CN1286578C - Method for self-deposition type surface treatment coating of microdevice orits components, and microdevice or its parts having self-deposition typesurface treatment coating - Google Patents
Method for self-deposition type surface treatment coating of microdevice orits components, and microdevice or its parts having self-deposition typesurface treatment coating Download PDFInfo
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- CN1286578C CN1286578C CN 02812241 CN02812241A CN1286578C CN 1286578 C CN1286578 C CN 1286578C CN 02812241 CN02812241 CN 02812241 CN 02812241 A CN02812241 A CN 02812241A CN 1286578 C CN1286578 C CN 1286578C
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02K—DYNAMO-ELECTRIC MACHINES
- H02K15/00—Methods or apparatus specially adapted for manufacturing, assembling, maintaining or repairing of dynamo-electric machines
- H02K15/12—Impregnating, heating or drying of windings, stators, rotors or machines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/107—Post-treatment of applied coatings
- B05D3/108—Curing
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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 the micromachine of magnet ring that micromachine core, stepper motor use etc. or its part from precipitation type surface treatment coating method, and have from the precipitation type surface treatment by the micromachine of overlay film or its part.
Background technology
Micromachine or its part have adopted electrophoretic coating, powder coating, solvent spraying etc. in order to have purposes such as insulating properties, corrosion resistance, design.Yet these machines, part adopt these coating method to be difficult to form uniformly and film in thin portion, the marginal portion of complicated shape along with to the microminiaturization development, become difficult point comparatively speaking.For example, require the micromachine core of harsh insulating properties, owing to adopt electrophoretic coating, the saturating property of the swimming that edge part grades is poor, though repeat to be coated with several times, even so present disqualification rate is still very high, and the required cost height of main equipment, in addition, energising operation etc. are also bothersome.Adopt powder coating, in order to keep enough insulating properties, need the above thickness of 100 μ m, this requires in the extra-thin motor similar disk drive motor is a fatal problem, and case hardness can not anti-fully iron core coiling.
Also have, adopt the spraying method of spraying etc., evenly coating is very bothersome to thin portion, and have the problem of surface covered difference.
Several motions that address these problems are arranged, Te Kaiping 5-300681 communique proposes employing realizes the motor core in the method for the aqueous insulating compound of surperficial coating multiple of core filming, it can make the attenuation of filming, but coating is very bothersome on the contrary, production efficiency is low, and also there is the problem of operating environment difference in the insulating compound that uses solvent to be.
Te Kaiping 9-94521 communique has proposed to use has water-insoluble demoulding plasticizer, aqueous coating composition with 55 ℃ of glass transition temperatures, adopt simple equipment, operation to form by the method for overlay film, but gained is insufficient by the resistance to water of overlay film, corrosion resistance, the balance of case hardness and fragility is also insufficient in addition, has the shortcoming of be full of cracks easily when in fact the motor core being wound the line.In addition, though be water system, but still be the coating that contains organic solvent, so working life, operation existing problems.
The surface that Te Kaiping 9-233780 communique has proposed to make lamination motor core with contain contacting of resin emulsion, acid, oxidant, metal ion and water from the precipitation type water-based coating composition, form the method for insulating coating film at the motor wicking surface.Adopt the insufficient of this method acquisition, have the shortcoming that causes poor durability because of coiling by the overlay film case hardness.
In recent years, along with the universal of portable phone and to the miniaturization development, vibrator used the subminaturization of motor very necessary, and in the application to the used motor core of these equipment, the above-mentioned prior art of more difficult employing solves.
Summary of the invention
The present invention uses the environmental form superficial treatment system that is rich in the inaccessiable high operation of prior art, productivity, economy, provide form have good insulation properties, swimming property, corrosion resistance, hear resistance, solvent resistance and high surface hardness by the method for overlay film, and have adopt that this method handles by the micromachine of overlay film and part thereof.
The result that present inventors concentrate on studies in view of the problem that prior art exists, find to adopt following surface treatment procedure, promptly, micromachine or its piece surface are contacted with the type of analysing the certainly surface treatment liquid (A) that contains a kind water-soluble or water dispersible organic polymer resin (a) at least, separate out the operation that forms organic lining film on this surface, with make separate out formation organic by the surface of overlay film with contain operation that the aftertreatment fluid (B) of at least a kind of curing agent (e) of its curing can be contacted and the operation of carrying out heat drying, the type of analysing the certainly surface treatment coating method that makes micromachine surface or its piece surface form organic lining film is an effective method, thereby has finished the present invention.
In addition, also find with operation that aftertreatment fluid (B) contacts after, employing comprises the blowing operation, the surface treatment procedure of heat drying operation then, make it on micromachine surface or the type of analysing certainly surface treatment coating method that its piece surface forms organic lining film is an effective method, thereby finished the present invention.
From analyse type surface treatment liquid (A) except contain water-soluble or water dispersible organic polymer resin (a), also more preferably contain sour composition (b), further preferably contain oxidant (c), most preferably contain metal ion (d) in addition.Be more preferably at least a kind that from acrylic resin, epoxy resin, polyurethane resin, mylar, polyamide, selects from the organic polymer resin (a) of analysing type treatment fluid (A) use, in addition more preferably its at least a kind be the anionic property polyester, most preferably be the anionic property mylar that polyalcohol and acid compound condensation make.
The curing agent (e) of aftertreatment fluid (B) is more preferably at least a kind that selects from melmac, guanamine resin, urea resin, phenolic resins, epoxy resin, isocyanate compound, in addition, post-treatment agent (B) also preferably contains lubricant, and most preferably surface lubricant (f) is at least a kind the lubricant of selecting from fluororesin base lubricant, polyolefin wax, melamine urea cyanate, molybdenum bisuphide.
That is, the invention provides, or its piece surface forms the type of analysing the certainly surface treatment coating method of organic lining film, and have this method institute shape of employing by the micromachine of overlay film or part on above-mentioned micromachine surface.
Below be described in detail formation of the present invention.
The micromachine that the present invention uses, or its part is the micromachine core that the drive motors of the vibrator, floppy disk, hard disk, CD, minidisk, CDROM of portable phone etc. uses, in addition, be installed in stepper motor in OA machine, AV machine, the tame electrical article etc., material is steel plate, silicon steel plate or the ferrous materials such as agglomerated material that made by the powder metallurgy of ferrite, rubidium iron boron system etc.
What the present invention used is with the water system treatment fluid of resin as principal component from precipitation type surface treatment liquid (A), preferably contain water-soluble or water dispersible organic polymer resin (a) and sour composition (b), further preferably contain oxidant (c), most preferably contain metal ion (d).
Water-soluble or water dispersible organic polymer resin (a), it is at least a kind that from acrylic resin, epoxy resin, polyurethane resin, mylar, polyamide, selects, be to use the forced emulsification type organic polymer resin of the emulsifying agent water systemization of surfactant etc., or the part of this resin structure uses anionic property functional group modification water-soluble of carboxyl, sulfonic group, phosphate, phosphonate group etc., or self emulsifiable organic polymer resin.In addition, at least a kind of mylar that is more preferably anionic property selecting from these resins most preferably is the mylar of the anionic property that makes of polyalcohol and acid compound condensation.
Polyalcohol and acid compound as aforementioned mylar monomer, most preferably be polyalcohol (m1) and acid compound (m2), polyalcohol (m1) is the aliphatic polyol derivative (m1)-1 from general expression (1) expression, with at least a kind that selects in the aromatic polyol derivative (m1)-2 of general expression (2) expression.
(m1)-1
HO-R
1-OH (1)
In the general expression (1), R
1Be C
1～C
10Alkylidene, unsaturated alkylene, hydroxyl and/or the halogen-containing aforementioned alkylidene or the unsaturated alkylene of straight or branched.
As (m1)-1, can enumerate ethylene glycol, neopentyl glycol, dibromoneopentyl glycol, 1,2-propane diols, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, 3-methyl pentanediol, 1,4-cyclohexanedimethanol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, ammediol, 2,2 '-diethyl-1, ammediol, glycerine, pentaerythrite, trimethylolethane, trimethylolpropane etc.
(m1)-2
In the general expression (2), m, n are the integers more than 1, and 2≤m+n≤6.R
2, R
3, R
4, R
5It is at least a kind that from hydrogen, methyl, selects individually respectively.
As (m1)-2, can enumerate bisphenol-A epoxy ethane addition product, bisphenol-A epoxy propane addition product, Bisphenol F ethylene oxide adduct, Bisphenol F propylene oxide adduct.
Acid compound (m2) is at least a kind that selects the naphthalene derivatives (m2)-5 of pyromellitic dianhydride (m2)-4, general expression (7) expression of aromatic anhydride derivative (m2)-3, general expression (6) expression of aromatic derivant carboxylate (m2)-2, general expression (5) expression of aliphatic carboxylic acid derivative (m2)-1, general expression (4) expression from general expression (3) expression.
(m2)-1
X
1OOC-R
6-COOX
2 (3)
In the general expression (3), X
1, X
2Be respectively individually from hydrogen, C
1～C
10Alkyl in select at least a kind.R
6Be C
1～C
10Straight or branched alkylidene, unsaturated alkylene, contain-COOX
3(X here,
3Be hydrogen, C
1～C
10The alkylidene of straight or branched) aforementioned alkylidene or unsaturated alkylene.
As (m2)-1, can enumerate butanedioic acid, methylsuccinic acid, the ethyl butanedioic acid, the butyl butanedioic acid, diethyl succinate, diethyl succinate, the mono succinate butyl ester, dibutyl succinate, glutaric acid, methylglutaric acid, ethylglutaric acid, the butyl glutaric acid, monomethyl glutarate, dimethyl glutarate, the glutaric acid mono ethyl ester, ethyl glutarate, the glutaric acid mono, the glutaric acid dibutyl ester, adipic acid, adipic acid monomethyl ester, dimethyl adipate, monoethyl adipatee, dioctyl adipate, decanedioic acid, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, equal third dioctyl phthalate, butylene tetrabasic carboxylic acid etc.
(m2)-2
In the general expression (4), X
4, X
5Be respectively independently from hydrogen, C
1～C
3Alkyl in select at least a kind.Y
1, Y
2, Y
3And Y
4Be respectively individually from-COOX
6(X here,
6Be hydrogen, C
1～C
3Alkyl, Na, K, Ca, Ba, Li, NH
4) ,-SO
3Z
1(Z here,
1Be hydrogen, Na, K, Ca, Ba, Li, NH
4) in select at least a kind.
As (m2)-2, can enumerate terephthalic acid (TPA), terephthalic acid monomethyl ester, dimethyl terephthalate (DMT), terephthalic acid (TPA) mono ethyl ester, diethyl terephthalate, M-phthalic acid, M-phthalic acid mono-methyl, DMIP, M-phthalic acid dimethyl-5-sulfonate sodium, trimellitic acid, trimellitic acid 1,4-dimethyl ester, Pyromellitic Acid tetramethyl ester, Pyromellitic Acid tetra-ethyl ester etc.
(m2)-3
In the general expression (5), Y
5, Y
6Be respectively individually from hydrogen ,-COOX
7(X here,
7Be hydrogen, C
1～C
3Alkyl, Na, K, Ca, Ba, Li, NH
4) ,-SO
3Z
2(Z here,
2Be hydrogen, Na, K, Ca, Ba, Li, NH
4) in select at least a kind.
As (m2)-3, can enumerate phthalic anhydride, trimellitic anhydride, trimellitic anhydride ethyl ester etc.
(m2)-4
(m2)-the 4th, pyromellitic dianhydride.
(m2)-5
In the general expression (7), X
8, X
9Be respectively individually from hydrogen, C
1～C
3Alkyl in select at least a kind.Y
7, Y
8, Y
9And Y
10Be respectively individually from hydrogen ,-COOX
10(X here,
10Be hydrogen, C
1～C
3Alkyl, Na, K, Ca, Ba, Li, NH
4) ,-SO
3Z
3(this morning, Z
3Be hydrogen, Na, K, Ca, Ba, Li, NH
4) in select at least a kind.
As (m2)-5, can enumerate 1,2-naphthalenedicarboxylic acid, 1,2-naphthalene diformic acid dimethyl ester, 1,3-naphthalenedicarboxylic acid, 1,3-naphthalene diformic acid dimethyl ester, 1,4-naphthalenedicarboxylic acid, 1,4-naphthalene diformic acid dimethyl ester, 1,5-naphthalenedicarboxylic acid, 1,5-naphthalene diformic acid dimethyl ester, 1,6-naphthalenedicarboxylic acid, 1,6-naphthalene diformic acid dimethyl ester, 1,7-naphthalenedicarboxylic acid, 1,7-naphthalene diformic acid dimethyl ester, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalene diformic acid dimethyl ester, 2,6-naphthalenedicarboxylic acid, 2,6-naphthalene diformic acid dimethyl ester, 2,7-naphthalenedicarboxylic acid, 2,7-naphthalene diformic acid dimethyl ester etc.
Consider that from corrosion resistance, adhesiveness and hear resistance aspect at least a kind of selecting of acid compound (m2) contains 60 moles more than the % in all acid compound from (m2)-2, (m2)-3, (m2)-4.
(m2)-2, (m2)-3, (m2)-5 reach in (7) Y in general expression (4), (5)
1～Y
10At least a kind should be carboxyl or sulfonic group, that is, more preferably in all acid composition, contain from-COOX
6,-SO
3Z
1,-COOX
7,-SO
3Z
2,-COOX
8,-SO
3Z
3In select at least a kind be 1～40 mole of %, most preferably be 2～30 moles of %.The molecular weight of the mylar that uses does not have particular determination among the present invention, but can use the mylar of number-average molecular weight 2000～50000.
The synthetic method of the mylar that uses among the present invention is not the method for particular determination.For example, can be as required in the presence of the catalyst of Dibutyltin oxide, lead acetate, calcium acetate, normal-butyl titanate esters etc., under the following decompression of 10mmHg, carry out esterification or ester exchange reaction under 140～300 ℃ the temperature and make it polycondensation and make.
The present invention use from the employed sour composition of precipitation type surface treatment liquid (A) (b), for example, be at least a kind that from fluorine zirconic acid, fluotitanic acid, fluosilicic acid, fluoboric acid, hydrofluoric acid, phosphoric acid, nitric acid, selects, be more preferably hydrofluoric acid.
As oxidant (c), can be the oxidant that divalent iron ion with stripping in the object being treated that makes ferrous material is oxidized to 3 valency abilities, for example, can use potassium permanganate, hydrogen peroxide, natrium nitrosum etc., be more preferably hydrogen peroxide.
As the compound that can supply with metal ion (d), if stable in treatment fluid then do not have particular determination, can enumerate ferric nitrate, bifluoride iron, primary iron phosphate, nitrous acid zirconium etc., more preferably use bifluoride iron.
The present invention use in precipitation type surface treatment liquid (A), water-soluble or water dispersible organic polymer resin (a) is as the preferred 5～550g/L of solid portion concentration, more preferably 50～200g/L.Preferred 0.1～the 5.0g/L of concentration of acid composition (b), more preferably 0.5～3.0g/L.Preferred 0.01～the 3.0g/L of concentration of oxidant (c), more preferably 0.03～1.0g/L.The concentration of metal ion (d), as the metal in the compound that can supply with metal ion, preferred 0.1～50g/L, more preferably 0.5～5.0g/L.
From precipitation type surface treatment liquid (A), the any composition of conduct except that mentioned component, under the situation of not destroying the object of the invention, can contain, the film forming assistant of isobutyric acid trialkyl pentadiol ester, alkyl carbitol etc. for example, for example carbon black, phthalocyanine blue, the Chinese spread red etc. coloring pigment etc.
From separate out organic be the warm film that contains big water gaging by overlay film, aftertreatment fluid (B) makes this water be diffused into medium and by in the overlay film, solidifies to have the effect that improves case hardness, solvent resistance when heat drying.Aftertreatment fluid (B) is not to make from separating out organicly all to be solidified equably by overlay film, and because big by near the concentration ratio metal interface the overlay film, therefore effect is also big, so do not influence with the adhesiveness of base material but can give surface of good hardness, solvent resistance.Therefore, can not obtain same effect even for example can add the composition high concentration of this post-treatment agent (B) ground from separating out in the treatment fluid (A) to.
(B) describes in detail to post-treatment agent.
The curing agent that uses in the post-treatment agent (B), at least a kind of preferably from the amino resins of melmac, guanamine resin, urea resin etc., phenolic resins, epoxy resin, isocyanate compound, selecting.Melmac is alkoxy methyl melamine, imines type alkoxy methyl melamine, imines type melamine methylol, melamine methylol of methylated melamine, butylation melamine etc. etc., for example, can enumerate trimethylol melamine, tetra methylol melamine, hexamethylolmelamine, trimethoxy methyl dihydroxymethyl melamine, dibutoxy methyl trimethylol melamine etc.Wherein, owing to contain at least a kind of functional group who selects from methylol, imino group, the effect that can improve case hardness greatly and more preferably in molecule.
As the guanamine resin, can enumerate benzo guanamine resin, methyl guanamine resin etc.; Phenolic resins is phenol-formaldehyde resin, bis-phenol-formaldehyde resin etc., can enumerate resol type, line style, amino modified line style etc.; Epoxy resin is the resin that has 1 glycidyl in the molecule at least, can enumerate bisphenol type, pentaerythrite glycidol ether etc.; As isocyanate compound, can enumerate by blocked isocyanate prepolymer of end-blockings such as acid sulphite, oxime (for example the first industrial drugmaker system, ェ ラ ス ト ロ Application) etc., also can use the urea resin of urea and formaldehyde condensation.Curing agent (e) concentration in the aftertreatment fluid (B) is as the preferred 5～200g/L of nonvolatile component, more preferably 10～100g/L.
Post-treatment agent (B) also preferably contains lubricant (f), at least a kind of most preferably selecting from fluororesin base lubricant, polyolefin wax, melamine urea cyanate, molybdenum bisuphide of lubricant.
As the fluororesin base lubricant, can enumerate the aqueous dispersion of polytetrafluoroethylene (PTFE), polytrifluorochloroethylene etc., as polyolefin wax, can enumerate the water system dispersion of Tissuemat E, polypropylene wax etc.
Surface lubricant (f) is owing to reduce skin friction resistance, the motor core is implemented coiling waits stress when applying extraneous stress so have mitigation especially, prevents to injure the effect by overlay film or breakage.Also have, have raising by the effect of overlay film resistance to water.
Lubricant (f) concentration in the aftertreatment fluid (B) is as the preferred 0.5～100g/L of nonvolatile component, more preferably 1～50g/L.
In addition, when the curing agent (e) in the aftertreatment fluid (B) is the amino resins of melmac etc., in order to improve the stability in the inorganic agent, more preferably have the amines of alkanolamine etc. of the alkylamine, monoethanolamine, diethanol amine, triethanolamine etc. of ethamine, diethylamine, triethylamine etc., preferably make post processing pH remain on 7～10.
Processing method of the present invention is to make from precipitation type surface treatment liquid (A) contact object being treated, promptly contact micromachine or its piece surface and separate out the method that forms organic lining film on this surface, impregnation process liquid (A) there is not particular determination with the method that the object being treated surface contacts, but, more preferably object being treated is immersed in the treatment fluid (A) in order to be formed uniformly by overlay film in complex surfaces.Preferred 5～50 ℃, more preferably 10～40 ℃ of treatment temperatures.When treatment temperature was lower than 5 ℃, precipitation efficiency was poor, can not obtain enough by the overlay film amount, because reaction is too many, existed by the tendency of overlay film appearance variation and not preferred when surpassing 50 ℃.
During processing preferred 10～500 seconds, more preferably 20～300 seconds.When being lower than 10 seconds,, can not form fully by overlay film because evolution reaction is not enough.When surpassing 500 seconds, object being treated dissolves, and is increased by the Fe ion concentration in the overlay film, because the easy variation of outward appearance, corrosion resistance also reduces and not preferred.
Relevant aftertreatment fluid (B) does not similarly have particular determination to the method that contacts processed surface yet, but for the contact of whole surface preferably is immersed in object being treated in the aftertreatment fluid (B).Though treatment temperature is particular determination not, preferably 5～60 ℃, more preferably 10～40 ℃.2～500 seconds processing times, more preferably 5～200 seconds.Treatment temperature is lower than 5 ℃, or the processing time is when being lower than 5 seconds, the post processing composition is insufficient to separating out by the infiltration of overlay film, therefore the post processing composition is confined to the most surperficial, there is the tendency that becomes fragile in the result surface, treatment temperature surpasses 60 ℃ or processing time when surpassing 200 seconds, separates out by the tendency of overlay film and not preferred owing to exist to dissolve.
Processing method of the present invention is in order to improve outward appearance, corrosion resistance, more preferably before carrying out heat drying, promptly with after aftertreatment fluid (B) contacts, adopts blowing to remove remaining post processing and adheres to liquid.
Blowing is if using common spray gun etc. to remove remaining post processing adheres to liquid and then do not have particular determination, but more preferably regulate spray gun nozzle diameter, to make the pressure on object being treated surface with the distance of object being treated be 0.3～10kg/cm
2Because remaining aftertreatment fluid is attached to the easy position of stagnant liquid, disfeatures and make the disqualification rate rising so produce projection during heat drying easily on by overlay film.
Heating means do not have particular determination in the heat drying operation, can make electricity consumption or combustion gas as the heated air circulation type drying oven of thermal source, the heating furnace that utilizes far infrared, high-frequency heating, eddy-current heating etc.Preferred 60～300 ℃, more preferably 80～250 ℃ of heating-up temperatures.When being lower than 60 ℃, film forming is bad, and corrosion resistance, insulating properties are insufficient, when surpassing 250 ℃, and resin-coated film thermal decomposition and not preferred.For further improve in the heat drying operation by the overlay film outward appearance, more preferably behind the moisture that 60～100 ℃ the abundant drying of temperature is adhered to, heat in higher temperature effectively.
The simple declaration of accompanying drawing
Fig. 1 represents the material I that embodiment uses: motor core (silicon steel plate).
The optimum implementation of invention
Below according to embodiment and comparative example explanation the present invention, but present embodiment only is a simple example, does not limit the present invention.
Embodiment, and the processed material that uses in the comparative example is as follows.
I: micromachine core (silicon steel plate) (Fig. 1)
III:SPCC-SD (70 * 150mm thickness of slab 0.8mm)
As follows from the composition that precipitation type surface treatment liquid (A) uses.
Water-soluble or water dispersible organic polymer resin (a)
A1～a5: the mylar that monomer shown in the table 1 is formed
Table 1
| Form | a1 | a2 | a3 | a4 | a5 | ||
| m1 | (m1)-1 | Neopentyl glycol | 90 | 30 | 10 | ||
| Ethylene glycol | 70 | 70 | 50 | 90 | |||
| 1, the 4-butanediol | 30 | 20 | |||||
| Trimethylolpropane | 10 | ||||||
| (m1)-2 | Bisphenol-A epoxy propane addition product | 10 | |||||
| m2 | (m2)-1 | Decanedioic acid | 5 | 10 | |||
| (m2)-2 | M-phthalic acid | 40 | 45 | 40 | 53 | ||
| Terephthalic acid (TPA) | 41 | 45 | 81 | 35 | 20 | ||
| M-phthalic acid dimethyl-5-sodium sulfonate | 2 | 3 | 2 | 4 | 2 | ||
| Trimellitic acid | 17 | ||||||
| (m2)-3 | Trimellitic anhydride | 17 | 5 | ||||
| (m2)-4 | Pyromellitic dianhydride | 7 | 16 | ||||
| (m2)-5 | 2, the 6-naphthalenedicarboxylic acid | 10 | |||||
A6: oiling Shell epoxy corporate system epoxy resin
ェピレッツ3522W60(NVC.60％)
A7:Rohm﹠amp; Hass corporate system acrylic resin
ロ one プ レ Star Network ス WL-91 (NVC.41.5%)
A8:W.R.Grace corporate system polyvinylidene chloride resin
Daran SL143(NVC.55％)
The mylar that monomer shown in the table 1 is formed the a1～a5 that constitutes adopts following method synthetic.
In the round-bottomed flask of the 1000ml that Clarkson pipe, aerial cooler are installed, add 1 mole of total acid composition (or ester composition), 2 moles of total pure compositions, the calcium acetate 0.25g as catalyst, tetrabutyl titanate 0.1g, to nitrogen replacement in the system, make the content fusion 180 ℃ of heating.
Bathe temperature rise to 200 ℃, heating stir about 2 hours (esterification or ester exchange reaction).Then, will bathe temperature rise to 260 ℃, after about 15 minutes the 0.5mmHg that reduces pressure in the system be reacted about 3 hours (polycondensation reaction).Reaction finishes the back and transfers cold taking-up content at feeding nitrogen.Adding an amount of ammoniacal liquor (water is 25% amount of solid constituent) in the resin that takes out, to make final pH be 6～7, adds thermal agitation under 100 ℃ and made the water serial emulsion resin in 2 hours in autoclave.
Acid composition (b)
Employed sour composition (b) is expressed as follows.
b1：HF
b2：H
2ZrF
6
b3：H
3PO
4
Oxidant (c)
Employed oxidant (c) uses hydrogen peroxide.
C: hydrogen peroxide
Metal ion (d)
The metal ion (d) that uses is expressed as follows.
D1: bifluoride iron
D2: ferric nitrate
Other compositions (g)
Pigment: adret pigment corporate system (ェ マ コ one Le Block ラ ッ Network D305)
To form from the treatment fluid of precipitation type surface treatment liquid (A) and be shown in table 2.
Table 2
| Composition | From precipitation type surface treatment liquid A (g/L) | ||||||||
| A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A9 | |
| a | a1 (200) | a2 (233) | a2 (120) | a3 (160) | a3 (240) | a4 (240) | a5 (120) | a7 (120) | a8 (91) |
| a6 (16.7) | a7 (24) | a5 (120) | a6 (33) | ||||||
| b | b1 (1.0) | b1 (1.0) | b1 (0.5) | b1 (0.5) | b3 (2.0) | b2 (0.5) | b1 b3 | b1 (1.0) | b1 (1.0) |
| b2 (0.5) | b2 (0.5) | b3 (1.0) | |||||||
| c | (0.1) | (0.1) | (0.1) | (0.1) | (0.1) | (0.1) | (0.1) | (0.1) | (0.1) |
| d | d1 (3.0) | d1 (3.0) | d1 (2.0) | d1 (4.0) | d2 (1.5) | d1 (2.0) | d1 (3.0) | d1 (0.1) | d1 (0.1) |
| d2 (0.5) | d2 (1.0) | ||||||||
| g | (0.1) | (0.15) | (0.15) | ... | (0.15) | ... | ... | (0.15) | (0.15) |
The composition that aftertreatment fluid of the present invention (B) uses is as follows.
Curing agent (e)
E1: Mitsui サ ィ テ ッ Network corporate system part methyl melmac
サィメル730(NVC.88％)
E2: Mitsui サ ィ テ ッ Network corporate system hyper-methylation cyanamid dimerization resin
サィメル300(NVC.100％)
E3: the flourish chemical industrial company of group system phenolic resins
レチトツプPL4664(NVC.50％)
E4: the first industrial drugmaker system blocked isocyanate prepolymer
ェラストロンBN5(NVC.15％)
Lubricant (f)
F1: Sumitomo 3M corporate system fluororesin base lubricant
ダィニォン
TMPTFE5035(NVC.60％)
F2: molybdenum bisuphide
F3: Mitsui Chemicals corporate system polyolefin wax
ケ ミ パ one Le W900 (NVC.40%)
Other additive (h)
H1: ammoniacal liquor
H2: triethanolamine
H3: triethylamine
The treatment fluid content of aftertreatment fluid (B) is shown in table 3.
Table 3
| Composition | Aftertreatment fluid B (g/L) | ||||
| B1 | B2 | B3 | B4 | B5 | |
| e | e1(68) | e2(40) | e3(20) | e2(60) | e4(50) |
| f | f1(15) | f1(13) | f3(8) | f1(10) f2(5) | f2(6) |
| h | h1(5) | h2(6) | h2(6) | h3(10) | ... |
Below to treatment process, treatment conditions describe.By following order carry out following shown in operation.
1, degreasing
Use Japanese パ one カ ラ ィ ジ Application グ corporate system: alkali cleaner Off ァ ィ Application Network リ one Na 1 (20g/L reduction dye vat, 60 ℃, dipping 5 minutes) carries out degreasing.
2, washing 1.
Carried out running water drip washing 30 seconds.
3, washing 2.
Dipping is 30 seconds in deionized water.
4, handle from precipitation type
Be immersed in precipitation type surface treatment liquid (A) and separate out by overlay film.
22 ± 2 ℃ of [condition 1.] treatment fluid temperature, dipping 180 seconds.In treatment fluid, shake object being treated (1 time/second) up and down lightly.
30 ± 2 ℃ of [condition 2.] treatment fluid temperature, dipping 120 seconds.Use magnetic stirring apparatus to stir (top 30mm, speed 200rpm) treatment fluid in the 1L beaker (1L).
5, washing 3.
Running water is stored in the rustless steel container of 10L,, the object being treated dipping was shaken moving (1 time/second) in 2 minutes up and down gently making it in the washing bath of overflow by the flow of 2L/ branch is additional.
6, post processing
Be immersed in the post processing medicament (B) by following condition.
22 ± 2 ℃ of [condition 3.] treatment temperatures, dipping 20 seconds.In treatment fluid, shake object being treated (1 time/second) up and down lightly.
40 ± 2 ℃ of [condition 4.] treatment fluid temperature, dipping 10 seconds.In treatment fluid, shake object being treated (1 time/second) up and down lightly.
7, blowing
Used ァ ネ ス ト rock field corporate system spray gun W77 under following condition, to dry.
[condition 5.] regulate nozzle diameter and with the distance of object being treated, the pressure that air is ejected on the object being treated is 4～5kg/cm
2, from object being treated just above repeat the intermittent cyclic operation of 5 times (blow and stopped for 3 seconds for 2 seconds one).
[condition 6.] regulate nozzle diameter and with the distance of object being treated, the pressure that air is ejected on the object being treated is 3～4kg/cm
2, blew for 10 seconds continuously above just from processed.
8, heat drying
Use heated air circulation type drying oven ( バ ィ corporate system パ one Off ェ Network ト ォ one Block Application PS112) to carry out heat drying by following condition.
[condition 7.] at 80 ℃ of following heat dryings after 5 minutes, make the temperature in the stove be raised to 180 ℃ with 10 minutes, place 5 minutes (wind speed: the 2m/ branch) again after being raised to 180 ℃ in stove.
[condition 8.] at 100 ℃ of following heat dryings after 5 minutes, are warmed up to 200 ℃ with 10 minutes, be raised to 200 ℃ and place 5 minutes (wind speed: the 2m/ branch) later on again in stove.
[condition 9.] is at 20 minutes (wind speed: the 2m/ branch) of 110 ℃ of following heat dryings.
The content of embodiment and comparative example is shown in table 4.
Table 4
| From separating out treatment fluid (A) | Aftertreatment fluid (B) | Blowing [condition] | Heat drying [condition] | ||||
| Treatment fluid | [condition] | Treatment fluid | [condition] | ||||
| Embodiment | 1 | A1 | ① | B1 | ③ | ⑤ | ⑦ |
| 2 | A1 | ① | B1 | ④ | ⑤ | ⑧ | |
| 3 | A1 | ② | B2 | ③ | ⑤ | ⑦ | |
| 4 | A1 | ② | B2 | ③ | ⑧ | ||
| 5 | A2 | ① | B1 | ③ | ⑥ | ⑦ | |
| 6 | A2 | ① | B2 | ③ | ⑥ | ⑦ | |
| 7 | A2 | ① | B4 | ③ | ⑤ | ⑦ | |
| 8 | A2 | ② | B4 | ③ | ⑧ | ||
| 9 | A3 | ① | B1 | ④ | ⑤ | ⑦ | |
| 10 | A3 | ① | B3 | ③ | ⑥ | ⑦ | |
| 11 | A4 | ① | B2 | ③ | ⑤ | ⑦ | |
| 12 | A4 | ① | B5 | ④ | ⑥ | ⑧ | |
| 13 | A5 | ② | B2 | ③ | ⑤ | ⑦ | |
| 14 | A6 | ① | B4 | ③ | ⑤ | ⑧ | |
| 15 | A6 | ② | B2 | ③ | ⑤ | ⑦ | |
| 16 | A7 | ① | B1 | ③ | ⑤ | ⑦ | |
| Comparative example | 1 | A1 | ① | … | … | … | ⑦ |
| 2 | A2 | ② | … | … | ⑤ | ⑧ | |
| 3 | A8 | ① | … | … | … | ⑦ | |
| 4 | A9 | ① | … | … | … | ⑨ | |
Comparative example 5
Except to interpolation curing agent (e1) 3g/L in precipitation type treatment fluid (A1), other and comparative example 1 similarly carry out.
Comparative example 6
After proceeding to washing 2. by aforesaid treatment process, the coating polyester based resin be the powder coating (polyester V-PET#4000 (big Nippon Paint Co., Ltd. system)) of principal component to make the thickness of planar section be 20 μ m, in hot-air drying stove 180 ℃ dry 20 minutes down.
Comparative example 7
After proceeding to washing 2. by aforesaid treatment process, coating epoxy cation electrophoretic coating (ェ レ Network ロ Application 9400: Northwest paint company system), making the thickness on the planar section under voltage 200V is 20 μ m, and 175 ℃ were descended dry 20 minutes in hot-air drying stove.
Being undertaken by following standard that embodiment and comparative example are made for test material by overlay film rerum natura, the test of lining film properties and evaluation.
Outward appearance
Visualization is estimated by overlay film projection, be full of cracks, wrinkle, paint face etc. by the common example of following expression.
◎: do not have projection, be full of cracks, wrinkle, paint face
Zero: do not have projection, be full of cracks, wrinkle, paint face basically
△: projection, be full of cracks, wrinkle, paint face are arranged
*: a lot of projectioies, be full of cracks, wrinkle, paint face are arranged
Determining film thickness
Microscopic examination is measured the lining film thickness for the planar section of test material and the cross section of marginal portion.
Corrosion resistance
To carrying out salt spraytest (JIS-Z2371) 500 hours for test material, the estimation rust area is estimated.
◎：0％
Zero: less than 5%
△: 5% above less than 20%
*: more than 20%
Hardness of film
Adopt pencil test method (JIS-K5400) to estimate.
Hear resistance
Placing 30 minutes at 220 ℃ for test material, the weight slip % before and after using estimates.
Zero: less than 1%
△: 1% above less than 5%
*: more than 5%
In addition, the test material that supplies after the heat resistant test (placing 30 minutes for 220 ℃) is carried out checkerboard type cross-hatching belt stripping test (1mm square, 100).
Behind the tape stripping by the overlay film extant number
◎：100
○：90～99
△：80～89
*: below 79
The insulation characterisitic test
Estimate from the marginal portion of analysing the type surface-treated and becoming motor core (Fig. 1) winding portion carrying out.Peel off coated test material core by overlay film, connect the negative pole of test pin.To the positive pole of motor core winding portion scan test pin, the number (n) of the marginal portion that the statistics electric current leaks is estimated by disqualification rate=n/36.
Determining instrument: insulating-resistance meter FI-901 (Japanese テ Network one Na one De corporate system)
Apply voltage: 500V
Evaluation criterion
◎: n is 0
Zero: n less than 3
△: n is 3 above less thaies 10
*: n is more than 10
Specific insulation is measured
1) assay method: according to JIS-K6911
2) determinator: Advantest R8340A ultra-high resistance instrument
Electrode: Advantest R12704 resistivity is surveyed the chamber
3) method and condition:
Fixedly object being treated is measured the specific insulation (Ω cm) of filming in the following order.
1. 0V * 30 second discharge
2. 500V * 60 second charging
3. 0V * 30 second discharge
4) evaluation criterion
◎: 10
6More than the Ω cm
Zero: 10
5Above less than 10
6Ω cm
△: 10
4Above less than 10
5Ω cm
*: less than 10
4Ω cm
Solvent resistance
On the square silicon rubber of 1cm, twine gauze, MEK (MEK) is fully infiltrated in the gauze, back and forth wipe 50 times (loading 500g), estimate appearance then.
◎: fully not change
Zero: vestige slightly
△: destroy obviously (being come off by overlay film is only about half of)
*: expose substrate (being come off) by overlay film
The evaluation result of embodiment and comparative example is shown in table 5.
Processed material uses the micromachine core of aforementioned (I), and heat resistant test with, determination of pencil hardness with in use the SPCC-SD of aforementioned (III).
Table 5
| Embodiment | Thickness μ m | Outward appearance | Corrosion resistance | Pencil hardness | Hear resistance | Insulation Test | Specific insulation | Solvent resistance | |||
| Planar section | The marginal portion | Weight subtracts | Adhesiveness | ||||||||
| Embodiment | 1 | 22 | 25 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ |
| 2 | 20 | 22 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 3 | 21 | 22 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 4 | 18 | 20 | ○ | ◎ | 4H | ○ | ◎ | ○ | ○ | ◎ | |
| 5 | 18 | 19 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 6 | 20 | 19 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 7 | 22 | 20 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 8 | 23 | 20 | ○ | ◎ | 4H | ○ | ◎ | ○ | ◎ | ◎ | |
| 9 | 25 | 22 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 10 | 22 | 23 | ◎ | ◎ | 3H | ○ | ◎ | ◎ | ◎ | ○ | |
| 11 | 20 | 23 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 12 | 17 | 20 | ◎ | ◎ | 2H | ○ | ◎ | ◎ | ◎ | ○ | |
| 13 | 16 | 18 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 14 | 18 | 16 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 15 | 22 | 20 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| 16 | 23 | 21 | ◎ | ◎ | 4H | ○ | ◎ | ◎ | ◎ | ◎ | |
| Comparative example | 1 | 20 | 22 | ◎ | ◎ | H | ○ | ◎ | ○ | ○ | × |
| 2 | 20 | 22 | ◎ | ○ | H | ○ | ◎ | ○ | ○ | × | |
| 3 | 18 | 17 | ◎ | △ | H | ○ | ○ | △ | △ | × | |
| 4 | 23 | 22 | ◎ | ◎ | 2H | × | × | ◎ | ○ | × | |
| 5 | 20 | 22 | ◎ | ◎ | H | ○ | ◎ | ○ | ○ | × | |
| 6 | 22 | 8 | ◎ | △ | 2H | ○ | ◎ | × | ◎ | ○ | |
| 7 | 23 | 7 | ○ | △ | 3H | ○ | ◎ | × | ◎ | ○ | |
Clearly illustrate that to have embodiment 1～16 as processing method of the present invention by table 5 to the saturating property of the good swimming in edge, corrosion resistance, hear resistance, solvent resistance, insulating properties, in addition, by overlay film case hardness height, be fully anti-coiling pressure by overlay film.
In contrast to this, do not carry out the comparative example 1～4 of specific postprocessing working procedures in processing method of the present invention, the lining film hardness is insufficient, and solvent resistance is obviously poor.In addition, hear resistance is also poor among the embodiment 4.
The curing agent (e) that aftertreatment fluid (B) is used adds to from the comparative example 5 of separating out in the treatment fluid (A) in the method for the invention, can not obtain enough case hardnesses, solvent resistance.
In addition, the comparative example 7 that carries out the comparative example 6 of powder coating and carry out electrophoretic coating, poor to the saturating property of the swimming of marginal portion, can not obtain enough insulation characterisitics.In addition, corrosion resistance is also insufficient.
The possibility of utilizing on the industry
Miniature machine of the present invention or its part from precipitation type surface treatment coating method, it is the environment type surface treatment system that is rich in high workability, productivity, economic property, adopt method of the present invention to give over the saturating property of good swimming, corrosion resistance, heat resistance, solvent resistance, the insulating properties of unexistent edge to miniature machine or its part, miniature machine of the present invention or its part can fully adapt to the miniaturization of miniature machine or its part, the requirement of filming, and the present invention can deserve to be called extremely useful in actual use.
Claims (10)
1. from precipitation type surface treatment coating method, be to make micromachine surface or its piece surface form organic lining film by surface treatment procedure, this surface treatment procedure comprises: make micromachine surface or its piece surface and contain contacting from precipitation type surface treatment liquid A of the water-soluble or water dispersible organic polymer resin a of at least a kind of selecting from acrylic resin, epoxy resin, polyurethane resin, mylar, polyamide, thereby make the operation of separating out the organic lining film of formation on this surface; Make separate out formation organic by the surface of overlay film with contain the operation that the aftertreatment fluid B of at least a kind of curing agent e selecting the epoxy resin that has a glycidyl in melmac, guanamine resin, urea resin, phenolic resins, molecule at least of its curing, the isocyanate compound can be contacted; And carry out the operation of heat drying.
2. claim 1 is described is characterized in that from precipitation type surface treatment coating method, also contains from precipitation type surface treatment liquid A to be selected among sour composition b, oxidant c and the metal ion d any.
3. claim 1 or 2 describedly is characterized in that from precipitation type surface treatment coating method at least a kind of the organic polymer resin a that uses is the anionic property polyester in precipitation type treatment fluid A.
4. claim 1 or 2 describedly is characterized in that from precipitation type surface treatment coating method at least a kind of the organic polymer resin a that uses is the anionic property mylar that polyalcohol and acid compound polycondensation make in precipitation type treatment fluid A.
5. claim 1 is described is characterized in that from precipitation type surface treatment coating method aftertreatment fluid B also contains at least a kind of surface lubricant f.
6. claim 2 is described is characterized in that from precipitation type surface treatment coating method aftertreatment fluid B also contains at least a kind of surface lubricant f.
7. claim 5 or 6 described from precipitation type surface treatment coating method, wherein, the surface lubricant f among the aftertreatment fluid B is at least a kind of lubricant selecting from fluororesin base lubricant, polyolefin wax, melamine urea cyanate, molybdenum bisuphide.
8. claim 1,2,5 or 6 described from precipitation type surface treatment coating method, wherein, with operation that aftertreatment fluid B contacts after, also comprise and adopt blowing to remove operation and the operation of carrying out heat drying that residue is adhered to liquid.
9. micromachine or its part, its have the claim 1,2 of employing, 5 or 6 described from precipitation type surface treatment coating method formed from the precipitation type surface treatment by overlay film.
10. micromachine or its part, its have the claim 8 of employing described from precipitation type surface treatment coating method formed from the precipitation type surface treatment by overlay film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP222302/2001 | 2001-06-18 | ||
| JP2001222302 | 2001-06-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1516626A CN1516626A (en) | 2004-07-28 |
| CN1286578C true CN1286578C (en) | 2006-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02812241 Expired - Fee Related CN1286578C (en) | 2001-06-18 | 2002-06-10 | Method for self-deposition type surface treatment coating of microdevice orits components, and microdevice or its parts having self-deposition typesurface treatment coating |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1286578C (en) |
| TW (1) | TW565983B (en) |
| WO (1) | WO2002102525A1 (en) |
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| CN103662292A (en) * | 2013-11-20 | 2014-03-26 | 青岛天人环境股份有限公司 | Manufacturing method of organic polymer anticorrosive assembled tank |
| CN104148269A (en) * | 2014-08-20 | 2014-11-19 | 国家电网公司 | Coating method for RTV anti-contamination flashover coating of suspension insulator |
| CN115571728B (en) * | 2022-12-07 | 2023-03-10 | 中科摩通(常州)智能制造股份有限公司 | Finished product end-sealing equipment for winding machine and end-sealing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5847234B2 (en) * | 1975-12-03 | 1983-10-21 | ニツポンペイント カブシキガイシヤ | metal coating houhou |
| JPH07132574A (en) * | 1993-11-09 | 1995-05-23 | Nippon Parkerizing Co Ltd | Method for coating metal surface |
| JP3648320B2 (en) * | 1996-02-21 | 2005-05-18 | 日本パーカライジング株式会社 | Method for coating an electrically insulating coating on the surface of a laminated motor core |
-
2002
- 2002-05-24 TW TW91110983A patent/TW565983B/en active
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| TW565983B (en) | 2003-12-11 |
| WO2002102525A1 (en) | 2002-12-27 |
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