JPS61120845A - Resin composition for plating - Google Patents

Abstract

PURPOSE:To provide the titled compsn. yielding plating films excellent in thermal cycling resistance and peeling strength, by incorporating three particular copolymers with an org. silicon compd. CONSTITUTION:15-75pts.wt. polybutadiene latex, 5-95pts.wt. graft copolymer in which an arom, monovinyl monomer (a) and a vinyl cyanide monomer (b) are partially grafted onto said polybutadiene latex, 100pts.wt. mixture of 95-5pts.wt. graft copolymer in which the component (a) and the component (b) are partially grafted onto 15-75pts.wt. styrene/butadiene copolymer latex having the content of styrene of 5-45pts.wt. with 0-85pts.wt. copolymer of 50-85pts.wt. component (a) and 50-15pts.wt. component (b), and 0.01-0.5pts.wt. org. silicon compd. having a viscosity at 25 deg.C of 10-100,000cst, a surface tension of 0.25wt% soln. in toluene at 25 deg.C of 26.5dyne/cm or less, and a repeating unit of the formula (wherein R1-2 are H, alkyl, aralkyl, carboxymethyl; n is 1 or above) are incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to an ABS resin composition that has particularly excellent plating film strength and heat cycle resistance.

<Conventional technology> Conventionally, ABS resin has been the mainstream resin used for plating, and its plating film is beautiful, the plating film has great peeling strength, and it also has excellent 1liiJ heat cycle performance. For this reason, it has established a solid position in plastic plating applications.

However, recently, heat-resistant cycle properties have been developed mainly for automobile applications.
The current situation is that the requirements for metallization are becoming more and more severe, and the existing menki grades cannot meet them. For example, even if a thermal cycle of -40℃ to 85℃ is applied 3 to IO times,
It is required that there be no change in the appearance of plated products.

Special Publication No. 50-622 for the purpose of increasing the adhesion strength of plating film
Publication No. 2 proposes a method of adding a styrene-butadiene-Bronok copolymer to ABS resin, but although this method increases the adhesion strength of the plating film, the smoothness of the molded product surface may be lost. However, there were many problems such as easily damaging the molded product, and it was not practical. On the other hand, methods of adding organosilicon compounds to ABS resin to impart special functions are described in Japanese Patent Publication No. 1118/1973 and Japanese Patent Publication No. 49/1979 = 299.
As seen in Publication No. 47, it has long been adopted in the field of impact resistance improvement. Furthermore, heat resistance A, BS and heat resistance A, BS
By adding an organosilicon compound to an alloy, a heat-resistant ABS composition that can be plated was developed in JP-A-56-81355.
It has been proposed in the following publications.

<Problems to be solved by the invention> □This heat-resistant ABS containing an organosilicon compound exhibits extremely excellent heat-resistant cycle properties, but the 7-trinox resin layer of the heat-resistant resin is difficult to be etched, so the etching conditions [1] are There were problems such as narrowness and the addition of organosilicon compounds, which led to a decrease in the rigidity of the molded product.

<Means for Solving the Problems> 31 In view of this situation, the present inventors have developed a plating film that has excellent heat resistance and peeling strength, and has a plating condition range that is comparable to that of conventional ABS for plating. As a result of intensive research aimed at providing a composition with desirable characteristics as a plating composition, such as a wider range of products and fewer bleeds during molding, we found that ABS alloys were combined with styrene-butadiene copolymers and organosilicon compounds. The present invention was achieved by discovering that an excellent ABS composition for plating that has no practical problems in both heat-resistant and general applications can be obtained by adding a very small amount of an organosilicon compound. It is.

That is, the present invention provides: (a) polybutadiene latex 15 to 75 iJ
5 to 95 parts by weight of a graft copolymer obtained by partially graft-polymerizing an aromatic monovinyl monomer and a vinyl cyanide monomer in advance, and (b) 5 to 45 parts by weight of styrene. Contains styrene
Graft copolymer (B
A copolymer (Q 0 to 85 parts by weight of a mixture (with a total of 1000 parts) having a viscosity at 25°C of 10 to 100,000 centistokes and a 0.5% by weight solution in toluene.
The surface tension at 5°C is less than 26.5 dyn/yl! , -') A plating resin composition having excellent plating properties, which contains 0.01 to 0.5 parts by weight of an organosilicon compound having a repeating unit represented by the following formula (I).

(Here, R+ and R2 are hydrogen atoms, alkyl groups, aralgyl groups, carboxymethyl groups, polyetheralkyl groups, epoxyalkyl groups, 1-U fluoromethyl groups,
It represents one or more groups selected from phenyl groups, and n represents an integer of 1 or more. ).

The present invention will be explained in detail below.

The resin used in the present invention can be obtained as follows.

The aromatic monovinyl monomer used in the present invention includes:
Styrene, α-methylstyrene, pinyltoluene/, 0-
Acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like are used as the aromatic monovinyl single Fd-based monomers such as ethylstyrene, o, p-chlorostyrene, and anionized vinyl monomers. The monomer composition ratio in graft polymerization is aromatic monovinyl monomer and cyan 1.
The vinyl monomers are used in a mixture of 1,000 to 100% by weight, preferably 6 to 80% by weight of the aromatic monovinyl monomer, 4% by weight of the aromatic monovinyl monomer, and 4% by weight of the vinyl monomer.
Selected from the range of 0 to 20 double stars.

The graft copolymer (2) used in the present invention is firstly prepared by polybutadiene latin 2 with 15 to 75 polymer parts, preferably 30 to 7 polymer parts.
It can be obtained by charging 0 parts by weight into a polymerization tank in advance, and then continuously feeding unreacted monomer. The polymerization initiator may be either oil-soluble or water-soluble, or they may be used in combination.

The graft copolymer σ used in the present invention can be produced in the same manner as the graft copolymer 2. In addition, polybutadiene latex and styrene-butadiene copolymer latex may be graft-polymerized individually, but it is also possible to blend them in advance and then subject them to graft polymerization. According to this method, the graft polymer (
2), 0 can be manufactured at the same time.

The method for obtaining the resin from the polymer latex is arbitrary, and for example, the polymer latex may be coagulated with a mineral acid, an electrolyte, etc., and the polymer may be recovered by filtration, washing, dehydration, and drying.

The resin powder thus obtained is a styrene-acrylonitrile copolymer made by any method such as lumping or suspension so that the proportion of the rubbery polymer in the final resin component is preferably 5 to 30% by weight. By kneading α-methylstyrene-styrene/acrylonitrile copolymer or the like using a Brentoshi, Banbury mixer, roll, extruder, etc., a mixture of 4′ graft polymers ①, ②, and copolymer (Q) can be obtained.Graft Copolymer (c) and graft copolymer 0 are 5/95 to 951
For example, when the styrene content of a styrene-butadiene copolymer latex with a graft copolymer of 0 is 25%, the blend can be made in any weight ratio within the range of 40/60 to 90/l O. is preferred. If the content of the graft copolymer is small, impact resistance will not be developed.<<, -8
On the other hand, if the content of graft copolymer 0 is too small, the effect of improving heat cycle resistance will be reduced.

The organosilicon compound used in the present invention is ゛, 25
The viscosity at °C is lO ~ 1 (to, 000 centistokes), the surface tension at 25 °C of a 0.5 wt% solution in toluene is 265 dyn/L or less, and the repetition rate is expressed by the following formula (1). It has a unit.

Here, R+ and R2 represent one or more groups selected from a hydrogen atom, an alkyl group, a carboxylmethyl group, an aralkyl group, a polyether alkyl group, an epoxyalkyl group, a trifluoromethyl group, and a phenyl group, and n is 1 Indicates the following integer.

Preferred specific examples of R and R2 include a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aralkyl group such as a phenylmethyl group, a phenylethyl group, a tolylmethyl group, and a quinolylmethyl group; Polyether argyl groups such as nooxide methyl group, polymethylene oquindomethyl group, and polyethylene oquindoethyl group; evoquine methyl group such as glycidium/14, l, 3 epoxypropyl methyl group, trifluoromethyl group, carphoki/methyl group, phenyl group, etc.

Particularly preferred examples include a hydrogen atom, a methyl group, a phenyl group, a polyethylene quindomethyl group, a glyc/zyl group, and a carboxymethyl group.

The viscosity of such organosilicon compounds ranges from lO to 100,000 centistokes at 25°C, preferably from 100 to 50,000 centistokes. Low-viscosity paints have many volatile components, which can cause mold stains and cause paint to splatter during painting.

On the other hand, those of 100,000 C8 or more are difficult to handle and require a large amount of energy for dispersion, making them impractical.

Furthermore, the surface tension of the organosilicon compound used in the present invention in a 0.5% solution of badruene is 26.5 dyn/
(7) It is necessary that the following is true. The surface tension is 26.
If it exceeds 5 dyn/ax, the effect of improving the heat cycle resistance of the plating film is significantly reduced, which is not desirable.

The amount of organosilicon compound added is determined by the amount of the graft copolymer■
, 0 and copolymer 0 per 100 parts by weight
．． 01 to 05 parts, preferably 0.03 to 0.3 parts
Department. If it is less than 0.01 part, the effect of improving heat cycle resistance will be small, and if it is more than 0.5 part, it will bleed onto the surface of the molded product, causing mold stains, or weakening the adhesion strength of the plating film, which is not preferred.

In addition to the organosilicon compound, the resin composition of the present invention may contain commonly used stabilizers, plasticizers, pigments, etc., if necessary.

The final resin composition obtained was molded by injection molding, extrusion molding, or other molding methods.
Plating can be performed by a conventional method using J3S plating equipment.

<Example> Hereinafter, the method of the present invention will be explained in detail with reference to Examples. Note that the heat cycle resistance, peeling strength, impact strength, and viscosity used in the examples were measured according to the following methods.

Heat cycling resistance: Plated product (175 mm x 35 mm x 901 mm thickness 2
ay, 4-point gate box) was left at room temperature for 24 hours, then 85
Place in the open at ℃ and leave for 1 hour. Take it out, leave it at room temperature for 15 minutes, then immediately put it in a -40°C freezer and leave it for 1 hour. Repeat this process for 1 cycle (15 minutes at room temperature → 85 minutes)
C. for 1 hour → room temperature for 15 minutes → -40 DEG C. for 1 hour) for a total of 3 cycles, and it was examined whether there were any changes in the appearance of the plating film and the shape of the molded product after the test + Sil.

Plating peeling strength: Square plate plated with matte copper to a thickness of 25 to 40μ (12
6 shoulders x 75M, thickness 3Mm) with 25 silk 1
The plating film was peeled off over a length of tIy, and the average peel strength was measured.

Since the peeling load differs depending on the thickness of the plating film, the peeling strength in the case of a plating film thickness of 30 μm was determined from the following formula.

P: Pt (A0/t)k/W (k
g/”)P: Peeling strength (kg/α)p
t: Average peeling load (kg) t: Plating film thickness (μ) W: Peeling 11] (z
) Physical properties: Physical properties such as impact strength were determined in accordance with the ASTIVI test method. (l/2"I ZOD : ASTI-I
D256) Viscosity: The viscosity of the organosilicon compound was measured using an Ubbelohde viscosity tube. (JIS-2283.1969) The measured temperature was 2500 l'C.

Examples 1 to 8 Parts in the examples indicate parts by weight.

Polybutadiene latex "13 K-1" (manufactured by Toshi <fAζ, average particle size 0.36μ), sodium pyrophosphate, glucose, ferrous sulfate with the composition shown in Table 1.
7? was charged into a reaction tank. The temperature was raised to 60° C., a monomer containing a chain transfer agent and an emulsified oil-soluble initiator were continuously added, and the polymerization was completed in 7 hours. After adding an antioxidant, the polymerized latex was coagulated with sulfuric acid, neutralized with caustic soda, filtered, washed, dehydrated, and dried to recover a uniform powder (hereinafter referred to as PB-1).

Styrene/butadiene copolymer latex is SBi<-
1 (styrene content 25%, average particle size 0.6011) was used. Polymerization was carried out under the same conditions as in the case of using BR-1, and a uniform powder was obtained by post-treatment in the same manner (hereinafter referred to as 513-1). Hereinafter, by changing the charging composition as shown in Table 1 under the same graft polymerization conditions, S1-3-2 to S)3-5 were obtained.
Noko.

Nao, styrene/butadiene copolymer latex S B
1<-2, S]3R-3, SBI-4,5BR=5
were as follows.

5BR-2: Styrene content 25%, average particle size 0.37
μ5BR-3: // 12%, /7 0.
56μ5BR-4: 40%, yy O,
68μ5BR-5: // 55%, //
0.2811 The resin composition for dilution is a bulk polymerized styrene/acrylonitrile copolymer (SA, N-1) (i(
AN/5=28/72) manufactured by Shiku (Shu) was used.

As an organosilicon compound, l--Lenricone Co., Ltd.
"=SI (-200") (Polydimetern Logisa/, viscosity 30,000 C8) was used.
% surface tension was 24.8 dyn/z.

Table 2 shows the blending ratio of the resin compositions used in the evaluation and the evaluation results.

Example 9 1N silicon compound manufactured by Toray/Ricone Co., Ltd.
SF8418” (carbogin methyl modified, viscosity 250
A resin composition was obtained in the same manner as in Example 1 except that 0C5) was used. The surface tension of 5F-8418-15-□ at 0.5% in toluene is 25. Odyn/
/LOM. The evaluation results are shown in Table 3.

Example IO As an organosilicon compound, "manufactured by Toray Silicone Co., Ltd."
5F842F (epoxybolyether modified, viscosity 3.5
A resin composition was obtained in the same manner as in Example 1 except that 00C5) was used.

The surface tension of 0.5% of 5F8421 in toluene is 254
[1yn/rM.

Example 11 A resin composition was prepared in the same manner as in Example 1, except that ``5f (-1107' (methyl hydrodioxyborosiloxane, viscosity 30C5) manufactured by Thorenlicon (1 vermilion) was used as the organosilicon compound. I got it.

51 (-1107) The surface tension of 0.5% in toluene is 26. l dyn /an t, =.

Example 12 A silicon compound having a viscosity of 35 at 25°C
It is 0C5. A resin composition was obtained in the same manner as in Example 1 using the following repeating units.

(Here, the molar ratio of X and y was x:y=98:2.

) The surface tension of this material in 05% toluene is 25, l
dyn/n te;J) ツf,=.

Example 13 As an organosilicon compound, "manufactured by Torenlicon Co., Ltd."
FS-1265” (7) Raw oil, viscosity 1.0O
A resin composition was obtained in the same manner as in Example 1 except that OC3) was used.

The surface tension of FS-1265 in toluene at 0.5% is 25
．． It was 7 dyn/(7).

Comparative Example 1 Butadiene copolymer alone (PB-]) was evaluated without adding any organosilicon compound. The evaluation results are shown in Table 4.

The heat cycle resistance of this plated film was extremely poor.

Comparative Example 2 Styrene-butadiene copolymer alone (SB-1) 100
Add 0.05 part of '5f (-200)' to the part and evaluate (+Il
It's iL.

The surface of the plating film of this product was cloudy and the impact resistance was low.

Comparative Example 3 Styrene/butadiene copolymer 1.11 (SB-2)
0.05 part of ==SI(-200'' was added to 100 copies and evaluated as f+lIi.

This product had excellent plating properties, but poor impact resistance.

IT Comparative Example 4 100 parts of a combination system of polybutadiene copolymer (PB-1) and styrene butadiene copolymer (SB-j) were added with "S[(
-2(Nl") was added.

The heat cycle resistance of the plating film was poor.

Comparative Example 5 "PB-11SB-" S f (-2
1.0 part of 00'' was added.

The surface of this plated film was partially uneven, and the adhesion strength of the plated film was low.

Comparative Example 6 100 parts of styrene-containing fjt 12% styrene-exposed butadiene copolymer (SB-3) SH-20
0.05 part of 0'' was added.

The surface of the plating film was cloudy.

Comparative Example 7 100 parts of a styrene-butadiene copolymer (SB-4) containing styrene (1IL4o%) [0.05 part of S f (-200) was added.

The surface of the plating film of this product was cloudy, and the impact resistance was extremely low.

Comparative Example 8 Styrene 1-butadiene rubber latex 5I3R-
5 (styrene content 55%, average particle size 0.28 mez) was used. Grafting conditions were the same as PB-1 (
SB-5).

100 parts of a mixture of P B-1 and S f3-5 blended at a ratio of 70/30 (to which 0.05 part of 5H-200 was added).

The plating properties of this product were excellent, but the impact resistance was low.

Comparative Example 9 As an organosilicon compound, the viscosity at 25°C is 500
The following phenylmethyl heat-resistant oil, C3, was used.

The surface tension of a 0.5% by weight solution of this substance in toluene is 2
6.7 Ivy on dynlon.

(Here, the molar ratio of +Y was x:y = 1:1.) Even if an organosilicon compound with a small decrease in surface tension is added, the heat cycle resistance of the plating film is still sufficient. was not improved.

<Effects of the Invention> The resin composition for barley of the present invention has excellent plating film strength, heat cycle resistance, and peel strength.
The physical properties, especially the impact strength, are also good.

Therefore, it is possible to obtain an excellent plated product that has no practical problems in both heat-resistant applications and general applications.

Patent applicant Higashi Shikikai Co., Ltd. 27-1

Claims (1)

[Scope of Claims] (a) A graft copolymer obtained by partially grafting an aromatic monovinyl monomer and a vinyl cyanide monomer to 15 to 75 parts by weight of polybutadiene latex (
A) 5 to 95 parts by weight and (b) 15 to 75 parts by weight of a styrene-butadiene copolymer latex containing 5 to 45 parts by weight of styrene, and an aromatic monovinyl monomer and a vinyl cyanide monomer. Graft copolymer (B) partially graft-polymerized in advance
Copolymer (C) 0 to 95 parts by weight, (c) 50 to 85 parts by weight of aromatic monovinyl monomer, and 50 to 15 parts by weight of vinyl cyanide monomer 85 parts by weight of the mixture ((A)+
(B) + (C) totaling 100 parts by weight);
Compounding 0.01 to 0.5 parts by weight of an organosilicon compound having a surface tension of 26.5 dyn/cm or less at 5°C and having a repeating unit represented by the following formula (I),
A plating resin composition with excellent plating properties. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (Here, R_1 and R_2 are hydrogen atoms, alkyl groups, aralkyl groups, carboxymethyl groups, polyetheralkyl groups, epoxyalkyl groups, trifluoromethyl represents one or more groups selected from phenyl group, phenyl group, and n represents an integer of 1 or more.)