CN106661739A - Etching agent and replenishing liquid - Google Patents
Etching agent and replenishing liquid Download PDFInfo
- Publication number
- CN106661739A CN106661739A CN201580037324.5A CN201580037324A CN106661739A CN 106661739 A CN106661739 A CN 106661739A CN 201580037324 A CN201580037324 A CN 201580037324A CN 106661739 A CN106661739 A CN 106661739A
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- China
- Prior art keywords
- etchant
- weight
- iron steel
- resin
- acid
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
Abstract
This etching agent for iron and steel materials is an acidic aqueous solution containing ferrous ions, ferric ions, and a water-soluble compound containing acetylene groups. When the concentration of ferrous ions in the etching agent is A wt% and the concentration of ferric ions is B wt%, the A/B value is preferably 0.1 to 2.5. This replenishing liquid is a replenishing liquid that is added to the etching agent when the etching agent is continuously or repeatedly used, and is an aqueous solution containing a water-soluble compound containing acetylene groups.
Description
Technical field
The present invention relates to the etchant and its bulking liquor of a kind of iron steel.
Background technology
Develop skills integrated by material is connect such as iron steel and resins in the various industrial fields based on automotive field
Art.For example in following patent documents 1 a kind of method is proposed, in order to lift the contiguity that iron steel and fibre strengthening plastic cement etc. are connect material
Property, after iron steel are roughened so that non-oxidizable strong acid aqueous solution is etched again with connect material contiguity.
Prior art literature
Patent document
Patent document 1：International Publication No. 2008/146833.
The content of the invention
Invent problem to be solved
But Jing present inventors self-criticism finds, even if thick with the non-oxidizable strong acid aqueous solution described in the patent document 1
Change iron steel, still have deficiency in terms of iron steel and the adhesion for being connect material are lifted.
The present invention in view of the problem of the prior art point and study, there is provided it is a kind of to lift iron steel and connect the close of material
The etchant and its bulking liquor of the iron steel of connecing property.
The technological means of solve problem
The etchant of the present invention is the etchant of iron steel, comprising ferrous ion, ferric ion and contains acetenyl
Water soluble compound acidic aqueous solution.In the etchant, ferrous ion amount and ferric ion amount
Than in particular range.
The bulking liquor of the present invention makes an addition to the etchant in etchant that is continuous or reusing the present invention, and
It is the aqueous solution comprising the water soluble compound containing acetenyl.
The effect of invention
By the etchant process iron steel of the present invention, micro concavo-convex shape, institute can be equably formed in iron steel surface
State the adhesion that micro concavo-convex is shaped to and is connect material.Iron steel and resin with the etchant process of the present invention etc. are connect material
Adhesion it is excellent.
Description of the drawings
Fig. 1 is the stereogram of the composition for representing stretching shearing strength measure test portion.
Fig. 2 is to be shone with the scanning electron microscope on cold rolling steel (SPCC) surface of the etchant roughening treatment of embodiment
Piece.
Fig. 3 is with the scanning electron microscope photo on the SPCC surfaces of the etchant roughening treatment of comparative example.
Fig. 4 is the scanning electron microscope photo on the SPCC surfaces before etch processes.
Specific embodiment
[etchant]
The etchant of the iron steel of the present invention includes ferrous ion, ferric ion, the water solubilityization containing acetenyl
The acidic aqueous solution of compound.Hereinafter illustrate each composition that the etchant of the present invention is included.
(ferric ion)
Ferric ion is the composition of iron oxide steel, can be contained in etchant with ferric ion source by mixing.
The ferric ion source is not particularly limited, and can enumerate ferric sulfate, iron chloride, ferric nitrate, iron hydroxide, ferric sulfate (III) ammonium
Deng these can be used alone or in combination of two kinds or more.From the viewpoint of to maintain appropriate etching speed, the ferric ion source
In be preferably ferric sulfate, iron hydroxide, ferric sulfate (III) ammonium.
(ferrous ion)
The etchant of the present invention contains ferrous ion.Etchant in addition to ferric ion again containing ferrous iron from
Son, thereby can form micro concavo-convex in iron steel surface.Ferrous ion can be contained in erosion by mixing with ferrous ion source
In carving agent.The ferrous ion source is not particularly limited, and can enumerate ferrous sulfate, frerrous chloride, ferrous nitrate, hydroxide
Iron, ferric sulfate (II) ammonium etc., these can be used alone or in combination of two kinds or more.From formed be suitable to lifted adhesion micro concavo-convex,
And from the viewpoint of reduces cost, ferrous sulfate, ferrous hydroxide, ferric sulfate (II) are preferably in the ferrous ion source
Ammonium.
(water soluble compound containing acetenyl)
Water soluble compound containing acetenyl in order to iron steel surface equably formed micro concavo-convex mix match somebody with somebody into
Point.As long as compound of the water soluble compound containing acetenyl with acetenyl and for weight % of water dissolves 0.01 with
On, then it is not particularly limited, can for example use the compound with acetenyl and hydrophily base.Hydrophily base can enumerate hydroxyl, amine
Base, carboxyl, level Four ammonium etc..From the viewpoint of equably forming micro concavo-convex in iron steel surface, wherein be preferably having
The compound of acetenyl and hydroxyl.Also, the hydroxyl of the water soluble compound containing acetenyl can be the hydroxyl of carboxylic acid (that is, containing
The compound of hydroxyl includes the compound containing carboxyl).Water soluble compound containing acetenyl can be have 2 in a molecule
The dialkyne of above acetenyl or three alkine compounds etc., and can have more than 2 hydroxyls in a molecule.
The compound with acetenyl and amido can illustrate such as propargylamine, N, N- diethyl -1- propine -1- amine.Tool
The compound for having acetenyl and level Four ammonium can illustrate such as N, N, N- trimethyl -2- propine -1- aluminium.It is described with acetenyl and hydroxyl
The compound of base can illustrate such as 2- butyne-1-ols, valerylene -1- alcohol, 3- pentyne-1-alcohols, 3- hexin -1- alcohol, 2- hexin -1-
Alcohol, 3- heptyne -1- alcohol, 4- heptyne -2- alcohol, 2- heptyne -1- alcohol, 5- heptyne -3- alcohol, 3- octyne -1- alcohol, 3- phenyl -2- propine -
1- alcohol, 3- n-heptylacetylene -1- alcohol, 2- decine -1- alcohol, 3,5- dimethyl -1- hexin -3- alcohol, 3- decine -1- alcohol, 4- diethyl amidos -
The chemical combination with 1 acetenyl and 1 hydroxyl such as 2- butyne-1-ols, 4- (3- aminocarbonyl phenyls) -2- methyl -3- butyne-2-alcohols
Thing；2,2,8,8- tetramethyl -3,6- nonyl diine -5- alcohol, 4,6- nonadecane diine -1- alcohol, 10,12- pentacosane diine -1- alcohol
Deng the compound with 2 acetenyls and 1 hydroxyl；2- butine -1,4- glycol, 3- hexin -2,5- glycol, 2,5- dimethyl -
Double (2- the hydroxyl-oxethyls) -2- butine of 3- hexin -2,5- glycol, 3,6- dimethyl -4- octyne -3,6- glycol, 1,4-, 2,4,7,
9- tetramethyl -5- decine -4,7- glycol, 2,4,7,9- tetramethyl -5- decine -4,7- glycol, 3,6- dimethyl -4- octyne -3,
6- glycol, 3,6- dimethyl -4- octyne -3,6- glycol, 5- phenyl -4- pentyne-1-alcohols etc. have 1 acetenyl and 2 hydroxyls
Compound；The compounds with 1 acetenyl and 2 hydroxyls such as 2,4- hexadiine -1,6- glycol；2- tetrolic acid, 2- hexins
The compound with 1 acetenyl and 1 carboxyl such as acid, 2- heptynoic acids, phenyl propiolic acid；Acetylenedicarboxylic acid etc. has 1 second
The compound and its salt (acetylenedicarboxylic acid potassium etc.) of alkynyl and 2 carboxyls；2,4- pentadecane diacetylenic acids, 10,12- heptadecane diines
Acid, 2,4- nonadecane diacetylenic acids, 2,4- heneicosane diacetylenic acids, 10,12- tricosane diacetylenic acids, 10,12- pentacosanes two
Compound with 2 acetenyls and 1 carboxyl such as acetylenic acid etc..In the present invention, the water soluble compound containing acetenyl can be single
Solely using a kind or combine two or more and use.
(sour composition)
The etchant of the present invention is acidic aqueous solution, therefore containing sour composition.The sour composition is by by ferric ion
The composition dissolved Deng oxidation and from the metal (predominantly ferrous ion) of iron steel dissolution.The sour composition can enumerate hydrogen fluorine
The halogen acids of acid, hydrochloric acid (hydrochloric acid), hydrobromic acid, hydroiodic acid etc.；Sulfuric acid, nitric acid, excessively phosphoric acid, other nothings such as chloric acid, amine sulfonic acid
Machine acid；Or the organic acid such as sulfonic acid, carboxylic acid.In the present invention, these can be used alone or in combination of two kinds or more.From raising etchant
Acid concentration and keep from the viewpoint of appropriate etching speed, inorganic acid is preferably in the sour composition.Especially from iron steel
Uniform surface ground is formed from the viewpoint of micro concavo-convex and reduces cost, preferably sulfuric acid, amine sulfonic acid and sulfonic acid.
(concentration of each composition)
As described, the etchant of the present invention includes ferrous ion, ferric ion, the water-soluble chemical combination containing acetenyl
Thing and sour composition.By making the concentration of these each compositions in particular range, and can equably form feature in iron steel surface
The micro concavo-convex of shape.
It is A weight %, the ferric ion concentration as B with the ferrous ion concentration in the etchant of the present invention
During weight %, A/B values are preferably 0.1 to 2.5, more preferably 0.15 to 2.0, and more preferably 0.2 to 1.5.Ferrous ion
Then micro concavo-convex can be formed with the concentration ratio A/B value of ferric ion in iron steel surface in the scope.
Ferric ion concentration in the etchant of the present invention is preferably 0.2 weight % to 20 weight %, and more preferably 0.5
Weight % is to 15 weight %, and more preferably 1.0 weight % are to 10 weight %.Ferric ion concentration is more than 0.2 weight %
Appropriate etching speed can then be maintained.On the other hand, ferric ion concentration is below 20 weight %, then can to maintain three in etchant
The steady dissolution of valency iron ion simultaneously easily suppresses etch quantity.
Ferrous ion concentration is preferably 0.02 weight % to 5 weight %, more preferably 0.03 weight % to 4 weight %,
Again more preferably 0.05 weight % is to 3 weight %.Ferrous ion concentration is more than 0.01 weight %, then easily to be formed and be suitable to carry
Rise the micro concavo-convex of adhesion.On the other hand, ferrous ion concentration is can then to maintain appropriate etching speed below 5 weight %.
From from the viewpoint of equably forming micro concavo-convex in iron steel surface, the water soluble compound containing acetenyl is dense
Degree is preferably 0.01 weight % to 5 weight %, and more preferably 0.02 weight % is to 2 weight %, and more preferably 0.05 weight %
To 1 weight %.Also, during with the water soluble compound concentration containing acetenyl as S weight %, the water-soluble chemical combination containing acetenyl
Thing is preferably 0.001 to 100, more preferably 0.01 to 10, and more preferably 0.07 to 5 with concentration ratio S/B of ferric ion.
The sour constituent concentration is preferably 0.02 weight % to 1.3 weight %, more preferably 0.03 weight with hydrogen ion concentration
Amount weight % of % to 1.0, but more preferably 0.05 weight % is to 0.8 weight %.Hydrogen ion concentration be 0.02 weight % more than then
The etching speed (dissolution velocity) of iron steel can be prevented to be reduced.On the other hand, hydrogen ion concentration is below 1.3 weight %, then may be used
The crystallization of slaine when preventing liquid temperature from reducing is separated out.Workability can be lifted again and is easy to reduces cost.
(other compositions)
In the range of effect of the present invention described in without prejudice to, the etchant of the present invention can add other compositions.Other compositions
Can illustrate such as interfacial agent, in compound (metal complex), the defoamer of metal-complexing.Also, it is described other into
It is divided into different with the water soluble compound containing acetenyl.Metal complex can illustrate such as carboxylic serials chelating agent, phosphine
Acid is chelating agent, nitrogen-containing compound, sulfur-containing compound of chelating agent, amine system chelating agent etc. etc..Metal complex is coordinated in
The metal of iron steel surface simultaneously suppresses metal ion from iron steel surface dissolution, or be coordinated on the contrary molten from iron steel surface
Go out metal ion and promote the dissolution of metal ion, thereby can control the concaveconvex shape of iron steel surface.Therefore, can be by appropriate
One kind or two or more metal complex is selected, and the concaveconvex shape of iron steel surface is controlled to and is suitable to be lifted and is connect
The shape of the adhesion of material.When adding these other compositions, its concentration is preferably 0.01 weight % to 10.0 weight % or so.
The etchant of the present invention can be easily modulated by the way that each composition is dissolved in into ion exchange water etc..
[bulking liquor]
The bulking liquor of the present invention makes an addition to the etchant in etchant that is continuous or reusing the present invention, and to wrap
The aqueous solution containing the water soluble compound containing acetenyl.The appropriate etchant can be maintained by adding the bulking liquor
Each composition ratio, can stablize maintain it is described the present invention etchant effect.
When the bulking liquor is made an addition into the etchant of the present invention, in order to adjust the acid concentration of etchant or in order to suppress
The variation of acid concentration is stated, the bulking liquor is preferably acidic aqueous solution.Also, can further mix with divalence in the bulking liquor of the present invention
Iron ion, ferric ion etc. make an addition to the composition of etchant.Each composition in the bulking liquor is assigned in described with mixing
The composition of bright etchant is identical.
In the bulking liquor concentration of the water soluble compound containing acetenyl can in response in etchant containing acetenyl
The concentration of water soluble compound and suitably set, but from it is stable maintain it is described the present invention etchant effect from the viewpoint of,
Preferably 0.01 weight % is to 7.5 weight % or so.
[using method of etchant]
Then the suitable using method (hereinafter referred to as this using method) of the etchant of the present invention is illustrated.This using method can
The iron steel of etching can illustrate such as cold-rolled steel to refer to the iron steel such as carbon steel, high tension steel, cryogenic steel, nuclear reaction stove steel plate
Material (SPCC), hot-strip (SPHC), automobile construction hot-rolled steel sheet material (SAPH), automobile processing hot rolling high tension steel sheet material
(SPFH) the general construction that is machined, is mainly used for rolling the institute such as body, part that prolongs the various machineries such as steel (SS materials)
The construction for using iron steel.These many iron steel can press process, machining etc., therefore can unrestricted choice construction, shape.
Also, so-called iron steel of the invention are not limited to the iron steel, including JIS (JIS), the International Organization for Stand (ISO)
Deng the various iron steel of defined.Can implement (to be gone including part to etch the process for removing iron steel by this using method
Except) or iron steel surface treatment etc..Especially implement the surface treatment (microetch of iron steel using the etchant of the present invention
Carve), the micro concavo-convex with character shape thereby can be formed in the uniform surface of iron steel, can be substantially improved and the quilt such as resin
The adhesion of junctor.
(pre-treatment)
In this using method, before with the etchant process iron steel of the present invention, can implement at degreasing in iron steel surface
Reason；Sandblasting processing, pearl are hit the mechanical lapping of (shot blast) processing, grinding processing, cylinder mill processing etc. and are processed；Or chemical grinding
Process etc..
(etch processes)
In the method for the etchant process iron steel of the present invention, for example, can enumerate in the iron steel surface spraying etching for processing
The method of agent, the method that impregnated in the iron steel of process in etchant etc..It is preferably with 20 DEG C of etchant temperature extremely during spraying
40 DEG C, spraying pressure 0.05MPa to 0.3MPa, 30 seconds to 300 seconds condition etching.It is preferably with 30 DEG C of etchant temperature during dipping
To 60 DEG C, the condition etching of 60 seconds to 600 seconds.
Micro concavo-convex can be equably formed if using the etchant process iron steel surface in iron steel surface.By molten
The weight of the iron steel of solution, proportion and surface calculate the average etch amount using iron steel depth direction during the etchant
When (meltage), preferably 0.5 μm to 10.0 μm, more preferably 0.75 μm to 8.0 μm, and more preferably 1.0 μm to 5.0 μm.
Etch quantity is more than 0.5 μm then can easily form the micro concavo-convex of the shape for being suitable to lift adhesion.Also, etch quantity is 10.0 μm
Hereinafter process time can then be shortened.Can be by the adjustment etch quantity such as treatment temperature, process time.
Also, in this using method, the comprehensive of iron steel surface can be processed during using the etchant process iron steel, also may be used
Part processes iron steel surface.For example when forming the complex of iron steel and resin etc., pair can be connect material junction surface with resin etc.
The iron steel surface for dividing carries out selective process.Also, in the range of the effect for not undermining the present invention, in this using method
Can simultaneously with by the Wet-type etching or various dry-etchings of other etchants.
(post processing)
After being processed using the etchant, iron steel surface because surface area increase become chemism, if with sky
Gas contact then quickly forms oxide film thereon.The oxide film thereon can hinder the contiguity of iron steel and resin etc., therefore with
For the purpose of removing oxide film thereon, pickling is preferably carried out only as post processing.Now acid there is no particular restriction, but using hydrochloric acid,
Iron steel surface is easily reoxidized during nitric acid.Therefore, post-process used acid to be preferably selected from beyond hydrochloric acid and nitric acid
Acid.Wherein, from the viewpoint of to prevent from reoxidizing, it is preferable to use the polyacid such as phosphoric acid, malic acid, citric acid, tartaric acid.
Pickling is preferably afterwards and is washed and be dried only.Promote oxygen again if having if iron steel surface residual chlorine compound ion
The tendency of change.Therefore, the washing after pickling is net is preferably with ion exchange water.Also, the iron steel surface after washing is remained
Also easily produce during moisture and reoxidize.Therefore, being preferably after washing carries out abundant heat drying.
The iron steel to drying are so carried out, to being connect material engaged with resin etc., oxygen again can be prevented
Zygosity caused by changing is reduced, therefore for preferred.In order to prevent reoxidizing, the preferably keeping of the iron steel after etch processes is in resistance
The sealing state of exhausted moisture.Furthermore, for the purpose of reoxidizing during preventing keeping, can implement anti-to the iron steel after etch processes
Rust process, the antirust agent for now being used can widely use the amine system, phosphate, nitrite, chromate, organic for generally using
The water soluble anti-rust agents such as the alkali metal salt of acid.Also, can be in steel when carrying out antirust treatment with solvent system antirust agent, emulsion system antirust agent
Material surface forms grease epithelium, there is the contiguity for hindering to be connect material.Also, replacing antirust treatment or except antirust treatment
In addition, it is possible to use to be impregnated with the antirust paper wrapper of dichan and the gimmick of keeping.
[purposes of iron steel after process]
The iron steel processed by this using method can use the material as aftermentioned iron steel-resin composite body, in addition
Also can use as the iron steel of wettability etc. given for various solvents.Also, the iron steel processed by this using method
Not only for resin, also can be lifted the phase for glass, metal coating, inorganic semiconductor, organic semiconductor, ceramics etc. are connect material
Adhesion effect.Also, this using method is not only roughening treatment, it is equally applicable to remove the process of iron steel by etching
(removing including part) etc..
[iron steel-resin composite body]
Then the Application Example of iron steel that explanation is processed by this using method, by iron steel and resin combination integrally
Iron steel-the resin composite body of change.Processed after iron steel by described using method, in process face engagement resin composition
Thing, thereby obtains iron steel-resin composite body.By the etchant process iron steel of the present invention, and can be equal in iron steel surface
The formation of one ground is suitable to the concavo-convex of the adhesion between lifting iron steel-resin combination, therefore can be lifted between iron steel-resin combination
Adhesion.It is not particularly limited in the method for the iron steel surface engagement resin combination processed with this using method, can adopts
With injection molding, extrusion molding, heat compressing, compression molding, shift mold formed, casting, laser welding shaping,
The resin molding methods such as reaction injection molding (RIM shapings), liquid injection mold shaping (LIM shapings).Also, in the coating of iron steel surface
Resin combination epithelium and when manufacturing the complex being made up of iron steel-resin combination epithelium, can be using resin be constituted
Thing is dissolved or dispersed in the cladding process or other various coating process of solvent and coating.Other coating process can illustrate such as sintering
Application, electricity connect application, electrostatic spraying, powder body coating, UV cured application etc..The shaping bar of the manufacturing process enumerated
Part, can adopt known condition in response to resin combination.
As long as the resin combination that the iron steel-resin composite body can be used can be engaged in the manufacturing process of enumerating
Iron steel surface, then be not particularly limited, can be in response to purposes from thermoplastic resin composition, the middle choosing of thermosetting resin composition
Select.
(thermoplastic resin composition)
During using thermoplastic resin composition, the thermoplastic resin of principal component can enumerate polyamide 6 or polyamide 66 etc. and gather
Amide resin；Polyvinyl resin, acrylic resin, acrylonitrile/styrene copolymerized resin, acrylonitrile/butadiene/styrene copolymerization
Resin, Corvic, polycarbonate resin, polyacetal resin, polybutylene terephthalate resin, poly terephthalic acid
Second diester resin, poly- naphthalene diethylester resin, polyphenylene sulfide, liquid crystalline polyester resin, polyimide resin, to arrange polyphenyl second
It is olefine resin, polycyclohexylene's dimethyl ester resin, fluororesin, polyvinyl acetate resins, modification polyphenylene oxide resin, poly-
Ether sulfone resin, amorphous polypropylene acid ester resin, aromatic polyether ketone resin, ethylene/vinyl acetate copolymer resins, ethylene/propylene
Olefin(e) acid copolymer resins, ethylene/methacrylic acid copolymer resins etc. combine these two or more persons etc..
As long as the constituent that the thermoplastic resin composition that can be used is made up of the thermoplastic resin enumerated is i.e.
Can, can be known each for the thermoplastic resin addition enumerated in the degree of effect for not undermining the present invention
Kind inorganic/organic filler, fire retardant, flame retardant, ultra-violet absorber, heat stabilizer, light stabilizer, colouring agent, carbon black,
The constituent of the additive of processing aid, nucleator, releasing agent, plasticiser, fibrous reinforcing material etc..
(thermosetting resin composition)
During using thermosetting resin composition as resin combination, the thermosetting resin of principal component can enumerate phenol tree
Fat, epoxy resin, urea-formaldehyde resin, melmac, unsaturated polyester resin, polyimide resin, phthalic acid
Two acrylate resins, alkyd resin, polyurethane resin, cyanate ester resin, polysilicone etc. combine these two or more persons
Deng.
As long as the constituent that the thermosetting resin composition that can be used is made up of the thermosetting resin enumerated is i.e.
Can, can be known each for the thermosetting resin addition enumerated in the degree of effect for not undermining the present invention
Kind inorganic/organic filler, fire retardant, flame retardant, ultra-violet absorber, heat stabilizer, light stabilizer, colouring agent, carbon black,
The constituent of the additive of processing aid, nucleator, releasing agent, plasticiser, fibrous reinforcing material etc..
(other resin combinations)
The resin combination that other can be used can enumerate the photo-hardening tree containing acrylic resin, styrene resin etc.
The various resin combinations such as fat composition or the reaction hardening resin composition containing rubber, elastomer etc..
Iron steel-the resin composite body is adapted to be used in e-machine part, home appliance part or conveyer
The manufacture of the various machinery parts such as tool part etc., the various e-machines for being specifically suitable to portable purposes etc. use zero
It is part, family's electrical article part, medical machine part, vehicle detail of construction, vehicle boarded with part etc..
(embodiment)
Then embodiments of the invention and comparative example are illustrated.Also, the present invention is not limited to following embodiments.
[by the process of etchant]
Prepare the delustring cold-rolled steel sheet (King Company's system is lived by Nippon Steel) of width 20mm, length 30mm, thickness 2.3mm as examination
Substrate is tested, acetone is impregnated in as pre-treatment and is applied ultrasonic while carrying out ungrease treatment in 15 minutes.Then, in table
1 and each etchant shown in table 2 in substrate is tested described in impregnation process, adjustment etching period makes the etch quantity of iron become 2.0 μm,
50 DEG C are implemented etching.Also, each etchant shown in table 1 and table 2 mixes the nubbin with composition for ion exchange water, the % of concentration
It is all weight %.
The etch processes face that substrate is tested after etching impregnated in after 5% tartaric acid solution 15 seconds of 25 DEG C of temperature, with
Ion exchange water is washed, the dry drying in 10 minutes in 120 DEG C of baking oven after draining.
[stretching shearing strength determination test]
The surface of test substrate 1 after the treatment the, through (5mm × 10mm of epoxy impregnation glass fabric prepreg 5
× thickness 0.1mm；Panasonic company systems, the name of an article：R-1661 the FRP plate that) coincides 3 (width 10mm, length 30mm, thickness
1.6mm), after temporarily being fixed with polyimides heat resistant adhesive tape, heat 90 minutes in 160 DEG C of baking ovens and harden prepreg, and make
Make the stretching shearing strength measure test portion shown in Fig. 1.
The steel plate portion and FRP portions of measure test portion are clamped, and using automatic mapping machine (Shimadzu Seisakusho Ltd.'s system, model:AGS-
X10kN the stretching shearing strength at junction surface) is determined.As a result table 1 and table 2 are shown in.
[table 1]
[table 2]
Fig. 2 to 4 observes photo for the scanning electron microscope (SEM) on SPCC surfaces, and (accelerating potential 20kV, test portion are inclined
45 ° of angle, 3500 times of multiplying power).Fig. 2 is the SPCC after the etchant process of embodiment 9, and Fig. 3 is the etching by comparative example 8
SPCC after agent process, Fig. 4 are the SPCC of before processing (comparative example 8).Compared with the surface of Fig. 4 of etch processes is not carried out, can
Know that the SPCC surfaces in Fig. 2 and Fig. 3 for implementing etch processes form concavo-convex and surface area and increase.Knowable to contrast Fig. 2 and Fig. 3, Fig. 3
In form the convex portion of mountain range shape nettedly and only form smooth concavo-convex between the shape convex portion of mountain range, in this regard, by the present invention
Etchant process Fig. 2 in, being formed between the shape convex portion of mountain range has the concavo-convex of a little sharp portion.Entered with the etchant of the present invention
Row surface treatment, thereby can equably form the concaveconvex shape of the feature, it is taken as that high anchor can be played in iron steel surface
Determine effect (throw anchor effect) and be substantially improved with by the adhesion of junctor.
The result of table 1 and table 2, the water not contain ferrous ion, ferric ion and containing acetenyl are examined in detail
Soluble compound any one comparative example 1 to 4 and comparative example 7 etchant process when, the stretching shearing strength at junction surface is
20MPa or so (table 2).Also, with the ratio A/B of ferrous ion concentration (A) and ferric ion concentration (B) less than 0.1 comparison
During the etchant process of the comparative example 6 of example 5 and A/B more than 2.5, stretching shearing strength is also 20MPa or so.In this regard, using containing
There is the enforcement of ferrous ion, ferric ion and water soluble compound and A/B containing acetenyl in particular range etchant
In example 1 to 9 (table 1), stretching shearing strength is all 30MPa or so or more, understands to obtain 1.5 times of left sides compared to comparative example 1 to 7
High contiguity intensity more than right.
Claims (7)
1. a kind of etchant, it is characterised in that for the etchant of iron steel, and be comprising ferrous ion, ferric ion and
The acidic aqueous solution of the water soluble compound containing acetenyl；
With the concentration of the ferrous ion as A weight %, the concentration of the ferric ion for B weight % when, the value of A/B is
0.1 to 2.5.
2. etchant as claimed in claim 1, it is characterised in that the water soluble compound containing acetenyl is with second
The compound of alkynyl and hydroxyl.
3. etchant as claimed in claim 1 or 2, it is characterised in that the concentration of the ferric ion be 0.2 weight % extremely
20 weight %, the concentration of the water soluble compound containing acetenyl is 0.01 weight % to 5 weight %.
4. the etchant as described in any claim in claims 1 to 3, it is characterised in that the acid concentration of the etchant
0.02 weight % is calculated as to 1.3 weight % with hydrogen ion concentration.
5. the etchant as described in any claim in Claims 1-4, it is characterised in that the ferrous ion it is dense
Spend is 0.02 weight % to 5 weight %.
6. a kind of bulking liquor, it is characterised in that continuous or reuse in claim 1 to 5 described in any claim
The etchant is made an addition to during etchant, and is the aqueous solution comprising the water soluble compound containing acetenyl.
7. bulking liquor as claimed in claim 6, it is characterised in that the bulking liquor is acidic aqueous solution.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-140947 | 2014-07-08 | ||
| JP2014140947A JP2016017209A (en) | 2014-07-08 | 2014-07-08 | Etching agent and replenishing liquid |
| PCT/JP2015/066299 WO2016006373A1 (en) | 2014-07-08 | 2015-06-05 | Etching agent and replenishing liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106661739A true CN106661739A (en) | 2017-05-10 |
Family
ID=55064015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580037324.5A Pending CN106661739A (en) | 2014-07-08 | 2015-06-05 | Etching agent and replenishing liquid |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20170167033A1 (en) |
| EP (1) | EP3168328A4 (en) |
| JP (1) | JP2016017209A (en) |
| KR (1) | KR20170028881A (en) |
| CN (1) | CN106661739A (en) |
| TW (1) | TW201606136A (en) |
| WO (1) | WO2016006373A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113802121A (en) * | 2021-09-17 | 2021-12-17 | 深圳市板明科技股份有限公司 | Nickel-iron alloy roughening liquid and preparation method thereof |
| CN114980531A (en) * | 2022-05-16 | 2022-08-30 | 东莞市百良电子科技有限公司 | Micro-etching solution, copper surface regeneration micro-etching method, copper plate and circuit board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6769760B2 (en) | 2016-07-08 | 2020-10-14 | 関東化学株式会社 | Etching liquid composition and etching method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002543A (en) * | 1974-04-01 | 1977-01-11 | Oxy Metal Industries Corporation | Electrodeposition of bright nickel-iron deposits |
| US4421611A (en) * | 1982-09-30 | 1983-12-20 | Mcgean-Rohco, Inc. | Acetylenic compositions and nickel plating baths containing same |
| JPS6487788A (en) * | 1986-07-15 | 1989-03-31 | Asahi Denka Kogyo Kk | Etching method |
| JP2003166089A (en) * | 2001-11-30 | 2003-06-13 | Asahi Kagaku Kogyo Co Ltd | Corrosion inhibitor for metal pickling, composition containing the same, and metal pickling method using the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5368643A (en) * | 1976-12-01 | 1978-06-19 | Yoshizaki Kozo | Etching liquid of irons |
| JPH01301869A (en) * | 1988-05-27 | 1989-12-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Etching accelerating additive |
| JPH02141589A (en) * | 1988-11-22 | 1990-05-30 | Dai Ichi Kogyo Seiyaku Co Ltd | Etching promoting additive |
| JPH06200385A (en) * | 1991-03-14 | 1994-07-19 | Asahi Kagaku Kogyo Kk | Composition for etching iron-base metal and etching method |
| JP3431931B2 (en) * | 1992-07-16 | 2003-07-28 | 旭電化工業株式会社 | Copper and copper alloy surface treatment method |
| JP2006111953A (en) * | 2004-10-18 | 2006-04-27 | Mec Kk | Etching agent for copper or copper alloy, its manufacturing method, replenishing liquid, and method for manufacturing wiring substrate |
| JP4669375B2 (en) * | 2005-11-09 | 2011-04-13 | 新日本製鐵株式会社 | Steel pickling method and steel pickling solution |
| JP2008146833A (en) | 2006-12-05 | 2008-06-26 | Mitsubishi Heavy Ind Ltd | Joining method of mea, and press jig for mea joining |
-
2014
- 2014-07-08 JP JP2014140947A patent/JP2016017209A/en active Pending
-
2015
- 2015-06-05 WO PCT/JP2015/066299 patent/WO2016006373A1/en active Application Filing
- 2015-06-05 EP EP15818704.7A patent/EP3168328A4/en not_active Withdrawn
- 2015-06-05 KR KR1020167034438A patent/KR20170028881A/en unknown
- 2015-06-05 US US15/323,856 patent/US20170167033A1/en not_active Abandoned
- 2015-06-05 CN CN201580037324.5A patent/CN106661739A/en active Pending
- 2015-06-17 TW TW104119551A patent/TW201606136A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002543A (en) * | 1974-04-01 | 1977-01-11 | Oxy Metal Industries Corporation | Electrodeposition of bright nickel-iron deposits |
| US4421611A (en) * | 1982-09-30 | 1983-12-20 | Mcgean-Rohco, Inc. | Acetylenic compositions and nickel plating baths containing same |
| JPS6487788A (en) * | 1986-07-15 | 1989-03-31 | Asahi Denka Kogyo Kk | Etching method |
| JP2003166089A (en) * | 2001-11-30 | 2003-06-13 | Asahi Kagaku Kogyo Co Ltd | Corrosion inhibitor for metal pickling, composition containing the same, and metal pickling method using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113802121A (en) * | 2021-09-17 | 2021-12-17 | 深圳市板明科技股份有限公司 | Nickel-iron alloy roughening liquid and preparation method thereof |
| CN113802121B (en) * | 2021-09-17 | 2022-06-28 | 深圳市板明科技股份有限公司 | Nickel-iron alloy roughening solution and preparation method thereof |
| CN114980531A (en) * | 2022-05-16 | 2022-08-30 | 东莞市百良电子科技有限公司 | Micro-etching solution, copper surface regeneration micro-etching method, copper plate and circuit board |
| CN114980531B (en) * | 2022-05-16 | 2024-04-19 | 东莞市百良电子科技有限公司 | Microetching solution, copper surface regeneration microetching method, copper plate and circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| US20170167033A1 (en) | 2017-06-15 |
| TW201606136A (en) | 2016-02-16 |
| EP3168328A1 (en) | 2017-05-17 |
| WO2016006373A1 (en) | 2016-01-14 |
| JP2016017209A (en) | 2016-02-01 |
| EP3168328A4 (en) | 2018-03-21 |
| KR20170028881A (en) | 2017-03-14 |
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Application publication date: 20170510 |