JPS6189265A - Corrosion-protecting material for clean room - Google Patents

Abstract

PURPOSE:To provide the titled protecting material having high stainproofing property, transparency, and corrosion-resistance, and having a protecting layer containing a crosslinked product of a copolymer of chlorotrifluoroethylene, fluoro(lower alkyl) vinyl ether and hydroxyalkyl vinyl ether. CONSTITUTION:The objective protecting material can be produced by compounding (A) a copolymer composed of (i) chlorotrifluoroethylene or tetrafluoroethylene, (ii) fluoro(lower alkyl) vinyl ether, preferably 2,2,3,3- tetrafluoropropyl vinyl ether, etc. and (ii) hydroxyalkyl vinyl ether, preferably hydroxybutyl vinyl ether, etc. with (B) a crosslinking agent (e.g. hexamethylene diisocyanate), applying the obtained coating composition to an interior material, and curing the coating layer. The molar ratios of the components (i):(ii):(iii) are preferably (40-60):(20-40):(1-30), and the amount of the component B is preferably 0.5-2 equivalent based on the OH in the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a corrosion-resistant protective material for clean rooms. More specifically, the present invention relates to a corrosion-resistant protective material for clean rooms provided with a protective layer having excellent stain resistance, transparency, and corrosion resistance.

[Conventional technology] Traditionally, in manufacturing factories in the semiconductor industry, etc., garbage,
Clean rooms are used to reduce the harmful effects of dust.

By the way, in the semiconductor manufacturing process, hydrofluoric acid,
Etching agents such as acetic acid, nitric acid, phosphoric acid, and halogenated gases; insulating film forming agents such as halogenated silanes, halogenated borons, halogenated phosphorous compounds, hydrogenated silanes, boron hydrides, phosphorus hydrides, and arsenic hydrides; Gases such as dopant agents are often used. If the interior materials in the clean room are corroded by these gases or the corrosive gases generated by their decomposition, garbage will be generated.In order to prevent corrosion, corrosion-resistant protective materials such as phenolic resins are installed in the clean room. It is often used.

[Problems to be Solved by the Invention] Corrosion-resistant protective materials such as phenol resin-based materials have a property that their surfaces are easily contaminated, and therefore require repair every 2 to 3 months.

On the other hand, since clean rooms are closed rooms, it is necessary to be able to see between the inside and the outside, and the corrosion-resistant protective materials used there are required to have excellent transparency. However, the conventionally used polymethacrylate materials and polycarbonate materials have problems in corrosion resistance.

An object of the present invention is to provide a corrosion-resistant protective material for clean rooms that has excellent corrosion resistance, antifouling properties, and transparency.

Means for Solving Problem E] The present invention provides (ω-chlorotrifluoroethylene (hereinafter referred to as CTFE) or tetrafluoroethylene (hereinafter referred to as TFE), (b) fluoro lower alkyl vinyl ether and TC
) A corrosion-resistant protective material for clean rooms provided with a protective layer containing a crosslinked copolymer mainly composed of hydroxyalkyl vinyl ether.

[Function and Examples] The protective layer in the present invention comprises (ω component and (to acid component (C
) component (hereinafter referred to as a fluorine-containing copolymer) and a crosslinking agent, and a film thickness of 5 to 100 obtained by applying a fluororesin paint and crosslinking and curing at room temperature. - It is of a degree.

The fluorine-containing copolymer has properties that conventional fluororesins do not have, namely, it cures at room temperature to form a hard film, and the formed coating film has the corrosion resistance, transparency, and anti-corrosion properties of the fluoropolymer. It retains its properties such as stain resistance. It also has good adhesion to wood, plastics, and metals. Each component, composition, etc. of such a fluorine-containing copolymer is explained in detail in Japanese Patent Application No. 58-63399 and Japanese Patent Application No. 58-175123. Among these (b+ acid component), particularly preferred are alkylvinyethers in which the alkyl group has 1 to 10 carbon atoms, and in which the hydrogen atoms of the alkyl group are partially or completely substituted with fluorine atoms. Specific examples include 2,2,2-trifluoroethyl vinyl ether,
2,2,3.3-tetrafluoropropyl vinyl ether, 2,2,3゜3.3-pentafluoropropyl vinyl ether, 2.2,3,3,4,4,5.5-octafluoropentyl vinyl ether, 2 ,2,3,3,4
, 4,5,5,6,6,7,7,8,8,9°9-hexadecafluorononyl vinyl ether.

In addition, as component (C), the alkyl group has 2 to 10 carbon atoms.
Particularly preferred is one. Specific examples include hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, 1
-Methyl-3-hydroxypropyl vinyl ether and the like.

The fluorine-containing copolymer in the present invention has (ω component unit 40
~60 mol%, <b) component unit 5-50 mol%, (C)
Those containing 0.5 to 40 mol% of component units are preferable, especially (ω component units 40 to 60 mol%, city) component units of 20 to 40 mol%.
45 mol%, preferably containing 1 to 30 mol% of (C) component units. Note that other ethylenically unsaturated monomers may be copolymerized as long as the desired properties are not impaired.

Examples of copolymerizable ethylenically unsaturated monomers include ethylene, propylene, isobutylene, vinyl acetate,
Vinyl chloride, vinylidene chloride, (meth)acrylic acid, (
Examples include meth)acrylic acid esters.

As a method for producing the fluorine-containing copolymer used in the present invention, for example, (ω component, (b>component and (C) component) are mixed using a polymerization catalyst in the presence of a solvent at -20 to 150°C, preferably at 50°C. Temperature of ~95°C and 0-30 Ka/ci2
Methods such as emulsion polymerization, suspension polymerization or solution polymerization in an aqueous medium under pressure conditions of G, preferably 10KMC112G or less may be employed.

The retention layer II in the present invention is usually prepared by blending a crosslinking agent with a fluorine-containing copolymer as described above and uniformly mixing it in an appropriate solvent.
It is formed by applying a coating composition obtained by dissolving it to interior materials and interior items for clean rooms, such as wood, plastic, or gold fill, and crosslinking and curing it at room temperature. Curing proceeds quickly at room temperature, and a hard coating film is usually obtained in 1 to 10 days, but the time required for curing can be shortened by increasing the concentration and drying to a level that does not cause any negative effects on the substrate.

Examples of the crosslinking agent include compounds having two or more functional groups that can react with the hydroxyl groups contained in the fluorine-containing copolymer, and cure the copolymer by reacting with the hydroxyl groups.

Specific examples of the crosslinking agent include hexamethylene diisocyanate, its derivatives such as its 3-diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated -4,4°-diphenylmethane diisocyanate, block type isocyanate, etc. Examples include isocyanates, acid anhydrides, polyvalent amines, amino resins, and compounds having epoxy groups. The amount of the crosslinking agent blended is preferably adjusted to 0.5 to 2 equivalents relative to the hydroxyl groups in the fluorine-containing copolymer.

As the solvent, unlike conventional fluorine-containing copolymers, a wide variety of ordinary solvents can be used. Specific examples include esters such as ethyl acetate, butyl acetate, isobutyl acetate, and cellosolve acetate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran Amides such as dimethylformamide and todimethylacetamide; Alcohols such as methyl alcohol, ethyl alcohol, and butyl alcohol; Aromatic hydrocarbons such as toluene and xylene, etc. One or more of these can be mentioned.

The concentration of the fluorine-containing copolymer varies depending on the coating method and coating manufacturing method, but is usually 5 to 70% by weight, preferably 20 to 60% by weight.

The fluorine-containing copolymer coating composition may optionally contain other polymers, curing accelerators, fillers, viscosity modifiers, leveling agents, gelling inhibitors, ultraviolet absorbers, light stabilizers, and peeling agents. Inhibitors, dispersants, antifoaming agents, etc. may be added. If coloring is required, pigments used in general paints,
It is advisable to add dyes, etc. Further, an antistatic agent or the like may be added to the extent that the physical properties are not impaired.

The corrosion-resistant protective material for clean rooms of the present invention can be applied to interior materials made of wood, plastics, FRP 1 metal, etc.
(It is obtained by applying a fluororesin paint containing an ω component, a (tn component, a component (c), and a crosslinking agent, and crosslinking and curing it at room temperature to heating.

When painting, it may be applied directly to interior materials, etc. In addition, in the case of metal interior materials, etc., if necessary, provide other layers on the interior materials, such as 11 or 2 or more layers of commonly used undercoat paints such as wash primer and zinc rich paint, and apply the present invention on top of that. A protective layer for use may be formed.

Application to interior materials and the like can be carried out by conventional methods such as spraying, coating, dipping, roll coating, and knife coating.

In this way, it may be applied directly to interior materials in the clean room, or a board or sheet coated in advance may be attached to the interior of the clean room. Furthermore, in the case of repair, the repaired area may be coated over again.

The corrosion-resistant protective material for clean rooms of the present invention is applied as a protective material for interior materials such as wall materials and window glass materials of clean rooms, and interior items such as glass parts and various devices used in clean rooms.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 50 parts (parts by weight, same below) of a fluorine-containing copolymer consisting of 5 parts mol% CTFE, 40 mol% 2,2,3.3-tetrafluoropropyl vinyl ether, and 10 mol% human O-xybutyl vinyl ether n-butyl acetate 35
%, 10 parts of xylene, and 5 parts of methyl isobutyl ketone. A coating composition was prepared by adding 9 parts of a polyisocyanate-based crosslinking agent and mixing uniformly.

On the other hand, a glass substrate having a length of 100 strands, a width of 50 strands, and a thickness of 2 m was degreased and cleaned with a fluorocarbon solvent (Daiflon 113 manufactured by Daikin Industries, Ltd.) to prepare a glass substrate.

The coating composition was applied to this glass substrate using a spatula to form a coating film having a thickness of 32 mils, and was cured at 25° C. for 7 days to form a protective layer.

Example 2 The coating composition shown in Example 1 was manufactured by Nippon Test Panel Industry ■
A protective layer was formed in the same manner as in Example 1, except that it was coated on a chemical conversion-treated aluminum plate (BT 712) manufactured by Co., Ltd.

Example 3 A protective layer was formed in the same manner as in Example 1, except that the coating composition shown in Example 1 was applied to a polymethacrylate substrate (Acrylite [manufactured by Mitsubishi Rayon ■).

Example 4 The coating composition shown in Example 1 was applied to a polycarbonate substrate (
A protective layer was formed in the same manner as in Example 1, except that the protective layer was coated on Panlite (manufactured by Yojin Kasei).

Examples 5 to 7 The coating compositions shown in Table 1 were applied to glass plates in the same manner as in Example 1 to form protective layers.

Comparative Examples 1 to 3 Glass substrates used in Examples, Example 3, and Example 4,
A polymethacrylate substrate and a polycarbonate substrate were used as samples of Comparative Examples 1 to 3, respectively.

Comparative Example 4 New Acnon manufactured by Kansai Paint ■ was applied to a base glass plate in the same manner as in Example 1 to a film thickness of 37 mm, and heated at 25°C.
This was cured for 7 days to form a protective layer.

In addition, each abbreviation in Table 1 represents the following compound.

4FVE: 2,2,3,3-tetrafluoropropyl vinyl ether 5FVE: 2,2,3,3,3-pentafluoro[]
'70hi/Lz vinyl ether 8FVE: 2,2,3,3,4,4,5.5-octa7 JL/orohentyl vinyl ether HBVE: Hydroxybutyl vinyl ether Example 1
The following tests were conducted on the samples obtained in -4 and Comparative Examples 1-2, respectively.

[Contact angle] One drop each of water and n-cetane was added to the sample, and the contact angle was measured using a goniometer manufactured by Elma Optical ■.

The results are shown in Table 2. A large contact angle is an indicator of excellent stain resistance.

[Transparency] The light transmittance of the sample was measured using a direct reading phase meter (standard light source C) manufactured by Toyo Seiki Seisakusho. The results are shown in Table 2.

[Corrosion resistance] The sample surface was exposed to humid air containing 20% hydrofluoric acid gas, 20% acetic acid gas, and 20% chlorine gas for 10 days to determine the presence or absence of abnormalities. The results are shown in Table 3.

Margin below E] [Effects of the invention] As described above, the fluorine-containing copolymer containing the components (a), (to, and (C)) as main components can be cured at room temperature, and has transparency, Since a coating film with excellent stain resistance and corrosion resistance can be formed regardless of the type of interior material or interior parts of a clean room, the corrosion-resistant protection for clean rooms of the present invention is provided with the coating film as a protection II. The material has excellent transparency, stain resistance, corrosion resistance, and excellent durability.

Claims (1)

[Scope of Claims] 1. A protective layer containing a crosslinked product of a copolymer mainly composed of (a) chlorotrifluoroethylene or tetrafluoroethylene, (b) fluoro lower alkyl vinyl ether, and (c) hydroxyalkyl vinyl ether is provided. A corrosion-resistant protective material for clean rooms.