JPH06238805A - Transparent plastic molded product - Google Patents

Abstract

PURPOSE:To obtain a transparent plastic molded product excellent in heat resistance and having solvent resistance and low gas permeability by providing a transparent film composed of insulating metal oxide to the single surfaces or both surfaces of a film or sheet of a polymer containing a norbornane ring. CONSTITUTION:A monomer composed of at least one kind of a norbornane derivative or a compsn. consisting of this monomer and a monomer copolymerizable therewith is subjected to ring opening polymerization to obtain a polymer and this polymer is further hydrogenated to obtain a hydrogenated polymer which is, in turn, molded into a film or sheet by extrusion, injection, compression or wet casting to obtain a transparent plastic molded product. Insulating metal oxide is formed on this molded product by a sputtering method using opposed targets. Since a sputting region and a film forming region are separated in the sputtering method, the collision of plasma with the molded product at the time of the formation of a film is eliminated and the damage of accumulated oxide or the temp. rise of the molded product is prevented and an insulating film reduced in internal stress can be formed at low temp.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent plastic molded product, and more particularly to the structure of a transparent plastic molded product.

[0002]

2. Description of the Related Art In recent years, transparent plastic molded products are thin,
From the viewpoint of light weight, it has been used as a substitute for a glass substrate for display applications such as substrates for liquid crystal display elements and substrates for electroluminescence, and for various applications such as substrates for touch panels and substrates for surface heaters. Examples of the material of the transparent plastic molded product used for this purpose include polyethylene terephthalate, polyethylene sulfone, polyarylate, polycarbonate and the like. In addition, a thin glass plate is currently used in a CCD lid, but a plastic substitute is required to reduce costs and improve workability. However, in the CCD, water permeability is maintained in order to maintain chip performance. No, it is required to adhere to the CCD case (ceramic material). With plastics, this water permeability and poor adhesion to ceramics pose problems.

[0003]

However, when these transparent plastic molded products are used as substrates for displays, a transparent conductive film is formed on the surface of the transparent plastic molded product, and the transparent conductive film is subjected to a photoetching method or the like. It is used to form a desired shape pattern. In this process, water,
Acids, alkalis, and organic solvents are used, but the transparent plastic moldings do not have sufficient resistance to these chemicals and cause swelling or dissolution, which poses a practical problem.

Further, when these transparent plastic molded products are used for liquid crystal display devices, the amount of gas permeation is very large as compared with liquid crystal display devices using glass substrates, so gas and water vapor in the air are transparent plastic molded substrates. However, there is a problem that the gas accumulated due to an external force or a sudden temperature change is generated as bubbles.

Therefore, in order to improve the gas permeation resistance of the transparent plastic molded product, a technique has been proposed in which a low gas permeable organic film is applied to the surface of the transparent plastic molded product or another organic film is attached. ing. However, in the method of applying an organic film or bonding another organic film, there is a problem that bubbles are mixed or impurities are mixed at the time of film formation and bonding, which causes a problem in sufficient gas barrier performance and long-term reliability of the liquid crystal display element. There is. Furthermore, as another method for improving gas permeability, a method of forming an inorganic film on the surface of a transparent plastic molded product has been proposed, but deformation of the transparent plastic molded product due to heat during film formation, There has been a problem that the inorganic film formed on the transparent plastic molded product is distorted due to the temperature change and a sufficient gas barrier effect cannot be obtained.

An object of the present invention is to solve the problems of the transparent plastic molded product and to provide a transparent plastic molded product having improved heat resistance, solvent resistance and gas barrier property.

[0007]

In order to achieve the above object, according to the present invention, a monomer consisting of at least one norbornane derivative represented by the following formula (I) or a monomer thereof and a monomer thereof On the surface of a hydrogenated polymer molded product obtained by further hydrogenating a polymer obtained by ring-opening polymerization of a polymerizable copolymerizable monomer, an insulating metal is used by using a facing target type sputtering device. It is intended to provide a transparent plastic molded product formed by forming an oxide.

[0008]

[Chemical 1]

(Wherein A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, C and D are hydrogen atoms or monovalent organic groups, and at least one of C and D is Has a polar group other than a hydrogen atom and a hydrocarbon group.) The hydrogenated polymer used in the present invention is described, for example, in JP-A-1-240517 and JP-B-57-8815. The thermoplastic resin etc. which are used can be mentioned.

In the tetracyclododecene derivative represented by the above formula (I), it is preferable that A, B, C and D contain a polar group from the viewpoint of adhesion to the insulating metal oxide. Here, the polar group is more preferably a carboxylic acid ester group represented by-(CH2) nCOOR1 from the viewpoint that the hydrogenated polymer obtained has a high glass transition temperature. In particular, the polar substituent group composed of this carboxylic acid ester group is preferable in that the hygroscopicity can be lowered while maintaining the high heat resistance of the tetracyclododecene derivative of the formula (I).

Further, among the carboxylic acid ester groups represented by-(CH2) nCOOR1, those having a smaller value of n are preferable because the glass transition temperature of the hydrogenated polymer obtained becomes higher. In the above formula (I), R1 is a hydrocarbon group having 1 to 20 carbon atoms, and it is preferable that the number of carbon atoms increases, as the hygroscopic property of the hydrogenated polymer obtained becomes smaller, but the hydrogenated polymer obtained is preferable. From the viewpoint of the balance with the glass transition temperature of, a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms is preferable, and a methyl group, an ethyl group or a cyclohexyl group is particularly preferable. Is preferred. Furthermore, the tetracyclododecene derivative of the formula (I) in which a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which the carboxylic acid ester group is bonded is a hydrogenated polymer to be obtained. It is preferable because it lowers the hygroscopicity without lowering the glass transition temperature. In particular, the tetracyclododecene derivative of the general formula (I) in which this substituent is a methyl group or an ethyl group is
It is preferable because its synthesis is easy.

In the present invention, the hydrogenated polymer has an intrinsic viscosity ([η] in) measured at 30 ° C. in chloroform.
h) is preferably in the range of 0.3 to 1.5 dl / g. Further, in the present invention, the hydrogenated polymer generally has a weight average molecular weight of 5,000 to obtain sufficient strength.
It is 1,000,000, preferably 8,000 to 200,000. The hydrogenation rate of the hydrogenated polymer is 60 MHz, ¹ H
-The value measured by NMR is 50% or more, preferably 90%
Or more, more preferably 98% or more. The higher the hydrogenation rate, the better the stability to heat and light. The hydrogenated polymer used in the present invention has a gel content of 5% by weight contained in the hydrogenated polymer.
It is preferably not more than 1% by weight, more preferably not more than 1% by weight.

If necessary, the thermoplastic polymer used in the present invention may be blended with other thermoplastic resins. The hydrogenated polymer includes stabilizers, antioxidants, lubricants, antistatic agents, ultraviolet absorbers, optical brighteners, plasticizers, additives such as release agents, quartz fibers, glass fibers, and Reinforcing materials such as aromatic polyamide fibers and high-strength and high-elasticity polyethylene fibers can also be blended.

The transparent plastic molded product of the present invention is a transparent plastic molded product (hereinafter simply referred to as "molded product") obtained by extruding the above hydrogenated polymer and molding it into a film or sheet by a known method such as injection, compression or wet casting. )above,
The insulating metal oxide is formed by the sputtering method using a facing target. In the present invention,
This molded product may be selected depending on the application, but when it is used as a substitute for a glass substrate, it usually has a thickness of 0.01.
It is formed into a film or sheet having a thickness of 10 mm.

The insulating metal oxide film (hereinafter simply referred to as "insulator") of the present invention has a volume resistivity of 10 ⁹ ohm meters or more, and is made of a Group IIIA oxide such as aluminum oxide or indium oxide. Mention may be made of Group VB oxides such as niobium oxide, tantalum oxide, silicon oxide and mixtures of these oxides. Of these, aluminum oxide and tantalum oxide are preferable.

In the present invention, the thickness of the insulating film is preferably 200 to 4000 angstroms, more preferably 500 to 2 angstroms, from the viewpoint of chemical resistance and gas barrier property.
000 angstroms. A sputtering device using a facing target (hereinafter simply referred to as "sputtering device") is suitable for forming the insulating film. In the sputtering apparatus, the target electrodes are arranged in parallel to each other with a pair of targets separated from each other, and the sputtering region and the film forming region of the target are completely separated. Both targets are connected to DC power supply and high frequency power supply,
Either DC sputtering or high frequency sputtering can be selected by switching the power source.

In the sputtering device using the facing target, a plasma converging magnetic field is formed between the targets. The γ-electrons emitted from the target are confined in the space between the targets by the plasma converging magnetic field and reciprocate between the opposing targets while being bound by the magnetic field. During this time, the γ-electrons collide with the argon gas (sputtering gas) introduced into the apparatus to generate argon ions and electrons, and further accelerate the emission of γ-electrons from the target and the ionization of the argon gas. As a result, a high density plasma is generated between the targets, and the target is sputtered by the plasma. Sputtered particles (sputtered metal particles)
Reacts with the oxygen gas introduced from the oxygen gas introduction system into the sputtering apparatus and accumulates on the surface of the molded body.

In the above sputtering method according to the present invention,
Since the sputter region and the film formation region are separated, plasma collision does not fly to the compact during film formation, damage to the deposited oxide and temperature rise of the compact can be prevented, and internal stress at low temperatures can be prevented. A small amount of insulating film can be formed.

[0019]

In the present invention, since a polymer containing a norbornane ring is used as a molding material, it has excellent heat resistance. Further, since an insulating film is formed on the surface of the molding with a sputtering device, it is resistant to solvent and gas permeation. A transparent plastic molded product having excellent barrier performance can be provided.

[0020]

EXAMPLES The present invention is described in detail below based on examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. Also, various measurements in the examples,
It is as follows.

Reference Example 1 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7 , 10,} ] dodeca-3-en 10
0 g, 1,2-dimethoxyethane (60 g), cyclohexane (240 g), 1-hexene (25 g), and dimethylaluminum chloride (0.96 mol / l) in a toluene solution (3.4 ml) were added to an autoclave having an internal volume of 1 liter.

On the other hand, in another flask, 20 ml of a 1,2-dimethoxyethane solution containing 0.05 mol / l of tungsten hexachloride and 0.1 mol / l of paraaldehyde are added.
Ten milliliters of 1,2-dimethoxyethane solution were mixed. 4.9 ml of this mixed solution was added to the mixture in the autoclave. After sealing, the mixture was heated to 80 ° C. and stirred for 3 hours. To the obtained polymer solution was added a mixed solvent of 1,2-dimethoxyethane and cyclohexane in a ratio of 2/8 (weight ratio) to obtain a polymer /
After the solvent was adjusted to 1/10 (weight ratio), 20 g of triethanolamine was added and stirred for 10 minutes. To this polymerization solution, 500 g of methanol was added, stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, the mixture was stirred and left standing, and then the upper layer was removed. The same operation was repeated twice, and the obtained lower layer was appropriately diluted with cyclohexane and 1,2-dimethoxyethane to obtain a cyclohexane-1,2-dimethoxyethane solution having a polymer concentration of 10%.

To this solution was added 20 g of palladium / silica magnesia [manufactured by JGC Chemical Co., Ltd., amount of palladium = 5%] hydrogenation catalyst, and hydrogen pressure was 40 kg in an autoclave.
/ Cm ² after 4 hours of reaction at 165 ° C. as the hydrogenation catalyst was removed by filtration to obtain a hydrogenated polymer solution.
Further, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], which is an antioxidant, was added to the hydrogenated polymer solution.
After adding 0.1% to the hydrogenated polymer, the solvent was removed at 380 ° C. under reduced pressure. Then, the molten resin,
It was pelletized by an extruder in a nitrogen atmosphere to obtain a hydrogenated polymer having an intrinsic viscosity of 0.5 deciliter / g (30 ° C., in chloroform), a hydrogenation rate of 99.5%, and a glass transition temperature of 168 ° C.

[0024]

Example 1 Using the pellets of the hydrogenated polymer obtained in Reference Example 1 as a raw material, a film-shaped molded product having a length of 200 mm, a width of 200 mm and a thickness of 0.1 mm was produced. An aluminum oxide film was formed on the obtained molded body by a direct current reactive sputtering method using a facing target type sputtering apparatus (manufactured by Osaka Vacuum Co., Ltd.). Before forming an insulating film, the surface of the molded body was subjected to argon etching to remove adsorbed substances on the surface. To make aluminum oxide,
Using a facing target type sputtering apparatus having a target interval of 140 mm and a distance between the center of the substrate and the center of the target of 130 mm, a target material of size 100φ × 5 mmt,
Exhaust pressure 5 × 10 ^-4 using 4N up aluminum
Under the conditions of Pa, introduced argon pressure 0.23 Pa, introduced oxygen partial pressure 5.8 × 10 ⁻³ Pa and sputtering power 0.1 KW, aluminum oxide having a thickness of 1500 angstrom was produced on one surface of the compact. . Then, under the same conditions, aluminum oxide having a thickness of 1500 angstrom was formed on the other surface of the molded body. The oxygen gas introduced at the time of sputtering was arranged on the film formation region side in the sputtering apparatus in order to improve the oxidation degree of the insulating film and prevent the metal target from being oxidized.

The solvent resistance of the molded article of this example was tested by immersing it in the organic solvent shown in Table 1 at a temperature of 25 ° C. for 1 hour. For comparison, the same test was performed on the solvent resistance of the molded product having no insulating film. The results are shown in Table 1. As is clear from the table, the molded article provided with the insulating film of the present example has a very excellent solvent resistance against dissolution by the following solvent immersion in the molded body alone. .

[0026]

[Table 1]

Further, the oxygen gas permeability of the above-mentioned molded product was tested, and the oxygen gas permeability coefficient of the molded product was also tested. As a result, the molded product alone was 1.5 × 10 ⁻¹⁰ (cm ³ · cm / c).
m ² · sec · cmHg), but in the molded article provided with the oxide of this example, 3.5 × 10 ⁻¹³ (cm ³ · cm /
cm ² · sec · cmHg), and has a very excellent gas barrier property as compared with the molded product.

[0028]

According to the present invention, a transparent plastic molded article having excellent heat resistance, solvent resistance and low gas permeability can be obtained.

Claims (2)

[Claims] 1. A transparent plastic molded product comprising a film of a polymer containing a norbornane ring or a sheet, and a transparent film made of an insulating metal oxide provided on one or both sides of the sheet. 2. The transparent plastic molded product according to claim 1, wherein the insulating metal oxide is formed by a sputtering method using a facing target.