JPS60260628A - Thermoplastic resin molding coated with plasma polymer film - Google Patents

Abstract

PURPOSE:The titled resin molding excellent in gas barrier property, moisture impermeability and liquid barrier property and high in the production rate, prepared by forming a plasma polymer film of a specified monomer on the surface of a specified thermoplastic resin molding. CONSTITUTION:The desired thermoplastic resin molding is obtained by coating the surface of a molding of at least one thermoplastic resin selected from among polycarbonate resins, styrene resins and polyolefin resins with a plasma polymer film of at least one monomer selected from among tetrafluoroethylene, acrylonitrile, acrylic acid, methyl methacrylate, vinyl chloride and vinylidene chloride. In order to activate the surface of the thermoplastic resin molding, it is desirable to pretreat the surface of the molding by ion bombardment in a plasma of an inert gas such as helium or argon.

Description

Detailed Description of the Invention [Technical Field 1 of the Invention] The present invention relates to a thermoplastic resin molded article coated with a plasma polymerized film, and more specifically, it has excellent gas barrier properties, moisture impermeability, and liquid barrier properties, and is easy to manufacture during production. The present invention relates to a thermoplastic resin molded article coated with a plasma polymerized film having high properties.

[Technical background of the invention and its problems] Thermoplastic resins such as polycarbonate resins, styrene resins, and polyolefin resins are widely used in various fields.

However, these thermoplastic resins have limited gas barrier properties.
Because these resins have poor water resistance and moisture impermeability, when food packaging containers, hydrocarbon storage containers, etc. are manufactured using these resins, problems such as oxidation of the contents and deterioration of the containers themselves may occur. There is.

In order to avoid this situation, a method has been used to coat the surface of these thermoplastic resin molded bodies with a resin having excellent gas barrier properties. There are disadvantages such as peeling phenomenon that occurs easily, and (1) manufacturing process becomes complicated.

Furthermore, as disclosed in Japanese Patent Application Laid-Open No. 55-8043i3, a method has been proposed in which a thin polymer film is formed on a thermoplastic resin molded body by plasma polymerization. However, the plasma-polymerized membrane obtained by this method cannot avoid the problems of (1) insufficient gas barrier properties and (2) low productivity due to slow reaction rate in plasma polymerization.

[Objective of the Invention J] The present invention solves the problems mentioned above and provides a plasma-polymerized film-coated thermoplastic resin that has excellent gas barrier properties, moisture impermeability, abrasion resistance, and chemical resistance, and has high productivity. The purpose is to provide molded objects.

[Summary of the Invention] As a result of extensive research in order to achieve the above object, the present inventors have found that when a plasma polymerized film is formed on the surface of a thermoplastic resin molded article, using a chisel described below, The present invention was completed after discovering the fact that the above-mentioned problems can be achieved.

That is, the plasma polymerized film-coated thermoplastic resin molded article of the present invention comprises a thermoplastic resin molded article and a plasma polymerized membrane that covers the surface of the molded article. The plastic resin molding is one or more resin moldings selected from polycarbonate resin, styrene resin, and polyolefin resin, and the plasma polymerized film is made of tetrafluoroethylene, acrylonitrile, acrylic acid, methacrylate. It is characterized by being a plasma polymerized membrane containing one or more monomers selected from acid methyl, vinyl chloride, and vinylidene chloride.

First, the thermoplastic resin molded article of the present invention is made of polycarbonate resin, which has excellent mechanical properties and is relatively easy to mold.
1 selected from styrene resin and polyolefin resin
It is a molded article of a thermoplastic resin or two or more kinds of thermoplastic resins.

The polycarbonate resin used in the present invention can be prepared by solvent method,
That is, a resin produced by the reaction of a divalent phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight modifier; (It is a resin produced by the cross-esterification reaction of phenol and diphenyl carbonate with a carbonate precursor.

Here, as the dihydric phenol that can be used, bisphenols are preferable, and 2,2-bis(4-hydroxyphenyl)furopane (bisphenol A) is particularly preferable. Alternatively, part or all of bisphenol A may be substituted with other dihydric phenol. Examples of dihydric phenols other than bisphenol A include hydroquinone, 4.4°-dihydroxydiphenyl, and bis(
4-hydroxyphenyl)alkane, bis(tohydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)
Compounds such as sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ether or halogenated bisphenols such as bis(3,5-dibromo-4-hydroxyphenyl)furopane may be mentioned. . A homopolymer or a copolymer or blend of two or more of these dihydric phenols may be used. Furthermore, it may be a thermoplastic randomly branched polycarbonate made by reacting a polyfunctional aromatic compound with a dihydric phenol and/or a carbonate precursor.

The polycarbonate resin used has a viscosity average molecular weight of 10.000 to 1 in terms of mechanical strength and moldability.
00,000 is preferable, especially 20,000 to 4
0,000 is preferred.

Examples of the styrenic resin used in the present invention include the following.

(A) a styrene homopolymer known as general purpose polystyrene (GPPS); (B) other monomers other than styrene, such as α-methylsulfone.

A copolymer of styrene and a styrene derivative such as 0-chlorostyrene, acrylonitrile, α-methylacrylonitrile, maleic anhydride, etc.; (C) Polymerization of styrene and other monomers as described above in the coexistence of synthetic rubber. Examples of copolymers include mixtures of resins (A), (B), and (C) and synthetic rubber. These styrene resins have a melt index (XI) of 0.3 to 5.
．． A material having a fluidity of 0 g/10 minutes is preferable.

Examples of the polyolefin resin used in the present invention include the following. That is, α-olefin homopolymers such as low-density polyethylene, high-density polyethylene, polypropylene, and polybutene; ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-
Copolymers of ethylene or propylene with other unsaturated monomers, such as acrylic acid copolymers; chlorinated polyethylene.

chlorinated polypropylene; etc.

The above-mentioned thermoplastic resins are used individually or in combination of two or more, and thermoforming methods such as injection molding, blow molding, and vacuum forming are applied to mold them into films, sheets, and other desired shapes. do. The molded body formed in this manner can be applied not only to tableware packaging containers and medicine containers, but also to, for example, helmets, home appliances/Usings, camera bodies, substrates for plated products, optical memory disks, and the like.

The raw materials for the plasma polymerized film according to the present invention include one or more selected from tetrafluoroethylene, acrylonitrile, acrylic acid, methyl methacrylate, vinyl chloride, and vinylidene chloride.

When the above-mentioned molded article is coated with a plasma polymerized film using the monomers mentioned above, the gas barrier properties will be improved regardless of which monomer is used, but the effect exerted by each monomer will be different. Therefore, each monomer is shown below.

First, when tetrafluoroethylene is used, gas barrier properties, moisture impermeability, chemical resistance, and wear resistance are improved; when acrylonitrile is used, gas barrier properties are improved.
properties and moisture impermeability are improved, and when acrylic acid is used, gas barrier properties and adhesion to molded articles are improved. In addition, when methyl methacrylate is used, the gas barrier
When vinyl chloride and vinylidene chloride are used, gas barrier properties and weather resistance are improved.・, (In manufacturing the plasma polymerized film-coated thermoplastic resin molded body of the present invention, first, prior to forming the plasma polymerized film, helium, argon, etc. Preferably, the surface of the compact is pretreated by using an ion pumper in an inert gas plasma.

Next, for plasma polymerization, the pretreated thermoplastic resin molded body is set in a reactor, and a gas consisting of the above-mentioned monomer is supplied into the reactor at a predetermined flow rate. Glow discharge is performed at a predetermined output using one of the frequencies, and the monomer is subjected to low-temperature plasma polymerization. By performing glow discharge for a predetermined period of time, a polymer film is formed on the surface of the molded body that is in contact with the discharge area. In this case, a polymer film can be formed on the whole or a part of the molded body.

The polymerization conditions during plasma polymerization depend on the type of molded product, its purpose,
It is selected as appropriate depending on the required performance and the type of monomer used, but the temperature is room temperature to 60°C; the pressure is 0.1 to I
h+mHg, preferably 0.2 to 5 m+nHg; discharge time is preferably in the range of 1 to 10 minutes; The frequency and output of the discharge power supply are different.

In the case of high frequency discharge, usually 13.58MHz, +(1
~200W;? For microwave discharge, 2450M
Hz, loo~5000W; For low frequency discharge,
It is recommended to set the frequency to 0.1 to 20kHz and 10 to 200W.

Among these, high-frequency discharge is preferable from the viewpoint of uniformly forming a polymer film. Incidentally, the atmospheric gas contains He, At
It is preferable that an inert gas such as , N2, etc. coexist.

The thickness of the polymer film is appropriately determined depending on the use of the molded article, etc., but is usually in the range of 100A to ]Ogm.

[Examples of the Invention] Examples 1 to 17 The following thermoplastic resin molded bodies were prepared. That is, PC board: polycarbonate resin with a viscosity average molecular weight of 28,000 molded into a board with a thickness of 2flffl by injection molding, LDPE film: density 0.910.
A 20ILm thick film made of low density polyethylene of 0.5g/10min, HOPE film: A 20ILm thick film made of high density polyethylene with a density of 0.945, 1g/10min, PP film. : Density 0.810 and I7. This is a 40 lm thick film made of polypropylene of Og/10 minutes, and a GPPS plate made of general-use polystyrene with a molecular weight of 250 and molded into a 2II1 m thick plate by injection molding.

The following monomers were prepared. That is, tetrafluoroethylene (TFE), acrylonitrile (
AN), acrylic acid (AA), methyl methacrylate (H
MA), vinyl chloride (VC), vinylidene chloride (VO
C).

The thermoplastic resin molded body was placed in a reactor of a low-temperature high-frequency plasma device, and the pressure inside one reactor was reduced to 10 −3 mmHg. Next, argon gas was supplied into the reactor, the pressure inside the reactor was maintained at 0.05 mmHH, and 13.
A pretreatment was performed by activating the surface of the molded article by performing a discharge for 10 minutes at an output SOW using a high frequency power source of 5f1 MHz. Next, plasma polymerization was carried out using the combinations of molded bodies and monomers shown in the table under the plasma polymerization conditions shown in the table. In Example 16, a mixture of TFE and MMA in a ratio of 1:1 was used. Measurement of the film thickness, oxygen permeation amount, water vapor permeation amount, and taper abrasion test of each obtained polymeric film were performed according to the following specifications.

Polymer film thickness: Measured using a reflection phase contrast microscope.

Oxygen permeation rate: Based on ASTM D-1434-86.

Temperature 40℃, humidity 80%, 24 hours, thickness 100#L
Displayed in m.

Water vapor permeation amount: Based on JIS 20208. thickness 10
Displayed in terms of 0 μm.

Taper wear test: Based on ASTM Row 1044-73. Using a wear wheel C5-10, measure the haze after performing taper wear 100 times under a load of 500g.

Comparative Examples 1 to 5 Oxygen permeation amount, water vapor permeation amount, and wear test when the molded body is not coated with a plasma polymerized film
1°“e, ,t.

2 [Effects of the Invention] As is clear from the above, the thermoplastic resin molded article coated with a plasma polymerized film of the present invention can contain oxygen, nitrogen, carbon dioxide, hydrogen,
Excellent gas barrier properties such as helium, moisture impermeability, and barrier properties against liquids such as organic solvents, gasoline, and kerosene. Furthermore, the product of the present invention has excellent abrasion resistance and strong adhesion between the polymer film and the molded article. In addition, since plasma polymerization is used, which has a high reaction rate, it is easy to manufacture and has high productivity.

Due to the above-mentioned excellent performance, the product of the present invention can be applied to a wide range of fields such as packaging films, various containers, sheets, home appliances, and various parts in the automobile field, and will greatly contribute to the industrial world.

4

Claims (1)

[Claims] In a plasma polymerized film-coated thermoplastic resin molded product comprising a thermoplastic resin molded product and a plasma polymerized film covering the surface of the molded product, the thermoplastic resin molded product is made of polycarbonate resin, styrene resin, polyolefin resin. The plasma polymerized film is one or more resin molded products selected from the following, and the plasma polymerized film is one or two resin molded products selected from the group consisting of tetrafluoroethylene, acrylonitrile, acrylic acid, methyl methacrylate, vinyl chloride, and vinylidene chloride. A thermoplastic resin molded article coated with a plasma polymerized film, characterized in that it is a plasma polymerized film containing the above monomers.