JPS58130295A - Pattern electroplating method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a patterned electroplating method for forming an electroplated film having an uneven pattern.

Conventionally, as a method for obtaining a plated product tube with an uneven vertical pattern T-, the material HLIIi! , processing, printing methods, casting methods, electroforming methods, engraving methods, etching methods, etc. are known. However, all of these methods are mechanical, physical methods, or chemical methods. Even if there were, a sealer or caster was required for the object to be plated. Therefore, the process of forming three-dimensional patterns is complicated,
In addition, it requires a considerable amount of labor and effort, and patterning requires materials and equipment, resulting in high costs. Furthermore, when using the press method or injection molding method, there are restrictions on the materials that can be patterned, and the precision of the pattern is not fully satisfactory.

The present invention has been made in view of the above circumstances, and uses a general electroplating method to easily and reliably produce a ring-like, highly effective electrolytic plate with an uneven pattern without requiring any mechanical processing or the like. The object of the present invention is to provide a patterned electroplating method capable of forming a plating film.

That is, in order to achieve the above objects, the present invention includes one or more compounds selected from phosphorous acid, hypophosphorous acid, and metal salts thereof f 0.01 to IP/l # 7 in an electroplating bath.
10 and 1 selected from alcohols and sulfonates each having one or more C=C bond tubes in one molecule.
To provide a patterned electroplating method in which an electroplated film having an uneven pattern is entirely released, which is characterized by adding at least one compound i of 0.05 to 1 P/1 and performing electroplating using this bath. It is.

In addition, conventionally, 10, 5 using phosphorous acid or hypophosphorous ff
~20 Strongly acidic electrolytic nickel-phosphorous alloy plating method is known, but this bath usually contains phosphorous acid or hypophosphorous W&
011/1 or more, which is considerably higher than the concentration of phosphorous acid or hypophosphorous acid in the electroplating bath used in the method of the present invention, and which has a surface roughness that is the object of the present invention from this known nickel-phosphorus alloy plating bath. A patterned plating film cannot be obtained. In the present invention, 0.03 to 11! A small amount of phosphorous acid or hypophosphorous acid, or a metal salt thereof, is used in combination with an alcohol or sulfonate containing 2-butyne-1,4, and a patterned plating film with an uneven pattern is obtained for the first time. This is a new finding by the inventors of the present invention.

The present invention will be explained in more detail below.

The plating baths used in the pattern electroplating method according to the present invention include acidic nickel plating baths, nickel-cobalt alloy plating baths, nickel-iron alloy plating baths, cobalt plating baths, and cobalt alloy plating baths. Suitably used.

The type of plating bath is not particularly limited, and may include Watt type bath, high chloride bath, low metal ion concentration bath, sulfur iy@
A variety of baths, fluoride baths, etc. can be used, but I/
IIK A bath having the following composition is suitable.

Nickel ion 20~130P/1 Nickel chloride (as hexahydrate) θ~100 #sulfur Cobalt (as heptahydrate) 0~100 1 Sulfuric acid chart-iron (as heptahydrate) 0-1001iFI II!
P)'1 of the 20-501 plating bath is acidic, preferably 2-6, particularly 3-5.

The present invention provides Jal or two or more of phosphorous acid, hypophosphorous acid, and metal salts thereof (for example, sodium group ring) in the bath, and an alcohol and a sulfone each having one or more C═C bond in the molecule. One or more types of acid salts are added to the bath, and electroplating is performed using this bath.

In this case, alcohols and sulfonates each having one or more C=C bonds in the molecule include 2-butyne-1,4-diol (HO-CHI-C=C-C-OH), its derivatives , for example, HO-C City Kumi IIC City-〇-C City Kumi C Jin-OH.

HO-C)it-C=C-CL-0-CH2-C3C@
[1-i)-C)It-C:C-C-OH.

HO-C)lI CHI -0-CHs -C=C-C
) It -0-CHs CHI -OR.

HO-C City, C-Yor-C'H2-0-C-OH-C City OH, etc., and 10 Tsuyagyl alcohol and its derivatives.

74ch L/y system 7 Lej - Le, H-C=C-CL-8
Acetylene sulfonates such as OsNa are exemplified, but butynediol and its derivatives (particularly butynediol in the two- and three-diol forms) are particularly preferred. By using tindiol, its 2tK, trimer, a wide current v1! It is possible to obtain a patterned plating film with irregularities within a range of degrees.

In this book, the amount of the compound selected from phosphorous acid, hypophosphorous acid, and metal salts thereof added to the plating bath is 0.01-I PI3. More preferably 0.05~
0.5 F/j, the amount of addition of a compound having one or more C30 bonds in the molecule is 0.05 to 1 P/l, more preferably 0.2 to 0.7 P/l. It's necessary,
If the amount added is outside the above range H, a good uneven patterned plating film cannot be obtained.

When electroplating is carried out in a plating bath with the addition of the above-mentioned additives, the plating temperature and average cathode current density are not particularly limited, but the usual temperature is 20 to 70°C.

Plating bath 0811111 in the range H of average cathode current density f O,tll ~ 30 A/υ. Appropriate selection will be made depending on the purpose etc. The electroplating bath to which the above-mentioned additives have been added has an average cathode current fa of 0. An uneven pattern occurs in the range of O1 to 30 Ald&, and the film thickness of the convex part is about 1.5 to 2% at 1%.
A clear pattern is formed above Am. In this case, thickening is possible, and the pattern will not disappear even if it is thickened.

In addition, as a power source for plating, a DC power source, a pulse power source, an AC/DC combined power source, and a pulsating current power source can be used, and in addition to the normal TIER, a waveform electric current R1- can be used for plating.

Further, although the above-mentioned matting bath to which the following additives have been added can be operated without stirring, it is preferable to fluidize the plating bath by an appropriate method or to move the article to be plated using a rocking ring. In this case, air agitation, liquid agitation using a stirrer such as an inflator agitator, a liquid flow method using a lunder, a liquid vibration method using ultrasonic waves (C), etc. can be adopted as the liquid flow method. As a method for moving the article (cathode) to be plated, a quad rocker method, a barrel plating method, a rotating cathode focusing method, etc. can be adopted, and one or more of these liquid flow methods and article shaking methods can be used in combination. By performing plating, a unique pattern is formed depending on the method used, the direction and speed of movement of the liquid and the item, etc.

For example, when phosphorous acid or its salt and butyne diol or its dimer or dimer are combined in a soaking bath under static conditions or with weak air agitation, relatively fine irregularities are alternately repeated. An uneven patterned plating film having an appearance similar to a matte plating film (matte plating film) is obtained. In contrast, the above bath requires air agitation or strong air agitation to the extent that is used in normal bright nickel plating methods. When agitation is applied twice, a textured pattern appears.

For example, a patterned plating film consisting of repeated linear or curved concave and convex portions with a width of about 0.1 to 2111 cm and a length of about 2 to 1Q cm can be obtained. In this case, the high current density f
The width between the protrusions becomes narrower as the flow of the plating solution becomes gentler.

Furthermore, when normal or strong air agitation is applied to a plating bath to which hypophosphorous acid or its salt and gutinol or its dimer or dimer are added, the moth will be about 01 in width →, -
A pattern with a length of about 0.3 to 2 tm consisting of repeated linear or curved depressions and protrusions is formed. The distance is small, and the pattern formed by the unevenness is smaller, giving a pattern with a darker tone.

In the plating bath used in the method of the present invention, if necessary, a primary brightener for ordinary nickel plating or nickel alloy plating, such as naphthalene monosulfone powder, J, 5-
, 1.6- , 2.5-naphthalene disulfone sodium chloride, J, 3.6- , 1.3.7- sodium trisulfonate, sodium benzenesulfonate sulfonic acids, penzenosulfone 7miP, 7 $9) Sulfonic acids such as luenesulfonamide V, sulfonimides such as dibenzenesulfonamide, saccharin sodium, sulfinic acids, sulfones, etc. can be used alone or in combination. Please note that other secondary brighteners include arylsulfonic acids, vinylsulfonic acids, chloral hydrate and its derivatives, ethylene cyanohydrin and its derivatives, thiourea and its derivatives, azo dyes, Coumarin, formalin, etc. can be used alone or in combination.

The additive MJI of these brighteners is 0. O1~IP/
It is preferable to set it to 1.

Additionally, a bit inhibitor and a wetting agent may be added to the plating bath.

Furthermore, the plating bath of the present invention may contain known additives for forming a satin plating, and as other additives for forming a satin plating, the following formula (al (where R and π are each an organic residue) may be added. (m and n each represent an integer of 1 to 3000. and R
' are 10H group, -0CHI group, -OCm& group, and -0COCHII group, respectively.

is a partially saponified product of I-vinyl acetate, /livinyl lfk
Ether, I-rivinylpyroliton and their combinations 〇-Conductors, copolymers of these combinations to, O1-10
971 can also be added. In addition, as a partially saponified product of vinyl acetate, saponification degree is 65 to 90%, polymerization [
1 to 2200 may be conveniently used, but polymerization &
1 to 550 is more preferable. Nippon Synthetic Chemical Industry Co., Ltd. as a partially saponified product of vinyl chloride
Gohsenol KH-20, Bousenol KH-17
, these oxidized decomposition products with potassium permanganate, etc. can be used. Further, as the polyvinyl methyl ether, polyvinyl methyl ether having a polymerization [10-100 and a molecular weight of 600 to 6000 can be suitably used. For example, as polyvinyl methyl ether, those having a relatively high molecular weight include Lutona 1M40 manufactured by BASF, and /IJ Vinyl manufactured by Tokyo Kasoko Co., Ltd. Methyl ether (30% water bath liquid 0%!
if is 25C and 3400 cp) etc. are used,
Also preferably used are compounds with relatively low molecular weight synthesized from vinyl methyl ether using an organic peroxide as a catalyst. Furthermore, as I-rivinylpyrrolidone, the degree of polymerization is 100.
~360, for example Kollido manufactured by BASF
n 17, 25.30, etc. may be used.

Furthermore, as another semi-gloss or satin finish forming additive, the following formula tb+ -Rs -0-Rr -R-&+E ・
...(bl or the following formula 1et (-0-Rs -0-Rr -Rt÷8...(c
) (However, R is the C city group and the number of carbon atoms is 1.) (RJ is the number of carbon atoms
~3, R3 is a substituted or unsubstituted linear or branched aliphatic saturated hydrocarbon group having 1 to 4 vertical marks and 1 to 6 carbon atoms, and X is 1 to 300o,' is represented by the formula ( 1) and formula (2
Is one I-lyethylene oxide group, ? A mixed addition group of a rideropylene oxy-V group and an ethylene oxy-P group and a propylene oxy-P group is not formed. ) A compound having a 4-reactor bond represented by the following formula (b') or (C') Kl +0-R
1-0-Rt -R- &tKj(b')KJ +0-
Rl-0-Rr-& +xlCs (c
') (However, in the above formulas (b') and (c'), Kl and Ktfl each represent an organic residue or an inorganic residue. Preferably.

K+H is a hydrogen atom or a residue of an aliphatic alcohol, an aromatic alcohol, an aliphatic saturated cardanoic acid, an unsaturated carbanoic acid, or an alkyl or nooxycarboxylic acid, and 1 is a hydrogen atom, a water group, or a fatty acid. group saturated carmenic acid residues (especially acetyl groups). Note that % RIR+, Ra +Ra
, x have the meanings described above. ), the compound shown by
IE precisely, a cyclic ether Ill represented by the following formula td) or the following formula tel 3-0 (wherein R, Rr, R4, and R1 each have the above-mentioned meaning), * is 1.3
-dioquinolane, 1,3-dioxane, 1,3-dioxenoyan, 1,3.5-) rioxane, 1,3.
6-Trioxe/Yang, 1,3.6-) From rioxonane and compounds in which the hydrogen atom of the methylene group on the - or two-line of these compounds is replaced with a lower alkyl group with a vertical number of 1 to 5 or an I/R7 atom Addition of aliphatic alcohols, aromatic alcohols, aliphatic saturated cardanoic acids, unsaturated cal&/acids or alkinooxycarboxylic acids to the open-concentration polymerization group of the selected cyclic ether or to the open-drift polymerization with the selected cyclic ether. 1 H compound is used, and in one molecule, the hydrogen atom of the -C-C-C-C-0-C-C-X-〇- group or the methylene group on the - or two lines of this group is added to the lower level of 5 to 5 vertical marks. Arsenic metals containing groups substituted with alkyl groups or halogen atoms.

Preferably 1r having an average molecular weight of about 10,000 or less, total 0.
01 P/l or more, preferably 0. O1-2
It is also possible to add P/1. In addition, the following are illustrated as aliphatic alcohols, aromatic alcohols, aliphatic saturated cargeno acids, unsaturated cardanic acids, and alkinooxycarmenic acids.

Table 1 Examples of aliphatic alcohols Table 2 Examples of aromatic alcohols Table 3 Examples of aliphatic saturated Cal M y @ 41! Unsaturated car dly @0 example @Table 5 Examples of alkinooxyalkane carmenic acid t+, the plating bath of the present invention includes:
It is also possible to add or suspend the additives described in Japanese Patent Publication No. 43-405 and other inorganic or organic particles to co-deposit these particles.

The above-mentioned material KnQ that should form a well-patterned plating film
It can be applied to steel, iron alloys, copper, steel alloys, nickel, nickel alloys, zinc, aluminum, magnesium, silver, gold, other gold deposits, ABS resin, and other plastic materials without restriction. Predetermined pretreatment in the usual way according to six! 1, the pattern plating method described above may be performed on this. For example, in the case of a metal base as a pretreatment, it is generally possible to employ a method in which the metal surface is degreased with dialkali by a dipping method and/or an electrodrop method, and then neutralized with an acid.

In the case of an aluminum substrate, a method can be adopted in which the surface is activated and then replaced with zinc. In addition, in the case of a glass base material, after roughening the surface of the plastic nack by etching with a chromic acid-*H mixture or mechanical roughening, the roughened plastic nack is A method can be adopted in which the plastic surface is completely metalized by carrying out the process Activation 1 in which a catalytic metal nucleus such as palladium is attached to the surface, and then carrying out electroless plating I such as electroless steel plating or electroless nickel plating.

For items on which a patterned plating coating is to be formed, the patterned coating may be applied directly to the base material, or if necessary, after applying a base plating, the patterned plating coating may be applied on the base plating film.
It may also have an It-shaped bottom.

In this case, the base plating may be iron plating, brass plating, steel plating, or nickel plating (matte).

Strike, semi-bright, bright, satin-like nickel plating, double-layer nickel plating, multi-layer nickel plating such as Sanchi Nickel Plating, etc.), silver plating, solid plating, nickel alloy plating, iron alloy plating, etc. can be selected. .

If necessary, mat is further applied on the patterned plating film described above.
Metal plating, chrome plating, gold plating, chain plating, other precious metal plating, nickel plating, tin plating, tin alloy plating, nickel alloy plating, etc. can be applied.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples.

[Ki IIl Ga 1] Nickel sulfate hexahydrate 280 P/l Nickel chloride hexahydrate 451 Boric acid 40 P/IP) l
4.2 Adding phosphorous acid to the Watt-type nickel plating bath prepared above
Add t50sv//2-butyne-1,4-diol 450 #, respectively, 1111zsoc
, average cathodic current density [3A/dl? ? Plating was carried out for 5 minutes on a mirror-polished brass plate under strong air agitation under the following conditions.

The resulting flecked film has a width of 0.1 to 2 mm and a length of 2 to 40 mm.
It was covered with a beautiful silvery white plating film with a pattern consisting of repeating uneven parts at position a1.

[Example 2] Hypophosphorus 9 501111/12-butyne was added to a Watt-type nickel plating bath having the same composition as in Example 1.
450 g of 1,4-diol was added to each plate, and plating was performed for 5 minutes on a mirror-polished brass plate under strong air agitation under the same conditions as in Example 1.

The resulting frosted coating has a width of 0.05 to 0.5-0 and a length of 0.
．． It was a beautiful, glossy plating film with a pattern consisting of repeating uneven parts of about 3 to zam.

[Example 3] Nickel sulfate - hexahydrate 200 P/1 Nickel chloride @ hexahydrate 30g (jlll)"ruto, heptahydrate 50r boric acid
301, ) 1 4.2 Phosphorous acid 15011 in the nickel leaf/4rut alloy plating bath for the above cordori? /12-butyne-
450 g of 1,4-diol was added to each plate, and plating was carried out in a static bath for 6 minutes on a mirror-polished brass plate under the conditions of a temperature of 50C1 and an average cathode flow density of 3A/4111/.

The resulting hime-zuki coat had a beautiful silvery-white pear-like appearance, consisting of 〈9 turns of approximately 0.1 uta x 0.1 tsuru σ) uneven portions.

[Example 4] Implementation 1'l! Hypophosphorus @ 50 ni 12- in the Nikkeru Kono Kairuto alloy plating bath with the same composition as 3.
1tin-1,4-diol 450I was added to each, and plating was carried out for 5 minutes on a square brass plate, which was mirror-polished under strong air agitation under the same conditions as in Example 3.

The resulting nine-plated film was as beautiful as the dazzling film obtained in Example 2.

[Example 5] Nickel sulfate hexahydrate 320 P/1 salt 1 dinickel hexahydrate 20 1 ferrous sulfate heptahydrate
18 11MH30# PH3.0 Sodium saccharin in a nickel-iron alloy plating bath with the above composition 1. OP/1 phosphorous acid
0.2IHC3C-CL-0-CHsCH
All of s-OHO, 05# was added, and plating was carried out for 5 minutes on a brass plate that had been mirror-polished using a 5 ml can-Shiritzka one-way system under the conditions of temperature [50 C1 average cathode current density f3 A/dm].

The resulting frosted coating was a beautiful silvery-white plating consisting of repeating uneven portions of approximately 0.2×0.5 dimensions.

[Example 6] Total nickel ions 901/1 nickel chloride e6 hydrate 15 1 boric acid 3o l-
4,0 Phosphorous @ in the sulfamic acid dichloride plating bath with the above composition
0.1P/IHC MiC-CH
5-8OsNaO, if/1 were added respectively, the temperature was 50 C, the average gap electrode current density f 3 A/
Under conditions of dI9/, under 9 atmospheres of agitation similar to that used for bright nickel plating, 55% was applied to a mirror-polished brass plate.
Plating tubes was carried out for minutes.

The resulting plating film was a beautiful silvery-white plating film having a pattern of repeating irregularities with a width of about 0.1 to 2 IIB and a length of about 2 to 10 mm.

[Implementation gaff]

Into the electric plating bath described in Example 1, phosphorous H0,2Ml HO-CH2CH2-0-CH2-C:EC-CH2-
0-CH Bamanichi-0HO, 311/1 4 ribinyl methyl ether 0.2f
/1 (Lutonal M4 (J
) Saccharin sodium 2 f/
1 was added to each, the temperature was 500, and the average cathode was flowed to 1i.
Plating was carried out for 8 minutes on a mirror-polished brass plate under the conditions of: 3 A/d- using a one-way Kadrotsuka method.

The obtained N is the width of the sail 1-1111. Length approx. 1
It was a complete matte plating film with a pattern consisting of repeating uneven parts of about 5 am.

Next, on this nickel plating film, a Sargent chromium plating bath Cr01250/I Cr''lg HISO41,51 was applied to the temperature 45C1 average cathode current density flSA/dm'.
Chrome plating was performed for 2 minutes under the following conditions.

Nickel plated WXO irregularities 5tf - chromium is electrodeposited on all parts, resulting in a beautiful patterned matte plating film.

Applicant Uemura Kogyo Co., Ltd. Agent Patent Attorney Takashi Kojima Agent Masuto Takahata Hatayo

Claims (1)

[Claims] 1. One or more compounds selected from phosphorous acid, hypophosphorous acid, and metal salts thereof are added to the electroplating bath in an amount of 0.01-1
f/l and one or more compounds selected from alcohols and sulfonates each having one or more CmiC bonds in the molecule f 0.05 to ljl/7fi
mL, a patterned electroplating method for forming an electroplated film having an uneven pattern, characterized by electroplating using this bath. 2. Claims l where the electroplating bath is an acidic nickel plating bath or an acidic nickel-containing gold plating bath! l The plating method described in item 1.