JPS5941337A - Coating of polyolefin molded article with resin composition curable with light or radiation - Google Patents

Abstract

PURPOSE:To form a coating film having excellent scratch resistance, hardness and adhesivity, by coating a pretreated polyolefin molded article with an undercoating agent containing halogenated polyolefin, curing the undercoating layer, and applying a light- or radiation-curing composition thereto. CONSTITUTION:A polyolefin resin molded article (e.g. polyethylene) is pretreated with a halogenated hydrocarbon solvent (e.g. chloroform), and coated with an undercoating agent obtained by dissolving a halogenated polyolefin (e.g. chlorinated polypropylene) having a chlorine-content of 5-35wt% in a solvent (e.g. trichloroethylene, toluene, etc.). After drying the undercoating agent, the surface is coated with a light- or radiation-curing resin composition (e.g. unsaturated polyester resin), and if necessary, ethylenic unsaturated monomer (e.g. styrene), photopolymerization initiator (e.g. benzoin), pigment, colorant, plasticizer, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for applying a light- or radiation-curable resin composition to a polyolefin resin IJI molded article.

For more details, please refer to the air pressure molding of polyolefin resin Il&.
After obtaining various plastic molded products (hereinafter referred to as plastic molded products) by extrusion molding, injection molding, etc., the molded products are treated with halogenated hydrocarbon. After the treatment, a smearing agent mainly composed of halogenated polyolefin, C and a solvent is applied, and after drying, a photo- or radiation-curable resin composition is applied to the surface.

Polyolefins are used in a wide range of applications because they have excellent mechanical properties such as rigidity and tensile strength, are highly chemical resistant, and have poor processability. However, polyolefins have the disadvantage of poor ulcer resistance.

Possible means to cover this defect include a method of blending a modifier and a method of applying it to the surface.

However, the former deteriorates other physical properties of polyolefin,
However, since the polyolefin is a non-polar polymer, there is a problem in that good adhesion cannot be obtained between the coating agent and the polyolefin.

In order to solve these problems, the present inventors have developed a sharp U-shape R1.
As a result, they discovered a method that provides good adhesion and improved hardness and one-piece bonding properties, resulting in the present invention.

That is, after a polyolefin resin molded article is treated with a halogenated hydrocarbon, an undercoat whose main components are a halogenated polyester fin and a solvent is applied, and after drying, the surface is cured with light or radiation. This is a method of applying a resin composition.

Typical polyolefins used in the present invention include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-ethylene-butene terpolymer, ethylene-pentene copolymer, polybutene, and combinations thereof. can be mentioned. Further, if necessary, a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, and fillers such as glass fines, talc, wood flour, and calcium carbonate may be added.

Although the halogenated hydrocarbon solvent used as the pretreatment agent used in the present invention is not preferable in terms of working environment, it has many desirable features such as being flame retardant or noncombustible and having little risk of fire. Examples of halogenated hydrocarbon solvents include methylene chloride, chloroform, carbon tetrachloride, 1.1.1
-trichloroethane, 1.1.2.2-tetrachlorethylene.

)-IJ chlorethylene, perchlorethylene, methylene bromide, bromoform, furunone IB.

Examples include Freon f3 F.

Methods for this surface treatment include steaming with halogenated hydrocarbon steam, wiping with the same solvent, or immersion, but steaming with steam is preferred as a method that facilitates homogeneous work.

Examples of the halogenated polyolefin used as an undercoat agent in the present invention include chlorinated polyethylene, chlorinated polypropylene, and chlorinated ethylene-propylene copolymer. In particular, chlorinated polypropylene is produced on an industrial scale and is used in the present invention. Industrial implementation is extremely easy and advantageous. The halogen content of the halogenated polyolef 7f is preferably 5 to 85%, preferably 20 to 80% by weight.

As a solvent that can be used for halogenated poly(S-1/F), it is industrially available in a large quantity, has suitable volatility, and has a history of halogenated ((S-poly*1/), indium. Completely #j
It is preferable to dissolve or evenly spread the water over 1) Q series. For this purpose, for example, the four j1. ．． f f11 carbon, l-lychlorethynon, 1
．． ], ]11-Rik1]/'% rogenated aliphatic carbons such as lueta, hydrogen, 1 and 1 ruene, aromatic hydrocarbons such as benzene, decalin, tetrane, chloro, etc. Benzene a which λloge/change: I'? It can also be used as a mixed solvent of group 9 hydrocarbons, acetone, methyl enalthione, etc., tetrahydrofuran, etc., or a mixed solvent of two or more oils.

The method for applying the lower Pjifl agent is to apply it to the surface of the IJ Poly 4 Refine resin molded product using a dipstick, tα, spray, etc., or to immerse the plastic molded product in the lower Pjifl agent solution. This method requires no installation fee.

The light- or radiation-curable resins used in the present invention include conventionally known polyester resins, urethane-acrylic resins, melamine-acrylic resins, acrylated polyester resins, and epoxy-acrylic resins. It can be used in one dish or a combination of two types.

- In addition to light distribution or radiation curing resins, commonly used ethylenically unsaturated monomers such as styrene, vinyl acetate, 2-vinylpyridine, N-vinyl Pyrrolidone, N-vinylcarbazole, methyl acrylate, ethyl acrylate, butyl acryle-1, lauryl acrylate-1
・, stearyl acrylate, benzyl acrylate,
Bidrogyethyl acrylate, cyclohexyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate-ethyl methacrylate, butyl methacrylate-1・, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate-1, triethyl 1 non-glycol dimethacrylate, 1,6-hex→non-diol dimethacrylate-1, trimethylolpropane trimethacrylate-1
・, pentaerythritol tetramethacrylate 1, etc. can be used for 1 month. Of course, these are Chinese and German.
-) '(-Also 2) Even if 11 polyester resin, acrylic resin 1, alkyd resin, polymers such as ethylene-vinyl acetate copolymer, pigments, -6 colorants, plasticizers, etc. are used. There is no problem as long as it does not impair the essence of the present invention.

The photocoat of the present invention is to cure the radiation-curable resin composition by irradiation with purple I-rays or electron beams. It can be carried out using benzophenone, ketones such as micellar ketone, azobi, or by various combinations of these.

Furthermore, the light- or radiation-curable resin of the present invention may be diluted with a solvent such as ethyl acetate or n-butyl acetate as necessary.

Methods for applying the light- or radiation-curable 1 fat-resistant composition to molded articles include commonly used methods such as grouping, spray painting, and dipping.

The present invention will be explained below with reference to Examples.

Synthesis Example 1 Hexamethoxymethylmelamine (manufactured by Sumitomo Chemical Co., Ltd., Sumimaru M-100) 890y, ethylene glycol monoacrylate-1-480f, 2-metalha-C droquinone 0.88/l in a stirrer, Fuchi/l'# Pour into a flask equipped with L1 vacuum device and cooling condenser, and reduce to 85%.
Add 0.9 txt of phosphoric acid and react under reduced pressure at 80-85°C. When the distillate reaches 128y, return to normal pressure and cool, resulting in light-cured light yellow transparent viscous material. Resin liquid (
A) was obtained.

Example 1 A polypropylene block copolymer (melt index -2) containing 16% by weight of ethylene was molded using a molding machine to a thickness of 2 mm at a molding temperature of 280°C.
Injection molded plates of RL+ 90 mm were molded and subjected to testing.

After steaming the above molded plate with 1.1.1-1-lichloroethane vapor at 74°C for a0 seconds, spraying a lower f4 r) agent solution 8y containing Chlorinichi PP (chlorine content 28%) as the main component. was applied.

Thereafter, a photocurable resin composition prepared according to the following formula was applied to the undercoat coated plate using a parker #26 (film portion 26/L), and then a belt conveyor speed of 1 ( Irradiation was performed 15 times at 1+n/min.

3! The ratio was 100/100.

Also, -20°Oq 2]+r-*2B"c, 0.5h
r->70°C52hr is 1 cycle T: I
O9-('/ /l/ After leaving it, I looked at it in the evening and peeled it off with cellophane tape, but no abnormality was detected.Furthermore, Irradiation with a sunshade λ-in-weather meter (black) No decrease in gloss was observed even after the panel temperature was 68°C and water was heated to 40 lbs.

The pencil hardness of the polypropylene molded product used in Comparative Example 1 Actual Example was 2B.

Comparative Example 2 A photocurable resin composition was applied to a polypropylene molded product in the same manner as in Example 1, except that the application of the primer was omitted. The remaining ratio was 90/100.

Comparative Example 8 A test was carried out in the same manner as in Example 1, omitting the off treatment using a halogenated hydrocarbon solvent.'=A! ,
As a result, the residual rate of the 1qf adhesion test using Sellotape (■) was 9 F+/10 G.

Example 2 A polypropylene block copolymer containing 1% by weight of talc in a polypropylene molded product
f using August sentence hi%, melt index -2)
The test was conducted using the same chisel as in Example I.

As a result, the pencil hardness was 100/100 in the adhesion test compared to Fb Cellotape ■.

The pencil hardness of the polypropylene molded product used in Example 2 was 3B.

Example 8 JJ was completed in the same manner as in Example 1 up to the application of the primer.

After that, the photocurable resin composition prepared according to the recipe was applied to the undercoat coated plate ξ
ζ Each Park A-tar 1 $7 (membrane) 46 nol), #12
(Film thickness 12) 1) and Jt 26 (Film thickness 26) 1) were coated, and then irradiation was performed 20 times with a 80 W/- mercury lamp at a belt conveyor speed of 10 m/min.

The pencil hardness of the obtained test pieces was F (film thickness 671),
F<g thickness 12 units), l■ (film thickness 26) 1). In addition, the remaining rate of adhesion test with sellotape ■ is 10 for all 1 pieces.
It was 0/100.

Example 4 Test J3 was conducted in the same manner as in Example except that the photocurable resin composition shown in item 6 below was used.

As a result of the photocurable resin composition, the residual ratio of lead 111 was F, and the adhesion test with Sellotape (■) was 100/100.

Procedural amendment (spontaneous) 11S phase 30th month of 1958 Kazuo Wakasugi, Commissioner of the Patent Office, I υj (indication of '11: ++ Mwa 57th year Patent 1i/l No. 144875 Bow 2 6th name of Ming. 1+
Coating method of q-ray curable resin composition 8 Relationship with the person who makes the amendment
09) Hijikata, Representative of Sumitomo Chemical Ohri Co., Ltd.
Take 4, Agent Address: 5-15-5 Kitahama, Higashi IK, Osaka City Subject of amendment: ``I'' of the invention in the letter I, 4U of detailed explanation, 'd16
The detailed statement of contents of the amendment is detailed as follows.

(1) Add "1-compression molding," after "polyol/fin resin" in the second row from the bottom of liK, where 1=1.

(2) In the second line from the top, add ['compression molding,'] before ''compression molding.'

(3) 1 after 1-taluk in the 8th line from 11-sada
-24 J added 1° or more

Claims (1)

[Claims] After pre-treating the polyolefin resin molded article with a halogenated hydrocarbon solvent, an undercoat whose main components are a halogenated polyolefin with a chlorine content of 5 to 85 to V[%] and a solvent is applied, dried, and then the surface is exposed to light. Or a method for applying a light- or radiation-curable resin composition to a polyolefin resin molded product, which has excellent ambivalence, hardness, and adhesion (peel strength) on the coated surface, which is characterized by a small coating surface of the radiation-curable resin composition. .