JPH0395264A - Thermoplastic composite resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can afford a molding which has a low hygroscopicity and excellent flame retardancy by compounding a polyamide, a thermoplastic polyester, a fibrous inorganic filler, a brominated flame retardant, and an inorganic flame-retardant assistant in a specified ratio. CONSTITUTION:The title composition comprises 18-74wt.% polyamide, 5-40wt.% thermoplastic polyester, 10-40wt.% fibrous inorganic filler, 10-30wt.% brominated flame retardant, and 1-10wt.% inorganic flame-retardant assistant, wherein the compounding ratio of the polyamide to the polyester is 9/1 to 5/5 by weight. A preferable polyamide is one with a limiting viscosity of 3.0dl/g or less. A preferable polyester is one with a limiting viscosity of 0.8dl/g or less. A preferable fibrous filler is a glass fiber with a diameter of 5-15mum. A preferable flame retardant is an aromatic bromine compound. A preferable assistant is antimony trioxide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to thermoplastic composite resin compositions and articles, and particularly to resin compositions for low moisture absorption plastic products.

[Prior Art] Polyamide resins have conventionally been used as resin materials for plastic products such as industrial precision parts that require low moisture absorption. However, conventional plastic products prepared from polyamide-based resins with low hygroscopicity do not necessarily exhibit sufficiently low hygroscopicity, causing dimensional changes and physical property deterioration (particularly rigidity deterioration) due to moisture absorption.

Various methods have also been proposed to overcome these shortcomings. For example, there is a method of incorporating an inorganic filler (eg, glass fiber) into polyamide, but the hygroscopicity cannot be sufficiently reduced, and moreover, the appearance of some molded products is likely to be poor. Polyamide/bolyolefin blends have also been proposed, but they lack the inherent strengths of polyamides, such as impact resistance and heat resistance. Also, Boriamite/Borio 1/
Fin/mineral filler formulations are also known, or plastic articles from these formulations have reduced heat resistance. Furthermore,
Even among modified polyamides, there is no material that has sufficiently improved hygroscopicity. In addition, the four types of compounds mentioned above are treated with flame retardant treatment (
For example, in these flame retardant formulations, decomposition and deterioration during kneading, generation of off-flavors, and bleeding of the flame retardant occur.

Therefore, an object of the present invention is to provide a polyamide-based resin material for use in low-hygroscopic plastic products, which eliminates the above-mentioned drawbacks.

[Several Steps to Solve the Problems] According to the present invention, polyamide 18-74% by weight, thermoplastic polyester 5-40%, ma-shaped S
It contains 10 to 40% by weight of a mechanical filler, 10 to 30% by weight of a brominated flame retardant, and 1 to 10% by weight of an inorganic flame retardant aid, and the blending ratio of the polyamide and the thermoplastic polyester is 9/1 by weight. This can be achieved by a thermoplastic composite resin composition characterized in that the temperature is 5/5.

The composite of the present invention contains 18 to 74% by weight of polyamide, preferably 20 to 70% by weight, particularly preferably 25 to 45% by weight.
Contains % by weight. If the polyamide content is less than 18% by weight, it is impossible to obtain the strength (impact resistance, bending strength, etc.) that is the advantage of polyamide, and discoloration is likely to occur during display. When the content exceeds 74% by weight, the strength decreases, the flame retardance decreases, the water absorption rate increases, and the dimensional change upon water absorption increases.

Examples of boriamite include 6-nylon, 6,6-
Nylon, 12-nylon, 4,6-nylon or mixtures thereof can be used. The polyamide used in the present invention preferably has an intrinsic viscosity of 3.0 dl/g or less. When using a material with an intrinsic viscosity greater than 3.0 dl/g. During kneading, the torque increases, which may break the fibrous inorganic filler (eg, glass fiber) and deteriorate the physical properties of the shaped product.

The content of thermoplastic polyester is 5-40% by weight,
Preferably it is 8 to 35% by weight, particularly 8 to 25% by weight. If the content is less than 5% by weight, the illt impact strength and bending strength will decrease, and if it exceeds 40% by weight, the bending strength will decrease and the discoloration will increase when forming.As a thermoplastic polyester, the intrinsic viscosity It is preferable to use one with a concentration of 0.8 dl/g or less. If a material with an intrinsic viscosity greater than 0.8 dl/g is used, the physical properties of the shaped product will deteriorate. Examples of thermoplastic polyesters include polyethylene terephthalate and polybutylene terephthalate (PBT).
．． Alternatively, these copolymers or mixtures thereof can be used.

The content of the fibrous inorganic filler is 10 to 40% by weight, preferably 13 to 115% by weight, particularly 25 to 30% by weight. When the content is 10% by weight, the bending strength becomes low and the dimensional change upon water absorption becomes large. If the content exceeds 40% by weight, the impact strength will decrease and the shapeability will also decrease. As the fibrous inorganic filler, it is preferable to use a glass material having a fiber diameter of 5 to 15 pm. The sizing agent for glass ma is not particularly limited, but epoxy-based or urethane-based polymers are suitable. The content of the brominated flame retardant is 10 to 30% by weight, preferably 15 to 25% by weight. If the content is less than 10% by weight, sufficient flame retardancy will not be obtained, and if it exceeds 30% by weight, impact strength will decrease. As the brominated flame retardant, it is preferable to use a bromine-containing aromatic compound or the like.

The content of the inorganic flame retardant aid is 1 to 10%, especially 2 to 8%.
Weight%. If the content is less than 1% by weight, sufficient flame retardance will not be obtained, and if it exceeds 10% by weight, it will easily discolor when molded.It is preferable to use antimony trioxide as the inorganic filler, and especially if the surface is coated with silane. Preferably, the particles are treated or titanated and have a particle size of Igm or less. If the surface is not treated, discoloration and changes in physical properties occur during cutting.

The coulometric ratio of polyamide and thermoplastic polyester is 9
/1 to 5/5, preferably 5/1 to 3/2.

If the weight ratio is lower than 5/5, discoloration is likely to occur during prescribing, and if it exceeds 9/1, the prescribing performance becomes poor.

In addition, in the assembly R & product of the present invention, the content of each of the above five essential components is 5! ! This is based on the total weight of only the ingredients (excluding the following additives that may be added if necessary).

Optionally, known additives such as antioxidants, process stabilizers, colorants, lubricants, etc. may be added to the composition of the present invention. The blending amount of these additives is 0.5 to 0.5% by weight based on the total weight of the composition. The composition of the present invention can be prepared by uniformly mixing the above-mentioned five essential components and optionally an additive, and kneading and granulating the mixture in advance using a single-screw or twin-screw extruder, or The mixture may be mixed uniformly and directly subjected to molding. Moreover, these molding ingredients can be added in any order.

The composite of the present invention can be made into a shaped article by using any known shaping method for thermoplastic resins (for example, injection molding method, extrusion molding method). The composite of the present invention is preferably used as a material for plastic products that require low moisture absorption and flame retardancy, and are desirable to have little dimensional change or deterioration in physical properties upon water absorption. For example, it can be used in telecommunication equipment (particularly connectors, switches, relay cases), electromechanical equipment, and automobile parts and accessories.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples. However, these do not limit the scope of the present invention. In each of the Examples and Comparative Examples below, a composite material was prepared with the ingredients and compounding ratios shown in each table, and an antioxidant (marked AO- [10: Adeca Argus) 0.3 1ffi and process stabilizer (
PEP-24C: Adeca Argus) 0.1 weight carbonate was added, and after kneading and extrusion at 270 to 290°C, a pellet was prepared by strand cutting. Sample pieces for physical property tests were prepared using Nissei Jushi Kogyo Co., Ltd.

In addition, unless otherwise specified, the ingredients of the composition are as follows:
The following materials were used. In addition, the numerical values in each table are weight %.

Boryamide: 6.6-nylon ((:M3007:
Toray) Polyester: Polyethylene terephthalate glass mta: Glass fiber using epoxy sizing agent (fiber diameter: 10 ALm) Flame retardant: Brominated aromatic compound (brominated polystyrene: bromine aa$) Flame retardant aid: Surface silane treated trioxide Antimony (particle size: 0.5 to 0.7 μm) Matte silver (The physical properties of the sample pieces described above were evaluated by the following methods.

Impact resistance strength: Evaluated by Izod impact test according to AST@D-256 (Unit: Kg-cm"). The values in brackets in each table are those at the time of water absorption (described later).

Bending strength: Evaluated according to ASTM D-790 (unit: 2κg-CI12) The values in brackets in each table are those at the time of water absorption (described later). Water absorption rate: A dry sample piece was immersed in warm water at 40°C for 24 hours (this is referred to as the time of water absorption), and evaluated by the change in weight compared to the time of absolute dryness (unit: 2). Dimensional change upon water absorption: A sample piece of aox aox 2+*s was evaluated based on dimensional change in the TD direction between absolute dryness and water absorption (unit = 2). Retained color: After a cycle consisting of 1 second of injection and 5 minutes of cooling was repeated three times, the change in color of the sample piece was visually evaluated on the following three scales.

No change...○ Machiishi Kuishinentrust 8! Discoloration throughout the field... × Fuel quality: IIL-! Evaluated based on +4 fuel test method. Formability: The lowest value of injection gauge pressure measured when filling a certain material into an injection molding machine (unit: Kg/c!l2.G).
Evaluated by.

Examples 1 to 4 and Comparative Examples 1 and 2 As shown in Table 1, the boliacid content was varied in 6 steps from 15% by weight to 80% by weight, and the contents of other components were changed accordingly. Sample pieces were prepared and their physical properties were evaluated. The results are shown in Table 2.

[Hereinafter, blank spaces] Table 1 Table 2 (M! Ki) As is clear from Tables 1 and 2 of Table 2, the combination J & product manufactured by the tree invention exhibits excellent physical properties in all of the measured items. On the other hand, when the content of Boriamic 1 is small and the Boriamic/polyester weight ratio is less than 1, the resistance to! 1
Impact strength and bending strength decrease, and discoloration occurs (Comparative Example 1)
). In addition, if the polyester content is high and the flame retardant content is low, the bending strength decreases, the dimensional change upon water absorption and the water absorption rate increase, and the flame retardance decreases (Comparative Example 2). ). Examples 5 to 7 and Comparative Examples 3 and 4 As shown in Table 3, the polyester content was varied from 3% to 45%, and the content of the pond components was changed accordingly. Sample pieces were prepared and their physical properties were evaluated. Ayuka is shown in Table 4. For convenience of comparison, the results of Example 2 are also shown.

Table 3 Table 4 Table 4 (Continued) [Hereinafter, as is clear from Tables 3 and 4 in the margin, the T & product set according to the present invention exhibits excellent physical properties in all of the measured items 1. On the other hand, if the polyester content is low,
191 strength and bending strength decrease (Comparative Example 3). In addition, when the polyester content is high and the polyamide content is low, the bending strength decreases, and the entire shaped product (comparative example 4) shows discoloration. As shown, the miscellaneous content of glass is O weight g.1%
to 501'[(il%), and the contents of other components were changed accordingly to prepare sample pieces and evaluate their physical properties.The results are shown in Table 6. For convenience, the results of Example 3 are also shown.

Table 5 ffi Table 6 Table 6 (Continued) As is clear from Tables 5 and 6, the IJI composite material of the present invention exhibits excellent physical properties in all of the measured gauges. On the other hand, if glass fiber is not included, the 1ilI strength decreases and the dimensional change upon water absorption becomes large (Comparative Example 5)
). Moreover, when the glass am content is high, the Iff resistance strength decreases and the shapeability decreases (Comparative Example 6).

10 and Comparison 7 and 8 As shown in Table 7, the flame retardant content was increased from 5% by weight to 35% by weight.
Sample pieces were prepared by varying the content of other components up to 1%, and their physical properties were evaluated. The results are shown in Table 8. For convenience of comparison, the results of Example 2 are also shown. Table 7 Table 8 Table 8 (Continued) [As is clear from Tables 7 and 8 below, the composite made by IJ of the present invention exhibits excellent physical properties in all of the measured items. On the other hand, if the flame retardant content is too low, sufficient flame retardancy cannot be obtained (Comparative Example 7).

Also, as the content increases, the impact strength decreases. (Comparative Example 8). Example 1l and Comparative Examples 9 and 10 As shown in Table 9, the content of flame retardant aid was 0.5% by weight.
Sample pieces were prepared by varying the polyamide and/or polyester content from 1% to 1% to 1%, and their physical properties were evaluated. The results are shown in Table 10. For convenience of comparison, the results of Example 2 are also shown. Table 9 W410 Table io (Continued) [Hereafter, blank spaces] As is clear from Tables 9 and 10, the composite of the present invention exhibits excellent physical properties in all measurement items, whereas If the content of the flame retardant auxiliary agent is less than 111, sufficient flame retardancy cannot be obtained (Comparative Example 9), and if the content is too large, residual color appears and the l&formability deteriorates (Comparative Example 10).

Examples 12 to 15 and Comparative Examples 11 and 12 As shown in Table 11, sample pieces were prepared with varying weight ratios of polyamide and polyester, and their physical properties were evaluated. The results are shown in Table 12. Table 11 Table 12 (Continued) (Note) The numbers in brackets in the columns of bolyamide and polyester indicate the relative proportions of both.

[Hereafter, blank space] As is clear from Tables 11 and 12, the composition of the present invention exhibits excellent physical properties in all measurement items, but as the air volume ratio of polyester to polyester increases, the water absorption rate decreases. The top moldability deteriorates (Comparative Example 11), and as the weight ratio decreases, retained color appears (Comparative Example 1).
2). As shown in Table 13, sample pieces according to the present invention were prepared using a polyester mixture and the mixing ratio was varied, and their physical properties were evaluated. As shown in Table 14. To,
It showed excellent physical properties in all measured items. In addition,
Polyester mixtures include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
) (N1300L: Teijin> was used. [Hereafter, margins] Table 13 Table 13 (Continued) [Below, margins] Table 14 Table 14 (Continued) Sharp 12 Yu: Use 2 Ldan Sample pieces were prepared by repeating the procedure of Example 2, except for changing the type of polyamide, and their physical properties were investigated. As shown in Table 15, all measurements q4
It showed excellent physical properties regarding eyes. In addition, as boryamide, tonylon (81Q221
1R: Unitika) Example 22>, 4.6-nylon (FSOOO: Unitika) Example 23>, 12-nylon (EMS L-15: EMS Co., Ltd.) Example 2
4>, the above-mentioned 5-nylon and 5.6-nylon (CM3
007: Toray) (Intrinsic viscosity - 2.8 cil/g)
1=1 mixture with <Example 25>, and the above 6.6-
A l=1 mixture of nylon and 4,S-nylon was used. [Hereafter, blank space] Table 15 Table 15 (Continued) When we investigated their physical properties, as shown in Table 16,
It showed excellent physical properties in terms of all measured pull marks.
As the polyester, copolymerized PET (26SE: Kuraray) (intrinsic viscosity -0.80 dl/g) <Example 27>
A 1:1 mixture of the copolymerized PET and the polyethylene terephthalate used in Example 2 (Example 28) was used.

Table 16 A sample piece was prepared by repeating the operation of Example 2, except for changing the type of polyester used, and a sample piece was prepared by repeating the operation, except for changing the type of glass fiber used, When their physical properties were investigated, as shown in Table 17, they showed excellent physical properties in all measurement items. In addition, the glass fibers include glass fiber m < fiber diameter = l [l end -><Example29> using a urethane-based sizing agent and glass fiber using an epoxy-based sizing agent (fiber diameter = 6 gm).
) <Example 30> was used.

When the physical properties of Table 17 and others were investigated, as shown in Table 18, surface titanate-treated antimony dioxide (particle size = 0.5-0,
The composition of the present invention, Example 31, using 7 rue> showed excellent physical properties with respect to all measurement items. In the composition (Comparative Example 13), a retained color appeared. Table 18 Table 17 (continued) Table 18 (continued) Example 2 except for changing the type of flame retardant aid used.
A sample piece was prepared by repeating the above procedure, and the flame retardant was decabromodiphenyl ether (bromine content 83%) (Comparative Example 14) and an organochlorine compound 9i (Techloranbras: Hooker Chemicals Antoplastics, Inc., USA).
(a! Elementary content 65%) When the operation of Example 2 was repeated except for using <Comparative Example tS>, none could be molded. [Effects of the Invention] Plastic products molded from the assembly of the present invention have an extremely low water absorption rate (less than half that of conventional flame-retardant Boriat-based products), and are free from dimensional changes and physical property deterioration due to water absorption. small. Furthermore, it has excellent flame retardancy, and there is no odor caused by the decomposition of the flame retardant, and there is no bleat in certain shapes. Furthermore, since it can be molded at a low temperature, there is less thermal deterioration within the cylinder and less color change in the molded product. Furthermore, since it has good fluidity, it can be made into a thin wall and has excellent high cycle performance.

Claims (1)

[Claims] Polyamide 18-74% by weight, thermoplastic polyester 5
~40% by weight, 10-40% by weight of fibrous inorganic filler, 10-30% by weight of brominated flame retardant, and 1-10% by weight of inorganic flame retardant aid.
% by weight, and the blending ratio of the polyamide to the thermoplastic polyester is from 9/1 to 5/5 by weight.