• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1394164 Amine complexes SCHERING AG 27 March 1972 [30 March 1971] 14161/72 Heading C2C [Also in Division C7] A complex compound for activating substrates prior to electroless coating has the formula M-(L) x -A where M is Pd, Pt, Ag, Au, Os, Ir, Rh or Ru, L is an organic nitrogen containing radical, x is an integer of at least 1, and A is an organic or inorganic acid radical. L may be aliphatic and cycloaliphatic mono-, di- and polyamines, aromatic mono-, di- and polyamines, heterocyclic mono-, di- and polyamines. Many examples of amines are described. A may be chloride, sulphate, phosphate, nitrate, perchlorate, acetate, propionate or oxalate.
    公开号:SU747437A3
    申请号:SU782562407
    申请日:1978-01-05
    公开日:1980-07-23
    发明作者:Эрих Ханс-Юрген；Клаусс Вольфганг；Малков Хартмут
    申请人:Шеринг Аг (Фирма)；
    IPC主号:
    专利说明:

    Compound of gold or precious metal VIM of the periodic system of elements with pyridine or 2-amino-pyridine or pyridine-3-sulfonic acid, having the structural formula Me- (L) x-- A, where Me is gold or a noble metal from VI11 groups of the periodic system of the elements., py-pyridine, 2-aminopyridine and 3-sulfopyridine, A - chlorine ion, X - NUMBER; 2-4 with the following content of components: Complex compound of gold or noble chloride: meta group Vi f I group, periodic system of elements with pyridine or 2-aminopyridine or pyridine-3-sulfonic acid, g-0.5-1 Solvent, l - to 1 Alkali metal hydroxide to pH 6.4 It is especially beneficial if the solution for enhancing the adsorption of the noble metal complex on the synthetic material contains an additional soluble organic polymer compound, preferably with Eev protein or polyethyleneimine in concentrate radios from about 0.01 g / L to the solubility limits. If the high polymer compound contains N-containing ligations for complexation with noble metals, it can replace the above-mentioned low molecular weight complexes and, under known conditions, the property of increasing adsorption can be combined with the properties of complexation. These high molecular weight N-containing compounds naturally do not form single complex compounds. In their preparation, a lower ratio of metal to N-containing compound is chosen, at least as the maximum coordination number of the noble metal to chrome p monomeric units having one N-ligand. The solution is prepared as follows. First, a complex connection of the noble metal is obtained. Complexes with palladium: a) dichloro-2,2-dipyryl-palladium (11) (Pd / CjH N-CS Nd N / Cf2) is formed from 0.5 g of dipyridyl in 30 ml of alcohol and 0.9 g (NH) 2 . in 10 ml and 50 ml of alcohol due to heating. From this solution, crystals of the desired compound are formed upon cooling; b) dichloro-bisCh2-aminopyridine; -palladium- (I G) (Pd / Cj H N-NH / cpj) or dichloro-tetradis (2-aminopyridine) -palladium - ((1) (Pd / CgН N-NHjД CCе ) are formed by combining a concentrated KjPdCK aqueous solution with 2 or 4 moles of 2-aminopyridine. Complexes with platinum: a) dichloro-dipyridine-platinum (I i) (P t / C HgN / j Cfg). A solution of 10 g of pure KpPtCf in 100 ml of cold water is mixed with a solution of 3.7 g of pyridine in 25 ml of water and left for 24 hours; the precipitate formed is washed with cold water and air dried; b) dichloro-tetrapiridine-platinum- (I) (Pt / CsH MD C) is prepared by heating P t (C,) C with an excess amount of pyridine and subsequent evaporation of the solution at room temperature; c) dichloro-bis- (2-aminopyridine) -platin-11 / (P1 / C5H4 -NH2 / 2 CP2). A solution of K2 (PtCf4) (1 mol) in a small amount of water is mixed with exactly 2 moles of 2-aminopyridine in an aqueous solution. After 23 hours, the compound begins to precipitate as a yellow, yellow-green precipitate. The precipitate is washed with a small amount of water. d) dichloro-tetrakis- (2-aminopyridine) -platinum (II) (P t / C Nl-NN2 / 4 Cf). To obtain dichloro-bis (2-aminopyridine) platinum- (II) is treated with an excess of 2 -aminopyridine in a small amount of water and heated for 5-6 hours in a water bath. After concentration under slight vacuum, the desired compound precipitates gradually. Complex with rhodium: trichloro-tri-pyridine-rhodium (III) (RH / CS HS N / d CEj. To obtain in a water bath, 3 g x 12 HjO and 2.4 g pyridine are heated with 12 ml of water, first of all dropping out the oil slowly crystallizes. Crystals can be purified by recrystallization from alcohol. If the tripyridine compound is heated for a long time in pyridine, trichloro-tetrapypyridine-rhodium (II) is obtained. Ruthenium complex: ruthenium (III) dichloro (Ru / CgHgN / CPj) is formed by boiling ammonium chlorine ruthenate- (III) in pyridine for many hours. When cooled to crystallize yellow crystals. Complex with iridium: trichloro-tripyridine-iridium- (I) (Ar / C5 Hg N / - CBj). To obtain, heat the pyridine CEG / Cb HS / 2 C, which can be obtained from pyridine / HgO, and x several hours in a water bath. Yellow crystals slowly precipitate during the reaction. Osmium complex: perchlorate-three (-2,2-dipyridine-osmium- (1I) (0s / / 05 Н, N / J CFF. Lmmonihexabrom -OGMaT- (lV) is heated in a water bath in the presence of sodium tartrate and 3 moles of dipyridine. To isolate the complex, the reaction solution is mixed (supplied) with perchloric acid, after which the desired compound crystallizes. Complex with gold: trichlor-dipyridine-eoloto (Li / SdN / S, CCj). to the ether solution of gold chloride- (II pyridine is added dropwise, and immediately a yellow precipitate falls, which can be recrystallized from alcohol. Other complex compounds can be prepared in the same way. The complex compounds thus obtained are dissolved in water. The complex-soluble compounds dissolve in water in an aqueous solution of caustic soda or potassium, as well as in organic solvents, such as methanol, ethanol or acetic acid. The process of activation in the prepared activating solutions for example, due to simple dipping, activating materials into these solutions at temperatures from about 0 to up, preferably from. The duration of the α-activation process depends on the type of material being activated and can be from about 0.5 to 20 minutes. treated with an activating solution, are introduced into a recovery solution that reduces noble metal ions to a metal. As a reducing agent, especially dimethylaminoborane, nat iyboranat, hydrazine and alkali metal hypophosphite, e.g. natriygipofosfit. Using the invented solutions, it is possible to activate the surface of the formation of masses based on acrylonitrile-butadiene styrene polymers (LVS polymers), propylene floor, epoxides glass-reinforced epoxides. Adding in soluble polymeric organically compounds to the invented solution, an unexpected increase in the adsorption of these complexes is obtained, which precipitate due to their greater affinity for the plastic, preferably on its surface and does not precipitate on the metal. The proposed solutions are suitable for activating molded plastic products or, in particular, copper-laminated base materials used in the manufacture of printed circuits. The following activating solutions were tested. Example 1. Take 0.34 g of PdCfj and 1.28 g of pyridine-2-sulfonic acid; topped up to 1 liter with water; pH of the solution: 2.2 with NaOH set at 7. Example 2. 0.34 g of PdCpj and 0.95 g of 2-amine-pyridine, up to 1 liter with water; pH of the solution: 6.4; the addition of 0.2 g of soy protein. Example 3. Take 0.34 g PdCCj and 0.14 g NH; Topped up to 1 liter with water, solution pH: 7.0; the addition of 0.2 g of soy protein. Example 4. This is 0.28 g and 0.62 g pyridine; topped up to 1 liter with water; pH of the solution: 3.3; using NaOH set at 7.0. Copper-lined base plates of cured phenolic resin or glass-fiber-reinforced epoxy resin served as the starting material. For the purpose of the subsequent formation of the conductor, these plates are stamped or drilled and cleaned or pickled by one of the known methods in order to preliminarily prepare the surface of the inner wall of the channel opening to adsorb the activator. After thorough washing in water, the material was immersed for 5 minutes at 60 ° C in a solution, the coatings according to examples 1-4 were washed again and for 1-3 minutes at 40 ° C were exposed to a reducing agent, for example, 1% sodium hypophosphite or dimethylaminoborane solution . After that, they were again washed in water and were metallized in a known manner without current in a chemical copper bath. This formed a copper layer growing from the nuclei (nuclei) of noble metals, which can then be electroplated. The resulting metallic coatings show exceptional electrical conductivity and adhesive strength. To prove the higher stability of the invented solution compared to the known solution 2, the following experiments were carried out. The following solutions were prepared in accordance with the invention: 1) 0.34 g 1.28 g pyridine-3-sulfonic acid. The volume of the solution was brought to 1 liter with water. At the same time, its pH was 2.2. Then, the pH of the solution with NaOH was set equal to 7. 2) 0.34 g PdCE, JI 0.95 g 2-aminopyridine. The volume of the solution was adjusted to 1 liter of water, the pH of the solution was 6.4K. 0.2 g of soy protein was added to the solution. 1 g of metallic copper in the form of copper shavings was added to each of the cooked thieves. Once a week, an analysis of the thief was carried out. After 6 weeks, the composition of the solution remained unchanged, after which the experiment was terminated. A known solution of the following composition was prepared: 1.5 g / l 1.2 ml / l NH OH. 1 g of metallic copper in the form of copper shavings was added to this solution. It was established that immediately after the addition of metallic honey, precipitation of metallic copper and silver metallic sedimentation occurred, as a result of which the solution was completely unsuitable for consumption. Thus, the invented solution is more stable than the known one. Forg / tula of the invention A solution for activating a non-metallic surface prior to chemical metallization, including an amine-containing complex compound of a noble metal and a solvent, which in order to increase the stability of the solution, it additionally holds an alkali metal hydroxide. . The property of the amine-containing complex noble metal compound - a compound of chloride from an or noble metal of the periodic system of elements of pyridine or 2-amino-pyridiyl or pyridine-3-sulfonic acid o, having the structural formula MEK L) x -A: -Not - gold or a noble metal from group VIII of the periodic table, L - pyridine, 2-aminopyridine or 3-sulfopiridin, chlorine ion. the following contents of the components; Complex compound of gold chloride or a noble metal of the VIII group of the periodic system of elements with pyridine or 2-aminopyridine or pyridine- 3-sulfonic acid, g -0.05-1 Solvent, l-up to 1 Alkali hydroxide to pH 6.4-7. Sources of information that are considered in the examination 1. Rozovsky G.I. and Bashk Lis A.I. Copper plating. Vilnius, Intut Chemistry and Chemical Technology of the Lithuanian SSR, 1966, p. 12-13. 2.M. Matsunaga etc. Adhesion of ctrodeposition to Pfastis. taE Finishing, v. 66, No. 11, 8, p. 80-84.
    权利要求:
    Claims (2)
    [1]
    Claim
    A solution for activating a nonmetallic surface before chemical metallization, comprising a 30 amino-containing complex compound of a noble metal and a solvent, characterized in that, in order to increase the stability of the solution, it additionally contains alkali metal hydroxide, and as an amino-containing complex compound, noble metal - a compound of gold chloride or a noble metal of group VI11 of the periodic system of elements with pyridine or 2-amino-pyridine or pyridine-3-sulfonic acid oh having a structural formula
    Me- (L) x -A, where: Not - gold or a noble metal from group VIII of the periodic system of elements,
    L is pyridine, 2-aminopyridine or 3-sulfopyridine,
    A is a chlorine ion,
    X is the number 2 or 4, with the following components: Complex compound of gold chloride or a noble metal of group VIII of the periodic system of elements with pyridine or 2-aminopyridine or pyridin-3-sulfonic acid, g Solvent, l Alkali metal hydroxide
    Sources
    - 0.05-1
    - up to 1 to pH = 6.4-7.
    information taken into account during the examination
    1. Rozovsky G.I. and Vashkyalis A.I.
    Chemical copper plating. Vilnius, Institute of Chemistry and Chemical Technology
    Academy of Sciences of the Lithuanian SSR,
    [2]
    2.M. Matsunaga Electro de ro si t i on Me taE Finishing 1968, p. 80-84.
    1966, c. 12-13. etc. Adhesion of to PEastis.
    v. 66, No. 11,
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    同族专利:
    公开号 | 公开日
    IE36236L|1972-09-30|
    DE2116389A1|1972-10-26|
    CH587878A5|1977-05-13|
    BE781483A|1972-10-02|
    AT314934B|1974-04-25|
    GB1394165A|1975-05-14|
    CA975503A|1975-10-07|
    IT956226B|1973-10-10|
    GB1394164A|1975-05-14|
    FR2132172A1|1972-11-17|
    SE7502045L|1975-02-24|
    ZA722182B|1972-12-27|
    DK144767C|1982-10-25|
    US4248632A|1981-02-03|
    FR2132172B1|1976-08-06|
    NL175533B|1984-06-18|
    ES400886A1|1975-01-16|
    IE36236B1|1976-09-15|
    NL175533C|1984-11-16|
    SE396233B|1977-09-12|
    NO132103C|1975-09-17|
    DE2116389B2|1979-08-02|
    IE36235B1|1976-09-15|
    NL7204414A|1972-10-03|
    IE36235L|1972-09-30|
    DK144767B|1982-06-01|
    DE2116389C3|1980-04-03|
    JPS5234573B1|1977-09-03|
    NO132103B|1975-06-09|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2116389A|DE2116389C3|1971-03-30|1971-03-30|Solution for activating surfaces for metallization|
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