JPS5819687B2 - Polyolefin resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a polyolefin that can be plated with a plated product with good adhesion of the plating film, regardless of the shape of the molded product, by plating a molded product of a modified polyolefin with a specific composition. This relates to a plating method.

Regarding conventional polyolefin plating methods, many methods have been introduced in literature, patent publications, etc., but not all of them are necessarily practical.

For example, when polypropylene is added with rosin, a modified product thereof, or a petroleum resin, a plated product with good adhesion can be obtained by press molding, but a plated product with good adhesion cannot be obtained by injection molding, making it impractical. The situation is unbearable.

By adding an inorganic filler to these rosins or petroleum resins, the adhesion of injection molded products may be greatly increased, but depending on the shape of the molded product, good adhesion may not be obtained. There are many cases where there is no.

Especially when the wall thickness of the molded product is small, or when the molded product is not flat but spherical or rounded, such as a bowl or a washbasin, good adhesion cannot be obtained. hard.

As a result of repeated research to improve the shortcomings of the conventional method, the present inventors have determined whether or not the shape of the molded product causes a decrease in the adhesion of the plating, and even if it does, what are the effects of this? The present invention was achieved by discovering a modified polyolefin that is extremely small and poses no problem in practice.

The present invention is based on (a) a crystalline polypropylene resin and a bromine number of 40[
:, F/100g sample] 7 to 20% by weight of at least one petroleum resin, or crystalline polyethylene resin and bromine number 30 Cg/100g sample] of at least one petroleum resin of 2 to 20% by weight, (0) 3 to 20% by weight of titanium oxide, (c) 0.2 to 1% by weight of a nonionic surfactant with a hydrophilic-lipophilic balance of 15 or less, or 0.2 to 1% by weight of the nonionic surfactant. % and a plasticizer by 0.2 to 2% by weight, and a plate-shaped, spherical or round shape with a thickness of 3 mm or less obtained by molding a modified polyolefin containing the above (a), (==), and (c). This is a polyolefin plating method characterized by plating a molded body having a polyolefin.

The polyolefin used in the present invention is ethylene,
One or more crystalline homopolymers or copolymers of lopylene, phytene-1,4-methylpentene-1,
Alternatively, it also includes a crystalline copolymer containing one or more of the above monomers as a main component and other monomers.

For example, polyethylene, polypropylene, polybutene-1
, poly-4-methylpentene-1, ethylene-propylene copolymer, and propylene-4-methyl-pentene copolymer ring.

As petroleum resins, those having good compatibility with polyolefins are used, including olefins, naphthenes, aromatic petroleum resins, terpene resins obtained by polymerizing α-pinene or β-pinene, coumaron, and indene. and coumarone-indene resin obtained by copolymerizing styrene, and cyclopentadiene resin.

The blending ratio of petroleum resins is 7 to 20% by weight of bromine number 40 (9/100J sample) when crystalline polypropylene resin is used, and bromine number 30 (9/100J sample) when crystalline polyethylene resin is used. g/100g sample] or more can be used in an amount of 2 to 20% by weight to obtain preferable results.

It is also possible to use one type or a combination of two or more of the above resins.

In the present invention, better results can be obtained by using titanium oxide as an inorganic filler than, for example, by using talc, and the amount used is 3 to 2 ml based on the modified polyolefin.
It is 0% by weight.

As nonionic surfactants, those with good compatibility with polyolefins are effective, and the hydrophilic-lipophilic balance (H
, L, B, values.

) is 15 or less, it is possible to obtain an advantageous adhesion of plating to a plate-like molded product having a small wall thickness, or a molded product having a spherical or rounded shape.

The hydrophilic groups handled for nonionic surfactants are polyoxyethylene chains and polyhydric alcohols (glycol, glycerin, sorbitol, etc.), and by focusing on the weight of the hydrophilic groups in the nonionic surfactant molecules, the following formula is obtained. The relationship is known.

E(, L, B, = 20 Neugen ET140, a polyoxyethylene alkyl ether manufactured by Kogyo Yakuhin ■ (the alkyl group is an oleyl group).

H, L, B. -14), Neugen ET102 (alkyl group is based on lauryl group).

Neugen EA80 (the alkyl group is a nonyl group) of polyoxyethylene alkylphenol ethers such as H, L, B, = 10).

H, L, B, -8\Neogen EA142 (alkyl group is based on octyl group).

H, L, B, = 14), Neugen EA73 (
The alkyl group is a dodecyl group.

Neugen ES120 (having an oleic acid group) of polyoxyethylene alkyl esters such as H, L, B, -7).

H, L, B, = 1'2), Neugetsu ES140 (contains oleic acid group).

Solgen 90 (manufactured by Daiichi Kogyo Seiyaku ■), which is a sorbitan alkyl ester such as H, L, B, = 14), has a lauric acid group.

Sorgen TW60 (H, L, B, = 8.6) etc. of polyoxyethylene sorbitan alkyl ester
It has a stearic acid group.

H, L, B, = 14.9), etc.

Preferable results can be obtained with a blending amount of 0.2 to 1% by weight; if too much is used, the molded product may tend to soften and cause rib-bleeding.

As in the case of nonionic surfactants, plasticizers having good compatibility with polyolefins are effective, and those having a boiling point higher than the processing temperature of polyolefins are preferred.

The main ones are phthalate ester plasticizers (e.g. dioctyl phthalate, didecyl phthalate, ditridecyl phthalate, etc.) and adipic acid ester plasticizers (e.g. dioctyl adipate, didecyl adipate, octyldecyl adipate, etc.) , sepatic acid ester plasticizers (e.g. dioctyl sebacate, butylbenzyl sebacate, etc.), azelaic acid ester plasticizers (
For example, dioctyl azelate, dioctyl azelate, etc.), citric acid ester plasticizers (for example, tributyl citrate, tri-2-ethylhexyl acetyl citrate, etc.),
Chlorinated plasticizers (e.g. chlorinated paraffin, chlorinated fatty acid ester), fatty acid ester plasticizers (e.g. butyl stearate, etc.), polyester plasticizers (e.g. polypropylene, adipate, polypropylene sebacate, etc.)
etc. can be mentioned.

The amount of plasticizer used is from 0.2 to 0.2 based on the modified polyolefin.
Preferable results can be obtained with 2% by weight.

In addition, the modified polyolefin of the present invention may contain other additives that are normally added to polyolefins in order to improve the processability or physical properties of polyolefins, such as stabilizers, dispersants, pigments, etc.
There is no problem in adding such things.

These additives can be mixed using a mixing and kneading machine commonly used for plastics or rubber, such as a kneader, mixing roll, Banbury mixer 1 extruder, or a Henschel mixer. It is also possible to mix the mixture using a , super mixer, etc., and then directly apply it to an injection molding machine.

In the present invention, the plating process can be performed using conventional, well-known techniques, and there are no particular limitations on the process.

Therefore, the most commonly used plastic plating process, which is degreasing → etching → sensitizing → activating → chemical plating → electroplating, is sufficient for plating.

According to the method of the present invention, a plated product with high plating adhesion can be obtained, whether it is a pressed product or an injection molded product, and in particular, a plated product that does not suffer from a decrease in adhesion due to the shape of the molded product can be obtained. has great advantages.

Therefore, plated products with high adhesion can be obtained even for thin molded products or rounded molded products like a bowl.This solves one of the major obstacles in the conventional polyolefin plating method, and can be used for many applications of polyolefin. becomes even wider.

Applications include automobile parts, home appliance parts, miscellaneous goods, etc., and expectations are particularly high for large molded products and decorative items with complex shapes.

Examples are shown below.

Examples 1-3 Comparative Examples 1-22 Plating was applied to molded products using the materials described below.

Crystalline polypropylene (specific gravity 0.902, J/L
/Toflow index 5.6g710min In the table, PP
It is abbreviated as

) (B) Petroleum resin B-1 bromine number 501 J'/10 (Bi' sample), softening point 60°C, unsaturated hydrocarbon type In the table, it is abbreviated as (50).

B-2 bromine number 36 [1i'/100g sample], softening point 1
00°C, abbreviated as (36) in the diene/olefin system table.

B-3 Bromine number 30 [I/100g sample], softening point 85°
C1 diene/olefin system In the table, it is abbreviated as (30).

B-4 bromine number 251J'/100g sample], softening point 70
°C1 diene/olefin system In the table, it is abbreviated as (25).

B-5 bromine number 2.4 (g7100g sample), softening point 10
0°C, alicyclic hydrocarbon type In the table, it is abbreviated as (2,4).

(C) Inorganic filler C-1 titanium oxide (average particle size 0.3μ In the table, TlO2
It is written as

) C-2 barium sulfate (average particle size 0.6μ In the table, Ba
Write it as salt.

) C-3 talc (average particle size 8μ) C-4 clay (average particle size 1.5μ) (D) Nonionic surfactant polyethylene glycol octylphenyl ether (Neugen EA142 manufactured by Daiichi Kogyo Yakuhin ■, molecular weight approx. 630.H)
, L, B, = 14 In the table, it is abbreviated as Neugen.

) (D-lipolyethylene glycol (molecular weight approximately 300. H, L, B, = 20, abbreviated as PEG in the table.

) (mouth plasticizer Dioctyl phthalate In the table, abbreviated as DOP.

(F) Sulfur-containing compound dilauryl thiodipropionate In the table, it is abbreviated as 5cpd.

The above formulations are blended in the proportions shown in Table 1,
After mixing with a tumbler mixer, an extruder (extrusion temperature 2
The mixture was kneaded and pelletized at 00°C.

Next, a flat plate with a size of 50×50×1.8 mm was molded at a molding temperature of 250° C. using a screw in-line injection molding machine, and plated by processing in the following order.

(a) Etching: sulfuric acid 600Ce, chromic anhydride 30
Treated with an etching solution having the composition of g at 70°C for 10 minutes and washed with water.

(b) Sensitizing: Immerse for 3 minutes at room temperature in a solution containing 100cc of water, 10g of stannous chloride, and 40cc of concentrated hydrochloric acid, and wash with water.

(c) Activation: Treatment in a solution containing 100 cc of water, 2 g of palladium chloride, and 2.5 cc of concentrated hydrochloric acid at room temperature for 3 minutes, followed by washing with water.

(to) Chemical plating; 11 contains 35 g of copper sulfate, 50 g of possible soda, 20 g of soda carbonate, Rochelle salt 1705',
Chemical steel plating was performed by immersing it at room temperature for 20 minutes in a plating solution prepared by mixing 5 volumes of an aqueous solution containing 20 CC of EDTA/triethanolamine and 1 volume of a 37% formalin solution.

(e) Electrolytic copper plating; copper sulfate 200g/l, sulfuric acid 50
g/l, in an acidic steel plating solution containing a commercially available brightener (UBAC=#=1 Ebara Infilco KK) at a negative electrode current density of 0.5 A/ffl for 5 minutes, and then the current density was increased to 5/l. Plating was carried out for 40 minutes by raising the temperature to CRJ.

Next, two notches were made on the plated surface at an interval of ICrrL, the notches were peeled off with a knife, and the peel strength of the plating was measured by pulling the plated layer in a 90 degree direction at a tensile rate of 3 crrt/min.

The results are shown in Table 1. Examples 4-5 Comparative example 23-
25 Plating occurred on a molded product using the material to be applied next.

High-density polyethylene (specific gravity 0.953, melt index 4.4 g/10 min. In the table, abbreviated as HDPE.

) Petroleum resin Bromine number 36 (,9/IoOg sample) Niscolella 1103U manufactured by Esso Standard Sekiyu ■ Contains some cyclic substances and contains no aromatic components It is abbreviated as Niscolella in Table 3.

Titanium oxide Same as Example 1.

Plasticizer Same as Example 2.

Sulfur-containing compound Same as Comparative Example 4.

The above ingredients are mixed in the proportions shown in Table 2,
After mixing with a tumbler mixer, an extruder (extrusion temperature 2
The mixture was kneaded at 00°C) and pelletized.

The subsequent steps were carried out in the same manner as in Example 1, and the molding was performed to avoid plating.

The results are shown in Table 2.

Abbreviations in the table conform to Table 1. Examples 6-7 Comparative example 2
6-29 The ingredients used in Examples 1 and 2 were mixed and molded into a flat plate of 80 mm x 80 mm x 3 mm at a molding temperature of 200°C using the same injection molding machine.

Thereafter, plating was performed in the same manner as in Example 1, and the evaluation was performed.

The results are also shown in Table 2. Abbreviations in the table conform to Table 1.

Examples 8-9 Comparative Examples 30-31 The ingredients used in Examples 1 and 2 were blended and the same injection molding machine was used to produce a bowl with a top diameter of 77 mm, a bottom diameter of 50 mm, a depth of 33 mm, and a side wall thickness of 3 mm. A shaped article was molded at a molding temperature of 200°C, and then the plating was rolled up in the same manner as in Example 1, and the peel strength in the circumferential direction of the plated film on the outer surface was evaluated.

The results are also shown in Table 2. Abbreviations in the table conform to Table 1.

Claims (1)

[Claims] 1. Based on the modified polyolefin after being contained in the polyolefin (a) a crystalline polypropylene resin and a bromine number of 40 [
g/100g sample] 7 to 20% by weight of at least one petroleum resin, or 2 to 20% by weight of at least one crystalline polyethylene resin and a petroleum resin with a bromine number of 30 or more [g/100g sample]. (b) 3 to 20% by weight of titanium oxide, (c) 0.2 to 1% by weight of a nonionic surfactant with a hydrophilic-lipophilic balance of 15 or less, or 0.2 to 1% by weight of the nonionic surfactant. % and a plasticizer by 0.2 to 2% by weight, having a flat, spherical or round shape with a thickness of 3 mm or less obtained by molding a modified polyolefin containing the above (a), (b), ()→ A polyolefin plating method characterized by plating a molded body.