blender, a mixer, a roll, an extruder or the like, and the remaining components can be mixed and homogenized by these mixers or extruders. Further, there is a method in which a composition which has been dry-blended in advance is melt-kneaded with a heated extruder, homogenized, extruded into a wire, and then cut into a desired length to obtain granules or pellets.

The molding composition thus produced is usually kept in a sufficiently dried state, charged into a molding machine hobber, and subjected to molding such as injection molding. Furthermore, the raw materials of the composition are dry-blended and directly molded. It is also possible to put into a machine hopper and melt-knead in a molding machine. In order to obtain the molded article of the present invention, the resin composition may be molded by a method known per se. For example, a desired molded product can be obtained by, for example, injection molding, compression molding, or extrusion molding of a granular material or a pellet made of the resin composition of the present invention.

As described above, the molded article of the present invention is subjected to a metal plating treatment to give a molded molded article having excellent flame retardancy and good adhesion to a metal surface. As the method of metal plating the molded article of the present invention, a method usually applied to a resin molded article, particularly to a polyamide resin molded article can be used. That is, by first performing an electroless plating process and then performing an electrolytic plating process, a target molded product can be obtained. To explain these plating processes in detail, for example, (1) after degreasing and cleaning the molded product surface, (2) etching with hydrochloric acid and the like, and (3) post-etching to remove the swollen layer on the surface I do. Next, the catalyst is applied in three steps of (4) catalyst list, (5) excelate, and (6) postaxate. Thereafter, it is composed of components such as a metal salt, a reducing agent, and a pH adjusting agent. (7) Ability to perform electroless plating In this case, metals that can be plated include copper, nickel, tin, and silver. Next, (8) Electrolytic plating is preferably performed using nickel, copper, and chromium metal, so that the liquid components, additives, film thickness, etc. can be changed according to the purpose. Any well-known electrolytic plating bath can be used.

Example

Hereinafter, the present invention will be described specifically with reference to examples.

In the examples, the components used, the molding conditions, the shape of the molded product, the plating recipe, the method for evaluating the performance of the metal plating (the plating property and the adhesion strength), and the measuring methods for the various characteristics in the examples are as follows. is there.

(1) Molding conditions

Molding machine: Toshiba IS75E Cylinder temperature: 280 to 300 ° C (Nine 46)

26 0 to 280 ° C (N / A 66)

25 0 to 27 0 ° C (Nylon 6)

Mold temperature: 1 20. C (Nyron 46)

80 ° C (Nylon 66, 6)

(2) Molded product shape (disk)

Diameter 50 mm, thickness 2 mm (side gate)

(3) Method of plating

_C electroless main Tsu key and electrolyte main Tsu key having conducted under the conditions shown in the following Table one 1

Table

1) Amount of reagent contained in 1 liter of solution (4) Mechanical strength: The bending test conformed to ASTM D790, and the impact test conformed to ASTM D256 (with Izod and notch).

(5) Flammability: Evaluated according to the method (U L 94) specified by Underwriters Laboratory, USA. (Thickness 0.70mm)

(6) Judgment of plating property: The plating property was determined using the following criteria.

〇: The surface of the test piece can be painted 100%.

X: The surface of the test piece cannot be painted 100%.

(7) Adhesive strength: The peel strength (kg / cm) of the adhesive film was measured at a 90 ° angle and a peeling speed of 20mm / min by cutting a strip of lOmra on the film surface of the test piece. .

(8) Ingredient

The product names, manufacturers and required properties of each component used are as follows.

Nylon 6 resin (NH-8001, Teijinsha),

Nymouth 66 resin (Leona 1300S, manufactured by Asahi Kasei Corporation)

Nylon 46 resin (STANYL, DSM, Netherlands), talc (P KNN, Hayashi Kasei),

Firing force oil (Translink 445, Engelhardt), Wallace Donite (CHC-62N-10, Hayashi Kasei),

Sodium antimonate (NA 1070L, manufactured by Nissan Chemical), antimony trioxide (Patox C, manufactured by Nippon Seimitsu),

Brominated polystyrene (bromine content 68.5% by weight;

Pie mouth check 68 PB, Nissan Hue mouth company, glass fiber (chopped strand cut 3 mm long)

Nippon Electric Glass Co., Ltd.)

Examples 1 to 9 and Comparative Examples 1 to 7

A twin-screw extruder with a bent (Tex- The pellet was extruded at 280 to 310 ° C at 44) to obtain a pellet. At this time, the glass fiber was a side feed. Prior to compounding, all polyamides were dried under reduced pressure of 110 and 10 T rr for 8 hours or more to reduce the water content to 0.1% or less.

Using the obtained pellets, a molded article shown in the above (2) Molded article shape (disc) was obtained under the above (1) molding conditions.

Subsequently, the obtained molded product was subjected to metal plating according to the above-mentioned plating treatment method to obtain a plated metal product. The results are shown in Tables 1 and 2 below. two

Table 1 2

Table 1 No. 3 Example 5 Example 6 Comparative Example 6 Comparative Example 7 Example 7 Example 8 Example 9

(Α) Horiamit resin (weight%) N / A 46 Nylon 46 Nylon 46 Nylon 46 N / A 46 N / A D / N 66 N / A 65.0 62.0 52.0 69.5 77.0 32 62.0 62.0

(Β) Talc (% by weight) 10 10 10 10 10 10 10 minutes (C) Brominated bromine ''; Styrene (% by weight) 20 30 20 5 20 20 20

(D) Sodium antimonate (% by weight) 5 8 0.5 8 8 8 8

(Ε) Glass fiber (wt%) 30 Flexural strength (MPa) 112 111 120 119 195 110 97 Object Flexural modulus (MPa) 5020 4970 4990 4890 10800 4980 4380 Notched eye impact (J / m) 59 55 60 58 50 56 51 Properties UL 94 (1/36 ") V-0 V-0 V-2 V-2 V-0 V-0 V-0 Meshing 〇〇〇〇〇〇〇 Adhesion strength (kg / cra) 1.7 1.5 1.6 1.5 .5 1.1.7 1.7

The meaning of each of the examples and comparative examples will be briefly described below. Examples 1 to 7 and Comparative Examples 1 to 7 are all examples using nylon 46 resin as the polyamide resin (component A).

Comparative Example 1 shows that even if an inorganic filler (component B) is simply added to a composition made flame retardant using antimony oxide, no sticking can be obtained.

Comparative Example 2 shows that antimony trioxide inhibits plating after flame retardation.

Comparative Example 3 shows that when no antimony compound was used, the flame retardancy was insufficient.

Examples 1 and 2 are evaluation results when talc was used as the inorganic filler (component B).

Example 3 is an evaluation result in the case of using a firing force oil as the inorganic filler (component B).

Example 4 is an evaluation result in the case where wollastonite was used as the inorganic filler (component B).

In Comparative Example 4, when the blending amount of the inorganic filler (component B) was too small, the stickiness was impaired. In Comparative Example 5, when the blending amount was too large, the flame retardancy was impaired and the purpose was reduced. Shows that a molded article of the resin composition cannot be obtained. Example 5 is an evaluation result in which the amount of the antimonic acid compound (component D) was changed.

Example 6 is an evaluation result in which the amount of the halogenated compound (component C) was changed.

Comparative Example 6 shows that if the amount of the antimonic acid compound (component D) is too small, the flame retardancy is impaired, and the desired resin composition molded article cannot be obtained.

Comparative Example 7 shows that when the amount of the halogenated compound (component C) is too small, the flame retardancy is impaired, and the desired resin composition molded article cannot be obtained. Example 7 is a molded product reinforced with 30% by weight of glass fiber (component E). However, it does not impair the flame retardancy, the adhesiveness, and the adhesion strength, and the bending strength, the bending elastic modulus, and the impact strength are improved. This shows that a molded article of a resin composition excellent in typical mechanical properties could be obtained.

Examples 8 and 9 are examples using nylon 66 and nylon 6, respectively, as the polyamide resin (component A). Similarly, resin molded articles having excellent flame retardancy and adhesion. It shows that was obtained.

Claims

The scope of the claims

1. (a) Polyamide resin (A component) 30-70% by weight

(b) Powdered inorganic filler mainly composed of gaylate (component B) 5 ~

40% by weight

(c) Halogenated compound (Component C) 10-40% by weight

(d) pentavalent antimony compound (component D) 2 to 10% by weight and

(e) A resin composition consisting essentially of a filler other than the B component (E component) 0 to 40% by weight.

2. The polyamide resin (A component) is an aliphatic polyimide.

The resin composition according to 1.

3. The resin composition according to claim 1, wherein the polyamide resin (component A) is at least one member selected from the group consisting of nylon 6, nylon 46, and nylon 66.

4. The resin composition according to claim 1, wherein the inorganic filler (Component B) is at least one selected from the group consisting of calcined kaolin, talc, wallastite and my strength.

5. The resin composition according to claim 1, wherein the halogenated compound (component C) is brominated polystyrene.

6. The resin composition according to claim 1, wherein the pentavalent antimony compound (component D) is antimony pentoxide, sodium antimonate, or a mixture thereof.

7. The resin composition according to claim 1, wherein the filler other than the component B (component E) is a fibrous material.

8. The resin composition according to claim 1, wherein the content of the component A is 35 to 65% by weight.

9. The resin composition according to claim 1, wherein the content of the B component is 8 to 35% by weight.

10. The tree according to claim 1, wherein the content of the C component is 15 to 35% by weight. Fat composition.

1 1. The resin composition according to claim 1, wherein the content of the D component is 5 to 8% by weight.

12. The resin composition according to claim 1, wherein the content of the E component is 3 to 30% by weight.

1 3. The resin composition according to claim 1, wherein the A component, the B component, the C component, the D component, and the E component are uniformly and densely mixed.

14. A molded article formed from the resin composition according to claim 1.

15. A metal molded article formed from the resin composition according to claim 1 and having a metal-plated surface.

1 6. The molded metal product according to claim 15, wherein the molded product is made of at least one metal selected from the group consisting of nickel, copper, and chromium.