JPH06312156A - Coating method - Google Patents

Abstract

PURPOSE:To form a good coating film by forming a gas phase deposition polymerized film of poly-p-xylylene by the specified film thickness on a base and then applying epoxy resin by the specified film thickness. CONSTITUTION:Di-p-xylylene of a solid dimer is gasified to generate p-xyhylene di-free-radical by means of heat decomposition, and the adsorption and polymerization of p-xylylene di-free-radical to a base are carried out simultaneously and a gas phase deposition polymerized film of poly-p-xylylene having the film thickness of 0.1-100mum is formed on the base. Then, epoxy resin is applied by the film thickness of 1-100mum. Thus the poly-p-xylylene film is reinforced with an epoxy resin film, and also the base is protected from dissolving into a diluent of epoxy resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coating a film on a surface of a substrate, and more particularly to a method for coating a double film of polyparaxylylene and epoxy resin.

[0002]

2. Description of the Related Art Conventionally, coating materials are scratched, dusty,
Protecting the base material from corrosion, increasing strength, reducing friction coefficient, imparting characteristics such as scratch resistance, ease of work,
It has been devised variously for the purpose of preventing damage at the time of shipping and improving productivity such as maintaining dimensional accuracy.

Acrylic resins, urethane resins, unsaturated polyester resins, silicone resins and the like are used as these coating materials, and the coating method includes depping, brush coating, spraying, film, etc., and the solvent vaporization type and heating as film forming methods. There are a reaction type, a water reaction type, a radiation irradiation type and the like, and it is innumerable to combine them.

Further, as a thin film coating by chemical vapor deposition, coating of a vapor deposition polymer film of polyparaxylylene has been utilized in a wide range of fields.

[0005]

However, these various types of coating materials have their respective drawbacks. For example, acrylic resin has a low surface hardness and is relatively inferior in material strength and heat resistance. Urethane resin is easily hydrolyzed, acid,
It is relatively weak against alkali and turns yellow by the action of heat and light. Unsaturated polyester resins have poor alkali resistance and boiling water resistance, and are inherently hard and brittle, so they must be reinforced in some way. Silicone resin deteriorates and decomposes with strong acids and strong alkalis, but is destroyed by hot water even in the presence of trace amounts of acids and alkalis.It also has poor adhesion to the base material and its weak cohesive power, which results in gas barrier properties. Remarkably small.

Epoxy resin is widely used as a coating material because it is excellent in electrical insulation, chemical resistance and durability. Generally, the coating with an epoxy resin is performed by diluting it with an organic solvent to form a low-viscosity liquid and spraying, depping, brushing or the like. However, when the base material is plastic, for example, polycarbonate resin, styrene resin, and acrylic resin are dissolved in an organic solvent, and therefore cannot be coated with an epoxy resin diluted with a solvent.

A vapor-deposited polymerized film of polyparaxylene can be used as a protective coating for electronic parts, circuit boards, etc., because a uniform film excellent in chemical resistance can be obtained. However, the vapor-deposited polymer film of polyparaxylene has low mechanical strength and coating hardness, and therefore is not suitable for coating a portion such as a sliding surface or a joint where mechanical strength is required.

Therefore, it is extremely difficult to satisfy all the properties such as strength, electric insulation, heat resistance, moisture resistance, chemical resistance, gas barrier property, etc. by using only one specific material among these various kinds of coating materials. is there.

Specifically, when a silicone resin is coated on the coil core of various motors, it is excellent in water resistance and cold resistance, but inferior in mechanical strength durability, or between the coil core and the silicone resin film. There is a problem that the water that has penetrated accumulates and causes corrosion.

When coated with a solvent-diluted epoxy resin, there is a problem in that coating unevenness and pinholes occur and the coil core cannot be completely insulation-coated.

Further, in the vapor-phase vapor deposition polymerized film of polyparaxylylene, the copper wire can be easily wound because of its lubricity, but since the coating film is soft, it is gradually deformed by the tightening pressure of the winding wire, and the coil core is gradually deformed. There is a defect that a void is generated between the winding and the winding, and the magnetic force is lowered and the winding is loosened.

An object of the present invention is to solve the above-mentioned various problems and provide a method for forming a good coating film.

[0013]

In order to solve the above-mentioned problems, a vapor-deposited polymerized film of polyparaxylylene having a film thickness of 0.1 to 100 μm is provided on a substrate, and then the film thickness is 1 to 100.
The epoxy resin is applied with a thickness of 0 μm.

[0014]

As described above, the defect of the polyparaxylylene film is reinforced by the epoxy resin film, and when the solution of the epoxy resin is applied, the base material is prevented from being dissolved in the solvent and any base material is prevented. It becomes possible to apply an epoxy resin solution to the.

[0015]

EXAMPLES The structure, production method, polymerization method, etc. of the basic polyparaxylylene used in the present invention are known, and specifically, the chemical formulas (A) to (F) of FIG. 2 (however, n is 50
00 or more) and the like. Of course, they may be used alone or in combination.

These polyparaxylylenes are formed by a vapor phase vapor deposition polymerization method, and the vapor deposition structure is composed of three steps.

That is, the first step ((A) in FIG. 1) in which vaporization of the raw material solid dimer diparaxylylene occurs, and the second step in which diradical paraxylene is generated by thermal decomposition of the dimer (FIG. 1). (B)), the third step in which the adsorption and polymerization of the diradical paraxylylene on the substrate are simultaneously formed, and the film formation of the high molecular weight polyparaxylylene occurs (Fig. 1).
(C)).

Note that FIG. 1 is a process diagram in the case of the case of the chemical formula of FIG. These polyparaxylylene films obtained by the vapor phase vapor deposition polymerization method can be conformally coated on the base material (conformal coating), and since the coating is performed at room temperature, heat history on the base material can be prevented. Do not give.

On the other hand, as the epoxy resin used in the present invention, diglycidyl ether derived from bisphenol A and epichlorohydrin and its derivatives, diglycidyl ether derived from bisphenol F and epichlorohydrin, and its derivatives are commonly known. Epbis type liquid epoxy resin, diglycidyl ether derived from polyhydric alcohol and epichlorohydrin, glycidyl ester derived from polybasic acid and epichlorohydrin, and derivatives thereof, glycidyl ether derived from hydrogenated pisphenol A and epichlorohydrin, 3 , 4
-Epoxy-6-methylcyclohexylmethyl-3,4
-Epoxy-6 methylcyclohexanecarboxylate, vinylcyclohexene oxide, bis (3,4-
Epoxy-6-methylcyclohexylmethyl) adipate and other aliphatic cyclic epoxies, and derivatives thereof, 5,5 ′
-Dimethylhydantoin type epoxy resin, triglycidyl isocyanurate, and substituted epoxy derived from isobutylene.

Further, as a curing agent for these epoxy resins, aliphatic, aromatic and alicyclic compounds such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, metaphenylenediamine, diaminediphenylmethane and triethanolamine can be used. Etc. and these modified amine compounds, aromatic acids, and their acid anhydrides, halogenated acids, their acid anhydrides, dicyandiamide, and their derivatives, boron halide complexes, organometallic complexes, ketimines, imidazoles. , And their derivatives, aromatic onium salts, metallocene compounds and the like can be used as appropriate.

The curing method of these epoxy resins is mainly by heating, but it is also possible to obtain a cured product by irradiation with radiation depending on the selection of the curing agent, and the cured structure is also added depending on the type of curing agent selected. Polymerization, cationic polymerization, anionic polymerization are various.

The epoxy resin used in the present invention includes, in addition to the above-mentioned base polymer and its curing agent, chloropropyltrimethoxysilane and γ-glypyrtri (dodecylbenzenesulfonyl) which have been conventionally used as additives for epoxy resins. ) A coupling agent such as titanate, an inorganic filler such as alumina, carbon black, talc, and a metal oxide, a flexibility-imparting agent such as thiols, alcohols, and carboxyl compounds can be appropriately added and used. .

EXPERIMENTAL EXAMPLE 1 Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd.) was used as an epoxy resin, Anchor 1040 (produced by AC1 Japan Ltd.) was used as a curing agent, and epoxy resin: curing agent = 100: 7 (weight ratio) was used. It was stirred.

Using this, a cured product having a thickness of 1000 μm was prepared under the conditions of 150 ° C. × 6 hours, and a sublimation temperature of 150 ° C., a decomposition temperature of 690 ° C., and a system pressure of 18 mTorr were applied on the cured epoxy resin product. Then, monochloroparaxylylene (manufactured by Union Carbide Co., Ltd.) was deposited to a thickness of 30 μm, and the volume resistivity, dielectric constant (1 kHz, 1 MHz), and dielectric loss tangent (1 kHz, 1 MHz) of the film were also measured. The results are shown in Table 1.

[0025]

[Table 1]

Experimental Example 2 On a 100 × 100 × 20 mm ceramic plate, sublimation temperature 150 ° C., decomposition temperature 700 ° C., system pressure 14 mTo.
Monochloroparaxylylene was formed into a film of 10 μm under the condition of rr, and one-component heat-curable epoxy resin Thr was further formed on the film.
eeBond2221C (manufactured by ThreeBond) is 100
μm was applied.

3.0 × on top of this uncured epoxy resin
Place a ceramic chip of 1.5 x 0.5 mm, and
The epoxy resin was cured under the condition of 30 ° C for 30 minutes.

This was placed in a constant temperature bath at 120 ° C. for 10, 20,
After standing for 30 days and returning to room temperature, the tip of the tension gauge was pressed into the ceramic chip at an angle of 30 °, and the heat resistance strength of the film consisting of the polyparaxylylene film to be destroyed and the cured epoxy resin was measured.

As a comparative example, a monochloroparaxylylene film was vapor-deposited on a ceramic plate to a thickness of 10 μm, and the monochloroparaxylylene film was left to stand in a constant temperature bath at 120 ° C. for 10, 20 or 30 days.
After returning to room temperature, one-component thermosetting epoxy resin Thr
For a sample in which eeBond2221C was applied in a thickness of 100 μm, a ceramic chip was placed on the eeBond2221C, and the epoxy resin was cured under the condition of 120 ° C. for 30 minutes, the heat resistance strength of only the polyparaxylylene film was obtained by the same method as in Experimental Example 1. It was measured.

At this time, a monochloroparaxylylene film was formed on a ceramic plate, an epoxy resin was further applied thereon by 100 μm, and a ceramic chip was placed at 120 ° C.
The film strength of the epoxy resin cured under the condition of 30 minutes was measured. The results are shown in Table 2. In this table, the film strength is shown in each period when the blank is 100%.

[0031]

[Table 2]

Experimental Example 3 An iron core of φ30 × 100 mm was degreased and washed, and then an ultraviolet curable epoxy resin ThreeBond3102 (manufactured by ThreeBond Co., Ltd.) was coated on the iron core to give an integrated light intensity of 5000.
The film was cured at mJ / cm ² to form a 40 μm cured epoxy resin film.

On the iron core coated with the cured epoxy resin, a sublimation temperature of 150 ° C. and a decomposition temperature of 700
10 μm of monochloroparaxylylene was formed into a film at a temperature of 20 ° C. and a system pressure of 20 mTorr, and a coated iron core having a wire diameter of 0.16 mm and a 2-PEW copper wire 2050 times,
It was wound under the conditions of a load of 100 g and 170 g.

After 48 hours, the copper wire was entirely wound up from the iron core, and the state of deformation of the coating material was observed. As a comparative example, the same experiment was conducted on an iron core only coated with a monochloroparaxylene film of 50 μm. The results are shown in Table 3.

[0035]

[Table 3] ◯: No deformation of coating material △: Some deformation of coating material ×: Deformation of coating material appeared clearly

Experimental Example 4 50 parts by weight of an epoxy resin ThreeBond 2287 (manufactured by ThreeBond Co., Ltd.) was diluted with 50 parts by weight of toluene to prepare a liquid coating material having a viscosity of 30 cps. This liquid coating material is polystyrene resin,
Polyparaxylylene film having a thickness of 10 μm was formed on a test piece plate of polycarbonate resin, the above polyester resin coating material was applied to have a thickness of 300 μm, and after air drying, 150 ° C. × 30
It was heat-cured under the condition of 1 minute.

The state of the test piece coated with the epoxy resin coating material was visually observed, and the tensile strength of the test piece after the epoxy resin was cured was measured.

As a comparative example, only the above epoxy resin coating material was applied without forming a film of polyparaxylylene,
After air-drying, heat curing was performed under the same conditions and the same measurement was performed.
As a blank for tensile strength, a test piece without coating was measured. Table 4 shows the measurement results
Shown in.

[0039]

[Table 4]

[0040]

As described above, according to the coating method of applying the epoxy resin on the vapor-deposited polymer film of polyparaxylylene of the present invention, the vapor-deposited polymer film of polyparaxylylene is made of epoxy resin. Prevents the substrate from dissolving in the diluting solvent. Therefore, it becomes possible to coat any base material with an epoxy resin, and it is possible to impart excellent coating film hardness, mechanical strength, chemical resistance, heat resistance, durability, and electrical insulation characteristics to the base material.

[Brief description of drawings]

FIG. 1 is a process chart in the case of using one kind of chemical formula of polyparaxylylene as an example, (A) is a first process chart in which vaporization of a solid dimer occurs, and (B) is a dimer. The second process diagram of the state in which the body is thermally decomposed, (C) is the third process diagram of the state in which a high molecular weight film is formed.

FIG. 2 is a chemical formula of basic polyparaxylylene (A) to (F) (where n is an integer of 5000 or more).
Are chemical formulas of each type.

Claims (1)

[Claims] 1. After forming a vapor phase vapor deposition polymerized film of polyparaxylylene in a film thickness of 0.1 to 100 μm on a substrate, a film thickness of 1 is obtained.
A coating method, which comprises applying an epoxy resin at a thickness of up to 1000 μm.