WO2002102525A1

WO2002102525A1 - Method for self-deposition type surface treatment coating of microdevice or its component, and microdevice or its parts having selfdeposition type surface treatment coating

Info

Publication number: WO2002102525A1
Application number: PCT/JP2002/005712
Authority: WO
Inventors: Mayumi Yamamoto; Hiroshi Nagae; Ryosuke Sako
Original assignee: Nihon Parkerizing Co., Ltd.
Priority date: 2001-06-18
Filing date: 2002-06-10
Publication date: 2002-12-27
Also published as: CN1516626A; TW565983B; CN1286578C

Abstract

A method for self-deposition type surface treatment coating of a microdevice or a component thereof, which comprises a step of contacting the surface of a microdevice or a component thereof with a self-deposition type surface treatment fluid (A) containing at least one water-soluble or water-dispersible organic polymer resin (a) to thereby effect deposition and form an organic coating, a step of contacting the formed organic coating with a post-treatment fluid (B) containing at least one curing agent (e) capable of curing the organic coating and a step of heating and drying, to thereby form an organic coating film on the surface of a microdevice or a component thereof; and a microdevice or a component thereof having a self-deposition type surface treatment coating.

Description

TECHNICAL FIELD The present invention relates to an autodeposition type surface treatment coating method for a micro device or a component thereof, and a micro device having an auto deposition type surface treatment coating or a component thereof.

TECHNICAL FIELD The present invention relates to a micro-motor core, a microphone opening device such as a magnet ring for a stepping motor, or a method for coating a self-deposition type surface treatment of a component thereof, a micro device having a self-deposition type surface treatment coating, or a component thereof. Background art

Electrodeposition coating, powder coating, solvent spray coating, and the like have been applied to microdevices and their components for the purpose of insulation, corrosion resistance, and design. However, as these devices and parts became more microminiaturized, it became difficult to apply a uniform coating film to the details of complicated shapes and the edges of these coating methods, making it difficult to respond. For example, in a micro motor core that requires strict insulation, electrodeposition coating is performed several times overcoating due to poor coverage such as edges, but the defect rate is still high at present. In addition, large-scale facilities were required, and the cost was high. In powder coating, a film thickness of 100 m or more is required to have sufficient insulation properties, which is fatal for motors that require ultra-thin, such as motors for flip-flop disk drives. In addition, the surface hardness was insufficient to withstand the core winding.

In addition, in the case of spray coating using a spray or the like, there is a problem that it takes a lot of time to uniformly coat the details, and the coating efficiency is poor.

There are several proposals to solve these problems. Japanese Unexamined Patent Publication No. 5-300681 discloses a method in which a liquid insulating agent is coated on the core surface in a multi-layered manner, which proposes to reduce the thickness of the motor core. On the other hand, There was also a problem that the time and labor required for coating were extremely low and productivity was poor, and that the working environment was poor due to the use of a solvent-based insulating agent.

Japanese Unexamined Patent Publication No. Hei 9-9144521 discloses that an aqueous coating composition having a water-insoluble release plasticizer and having a glass transition point of 55 ° C. can be used to prepare a skin with simple equipment and processes. Although it is proposed that the coating can be provided, the water resistance and corrosion resistance of the obtained coating are insufficient, and the balance between surface hardness and brittleness is also insufficient. There is a drawback that tends to occur. In addition, although it was water-based, it contained organic solvents and had problems with pot life and workability.

Japanese Unexamined Patent Application Publication No. 9-233700 discloses a motor core obtained by bringing a surface of a laminated motor core into contact with a self-extending type aqueous coating composition containing a resin emulsion, an acid, an oxidizing agent, metal ions and water. A method of forming an insulating film on the surface has been proposed. _C The film obtained by this method has insufficient surface hardness and is poor in durability due to winding.

In recent years, with the spread of mobile phones, miniaturization has progressed, and it has become necessary to miniaturize motors for piebrators. It's getting harder. Disclosure of the invention

The present invention uses an environmentally-friendly surface treatment system, which has not been achieved by the conventional technology, and has excellent workability, productivity, and economic efficiency, and has excellent insulation properties, throwing power, corrosion resistance, heat resistance, solvent resistance, And a method for forming a film having a high surface hardness, a micro device having a film treated by the method, and a component thereof.

The present inventors have conducted intensive studies in view of the problems of the prior art, and have found that the surface of a microphone opening device or the surface of a component thereof contains at least one water-soluble or water-dispersible organic polymer resin (a). Contacting with a self-deposition type surface treatment liquid (A) to form an organic film on the surface, and containing at least one curing agent (e) capable of hardening the surface of the formed organic film. Contact with post-treatment liquid (B) A self-deposition type surface treatment and coating method for forming an organic film on the surface of a micro device or its components by a surface treatment process including a contacting step and a heating and drying step was found to be effective. The invention has been completed. In addition, after the step of contacting with the post-treatment liquid (B), a self-deposition type surface treatment for forming an organic film on the surface of the micro device or its parts by a surface treatment process including an air pro process and a heat drying process The inventors found that the coating method was effective, and completed the present invention.

The self-deposition type surface treatment liquid (A) more preferably contains an acid component (b) in addition to the water-soluble or water-dispersible organic polymer resin (a), and the oxidizing agent (c) )), And more preferably a metal ion (d). The organic polymer resin (a) used in the self-precipitation treatment liquid (A) is more preferably at least one selected from an acrylic resin, an epoxy resin, a urethane resin, a polyester resin, and a polyamide resin. Further, at least one of them is more preferably an anionic polyester, and particularly preferably an anionic polyester resin obtained by condensing a polyhydric alcohol and an acid compound.

The curing agent (e) of the post-treatment liquid (B) is more preferably at least one selected from melamine resin, guanamine resin, urea resin, phenol resin, epoxy resin, and isocyanate compound. It is more preferable that the treating agent (B) contains a lubricant, and the surface lubricant (f) is at least one selected from the group consisting of a force S, a fluororesin-based lubricant, a polyolefin-based wax, melamine cyanurate, and molybdenum disulfide. Particularly preferred is one lubricant. That is, the present invention provides an autodeposition-type surface treatment coating method for forming an organic coating on the surface of the above-mentioned micro device or a component thereof, and a micro device having a coating formed by the method, or a component thereof. Is provided.

Hereinafter, the configuration of the present invention will be described in detail.

The micro devices or parts thereof to which the present invention can be applied include a cellular phone piebrator, a floppy disk, a node disk, a compact disk, and a micro disk. Micro motor cores used in drive motors such as discs and CD ROMs, or stepping motors used in OA equipment, AV equipment, and home appliances, etc. The material is steel, silicon steel, or ferrite, neodymium It is a ferrous material such as a sintered material obtained by powder metallurgy such as boron.

The autodeposition type surface treatment solution (A) used in the present invention is an aqueous treatment solution containing a resin as a main component, and contains a water-soluble or water-dispersible organic polymer resin (a) and an acid component (b). It is more preferable to contain the oxidizing agent (c), and it is particularly preferable to contain the metal ion (d).

The water-soluble or water-dispersible organic polymer resin (a) is at least one selected from an acrylic resin, an epoxy resin, a urethane resin, a polyester resin, and a polyamide resin. Forced emulsification type organic polymer resin which is water-based using an emulsifier, or a part of the structure of which is modified with an anionic functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group; Alternatively, it is a self-emulsifying organic polymer resin. Further, at least one selected from these resins is more preferably an anionic polyester resin, and particularly preferably an anionic polyester resin obtained by condensing a polyhydric alcohol and an acid compound. preferable.

It is particularly preferable that the polyhydric alcohol and the oxidized compound as the monomer components of the polyester resin are a polyhydric alcohol (ml) and an acid compound (m2). It is at least one selected from aliphatic polyhydric alcohol derivatives (ml) -1 represented by 1) and aromatic polyhydric alcohol derivatives (ml) -2 represented by general formula (2).

(m1) -1

HO-R-,-ΟΗ ")

In the general formula (1), R represents a straight-chain or branched-chain alkylene having 1 to 10 carbon atoms, an unsaturated alkylene, a hydroxy group, and a group containing no amino or halogen element. Or alkylene or unsaturated alkylene.

(ml) — 1 is ethylene glycol, neopentyl glycol, dibromoneopentyl glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6 monohexanediol, 3-methinolepentanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methylinole 1,3-propanediol, 2,2 'single Jechiru 1, 3-Puronoヽ⁰ Njioru, glycerin, Pentaeri scan Lithol, preparative Increment Chiro Honoré ethane, etc. preparative Rimechiro trimethylolpropane and the like.

(m) 1-2 (2)

In the general formula (2), m and ri are integers of 1 or more and 2 ≦ m + n6.

R ₂ , R ₃ , R ₄ , and R ₅ are each independently at least one selected from hydrogen and methyl groups.

Examples of (ml) -2 include bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct, and bisphenol F propylene oxide adduct.

The acid compound (m 2) is an aliphatic carboxylic acid derivative (m 2) —1 represented by the general formula (3), and an aromatic carboxylic acid derivative (m 2) —2—2 represented by the general formula (4). Aromatic acid anhydride derivative (m 2) — 3 represented by 5), pyromellitic anhydride (m 2) — 4 represented by general formula (6), naphthalene derivative represented by general formula (7) ( _M 2) — at least one selected from 5 (m2) -1

XiOOC-Rg—COOX ₂ )

—In the general formula (3), X and X ₂ are independently at least one selected from hydrogen and an alkyl group having 1 to 10 carbon atoms. R ₆ is a straight-chain or branched-chain alkylene having 1 to 10 carbon atoms, unsaturated alkylene, C 1 OX ₃ (where X ₃ is hydrogen, a straight-chain or branched-chain alkylene having 1 to 10 carbon atoms) ), Or unsaturated alkylene.

(m 2) 1 is succinic acid, methyl succinic acid, ethyl succinic acid, butinolesuccinic acid, monoethylenoestenolate succinate, getinoleestenole succinate, monobutyl ester oxalate , Dibutynoleestenolate succinate, glutanoleic acid, methinolegnoletanoleic acid, ethyl glutanoleic acid, butyl glutaric acid, monomethyl enoestenolate gnoolelate, dimethyl enoester gnoolelate, monoethyl ester glutarate, getyl monobutyl glutarate Ester, dibutyl glutarate, adipic acid, monomethyl adipic acid, dimethyl adipic acid, monoethyl adipic acid, dioctynoestenoate adipate, sebacic acid, getinoleestenole sebacate, se Examples include dibutynole bacinate, dioctyl sebacate, tricarballylic acid, butenetracarboxylic acid, and the like.

(m2) -2

In the general formula (4), X ₄ and X ₅ are each independently at least one selected from hydrogen and an alkyl group having 1 to 3 carbon atoms. Y l, Υ 2, Υ 3 and Υ 4 are each independently hydrogen, C 一 OX ₆ (where X ₆ is hydrogen, an alkyl group having 1 to 3 carbon atoms, Na, K, Ca, Ba, Li, NH ₄ ), -SO ₃ Z _x (where Z ₁ is hydrogen, Na, K, Ca, Ba, Li, NH ₄ ).

(m 2) One of the two is terephthalic acid, terephthalic acid monomethyl ester, terephthalenoic acid dimethynoleestenole, terephthalic acid / monoethyl ester, terephthalic acid getyl ester, isofphthalic acid, isofphthalic acid monomethyl ester, isofphthalic acid Dimethyl ester, dimethyl disophthalate 5-sodium sulfonate, trimellitic acid, 1,4-dimethyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate And the like. In the general formula (5), Y ₅ and Υ ₆ are each independently hydrogen, COOX ₇

(m2) -3

(Where X ₇ is hydrogen, an alkyl group having 1 to 3 carbon atoms, Na, K, Ca, Ba, L i, NH ₄ ), -SO 3 Z ₂ (where Z ₂ is hydrogen, N a, K, is a C a, B a, L i , at least one selected from NH _4).

Examples of (m 2) 13 include phthalic anhydride, trimellitic anhydride, and ethyl methacrylate trimellitate.

(m2) -4

(m 2) 14 is an anhydride of pyromellitic acid

—In the general formula (7), X ₈ and X ₉ are each independently at least one selected from hydrogen and an alkyl group having 1 to 3 carbon atoms. _{_{_{Y 7, Y s, Y 9}}} ,及Pi Upsilon i. Are independently of each other hydrogen, one COOX _{1 Q} (where X _{1 Q} is hydrogen, an alkyl group having 1 to 3 carbon atoms, Na, K, Ca, Ba, Li, NH ₄ ), S 0 ₃ Z ₃ (where Z ₃ is hydrogen, Na, K, Ca, Ba, Li, NH ₄ ).

(m 2) 15 is 1,2-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid dimethyl ester, 1,3-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid dimethyl ester 1,4-naphthalene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid dimethyl ester, 1,5-naphthalenedicarboxylic acid olevonic acid, 1,5-naphthalenedicarboxylic acid dimethinoester, 1,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid dimethyl ester, 1,7-naphthalenedicarboxylic acid, .1,7-naphthalene Dicanolevonic acid dimethyl ester, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid dimethyl ester, 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic olevonic acid dimethyl ester, 2,7- Naphthalene diolenoic acid and 2,7-naphthalene diolenoic acid dimethinoleate.

In the acid compound (m 2), at least one selected from (m 2) —2, (m 2) 13 and (m 2) 14 must contain at least 6 Omo 1% of the total acid compound. Are more preferable in terms of corrosion resistance, adhesion and heat resistance.

(m 2) — 2, (m 2) — 3, (m 2) — 5, where Y to Y i in the general formulas (4), (5), and (7). At least one is a carboxyl group or a sulfonate group, i.e., from one COOX 6, one so ₃ z, one C OOX ₇ , one so ₃ z ₂ , one COOX ₈ , one SO ₃ Z ₃ It is more preferable that at least one selected from the total acid components be contained in an amount of 1 to 40 m 0 1%, more preferably 2 to 30 mo 1%. The molecular weight of the polyester resin used in the present invention is not particularly limited, but those having a number average molecular weight of 2000 to 500,000 can be used.

The method for synthesizing the polyester resin used in the present invention is not particularly limited. For example, the polyhydric alcohol component and the acid compound component may be combined with dibutyltin oxide, lead acetate, calcium acetate, N — Can be obtained by esterification or transesterification at 140 to 3 ° C. under a reduced pressure of 10 mmHg or less in the presence of a catalyst such as butyl titanate and polycondensation. The acid component (b) used in the self-deposition type surface treatment solution (A) used in the present invention includes, for example, fluorodiconic acid, fluorotitanic acid, ky hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, At least one selected from phosphoric acid and nitric acid, and more preferably hydrofluoric acid.

The oxidizing agent (c) may be any oxidizing agent capable of oxidizing trivalent iron ions eluted from the iron-based material to be treated into trivalent. For example, potassium permanganate is used. , Hydrogen peroxide, sodium nitrite, etc. More preferably, it is hydrogen peroxide.

The compound capable of supplying the metal ion (d) is not particularly limited as long as it is stable in the processing solution, and examples thereof include ferric nitrate, ferric fluoride, ferrous phosphate, and cobalt nitrate. Although fisting, ferric fluoride is more preferred.

In the self-deposition type surface treatment liquid (A) used in the present invention, the water-soluble or water-dispersible organic polymer resin (a) preferably has a resin solid content concentration of 5 to 550 g / L, 0 to 200 g / L is more preferred. The concentration of the acid component (b) is preferably from 0.1 to 5.0 gZL, more preferably from 0.5 to 3.0 gZL. The concentration of the oxidizing agent (c) is preferably from 0.01 to 3.0 g ZL, more preferably from 0.03 to L.OgL. The concentration of the metal ion (d) as a metal in the compound capable of supplying the metal ion is preferably 0.1 to 50 g / L, and more preferably 0.5 to 5.0 g 7 L.

The self-deposition type surface treatment liquid (A) may be used as an optional component in addition to the above components, for example, a film-forming auxiliary such as trialkylpentanediol isobutylate or alkyl carbitol, for example, carbon black, phthalocyanine blue, Color pigments such as Hansa Yellow can be contained to such an extent that the object of the present invention is not impaired.

The self-deposited organic film is a wet film containing a large amount of water.The post-treatment liquid (B) diffuses this water into the film and hardens it when heated and dried to increase the surface hardness and solvent resistance. There is action. The post-treatment liquid (B) does not harden the entire self-precipitating organic film uniformly, but has a higher concentration near the film surface than the metal interface and has a large effect, so it is excellent without hindering the adhesion to the material. Surface hardness and solvent resistance can be imparted. Therefore, even if the components of the post-treatment agent (B) can be added to the autodeposition-type treatment solution (A) at a high concentration, the same effect cannot be obtained.

The post-treatment agent (B) will be described in detail.

The curing agent used for the post-treatment agent (B) is an amino resin such as a melamine resin, a guanamine resin, a urea resin, a phenol resin, an epoxy resin, or an isocyanate. It is preferable that at least one selected from compounds is used. Melamine resins include methylated melamine, alkoxylated melamine such as butylated melamine, imino-type alkoxymethylated melamine, imino-type methylol melamine, methylol melamine and the like, for example, trimethylol melamine, tetramethylol. Melamine, hekinothyrono remelamine, trimethoxymethyl dimethylol melamine, dibutoxymethyl trimethylol melamine and the like. Among them, it is more preferable that at least one functional group selected from a methylol group and an imino group is contained in one molecule, because the effect of increasing the surface height is large.

Examples of the guanamine resin include a benzoguanamine resin and a methyldanamin resin. Examples of the phenol resin include a phenol-formalin resin and a bisphenol-formalin resin, and include a resole type, a novolak type, and an amino group-modified novolak. Epoxy resins are resins having at least one glycidyl group in the molecule, and include bisphenol-type and pentaerythritol glycidyl ether. Examples of the isocyanate compound include a block isocyanate prepolymer (eg, Elastron, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) blocked with bisulfite, oxime, etc., and urea obtained by condensing urea with formalin Resins can also be applied. The concentration of the curing agent (e) in the post-treatment liquid (B) is preferably from 5 to 200 gZL, more preferably from 100 to 100 gZL, as the nonvolatile component.

The post-treatment agent (B) more preferably contains a lubricant (f), and the lubricant is at least one selected from a fluororesin-based lubricant, a polyolefin-based wax, melamine cyanurate, and molybdenum disulfide. It is particularly preferred that it is a seed.

Aqueous dispersions such as polytetrafluoroethylene (PTFE) and polytrifluoroethylene at the mouth are used as fluororesin lubricants, and aqueous dispersions such as polyethylene wax and polypropylene pettas are used as polyolefine lubricants. Dispersion is mentioned.

The surface lubricant (f) reduces the surface frictional resistance, It has the effect of relieving the stress when external stress is applied, such as winding the tercore, and preventing the coating from being scratched or damaged. It also has the effect of improving the water resistance of the coating.

The concentration of the lubricant (f) in the post-treatment liquid (B) is preferably from 0.5 to 100 gZL, more preferably from 1 to 50 gZL, as a nonvolatile component.

When the curing agent (e) in the post-treatment liquid (B) is an amino resin such as a melamine resin, alkylamines such as ethylamine, getinoleamine, and triethylamine are used to improve the stability in the processing agent. It is more preferable to have an amine compound such as alkanolamine such as monoethanolamine, diethanolamine and triethanolamine, and to maintain the post-treatment pH at 7 to 10. The treatment method of the present invention is a method in which an object to be treated, that is, a surface of a microphone device or a component thereof is brought into contact with an autodeposition type surface treatment solution (A) to deposit and form an organic film on the surface. The means for bringing the immersion treatment liquid (A) into contact with the surface of the object to be treated is not particularly limited, but in order to form a uniform film on a complex surface, the object to be treated is immersed in the treatment liquid (A). Is more preferable. The processing temperature is preferably 5 to 50 ° C, more preferably 10 to 40 ° C. If the treatment temperature is lower than 5 ° C, the deposition efficiency is poor and a sufficient amount of coating cannot be obtained. If the processing temperature is higher than 50 ° C, the film surface appearance tends to deteriorate due to excessive reaction, which is not preferable.

The processing time is preferably from 10 to 500 seconds, more preferably from 20 to 300 seconds.

If the time is less than 10 seconds, a sufficient film cannot be formed due to insufficient precipitation reaction. If the time exceeds 500 seconds, the dissolution of the object to be treated proceeds, the Fe ion concentration in the film increases, the appearance tends to be poor, and the corrosion resistance decreases, which is not preferable.

Similarly, the means for bringing the surface of the object to be treated into contact with the post-treatment liquid (B) is not particularly limited. However, immersing the object to be treated in the post-treatment liquid (B) may contact the entire surface. It is preferable because it is possible. Although the treatment temperature is not specified, it is preferably 5 to 60 ° C, more preferably 10 to 40 ° C. The processing time is preferably from 2 to 500 seconds, more preferably from 5 to 200 seconds. If the processing temperature is below 5 ° C or the processing time is below 5 seconds, the penetration of the post-treatment components into the deposited film is insufficient. After treatment, the post-treatment components are localized on the outermost surface, and as a result, the surface tends to become brittle.If the treatment temperature exceeds 60 ° C or the treatment time exceeds 200 seconds, the deposited film is dissolved. This is not preferred because of the tendency to end up.

In the treatment method of the present invention, before performing heating and drying, that is, after contacting with the post-treatment liquid (B), removing excess post-treatment adhering liquid by an air processor may improve the appearance and corrosion resistance. preferable.

Air blowing, without regard if remove excess aftertreatment deposition solution by using a conventional air gun is not particularly limited, the pressure of the workpiece surface, 0. 3~ 1 0 K cm 2 to become so It is more preferable to adjust the nozzle diameter of the gun and the distance to the object to be processed. If heating and drying is performed with excess post-treatment liquid adhering to areas where liquid pools are likely to accumulate, the film at that area tends to boil, impairing the appearance and increasing the defect rate.

The heating means is not specified in the heating and drying process, and a hot-air circulation drying oven using electricity or gas as a heat source, a heating oven using far-infrared rays, high-frequency heating, induction heating, or the like can be used. The heating temperature is preferably 6 0~ 3 0 0 ° C, and more preferably 8 0~ 2 5 0 ^D C. If the temperature is lower than 60 ° C, the film formation becomes poor and the corrosion resistance and insulation properties are insufficient. If the temperature exceeds 250 ° C, the resin film is thermally decomposed, which is not preferable. In order to further improve the appearance of the film in the heating and drying step, it is effective and more preferable to sufficiently dry the adhered water at a temperature of 60 to 100 ° C. and then heat it at a temperature higher than that. BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 shows the material I: motor core (silicon steel sheet) used in the examples. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described with reference to examples and comparative examples. However, the present examples are merely examples, and do not limit the present invention. The materials to be treated used in Examples and Comparative Examples are as follows. I: Micro motor core (silicon steel plate) (Fig. 1)

I I I: SPC C—S D (70 X 150 mm, plate thickness 0.8 mm) The components used in the self-deposition type surface treatment solution (A) are as follows.

Water-soluble or water-dispersible organic polymer resin (a)

a1 to a5: Polyester resin with the monomer composition shown in Table 1

a 6 Yuka Shell:! Epoxy resin manufactured by Kishi Corporation

Epilet 3 5 2 2W6 0 (N V C. 60%)

a 7 Rohm & Hass acrylic resin

Rhoplex WL-91 (N V C. 41.5%)

a 8 W.R.Grace polyvinylidene chloride resin

Daran SL143 (NV C. 55%) The polyester resins a1 to a5 having the monomer compositions shown in Table 1 were synthesized by the following method. In a 1000 ml round bottom flask equipped with a Claisen tube and an air cooler, put 1 mol of total acid component (or ester component), 2 mol of total alcohol component, 0.25 g of calcium acetate and 0.1 g of N-butyl titanate as a catalyst. Was replaced with nitrogen and heated to 180 ° C. to melt the contents.

The bath temperature was raised to 200 ° C, and the mixture was heated and stirred for about 2 hours (esterification or ester exchange reaction). Next, the bath temperature was raised to 260 ° C, and after about 15 minutes, the pressure in the system was reduced to 0.5 mmHg, and the reaction was carried out for about 3 hours (polycondensation reaction). After the completion of the reaction, the content was taken out by cooling under nitrogen. Add an appropriate amount of ammonia water to a final pH of 6 to 7 to the extracted resin (water becomes an amount of 25% solids), and heat and stir at 100 ° C for 2 hours in an autoclave. And Acid component (b)

The acid component (b) used is shown below.

b 1 H F

b 2 H ₂ Z r F ₆

b ₃ H 3 P 0 ₄ oxidizing agent (c)

The oxidizing agent (c) used was hydrogen peroxide.

c: hydrogen peroxide metal ion (d)

The used metal ion (d) is shown below.

d 1: Ferric fluoride

d 2: Ferric nitrate Other components (g)

Pigment: Sanyo Dye Co., Ltd. “Emacol Black D 3 05 j Table 2 shows the composition of the autodeposition type surface treatment solution (A). Table 2

The components and components used in the post-treatment liquid of the present invention (B) are as follows. '

Curing agent (e).

e 1: Partially methylated melamine resin manufactured by Mii Cytec Co., Ltd.

Cymel 730 (N V C. 88%)

e 2: Highly methylated melamine resin manufactured by Mitsui Cytec Co., Ltd.

Cymel 300 (N VC ... 100%)

e 3: Fuyunol resin manufactured by Gunei Chemical Industry Co., Ltd.

Laptop P L 46 6 4 (N V C. 50%)

e4: Daiichi Kogyo Seiyaku Co., Ltd. block isocyanate prepolymer. Elastron BN5 (NVC 15%) lubricant (f)

f 1 _: Fluororesin lubricant made by Sumitomo 3M Co., Ltd.

Daiyuon _{TM PTFE 50 3.5 (NV C. 60} %> f 2: molybdenum disulfide

f 3: Polyolefin wax manufactured by Mitsui Chemicals, Inc.

Cheminocle W900 (NVC. 40%) Other additives (h)

1 Ammonia water

h 2 Triethanolamine

h 3 DOO Ryechiruami emissions post-treatment liquid (B) _c treatment liquid contents shown in Table 3

Table 3

Next, processing steps and processing conditions will be described. The following steps were performed in the following order.

1. Degreasing

Manufactured by Nippon Parkerizing Co., Ltd .: Fine cleaner

Degreasing was performed using 4360 (20 g / L bath, 60 ° C, 5 minute immersion)

2. Washing water

Tap water spray was given for 30 seconds.

3. Washing water

It was immersed in deionized water for 30 seconds.

4. Autodeposition type treatment

The film was immersed in a self-deposition type surface treatment solution (A) to deposit a film.

[Condition 1] Processing solution temperature 2 2 ± 2. C, soak for 180 seconds. The object was gently swung up and down in the processing solution (one second). [Condition ②] Immersion for 120 seconds at a processing solution temperature of 30 ± 2 ° C. The treatment liquid (1 L) in a 1 L polybeaker was stirred with a magnetic stirrer (tip 30 mm, speed 200 rpm).

5. Rinse ③

Tap water was stored in a 10-liter stainless steel container, immersed for 2 minutes in a flushing tub that was overflowed with a flow rate of 2 liters, and the object was gently rocked up and down (once / second). .

6. Post-processing

It was immersed in the post-treatment agent (B) under the following conditions.

[Condition ③] Immersion for 20 seconds at a processing solution temperature of 2 2 ± 2 ° C. The object was gently swung up and down in the processing solution (once / second).

[Condition 1] Immersion for 10 seconds at a temperature of 40 ± 2 ° C. The workpiece was gently swung up and down in the processing solution (1 time 7 seconds)

7. Ryoichibu π—

The test was performed under the following conditions using an air gun W77 manufactured by Anest Iwata Co., Ltd.

Condition ⑤] to adjust the distance between the air by sea urchin nozzle diameter and the object to be treated that the pressure is. 4 to 5 k gZ cm ² which corresponds to the object to be processed, from directly above the object to be treated, (2 seconds blanking opening 3 5 seconds intermittent cycle)

Condition ⑥] to adjust the distance between the air pressure 3~ 4 kg Z cm ² becomes due urchin nozzle diameter and the processing object that corresponds to the object to be processed 1 0 sec Pro continuously from directly above the object to be treated I did.

8. Heat drying

The drying was performed under the following conditions using a hot-air circulation drying oven (Perfect Oven PS 112 made by Tabai Co., Ltd.).

[Condition ⑦] After heating and drying at 80 ° C for 5 minutes, raise the temperature in the furnace to 180 ° C in 10 minutes, and then raise the temperature to 180 ° C, and then heat the furnace for another 5 minutes. (Wind speed: 2 mZ min).

[Condition ⑧] After heating and drying at 100 ° C for 5 minutes, the temperature in the furnace was raised for 10 minutes. The temperature was raised to 200 ° C, and the temperature was raised to 200 ° C, and then left in the furnace for another 5 minutes. Wind speed: 2 mZ).

[Condition ⑨] Heat drying was performed at 110 ° C for 20 minutes (wind speed: 2 mZ minute).

Table 4 shows the contents of Examples and Comparative Examples.

Table 4

Comparative Example 5

The procedure was performed in the same manner as in Comparative Example 1 except that 3 g / L of the curing agent (el) was added to the autodeposition treatment liquid (A 1). Comparative Example 6

After the washing process according to the above-mentioned processing steps, the polyester resin is mainly used. Powder coating (Polyester V—PET # 400000 (Dai Nippon Paint Co., Ltd.)) was applied so that the film thickness on the flat part became 20 μm, and the powder was placed in a hot air drying oven. Dry at 0 ° C for 20 minutes. Comparative Example 7

After performing the washing process according to the above-described processing steps, an epoxy-based cationic electrodeposition coating (Electron 9400: manufactured by Kansai Paint Co., Ltd.) was applied at a voltage of 200 V and a film thickness of 20 / m on a flat surface portion. It was painted and dried in a hot-air drying oven at 175 ° C for 20 minutes. The film properties, film performance tests, and evaluations of the test materials prepared in Examples and Comparative Examples were performed according to the following criteria.

Appearance

The film swelling, bleeding, bleeding, repelling, etc. were visually evaluated using the legends shown below. ◎: No swelling, no blemishes, no blemishes, no cissing

：: swelling, blemishes, seaweed, almost no cissing

Δ: swelling, blemishes, blemishes, cissing

X: swelling, blemishes, blemishes, cissing considerably

Microscopic observation of the cross section of the flat part and the edge part of the test material and measurement of the film thickness Corrosion resistance

The test material was subjected to a saltwater mist test (JIS-Z2371) for 500 hours, and evaluated by estimating the emission area.

◎: 0%

〇: less than 5%

△: 5% or more and less than 20% X: 20. /. that's all

Evaluation was made by the pencil scratch test method (JIS—K540). Heat-resistant

The test material was allowed to stand at 220 ° C. for 30 minutes, and the weight loss rate before and after was evaluated.

〇: less than 1%

Δ: 1% or more5. /. Less than

X: 5% or more

After the heat resistance test (left at 220 ° C for 30 minutes), a cross cut tape test (1mm square, 100 pieces) was performed on the test material.

Number of films remaining after tape peeling

◎: 1 0 0

〇: 90-99

Δ: 80 to 89

X: 79 or less Insulation property test

The winding edge of the motor core (Fig. 1) that had been subjected to the self-deposition type surface treatment was evaluated. Peel off the film at the center of the painted test material and connect the negative electrode of the test needle. The positive electrode of the test needle was scanned with respect to the winding part of the motor core, and the number (n) of edges where current leaked was checked. Measuring equipment: Insulation resistance meter F I-910 (Nippon Technard Co., Ltd.) Applied voltage: 500 V

Evaluation criteria

◎: n is 0

〇: ri force S less than 3 Δ: η is 3 or more and less than 10

X: η force S 10 or more Volume resistivity measurement

1) Measurement method: According to JIS-K6911

2) Measuring device: Advantest R8340A Ultra High Resistance Meter

Electrode: Advantest R12704 Resistivity Chamber

3) Methods and conditions;

The object to be processed was set, and the volume resistivity (Ω · cm) of the coating film was measured by the following procedure.

① O V X 30 seconds d i s c h a r g e

② 500 V X 60 seconds of ch a r g e

③ O VX 30 seconds d i s c h a r g e

4) Evaluation criteria

◎: 1 0 ⁶ Ω · cm or more

0: 1 0 ⁵ or more 1 0 ⁶ Ω - less than cm

△: 1 0 ⁴ or more 1 0 less than ^{5 Ω} · cm

X: 1 0 ⁴ Ω · cm less than solvent resistance

Gauze was wound around silicone rubber of 1 cm square, the gauze was sufficiently impregnated with MEK (methyl ethyl ketone), and rubbed 50 times back and forth (load: 500 g), and then the surface appearance was evaluated.

◎: No change

〇: Some traces

Clearly damaged (coating almost half dropped off)

X: Substrate is visible (film detachment) Table 5 shows the evaluation results of the examples and the comparative examples.

The micro motor core of (I) was used as the material to be treated, but the SPC C-SD of (I I I) was used for the heat resistance test and the pencil hardness measurement. Table 5

From Table 5, it is clear that Examples 1 to 16, which are the processing methods of the present invention, It shows that the film has the properties of covering around edges, corrosion resistance, heat resistance, solvent resistance, and insulation, and has a high film surface hardness and can withstand the pressure of the winding wire. .

In comparison, Comparative Examples 1 to 4, in which the post-treatment step specified in the treatment method of the present invention was not performed, had insufficient film hardness and extremely poor solvent resistance. In Example 4, the heat resistance was also inferior.

In Comparative Example 5 in which the curing agent (e) used in the post-treatment liquid (B) was added to the autodeposition treatment liquid (A) by the method of the present invention, sufficient surface hardness and solvent resistance could not be obtained. Was.

Further, in Comparative Example 6 where powder coating was performed and Comparative Example 7 where electrodeposition coating was performed, the covering property to the edge portion was poor, and sufficient insulating properties could not be obtained. The corrosion resistance was also insufficient. Industrial applicability

The self-precipitation type surface treatment coating method of the microphone opening device or the component thereof according to the present invention is an environmental type surface treatment system with high workability, productivity, and economic efficiency. It is possible to impart excellent peripheral properties to edges, corrosion resistance, heat resistance, solvent resistance, and insulation to micro devices or components thereof.The micro devices of the present invention or the components thereof can be used for micro devices, In addition, the requirements for miniaturization and thinning of the parts can be sufficiently satisfied, and it can be said that the present invention is extremely useful in practical use.

Claims

The scope of the claims

1. Contact the surface of the micro-device or its component with the autodeposition type surface treatment solution (A) containing at least one water-soluble or water-dispersible organic polymer resin (a). A step of depositing an organic film on the surface, and a post-treatment liquid containing at least one curing agent (e) capable of curing the surface of the deposited organic film.

(B) A self-praying type surface treatment coating method in which an organic film is formed on the surface of a micro device or its components by a surface treatment step including a step of contacting with (B) and a step of heating and drying.

2. The self-precipitation type surface treatment coating method according to claim 1, further comprising an autodeposition type surface treatment solution (A), a force S, and an acid component (b).

3. The self-deposition type surface treatment coating method according to claim 1 or 2, further comprising an autodeposition type surface treatment solution (A), a force S, and an oxidizing agent (c).

4. The self-deposition type surface treatment coating method according to any one of claims 1 to 3, wherein the self-deposition type surface treatment solution (A) further contains a metal ion (d).

5. It is characterized in that it is at least one selected from the group consisting of an organic polymer resin (a), an acryl resin, an epoxy resin, a urethane resin, a polyester resin, and a polyamide resin used in the self-precipitation treatment liquid (A). The self-precipitation treatment coating method according to any one of claims 1 to 4.

6. The self-precipitation surface treatment according to claims 1 to 5, wherein at least one of the organic polymer resins (a) used in the self-precipitation treatment liquid (A) is an anionic polyester. Coating method

7. Anionic polyester resin obtained by condensing a polyhydric alcohol and an acid compound with at least one kind of anionic polyester resin (a) used in the organic deposition resin (A) The autodeposition treatment coating method according to any one of claims 1 to 6, wherein:

8. The curing agent (e) of the post-treatment liquid (B) is selected from melamine resin, guanamine resin, urea resin, phenol resin, epoxy resin, and isocyanate compound. The autodeposition type surface treatment coating method according to any one of claims 1 to 7, which is at least one kind.

9. The post-treatment liquid a) (B) The self-precipitation type surface treatment coating method according to claims 1 to 8, comprising at least one type of surface lubricant (f).

10 0. Surface lubricant of post-treatment agent (B) (f) Power At least one lubricant selected from fluororesin-based lubricant, polyolefin-based wax, melamine cyanurate, and molybdenum disulfide 9. The self-deposition type surface treatment / coating method according to range 1-9.

1 1. contacting the surface of the micro device or its component with the self-deposition type surface treatment solution (A) according to claims 1 to 8 to deposit and form an organic film on the surface; The method according to any one of claims 1 to 10, which includes a step of contacting with a post-treatment liquid (B) capable of curing the surface of the film, a step of removing excess adhesion liquid by air blowing, and a step of heating and drying. A self-deposition type surface treatment coating method in which an organic film is formed on the surface of a microphone or a component thereof by a surface treatment step.

1 2. A micro device having a self-deposition type surface treatment film formed by any one of claims 1 to 11, or a component thereof.