Formulation for the etching of polymeric materials prior to coating them (Machine-translation by Goo

专利摘要:
The present invention relates to a new formulation of polymer etching treatment baths prior to the metallization or coating of the polymer by technologies known and described in the state of the art, which are based on the use of salts and/or complexes of the Cr (III) cation. The formulation of the present invention consists of a salt and/or a Cr (III) complex in which the Cr (III) is coordinated to at least one or more mono, bi, tri, tetra, penta, hexadentate or bridge that are coordinated to chromium by the atom of oxygen, sulfur or nitrogen or several of these atoms to ligands. Once the polymeric part has been etched with the etching formulation described above, the metallic coating is applied by applying chemical and electrolytic baths in the case of metallisations, or by applying paint or another organic base coating. (Machine-translation by Google Translate, not legally binding)
公开号:ES2646237A1
申请号:ES201731155
申请日:2017-09-28
公开日:2017-12-12
发明作者:Julio Gomez Cordon；Luis OTAÑO JIMENEZ；Javier Perez Martinez
申请人:Avanzare Innovacion Tecnologica S L；Avanzare Innovacion Tecnologica SL；
IPC主号:

专利说明:

DESCRIPTION
FORMULATION FOR THE MORDENTING OF POLYMER MATERIALS PRIOR TO THE COATING OF THEMSELVES
5 SECTOR OF THE TECHNIQUE
The present invention relates to treatment baths of polymer biting prior to the metallization or coating of the polymer by technologies known and described in the state of the art, which are based on the use of salts and / or complexes of the Cr (III cation) ).
10 BACKGROUND OF THE INVENTION
At present, the technological development and industrial applications of pretreatment, treatment and biting baths of polymers, mainly ABS and their mixtures such as ABS-Polycarbonate, Polyamide, polypropylene and thermosets, without or with the addition of inorganic fillers and other additives in The mass of the polymer is based on the use of aqueous baths containing chromium salts in oxidation state VI. The baths generally contain sulfuric acid and a chromium (VI) compound mainly chromic acid, chromium trioxide or dichromates in a concentration of up to 400 gr / l
This process of superficial or biting treatment is the initial key treatment and then a system of multiple functional layers of activation, acceleration, deposition of chemical nickel, copper, copper electrodeposition of nickel and even chrome finish, with their corresponding finish is applied Intermediate washes resulting in a metallized plastic on its surface.
In the case of organic or painted coatings, after the initial key process of the aforementioned surface treatment, the plastic is coated or painted by one of the different methods currently available in the state of the art.
Only the combination of a suitable pretreatment or biting, and optimal subsequent treatments provide all the necessary key requirements for the respective applications required, the initial biting treatment being the fundamental factor of the entire process.
The chromium salts in oxidation state VI used in the biting have been shown to be toxic and carcinogenic to humans, which has led to an interest in replacing the use of said chromium (VI) salts for any use of
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these salts and specifically for use in treatment baths and polymer bites.
Different options have been proposed for the substitution of baths containing Cr (VI) salts with other chemical oxidants, mainly Mn (VII), Mn (VI) salts and even Mn (III) salts in both acidic medium and medium. basic, as shown in US8603352 B1, US20130186774.
However, these systems based on salts of Mn do not produce the same results of adhesion in the metallization or subsequent coating of the polymer parts and need very complex washes due to the need to eliminate the products of reduction of the salts of Mn, being also unstable baths in time and short duration for industrial applications.
Alternatively, systems based on hydrogen peroxide have been proposed as in DE19740431 C1, peroxides and salts of iron and / or copper as in US6559242 B1, anionic complexes with ligand of transition metal chloride US4568571 A, organometallic complexes of transition metals in organic solvent EP0081129 A1, salts of chlorides or nitrates of transition metals without the use of complexes in slightly acidic aqueous medium US20070099425 A1
In no case, at present it has been possible to obtain results applicable to the final adhesion requirements demanded by the automotive sector among others and that if they are achieved through treatments based on Cr (VI) salts. A review article on this topic has recently been published: “Plating on acrylonitrile-butadiene-styrene (ABS) plastic: a review Journal of Materials Science 2016, 51,36573674”. Therefore, there is a need in the state of the art to have efficient biting baths in terms of adhesion results of metallized or coatings of other types on the polymer, stability of the bath over time and use, characteristics of safety, non-toxicity for people and the environment, ease of recovery, recycling or disposal in environmentally appropriate conditions of said treatment baths and free of Cr (VI).
OBJECT OF THE INVENTION
The object of the present invention is the pretreatment, treatment and / or biting of polymers through the use of aqueous solutions containing salts and / or chromium (III) complexes in acidic medium.
The invention is based on the use of the Cr (III) cation added as a salt and chemically coordinated with at least one or more mono, bi, tri, tetra, penta, ligands,
hexadentates or bridge that are coordinated to chromium by the atom of oxygen, sulfur or nitrogen.
The treatment is applied to organic polymers with the purpose of modifying its surface both physically and chemically, so that a coating showing adhesion can be made on the polymer surface or can be metallized by technologies currently described in The state of the art.
DESCRIPTION
The coating of polymers by metals or by organic coatings requires a pretreatment of biting so that the surface of the polymer to be coated 10 has an adhesion that meets the application requirements of the product finally obtained.
The polymers on which this biting treatment process is used are thermoplastics such as ABS, mixtures of ABS with other polymers such as polycarbonate, polyamide, PVC, polycarbonate, polyester, polyacetal, polyolefins, thermosetting epoxy resins, unsaturated polyester resins , vinyl ester epoxy resins or elastomers such as SBR, EPDM or thermoplastic elastomers of the different types that exist in the market. The polymers may contain different types of inorganic fillers such as quartz, calcium carbonate, wollastonite, silicates, talc and the corresponding additives necessary for extrusion processing, injection, hot plate molding, or the different techniques used to manufacture objects. , plates or shapes in thermosets or elastomers.
The process of surface treatment or biting of polymers is a process that requires prerequisites, compositions of the treatment or biting baths and the action or treatment of these baths at controlled temperatures and times.
Prerequisites of the biting process:
The surface of the substrate to be treated initially must be free of contaminants, greases, corrosive products and other materials, therefore, an adequate preparation of the base substrate is a prerequisite process requirement, although it is not strictly necessary. The previous preparation of the substrate is known in the state of the art.
The compositions of the baths to be used in the biting process are aqueous baths:
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The baths are prepared by adding salts or complexes of chromium (III) and are based on the use of at least one or several mono, bi, tri, tetra, penta, hexadentate or bridge ligands that coordinate to the chromium by the oxygen atom, sulfur or nitrogen from the ligand.
Among others, the possible ligands to be used for chromium in the oxidation state (III) are formate, acetate, propanoate, buatanoate, benzoate, phenylacetate, phenylpropionate, cyanamate, alkylbenzoates, pyruvate, levulinate, citrate, isocitrate, aconite, trimellitate, glycinate , valineate, leuccinate, threoninate, lysinate, tryptophanate, histidinate, phenylalaninate, isoleucinate, argininate, methioninate, alaninate, prolinate, serinate, cysteinate, asparaginate, glutamine, tyrosinate, aspartate, polyaspartate, glutamate, oxytateinate, glutamate, oxynateinate, glutamate, oxylateinate, glutamate, oxylateinate, glutamate, oxylateinate, glutamate, oxybateinate, glutamate, oxytate , propanedioate, butanedioate, pentanedioate, hexanedioate, maleate, fumarate, phthalate, isophthalate, terephthalate, tartrate, itaconate, mesaconate, citraconate, glycolate, lactate, mandelate, salicylate, gluconate, ethylenedianediamine, trichloroacetate
ethylenediamine disuccinate, methyl glycinate diacetate, N, N, diacetate glutamate, cyclohexylenedinitrilotetraacetate, diethylene notriamaine pentaacetate,
aminoetiletilenglicoltetraacetato, trietilentetraminahexaacetato, dihidroxietilglicinato, iminodiacetate, oxamate, nitrilotripropionato, etilenodiaminadipropionato thiodipropionate, ditiodipropionato, aminopropanoate, aminopentanoate, aminohexanoate, 2-aminobenzoate, 3-aminobenzoate, 4-aminobenzoate, 3- cyclohexylamino-propylamine, ethylenediamine, 1,3-diaminopropane,
dimethylaminopropylamine, diethylaminopropylamine, bis (3-aminopropyl) -methylamine, diethylenetriamine, dipropylenedriamine, triethylenetetramine, tetraethylenepentamine, polyamines, 3- (2-aminoethyl) amino-propylamine, N, N'-bis (3-aminopropylamine) cyclopenediamine , hexane-1,6-diamine, imidazole, 1- methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl-l-imidazole, N- (3-Aminopropyl) -imidazole, pyrazole, nicianamide, bipyridine, phenanthroline or mixtures thereof.
The ligands preferably used are formate, acetate, propionate, glycinate, argininate, aspartate, polyaspartate, glutamate, nicotinate, oxalate, propanodioate, butanedioate, pentanedioate, hexanedioate, maleate, fumarate, phthalate, salicylate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutarate, citrate, glutamate, citrate , ethylenediamine tetraacetate, nitrilotriacetate, 2-aminobenzoate. The ligands most preferably used are oxalate, propanedionate, butanedionate, maleate, fumarate, phthalate, glycolate, lactate, salicylate, glycinate, glutamate or mixtures thereof.
The chromium (III) complexes contained in the bath can be supplied to the bath in the form of a chromium (III) complex prepared and isolated from the above ligands,
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as indicated in the scientific literature, for example, for oxalate-type complexes in “Complex Ions of Chromium. III. Reactions between Hexaquochromium (III) and Oxalate Ions ”Randall E. Hamm, Robert E. Davis J. Am. Chem. Soc., 1953, 75, pp 30853089 (1953)
Cr (III) complexes can also be formed in situ in the bath by adding separately a chromium (III) salt and the ligand that will form the required complex as indicated for example for fumarate complexes in the patent US 3,900,689.
In the case of the in situ formation of the chromium (III) complex, the starting salts of these complexes can be salts of inorganic anion or organic anion such as: Chloride, bromide, perchlorate, hydroxide, oxides, sulfate, sulphite, sulphide, nitrate, nitrite, phosphate, diphosphate, metaphosphates, polyphosphates, borate, silicate, formate, acetate, benzoate, lactate, methanesulfonate, ethanesulfonate, propanesulfonate, butanesulfonate, carboxylates, alkyl phosphates or mixtures thereof. Once these salts have been added to the aqueous bath, the corresponding ligand or form is added to this bath in its protonated form or in the form of an alkali or alkaline earth metal salt or free form, necessary to form the complex.
In this way, the chromium (III) complex required in the biting bath is obtained.
Finally, it is also possible to obtain the necessary Cr (III) complex in the bite bath by chemical reaction of the ligand to be used or a reduced form of the ligand to be used and the addition to the bath of a Cr (VI) compound which is Reduces the complex in oxidation state (III) either by direct action of the ligand with which it is intended to form the complex if it is a reducer or by adding a reducing agent other than the ligand as ascorbic acid, ascorbates, thiosulfates, sulphites , sulfides, nitrites, phosphites, hypophosphites, formaldehyde sulfoxylates, dithionites, oxalates, alkali metal or alkaline earth metal carboxylates, hydrazine and its derivatives, hydroxylamine, or any other reducing agent known in the state of the art.
The concentration of Cr (III) complex present in the bath can be between 2 mM and 2 M and more preferably between 5 mM and 1 M and even more preferably between that of 0.01 M and 0.4 M.
The Cr (III) complexes indicated are used in aqueous acidic medium and the acids contained in the biting bath can be sulfuric acid, aminosulfuric acid (sulfamic acid), phosphoric acid, diphosphoric acid, metaphosphoric acid, polyphosphoric acid, methanesulfonic acid, acid ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkanesulfonic acids, benzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, alkylbenzenesulfonic acids, monoalkylphophoric acids, dialkylphosphoric acids, isethionic acid, perchloric acid
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chloric, nitric acid, trifluorometasulfonic acid, trifluoroacetic acid, tetrafluroboric acid, hexafluorophosphoric acid, hexaflurosilicic acid, fluorhydric acid, boric acid or mixtures thereof. Preferably, the acids present in the mordentate bath can be sulfuric acid, phosphoric acid, diphosphoric acid, metaphosphoric acid, polyphosphoric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mono-alkylphonic acidic acid dialkyl phosphoric acids or mixtures thereof and more preferably the acids present in the bath may be sulfuric acid, phosphoric acid or mixtures thereof.
The acid concentration in the biting bath can be from 10% to 98%, preferably between 40% and 95% and more preferably between 55% and 92% considering the total acid content in mass percentage / mass being the rest complexes of Cr (III) and water. This whole acid may be formed by the mixture of two or more acids.
The temperature of use of the bite bath can vary between 10 ° C and 95 ° C, more preferably between 15 ° C and 80 ° C and even more preferably between 20 ° C and 75 ° C. To achieve working temperatures, the treatment tanks are heated or cooled until the optimum working temperature is maintained by applying any appropriate technology for this purpose.
The pieces of any shape and size of polymer to be treated by the biting bath, are immersed therein for a time between 30 seconds and one hour or preferably between 1 minute and 45 minutes or more preferably between 2 minutes and 30 minutes.
After the biting process referred to in the present invention, the necessary washing steps are carried out with water, aqueous solutions or organic liquids of known characteristics in the current state of the art.
After washing, the necessary processes are performed to obtain the metallic coating of required characteristics, whether wet processes or dry processes.
Alternatively, after washing, the pieces may or may not be dried if polymeric coatings such as varnishes or paints are to be carried out on the treated parts.
EXAMPLES
The substrates used referred to in the following examples are substrates obtained by injection of the corresponding thermoplastic polymer: ABS, ABS-polycarbonate, polyamide 6, polyamide 6 with 20% inorganic filler wollastonite, polypropylene or 5 polypropylene with inorganic filler 20% talc.
In the case of thermostable type substrates, they are cured by methods known in the state of the art and are: unsaturated polyester resin with 40% glass fiber and epoxy resin with 40% glass fiber.
In all cases, the substrate is washed before being bitten. Washing 10 is carried out by immersion in water bath, 1% aqueous sodium dodecyl sulfate solution bath and two subsequent rinses by immersion in two water baths. The prewash is intended to remove dirt and grease from the substrates and / or prepare the surface for biting. Depending on the process of preparing the pieces, this washing can be avoided
15 The treatment of biting is carried out with the corresponding baths presented in the following examples.
After the biting process, two successive rinses are carried out by immersion in water baths.
Once the polymer has been bitten, the deposition of autocatalytic chemical nickel 20, also known as chemical nickel, is performed by a process known in the state of the art:
Immersion treatment in activating bath at 25 ° C for 2 minutes. Rinse in water bath. Accelerator bath treatment at 25 ° C for 2 minutes. Rinse in water bath. Immersion bath for chemical nickel plating at 29 ° C for 8-25 min. Two washes by immersion in water bath.
Similarly, once the biting has been carried out and the substrates dried, the polymer coating is carried out by means of an organic base coating or paint.
EXAMPLE 1
As a reference on the results obtained in the Biting process, the biting process is performed in a bath based on the use of Cr (VI) salts with the following composition:
The biting bath contains 380 g / L of chromic acid and 400 g / L of concentrated sulfuric acid.
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The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 2:
Biting bath based on Cr (III) salts, in which the chromium-coordinated ligand is acetate and is prepared by a solution of 62% H2O; 4% chromium (III) acetate; 34% H2SO4;
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 3:
Biting salt based on Cr (III) salts, in which the chromium-coordinated ligand is benzoate and is prepared by a solution of 40% H2O; 3% chromium (III) benzoate; 57% methanesulfonic acid;
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 4:
Biting salt based on Cr (III) salts, in which the chromium-coordinated ligand is glycinate and is prepared by a solution of 21% H2O; 2.5% chromium glycinate (III); 65.5% H2SO4;
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 5:
Biting salt based on Cr (III) salts, in which the ligand that coordinates to chromium is aminohexanoate and is prepared by a solution of 21% H2O; 2.2% CrCl3-6H2O; 1.3% aminohexanoic acid; 36.5% H3PO4 (75% in water); 39% H2SO4;
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 6:
Biting bath based on Cr (III) salts, in which the ligand that coordinates to chromium is citrate and is prepared by a solution of 17% H2O; 1.2% Cr (NO3) 3.9H2O; 2.6% citric acid; 39.7% H3PO4 (75% in water); 39.5% H2SO4;
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
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EXAMPLE 7:
Biting salt based on Cr (III) salts, in which the ligand that coordinates to chromium is triethylene tetratraamine and is prepared by a solution of 19% H2O; 0.8% Cr (NO3) 3.9H2O; 1.1% triethylenetetraamine; 38.4% H3PO4 (75% in water); 40.7% H2SO4;
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 8:
Biting salt based on Cr (III) salts, in which the chromium-coordinated ligand is thiodipropionate and is prepared by a solution of 18.5% H2O; 0.7% CrCl3-6H2O; 0.9% thiodipropionic acid; 38% H3PO4 (75% in water); 41.9% H2SO4. The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 9:
Biting salt based on Cr (III) salts, in which the ligand that coordinates to chromium is ethylenediamine teraacetate (EDTA) and is prepared by a solution of 18% H2O; 0.6% Cr (NO3) 3.9H2O; 0.3% ethylenediaminetetraacetic acid; 39.7% H3PO4 (75% in water); 41.4% H2SO4. The pieces to be bitten into the bath for 3 minutes at a temperature of 25 ° C.
EXAMPLE 10:
Biting salt based on Cr (III) salts, in which the chromium-coordinated ligand is ethylenediamine teraacetate (EDTA) and which is prepared by a solution of 18.3% H2O; 0.6% Cr (NO3) 3.9H2O; 0.5% disodium acid salt
ethylenediaminetetraacetic; 39.2% H3PO4 (75% in water); 41.4% H2SO4. The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 11:
Biting salt based on Cr (III) salts, in which the chromium-coordinated ligand is ethylenediaminetetraacetate (EDTA) and which is prepared by a solution of 18% H2O; 0.6% Cr (NO3) 3.9H2O; 0.3% ethylenediaminetetraacetic acid; 39.7% H3PO4 (75% in water); 41.4% H2SO4. The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 40 ° C.
EXAMPLE 12:
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Biting salt based on Cr (III) salts, in which the ligand that coordinates to chromium is ethylenediamine teraacetate (EDTA) and is prepared by a solution of 18% H2O; 2% Cr (NO3) 3.9H2O; 1% ethylenediaminetetraacetic acid; 35.5% methanesulfonic acid (75% in water); 43.5% H2SO4. The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 13:
Biting bath based on Cr (III) salts, in which the chromium-coordinated ligand is fumarate and is prepared by a solution of 18% H2O; 0.6% Cr (NO3) 3.9H2O; 0.3% smoking acid; 39.7% H3PO4 (75% in water); 41.4% H2SO4.
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 14:
Biting salt based on Cr (III) salts, in which the ligand that coordinates to chromium is oxalate composed of a solution of 18% H2O; 0.9% Cr (NO3) 3.9H2O;
0.6% oxalic acid H2C2O4.2H2O; 39.7% H3PO4; 40.8% H2SO4. The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 15:
Biting bath based on Cr (III) salts, in which the chromium-coordinated ligand is oxalate composed of a solution of 17.7% H2O; 1.2% Cr (NO3) 3.9H2O;
0.6% oxalic acid H2C2O4.2H2O; 39.7% H3PO4 (75%); 40.8% H2SO4. The pieces to bite are introduced into the bath for 15 minutes at a temperature of 25 ° C.
EXAMPLE 16:
Biting broth based on Cr (III) salts, in which the chromium-coordinated ligand is salicylate and which is prepared by a solution of 18% H2O; 0.6% Cr2O3;
0.8% salicylic acid; 39.7% H3PO4 (75% in water); 40.9% H2SO4. The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
EXAMPLE 17:
Biting broth based on Cr (III) salts, in which the chromium-coordinated ligand is salicylate and which is prepared by a solution of 18% H2O; 0.6% Cr2O3;
0.8% salicylic acid; 39.7% H3PO4 (75% in water); 40.9% H2SO4. The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 60 ° C.
EXAMPLE 18:
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Biting salt based on Cr (III) salts, in which the chromium-coordinated ligand is gluconate and which is prepared by a solution of 18% H2O; 0.6% Cr2 (SO4) 3-H2O; 2% sodium gluconate; 38% H3PO4 (75% in water); 41.4% H2SO4;
The pieces to bite are introduced into the bathroom for 3 minutes at a temperature of 25 ° C.
The metallic parts are subjected to the Adhesion test by means of the lattice cut test (ISO 2409), which is one of the methods commonly used to determine the adhesion of coatings on polymers. The adhesion result is rated from 0 to 5, 0 being an excellent adhesion and the peeling method following DIN 53494.
The results of adhesion of the metallic layer obtained after biting and metallizing the pieces are shown in the following table:
 BATH EXAMPLE  ISO 2409 POLYMER AVERAGE FORCE PER N / cm
 Example bathroom 1  ABS 0 8.5
 Example bathroom 1  ABS-polycarbonate 0 4.3
 Example bathroom 1  Polyamide 6 1 2.2
 Example bathroom 1  Polyamide 6 with 20% wollastonite 0 3.2
 Example bathroom 1  Polypropylene 4 0.4
 Example bathroom 1  Polypropylene load 20% talc 4 0.6
 Example bathroom 1  Unsaturated polyester fiberglass 1 2.1
 Example bathroom 1  Epoxy fiberglass 0 3.1
 Example bathroom 2  ABS 0 7.4
 Example bathroom 2  ABS Polycarbonate 0 3.8
 Example bathroom 3  ABS 0 8.1
 Example bathroom 3  ABS Polycarbonate 0 4.2
 Example bathroom 4  ABS 0 7.9
 Example bathroom 4  ABS-polycarbonate 0 4.4
 Example bathroom 4  Polyamide 6 2 1.6
 Example bathroom 4  Polyamide 6 with 20% wollastonite 1 2.5
 Example bathroom 5  Unsaturated polyester fiberglass 2 1.3
 Example bathroom 5  Fiberglass epoxy 0 4.7
 Example bathroom 6  ABS 0 7.3
 Example bathroom 7  ABS 0 6.9
 Example bathroom 8  ABS 0 6.6
 Example bathroom 9  20% polypropylene talc 3 0.9
 Example bathroom 10  Polypropylene 20% talc 3 0.8
 Example bathroom 11  20% polypropylene talc 4 0.6
 Example bathroom 12  Polypropylene 20% talc 4 0.5
 Example bathroom 13  ABS 0 8.2
 Example bathroom 14  ABS 0 8.0
 Example bathroom 14  ABS Polycarbonate 0 4.9
 Example bathroom 14  Polyamide 6 with 20% wollastonite 0 3.7
 Example bathroom 14  Polypropylene load 20% talc 3 1.0
 Example bathroom 15  ABS 0 7.9
 Example bathroom 16  ABS 0 7.5
 Example bathroom 17  ABS 0 7.5
 Example bathroom 18  ABS 0 7.7
The parts covered with paint or organic coating are prepared after treatment of the bath by drying in a stream of air at 40 ° C for 2 hours and subsequent coating by airbrush. The paint used is of the standard type called 5 100% solids based on triethylene glycol diacrylate and UV curing that is applied according to
manufacturer recommendations
The adhesion results of the paint submitted to the ISO2409 test:
 BATH EXAMPLE  ISO 2409 POLYMER
 Example bathroom 1  20% polypropylene talc 3
 Example bathroom 2  20% polypropylene talc 3
 Example bathroom 3  20% polypropylene talc 3
 Example bathroom 10  20% polypropylene talc 3
 Example bathroom 11  20% polypropylene talc 3

权利要求:
Claims (10)
[1]
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1. A formulation of acid etching of polymeric materials, both thermoplastic, thermosetting or elastomeric, through a chemical process based on the use of Cr (III) coordination complexes and whose purpose is its subsequent metallization or coating.
[2]
2. A formulation of acid biting baths of polymeric materials to achieve their subsequent metallization or coating according to claim 1 wherein the chromium (III) complex is based on the use of at least one or more mono, bi, tri ligands , tetra, penta, hexadentates or bridge that are coordinated to chromium by the oxygen, sulfur or nitrogen atom or several of these atoms.
[3]
3. A formulation according to claim 2 wherein the ligands are found between
formate, acetate, propanoate, buatanoate, benzoate, phenylacetate, phenylpropionate, cyanamate, alkylbenzoates, pyruvate, levulinate, citrate, isocitrate, aconitate, trimellitate, glycinate, valinate, leuccinate, threonate, lysinate, trypinate, arcinate, titinate methioninate, alaninate, prolinate, serinate, cysteinate, asparaginate, glutamine, tyrosinate, aspartate, polyaspartate, glutamate, cysteinate, homocysteinate, ornithinate, nicotinate, oxalate, propanedioate, butanedioate, pentanodiolate, hexatolate, phthalate, tetanodiolate, maleate tartrate, itaconate, mesaconate, citraconate, glycolate, lactate, mandelate, salicylate, gluconate, ethylenediamine tetraacetate, nitrilotriacetate, iminodisuccininate, ethylenediamineadisuccinate, methylglycinate acetate, N, N, diacetate, glutamate acetate
diethylenetriamine pentaacetate, aminoethylethylene glycol tetraacetate,
trietilentetraminahexaacetato, dihidroxietilglicinato, iminodiacetate, oxamate, nitrilotripropionato, etilenodiaminadipropionato thiodipropionate, ditiodipropionato, aminopropanoate, aminopentanoate, aminohexanoate, 2-aminobenzoate, 3- aminobenzoate, 4-aminobenzoate, 3-cyclohexylamino-propylamine, ethylenediamine, 1,3-diaminopropane, dimetilaminopropilamine, diethylaminopropylamine, bis (3- aminopropyl) -methylamine, diethylenetriamine, dipropylenedriamine, triethylenetetramine, tetraethylenepentamine, polyamines, 3- (2-aminoethyl) amino-propylamine, N, N'-bis (3- aminopropyl) ethylenediamine, neopentanediamine, cyclohenediamine -1,6-diamine, imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2- ethylimidazole, 2-ethyl-4-methyl-imidazole, N- (3-Aminopropyl) -imidazole, pyrazole, nicianamide , bipyridine, phenanthroline, preferably: formate, acetate,
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propionate, glycinate, argininate, aspartate, polyaspartate, glutamate, nicotinate, oxalate, propanodioate, butanedioate, pentanedioate, hexanedioate, maleate, fumarate, phthalate, salicylate, tartrate, citrate, glycolate, ethylacetate, glutamate, nitrateacetate, glutamate, nitrateacetate, glutamate, nitrateacetate, glutamate, nitrateacetate, glutamate, nitrateacetate, glutamate, nitrateacetate, glutamate, nitrateacetate, glutamate, nitrateacetate, glutamate acetate more preferably oxalate, propanedionate, butanedionate, maleate, fumarate, phthalate, glycolate, lactate, salicylate, glycinate, glutamate or mixtures thereof.
[4]
4. A formulation according to claims 1 to 3, wherein the concentration of the Cr (III) complex is in the range of 2 mM and 2 M and more preferably between 5 mM and 1 M and even more preferably between 0.01 M and 0.4 M.
[5]
5. An acid biting formulation to achieve metallization or coating
of polymeric materials according to claim 1 to 4 in which the acids may be sulfuric acid, aminosulfuric acid (sulfamic), phosphoric acid, diphosphoric acid, metaphosphoric acid, polyphosphoric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzene sulfonic acid
toluenesulfonic acid, cumenesulfonic acid, alkylbenzenesulfonic acids, monoalkyl phosphoric acids, dialkylphosphoric acids, isethionic acid, perchloric acid, chloric acid, nitric acid, trifluorometasulfonic acid, trifluoroacetic acid, heflorophoretic acidic acid, hydrofluorophonic acid, hydrofluorophonic acidic acid, hydrophobic acidic acid, hydroxophloric acidic acidic acidic acidic acidic acidic acidic acidic acidic acidic acidic acidic acid; preferably sulfuric acid, phosphoric acid, diphosphoric acid, metaphosphoric acid, polyphosphoric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, acid
toluenesulfonic acid, cumenesulfonic acid, alkylbenzenesulfonic acids, monoalkyl phosphoric acids, dialkyl phosphoric acids or mixtures thereof and more preferably: sulfuric acid, phosphoric acid or mixtures thereof.
[6]
6. A formulation of acid etching to achieve the metallization or coating of polymeric materials according to claim 5 wherein the percentage by weight of acids is between 20 and 98% and more preferably between 40 and 95% and even more preferred between 55% and 92%.
[7]
7. A formulation according to claims 1 to 6, wherein the working temperature is between 10 ° C and 95 ° C, more preferably between 15 ° C and 80 ° C and even more preferably between 20 ° C and 70 ° C
[8]
8. A formulation according to claims 1 to 7, wherein the biting time is between 30 seconds and 1 hour, more preferably between 1 minute and 45 minutes and even more preferably between 2 minutes and 30 minutes
[9]
9. Use of the formulation of claims 1 to 8 which allows the metallization of polymeric materials by chemical methods.
[10]
10. Use of the formulation of claims 1 to 8 which allows the painting, varnishing or coating of polymeric materials by means of paints or coatings of
5 organic base.

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同族专利:

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公开号 | 公开日

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LT3565915T|2021-04-26|

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ES2868080T3|2021-10-21|

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EP3848483A3|2021-11-03|

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ES2646237B2|2018-07-27|

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US20200080203A1|2020-03-12|

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EP3689477A1|2020-08-05|

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BR112020006241A2|2020-10-06|

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WO2019063773A1|2019-04-04|

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EP3565915A1|2019-11-13|

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EP3848483A2|2021-07-14|

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EP3689477A4|2021-08-11|

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US20200255947A1|2020-08-13|

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WO2019063859A1|2019-04-04|

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JP2020537713A|2020-12-24|

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CN111201091A|2020-05-26|

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JP2020535322A|2020-12-03|

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US20190136381A1|2019-05-09|

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JP2021183724A|2021-12-02|

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BR112020006236A2|2020-10-06|

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KR20200063175A|2020-06-04|

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KR20200096486A|2020-08-12|

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