KR890004333B1 - Composition of thermoplastic resin - Google Patents

Abstract

Fire retardant thermoplastic resin for metal plating or coating is composed of (A) 10-80 parts graft copolymer of styrene or α -methyl styrene, acrylonitrile and butadiene, (B) 5-50 parts copolymer of styrene or α -methyl styrene and acrylonitrile, (C) 20-80 parts polycarbonate [I; R1, R2=H, C1-6 alkyl, phenyl; n=40-300 , (D) 1-30 parts block copolymer of styrene or α -methyl styrene and butadiene or isoprene or olefinic resin, (E) 1-20 parts fire retardants such as decabromodiphenyl oxide, octabromodiphenyloxide, brominated epoxy, (F) 1-20 parts antimontrioxide, (G) 0.05-5 parts maleic acid and (H) 0.05-5 parts polydimethylsilane.

Description

Thermoplastic resin composition

The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition for plating excellent in flame retardancy.

In recent years, in accordance with the trend of high quality and light weight products, in the plastic field, parts that require flame retardancy and metal plating or metal coating are rapidly increasing in the plastic field. Until now, no plating resin has been developed, which has been imparted with flame retardancy, thus simplifying spraying of flame retardant resins, die casting of metals, EMI shielding, etc., but these have the following problems.

First, simplified spray of flame-retardant resin: Up to now, ABS resin is mainly used, but expensive imported resin should be used for parts requiring mechanical and thermal properties. Not only is it worse than the appearance of this plated product, but also the adhesion of the resin is not good, and the sprayed metal comes off when used for a long time.

Second, die casting of metals: manufacturing costs are expensive and heavier than plastics.

Third, EMI shielding: It is currently under development to give plastic conductivity but it is poor in processability, so it is not only difficult for general injection, but also due to the inhalation of metal flake, mechanical strength such as impact resistance, surface condition and appearance are poor, and flame retardancy A large amount of flame retardant is required for the grant.

On the other hand, in the manufacture of the resin for plating, in order to increase the adhesion of the plating, the rubber content in the resin adjustment should be high, but when the rubber content is increased, the flame retardancy is worsened, and the viscosity is increased in the molten state, thereby causing problems in injection molding. Cause, and no suitable product has been developed.

The present inventors have steadily researched to solve the above problems, in order to solve the problems of mechanical and thermal properties of the universal plating resin, polycarboate resin and ABS (Acrylonitrile-Butadiene excellent in mechanical and thermal properties) -Styrene resins are mixed to improve the mechanical and thermal properties to solve the problem of spray appearance, poor adhesion, heavy casting problems, and expensive plastic plating problems. In addition, in general, in view of the fact that the flow of the resin greatly influences the plating property, the resin composition of the present invention uses a block copolymer having a low molecular weight to lower the melt viscosity, thereby greatly improving the moldability, thereby providing excellent plating properties of the final resin. It can be applied to large molded products and precision parts. Flame retardant imparting to the resin for plating, by adding a diene-type rubber to maintain a good plating adhesion, while using a flame retardant selected by using a flame retardant, it can be found that a thermoplastic resin composition excellent in plating properties, flame retardancy and melt flowability The invention was completed.

That is, this invention provides the thermoplastic resin which has each component of following (A), (B), (C), (D), (E), (F), (G), (H) as a main component.

(A) Aromatic monoalkenyl monomers and one or more monomers selected from vinyl cyan monomers and / or alkyl ester monomers of acrylic acid or methacrylic acid are subjected to bulk, suspension or emulsion polymerization in the presence of a diene rubber component. 10-80 parts by weight of the graft copolymer obtained, (B) an aromatic monoalkenyl monomer and one or more monomers selected from vinyl cyan monomer and / or alkyl ester monomer of acrylic acid or methacrylic acid are bulked, suspended or 5-50 parts by weight of the copolymer obtained by emulsion polymerization, (C) 20-80 parts by weight of polycarbonate, (D) block obtained by bulking, suspending or emulsion polymerizing a diene rubber component or an olefin resin with 1-30 parts by weight of the copolymer (A), (B), (C) the resin composition, (E) an organic or polymer containing one or more halogen elements 1-20 parts by weight based on 100 parts by weight of the (A), (B) and (C) resin compositions of the softener or a mixture thereof, and (F) the antimony trioxide (A), (B), (C) 1-20 parts by weight based on 100 parts by weight of the composition, (G) at least one acid compound selected from inorganic acids, organic acids or organic acid anhydrides is 0.05- to 100 parts by weight of the (A), (B), (C) resin composition 5 parts by weight, 0.05-5 parts by weight of (H) the organo-silicon compound, based on 100 parts by weight of the above (A), (B) and (C) resin compositions.

The graft copolymer of component (A) used in the present invention can be prepared by bulk, suspension, emulsion polymerization or a mixture thereof. For example, in the emulsion polymerization method of the ABS resin, butadiene is first polymerized to form polybutadiene latex, and then vinyl cyan monomer and styrene or α-methyl styrene monomer are added to graf the polybutadiene and these monomers to multicomponent components. To prepare a polyphase ABS resin. At this time, the composition ratio of each component can be arbitrarily adjusted by adding the remaining monomer to the polybutadiene latex.

Examples of the rubber component used in the graft copolymer include butadiene rubber and isoprene rubber, and the amount of the graft copolymer is 10-70 parts by weight, preferably 20, based on the graft copolymer weight ratio of the component (A). It is -50 weight part, and the particle diameter of rubbers is 0.01-1.5 micrometer, Preferably it is 0.1-0.5 micrometer.

Examples of aromatic monoalkenyl monomers include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, halogen chiwan styrene, or mixtures thereof, and preferably styrene, α-methylstyrene, or mixtures thereof. -70 parts by weight may be used.

As an example of a vinyl cyan monomer, acrylonitrile, methacrylonitrile, (alpha)-chloro acrylonitrile, etc. are mentioned, Preferably 15-35 weight part of acrylonitrile can be used. In addition, the vinyl monomers copolymerizable with the above two types of monomers may be used in the same amount.

As an example of such a monomer, vinyl monomers, such as maleimide, N-substituted maleimide, an alkyl acid ester, methacrylic acid ester, an alkyl acid, methacrylic acid, are mentioned. In the present invention, the graft copolymer of component (A) thus produced is used in an amount of 10-80 parts by weight, preferably 20-50 parts by weight. The copolymer of (B) component can be manufactured by bulk suspension, emulsion polymerization, or the mixing method like the case of (A) component.

As the aromatic mono alkenyl monomer, vinyl cyan monomer, and vinyl monomer copolymerizable therewith, the same as those used in the production of component (A) can be used, and the amount of the aromatic monoalkenyl is used. 60-80 parts by weight of the monomer and 20-40 parts by weight of the vinyl cyan monomer are used. The copolymer of component (B) thus produced is used in an amount of 5-50 parts by weight, preferably 10-50 parts by weight.

It is as follows of the general formula of the polycarbonate of (C) component.

In the above formula, A is a component having an aromatic radical at both ends of the dihydric phenol, and the specific formula is as follows.

(Wherein R1 and R2 are hydrogen, an alkyl group or a phenyl group, the carbohydrate in the alkyl group is 1-6, and the n value is an integer of 40-300.)

As the polycarbonate, an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, or the like can be used. More specifically, 2,2-bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) ether Polymers or copolymers of bisphenols or halogenated bisphenols such as bis (4-hydroxyphenyl) sulfoxide may be used.

Polycarbonate resins as described above are disclosed in the Federal Republic of Germany Patent No. 1546311 and 962274, US Patent Nos. 3248414, 3251668, 3187065, 3028365, 2999846, 2964974, 2970137, 2991273, 2999835, 3334154, 4131575 and 4001843 It can be prepared in the same manner, and examples of the representative polycarbonate resin are Encyclopedia of Polymer Science and Technology Vo1. 10, pages 710-764 (1969). The polycarbonate resin of this component (C) is used 20-80 parts by weight, preferably 30-70 parts by weight. When the polycarbonate resin is used in an amount of 20 parts by weight or less, or in an amount of 80 parts by weight or more, it is impossible to exhibit the characteristics of the resin composition as described above.

The block copolymer of component (D) may be prepared by bulk, suspension, emulsion polymerization or a mixing method thereof. Examples of aromatic monoalkenyl monomers used in the preparation of such block copolymers include styrene, α-methylstyrene, Vinyltoluene, halogen-substituted styrene, or a mixture thereof. Examples of the diene rubber and olefin resin include butadiene, isoprene, ethylene, propylene, and the like. Specifically, the block copolymer of the above-mentioned component (D) is a block copolymer such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylenebutylene-styrene, and the amount of use thereof is (A), ( B), (C) 1-30 parts by weight, preferably 3-20 parts by weight based on 100 parts by weight of the resin composition.

Organic or polymeric flame retardants containing halogen elements and antimony trioxide, which are the components (E) and (F), cannot be expected to have a large flame retardant effect when used alone, and excellent flame retardance is obtained by mixing these components simultaneously. Effect.

Examples of the organic flame retardant which is the component (E) of the present invention include halogens such as 1,2-bis- (2,4,6-tribromophenoxy) -ethane, decabromo diphenyloxide, octabromo diphenyl oxide, and the like. Aromatic organic flame retardants comprising an element or mixtures thereof, and aliphatic organic flame retardants comprising halogen elements such as 2,2-bis (3,5-dichlorophenyl) propane, bis (2,6-dibromophenyl) methane and the like And polymers such as cyclic aliphatic organic flame retardants containing halogen elements such as bis (3,5-dichlorophenyl) cyclohexyl methane and the like, polydibromo phenylene oxide, brominated epoxy bromine polycarbonate oligomers, and the like. Flame retardants and the like. Preferably aromatic organic flame retardants or polymer flame retardants may be used. 5-30 weight part of the usage-amount is used with respect to 100 weight part of said (A), (B), and (C) resin composition. If the amount of the flame retardant is less than 5 parts by weight, it is difficult to expect the flame retardant effect of the resin composition, and if the amount of the flame retardant is more than 30 parts by weight, there is a sudden decrease in physical properties and the manufacturing cost is high and there is no economy.

The usage-amount of antimony acid oxide which is (F) component is 1-20 weight part with respect to 100 weight part of said (A), (B), and (C) resin composition, Preferably 3-10 weight part is used.

The at least one acid compound selected from the inorganic acid, the organic acid or the organic acid anhydride, which is the component (G), is used to increase the retention thermal stability during processing of the resin composition of the present invention. 58-11550 and US Pat. No. 42,999,29.

Examples of such an acid compound include maleic acid, butyric acid, maleic anhydride, and butyric anhydride, and the amount of its addition is used in an amount of 0.05-5 parts by weight based on 100 parts by weight of the resin compositions (A), (B) and (C). do. When the amount of use is less than 0.05 part by weight, the retention heat stability of the resin composition cannot be expected to increase, and when the amount of use is more than 5 parts by weight, the heat resistance of the resin composition is greatly reduced.

As an organo-silicon compound which is (H) component, the polysiloxane represented by the following general formula, or the silane of R1R2R3R4Si etc. can be used.

In the above, R 1 -R 4 is a lower alkyl or alkyl group and m is an integer of 1-2000. As a specific example of these compounds, polymetal ethylsiloxane, tetraethylsilane, etc. are mentioned. The addition amount thereof is 0.05-5 parts by weight, preferably 0.5-2.5 parts by weight based on 100 parts by weight of the resin compositions (A), (B) and (C).

If the amount of use is less than 0.05 parts by weight, no increase in low-temperature properties can be expected. If the amount of use is more than 5 parts by weight, other physical properties are greatly reduced.

The resin composition of the present invention composed of the main components as described above, according to the purpose of use, by adding an appropriate amount of additives such as lubricants, antioxidants, ultraviolet stabilizers, thermal stabilizers, processing aids, mold release agents, foaming agents, antistatic agents, pigments, dyes The resin composition of the invention can be further diversified.

In addition, in order to prevent the fall of the flame during the flame retardant test of the flame retardant resin composition, the resin of the present invention is added by adding polytetrafluoroethylene or thermoplastic phenoxy resin usable for this purpose as disclosed in US Pat. No. 4,355,126. The composition may exhibit a spark fall prevention effect.

Hereinafter, the present invention will be described in more detail according to its embodiments.

Preparation of Basic Components Example 1), Preparation of Graft Copolymer (A): 100 parts by weight of butadiene, a diene rubber component, 120 parts by weight of ion-exchanged water, 0.2 parts by weight of sodium lauryl sulfate in a closed-string reactor 0.2 parts by weight of dodecyl mercaptan was added, and 0.1 parts by weight of potassium persulfate was added at a reactor temperature of 40 ° C to polymerize for 15 hours to obtain polybutadiene latex. 40 parts by weight of the polybutadiene latex, 100 parts by weight of ion-exchanged water, 45 parts by weight of styrene as an aromatic monoalkenyl monomer, 15 parts by weight of acrylonitrile as a vinyl cyan monomer, 0.3 part by weight of sodium lauryl sulfate and t-dode 0.3 parts by weight of sil mercaptan was added and polymerized at a reactor temperature of 100 ° C. for 2 hours to obtain a graft copolymer. The graft copolymer thus obtained is referred to as "ABS-1".

In addition, 50 weight part of said polybutadiene latex, 0.3 weight part of sodium lauryl sulfate, 100 weight part of ion-exchange water, 15 weight part of (alpha) -methylstyrenes which are aromatic monoalkenyl monomers, 25 weight part of styrene, and a vinyl cyan monomer 10 parts by weight of phosphorus acrylonitrile and 0.1 parts by weight of t-dodecyl mercaptan were added to the reactor and polymerized at a reaction temperature of 90 ° C. for 2 hours to obtain another graft copolymer. The graft copolymer thus obtained is referred to as "ABS-2".

Preparation Example 2 of the basic component, Preparation of the copolymer (B): 100 parts by weight of ion-exchanged water, 75 parts by weight of styrene as an aromatic monoalkenyl monomer, 25 parts by weight of acrylonitrile as a vinyl cyan monomer, in a closed reactor 0.3 parts by weight of sodium lauryl sulfate and 0.3 parts by weight of t-dodecyl mercaptan were added, and the mixture was polymerized at a reactor temperature of 100 ° C. for 2 hours to obtain a copolymer. The copolymer thus obtained is referred to as "SAN".

Example 1

30 parts by weight of the graft copolymer "ABS-1" prepared in Preparation Example 1 of the above-mentioned basic component, 20 parts by weight of the copolymer "SAN" prepared in Preparation Example 2 of the basic component, polycarbonate resin (Teijin Kasei Product: Panite L-12Y) 50 parts by weight, block copolymer (KRATON D-4222, manufactured by SHELL, USA) 5 parts by weight, 16 parts by weight of organic flame retardant, tecbromodiphenyl oxide, 5 parts by weight of antimony trioxide In addition, a resin mixture composed of 0.3 parts by weight of maleic acid as a thermal retention stabilizer, 1.0 parts by weight of polydimethylsiloxane for low temperature properties, 0.2 parts by weight of ethylene bissteamide and 0.5 parts by weight of a heat stabilizer as a lubricant was subjected to a Henschel mixer. After uniform mixing for 5 minutes, the resultant was extruded using an extruder at a temperature of about 230 ° C. to 260 ° C., and then pelletized. To measure the toxic properties, plating adhesion, flame retardancy, and physical properties by ASTM property test method, the pellets were pre-dried at 110 ° C. for about 3 hours using a dehumidifying dryer or a hot air dryer. Measured in the same manner.

a) Toxic properties: Melt viscosity was determined by Instron capillary rheometer (Rheomter) at 250 ° C and 352.2 Sec ^-1 shear rate.

b) Flame retardancy test: Example 1) Forming a flame retardant specimen (1/2 "x5" x1 / 16 ") using a 2.5 ounce injection machine to produce pellets in accordance with UL-94 vertical flame retardancy test. And V-0, V-1, and V-2 determination methods.

c) Coating Adhesion Test: The pellet of Example 1) was tested by molding a test specimen for plating adhesion test (4 "x3" x1 / 8 ") using an injection machine as in ASTM B 533-70 method.

d) Physical property test: The pellets of Example 1) were tested by using a 2.5-ounce injection machine to make tensile strength, impact strength, and heat deflection temperature test specimens according to ASTM specification.

Plating order

: 알칼리 성분의 계면활성제 용액으로 70℃, 10분간 처리

: Treatment with alkaline surfactant solution at 70 ° C for 10 minutes

: 황산-무스크롬산 혼합물로 70℃, 10분처리

: Sulfuric acid-chromic acid mixture at 70 ℃ for 10 minutes

: 염산 수용액에서 2분간 처리

: 2 minutes treatment in aqueous hydrochloric acid

: 염화팔라듐과 염화제 1주석의 수용액으로 40℃, 5분간 처리

: Aqueous solution of palladium chloride and stannous chloride solution at 40 ℃ for 5 minutes

: 황산수용액으로 55℃에서 3분간 처리

: Treatment with sulfuric acid aqueous solution at 55 ℃ for 3 minutes

:황산구리용액, 황산니켈용액으로 화학구리 및 니켈도금처리

: Copper and nickel plating treatment with copper sulfate solution and nickel sulfate solution

Electroplating: Electroplating-Electronickel Plating-Electrochrome Treatment

After plating in the above-described plating sequence, cut at 1 "intervals as in the AVTM B533-70 method, and a Pellirelgram on UTM of Instron

TABLE 1

* Plating Adhesion Test: ASTM B 533-7

(Parausek gram) was attached and the adhesion test of the plating surface was done. The above test results are shown in Table 1.

Example 2

In order to observe the effect of component D) used in the present invention, 4 parts by weight of block copolymer (KRATON D-4222) was further added to the composition of Example 1. After extrusion and injection molding in the same manner as in Example 1, fluidity, flame retardancy, and plating adhesion were tested, and the results are shown in Table 1.

Example 3

In the component composition of Example 2, 60 parts by weight of polycarbonate, 25 parts by weight of "ABS-1", 15 parts by weight of "SAN", and 16 parts by weight of octabromodiphenyl oxide as a flame retardant, decabromo di Except for using instead of phenyl oxide, the same composition as in Example 2 was used, and the test was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example 4

3 parts by weight of a block copolymer (KRATON D-4222) was further added to the component of Example 3, and the test was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example 5

In the component composition of Example 3, the amount of polycarbonate resin was changed to 30 parts by weight, 24 parts by weight of "ABS-2" instead of "ABS-1", and the amount of "SAN" was changed to 46 parts by weight, and the present invention The same composition as in Example 3 was used as a block copolymer of component (D), except that a copolymer of another component (KRATON D-1652, manufactured by SHELL, USA) was used instead of the copolymer (KRATON D-4222). The test was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example 6

3 parts by weight of a block copolymer (KRATON D-1652) of the component of Example 5 was further added, and the test was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example 7

Preparation of the basic component 20 parts by weight of the graft copolymer "ABS-2" prepared in Example 1), 40 parts by weight of the copolymer "SAN" prepared in Preparation Example 2) of the basic component, polycarbonate resin 40 Parts by weight, 3 parts by weight of a block copolymer (KRATON D-1652), 16 parts by weight of brominated epoxy, a polymer flame retardant, 5 parts by weight of antimony trioxide, maleic acid, 0.3 parts by weight, 1.0 parts by weight of polysiloxane, ethylene bis steamide Table 1 shows the results of mixing, extruding, drying, and injection in the same manner as in Example 1 by mixing 0.2 parts by weight and 0.5 parts by weight of other stabilizers.

Example 8

4 parts by weight of a block copolymer (KRATON D-1652) was further added to the composition of Example 7, the test was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1

In order to investigate the influence of the polycarbonate resin content on the mechanical and thermal properties of the composition, in the composition of Example 1, the amount of polycarbonate used was changed to 20 parts by weight, "SAN" to 40 parts by weight, and the remainder was the same composition. , Mechanical and thermal properties were measured by the ASTM test method and the results are shown in Table 2 compared with Example 1.

Comparative Example 2

While processing the resin composition of the present invention, except for maleic acid in the composition of Example 1 for coastal qualitative measurement at the time of residence in the cylinder, the remainder was made in the same manner as in Example 1 to make a resin composition and heat Stability measurement was performed at 270 ° C. using a Proer tester (Flower tester, SPIRALTYPE), and the resin was poured into a cylinder at 260 ° C. and held for 5 minutes, followed by injection molding. Table 3 shows the result of the measurement.

Comparative Example 3

Except for the block copolymer of the component composition of Example 2 to observe the effect of the component D) used in the present invention, the test was carried out in the same manner as in Example 1 with the remainder the same and the results are shown in Table 4. .

Comparative Example 4

Of the component composition of Example 6, except for the block copolymer, the rest was prepared in the same composition, and then the composition was tested in the same manner as in Example 1, and the results are shown in Table 4.

Comparative Example 5

Of the component composition of Example 8, except for the block copolymer, the remainder was prepared in the same composition, and then the composition was tested in the same manner as in Example 1, and the results are shown in Table 4.

Comparative Example 6

Among the component compositions of Example 1, except for polydimethyl siloxane, the remainder was prepared in the same composition to test the effect of polydimethyl siloxane on the low temperature properties and the results are shown in Table 5.

TABLE 2

Tensile strength: ASTM D638

Impact Strength: ASTM D256 (Azod Impact Strength with Nuts)

Heat Deflection Temperature: ASTM D648 (No Annealing)

TABLE 3

As can be seen from Table 3, when a small amount of inorganic acid, organic acid, organic acid anhydride, or the like is added to the resin composition of the present invention, it can be seen that the retention thermal stability during processing is greatly increased.

TABLE 4

TABLE 5

As can be seen from the results in Table 5, it can be seen that the low impact strength was greatly increased by adding a small amount of organosilicon compound to the resin composition of the present invention.

Claims (2)

A thermoplastic resin composition composed of the following components (A)-(H). (A) 10-80 parts by weight of graft copolymer obtained by mass, suspension or emulsion polymerization of any one or more monomers of styrene or α-methyl styrene and acrylonitrile in the presence of butadiene, (B) styrene Or 5-50 parts by weight of any one or more monomers of α-methylstyrene and a copolymer obtained by bulk, suspension or emulsion polymerization of acrylonitrile, (C) 20-80 parts by weight of polycarbonate, (D) A block copolymer obtained by bulk, suspension or emulsion polymerization of any one or more monomers of styrene or α-methyl styrene with butadiene or isoprene or an olefinic resin is prepared by the above-mentioned components (A), (B), ( C) 1-30 parts by weight based on 100 parts by weight of the total, (E) organic or polymer type containing any one or more than one of decabromodiphenyl oxide, octabromodiphenyl oxide, brominated epoxy Reminding Flame Retardants (A), (B), (C) 1-20 parts by weight based on 100 parts by weight of the total weight, (F) antimony trioxide based on 100 parts by weight of the components (A), (B), (C) 1-20 parts by weight, (G) 0.05-5 parts by weight of maleic acid based on 100 parts by weight of the components (A), (B), (C), (H) the components (A), (B), ( C) 0.05-5 parts by weight of poly dimethylsiloxane relative to 100 parts by weight total. The thermoplastic resin composition according to claim 1, wherein the block copolymer is any one of styrene-butadiene-styrene, styrene-isoprene-styrene, and styrene-ethylenebutylene-styrene.