JPH09216845A - Polyoxyalkylene compound of bis(hydroxycyclohexyl) alkane or its derivative, and plating bath containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound effective for inhibiting the foaming of a plating bath, imparting low foamability and defoamability and improving the workability of the plating, when added to the plating bath on a plating work such as an electric plating work. SOLUTION: A bis(hydroxycyclohexyl)alkane(or its derivative) polyoxyalkylene compound represented by the formula [R1 , R2 , R10 are each H, an alkyl, etc.; A1 , A2 are each an alkylene; m1 , m2 are each an integer of 1-50; n1 , n2 are each an integer of 1-5; X, Y are each an alkyl, an alkenyl, a halogen, etc.], e.g. 1,1-bis(4- hydroxycyclohexyl)ethane polyethoxylate (E0 10 moles). The compound of formula I is obtained by synthesizing a bis(hydroxyphenyl)alkane or its derivative, reducing the benzene ring and subsequently subjecting the product to an alkylene oxide addition reaction in the presence of a catalyst such as NaOH or KOH at the atmospheric pressure or at an elevated pressure. The compound of formula can also be produced by the reverse method. The compound of the formula is preferably added to a plating bath in an amount of 0.01-200g/liter based on the whole amount of the plating bath.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel bis (hydroxycyclohexyl) alkane and its derivative, a polyoxyalkylene compound, and a plating bath containing this compound, which comprises two cyclohexane polyoxyalkylene ether chains on the same carbon. An alkane compound is newly synthesized and a plating bath having low foaming property and excellent work efficiency is provided by using the compound.

[0002]

2. Description of the Related Art Generally, in an electroplating bath or an electroless plating bath, the plating bath contains various surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether. By doing so, the plating film is densified and smoothed, and the plating appearance is improved.

On the other hand, in an ordinary electroplating bath, bubbles are generated due to violent solution movement and mixing with air.
It is not uncommon for problems (1) to (4), etc. to occur, hinder the progress of plating, and significantly reduce workability.

(1) When a part of the article to be plated is partially immersed so as to be below the liquid surface of the plating bath, it is preferable to have a boundary surface that clearly separates the unplated part and the plated part of the article. However, the formation of bubbles hinders the good formation of this interface. (2) The agitation pump of the plating bath may malfunction due to bubbles. (3) Bubbles are formed in the bath due to the overflow of the plating bath, and the plating bath is lost in the waste liquid. (4) Bubbles may cause discharge between the anode and cathode. In addition, electroless plating is similar to electroplating in that the progress of plating is adversely affected by the generation of bubbles and the workability is reduced.

[0005]

The plating bath containing the above-mentioned known nonionic surfactant has a high foaming property, and the bath itself foams during the plating operation, and also has a defoaming property after foaming. Since the workability of plating is deteriorated, the problem of work efficiency cannot be solved. It is a technical object of the present invention to synthesize a novel polyoxyethylene compound and to realize a low foaming property and a defoaming property of a plating bath by containing it to obtain high workability.

[0006]

The present inventors have conceived a compound having two cyclohexane polyoxyalkylene ether chains on the same carbon, and have proposed a polyoxyalkylene having bis (hydroxycyclohexyl) alkane and its derivative as a base. The present invention was completed by discovering that when a compound is newly synthesized and this compound is applied to a plating bath, a low foaming property and a defoaming property can be achieved.

That is, the present invention 1 has the following general formula (I)

[0008]

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(In the formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R
_{6, R 7, R 8,} R 9, R 10 is a C ₁ ~ ₅ alkyl, hydrogen; A _1, A ₂ is a C ₁ ~ ₄ alkylene; m _1, m ₂ is 1
Is an integer of 50; n ₁ and n ₂ are integers of 1 to 5;
X, Y is C ₁ ~ ₅ alkyl, C ₂ ~ ₅ alkenyl, halogen, benzyl, hydrogen. ) Is a polyoxyalkylene compound of bis (hydroxycyclohexyl) alkane and its derivative.

The second aspect of the present invention is a plating bath containing the polyoxyalkylene compound of the bis (hydroxycyclohexyl) alkane of the first aspect of the present invention and a derivative thereof.

The above polyoxyalkylene compound of bis (hydroxycyclohexyl) alkane and its derivative (hereinafter referred to as cyclohexanol-based polyoxyalkylene compound) has a structure in which a polyoxyalkylene ether chain of cyclohexane extends on the same carbon of the alkane skeleton. Have. And R bonded to the carbon atom having the two (cyclohexane) polyoxyalkylene ether chains
₁ and R ₂ are preferably hydrogen, methyl, ethyl, isopropyl, isobutyl and the like, and R ₁ and R ₂ may be the same substituents, but may be different such as hydrogen and methyl or methyl and ethyl. Absent. Further, R ₁ and R ₂ may combine to form a cycloalkane. Each of the substituents R _{3 to} R ₁₀ bonded to the cyclohexane ring is preferably hydrogen, methyl, ethyl, isopropyl, isobutyl, etc., like the above substituents R ₁ and R _2, and these may be the same or different. It doesn't matter.

Further, A ₁ , A ₂ in the polyoxyalkylene chain of the cyclohexanol-based polyoxyalkylene compound is preferably ethylene, propylene, butylene and the like, and A ₁ and A ₂ are each a single type of alkylene. However, a block copolymer composed of mixed species such as ethylene and propylene may be used. This can be represented by the following structural formula (1) or (2). (1) (X- (OE) _m1 -O) _n1- (C ₆ H ₁₀ ) -C (R ₁ R ₂ )-(C ₆ H ₁₀ )-[O- (E
O) _m2- Y] _n2 (EO is oxyethylene; provided that the number of hydrogens in the cyclohexane ring (C ₆ H ₁₀ ) decreases from 10 according to the values of n ₁ and n ₂ ) (2) [X- (OE) _r1- (OP) _s1 -O] _n1- (C ₆ H ₁₀ ) -C (R ₁ R ₂ )-(C ₆ H ₁₀ )
- _{[O- (EO) r2 - (PO} ) s2 -Y ] _n2 (EO is oxyethylene, PO is oxypropylene, r ₁
+ S ₁ = m ₁ , r ₂ + s ₂ = m ₂ , the positions of EO and PO can be changed arbitrarily; provided that the hydrogen of the cyclohexane ring (C ₆ H ₁₀ ) changes depending on the values of n ₁ and n ₂ . (The number decreases from 10)

Terminals X and Y of the polyoxyalkylene chain of the cyclohexanol-based polyoxyalkylene compound
Is preferably the following. (1) hydrogen, benzyl group (2) alkyl group, methyl, ethyl, isopropyl,
t-Butyl, etc. (3) For alkenyl groups, allyl group, vinyl group, butenyl group, etc. (4) For halogen groups, chlorine, bromine, etc.

The addition numbers m ₁ and m ₂ of the above oxyalkylene are each in the range of 1 to 50, preferably 3 to 15, and more preferably 5 to 10. Further, the number of substitution bonds n ₁ and n ₂ of the polyoxyalkylene chain to the cyclohexane ring is 1 for each.
It is possible to be 5 to 5, but 1 to 2 is preferable.

Then, preferred specific examples of the cyclohexanol-based polyoxyalkylene compound will be listed below.
It is as follows.

(1) 1,1-bis (4-hydroxycyclohexyl) ethane polyethoxylate (EO 10 mol): See the following formula (1).

[0017]

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(2) Bis (4-hydroxycyclohexyl)
Methane polyethoxylate (EO12 mol): See the following formula (2).

[0019]

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(3) 2,2-bis (4-hydroxycyclohexyl) propane polyethoxylate (EO 20 mol):
See the following formula (3).

[0021]

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(4) 2,2-bis (4-hydroxycyclohexyl) isohexane polyethoxylate (30 mol EO): See the following formula (4).

[0023]

[Chemical 6]

(5) 1,1-bis (4-hydroxycyclohexyl) cyclohexane polyethoxylate (EO16 mol): See the following formula (5).

[0025]

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(6) 2,2-bis (4-hydroxycyclohexyl) butane polyethoxylate (EO 20 mol): See the following formula (6).

[0027]

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(7) 2- (2-hydroxycyclohexyl)
-2- (4-hydroxycyclohexyl) -propane polyethoxylate (EO 20 mol) polypropoxylate
(PO4 mol): See the following formula (7).

[0029]

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(8) Bis (2-hydroxycyclohexyl)
Methane polyethoxylate (EO24 mol) polybutoxylate (BO4 mol): See the following formula (8).

[0031]

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(9) 1,1-bis (4-hydroxycyclohexyl) propane polyethoxylate (EO 20 mol)-
ω, ω′-dichloride: See the following equation (9).

[0033]

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(10) 2,2-bis (2,4-dihydroxycyclohexyl) butane polyethoxylate (32 mol of EO) -ω, ω ', ω'',ω'''-tetramethyl ether: )reference.

[0035]

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(11) Bis (4-hydroxycyclohexyl)
Methane polyethoxylate (EO 24 mol) -ω, ω'-
Dibenzyl ether: See the following formula (11).

[0037]

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(12) 2,2-bis (3,5-dimethyl-4-)
Hydroxycyclohexyl) propane polyethoxylate (30 mol EO) -ω, ω'-diallyl ether:
See (12).

[0039]

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(13) 2,2-bis (4-hydroxycyclohexyl) propane polypropoxylate (PO4 mol) polyethoxylate (EO16 mol): See the following formula (13).

[0041]

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However, in the above structural formulas (1) to (12),
EO is oxyethylene, PO is oxypropylene, BO
Is oxybutylene (the same applies hereinafter).

The above cyclohexanol-based polyoxyalkylene compound is synthesized by bis (hydroxyphenyl) alkane and its derivative, reducing the benzene ring, and then using sodium hydroxide or potassium hydroxide as a catalyst at atmospheric pressure blowing method. It is produced by adding oxyalkylene according to a conventional method such as pressure reaction in an autoclave, or by adding alkylene oxide to a bis (hydroxyphenyl) alkane and its derivative according to a conventional method and then reducing the benzene ring. It is based on.

The above cyclohexanol-based polyoxyalkylene compounds can be used alone or in combination, and the addition amount thereof is generally 0.01 to 200 g / l, preferably 1 to 100 g / l, and more preferably to the entire plating bath. 2-20g
/ L. If the addition amount is less than 0.01 g / l, there is no effect of improving the stability of the plating bath, and if it exceeds 200 g / l, the effect of low foaming property and defoaming property decreases.

The plating bath of the present invention 2 is an electroplating bath,
Metals such as tin, lead, zinc, copper, cadmium and nickel, or tin-lead, tin-, regardless of electroless plating bath
Alloys such as bismuth, tin-zinc, nickel-tin, etc.
It means a plating bath in a broad sense of metals that can be plated. And, as the plating bath, a sulfuric acid bath, a boric acid bath, a borofluoride bath, a silicofluoride bath, a chloride bath, an organic sulfonic acid bath, or a sulfamic acid bath is mainly used. Any medium system used for a normal electroplating bath or an electroless plating bath can be used without limitation.

Further, for example, in a tin-lead alloy solder plating bath, an organic sulfonic acid, that is, an alkane sulfonic acid, an alkanol sulfonic acid or an aromatic sulfonic acid, is added.
A plating bath having a basic composition containing a source of tin and lead added is preferable. In this case, the above organic sulfonic acids can be used alone or in combination, and the addition amount thereof is generally 30 to 400 g /
1, preferably 70 to 150 g / l.

The alkanesulfonic acid has the following general formula: R--SO ₃ H (wherein R = C _1-5 alkyl group). Specifically, methanesulfonic acid, ethanesulfonic acid, propane Examples thereof include sulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid and pentanesulfonic acid.

The above alkanol sulfonic acid has the following general formula: HO--R--SO ₃ H (wherein R = C _1-5 alkyl group, provided that the OH group is at any position of the alkyl group. Specifically, isethionic acid (2-hydroxyethane-1)
-Sulfonic acid), 2-hydroxypropane-1-sulfonic acid, 1-hydroxypropane-2-sulfonic acid, 3-
Hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 4-hydroxybutane-1-
Examples thereof include sulfonic acid and 2-hydroxypentane-1-sulfonic acid.

The aromatic sulfonic acid is basically phenol sulfonic acid or cresol sulfonic acid.

On the other hand, in the plating bath of the present invention 2, in order to enhance the dispersibility of the bath and obtain smooth plating, various surfactants such as nonionic, anionic and amphoteric surfactants are added as described above. can do.

The nonionic surfactants that can be effectively used in the present invention include higher alcohols, phenols, alkylphenols, naphthols, alkylnaphthols,
Examples include styrenated phenols, fatty acids, aliphatic amines, alkylenediamines, aliphatic amides, sulfonamides, phosphoric acid, polyhydric alcohols such as glycerin and sorbitan, and oxyethylene (or oxypropylene etc.) adducts such as glycosides. Or a polyalkylene glycol such as a block copolymer of oxyethylene and oxypropylene. Specifically, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, and the like.

Examples of the anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates and alkylbenzene sulfonates.

Examples of the amphoteric surfactant include imidazoline, betaine, sulfobetaine, aminocarboxylic acid and the like.

The amount of the above nonionic surfactant added is generally 0.1 to 50 g / l, preferably 0.1 to 20 g / l.
It is. In addition, the amount of the anionic surfactant and the amphoteric surfactant which are appropriately used in combination is generally 0.01 to 20 g.
/ L, preferably 0.1-5 g / l.

On the other hand, various additives such as a leveling agent, a brightening agent, a semi-brightening agent, or a stress reducing agent may be added to the plating bath of the present invention 2 if necessary. That is, for example, aromatic aldehydes such as 1-naphthaldehyde and o-chlorobenzaldehyde, aliphatic aldehydes such as formalin and acetaldehyde, sodium 1,5-naphthalene disulfonate, sodium 1,3,6-naphthalene trisulfonate, and the like. Well-known additives for plating baths such as sulfonic acid derivatives, benzothiazole derivatives such as 2-methylbenzothiazole, and 2-mercaptobenzothiazole can be appropriately used.

In addition, an antioxidant or the like can be added to the electroplating bath. For example, in a plating bath such as tin or solder, the above-mentioned antioxidant is added in order to prevent tin from oxidizing from divalent to tetravalent, and specifically, hydroquinone, resorcin, catechol, phloroglucin, pyrogallol, α- or β-naphthol, phenolsulfonic acid, cresolsulfonic acid, etc. are used.
The addition amount of the above-mentioned antioxidant is generally 0.01 to 5 g /
1 and preferably 0.1 to 2 g / l.

Further, in the case of an electroless plating bath, thiourea and its derivative, ethylenediaminetetraacetic acid are usually used.
Complexing agents such as (EDTA) and its derivatives, hypophosphite compounds (hypophosphorous acid, its ammonium, lithium, sodium, potassium or calcium salts, etc.), amine boranes, borohydride compounds, hydrazine derivatives Add a reducing agent, etc.

[0058]

The cyclohexanol type polyoxyalkylene compound of the present invention 1 has two polyoxyalkylene chains of cyclohexanol on the same carbon of the alkane skeleton and is a newly synthesized compound. When this compound is added to an electroplating bath or an electroless plating bath, as shown in the test examples below, it is possible to suppress foaming during plating work and achieve low foaming properties. Even if it does, it has excellent defoaming properties. That is, by containing the above compound, low foaming property and defoaming property can be imparted to the plating bath, so that the workability of plating can be effectively improved (see Test Examples described later). Moreover, in the plating bath containing the compound, the characteristics of the plating film can be improved, the film can be densified, and the appearance of the plating can be improved (see Test Examples described later).

[0059]

[Examples] The production examples of the cyclohexanol-based polyoxyalkylene of the present invention will be sequentially described below, and a plating bath containing the various compounds produced will be prepared, and the foaming test of the plating bath and the hull cell of the plating film will be described. The test results are also shown. It should be noted that the present invention is not limited to the following embodiments, and many modifications can be made within the scope of the technical idea of the present invention.

<Production Example 1> 1,1-bis (4-hydroxycyclohexyl) ethane polyethoxylate (10 mol of EO) was produced by the following procedure (see the structural formula (1) above). That is, 22.4 g of 1,1-bis (4-hydroxyphenyl) ethane polyethoxylate (10 mol of EO), 200 ml of ethanol and 5% as a catalyst in an autoclave.
Retinium-activated carbon (1.1 g) was added and hydrogen reduction was carried out under the conditions of 100 ° C. and 100 atm. After absorbing 0.1 mol of hydrogen, the reaction product is filtered and the solvent is distilled off from the filtrate to give the cyclohexanol-based polyoxyalkylene compound 2
2.3 g were obtained.

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₃₄ H ₆₆ O ₁₂ (%): C 61.26; H 9.91 measured value (%): C 60.87; H 10.12 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- )

<Production Example 2> Bis (4-
Hydroxycyclohexyl) methane polyethoxylate
(EO12 mol) was produced (see the structural formula (2) above). That is, 43.1 g of bis (4-hydroxycyclohexyl) methane and 0.047 of potassium hydroxide were placed in the autoclave.
g, and at 180 ° C., 108 g of ethylene oxide was added little by little. The reaction was completed when the internal pressure of the autoclave returned to normal pressure, and 147.8 g of the cyclohexanol-based polyoxyalkylene compound was obtained.

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₃₇ H ₇₂ O ₁₄ (%): C 60.00; H 9.73 measured value (%): C 59.82; H 10.04 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- )

MANUFACTURING EXAMPLE 3 By the same operation as in Manufacturing Example 2, 28.7 g of 2,2-bis (4-hydroxycyclohexyl) propane was substituted for bis (4-hydroxycyclohexyl) methane. Add ethylene oxide and add 2,2-bis (4-hydroxycyclohexyl) propane polyethoxylate (EO 20 mol) 131.
4 g was obtained (see the structural formula (3) above).

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₅₅ H ₁₀₈ O ₂₂ (%): C 58.93; H 9.64 measured value (%): C 58.22; H 9.92 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- )

MANUFACTURING EXAMPLE 4 By the same procedure as in Manufacturing Example 2 above, 23.5 g of 2,2-bis (4-hydroxycyclohexyl) isohexane was substituted for bis (4-hydroxycyclohexyl) methane. Ethylene oxide was added to obtain 130.7 g of 2,2-bis (4-hydroxycyclohexyl) isohexane polyethoxylate (EO: 30 mol) (see the above structural formula (4)).

The identification results of the cyclohexanol type polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: Calculated as C ₇₈ H ₁₅₄ O ₃₂ (%): C 58.43; H 9.61 Actual value (%): C 58.11; H 9.98 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- )

<Production Example 5> The reaction temperature was set to 195.
Bis (4-hydroxycyclohexyl) methane was replaced with 38.1 g of 1,1-bis (4-hydroxycyclohexyl) cyclohexane by the same operation as in Production Example 2 except that the temperature was set to 0 ° C., and ethylene oxide was added. 1,1-bis (4-hydroxycyclohexyl) cyclohexane polyethoxylate (EO 16 mol)
131.5 g was obtained (see the structural formula (5) above).

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₅₀ H ₉₆ O ₁₈ (%): C 60.98; H 9.76 actual value (%): C 60.39; H 10.11 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- )

MANUFACTURING EXAMPLE 6 By the same operation as in Manufacturing Example 2, bis (4-hydroxycyclohexyl) methane was replaced with 2,6-bis (4-hydroxycyclohexyl) butane (30.6 g). Add ethylene oxide and add 2,2-bis (4-hydroxycyclohexyl) butane polyethoxylate (EO 20 mol) 135.1
g was obtained (see the structural formula (6) above).

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₅₆ H ₁₁₀ O ₂₂ (%): C 59.26; H 9.70 actual value (%): C 58.78; H 10.23 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- )

<< Production Example 7 >> 2- (2-
Hydroxycyclohexyl) -2- (4-hydroxycyclohexyl) propane polyethoxylate (EO 20 mol) polypropoxylate (PO 4 mol) was produced (see structural formula (7) above). That is, by the same operation as in Preparation Example 2, 28.7 g of 2- (2-hydroxycyclohexyl) -2- (4-hydroxycyclohexyl) propane was substituted for bis (4-hydroxycyclohexyl) methane, and ethylene was added thereto. Addition of oxide to give 2- (2-hydroxycyclohexyl) -2- (4-hydroxycyclohexyl) propane polyethoxylate (EO 20 mol) 13
0.8 g was obtained. Then, 115.7 g of this compound, 0.78 g of potassium hydroxide, and 24 g of propylene oxide were added in an autoclave, and the reaction was carried out at 180 ° C. in the same manner as the above operation to obtain 136.1 g of the above cyclohexanol-based polyoxyalkylene compound. Obtained.

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₆₇ H ₁₃₂ O ₂₆ (%): C 59.47; H 9.76 measured value (%): C 58.92; H 10.14 (2) IR: 1380 cm _{^{-1 (-CH (CH 3) -CH}} 2 -O-) 1110~1100cm -1 (-CH 2 -O-CH 2 -, - CH 2 -
_{O-CH (CH 3) -} )

<Manufacturing Example 8> Bis (2-
Hydroxycyclohexyl) methane polyethoxylate
(20 mol EO) polybutoxylate (4 mol BO) was produced (see structural formula (8) above). That is, bis (2-hydroxycyclohexyl) methane was replaced with 22.5 g of bis (2-hydroxycyclohexyl) methane by the same operation as in Preparation Example 2 above, and ethylene oxide was added thereto to give bis (2-hydroxycyclohexyl) methane. 132.6 g of hydroxycyclohexyl) methane polyethoxylate (20 mol EO) were obtained.
Then 111.6 g of this compound in an autoclave,
0.81 g of potassium hydroxide and 25.5 g of 2,3-butylene oxide were added, the same reaction as above was carried out at 195 ° C., and post-treatment was carried out by a conventional method to obtain the cyclohexanol-based polyoxyalkylene compound 132. 6 g was obtained.

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₇₇ H ₁₅₂ O ₃₀ (%): C 59.38; H 9.77 actual measurement value (%): C 58.81; H 10.08 (2) IR: 1380 cm _{^{-1 (-CH (CH 3) -CH}} (CH 3) -
O-) 1110 to 1100 cm ^-1 (-CH ₂ -O-CH _2- , -CH
(CH ₃ ) -O-CH (CH ₃ )-)

Production Example 9 1,1-bis (4-hydroxycyclohexyl) propane polyethoxylate (20 mol of EO) -ω, ω'-dichloride was produced by the following procedure (see the structural formula (9) above). ). That is, the manufacturing example 2
By the same operation as described above, bis (4-hydroxycyclohexyl) methane was replaced with 29.3 g of 1,1-bis (4-hydroxycyclohexyl) propane, and ethylene oxide was added thereto to give 1,1-bis (4 -Hydroxycyclohexyl) propane polyethoxylate (EO 20 mol)
134.0 g was obtained. Then, 20.3 g of this compound was treated with 6 g of thionyl chloride and 3.87 g of pyridine to introduce chlorine at the polyethoxylate terminal, and post-treated in a conventional manner to give 20.62 g of the above cyclohexanol-based polyoxyalkylene compound. Obtained.

The identification results of the cyclohexanol type polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₅₅ H ₁₀₈ O ₂₂ Cl ₂ (%): C 55.42; H 9.07; Cl 5.96 actual value (%): C 55.92; H 9. 15; Cl 5.11 (2) IR: 1110-1100 cm ^-1 (-CH ₂ -O-CH)
_2- )

<< Manufacturing Example 10 >> 2,2-
Bis (2,4-dihydroxycyclohexyl) butane polyethoxylate (EO32 mol) -ω, ω ′, ω ″
ω ″ ″-tetramethyl ether was produced (see structural formula (10) above). That is, by the same operation as in Production Example 2, 22.6 g of 2,2-bis (2,4-dihydroxycyclohexyl) butane was substituted for bis (4-hydroxycyclohexyl) methane, and ethylene oxide was added thereto. 2,2-bis (2,4-dihydroxycyclohexyl) butane polyethoxylate (EO 32 mol) 133.
4 g were obtained. Then, 23.7 g of this compound was dissolved in 10 ml of dioxane, and metallic sodium was added to the solution with stirring.
30 g was added to obtain a sodium salt. Next, 8.0 g of methyl iodide was added, reacted with the sodium salt under reflux, and post-treated by a conventional method to obtain 22.3 g of the above cyclohexanol-based polyoxyalkylene compound.

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₈₄ H ₁₆₆ O ₃₆ (%): C 57.60; H 9.48 measured value (%): C 57.69; H 8.86 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- )

<Manufacturing Example 11> Screws (4
-Hydroxycyclohexyl) methane polyethoxylate (EO 24 mol) -ω, ω'-dibenzyl ether was produced (see structural formula (11) above). That is, bis (4-hydroxycyclohexyl) methane was mixed with bis (4-hydroxycyclohexyl) by the same operation as in Production Example 2
Substituting 22.5 g of methane and adding ethylene oxide thereto, 131.7 g of bis (4-hydroxycyclohexyl) methane polyethoxylate (EO24 mol) was obtained. Then, 18.4 g of this compound was added to 10 m of dioxane.
It was dissolved in 1 and 0.67 g of metallic sodium was added with stirring to give a sodium salt. Then benzyl chloride 3.6
7 g was added, the mixture was reacted with the sodium salt under reflux, and post-treated by a conventional method to obtain 20.7 g of the cyclohexanol-based polyoxyalkylene compound.

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₇₅ H ₁₃₂ O ₂₆ (%): C 62.15; H 9.12 actual measurement value (%): C 61.78; H 9.09 (2) IR: 1600 cm ^-1 , 1500 cm ^-1 (C ₆ H _5- ) 1110 to 1100 cm ^-1 (-CH ₂ -O-CH _2- )

[Manufacturing Example 12] 2,2-
Bis (3,5-dimethyl-4-hydroxycyclohexyl) propane polyethoxylate (EO30 mol) -ω,
ω'-Diallyl ether was produced (see structural formula (12) above). That is, bis (4-hydroxycyclohexyl) methane was replaced with 2,2-bis (3,5-dimethyl-4-hydroxycyclohexyl) by the same operation as in Production Example 2 above.
2,2-bis (3,5-dimethyl-4-hydroxycyclohexyl) propane polyethoxylate by substituting 24.4 g of propane and adding ethylene oxide thereto
130.9 g of (EO30 mol) was obtained. Next, 22.7 g of this compound was dissolved in 10 ml of dioxane, and 0.65 g of metallic sodium was added with stirring to obtain a sodium salt. Next, 3.4 g of allyl bromide was added, reacted with the sodium salt under reflux, and post-treated by a conventional method to give the cyclohexanol-based polyoxyalkylene compound 2
2.4 g were obtained.

The identification results of the cyclohexanol-based polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₈₅ H ₁₆₄ O ₃₂ (%): C 60.14; H 9.67 actual value (%): C 59.68; H 9.51 (2) IR: 1110 ~ 1100 cm ^-1 (-CH ₂ -O-CH
_2- ) ¹ H-NMR (CDCl ₃ ; δppm) 5.5-6.0 (m, 6
H)

<Manufacturing Example 13> 2,2-
Bis (4-hydroxycyclohexyl) propane polypropoxylate (PO4 mol) polyethoxylate (EO1
6 mol) was produced (see structural formula (13) above). That is, 33.8 g of 2,2-bis (4-hydroxycyclohexyl) propane, 0.3 g of potassium hydroxide and 33 g of propylene oxide were added to the autoclave and reacted at 180 ° C. Then, when the internal pressure of the autoclave returns to normal pressure, the reaction is terminated, and 2,2-bis (4-hydroxycyclohexyl) propane polypropoxylate (PO4
(Mole) 65.2 g was obtained. Next, 55.8 g of this compound and 0.062 g of potassium hydroxide were added to the autoclave, and 84 g of ethylene oxide was added little by little at 180 ° C. Then, 136.3 g of the above cyclohexanol-based polyoxyalkylene compound was obtained, with the time when the internal pressure of the autoclave returned to normal pressure as the reaction end time.

The identification results of the cyclohexanol type polyoxyalkylene compound by various instrumental analyzes were as follows. (1) Elemental analysis value: calculated as C ₅₉ H ₁₁₆ O ₂₂ (%): C 60.20; H 9.86 measured value (%): C 59.58; H 10.01 (2) IR: 1380 cm _{^{-1 (-CH (CH 3) -CH}} 2 -O-) 1110~1100cm -1 (-CH 2 -O-CH 2 -, - CH 2 -
_{O-CH (CH 3) -} )

Hereinafter, as shown in the following test examples 1 to 10,
Various plating baths were constructed using each cyclohexanol-based polyoxyalkylene compound of the above Production Examples, electroplating was performed, and the appearance and denseness of the plated film were evaluated by the Hull cell test. In addition, 40 ml of each plating bath was collected in a 100 ml graduated cylinder equipped with a stopper at 25 ° C., shaken vigorously for 5 seconds, and after 10 minutes, the foaming height of the plating bath was measured by measuring the foaming height. Carried out. However, a plurality of types of plating baths in which the above cyclohexanol-based polyoxyalkylene compound was replaced with a normal nonionic surfactant were used as comparative examples.

Test Example 1 Using the cyclohexanol-based polyoxyalkylene compound prepared in Production Example 11, a tin plating bath having the following composition was constructed. Stannous 2-hydroxypropanesulfonic acid (as Sn ²⁺ ) 20 g / l 2-Hydroxypropane sulfonic acid 100 g / l Bis (4-hydroxycyclohexyl) methane polyethoxylate- (EO24 mol) -ω, ω'-di Benzyl ether 8 g / l 1-naphthaldehyde 0.1 g / l methacrylic acid 1 ml / l catechol 0.5 g / l ion-exchanged water balance

Next, while stirring the plating bath with a stirrer, platinum-coated titanium was used as an anode, a copper plate was used as a cathode, the bath temperature was 20 ° C., the current density and the plating time were variously changed, and electroplating was carried out by a rack system. Was applied. Then, observing the state of the electrodeposition film at each current density,
The appearance of the film described above was evaluated (Test Example 2 below).
10 are the same). Further, in this test example, less foaming during plating, good low foaming and defoaming properties were observed, but from the viewpoint of ensuring the objectivity of the data, the foaming test was performed ( Test Examples 2 to 10 are the same).

Test Example 2 Using the cyclohexanol type polyoxyalkylene compound prepared in Production Example 2 above, a solder plating bath having the following composition was constructed. Stannous hydroxyethane sulfonate (as Sn ²⁺ ) 24 g / l Lead hydroxyethane sulfonate (as Pb ²⁺ ) 6 g / l Hydroxyethane sulfonate 100 g / l Bis (4-hydroxycyclohexyl) methane-polyethoxylate ( EO12 mol) 8.5 g / l sodium diethylnaphthalene sulfonate 0.5 g / l hydroquinone 0.3 g / l ion-exchanged water balance

Then, using the above plating bath, the bath temperature is adjusted to 2
Electroplating was performed under the same conditions as in Test Example 1 except that the temperature was set to 5 ° C.

Test Example 3 Using the cyclohexanol type polyoxyalkylene compound prepared in Production Example 3 above, a solder plating bath having the following composition was constructed. Stannous methanesulfonate (as Sn ²⁺ ) 54 g / l Lead methanesulfonate (as Pb ²⁺ ) 6 g / l Methanesulfonate 150 g / l 2,2-bis (4-hydroxycyclohexyl) propane-polyethoxylate (EO 20 mol) 8.5 g / l hydroquinone 0.5 g / l ion-exchanged water balance

Then, using the above plating bath, the bath temperature is set to 3
Electroplating was performed under the same conditions as in Test Example 1 except that the temperature was set to 0 ° C.

Test Example 4 Using the cyclohexanol-based polyoxyalkylene compound prepared in Production Example 4, a solder plating bath having the following composition was constructed. Stannous sulfamate (as Sn ²⁺ ) 28 g / l Lead sulfamate (as Pb ²⁺ ) 12 g / l Sulfamic acid 130 g / l 2,2-bis (4-hydroxycyclohexyl) isohexane-polyethoxylate (EO 30 mol) ) 7.5 g / l resorcin 0.5 g / l ion-exchanged water balance

Then, using the above plating bath, the bath temperature is adjusted to 2
Electroplating was performed under the same conditions as in Test Example 1 except that the temperature was set to 5 ° C.

Test Example 5 Using the cyclohexanol-based polyoxyalkylene compound prepared in Production Example 5, a tin plating bath having the following composition was constructed. Stannous sulphate (as Sn ²⁺ ) 40 g / l Sulfuric acid (specific gravity 1.84) 150 g / l 1,1-bis (4-hydroxycyclohexyl) cyclohexane-polyethoxylate (EO 16 mol) 9 g / l benzalacetone 0 .2 g / l 37% formalin 5 ml / l ion-exchanged water balance

Next, using the above plating bath, electroplating was performed under the same conditions as in Test Example 1 above.

Test Example 6 Using the cyclohexanol type polyoxyalkylene compound prepared in Production Example 6, a solder plating bath having the following composition was constructed. Stannous borofluoride (as Sn ²⁺ ) 24 g / l Lead borofluoride (as Pb ²⁺ ) 6 g / l Borohydrofluoric acid 150 g / l 2,2-bis (4-hydroxycyclohexyl) butane-polyethoxylate ( EO 20 mol) 6.5 g / l 1-naphthaldehyde 0.1 g / l acetaldehyde 2 g / l catechol 0.7 g / l ion-exchanged water balance

Next, using the above plating bath, electroplating was performed under the same conditions as in Test Example 1 above.

Test Example 7 Using the cyclohexanol-based polyoxyalkylene compound prepared in Production Example 7 above, a galvanizing bath having the following composition was constructed. Zinc chloride 60 g / l Potassium chloride 240 g / l Boric acid 50 g / l 2- (2-Hydroxycyclohexyl) -2- (4-hydroxy-cyclohexyl) propane polyethoxylate (EO 20 mol) -Polypropoxylate (PO4 mol) 7 g / L Benzalacetone 0.15g / l Ion-exchanged water balance

Then, using the above plating bath, the bath temperature is adjusted to 2
Electroplating was performed under the same conditions as in Test Example 1 except that the temperature was set to 5 ° C.

Test Example 8 Using the cyclohexanol-based polyoxyalkylene compound prepared in Production Example 8 above, a nickel-tin plating bath having the following composition was constructed. Nickel chloride 50 g / l Stannous sulfate (as Sn ²⁺ ) 3 g / l Ammonium chloride 15 g / l Boric acid 15 g / l Sodium citrate 80 g / l Bis (2-hydroxycyclohexyl) methane polyethoxylate- (EO 24 mol) Polybutoxylate (BO4 mol) 8g / l Ion-exchanged water balance

Then, the bath temperature is set to 3 using the above plating bath.
Electroplating was performed under the same conditions as in Test Example 1 except that the temperature was set to 0 ° C.

Test Example 9 Using the cyclohexanol-based polyoxyalkylene compound prepared in Production Example 9, a copper plating bath having the following composition was constructed. Copper sulfate 180 g / l Sulfuric acid (specific gravity 1.84) 50 g / l 1,1-bis (4-hydroxycyclohexyl) propane polyethoxylate- (EO20 mol) -ω, ω'-dichloride 8 g / l benzyldimethylhexadecyl ammonium -Methanesulfonate 1 g / l N-butylidene sulfanilic acid 2 g / l Ion-exchanged water balance

Then, using the above plating bath, the bath temperature is set to 3
Electroplating was performed under the same conditions as in Test Example 1 except that the temperature was set to 0 ° C.

Test Example 10 Using the cyclohexanol-based polyoxyalkylene compound prepared in Production Example 12, a cadmium plating bath having the following composition was constructed. Cadmium sulfate 30 g / l Sulfuric acid (specific gravity 1.84) 100 g / l 2,2-bis (3,5-dimethyl-4-hydroxycyclohexyl) propane-polyethoxylate (EO 30 mol) -ω, ω'-diallyl ether 8 g / L Cumylphenol polyethoxylate (EO 10 mol) 1.0 g / l 37% formalin 20 ml / l Ion-exchanged water balance

Next, the bath temperature is set to 2 using the above plating bath.
Electroplating was performed under the same conditions as in Test Example 1 except that the temperature was set to 5 ° C.

Comparative Example 1 Based on the solder plating bath of Test Example 2 above, the cyclohexanol-based polyoxyalkylene compound of Production Example 2 was used as a nonionic phenol polyethoxylate, which is a conventional nonionic surfactant.
Instead of (EO15 mol), electroplating was performed under the same content ratio and conditions as in Test Example 2.

Comparative Example 2 Based on the solder plating bath of Test Example 3 above, the cyclohexanol-based polyoxyalkylene compound of Production Example 3 was replaced with cumylphenol polyethoxylate (EO 12 mol), Electroplating was performed under the same content rate and conditions as in Test Example 3.

Comparative Example 3 Based on the tin plating bath of Test Example 5 above, the cyclohexanol-based polyoxyalkylene compound of Production Example 5 was replaced with laurylamine polyethoxylate (15 mol of EO), and the test example was repeated. 5
Electroplating was performed under the same content rate and conditions.

<< Evaluation of Test Results >> FIG. 1 shows the results of the above tests. (1) As shown in FIG. 1, in Test Examples 1 to 10 in which the novel cyclohexanol-based polyoxyalkylene compound of the present invention was contained in the plating bath, the bubbling height after 10 minutes was zero, or 0.0. In contrast to 2 cm or less, in Comparative Examples 1 to 3 in which these novel compounds were omitted and substituted with a normal nonionic surfactant, high foamability was observed. That is, when the novel compound of the present invention is applied to the plating bath, excellent low foaming property and defoaming property can be realized and the working efficiency of plating can be improved.

(2) As shown in FIG. 1, in Test Examples 1 to 10 in which the novel cyclohexanol-based polyoxyalkylene compound of the present invention was contained in the plating bath, various currents ranging from low current density to high current density were obtained. Even when electroplating was performed under a high density, the electrodeposition coating had good gloss or semi-gloss appearance, and a uniform and dense coating was obtained. On the other hand, in Comparative Examples 1 to 3, black sponge-like deposition was observed on the electrodeposition film in the high current density portion. Therefore, when the novel compound of the present invention is applied to the plating bath, it is possible to both suppress foaming during plating and improve the appearance and densification of the plating film.

[Brief description of drawings]

FIG. 1 is a chart showing the results of a foaming test of a plating bath containing a cyclohexanol-based polyoxyalkylene compound of the present invention and a Halcel test of an electrodeposition coating obtained from the plating bath.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // C25D 3/22 C25D 3/22 3/26 3/26 3/32 3/32 3/38 101 3/38 101 3/56 3/56 Z C

Claims (2)

[Claims] 1. A compound represented by the following general formula (I): (In the formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R _8, R _9, R ₁₀ is a C ₁ ~ ₅ alkyl, hydrogen; A _1,
A ₂ is a C ₁ ~ ₄ alkylene; m _1, m ₂ is an integer of 1~50; n _1, n ₂ is a integer from 1 to 5; X, Y is C ₁ ~ ₅ alkyl, C _2-5 alkenyl, halogen, benzyl, hydrogen. ) A polyoxyalkylene compound of bis (hydroxycyclohexyl) alkane and a derivative thereof represented by 2. A plating bath containing the polyoxyalkylene compound of the bis (hydroxycyclohexyl) alkane and its derivative according to claim 1.