JPS60162794A - Manufacture of surface-metallized molded article of polyester resin - Google Patents

Abstract

PURPOSE:To manufacture a surface-metallized molded article of polyester resin by roughening the surface of a molded article consisting of thermoplastic polyester, an olefinic copolymer contg. glycidyl groups and titanium dioxide with an alkali soln. and by carrying out plating. CONSTITUTION:A molded article of resin to be plated is composed of 100pts.wt. polyester resin and 5-200pts.wt. titanium dioxide. The polyester resin consists of 99.7-55wt% thermoplastic polyester and 0.3-45wt% olefinic copolymer contg. glycidyl groups. The molded article is immersed in an alkali soln. at 30-90 deg.C for 1-120min to roughen the surface, and it is washed, dried, and plated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for metallizing the surface of a polyester resin molded article by plating.

More specifically, the present invention relates to a method for producing a surface-metallized polyester resin molded article that has excellent plating film adhesion, thermal cycleability, and brightness of the plated metal, and has good mechanical properties of the plated article.

Generally, plastic plating treatment consists of (1) pretreatment, (2)
) roughening treatment (etching), (3) sensitization treatment, (4) activation treatment (activation), (5) electroless plating, and (6) electroplating steps in sequence. This is done by diagnosing the
The steps after step (3) above are usually called plating steps.

Above all, the surface roughening treatment (2) above affects the adhesion of the metal plating film applied in the subsequent plating process! ■Various means are used in important steps depending on the type of plastic.

As a means for roughening the surface in plating thermoplastic polyester resin, for example, a method of roughening a polyester resin containing a filler in advance (Japanese Patent Laid-Open No. 54-15
No. 977) is known. However, although these conventional methods slightly improve the adhesion of the plating film on polyester resin plated products, the thermal cycleability, plating brightness, and mechanical properties of the plated products are significantly inferior.
It was not possible to obtain a practically excellent surface metalized polyester resin molded product.

Therefore, the present inventors set out to obtain a surface-metallized polyester resin molded product that has excellent mechanical properties such as impact resistance, and also has excellent plating debonding properties, thermal cycling properties, and plating brightness. As a result of extensive research, we discovered that the above objective could be effectively achieved by roughening the surface of a molded product made of thermoplastic polyester, a glycidyl group-containing olefin copolymer, and titanium dioxide with an alkaline solution, and then plating it. The invention has been achieved.

That is, the present invention uses thermoplastic polyester 99.7 to 5
5% by weight and 0.5% by weight of glycidyl group-containing olefin copolymer.
Polyester resin composition 100 consisting of 3-45% heavy nails
A surface metallized polyplastic polyester and glycidyl characterized in that a resin molded article for plating containing 5 to 250 parts by weight of titanium dioxide is roughened using an alkaline solution and then plated. It is a polyester resin mixture containing a group-containing olefin copolymer.

The thermoplastic polyester referred to herein is a polymer obtained by condensation polymerization of a dicarboxylic acid component of which 60 mol % or more is a terephthalic acid component and a diol component.

Examples of the terephthalic acid component herein include terephthalic acid and ester-forming derivatives thereof.

In addition, other dicarboxylic acid components include isophthalic acid,
Orthophthalic acid, 2,6-naphthalene dicarboxylic acid, 1
．． 5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4.4
Aromatic dicarboxylic acids such as '-diphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 5-sodium sulfoisophthalic acid, 1,3
-Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, decanedioic acid, dodecanedioic acid, hexadecanedionic acid, octadecanone onoic acid, dimer acid, etc. Examples include aliphatic dicarboxylic acids and ester-forming derivatives thereof.

In addition, the diol component includes aliphatic glycols having 2 to 20 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-bucundiol, neopentyl glycol, 1,5-bentanediol, 1,6-hexanediol, and decamethylene glycol. , cyclohexane dimetatool, cyclohexane diol, and long chain glycols with a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and ester-forming derivatives thereof.

Specific examples of these polymers include yIF ribterene terephthalate, polybutylene terephthalate isophthalate, polybutylene terephthalate adipate, polybutylene terephthalate sebacate, polybutylene terephthalate-1.Φdecanedicarboxylate, and polyethylene terephthalate. ,polyethylene terephthalate·
Isophthalate, polyethylene terephthalate/adipate, polybutylene terephthalate/5-sodium sulfoisophthalate, polyethylene terephthalate/5
- Sodium isophthalate, polybutylene terephthalate, polybutylene terephthalate adipate, polybutylene terephthalate decanedicarboxylate, polyethylene terephthalate, polyethylene terephthalate adipate, polybutylene terephthalate 5- are used. Furthermore, these thermoplastic polyesters have a relative viscosity of 1.2 to 2.0, especially 1.5% when a 0.5% 0-chlorophenol solution is measured at 25°C.
A value in the range of 3 to 1.85 is preferred.

Further, two or more of these may be used in combination.

The content of these thermoplastic polyesters is preferably 99.7 to 55% by weight of the polyester resin composition.

The glycyl group-containing olefin copolymer used in the present invention is α-olefino 50 to 99.5 j [51% and α,β-unsaturated carboxylic acid purinyl ester 50 to 99.5
It is a copolymer consisting of 0.5% by weight and 0 to 49.5% by weight of vinyl acetate. The α-olefin referred to herein includes ethylene, propylene, butene-1, etc., and ethylene is preferably used.

Glycidyl esters of α,β-unsaturated carboxylic acids are compounds represented by the general formula (R in the formula represents a hydrogen atom or a lower alkyl group), and specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate. Among them, glycidyl methacrylate is preferably used.

a, β in glycidyl group-containing olefin copolymer
- The amount of copolymerized glycidyl ester of unsaturated carboxylic acid is suitably 0.5 to 50% by weight, especially 1 to 20% by weight, and the effect of the present invention cannot be obtained if it is less than 0.5% by weight.
Moreover, if it exceeds 50% by weight, the composition tends to gel during melt-kneading, which is not preferable.

Specific examples of glycidyl group-containing olefin copolymers include ethylene/glycidyl methacrylate copolymer, ethylene/glycidyl methacrylate +-/vinyl acetate copolymer, and ethylene/glycidyl methacrylate copolymer. Examples include rare acrylate copolymers and ethylene/glycidyl acrylate/vinyl acetate copolymers, among which ethylene/glycidyl methacrylate copolymers and ethylene/glycidyl methacrylate/vinyl acetate copolymers are preferably used.

Two or more of these glycidyl group-containing olefin copolymers can be used in combination.

The content of the glycidyl group-containing olefin copolymer is preferably 0.3 to 45% by weight of the polyester resin composition,
Particularly desirable is 1 to 40% by weight. If it is less than 0.3%, the effect of improving the impact resistance and thermal cycling property of the plated product will be small, and if it exceeds 45%, the adhesion of the plating film will be undesirably reduced to IJ.

When adding the glycidyl group-containing olefin copolymer, it is necessary to add organic sulfonic acid metal salts such as sodium dodecylbenzenesulfonate and sodium dodecylsulfonate, and alcohol sulfuric acid such as sodium lauryl sulfate. A small amount of ester salt or the like can be added together, and the effect of improving the impact resistance and thermal cycle of the plated product is further exhibited by the addition of these.

The titanium dioxide used in the present invention is anatase type and rutile type manufactured by sulfuric acid method or chlorine method with a purity of 95%.
The above titanium dioxide. Although the particle size of titanium dioxide is not particularly limited, those having an average particle size of 1 to 6 μm as indicated by the maximum frequency diameter (mode diameter) determined from the particle size distribution measured by the sedimentation balance method are particularly preferably used. be done.

The amount of titanium dioxide added is preferably 5 to 250 parts by weight, particularly 30 to 100 parts by weight, per 100 parts by weight of the polyester resin.If it is less than 5 parts by weight, the effect of improving the adhesion of the plating film is insufficient. .

If it exceeds 250 parts by weight, the surface roughness of the molded product becomes large, and the adhesion of the plating film and the brightness of the plating are lost, which is not preferable.

In addition, when blending the thermoplastic polyester with the glycidyl group-containing olefin copolymer and titanium dioxide, other thermoplastic resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene - polyolefin resins such as butene-1 copolymers, ethylene-propylene terpolymers, polyamides, ABS resins, polycarbonates, polyesters (other than the invention), and other additives, such as aluminum stearate, barium stearate. lubricants such as talc, clay, kaolin, crystal nucleating agents such as alumina, mold release agents such as monk wax, monk acid wax metal salts, plasticizers, heat stabilizers, ultraviolet absorbers, pigments,
Dyes, fibrous toughening agents, etc. can also be added as necessary.

Thermal-uJ F/j polyester, glycine group-containing olefinic copolymer, titanium dioxide, and other additives may be blended by any method and are not limited, for example, by simultaneously mixing them in a screw extruder, etc. Methods such as mixing can be adopted.

Production of resin molded products for plating from compounds is done by injection molding,
Any conventional thermoplastic resin molding method such as extrusion molding or blow molding can be used, and a resin molded product for plating in a desired shape can be easily obtained.

When performing plating treatment using the method of the present invention, it is important to first perform a preliminary treatment such as wiping off the oil film on the surface of the molded product as necessary (11), and then roughen the surface using an alkaline solution. The alkaline solution used for surface treatment is an alkali component such as potassium hydroxide, sodium hydroxide, magnesium hydroxide, etc. in a solvent such as water, phenols, alcohols, or a mixed solvent thereof.
It is a solution dissolved at a concentration of ~50%, and among them, an aqueous solution of sodium hydroxide and potassium hydroxide is preferably used.

The conditions for this surface roughening treatment (alkali etching) are 30~
It is desirable to immerse the molded article in an alkaline solution at 95° C. for 1 to 120 minutes, and then thoroughly wash it.

After sufficient washing, the surface may be further treated with an acidic aqueous solution having a pH of 3 or less. In this case, the acid component used is a mineral acid such as sulfuric acid or hydrochloric acid, and the appropriate treatment conditions are 5 to 70°C for 2 to 60 minutes.

By applying normal plating treatment to the surface-roughened resin molded product for plating in this way, it is possible to obtain a surface with excellent plating film adhesion, thermal cycle resistance, and plating brightness, as well as good mechanical properties of the plated product. A metallized polyester resin molded article can be obtained.

Plating treatments include, for example, centizing with a stannous chloride solution - activation with a palladium chloride solution - electroless copper or nickel plating - electroplating steps, or catalytic staining - accelerating - electroless Metsky electroplating. A normal plating method consisting of steps can be applied.

The surface metallized polyester resin molded article of the present invention has excellent heat resistance, mechanical properties, thermal cycling properties, plating film adhesion, and surface brightness, and is therefore useful as various automobile parts, electrical parts, and mechanical parts.

The effects of the present invention will be further explained below with reference to Examples.

Examples 1 to 9, Comparative Examples 1 to 10 Polybutylene terephthalate with a relative viscosity of 1.58 and the first
Resin composition “1” is a tri-blend of the glycidyl group-containing olefin polymers shown in the table in the proportions shown in Table 1.
00 parts by weight was further dry breaded with titanium dioxide having an average particle size of 3.0 μm in the proportions shown in Table 1, and this was melt-mixed using a screw extruder set at 250° C. and pelletized. Next, the obtained pellets were heated to 250°C.
1J50 x Length 80MII x Height 35 am - Thickness 2 under conditions of mold temperature 80℃.
．． 5 MM (7) Box-shaped molded product (test piece A) with mold notch 11"1/2' x length 2 1/2'
An impact test piece (test piece B) having a thickness of 1/8' was molded.

Next, each test piece was soaked in a 30% aqueous sodium hydroxide solution for 70 minutes.
℃ for 10 minutes, further immersed in a 2% aqueous hydrochloric acid solution at 30° C. for 10 seconds, and then thoroughly washed in running water to obtain a test piece with a roughened surface.

Each test piece with a roughened surface was subjected to plating treatment by the method shown below.

(1) Catalyst The sample was immersed in a solution of Catalyst A-30 (manufactured by Okuno Pharmaceutical Industries, Ltd.) at 25°C for 3 minutes.

(2) Washing with water (3) Accelerator 40% in 10% H2SO4 solution
It was immersed at ℃ for 3 minutes.

(4) Washing with water (5) Electroless nickel plating It was immersed in a TMP chemical nickel plating solution (manufactured by Okuno Pharmaceutical Industries, Ltd.) at 40°C for 8 minutes.

(6) Washing with water (7) RLJ, air plating (bright copper plating) The electroless plated test piece was treated with 200 g of concentrated sulfuric acid 50f1 copper sulfate (pentahydrate) and SCB-MU10ω and 5CB as brighteners.
-1.1cc (Okuno Pharmaceutical Co., Ltd. product) and water 10
Placed in an acidic steel bath consisting of 00CC and heated to a temperature of 25%.
Electroplating was performed under the conditions of ~30°C and a current density of 4A/dm' to form a copper plating film with a thickness of about 30μ.

(8) Washing with water (9) Electroplating (bright nickel plating) After bright copper plating, the test piece was boric acid 0f1 nickel chloride hexahydrate 5
0f1 nickel sulfate heptahydrate 300f1 was placed in a nickel plating bath consisting of Monolite ICr as a brightening agent, Acuna B-120CC (manufactured by Okuno Pharmaceutical Co., Ltd.) and water 1000Ω at a temperature of 50°C and a current density of 5 A / d
Electroplated under conditions of 15 μm thick to form a nickel plating film.

01 Water washing ol) Electroplating (Chrome plating) After bright nickel plating, the test piece was placed in a chrome plating bath consisting of 5F sulfuric acid, 250F chromium oxide, and 1000CC water, and the temperature was 5.
Plating was carried out under the conditions of 0°C, electric current, and density of 40 A/d m' to form a chromium plating film with a thickness of 0.2μ.

The adhesion strength of the plating film is measured by measuring the force <y> when peeling off the plating film of test piece A, which has been subjected to electroplating (bright copper plating) up to (7) above, using IJ over a length of 20 mm. Evaluated by.

Thermal cycle test of plated products is a-kami plating (
Test piece A, which has been subjected to chrome plating), was heated to -30°C (lhr
)-* 150° C. (lhr) c7) Nisarasuko in an atmosphere was taken as one cycle, and after 4 consecutive cycles, evaluation was made by visually observing and determining the presence or absence of abnormalities on the plating surface.

The impact resistance of the plated product was evaluated by measuring the Fizot impact strength of test piece B which had been electroplated (chromium plating). These results are shown in Table 1.

The abbreviations in Table 1 mean the following.

1) BT: polybutylene terephthalate P (E
/GMA): Ethylene/glycidyl methacrylate-1/copolymer copolymerization rate 90/10 (weight ratio) P (E/GMA/VA): Ethyl/:// Gu'J
#methacrylate-1/vinyl acetate copolymer copolymerization ratio 80/10/10 (weight ratio) As is clear from the results in Table 1, the surface gold-114 polyester molded product of the present invention is a thermoplastic polyester. Compared to the plated moldings of Ko-Germany, the plated moldings made of thermoplastic polyester and titanium dioxide, and the plated moldings made of thermoplastic polyester and glycidyl foundation IJ olefinic copolymer. Therefore, the adhesion of the plating film, the thermal cycling properties of the plated product, and the impact resistance of the special crystals of Ni-metal are well balanced and excellent.

Patent Applicant Toshi Co., Ltd. Company Procedures Amendment 1, Case Description 1982 Patent Application No. 18242 2, Title of Invention Process for Manufacturing Surface Metalized Polyester Resin Molded Products & Person Who Makes Amendments 4, Amendment Order Contents of voluntary amendments to the date of (1) Table 1 on page 18 of the alarm bell shall be changed as shown in the attached sheet.

Claims (1)

[Claims] 5-250 parts by weight of titanium dioxide is contained in 100 parts by weight of a polyester resin composition consisting of 99.7-55% by weight of thermoplastic polyester and 0.3-45% by weight of a glycidyl group-containing olefin copolymer. A method for producing a surface metallized polyester resin molded product, which comprises roughening the surface of a plating resin molded product using an alkaline solution, and then plating the product.