CN100419008C - Modified polyacetals for plating - Google Patents
Modified polyacetals for plating Download PDFInfo
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- CN100419008C CN100419008C CNB2004800173039A CN200480017303A CN100419008C CN 100419008 C CN100419008 C CN 100419008C CN B2004800173039 A CNB2004800173039 A CN B2004800173039A CN 200480017303 A CN200480017303 A CN 200480017303A CN 100419008 C CN100419008 C CN 100419008C
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Abstract
A polyacetal mixture for processing into a polyacetal article to be acid-etched and plated comprises a polyacetal resin blend comprising 97 - 99.9wt% polyacetal and 0.1 - 3wt% of semicrystalline or amorphous thermoplastic non-polyacetal resin of molecular weight 5,000 - 50,000; and acid-soluble particles such as calcium carbonate. The acid-soluble particles are present in an amount from 2 to 6% by weight of the polyacetal blend, at least 98% of said acid-soluble particles being in the size range preferably from 0.1 to 2 micrometers. The mixture preferably also comprises acid-insoluble inorganic particles in particular fumed silica, present in an amount from 1/5 to 1/50 the weight of the acid-soluble particles, the size of the acid-insoluble particles being from 1/20 to 1/100 the size of the acid-soluble particles. The plated polyacetal articles have superior aesthetic appearance while retaining good plating adhesion and good resistance of the polyacetal to chemical attack.
Description
Technical field
The present invention relates to the body modification of polyacetal, it is used to be processed into treats by acid etching and galvanized polyacetal articles, and relate to the polyacetal articles that for example obtains by molding, also relate to when carrying out etching and apply plating liquor, add the polyacetal articles that obtains when in the electrochemical method one or more are electroplated with plating catalyst, no electric metal.The present invention be more particularly directed to obtain galvanized polyacetal articles, it has excellent aesthetic appearance, keeps good plating adhesion and good polyacetal resistance to chemical attack simultaneously.
Background of invention
Polyacetal (being sometimes referred to as Derlin) is a class polyformaldehyde composition, and for example United States Patent (USP) 5,318, is put down in writing in 813,5,344,882 and 5,286,807.Polyacetal resin is especially by E.I.du Pont de Nemours and Company, Wilmington, and Delaware, USA is with trade mark
Commercialization.
Polyformaldehyde composition (polyacetal) is understood to include the composition based on the multipolymer of the cyclic oligomer of the homopolymer of the cyclic oligomer of formaldehyde or formaldehyde such as trioxane and formaldehyde or formaldehyde usually, the end group of wherein said homopolymer is by esterification or etherified sealed end, described multipolymer has the oxyalkylene group that contains at least two adjacent carbonss in main chain, its end group can hydroxyl stops maybe can be by esterification or etherified sealed end.
Based on relative high molecular, promptly 10,000 to 100, the composition of 000 polyoxymethylene is useful in preparation work in-process and finished product, by any technology of usually thermoplastic material being used, for example compression moulding, injection moulding, extrusion molding, blowing, rotational moulding, melt-spinning, punching press and thermoforming prepare work in-process and finished product.The finished product of based composition manufacturing has very ideal physicals thus, comprises high stiffness, intensity, chemical stability and solvent resistance.
As everyone knows, moulded parts by the polyacetal manufacturing is highly chemically stable and crystalline, it more is difficult to decorate or overmolding than other molding plastic material, and more particularly is difficult to metallization (by vacuum moulding machine), plating (electroless-plating or electrification are electroplated (galvanoplating)) or paint.
Generally speaking, plastics are chemically highly stable, and its moulded parts by manufacturings such as injection mouldings has smooth surface, are difficult to like this decorate its surface by printing, coating, deposition etc., and also are difficult to this surface is processed, and for example adhere to tackiness agent.Because the polyacetal resin surfactivity is low especially, and knownly do not have suitable solvent to have affinity for polyacetal, its finishing and adhesion are difficult to implement in practice, so polyacetal resin needing seldom to be applied to the application of this type of processing.
But the application of plastics is variation recently, and the application of higher category usually requires to satisfy simultaneously a plurality of standards, for example function and outward appearance or function and adhesion property.Therefore for polyacetal, the surface of good processing characteristics becomes more important.
The surface working performance of polyacetal can be improved to a certain extent by handling with acidic solution or oxidizing agent solution.Proposed the acidic solution of tosic acid, camphorsulfonic acid, phosphoric acid, ammonium acid sulfate etc.,, also proposed chromic acid-sulfuric acid mixture simultaneously as oxidizing agent solution.Improved plating processing also is provided, it be by above-mentioned carry out surface treatment with acid reagent solution before, molded article immersed carries out in quinoline, pyridine or the g-butyrolactone.
The purpose of these processing is to produce uneven surface, and the oxygenizement by solution forms reaction active groups on a part of polyacetal molecule simultaneously.But, if wish effect, will have problems so with this type of step enhanced surface treatment, for example the whole deterioration of polyacetal resin, cause loss of strength, formation crackle or poor surface smoothness.On the other hand, do not handle if use can not cause the condition of polyacetal deterioration, the surface-treated effect is tended to deficiency, and can not implement surface of good processing.
When handling polyacetal articles so that improving their surface working performance, make in the surface irregularity in control activation tendency with via chemical modification, and selecting to run into a large amount of problems in the polyacetal composition by the method that keeps its initial ensemble performance.High scrap rate has proved the difficulty of handling the polyacetal resin surface, particularly when the molded component with complexity immerses the poor adhesion of acidic solution or coating.Coating is represented lip-deep modification of the acid etching of paint molded polyacetal articles or functional layer.The most important thing is, wish to reach the good adhesion and the excellent surperficial aesthetic appearance of coating.
Make the record of the metallized difficult problem of polyacetal articles for example in GB-A 2 091 274, it proposes a kind of surface preparation by acid etching, for example uses the mixture of 30-60wt% sulfuric acid, 5-30wt% hydrochloric acid and 65-10wt% water; Perhaps use the mixture of 20-50wt% sulfuric acid, 30-50wt% phosphoric acid and 50-0wt% water.Also imagined the mixture of organic acid and mineral acid.After the acid etching, goods are immersed in the neutralization solution, prime, by cathode sputtering metallization and with the finish paint paint of acroleic acid polyurethane paint or acrylate paint systems with high concentrations of toluene diisocyanate.
French Patent specification sheets FR-A-2,703,074 surface preparation of having put down in writing polyacetal articles is used to electroplate to prepare them, undertaken by the mixed acid bath etching with sulfuric acid, phosphoric acid and hydrochloric acid, wherein mixed acid bath contains 30vol% sulfuric acid (96/98% purity), 20vol% phosphoric acid (85% purity), 5vol% hydrochloric acid (35/37% purity) and 45vol% water.This processing has obtained certain small-scale success for the plating by the goods of Copolyacetal manufacturing, but its enforcement on technical scale and unsatisfactory.
United States Patent (USP) 4,826,565 disclose by with the acidic solution etching polyacetal articles of molding being carried out surface roughening.It has discussed surface roughening process, comprises the material that interpolation can be dissolved in polyacetal resin in the acid etching process, for example metal carbonate.These methods of delivering provide required surface working performance, but for obtaining having the product of excellent surface characteristic, need carry out improved technology controlling and process to etching condition.In addition, the ability of etching solution can reduce in time, and etching solution is contaminated, has reduced the adhesion to goods of the surface working performance of polyacetal articles and electrolytic coating like this.United States Patent (USP) 4,826,565 suggestions are by comprising that in etching solution additive alleviates these problems, particularly thiocarbamide.In the mixed acid bath of forming by the mixture of sulfuric acid and phosphoric acid, have and do not add thiocarbamide, following polyacetal resin to be tested, it contains 3wt%, and granularity is the lime carbonate of 0.01 μ to 20 μ.Find to add thiocarbamide and can produce improvement.Except explanation can comprise typical additives, do not provide the concrete details of this polyacetal resin.
Although have some difficulties so far, be starved of polyacetal articles, especially for the polyacetal articles of appearance very important use, carry out surface treatment, the plating outward appearance that keeps the good physical-mechanical property of polyacetal simultaneously and have improvement.A kind of special application is the gold-plated sealing cover that is used for scent flask, because the outstanding mechanical property of polyacetal, promptly the stiffness of polyacetal and toughness and, compare with amorphous polymer, for the excellent chemical of alcohol, polyacetal is preferred with respect to other plastics especially for it.But, be used for the good gold-plated modification face of sealing cover needs of scent flask, keep good chemerosiveness resistent and good coating to adhere to simultaneously, this is unapproachable.
As mentioned above, in the plating of the polyacetal resin product of melt-processed, exist many problems to overcome now.Especially, also can not produce a kind of high-quality perfume lid of making by gold-plated polyacetal so far.As an alternative, used related other galvanized amorphous polymer such as the polyolefine inserts.
Summary of the invention
The invention provides a kind of polyacetal mixture, be used to be processed into and treat by acid etching and galvanized polyacetal articles, can on the acetal product surface of molding, produce highdensity hole/hole thus, so that for the deposition of electroplating metal level in the course of processing provides excellent mechanical set, the result provides the final adhesivity of excellent metal level and the surface with excellent aesthetic appearance.Hole/hole produces via selected chemical milling, and the solubility in acid mineral filler dissolving in etching process in the polyacetal stays the hole/hole with well-controlled distribution of sizes.What play a decisive role for this point is the size of etching solution, hole (zone that is covered by hole) and the discrete form of density and hole (uniformly).If etching is too serious, produce highdensity macroscopic void thus, if perhaps particulate is oversize, simultaneously discrete form difference and size-grade distribution are wide, form unacceptable surface so, when electroplating, will display surface aesthetic property difference and/or adhesivity a little less than.Therefore challenge is that abundant etching is carried out on the surface, so that form mechanical fixation point for producing competent adhesivity, can not damage appearance simultaneously.
One main aspect, the invention provides a kind of polyacetal mixture, be used to be processed into and treat by acid etching and galvanized polyacetal articles, this mixture comprises polyacetal resin blend and solubility in acid particle, wherein the polyacetal resin blend comprises that 97-99.9wt% polyacetal and 0.1-3wt% molecular weight are 5,000-50, the non-polyacetal resin of 000 hypocrystalline or amorphous thermoplastic; The solubility in acid particle is selected from carbonate, phosphoric acid salt, vitriol, acetate, the silicate of at least a period of element Table II family metal, described solubility in acid particle exists with 2 to 6wt% amount of polyacetal blend, and at least 98% described solubility in acid particulate is of a size of 0.1 to 5 micron.
Polyacetal mixture of the present invention is characterised in that good processing properties, for example molding and can not form defective in the product of producing.Polyacetal articles by mixture production of the present invention is characterised in that there is not manufacturing deficiency, molding defect particularly, for example fold, the interflow line, splay mark or swirl mark, throwing power (homogeneity and adhesivity) improves simultaneously, appearance ratings (plating outward appearance) improves and the good physical-mechanical property that keeps, i.e. stiffness and toughness.The feature of galvanized polyacetal articles also is, improves according to the surface smoothness of the decay visual evaluation of reflected image under light source.
Key character of the present invention is the excellent appearance grade that the plating polyacetal articles that obtains is consistent, and does not damage plating adhesion or polyacetal stability.The polyacetal articles that is obtained by mixture of the present invention also has the processing characteristics of improvement in acid etching and follow-up electroplating process.When immersing acidic etching solution, these goods have low scrap rate.Scrap rate is because the per-cent of acid etching and destructive parts or observe per-cent such as the parts of the defective (in the acid etching process or in the subsequent process steps process) of the crackle that forms on parts surface.
The advantage of polyacetal mixture of the present invention, the goods by this mixture production, acid etching goods and final plating polyacetal articles is many-sided:
I) improved the processing that makes mixture become goods, for example by molding, and basically eliminate manufacturing deficiency;
Ii) acid etching can be finished with low scrap rate (almost not having etching defect) in full acid bath (not having additive), and the etched surfaces with uniform small pores crack is provided;
Iii) etched surfaces has equally distributed many fine porositys, the distributing very evenly of pore dimension;
Iv) can strengthen the catalysis of etched surfaces, to improve plating catalyst adhesivity and processing property;
The plated item that v) obtains has consistent excellent appearance grade;
The coating that vi) applies has excellent adhesion; And
The physicals that has vii) kept polyacetal is particularly to the stability of chemical erosion.
Except to be processed, etching and galvanized polyacetal mixture, others of the present invention comprise the etched polyacetal articles that is easy to by this mixture production, the etching polyacetal articles that obtains by these goods of etching with even porous surface, and by apply in electroplating one or more of plating liquor and electrification with plating catalyst, no electric metal, preferred all plating polyacetal articles that obtain in conjunction with these acid etching polyacetal articles of plating of three kinds.The others that the present invention also has are to electroplate the method and the special polyacetal mixture of preparation of polyacetal articles, strengthen the adhesivity of the plating catalyst that applies and the method for effect.
The accompanying drawing summary
In the accompanying drawings:
Fig. 1 a and 1b are the photo that is presented at according to observed typical surface defective on the contrast polyacetal prescription electroless nickel plating polyacetal articles.
Fig. 1 c is the corresponding photo of the polyacetal articles of electroless nickel plating of the present invention.
Fig. 2 a is for being presented at inhomogeneous copper-plated photo on three contrast molding polyacetal parts.
Fig. 2 b is the corresponding photo of the copper facing polyacetal articles of the present invention's production.
Fig. 3 a is the molding of polyacetal prescription of the present invention and the SEM photo of etched surfaces.
Fig. 3 b is the molding of contrast polyacetal prescription and the SEM photo of etched surfaces.
Fig. 4 a is the SEM photo of the copper coatings of contrast polyacetal prescription.The quality that striped that exists on Fig. 4 a or pelmatogram have reduced reflected image causes part undesirable appearance outward appearance.
Fig. 4 b is the SEM photo of the copper coatings of polyacetal prescription of the present invention.
Describe in detail
The invention provides the polyacetal mixture, be used to be processed into by acid etching and galvanized polyacetal articles, produce have excellent visual appearance grade, in conjunction with the plating polyacetal articles of good adhesion and the good physical-mechanical property that keeps.
The present invention relates to some polyacetal composition, it carries out etching by mixed acid bath in melt-processed (for example by injection moulding) afterwards, described mixed acid bath contains at least three kinds of acid, be selected from sulfuric acid, phosphoric acid, hydrochloric acid and organic acid, and preferably contain four kinds of acid, be sulfuric acid, phosphoric acid, hydrochloric acid and acetate.This polyacetal composition contains a spot of functional modifier (as described below), and it helps to keep electroplating the good appearance of polyacetal and the physicals that keeps polyacetal.
Elaborate very much as following, the electroplating technology that uses resin combination of the present invention, surface treatment and apply obtains required high-performance (good adhesivity, stiffness, toughness and surface aesthetic).
Polyacetal
Term " polyacetal " comprises the homopolymer of the cyclic oligomer of formaldehyde or formaldehyde as used herein, its end group is by esterification or etherified sealed end, and the cyclic oligomer of formaldehyde or formaldehyde and other monomeric multipolymer, described other monomer is created on the oxyalkylene group that has at least two adjacent carbonss in the main chain, the end group of described multipolymer can be hydroxy-end capped maybe can be by esterification or etherified sealed end.
The polyacetal that is used for the present composition can be branching or line style, its number-average molecular weight is generally 10,000 to 100,000, preferred 20,000 to 75,000.Molecular weight can be used gel permeation chromatography, and 160 ℃ are used down that to have the nominal pore size be 60 and 100 in meta-cresol
DuPont PSM bimodal column equipment measure easily.According to required physics and processing characteristics, though can use polyacetal with higher or lower molecular-weight average, but above-mentioned polyacetal molecular-weight average has guaranteed that various component melts are mixed into the well blend of composition, and has the comprehensive physicals that needs most at the moulded parts of based composition manufacturing thus.
As noted above, polyacetal can be homopolymer, multipolymer or its mixture.Multipolymer can contain one or more comonomers, and for example those are generally used for preparing the comonomer of polyacetal composition.More generally the comonomer of the Shi Yonging alkylene oxide that comprises 2-12 carbon atom with and with the cyclic addition product of formaldehyde.The quantity of comonomer will be not more than 20wt%, preferably be not more than 15wt%, most preferably be about 2wt%.Most preferred comonomer is an oxyethane.Usually polyacetal homopolymer is better than multipolymer, because the stiffness of homopolymer and intensity are bigger.Preferred polyacetal homopolymer comprises that those its terminal hydroxy groups form ester or ether group respectively by chemical reaction, is preferably formed acetate groups or methoxyl group, and end capped homopolymer.
Polyacetal is usually at about 170 ℃-260 ℃, and preferred 185 ℃-240 ℃, 200 ℃-230 ℃ melt temperature melt-processed most preferably.
Functional modifier
Have now found that polyacetal can be mixed with composition, have the electrodepositable and the good physical-mechanical property that keeps of improvement.We recognize according to the performance that keeps, for example when under according to the stretching of ISO527/1-2 or when under Impact Test, testing according to ISO179/1eA, compare with unmodified and/or untreated molding polyacetal parts, the deterioration of physical-mechanical property is insignificant.
" functional modifier " of polyacetal or " stablizer " are a kind of hypocrystalline or the non-polyacetal resin of unbodied thermoplasticity, generally include at least a nitrogenous organic materials, and are generally polymeric amide.This at least a hypocrystalline or unbodied non-acetal thermoplastic polymer can be selected from those in extrusion molding and injection moulding processing, usually the thermoplastic polymer that uses or be used in combination with other separately.These polymkeric substance are well known to a person skilled in the art, as extrusion molding and injection moulding grade resin, it is different from those known resins that is used as a small amount of component (being processing aid, impact modifying agent, stablizer) in polymer composition.
For key of the present invention be that the polyacetal mixture comprises about 0.1 to 3wt%'s but at least a non-acetal thermoplastic polymer that is no more than, but preferred 0.5 to 2wt% at least a non-acetal thermoplastic polymer.More substantial non-polyacetal thermoplastic polymer causes the larger size distribution of etching polyacetal articles mesoporosity, and therefore causes appearance poor in plated item.
The functional modifier that contains hydroxyl, carbonyl, methacrylic ester, acid amides and/or amido and/or its combination is a fusile under the temperature of processing polyacetal.Term " fusible " represents that the combination of this functional modifier or difference in functionality properties-correcting agent has a main fusing point that is lower than the polyacetal melt processing temperature, thus under this processing temperature, it is liquid and preferably has low viscosity and present significant melt flow.Though the surface enrichment of said " low melting point-low viscosity " functional modifier may be described hardly in quantity, but it is believed that the latter will move to the surface in the molding course of processing, there is functional group's (for example measure by ESCA and confirm) down a bit in it on the so-called top layer microtexture of the polyacetal parts of processing or just thus.In addition, by adding these " low melting point-low viscosity " functional modifiers, in being with or without the acid etching process of oxidizing solution, the minimizing of breaking.Seemingly, when above-mentioned functions properties-correcting agent added prescription, internal stress or unrelieved stress partly discharged, for the polyacetal parts of processing provide the enhanced mechanical property.
For example, have the degree of crystallinity that low-melting relatively polymeric amide keeps certain level, but its low viscosity, high polarity and hydrogen bond make them can be used for purpose of the present invention.Polyolefine, preferred polar copolymer and terpolymer such as ethylene-vinyl acetate copolymer (EVA) and ethylene-propylene acid butyl ester-carbon monoxide terpolymer (EBACO) have been proved the surface adhesion that improves between polyoxymethylene base material and the various surface treatment agent useful.Also can use fusing point to be near or below the semicrystalline polyester of polyacetal fusing point, for example pla-pcl.Can non-acetal thermoplastic polymer be introduced composition with a kind of thermoplastic polymer or with blend more than a kind of thermoplastic polymer.The blend of thermoplastic polymer can be used for adjusting function, for example the consistency of toughness or main resin and polyoxymethylene.But preferred substrates comprises a kind of other or alternate polymkeric substance, for example amorphous thermoplastic polymers or semi-crystalline polymer.
No matter introduce or to introduce more than a kind of blend, the wt% of all non-acetal thermoplastic polymers of composition should not exceed the above wt% scope that provides with a kind of thermoplastic polymer.
Term " thermoplasticity " should be represented when being heated, but polymkeric substance softens to flow state, it can be forced or shift to enter cooling die from the heating die cavity under pressure, and when cooling off in this mould, the polymkeric substance sclerosis also presents mold shape.Thermoplastic polymer is definition in " plastics and elastomerics handbook " (Handbook of Plastics and Elastomers) (being published by McGraw-Hill) so.
Term " amorphous " should represent that polymkeric substance does not have crystalline melt point clearly, does not also have measurable melting heat (though along with cooling off very slowly from melt, perhaps annealing fully can improve certain degree of crystallinity).Melting heat is measured on differential scanning calorimeter (DSC) easily.Appropriate vol heat is counted 990 thermal analyzers of DuPont company, and parts number is 990000, has cell base II, and parts number is 990315, and the DSC cell, and parts number is 900600.For this tester, can measure melting heat with the heating rate of 20 ℃ of per minutes.Sample by alternately be heated to above the expection fusing point temperature and by cooling off fast with cooled with liquid nitrogen sample chuck.The melting heat of measuring the arbitrary heating period after first cycle should be the steady state value in the experimental error scope.According to this method, be less than 1cal/g in this melting heat of determining amorphous polymer.As a reference, molecular weight is that the melting heat of about 17,000 semicrystalline nylons 66 polymeric amide is about 16cal/g.
Useful thermoplastic polymer should be a melt-processable under the temperature of molten polyformaldehyde processing in the present composition.Polyoxymethylene is usually at about 170 ℃-260 ℃, and preferred 185 ℃-240 ℃, melt-processed under 200 ℃-230 ℃ the melt temperature most preferably.
Term " melt-processable " should represent that thermoplastic polymer should soften or have sufficient flowability, and it can be used for melt compounded under the particular melt processing temperature of polyoxymethylene like this.
Require the minimum molecular weight (1000) of thermoplastic polymer so that guarantee consistency, thermostability and keep mechanical property via the entanglement of chain, condition is that the polymerization degree of polymkeric substance is at least ten, and other condition is that polymkeric substance is (promptly in the pressure current downflow) of melt-processable under the temperature of melt-processed polyoxymethylene.The maximum molecular weight of thermoplastic polymer should be so not high so that thermoplastic polymer self can not carry out injection moulding according to the existing standard technology.The maximum molecular weight (50,000) that is used for the polymkeric substance of injection moulding processing will change with every kind of independent, specific thermoplastic polymer.But the described maximum molecular weight that is used for injection moulding processing is that those skilled in the art can understand easily.
At this useful amorphous or hypocrystalline polyamide thermoplastic is well known in the art.They are recorded in United States Patent (USP) 4,410, in 661.Especially, these amorphous or hypocrystalline polyamide thermoplastics are by the aromatic dicarboxylic acid of at least a 8-18 of a containing carbon atom and at least aly be selected from following diamines and obtain, described diamines comprises: (i) the positive structure aliphatics straight diamine of 2-12 carbon, the (ii) branching aliphatie diamine of 4-18 carbon, the (iii) alicyclic diamine that contains at least one alicyclic preferred cyclohexyl structure part of 8-20 carbon, and it is wherein optional, the polymeric amide of 50wt% can be by lactan that contains 4-12 carbon atom certainly or omega-amino acid at the most, or the unit composition that obtains of the aliphatic dicarboxylic acid that contains 4-12 carbon atom certainly and the polysalt that contains the aliphatie diamine of 2-12 carbon atom.
Term " aromatic dicarboxylic acid " should represent that carboxyl is directly connected to for example aromatic ring of phenylene, naphthalene etc.
Term " aliphatie diamine " should represent that amido is connected to for example chain that contains non-aromatic group of alkylidene group.
Term " alicyclic diamine " should represent that amido is connected to the alicyclic ring of being made up of 3-15 carbon atom.The alicyclic ring of 6 or 12 carbon is preferred.
The preferred embodiment of polyamide thermoplastic comprises that those fusing points are lower than about 180 ℃ polyamide thermoplastic, comprises multipolymer and terpolymers such as nylon 6,610,612.Polymeric amide is defined as by cyclic monomer (for example e-hexanolactam) and/or diamines/diacid (diacide), and for example hexanediamine and hexanodioic acid polymerization obtain, and include but not limited to nylon 6,10,11,12,46,66,69,610,612,1212 and 6T.Polymeric amide comprises various multipolymers, terpolymer, tetrapolymer and the interpolymer (interpolymer) by one or more dicarboxylic acid and one or more diamines condensation prepared; The condensation polymer of mono amino carboxylic acid; And the polymkeric substance of lactan.
Amorphous or hypocrystalline polyamide thermoplastic is moored less than 50,000 200 ℃ of demonstrations, preferably less than 20,000 melt viscosities of mooring, in 105 dynes per centimeter
2Shear-stress under record.Amorphous or semicrystalline polyamides is commercially available or can prepares by above-mentioned proportion of composing with the known polymer method of condensing.In order to form superpolymer, the integral molar quantity of the diacid of use should be approximately equal to the integral molar quantity of the diamines of use.
In addition, free dicarboxylic acid, its derivative as acyl chlorides, can be used for preparing polyamide thermoplastic.
The polymerization for preparing amorphous or hypocrystalline polyamide thermoplastic can be carried out according to known polymerization technique, for example melt polymerization, solution polymerization and interfacial polymerization technology, but preferably implement polymerization according to melt polymerization method.This method produces has the high-molecular weight polymeric amide.In polymerization, be equimolal amount hybrid diamine and acid or cyclic amide basically in diamine components and dicarboxylic acid component's ratio.In melt polymerization, be higher than the polymeric amide fusing point that obtains but be lower than heat contents under the temperature of its degradation temperature.Heating temperature is about 170 ℃ to 300 ℃.Pressure can arrive 300psi (approximately 2MPa) for vacuum.The method that adds initial monomers is not crucial.For example, can preparation and hybrid diamine and sour bonded salt.Same possible is the mixture that disperses diamines in water, at high temperature adds the mixture of the acid of specified amount in this dispersion, forms the mixture solution of nylon salt, makes this solution carry out polymerization then.
If desired, can in the mixture of initial salt or its aqueous solution, add unit price amine or preferred organic acid as viscosity modifier.
Functional modifier with OH group is defined as the interpolymer (co-interpolymer) (interpolymer represent 2,3,4 or more monomeric units) of polymkeric substance with ethene alcohol radical and/or phenylol and/or other hydroxyl.
Functional modifier can be can contain the acrylate of hydroxyl or methacrylic ester (MA), acid amides, imide, carboxylic acid and/or its salt and with such as following combination, for example vinylbenzene, methyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, glycidyl methacrylate, hydroxyethyl methylacrylate than low reaction activity or low functional monomer.The polymer stabilizer that is used for composition can be homopolymer or multipolymer, contains formaldehyde reaction activity-nitrogen groups, formaldehyde reaction activity-hydroxyl groups or formaldehyde reaction activity-nitrogen groups and formaldehyde reaction activity-hydroxyl groups." formaldehyde reaction activity " expression: hydroxyl groups contains aerobic, and hydrogen atom and its keyed jointing are arranged, and nitrogen groups contains nitrogen, and one or two hydrogen atom and its keyed jointing are arranged.Formaldehyde will with this polymer stabilizer-OH or-NH key reaction.These reactive sites are called the formaldehyde reaction reactive site at this.Preferably, the polymer stabilizer that contains formaldehyde reaction active nitrogen group or hydroxyl groups has the formaldehyde reaction reactive site of maximum number.For example, containing wherein has two hydrogen atoms to be directly connected in the polymer stabilizer of the formaldehyde reaction active nitrogen group of nitrogen-atoms, and being better than containing wherein only has a hydrogen atom to be directly connected in the polymer stabilizer of the formaldehyde reaction active nitrogen group of nitrogen-atoms.
The solubility in acid particulate additive
Polyacetal mixture of the present invention contains the particle of the salt that belongs to period of element Table II family metal, by remove this salt in the acid etching process, promotes to form the uniform micro uneven surface.This uneven surface promotes surface working again, particularly promotes to use plating catalyst, then is that no electric metal applies plating liquor and electrochemical method.
The solubility in acid particulate additive can be selected from least a from period of element Table II family metal, is generally carbonate, phosphoric acid salt, vitriol, acetate, the silicate of calcium and magnesium most.Preferred solubility in acid particle is made by lime carbonate.These particles can with or need not disperse for example stearate coating of reagent.
The amount that these solubility in acid particles are present in the polyacetal blend is 2 to 6wt%, and at least 98% described solubility in acid particulate is of a size of 0.1 to 5 micron.Preferred acid dissolubility particle exists with 3 to 5wt% amount of polyacetal blend, and the solubility in acid particulate of at least 98% (common 99%) is of a size of 0.1 to 2 micron.Under latter instance, the average basic granularity of solubility in acid particulate is about 0.7 micron.These particles and polyacetal resin are compatible and do not make polyacetal resin degraded, and should given size range produce the dispersion of the best, and it has the distribution of sizes of good control.
As described below, by using the solubility in acid particle of this narrow size distribution, and with the polyacetal blend gang with the non-polyacetal properties-correcting agent below 3%, etched molded polyacetal articles shows very fine and uniform microporosity, produce excellent plated item appearance, keep good plating adhesion and good polyacetal chemerosiveness resistent simultaneously.
Acid insoluble particle additive
The preferred embodiment of polyacetal mixture of the present invention further comprises sour insoluble inorganic particle additive, is selected from glass powder, kaolin and silicate, preferred fumed silica.These sour insoluble particles, particularly fumed silica exist with 1/5 to 1/50 amount of solubility in acid particle weight, and this acid insoluble particle is of a size of 1/20 to 1/100 of solubility in acid particle size.
When the solubility in acid particle with 3wt% when the preferred amounts of 5wt% exists, sour insoluble particle exists to the preferred amounts of 0.5wt% with 0.1wt%, the both is based on the weight of polyacetal blend.
The acid insoluble particle is significantly less than the solubility in acid particle.Preferably, sour insoluble particle is of a size of 5 to 40 nanometers, more preferably 10 to 20 nanometers (non-agglomeration basic granules size).These particles are further characterized in that 100 to 300m
2/ g, preferred 175 to 225m
2The high-specific surface area of/g.
The function of these sour insoluble particles is to strengthen the plating catalyst apply such as the activity and the effect of palladium.Therefore, add fumed silica so that improve the deposition of catalyzer in the hole that forms by acid etching (mechanical set position).It is believed that tiny silica dioxide granule is exposed to the surface and will helps electroplating catalysis after chemical milling dissolving carbonate particle.As main effect, improved adhesivity and formed electrodeposition of metals, thereby provide by embodiments of the invention outstanding surface aesthetic as described below in more uniform mode.
When polyacetal articles when containing the mixture molding of solubility in acid and sour insoluble particle, the mould polyacetal articles comprises solubility in acid particle and sour insoluble particle, described solubility in acid uniform particles is distributed in the polyacetal surface, and sour insoluble particle is fixed in the solubility in acid particle surface polyacetal blend on every side.In the acid etching polyacetal articles that obtains by this molded polyacetal articles of acid etching, removed the solubility in acid particle, individually stay sour insoluble particle, perhaps the form with agglomerate stays, it is believed that it has the overall dimension up to hundreds of nanometers, and be fixed on by in the polyacetal blend around the hole of removing the opening that the solubility in acid particle stays.
Other component of polyacetal
Polyacetal resin does not contain other mineral filler usually, but mixture of the present invention can comprise, except polyacetal has the finite quantity polymer stabilizer, and outside above-mentioned solubility in acid and the sour insoluble particle, be generally used for other component, properties-correcting agent and the additive of polyacetal mold resin, comprise oxidation inhibitor, pigment, colorant, ultra-violet stabilizer, toughner, nucleator and filler.
Melt-processed
The polyacetal mixture carries out melt-processed, for example compression moulding, injection moulding, extrusion molding, blowing, rotational moulding, melt-spinning, punching press and thermoforming by any technology that is generally used for thermoplastic material.
As mentioned above, the viscosity of polyacetal basis resin played an important role during the molding stage, and in the stage, shearing at the gate location intensive usually negatively to influence surface smoothness at molding.Just not saying the design concept that will use and criterion, when mould hypocrystalline engineering polymers such as polyacetal resin, low viscosity resin helps the homodisperse filler and still less tends to producing defective at cast gate.In addition, if the wall thickness of parts is quite little, low viscosity resin (melt flow index is about 20 to 40 grams/10 minutes, and ISO 1133) also will obtain better result, almost not have defective.Similarly factor is applicable to other method for melt processing.
Composition and its additive to the polyacetal blend of the present invention of patent protection are as requested selected, and obviously help to reduce the unnecessary artificial defect of transforming in the goods.For fear of surface imperfection, the viscosity of reply polyacetal blend is selected to process fully when by molding guaranteeing.For this point, the melt-flow index of measuring under 190 ℃ of 2.16kg according to ISO 1133 should be 2 to 40 grams/10 minutes, and preferred 20 to 30 grams/10 minutes are particularly for the molded parts with about little wall thickness of 0.5 to 5mm.
The viscosity of polyacetal basis resin not only plays an important role in the dispersion of mineral filler during the compounding stage but also during the molding stage, and wherein at molding in the stage, shearing at the intensive of mould gate position usually negatively to influence surface smoothness.At the cast gate place, shear maximum usually, here so be the place that most probable produces molding defect.Low viscosity resin will help the homodisperse filler and still less tend to producing defective at cast gate usually.In addition, if the wall thickness of parts is quite little, low viscosity resin also will produce better result, almost not have defective.
Acid etching
Will galvanized polyacetal surface pass through the mixed acid bath etch processes, described mixed acid bath contains at least three kinds of acid, be selected from sulfuric acid, phosphoric acid, hydrochloric acid and organic acid, especially, described surface is by the mixed acid bath etch processes that contains sulfuric acid, phosphoric acid, hydrochloric acid and acetate.The following mixing acid etch bath of forming of preparation is used for the simultaneous test of following record, and described mixing acid etch bath provides by example: sulfuric acid 34.5wt%; Phosphoric acid 29.0wt%; Hydrochloric acid 4.5wt%; Acetate 8.5wt% and water 23.5wt%.In this example, sulfuric acid is 1.18 to the weight ratio of phosphoric acid, and hydrochloric acid is 0.52 to the weight ratio of acetate.
If this surface treatment is used to not contain the polyacetal articles of functional modifier, will have problems so, the whole deterioration of polyacetal resin for example, it causes strength degradation and forms crackle.
On the other hand,, can reach the deterioration that surface modification prevented or reduced polyacetal articles simultaneously, keep good physical-mechanical property, and the adhesion of plated metal is improved if use polyacetal to handle with proper function properties-correcting agent.
The solubility in acid particulate has and helps improve the homogeneous surface microporosity, provides mechanical set for electroplating precursor and metal plating.By processing in the boundary that limits in the present invention, this microporosity provides the surface with excellent aesthetic appearance.
The etching of polyacetal articles and plating
Will galvanized molded polyacetal articles under the highest 50 ℃ of temperature, immerse weakly alkaline pH and have tensio-active agent that (for example PM 900, available from Shipley SAS of Paris, during bathing, cleaned 2 to 3 minutes by cleanser France), carry out etching again with water rinse then.
Etching 10 to 30 minutes in aforesaid 25 to 35 ℃ of mixed acid bath easily.Low-temperature condition needs longer processing.Can stirred solution so that the etching of polyacetal surface is even.For safety and artificial atmosphere, vapour discharge in etching process.
After etch bath shifted out, rinsing goods in water can reclaim the acid of taking out of by reverse osmosis therein.Use in 20ml/l ammonia solution or the 10g/l sodium hydroxide solution then and goods, the both at room temperature follows to stir and continues about 1 minute.Use the water rinse goods then, and before electroless coating, at room temperature immersed 10%HCl solution 1 minute.
In the solution that contains 50 to 100ppm palladiums, under 25 to 28 ℃, use the palladium colloid then, for example available from the catalyzer 9F of Shipley SAS, catalytic surface 1 to 5 minute.As known in the art, when using different catalysts, condition is adjusted: for example for the catalyzer DP available from Shipley SAS, handle under 35-40 ℃.This processing follows mechanical agitation or stirring to carry out.
Water rinsing goods and use promotor are once more handled as the preparaton PM 964 available from Shipley SAS then, remove stannous compound and strengthen the catalytic capability of palladium.This processing was carried out under 40 to 45 ℃ 2 to 4 minutes, perhaps carried out the longer time if necessary, followed water rinse again then.
Then, the concentration that goods are immersed in 25 to 35 ℃ of following nickel is 70% or 2.4g/l and to keep pH be that for example the PM 980 available from Shipley SAS bathes in 8.8 to 9 the electroless nickel bath by adding ammoniated material simultaneously.0.25 to 0.3 micron nickel dam was provided in lasting 8 to 12 minutes.The quality of electroless nickel deposition can be used lens examination, and regularization condition as required.
The goods of electroless nickel plating can be used for electrification at any time to be electroplated, and for example uses conventional Watts to bathe with the nickel electrification and electroplates, or also electroplate with conventional the bath with the chromium electrification.In addition, the electroless nickel plating coating can replace with the electroless copper coating, then electroplates with nickel, chromium or any other metal electrification.For Direct Electroplating, the sample of before handling is as mentioned above immersed depassivation solution, in catalyzer DP and promotor as 5wt% sulfuric acid, then directly with conventional plating coating.
In the long-term operation process, for example, make regular check on etch bath by measuring its proportion every day.Regularly add new concentrated acid with compensation " taking out of " loss.The pollution that periodic measurement is bathed from the metal pair of relevant anchor clamps (stainless steel and copper or nickel), for example every month.
Can ignore on following meaning and remove dissolved lime carbonate, that is, the most of salt that forms in the acid etching process is washed off at rinse stage, thereby takes etch bath out of.Strengthened this effect by selecting tetracid to bathe, many soluble salts are produced in described acid bath, similarly for example have the lime acetate of faint precipitation tendency.With FR-A-2,703,074 prior art etch bath is compared, etch bath of the present invention can be operated the identical or longer treatment time under lower temperature, this causes when at identical temperature operation, the handiness/tolerance in the processing higher (wideer processing battery limit (BL) window) and/or to the better control of treatment articles.
Contrast test
As described below, use commercial unmodifiedly or modified polyacetal resin is articles injection-moulded, promptly be designed for the bottle cap of the bottle that holds perfume.All parts carry out above-mentioned surface treatment in aforesaid mixing acid etch bath.
Select the quality of different judgement criterias with the parts of authentication process.Comprising mouldability, adhesivity and surface smoothness or aesthetic property.
Mouldability is represented the level of the surface smoothness that the representational parts of molding obtain afterwards.Under situation of the present invention, the perfume bottle cap of molding has quite little wall thickness (0.8mm).Best molded parts must be without any surface imperfection, such as but not limited to fold, interflow line, splay mark, pit or swirl mark.A kind of method of identifying mouldability is the surface smoothness of observing the etching part that immerses the molding after the electroless nickel plating.
Fig. 1 a represents to immerse the etching part that Ni bad molding is afterwards separated in electroless plating, wherein observes fold at gate location.These fold produce when using high viscosity acetal base resin and/or excessively low injection speed usually.Increase the weight of owing to gate size is little in addition.
On the other hand, Fig. 1 b shows swirl mark or high shear striped, usually in the too high amount of allocating into prescription, more specifically contain 10% or the prescription of more mineral filler such as lime carbonate in, observe.Usually these stripeds will cause the ununiformity that the adhesivity of electrolytic coating is inhomogeneous and also produce surface smoothness to a certain extent.
Fig. 1 c shows the corresponding photo that scribbles the molded parts of electroless nickel plating of the present invention.Its surface does not have above-mentioned defective, i.e. fold and swirl mark.Observed surface is uniformly and does not have defective.Usually will cause the defective that increases the weight of in the processing in the later stage in observed any defective of this stage.
The homogeneity of electroplating processes can be estimated with visual inspection.This molded parts immerses after the electroless nickel plating, must evenly be coated with chemical nickel.Fig. 2 a shows bad parts, and wherein white stripes is equivalent to uncoated area.The origin cause of formation of these stripeds can be many-sided; but those that show are bad dispersive consequences of mineral filler and/or relevant with the heterogeneity in the microtexture, and the scope of described microtexture outside using those compositing ranges that require patent protection carries out producing in the compounding and the molding course of processing.
Fig. 2 b shows the corresponding photograph of copper-plated molded parts of the present invention, shows excellent DOI (image definition), and the image reflection of the excellence of low thin portion decay is followed in its expression.In addition, its good adhesion with copper coating keeps appearance and unreactiveness simultaneously.
Adhesivity is measured according to iso standard 2409.Grade 0 is excellent, and class 5 is represented weak adhesivity.Under Fig. 2 a situation, adhesivity is inhomogeneous, and wherein there is no coating place in the value of counting 5.Under Fig. 2 b situation, the adhesivity grade is 0 to 1 (excellence).
Surface smoothness or aesthetic property.Examine and immerse electrochemical copper facing surface quality afterwards, and evaluation map image sharpness (DOI).Under light, the reflection of image must be best, only has minimum thin portion loss.According to this test, to the non-constant of evaluation of the sample of Fig. 2 a.
Fig. 4 a and 4b are respectively the SEM observations of the copper coatings of contrast polyacetal prescription and polyacetal of the present invention prescription.Striped that shows among Fig. 4 a or pelmatogram are the results of continuous metal layer difference in level, produce the surface aesthetic of difference.On the contrary, Fig. 4 b seems even and do not have visible defects, the appearance of improved copper coatings of the present invention on reflecting surface.
The viscosity, consistent dose, the type of mineral filler and the amount of amount and fumed silica that change the acetal base resin are carried out different experiments.
When test did not contain the prescription of any mineral filler, can obtain surface of good smooth finish did not still have adhesivity fully.
For having Different Ca CO
3The polyacetal prescription of distribution of sizes, with the average basic size of this filler particles from 0.7 micron rising during up to 15 microns, the appearance of strong pit has influenced outward appearance unfriendly on the parts.Can obtain best result with lime carbonate with narrow size distribution, and 0.7 micron of the basic granularity average out to of lime carbonate most preferably, the upper limit is located at 2 microns, and the particulate size of expression 99% is below 2 microns.
Has preferred CaCO
3The acetal prescription of content and distribution of sizes is also tested the polyacetal stabilizer of different levels.
Fig. 3 a and 3b are the SEM observations on the molded parts surface that preferred acid etching (20min) obtains afterwards.Two Photomicrographs by the lime carbonate with similar content (" superPflex 200 " are available from Specialty Minerals Inc.) but the stablizer of different amounts and the prescription of fumed silica obtain.Fig. 3 a represents to have the prescription of low-level stablizer (0.8%), and Fig. 3 b represents to have the prescription of higher level stablizer (5%).Shown in Fig. 3 b, it is harmful that the level of stablizer is elevated to 5% pair of surperficial aesthetic property, and reason is that Metal plating can not evenly cover the macroscopic void/hole of formation.
Use the SEM Photomicrograph of Fig. 3 a and 3b to carry out surface analysis.The mean sizes of the hole/hole on Fig. 3 a is 1.7 microns, and maximum value is 5.6 microns.The distribution of sizes of hole is narrow, and member of imparting is at the appearance of electrolytic coating and the best effect between the adhesivity.Among Fig. 3 a, hole adds up to 2337, and hole/hole covers 4% surface.
On the contrary, for the sample of Fig. 3 b, wide many of distribution of sizes, the particle median size is 2.8 microns, maximum value is 21.4 microns.Because particle size is big, observes lip-deep pit.The distribution of sizes of hole is wide.Among Fig. 3 b, hole adds up to 2599, and hole/hole covers 15% surface.It is poor that but this sample makes plated item have acceptable adhesivity surface aesthetic.
The better embodiment of the modified polyacetal goods of test contains or comprises that described polyacetal articles provides the surface working performance for galvanized improvement:
A) the solubility in acid inorganic salt of the II family metal of the periodic table of elements, preferred lime carbonate, described lime carbonate has relatively little mean particle size, is 0.1 to 5 micron, and most preferably 0.1 to 2 micron, 99% particle is less than 2 microns (narrow size distribution).
B) sour insoluble mineral compound comprises that the fumed silica of high dispersing, described fumed silica have the average basic granularity (better below 100nm) of about 12-15 nanometer, and with 0.1 to 1%, preferred 0.15 to 0.5% level is added.
C) acid etching of aforesaid employing mixed acid bath, described mixed acid bath contains sulfuric acid, phosphoric acid, hydrochloric acid and acetate.
These results clearly illustrate that, the parameter that the present invention who only makes the polyacetal of modification stand patent protection as requested selects just can obtain beneficial effect of the present invention.
Claims (22)
1. polyacetal mixture is used to be processed into and treats to be comprised by acid etching and galvanized polyacetal articles:
-polyacetal resin blend comprises that the polyacetal of 97-99.9wt% and the molecular weight of 0.1-3wt% are 5,000-50, the non-polyacetal resin of 000 hypocrystalline or amorphous thermoplastic; With
-solubility in acid particle is selected from least a salt of at least a period of element Table II family metal, and described solubility in acid particle exists with 2 to 6wt% amount of polyacetal blend, and at least 98% described solubility in acid particulate is of a size of 0.1 to 5 micron; With
-be selected from the sour insoluble inorganic particle of glass powder, kaolin and silicate, wherein said sour insoluble particle exists with 1/5 to 1/50 amount of solubility in acid particle weight, and the average primary particle of sour insoluble particle is of a size of 1/20 to 1/100 of solubility in acid particle size.
2. the polyacetal mixture of claim 1, wherein said sour insoluble particle is a fumed silica.
3. claim 1 or 2 polyacetal mixture, wherein the solubility in acid particle exists to the amount of 5wt% with 3wt%, and sour insoluble particle 0.1wt% exists to the amount of 0.5wt%, and the both is based on the weight of polyacetal blend.
4. claim 1 or 2 polyacetal mixture, wherein the non-agglomeration primary particle of sour insoluble particle is of a size of 5 to 40 nanometers.
5. claim 1 or 2 polyacetal mixture, wherein the non-agglomeration primary particle of sour insoluble particle is of a size of 10 to 20 nanometers.
6. claim 1 or 2 polyacetal mixture, wherein sour insoluble particle has 100 to 300m
2The high-specific surface area of/g.
7. claim 1 or 2 polyacetal mixture, wherein sour insoluble particle has 175 to 225m
2The high-specific surface area of/g.
8. claim 1 or 2 polyacetal mixture, wherein the polyacetal blend comprises the polyacetal of 98-99.5wt% and hypocrystalline or the non-polyacetal resin of amorphous thermoplastic of 0.5-2wt%.
9. the polyacetal mixture of claim 8, wherein the non-polyacetal resin of hypocrystalline or amorphous thermoplastic comprises at least a nitrogenous organic materials.
10. claim 1 or 2 polyacetal mixture, wherein said solubility in acid particle exists with 3 to 5wt% amount of polyacetal blend, and at least 98% described solubility in acid particulate is of a size of 0.1 to 2 micron.
11. the polyacetal mixture of claim 1 or 2, wherein the solubility in acid particle is made by lime carbonate.
12. treat by acid etching and galvanized polyacetal articles that produced by each polyacetal mixture in the claim 1 to 11, this polyacetal articles is included in the described solubility in acid particle in the polyacetal blend on its surface for one kind.
13. the polyacetal articles of claim 12 wherein should be fixed in the solubility in acid particle surface polyacetal blend on every side by the acid insoluble particle.
14. acid etching polyacetal articles, its polyacetal articles by acid etching claim 13 obtains, the solubility in acid particle is removed in described acid etching, stay the sour insoluble particle that is fixed in the open space polyacetal blend on every side, described open space stays owing to removing the solubility in acid particle.
15. electroplate polyacetal articles for one kind, it obtains by the acid etching polyacetal articles that applies at least a plating claim 14 in plating and the electrification plating with plating catalyst, no electric metal.
16. a method of electroplating polyacetal articles comprises:
-produce polyacetal articles by each mixture in the claim 1 to 11, wherein the solubility in acid particle is present in product surface,
This polyacetal articles of-acid etching to be removing the solubility in acid particle,
-apply plating catalyst to etched surfaces,
-do not have electric metal to apply plating,
-carry out electrification to electroplate.
17. the method for claim 16, wherein sour insoluble inorganic particle exists with 1/5 to 1/50 amount of solubility in acid particle weight, the average primary particle size of acid insoluble particle is 1/20 to 1/100 of a solubility in acid grain graininess, and wherein said sour insoluble particle is present in by removing on the pore surface in the granuloplastic etching polyacetal articles of solubility in acid.
18. the method for claim 17, wherein sour insoluble particle is a fumed silica.
19. the method for claim 16, wherein polyacetal articles etching in mixed acid bath, described mixed acid bath contains at least three kinds of acid that are selected from sulfuric acid, phosphoric acid, hydrochloric acid and acetate.
20. the method for claim 16, wherein polyacetal articles obtains by molding, extrusion molding or thermoforming.
21. the method for claim 19, wherein said mixed acid bath contains sulfuric acid, phosphoric acid, hydrochloric acid and acetate.
22. a method for preparing the polyacetal mixture, this method comprises:
-be 5 by blend polyacetal resin and molecular weight, 000-50, the non-polyacetal resin of 000 hypocrystalline or amorphous thermoplastic prepares the polyacetal blend, and the amount of polyacetal resin is 97-99.9wt%, and the amount of non-polyacetal resin is 0.1-3wt%;
The mixture of-preparation solubility in acid particle and sour insoluble particle, described solubility in acid particle is selected from least a salt of at least a period of element Table II family metal, described sour insoluble particle is selected from glass powder, kaolin and silicate, at least 98% described solubility in acid particulate is of a size of 0.1 to 5 micron, described sour insoluble particle exists with 1/5 to 1/50 amount of solubility in acid particle weight, and sour insoluble particle is of a size of 1/20 to 1/100 of solubility in acid particle size; With
-described granular mixture is mixed in the polyacetal blend, wherein said solubility in acid particle exists with 2 to 6wt% amount of polyacetal blend.
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| US48041603P | 2003-06-20 | 2003-06-20 | |
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| US10/816,151 | 2004-04-01 |
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| CN103554826B (en) * | 2013-11-04 | 2016-08-17 | 四川大学 | A kind of electrodepositable polyformaldehyde composition and preparation method thereof and electro-plating method |
| CN103757677B (en) * | 2013-11-29 | 2017-01-25 | 云南云天化股份有限公司 | Polyformaldehyde product surface processing method |
| JP5847261B1 (en) * | 2014-09-29 | 2016-01-20 | ポリプラスチックス株式会社 | Polyacetal resin composition and sliding member |
| CN110903638A (en) * | 2019-12-06 | 2020-03-24 | 广东银宝山新科技有限公司 | Composite material capable of being electroplated, preparation method thereof and electroplated composite material |
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