JPS6218467A - Transparent, heat-resistant thermoplastic resin composition having excellent platability - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent platability, heat resistance and transparency and useful as a material in the fields of automobile, household appliance, precision equipment, etc., by blending a thermoplastic resin consisting of an imide copolymer and a specified copolymer with a polycarbonate resin. CONSTITUTION:An arom. vinyl monomer (a), an unsaturated dicarboxylic acid imide derivative (b) (e.g. N-phenylmaleimide) and a copolymerizable vinyl monomer (c) (e.g. acrylonitrile), etc. are copolymerized in a solvent at 80-350 deg.C to obtain an imide copolymer (A) composed of 30-90% (by weight; the same applies herein below) residue of component (a), 3-7% residue of component (b) and 0-40% residue of component (c). 5-95% thermoplastic resin consisting of 10-90pts.wt. component A and 90-10pts.wt. rubbery copolymer having a number-average particle size of 200mmu or below, obtd. by grafting 30-80% arom. vinyl monomer, 0-40% vinyl cyanide monomer and 0-40% other copolymerizable monomer onto 3-7% rubbery polymer (e.g. polybutadiene) is blended with 95-5% polycarbonate resin.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermoplastic resin composition with excellent plating properties, transparency and heat resistance; %, home appliances, precision equipment, etc.

(Prior Art and its Disadvantages) A composition comprising a copolymer comprising an aromatic vinyl monomer and an unsaturated nocarboxylic acid anhydride and a polycarbonate resin has been known (Japanese Patent Publication No. 57-27133). Furthermore, for the purpose of improving the bonding strength, a composition comprising a copolymer comprising a co-modified aromatic vinyl monomer and an unsaturated socarboxylic acid anhydride and a polycarbonate resin has been proposed (Japanese Unexamined Patent Application Publication No. 1983-1999) -92950).

However, compositions of these unsaturated dicarboxylic anhydride copolymers and polycarbonate resins cannot be used at high temperatures due to the presence of acid anhydride groups resulting from the unsaturated nocarboxylic anhydride in the copolymer chain. Of course, against the water of time,
Chemical changes occur when exposed to heat, resulting in decomposition, which poses significant restrictions during injection or extrusion processing.Also, when processed products are brought into contact with water or steam or exposed to high temperatures, mechanical properties may deteriorate. There was a drawback that caused Although polycarbonate resin has excellent mechanical and thermal properties, it has been pointed out that its disadvantages include high melt viscosity, poor moldability, and poor oil resistance and hot water resistance.For example, it cannot be molded by injection molding. When manufacturing products, high injection pressure and high molding temperature are required, which causes molding distortion and thermal deterioration. Furthermore, if a molded product is immersed in oil such as gasoline or brake oil, or boiling water, cracks will occur and the strength will significantly decrease. Incidentally, in recent years, weight reduction has been promoted in the automobile field, and the replacement of metals with plastics has been actively promoted, but the reality is that plastics are not as durable as metals. Therefore, it has become common practice to plate plastics to improve their durability and give them decorative properties. However, polycarbonate resin, which is a transparent and heat-resistant resin, has the disadvantage of extremely poor plating properties.

(Means for Solving the Problems) As a result of repeated research to solve these drawbacks, the present inventor has found that
By mixing an unsaturated nocarboxylic acid imide derivative, a copolymer in which a rubber-like polymer is dispersed in a graft copolymer so that the number average particle size is 200 mμ or less, and a polycarbonate resin, a heat-resistant and transparent product can be obtained. A composition with excellent plating properties was obtained.

That is, the present invention has the following components: A component: 30 to 90% by weight of aromatic vinyl monomer residue, unsaturated radical ? 10 to 90 parts by weight of an imidized copolymer consisting of 3 to 70% by weight of phosphoric acid imide derivative residues and 0 to 40% by weight of vinyl monomer residues other than these groups, and component B: rubber-like polymer. 3 to 70% by weight of aromatic vinyl monomers, 30 to 80% by weight of vinyl cyanide monomers, and 0 to 40% by weight of vinyl monomers copolymerizable with these are graft copolymerized. 5 to 95% by weight of a thermoplastic resin containing 10 to 90 parts by weight of a copolymer in which the number average particle diameter of the rubbery polymer in the copolymer is 200 mμ or less, and C component Neelicarbonate resin. It is a transparent 1 heat-resistant thermoplastic resin composition with excellent plating properties consisting of 5 to 95% by weight.

First, the imidized copolymer of component A and its preparation method will be explained.

The first method for producing the component A copolymer includes aromatic vinyl monomers, unsaturated dicarboxylic imide derivatives, unsaturated dicarboxylic anhydride monomers, and vinyl monomers copolymerizable with these. A method of copolymerizing a mixture, the second production method is a polymer obtained by copolymerizing an aromatic vinyl monomer, an unsaturated nocarboxylic acid anhydride, and a vinyl monomer mixture copolymerizable with these. 0.8 for acid anhydride group
Examples include a method of converting an acid anhydride group into an imide group by reacting with 1.05 molar equivalents of ammonia and/or a primary amine, and an imidized copolymer can be obtained by any of the methods.

Aromatic vinyl monomers used in the first production method of component A copolymer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, and substituted monomers thereof. Of these, styrene is particularly preferred.

As unsaturated dicarboxylic acid imide derivatives, maleimide,
N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N
-Maleimide derivatives such as hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide, N-inglobylmaleimide, N-methylitaconic acid imide, itaconic acid imide derivatives such as N-phenyl itaconic acid imide, and the like, and among these, N-phenyl maleimide is particularly preferred.

As the unsaturated nocaldic acid anhydride, anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic acid anhydride are particularly preferred.

Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, and acrylic ester monomers such as methyl acrylate and ethyl acrylate. , methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, and methacrylic acid amide. Among these, acrylonitrile, Monomers such as methacrylic acid ester, acrylic acid, and methacrylic acid are preferred.

Further, as the aromatic vinyl monomer, unsaturated dicarboxylic acid anhydride, and vinyl monomer copolymerizable with these used in the second production method, those used in the first production method can be used.

In addition, ammonia and primary amines used in the imidization reaction may be in either an anhydrous or aqueous solution state, and examples of primary amines include methylamine, ethylamine,
Alkylamines such as butylamine and cyclohexylamine, chloro- or bromine-substituted alkylamines thereof, aromatic amines such as aniline, tolylamine, naphthylamine, and halodane-substituted aromatic amines such as chloro- or bromine-substituted aniline are mentioned.

Furthermore, when the imidization reaction is carried out in a solution or suspension state, it is preferable to use an ordinary reaction vessel such as an autoclave, and when carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used. good. Further, a catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is about 80 to 350°C, preferably 100 to 300°C.

If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer.

The solvent for imidization in a solution state includes acetone, methyl ethyl ketone, methyl iso/tyl ketone, acetophenone, tetrahydrofuran, dimethylformamide, etc. Among these, methyl ethyl ketone and methyl isobutyl ketone are preferred. Non-aqueous media for imidization in suspension in non-aqueous media include aliphatic hydrocarbons such as hebutane, hexane, pentane, octane, 2-methylpentane, cyclopentane, and cyclohexane.

The component A polymer contains 30 to 90% by weight of aromatic vinyl monomer residues, preferably 40 to 70% by weight, and 3 to 70% by weight of unsaturated dicardenimide derivative residues, preferably 10 to 6% by weight.
It is an imidized copolymer consisting of 0% by weight, and 0 to 40% by weight, preferably 0 to 30% by weight, of vinyl monomer residues that can be copolymerized with the compound forming the residue thereof.

If the amount of aromatic vinyl monomer residue is less than 30% by weight, moldability and dimensional stability will be impaired, and if it exceeds 90% by weight, impact strength and heat resistance will be impaired. Unsaturated radical? If the amount of the acid imide visiting conductor residue is less than 3% by weight, the effect of improving heat resistance will not be sufficient, while if it exceeds 70% by weight, the resin composition will become brittle and the moldability will deteriorate significantly. If the amount of vinyl monomer residues other than these groups exceeds 40% by weight, dimensional stability and heat resistance will be impaired.

Next, component B and its manufacturing method will be explained.

The rubbery polymer used for component B is a polymer consisting of butadiene alone or a vinyl monomer copolymerizable with it, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, or an acrylic ester alone. Alternatively, there are polymers such as vinyl monomers that can be copolymerized with this.

The aromatic vinyl monomer used in component B includes styrene monomers such as styrene, α-methylstyrene, and chlorostyrene, and their substituted monomers. Monomers are particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Vinyl monomers that can be copolymerized with these include acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methacrylic ester monomers such as methyl methacrylate and ethyl methacrylate. , vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, and methacrylic acid amide. Among these, methyl methacrylate, acrylic acid, and methacrylic acid are particularly preferred.

The method for producing the graft copolymer of component B is rubbery polymers 3 to 7.
30-80% by weight of aromatic vinyl monomer in the presence of 0i% by weight
It is obtained by graft copolymerizing 30 to 97 weight % of a monomer mixture consisting of 0 to 4 Ofi weight % of a vinyl cyanide monomer and 0 to 40 vinyl monomers copolymerizable with these monomers. Any known polymerization technique can be employed for polymerization, such as suspension polymerization, aqueous heterogeneous polymerization such as emulsion polymerization, bulk polymerization, solution polymerization, and precipitation polymerization of the resulting polymer in a non-solvent. Emulsion polymerization is preferred from the viewpoint of easy control of grain size. Further, the number average particle size of the rubbery polymer in the graft copolymer is 200 mμ or less, and if it is larger than 200 mμ, the transparency of the composition will be lost.

It has a repeating unit that becomes the polycargonate resin used for component C, and can be obtained by the fosquin method or the transesterification method.

Preferred 2-recarbonate resins are bis(hydroxyaryl)alkane-based polycargonate resins, such as bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ethane, 2,2-bis(
4-hydroxyphenyl) f/Jn, 2,2-bis(
Bis(hydroxydiaryl) alkanes such as 4-hydroxy-3,5-dichlorophenylprozene or bis(4-hydroxyphenyl)phenylmethane and phosgene or diarylcars can be obtained together with nates. used in combination.

In the present invention, the ratio of A component, B component and C component is A
10-90 parts by weight, preferably 20-80 parts by weight of component B, 5-95 parts by weight of thermoplastic resin, preferably 10-90 parts by weight of component B, preferably 1
0 to 80% by weight, C component 5 to 95% by weight, preferably 2
It is in the range of 0 to 90 fi quantity coefficient. If the amount of component A is less than 10 parts by weight, the effect of improving heat resistance will be insufficient, while if the amount of component A exceeds 90 parts by weight, impact resistance will decrease and moldability will also deteriorate. If the B component is less than 10 parts by weight, the impact resistance and plating properties will be insufficient, and if the B component exceeds 90 parts by weight, the heat resistance will be impaired. If the thermoplastic resin consisting of component A and component B is less than 10% by weight, heat resistance and plating properties will be insufficient, and if it exceeds 90% by weight, impact resistance will decrease. If the C component is less than 5% by weight, the impact resistance will decrease, and if it exceeds 95% by weight, the plating properties and moldability will decrease.

In the present invention, the method of mixing component A, component B, and component C is not particularly limited, and known means can be used. For example, a Banbury mixer, a tumbler mixer,
Examples include a mixing roll, a single-screw or twin-screw extruder, and the like. As for the mixing form, there are methods of obtaining a recombinant acid such as ordinary melt mixing, multi-stage melt mixing using master pellets, blending in a solution, etc.

A molded article obtained using the resin composition of the present invention is subjected to an etching treatment using an acid aqueous solution prior to chemical plating.

A preferred example of the acid aqueous solution used in the present invention is a mixture of chromic anhydride and concentrated sulfuric acid. As a method for plating the molded product whose surface has been roughened in this manner, a method generally used for plastic plating can be employed. The general method is to immerse the roughened molded product in an activating solution, then apply electroless plating to form a full copper or nickel coating, and then electroplate the metal'fI! Form a film.

(Examples) The present invention will be explained below with reference to Examples and Comparative Examples, in which all parts and parts are expressed on a weight basis.

100 parts of styrene in an autoclave equipped with a stirrer.
and 50 parts of methyl isobutyl ketone were charged, and the inside of the system was purged with nitrogen gas. After raising the temperature to 83 DEG C., a solution of 67 parts of hydrothermal maleic acid and 0.2 parts of benzoyl gum oxide dissolved in 400 parts of methyl isobutyl ketone was added over 8 hours. A portion of the viscous reaction solution was sampled and unreacted monomers were determined by gas chromatography. As a result, the polymerization rate was 99% for styrene and 99% for maleic anhydride. To the copolymer solution obtained here were added 63.6 parts of aniline and 1 part of triethylamine in an amount of 1.0 molar equivalent to maleic anhydride, and the mixture was reacted at 140° C. for 7 hours. The imidized polymer obtained by degassing is referred to as Polymer A-1.

1 part of styrene instead of 100 parts of styrene in Experimental Example (1)
00 parts and 17 parts of acrylonitrile, 67 parts of maleic anhydride was made into 50 parts, and 63.6 parts of aniline was made into 47.4 parts.
An imidized polymer was obtained by carrying out exactly the same operation as in Experimental Example (1) except that the amount was changed.

This will be referred to as Polymer A-2. The polymerization rate of this polymer was 98% for styrene and 98% for maleic anhydride.

100 parts of styrene in an autoclave equipped with a stirrer,
After charging 50 parts of methyl isobutyl ketone and purging the system with nitrogen, the temperature was raised to 83°C, and 85 parts of N-phenylmaleimide, 15 parts of maleic anhydride, and 0 parts of benzoyl peroxide were added.
．． A copolymer was obtained by carrying out the same operation as in Experimental Example (1) except that a solution of 2 parts dissolved in 400 parts of methyl isobutyl ketone was added over 8 hours. The polymerization rate is 96% of styrene, N-
It was 95% phenylmaleimide. This is polymer A-
Set it to 3.

80 parts of polybutanoene latex (solid content 50%, average particle size 100771μ), 1 part of sodium stearate, 0.1 part of sonorum formaldehyde sulfoxylate, 0.03 part of tetrasonorum ethylenediamine tetraacetic acid, sulfuric acid 0.003 parts of ferrous iron and 200 parts of water were heated to 65°C, and 60 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 0.3 parts of dodecyl mercaptaf, and Cumen Hydro A were added. 0.2 part of '-oxide was continuously added over 4 hours, and after the addition was completed, polymerization was further carried out at 65° C. for 2 hours.

The polymerization rate was 96%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water, and dried to obtain a white powdery polymer. This is indicated as ABS.

Example 1 130 parts of polymer A obtained in Experimental Example (1) (component A)
, 20 parts of ABS resin obtained in Experimental Example (4) (component B)
, polycarbonate resin (Teijin Kasei, Panlite = 1
300) (component C) was blended, and this blend was extruded into an islet using a screw extruder equipped with a 30 m x φ devolatilization device. After drying the obtained (lett), a test piece was molded using an Arburg molding machine.
25+++m x thickness 3cm) After degreasing and washing the obtained test piece, chromic anhydride 40017773 and concentrated sulfuric acid 200ml
/l for 5 minutes at 65° C., further treated with a neutralizing solution, and then chemically plated with an activating solution and a chemical nickel plating solution. The chemically plated test piece was subjected to electroplating in a sulfuric acid steel plating solution at a current of 3.5 for 90 minutes, washed with water, and then dried at 100° C. for 1 hour to obtain a metal-coated test piece. The peel strength of the plating film of these test pieces was measured. Table 1 shows the physical properties of the test piece and the peel strength of the plating film.

Examples 2 to 3 The same procedure as in Example 1 was carried out except that polymers A-2 and A-3 were used instead of polymer A-IK.

The same procedure as in Example 1 was carried out except that the amounts of component A, component B, and component C were changed.

Comparative Example 1 The same procedure was carried out except that the styrene-maleic anhydride copolymer obtained in Experimental Example (1) was used without being imidized.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the ABS resin of component B was not used.

Comparative Example 3 In Example 1, C component polycarbon? It was carried out using only nate resin.

The physical properties were measured by the following method.

(1) Vicat softening temperature: According to ASTM D-1525 with 5# load.

(2) Izot impact strength: Notched 1/4 (7 inches, according to ASTM D-256K).

(3) Peel strength: The effect of roughening the surface of a molded product by etching can be expressed by the adhesive strength between the coated metal film and the base resin. Strength when peeling off a coated metal surface with a width of 10 cm in the direction perpendicular to the base material #
/cm).

0) Heat cycle resistance: Because the thermal expansion coefficients of metal and resin are different, blisters and cracks occur due to sudden temperature changes.

Therefore, a thermal cycle test is generally performed in which plated molded products are exposed to alternately low and high temperature atmospheres. In the present invention, a test is performed for 10 cycles under the conditions of -40°C for 60 minutes and +90°C for 60 minutes, and those in which blisters or cracks have occurred in the metal film after the test are marked "x".
Those in which no blistering or cracking occurred were marked with "○".

(5) Molding processability: ``x'' indicates that the molding process is performed using an injection molding machine and requires a molding temperature and/or injection pressure that is equal to or higher than that of polycarnate resin; Items that can be molded at the molding temperature and injection pressure are marked with "○".
”.

(6) Oil resistance: The test pieces were immersed in gasoline at room temperature for 24 hours, and those with cracks were rated "x", and those with no cracks were rated "x".
Indicated with ○.

(7) Hot water Note 2 test pieces were immersed in boiling water for 24 hours, and those with cracks were marked with an "x", and those with no cracks were marked with an "o".

Claims (1)

[Claims] Component A: 30-90% by weight of aromatic vinyl monomer residues,
10 to 90 parts by weight of an imidized copolymer consisting of 3 to 70% by weight of unsaturated dicarboxylic acid imide derivative residues and 0 to 40% by weight of vinyl monomer residues other than these groups, and component B: rubbery. 3 to 70% by weight of the polymer, 30 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and 0 to 40% by weight of vinyl monomer copolymerizable with these are grafted together. 5 to 95 weight % of a thermoplastic resin containing 10 to 90 parts by weight of a polymerized copolymer in which the number average particle size of the rubbery polymer in the copolymer is 200 mμ or less, and component C: A transparent heat-resistant thermoplastic resin composition with excellent plating properties consisting of 95 to 5% by weight of polycarbonate resin.