JP2013129855A - Pretreatment agent for use in electroless plating, and pretreatment method for use in electroless plating employing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pretreatment agent for use in electroless plating and a pretreatment method for use in electroless plating, capable of improving adhesion of a coating film formed by electroless plating.SOLUTION: The pretreatment agent for use in electroless plating is characterized by including an aqueous solution containing a compound comprising a carbodiimide group. The pretreatment method for use in electroless plating is characterized by using the pretreatment agent for use in electroless plating.

Description

  The present invention relates to an electroless plating pretreatment agent and an electroless plating pretreatment method using the pretreatment agent.

  Electroless plating is used industrially as a method for obtaining coatings of nickel, nickel alloys, copper, silver, etc. Electroless plating of nickel alloys and cobalt is used as a magnetic recording material, etc. Silver electroless plating is used for mirror reflectors and the like as conductive films for printed circuits.

A pretreatment agent is used when electroless plating is performed on an object to be plated such as a substrate. As the pretreatment agent, for example, Patent Document 1 discloses an electroless plating pretreatment agent containing an alkali, a nonionic ether type surfactant and an amine complexing agent.
Further, in Patent Document 2, prior to catalyzing a resin substrate containing glass fiber or silica filler with a catalyst solution containing a palladium compound, the resin substrate is treated with a glass etching solution containing a fluorine compound. After that, a pretreatment method for catalyzing treatment is disclosed which is immersed in an oxidizing agent solution containing permanganate or chromic acid.

Patent Document 1 is a pretreatment agent for removing fillers with low adhesion exposed on the substrate surface by desmear treatment or the like, and is intended to increase the adhesion of the catalyst by removing the fillers. is there.
Patent Document 2 is intended to increase the adhesion of an electroless plating film by attaching a sufficient amount of a palladium catalyst for electroless plating.

JP 2010-229536 A JP 2001-316833 A

  The plating film obtained by the conventional electroless plating method has a problem in adhesion. As this cause, for example, when the object to be plated is a resin substrate containing a filler, some of the filler and glass fibers exposed on the surface are insufficiently bonded to the resin and have poor adhesion, Studies have been made to improve the adhesion of the electroless plating film by increasing the surface roughness or removing the filler using a pretreatment agent. However, as the body to be plated becomes thinner, it becomes difficult to increase the degree of roughening, and it may become a problem that the strength of the body to be plated decreases due to filler removal. Thus, an electroless plating pretreatment agent and an electroless plating pretreatment method capable of improving the adhesion of the electroless plating film without removing the filler are desired. Further, an electroless plating pretreatment agent for improving the adhesion of the electroless plating film on a plated body other than a glass substrate such as a stainless steel substrate, a quartz substrate, and soda lime glass, and a resin substrate represented by a silicon substrate. And an electroless plating pretreatment method is desired.

  Accordingly, an object of the present invention is to provide an electroless plating pretreatment agent and an electroless plating pretreatment method capable of improving the adhesion of an electroless plating film.

  As a result of intensive studies, the present inventors have used an electroless plating pretreatment agent comprising an aqueous solution containing a compound having a carbodiimide group for the object to be plated, and a pretreatment using the pretreatment agent. Before performing this, it was found that the above problem could be solved by treating the object to be plated with a solution containing an alkoxysilane compound having a carboxyl group, and the present invention was achieved.

  That is, the present invention provides an electroless plating pretreatment agent comprising an aqueous solution containing a compound having a carbodiimide group.

  Moreover, this invention provides the electroless-plating pretreatment method characterized by using said electroless-plating pretreatment agent.

  Furthermore, in the present invention, a pretreatment using a solution containing an alkoxysilane compound having a carboxyl group is applied to the object to be plated as a primary pretreatment, and the above pretreatment is applied to the object as a secondary pretreatment. An electroless plating pretreatment method characterized by being applied is provided.

  Further, the present invention provides the above-mentioned pretreatment method to the object to be plated, and further from the group consisting of copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium, tungsten, platinum, rhodium and ruthenium. The present invention provides a method for producing an electroless plating film that forms an electroless plating film by electroless plating selected one or more components.

  According to the present invention, an electroless plating film having high adhesion can be obtained by using the electroless plating pretreatment agent and the electroless plating pretreatment method.

Hereinafter, the electroless plating pretreatment agent and the electroless plating pretreatment method of the present invention will be described.
The compound having a carbodiimide group used in the electroless plating pretreatment agent of the present invention has reactivity with carbodiimide present on the surface of the object to be plated, or binds and has affinity with the group having affinity to be plated. By improving the surface, it serves to improve the adhesion strength between the object to be plated and the electroless plating film.

  Examples of the group having reactivity or affinity with carbodiimide include a carboxyl group as a preferable group, and a particularly preferable example is a case where an organic synthetic resin substrate subjected to desmear treatment is used as an object to be plated. Specifically, it reacts with a carboxyl group generated on the surface of the substrate by desmear treatment, and the surface of the substrate is modified by N-acyl urea formation on the surface of the substrate, so that the adhesion between the body to be plated and the plating film is improved. Strength can be improved.

  The compound having a carbodiimide group used in the electroless plating pretreatment agent of the present invention is not particularly limited as long as it is a compound having a carbodiimide group. For example, an organic diisocyanate, a phospholene compound, a metal carbonyl complex compound, and a phosphate ester are used. The isocyanate terminal carbodiimide compound obtained by making it react in presence of the catalyst which accelerates | stimulates carbodiimidation like these can be used. As the compound having a carbodiimide group, an aqueous carbodiimide compound obtained by reacting the isocyanate-terminated carbodiimide compound with a hydrophilic segment compound can also be used.

  Specific examples of the isocyanate-terminated carbodiimide compound include isocyanate-terminated isophorone carbodiimide, isocyanate-terminated dicyclohexylmethane carbodiimide, isocyanate-terminated hexamethylene carbodiimide, isocyanate-terminated diphenylmethane carbodiimide, isocyanate-terminated tolylene carbodiimide, isocyanate-terminated tetramethylxylylene carbodiimide, and the like. The degree of polymerization is preferably in the range of 1 to 30, but the degree of polymerization can be appropriately selected depending on the use conditions, desired adhesion strength, and the like.

  Specific examples of the aqueous carbodiimide compound include aqueous isophorone carbodiimide, aqueous dicyclohexylmethane carbodiimide, aqueous hexamethylene carbodiimide, aqueous diphenylmethane carbodiimide, aqueous tolylene carbodiimide, aqueous tetramethylxylylene carbodiimide, and the like. Moreover, like the said isocyanate terminal carbodiimide compound, Preferably a polymerization degree is suitably selected from the range of 1-30.

  The aqueous carbodiimide compound includes an aqueous carbodiimide compound having three types of ionicity, cationic, anionic and nonionic, depending on the selection of the hydrophilic segment compound. Specifically, for example, when the dialkylamino alcohol is used as the hydrophilic segment compound, it becomes cationic, and when an alkyl sulfonate having at least one reactive hydroxyl group is used, it becomes anionic and reactive. When poly (alkylene oxide) end-capped with an alkoxy group having at least one hydroxyl group is used, it becomes nonionic. Examples of the alkylene oxide of the poly (alkylene oxide) include ethylene oxide, propylene oxide, butylene oxide and the like. As said poly (alkylene oxide) used when making it nonionic, the thing of the polymerization degree of the range of 4-30 is used preferably. The term “aqueous” as used in the present invention means that the compound having a carbodiimide group according to the present invention has water-soluble properties, self-emulsifying properties, and other properties that are compatible with water. is there.

  As a method for dissolving or dispersing the compound having a carbodiimide group in water, a well-known general method can be used. For example, since an aqueous carbodiimide compound has a hydrophilic group introduced in the molecule, it can be dissolved in water by a self-emulsification (soap-free) method. The non-aqueous carbodiimide compound can be dispersed in water by a forced emulsification method (emulsion) using a nonionic emulsifier.

  A commercially available product may be used as the compound having a carbodiimide group. Commercial products of aqueous nonionic carbodiimide compounds dissolved in water by the self-emulsification (soap-free) method include carbodilite SV-02 (active ingredient concentration 40%, NCN equivalent 429), carbodilite V-02 (active ingredient concentration). 40%, NCN equivalent 600), Carbodilite V-02-L2 (active ingredient concentration 40%, NCN equivalent 385), Carbodilite V-04 (active ingredient concentration 40%, NCN equivalent 335), etc., nonionic emulsifier Examples of commercially available emulsion-type carbodiimide compounds dispersed in water using a forced emulsification method (emulsion) include carbodilite E-01 (active ingredient concentration 40%, NCN equivalent 425), carbodilite E-02 (active ingredient) Concentration of 40%, NCN equivalent of 445). Cal Co., Ltd.].

  The compound having a carbodiimide group used in the electroless plating pretreatment agent of the present invention is particularly preferably a nonionic polycarbodiimide compound from the viewpoint of high solubility, high effect of improving adhesion, and easy handling. Of these, those having a chemical formula amount per mole of carbodiimide groups (hereinafter sometimes referred to as NCN equivalents) of 100 to 650 are preferred, and those having a chemical formula amount of 300 to 500 are not used. The effect of improving the adhesiveness of the electrolytic plating film is particularly high, which is particularly preferable.

  The concentration of the compound having a carbodiimide group used in the electroless plating pretreatment agent of the present invention may be appropriately adjusted depending on the object to be plated, but is preferably 0.001 to 10%, preferably 0.005 to 5%. Is particularly preferred. Here, if it is less than 0.001% by mass, the effect of improving the adhesion is not exhibited, and this is not preferable.

  What is necessary is just to adjust suitably the preferable pH value in the electroless-plating pretreatment agent of this invention so that it may become pH 5-13. The pH of the electroless plating pretreatment agent of the present invention is particularly preferably 6 to 12 or more. In adjusting the pH, a pH buffer solution can also be used.

  The pH buffer solution is not particularly limited, and a well-known general pH buffer solution may be used. Examples thereof include an acetate buffer solution, a phosphate buffer solution, a citrate buffer solution, and a borate buffer solution. .

  The electroless plating pretreatment agent of the present invention can be mixed with other known additives as necessary as long as the effects of the present invention are not impaired. Examples of such other additives include a surfactant.

  Said surfactant is used in order to improve the wettability of the electroless-plating pretreatment agent. For example, surfactants such as cationic, nonionic, anionic, and betaine are listed, and cationic, nonionic, or anionic surfactants are preferably used. As for the usage-amount in the case of using surfactant, 0.01-5 mass% is preferable.

  Examples of the cationic surfactant that may be used in the electroless plating pretreatment agent of the present invention include alkyl (or alkenyl) trimethylammonium salt, dialkyl (or alkenyl) dimethylammonium salt, and alkyl (or alkenyl) quaternary. Ammonium salt, mono- or dialkyl (or alkenyl) quaternary ammonium salt, ether (or alkenyl) pyridinium salt, alkyl (or alkenyl) dimethylbenzylammonium salt, alkyl (or alkenyl) isoquinolinium containing ether group or ester group or amide group Salts, dialkyl (or alkenyl) morphonium salts, polyoxyethylene alkyl (or alkenyl) amines, alkyl (or alkenyl) amine salts, polyamine fatty acid derivatives, amino acids Alcohol fatty acid derivatives, benzalkonium chloride, etc. benzethonium chloride and the like, may contain fluorine atoms in these structures.

  Nonionic surfactants that may be used in the electroless plating pretreatment agent of the present invention include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers (ethylene oxide and propylene). The addition form of oxide may be random or block), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or its ethylene oxide adduct, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Esters, alkylpolyglucosides, fatty acid monoethanolamides or their ethylene oxide adducts, fatty acid-N-methylmonoethanolamide Is its ethylene oxide adduct, fatty acid diethanolamide or its ethylene oxide adduct, sucrose fatty acid ester, alkyl glycerin ether, alkyl polyglycerin ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid methyl ester ethoxylate, N-length Examples thereof include chain alkyldimethylamine oxide, and these structures may contain a fluorine atom.

  Examples of the anionic surfactant that may be used in the electroless plating pretreatment agent of the present invention include higher fatty acid salts, higher alcohol sulfate esters, sulfurized olefin salts, higher alkyl sulfonates, α-olefin sulfonic acids. Salt, sulfated fatty acid salt, sulfonated fatty acid salt, phosphate ester salt, sulfate ester salt of fatty acid ester, glyceride sulfate ester, sulfonate salt of fatty acid ester, α-sulfo fatty acid methyl ester salt, polyoxyalkylene alkyl ether sulfate Ester salt, polyoxyalkylene alkyl phenyl ether sulfate, polyoxyalkylene alkyl ether carboxylate, acylated peptide, sulfate ester of fatty acid alkanolamide or its alkylene oxide adduct, sulfosuccinate, alkyl base Benzene sulfonate, alkyl naphthalene sulfonate, alkyl benzimidazole sulfonate, polyoxyalkylene sulfosuccinate, N-acyl-N-methyl taurine salt, N-acyl glutamic acid or salt thereof, acyloxyethane sulfonate, Alkoxyethanesulfonate, N-acyl-β-alanine or a salt thereof, N-acyl-N-carboxyethyltaurine or a salt thereof, N-acyl-N-carboxymethylglycine or a salt thereof, acyl lactate, N-acyl Examples thereof include sarcosine salts and alkyl or alkenylaminocarboxymethyl sulfates, and these structures may contain a fluorine atom.

  The pretreatment method of electroless plating using the electroless plating pretreatment agent of the present invention is by bringing the electroless plating pretreatment agent of the present invention into contact with the object to be plated.

  The method for bringing the electroless plating pretreatment agent of the present invention into contact with the object to be plated is not particularly limited, and a known general pretreatment method may be used. For example, a pretreatment method using a dip method, a spray method, or a spin method can be used.

  In addition, the pretreatment method of electroless plating using the electroless plating pretreatment agent of the present invention can be incorporated in the desmear treatment process.

  For example, when electroless copper plating is carried out by incorporating a process by a pretreatment method using an electroless plating pretreatment agent of the present invention into a desmear treatment process on an epoxy resin substrate, (1) smear swelling process [Hereafter, it may be abbreviated as (1) step. ], (2) Micro-etching process [Hereafter, it may be abbreviated as (2) process. ], (3) Reduction step [hereinafter sometimes abbreviated as (3) step. ], (4) Steps by the electroless plating pretreatment method using the electroless plating pretreatment agent of the present invention [hereinafter sometimes referred to as (4) step. ], (5) Drying step [Hereafter, it may be abbreviated as (5) step. ], (6) Catalyst application process [Hereafter, it may be abbreviated as (6) process. ], (7) Electroless copper plating process [Hereafter, it may be abbreviated as (7) process. ], An electroless copper plating film can be formed on the object to be plated. A water washing step may be added between or during each step.

  Specifically, the surface of the epoxy resin substrate is in a state where carboxyl groups are exposed on the surface of the substrate by the steps (1) to (3), and the substrate is electrolessly electrolyzed according to the present invention in the step (4). By contacting with a plating pretreatment agent under appropriate conditions, the carboxyl group on the substrate surface is N-acyl uread. Furthermore, the electroless copper plating film which is excellent in adhesiveness can be obtained through steps (5) to (7).

  (4) In the electroless plating pretreatment step using the electroless plating pretreatment agent of the present invention, the conditions for bringing the electroless plating pretreatment agent of the present invention into contact with the object to be plated are not particularly limited. It can be set arbitrarily according to the shape and film thickness of the object to be plated. For example, when making it contact by immersing, 10 to 90 degreeC is preferable and, as for temperature, 30 to 80 degreeC is especially preferable. Since the temperature of the pretreatment agent may be increased by the heat of reaction, the temperature may be controlled by a known means so as to maintain it within the above temperature range if necessary. Further, the time is not particularly limited because it is sufficient to make the time sufficiently necessary for the surface of the object to be plated to be completely processed. For example, when an epoxy resin substrate is processed, pretreatment may be performed by contacting for about 1 to 30 minutes within the above temperature range.

  In addition, in an organic resin substrate, a stainless steel substrate or the like containing a filler, a sufficient adhesion effect may not be obtained only by the above steps (1) to (7). This is because organic resin bases and stainless steel bases containing fillers have sufficient reactivity with the carbodiimide on the surface of the base body only by the steps (1) to (3), or the affinity groups are not exposed. Conceivable. Therefore, in order to expose a group having reactivity or sufficient affinity with carbodiimide on the surface of an organic resin substrate or a stainless steel substrate containing a filler, the above (4) in the above steps (1) to (7) ) Electroless electrolysis with high adhesion even in the case of an organic resin substrate or a stainless steel substrate containing a filler by performing a step of treating the object to be plated with a solution containing an alkoxysilane compound having a carboxyl group before the step) A plating film can be obtained. As the timing for carrying out the step of treating the object to be plated with a solution containing an alkoxysilane compound having a carboxyl group, the interval between the steps (3) and (4) in the steps (1) to (7) is as follows. preferable. A pretreatment using a solution containing an alkoxysilane compound having a carboxyl group is applied to the object as a primary pretreatment, and the step (4) is applied to the object as a secondary pretreatment. The effect of improving the adhesion is synergistic, and a particularly large effect of improving the adhesion can be obtained as compared with the case where both the steps are performed alone.

  The method of treating the object to be plated with the solution containing the alkoxysilane compound having a carboxyl group is to bring the solution containing the alkoxysilane compound having a carboxyl group into contact with the object to be plated.

  The method of bringing the solution containing the alkoxysilane compound having a carboxyl group used in the present invention into contact with the object to be plated is not particularly limited, and a well-known general treatment method may be used. For example, a dip type, spray type or spin type processing method can be mentioned.

   For example, the conditions for contacting the object to be plated with a solution containing an alkoxysilane compound having a carboxyl group by a dip-type treatment method are not particularly limited, and the shape of the substrate to be electrolessly plated or It can be arbitrarily set according to the film thickness. For example, the temperature is preferably 10 ° C to 90 ° C, particularly preferably 30 ° C to 80 ° C. Since the temperature of the solution containing the alkoxysilane compound having a carboxyl group may rise due to heat of reaction, the temperature may be controlled by a known means so as to maintain it within the above temperature range if necessary. Further, the time is not particularly limited because it is sufficient to make the time sufficiently necessary for the surface of the object to be plated to be completely processed. For example, when processing a stainless steel substrate, the processing may be performed by contacting for about 1 to 30 minutes within the above temperature range.

  The alkoxysilane compound used in the solution containing the alkoxysilane compound having a carboxyl group used in the present invention is not particularly limited as long as it is adsorbed on the surface of the object to be plated. A compound having a silanol group (Si—OH) or a hydrolyzable functional group that gives a silanol group by hydrolysis is preferable because of good adsorptivity.

Examples of the hydrolyzable functional group include an alkoxy (—OR ^A ) group directly bonded to a Si atom. As R ^A constituting the alkoxy group, for example, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms is preferable. More specifically, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, A decyl group, an undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group and the like can be mentioned, and among them, a methyl group is preferable.

  More specifically, it comprises a monoanhydride or dianhydride formed by dehydrating an alkoxysilane compound represented by the following general formula (I) and a divalent or higher carboxylic acid compound or a divalent or higher carboxylic acid compound. It is preferable to use an alkoxysilane compound obtained by reacting at least one carboxylic acid compound or carboxylic acid anhydride selected from the group.

(R ¹ O) ₃ Si—Z—R ² (I)
[In the formula (I), R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² represents —NH ₂ , —NCO, an imidazolyl group or a triazolyl group, and Z represents a hydrocarbon group having 1 to ¹ carbon atoms. Represents 10 alkylene groups, and the alkylene group may be interrupted by —NH—, —O— or —S—. ]

In the alkoxysilane compound represented by the general formula (I), examples of the hydrocarbon group having 1 to 12 carbon atoms that can be used for R ¹ include an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl as shown below. Groups etc. can be used. Among these, since it is highly water-soluble, R ¹ in the general formula (I) is more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, amyl group, isoamyl group, hexyl group, heptyl group, Examples include isoheptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl (lauryl) group and the like.

  Examples of the alkenyl group include a vinyl group, 1-methylethenyl group, 2-methylethenyl group, propenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group and the like.

  Examples of the cycloalkyl group include cyclohexyl, cyclopentyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclopentyl, and the like. A hexenyl group, a methylcycloheptenyl group, etc. are mentioned.

  Examples of the aryl group include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-tertiarybutylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group and the like can be mentioned.

  Moreover, Z in the said general formula (I) represents a C1-C10 alkylene group. Examples of the alkylene group that can be used for Z include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and the like. It may be interrupted by —NH—, —O— or —S—. From the viewpoint of good water solubility, an alkylene group having 2 to 5 carbon atoms is more preferable. The alkylene group may be interrupted by —NH—, —O— or —S—, but is preferably not interrupted. Specific examples of such a compound represented by the general formula (I) include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane. N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Examples include triethoxysilane. Of these, 3-aminopropyltrimethoxysilane and 3-isocyanatopropyltrimethoxysilane are preferable.

  Examples of the monoanhydride or dianhydride formed by dehydrating the divalent or higher carboxylic acid compound or the divalent or higher carboxylic acid compound include dicarboxylic acid compounds, tricarboxylic acid compounds, tetracarboxylic acid compounds, and dicarboxylic acid compounds. A monoanhydride formed by dehydrating a tricarboxylic acid compound, a monoanhydride formed by dehydrating a tetracarboxylic acid compound, or a dianhydride.

  The dicarboxylic acid compound or dicarboxylic acid monoanhydride is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, and the like. Monoanhydride obtained by dehydration.

  Although it does not specifically limit as said tricarboxylic acid or tricarboxylic acid monoanhydride, For example, the tricarboxylic acid of (1-1-1-4) mentioned below is mentioned, Furthermore, these monoanhydrides formed by dehydrating Etc.

  Although it does not specifically limit as said tetracarboxylic acid, tetracarboxylic acid monoanhydride, or dianhydride, For example, the tetracarboxylic acid of (2-1 to 2-19) mentioned below is mentioned, Furthermore, these are these. Examples thereof include monoanhydrides and dianhydrides obtained by dehydration.

  Next, the manufacturing method of the alkoxysilane compound used for the solution containing the alkoxysilane compound which has a carboxyl group used for this invention is demonstrated. The manufacturing method of the alkoxysilane compound used for the solution containing the alkoxysilane compound which has a carboxyl group used for this invention is not specifically limited, It can manufacture by a well-known method. For example, an alkoxysilane compound having a carboxyl group, which is a target product, can be obtained by reacting by a method such as the following (A) or (B).

(A) When R ^{2 in the} general formula (I) is —NH ₂ , an imidazolyl group or a triazolyl group, a solution obtained by dissolving the compound of the general formula (I) in a solvent is dissolved in a carboxylic acid anhydride in the solvent. The solution is added dropwise to the solution at 0 to 25 ° C., and stirred at 5 to 60 ° C. for 0.1 to 5 hours after the completion of the addition.
(B) When R ² of the general formula (I) is —NCO, a solution obtained by dissolving the compound of the general formula (I) in a solvent is added to a solution obtained by dissolving a carboxylic acid anhydride in a solvent at 30 to 80 ° C. The solution is added dropwise, and stirred at 30 to 80 ° C. for 0.5 to 6 hours after completion of the dropping.

  The ratio of the compound represented by the general formula (I) and the monoanhydride or dianhydride obtained by dehydrating a divalent or higher carboxylic acid compound or a divalent or higher carboxylic acid compound is as follows: It is preferable to make it. Specifically, the ratio of the compound represented by the general formula (I) to a dihydride or higher carboxylic acid compound or a monoanhydride or dianhydride formed by dehydration of a divalent or higher carboxylic acid compound is a molar ratio. In formula (1), a monoanhydride or dianhydride obtained by dehydrating a divalent or higher carboxylic acid compound or a divalent or higher carboxylic acid compound = 1.5 / 1 to 1 / 1.5. Preferably, it is configured to be 1.2 / 1 to 1 / 1.2, more preferably 1.1 / 1 to 1 / 1.1. preferable.

  The solvent used in the above reaction is not particularly limited, but an aprotic polar solvent is preferable. More specifically, tetrahydrofuran, methyl tertiary butyl ether, 1,4-dioxane, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, 1,3-dioxolane, 2-methyltetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide , Acetone, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), acetonitrile, propionitrile, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone. More preferable examples include acetone, NMP, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide and the like, and it is more preferable to use NMP.

  The concentration of the alkoxysilane compound used in the solution containing the alkoxysilane compound having a carboxyl group used in the present invention may be appropriately adjusted depending on the object to be plated, but is preferably 0.001 to 10%, 0.005 ˜5% is particularly preferred. Here, if it is less than 0.001% by mass, the effect of improving the adhesion is not exhibited, and this is not preferable.

  The solvent that may be used in the solution containing the alkoxysilane compound having a carboxyl group used in the present invention is not particularly limited, and a known general solvent can be used. Examples of the solvent include water; alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol; acetates such as ethyl acetate, butyl acetate, and methoxyethyl acetate; tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. , Ethers such as triethylene glycol dimethyl ether, dibutyl ether and dioxane; ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone and methylcyclohexanone; hexane, cyclohexane , Methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene Hydrocarbons such as xylene; 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1, Hydrocarbons having a cyano group such as 4-dicyanocyclohexane and 1,4-dicyanobenzene; pyridine, lutidine, and the like. These may be used alone or in combination depending on the solubility of the solute, the use temperature and boiling point, the flash point, etc. Used as a mixed solvent of two or more.

  The solution containing the alkoxysilane compound having a carboxyl group used in the present invention can be mixed with other known additives as necessary within a range not impairing the effects of the present invention. Examples of such other additives include a pH buffer solution and a surfactant.

  The pH buffer solution is not particularly limited, and a well-known general pH buffer solution may be used. Examples thereof include an acetate buffer solution, a phosphate buffer solution, a citrate buffer solution, and a borate buffer solution. .

  Said surfactant is used in order to improve wettability. For example, surfactants such as cationic, nonionic, anionic, and betaine are listed, and cationic, nonionic, or anionic surfactants are preferably used. As for the usage-amount in the case of using surfactant, 0.01-5 mass% is preferable.

  Examples of the cationic surfactant that may be used in the solution containing an alkoxysilane compound having a carboxyl group used in the present invention include alkyl (alkenyl) trimethyl ammonium salts, dialkyl (alkenyl) dimethyl ammonium salts, alkyl ( Alkenyl) quaternary ammonium salt, mono- or dialkyl (alkenyl) quaternary ammonium salt containing ether group or ester group or amide group, alkyl (alkenyl) pyridinium salt, alkyl (alkenyl) dimethylbenzylammonium salt, alkyl (alkenyl) isoquinolinium Salt, dialkyl (alkenyl) morphonium salt, polyoxyethylene alkyl (alkenyl) amine, alkyl (alkenyl) amine salt, polyamine fatty acid derivative, amyl alcohol Fatty acid derivatives, benzalkonium chloride, etc. benzethonium chloride and the like, may contain fluorine atoms in these structures.

  Nonionic surfactants that may be used in the solution containing the alkoxysilane compound having a carboxyl group used in the present invention include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene polyoxypropylene Alkyl ether (addition form of ethylene oxide and propylene oxide may be random or block), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or its ethylene oxide adduct, sorbitan fatty acid Esters, polyoxyethylene sorbitan fatty acid esters, alkyl polyglucosides, fatty acid monoethanolamides or their ethylene oxide Adduct, fatty acid-N-methylmonoethanolamide or its ethylene oxide adduct, fatty acid diethanolamide or its ethylene oxide adduct, sucrose fatty acid ester, alkyl glycerin ether, alkyl polyglycerin ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid Examples thereof include esters, fatty acid methyl ester ethoxylates, and N-long chain alkyldimethylamine oxides, and these structures may contain a fluorine atom.

  Examples of the anionic surfactant that may be used in the solution containing the alkoxysilane compound having a carboxyl group used in the present invention include higher fatty acid salts, higher alcohol sulfate esters, sulfurized olefin salts, and higher alkyl sulfonic acids. Salt, α-olefin sulfonate, sulfated fatty acid salt, sulfonated fatty acid salt, phosphate ester salt, sulfate ester salt of fatty acid ester, glyceride sulfate ester salt, sulfonate salt of fatty acid ester, α-sulfo fatty acid methyl ester salt , Polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates, polyoxyalkylene alkyl ether carboxylates, acylated peptides, fatty acid alkanolamides or sulfur oxides thereof. Acid ester salt, sulfosuccinic acid ester, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl benzimidazole sulfonate, polyoxyalkylene sulfosuccinate, salt of N-acyl-N-methyltaurine, N-acyl glutamic acid or its Salt, acyloxyethanesulfonate, alkoxyethanesulfonate, N-acyl-β-alanine or a salt thereof, N-acyl-N-carboxyethyltaurine or a salt thereof, N-acyl-N-carboxymethylglycine or a salt thereof , Acyl lactate, N-acyl sarcosine salt, alkyl or alkenylaminocarboxymethyl sulfate, and the like, and a fluorine atom may be contained in these structures.

  The object to be plated that can be used in the pretreatment method of the present invention is not particularly limited. For example, metals such as copper, silver, gold, zinc, nickel, tin, cobalt, and chromium, and these metals such as stainless steel. Alloys, polysiloxane polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polystyrene, acrylonitrile butadiene styrene, polycarbonate, polyhexamethylene adipamide, norbornene resin, Synthetic resins such as nitrocellulose, urethane resin, phenol resin, urea resin, melamine resin, amide resin, acrylic resin, epoxy resin, acrylonitrile butadiene rubber, silicone rubber, glass, silica, alumina, zirconia, nitriding Ceramics such as iodine, silicon carbide, aluminum nitride, boron nitride, hydroxyapatite, fluorite, barium titanate, lead zirconate titanate, ferrite, mullite, steatite, forsterite, cordierite, sialon, machinable ceramics 1 type or 2 types or more are selected. In particular, stainless steel, glass, and synthetic resin are preferable because the effect of improving adhesion after electroless plating is high. When using 2 or more types together, it is preferable to use a synthetic resin in combination with at least one object to be plated that can be used under the above-mentioned preferable conditions. The to-be-plated body mentioned above may contain a filler and does not need to contain it. The surface of the object to be plated may or may not be roughened, and the degree of roughening may be high or low.

  The method for producing an electroless plating film of the present invention includes pretreatment of electroless plating using the electroless plating pretreatment agent of the present invention and pretreatment using a solution containing an alkoxysilane compound having a carboxyl group. An electroless plating is applied to a body to be plated as a primary pretreatment, and the electroless plating pretreatment method using the electroless plating pretreatment agent of the present invention is applied as a secondary pretreatment to the body to be plated. This is due to plating.

  As the electroless plating solution used in the method for producing an electroless plating film of the present invention, a known one can be used. For example, copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium , Tungsten, platinum, rhodium or ruthenium selected from the group consisting of one or more components for electroless plating, particularly plating copper, nickel and silver from the viewpoint of high adhesion improvement effect An electroless plating solution is preferable.

  The electroless plating production conditions used in the electroless plating film production method of the present invention are not particularly limited, and well-known general conditions and methods can be used according to the electroless plating solution used. .

  As an electroless copper plating condition when, for example, a 1 μm electroless copper plating film is manufactured by the method for manufacturing an electroless plating film of the present invention, the plating bath temperature is preferably 10 to 60 ° C., particularly 20 to 40 ° C. preferable. The electroless plating time is preferably 1 to 60 minutes, particularly preferably 1 to 30 minutes.

  The plated product manufactured using the pretreatment method of electroless plating of the present invention is not particularly limited. For example, automotive industrial materials (heat sinks, carburetor parts, fuel injectors, cylinders, various valves, Engine internals, etc., electronics industry materials (contacts, circuits, semiconductor packages, printed circuit boards, thin film resistors, capacitors, hard disks, magnetic materials, lead frames, nuts, magnets, resistors, stems, computer components, electronic components, laser oscillation) Element, optical memory element, optical fiber, filter, thermistor, heating element, high temperature heating element, varistor, magnetic head, various sensors (gas, temperature, humidity, light, speed, etc.), MEMS, etc., precision equipment (copier parts, Optical equipment parts, watch parts, etc.), aviation and ship materials (hydraulic equipment, screws, engines, Turbines, etc.), chemical industrial materials (ball, gate, plug, check, etc.), various molds, machine tool parts, vacuum equipment parts like, include those extensive. The electroless plating pretreatment method of the present invention is particularly preferably used for electronic industrial materials that require adhesion between the electroless plating and the object to be plated. In particular, the plating process is used in the manufacture of semiconductor packages and printed circuit boards. More preferably, the semiconductor package is more preferable.

Hereinafter, the present invention will be described in more detail with reference to examples and the like. However, the present invention is not limited by the following examples.
Example 1 Preparation 1 of Pretreatment Agent
By using the carbodiimide compounds shown in Table 1 and the compounds and blending amounts shown in Table 2, Example Composition No. 1 to 3 were prepared so that the total mass was 500 g.

Comparative Example 1: Preparation of Comparative Composition 1 Comparative composition 1 was prepared according to the compounds and blending amounts shown in Table 2 so that the total mass was 500 g.

表２中、実施例組成物Ｎｏ．１のｐＨは、９．６であり、実施例組成物Ｎｏ．２のｐＨは、９．３であり、実施例組成物Ｎｏ．３のｐＨは、１０．０であった。

In Table 2, Example Composition No. 1 has a pH of 9.6. The pH of No. 2 is 9.3. The pH of 3 was 10.0.

Example 2: Pretreatment 1
As the object to be plated, a filler-containing aromatic epoxy resin composition (roughness: Ra = 1.3 μm, shape: 50 mm × 130 mm × 1 mm) subjected to a smear swelling process, a microetching process, and a reduction process was used. This object to be plated was immersed in each composition prepared in Example 10 at 60 ° C. for 10 minutes, washed with water at room temperature for 1 minute, and dried at 130 ° C. for 15 minutes to perform pretreatment of electroless plating.

Evaluation Example 1: Adhesion evaluation 1
After applying a Pd catalyst to the object to be plated pretreated by the method described in Example 2, the object to be plated is immersed in an electroless copper plating bath adjusted to 32 ° C., and electroless copper plating is performed for 20 minutes with air stirring. Went. The electroless copper plating solution used was Atotech Co., Ltd., product name: MSK-DK. The obtained plating thickness is 1 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 150 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on the electroless copper plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 3.

  From the results of Table 3, the evaluation examples 1-1 to 1-3 have significantly improved Cu peel strength as compared with Comparative Example 1. It was found that a plating film with high adhesion can be obtained by performing pretreatment using 1 to 3.

Preparation of Solution Containing Alkoxysilane Compound Having Carboxyl Group According to the following Production Examples 1-1 to 1-5, Production Example Composition No. 1 is a solution containing an alkoxysilane compound having a carboxyl group. 1-5 were obtained.

Production Example 1-1 Production Example Composition No. Preparation of 1 Meso-butane-1,2,3,4-tetracarboxylic acid (23.4 g) was dissolved in NMP (158.2 g) and heated to 60 ° C. After heating, 3-isocyanatopropyltrimethoxysilane (20.5 g) was added dropwise over 10 minutes with stirring. After completion of dropping, the mixture was heated to 80 ° C. and stirred for 1 hour. The disappearance of 3-isocyanatopropyltrimethoxysilane was confirmed by gas chromatography and the process was completed. By mixing the obtained NMP solution (25.0 g) and ion-exchanged water (475.0 g), Production Example Composition No. 1 was obtained.

Production Example 1-2: Production Example Composition No. Preparation of 2 Meso-butane-1,2,3,4-tetracarboxylic acid (23.4 g) was dissolved in NMP (175.0 g) and heated to 60 ° C. After heating, 3-isocyanatopropyltriethoxysilane (24.7 g) was added dropwise over 10 minutes with stirring. After completion of dropping, the mixture was heated to 80 ° C. and stirred for 1 hour. The disappearance of 3-isocyanatopropyltriethoxysilane was confirmed by gas chromatography and the process was completed. By mixing the obtained NMP solution (25.0 g) and ion-exchanged water (475.0 g), Production Example Composition No. 2 was obtained.

Production Example 1-3: Production Example Composition No. Preparation of 3 Succinic anhydride (10.0 g) was dissolved in NMP (128.6 g) at room temperature. While stirring in a water bath, 3-aminopropyltriethoxysilane (22.2 g) was added dropwise over 10 minutes with stirring. After completion of dropping, the mixture was heated to 50 ° C. and stirred for 1 hour. The disappearance of 3-aminopropyltriethoxysilane was confirmed by gas chromatography and the process was completed. By mixing the obtained NMP solution (25.0 g) and ion-exchanged water (475.0 g), Production Example Composition No. 3 was obtained.

Production Example 1-4: Production Example Composition No. Preparation of 4 Meso-butane-1,2,3,4-tetracarboxylic acid (23.4 g) was dissolved in NMP (222.7 g) and heated to 60 ° C. After heating, 3-isocyanatopropyltrimethoxysilane (41.1 g) was added dropwise over 20 minutes with stirring. After completion of dropping, the mixture is heated to 80 ° C. and stirred for 1 hour. The disappearance of 3-isocyanatopropyltrimethoxysilane was confirmed by gas chromatography and the process was completed. By mixing the obtained NMP solution (25.0 g) and ion-exchanged water (475.0 g), Production Example Composition No. 4 was obtained.

Production Example 1-5: Production Example Composition No. Preparation of 5 Trimellitic anhydride (19.2 g) was dissolved in NMP (165.5 g) at room temperature. While stirring in a water bath, 3-aminopropyltriethoxysilane (22.2 g) was added dropwise over 10 minutes with stirring. After completion of dropping, the mixture was heated to 50 ° C. and stirred for 1 hour. The disappearance of 3-aminopropyltriethoxysilane was confirmed by gas chromatography and the process was completed. Triethanolamine (3.6 g) was added to the obtained NMP solution (25.0 g), and ion-exchanged water (471.4 g) was mixed, whereby Production Example Composition No. 5 was obtained.

Comparative Example 2: Preparation of Comparative Composition 2 Comparative composition 2 was obtained by mixing 3-aminopropyltrimethoxysilane (5.0 g) and ion-exchanged water (495.0 g).

Example 3: Pretreatment 2
As the object to be plated, a filler-containing aromatic epoxy resin composition (roughness: Ra = 1.3 μm, shape: 50 mm × 130 mm × 1 mm) subjected to a smear swelling process, a microetching process, and a reduction process was used. This object to be plated was immersed in a solution containing an alkoxysilane compound having a carboxyl group prepared in Example 3 and stirred at 40 ° C. for 5 minutes in an air atmosphere, followed by washing with water at 25 ° C. for 1 minute. Each was immersed in an aqueous solution containing a compound having a carbodiimide group prepared in Example 1, washed with water at 25 ° C. for 1 minute, and dried at 130 ° C. for 15 minutes to perform a pretreatment for electroless plating. Hereinafter, treatment with a solution containing an alkoxysilane compound having a carboxyl group was defined as primary treatment, and treatment with an aqueous solution containing a compound having a carbodiimide group was defined as secondary treatment.

Evaluation example 2: Adhesion evaluation 2
After applying a Pd catalyst to the object to be plated pretreated by the method described in Example 3, the object to be plated is immersed in an electroless copper plating bath adjusted to 32 ° C., and electroless copper plating is performed for 20 minutes with air stirring. Went. The electroless copper plating solution used was Atotech Co., Ltd., product name: MSK-DK. The obtained plating thickness is 1 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 150 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on the electroless copper plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 4.

  From Table 4, Comparative Examples 2-2 to 2-4 in which only the primary treatment was performed and Evaluation Examples 2-8 to 2-10 in which only the secondary treatment was performed were confirmed to have improved adhesion as compared with Comparative Example 1. did it. In addition, Evaluation Examples 2-1 to 2-7 subjected to the primary treatment and the secondary treatment are more closely adhered to Comparative Examples 2-1 to 2-4 and Evaluation Examples 2-8 to 2-10. It was confirmed that the performance was improved. Among these, in the secondary treatment, Example Composition No. In Evaluation Examples 2-2 and 2-4 to 2-7 using 2, it was confirmed that particularly high adhesion was obtained. From this, the synergistic adhesive improvement effect by the combination of the pre-processing method of this invention was able to be confirmed. On the other hand, when the alkoxysilane compound which does not have a carboxyl group was used for primary treatment like the evaluation example 2-11, the synergistic adhesive improvement effect was not able to be confirmed.

Evaluation Example 3: Adhesion evaluation 3
After the Pd catalyst was applied to the object to be plated pretreated by the method described in Example 3, the object to be plated was immersed in an electroless nickel plating bath adjusted to 60 ° C., and electroless nickel was stirred for 15 minutes under air stirring. Plating was performed. As the electroless nickel plating solution, an electroless nickel plating bath containing the components shown in Table 5 was used. The obtained plating thickness is 2.0 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 180 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on the electroless nickel plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 6.

  From the results of Table 6, the evaluation examples 3-1 and 3-2 are greatly improved in peel strength as compared with comparative example 3, and particularly in evaluation example 3-2, the peel strength is greatly improved. I was able to confirm. From this, it was found that the present invention has an effect of improving adhesion even in the case of electroless nickel plating.

Evaluation Example 4: Adhesion evaluation 4
After the Pd catalyst was applied to the substrate pretreated by the method described in Example 3, the object to be plated was immersed in an electroless silver bath adjusted to 25 ° C., and 10% glucose was stirred while stirring the bath in an air atmosphere. The aqueous solution was added dropwise over 7 minutes. After completion of dropping, the mixture was stirred for 30 minutes and electroless silver plating was performed. As the electroless silver plating solution, an electroless silver plating bath containing the components shown in Table 7 was used. The obtained plating thickness is 0.5 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 180 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on this electroless silver plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 8.

  From the results of Table 8, Evaluation Example 4-1 and Evaluation Example 4-2 have greatly improved peel strength compared to Comparative Example 4, and in particular, Evaluation Example 4-2 has greatly improved peel strength. I was able to confirm. From this, it was found that the present invention has an effect of improving adhesion even in the case of electroless silver plating.

Example 4: Pretreatment 3
As the object to be plated, a soda-lime glass substrate (roughness: Ra≈0.6 μm, shape: 50 mm × 130 mm × 1 mm) subjected to a smear swelling process, a microetching process, and a reduction process was used. This object to be plated was immersed in a solution containing an alkoxysilane compound having a carboxyl group prepared in Example 3 and stirred at 40 ° C. for 5 minutes in an air atmosphere, followed by washing with water at 25 ° C. for 1 minute. Each was immersed in an aqueous solution containing a compound having a carbodiimide group prepared in Example 1, washed with water at 25 ° C. for 1 minute, and dried at 130 ° C. for 15 minutes to perform a pretreatment for electroless plating.

Evaluation Example 5: Adhesion evaluation 5
After applying a Pd catalyst to the object to be plated pretreated by the method described in Example 4, the object to be plated is immersed in an electroless copper plating bath adjusted to 32 ° C., and electroless copper plating is performed for 20 minutes with air stirring. Went. The electroless copper plating solution used was Atotech Co., Ltd., product name: MSK-DK. The obtained plating thickness is 1 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 150 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on the electroless copper plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 9.

※１ 実験を試みたものの、無電解銅めっき被膜が付着しなかった。

* 1 Although an experiment was attempted, the electroless copper plating film did not adhere.

  From the results of Table 9, in Comparative Example 5, the electroless copper plating film could not be adhered, but in Evaluation Example 5-1, the electroless copper plating film could be adhered to the soda-lime glass substrate, and further peeled. The strength could be obtained. From this, it was found that the electroless copper plating film can be adhered to the soda-lime glass substrate by the pretreatment method of the present invention.

Example 5: Pretreatment 4
As the object to be plated, a stainless steel substrate (SUS-304, roughness: Ra≈0.2 μm, shape: 50 mm × 130 mm × 1 mm) subjected to a smear swelling process, a microetching process, and a reduction process was used. Each of the objects to be plated was immersed in a solution containing an alkoxysilane compound having a carboxyl group prepared in Example 1 and stirred in an air atmosphere at 40 ° C. for 5 minutes, followed by washing with water at 25 ° C. for 1 minute. Each was immersed in an aqueous solution containing a compound having a carbodiimide group prepared in Example 3, washed with water at 25 ° C. for 1 minute, and dried at 130 ° C. for 15 minutes to perform a pretreatment for electroless plating.

Evaluation Example 6: Adhesion evaluation 6
After applying a Pd catalyst to the object to be plated pretreated by the method described in Example 5, the object to be plated is immersed in an electroless copper plating bath adjusted to 32 ° C., and electroless copper plating is performed for 20 minutes with air stirring. Went. The electroless copper plating solution used was Atotech Co., Ltd., product name: MSK-DK. The obtained plating thickness is 1 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 150 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on the electroless copper plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 10.

※２ 実験を試みたものの、無電解銅めっき被膜が付着しなかった。

* 2 Although an experiment was attempted, the electroless copper plating film did not adhere.

  From the results of Table 10, the electroless copper plating film could not be attached in Comparative Example 6, but the electroless copper plating film could be attached to the stainless steel substrate (SUS-304) in Evaluation Example 6-1. Furthermore, peel strength could be obtained. From this, it was found that the electroless copper plating film can be adhered to the stainless steel substrate (SUS-304) by the pretreatment method of the present invention.

Claims (6)

  An electroless plating pretreatment agent comprising an aqueous solution containing a compound having a carbodiimide group.   The electroless plating pretreatment agent according to claim 1, wherein the compound having a carbodiimide group is a nonionic polycarbodiimide compound having a chemical formula amount of 300 to 500 per mole of the carbodiimide group.   A pretreatment method for electroless plating, which comprises pretreating an object to be plated using the pretreatment agent for electroless plating according to claim 1 or 2.   A pretreatment using a solution containing an alkoxysilane compound having a carboxyl group is applied to the object as a primary pretreatment, and the pretreatment according to claim 3 is further applied to the object as a secondary pretreatment. An electroless plating pretreatment method characterized by the above.   The said to-be-plated body is 1 type, or 2 or more types selected from the group which consists of copper, silver, gold | metal | money, zinc, nickel, tin, cobalt, chromium, stainless steel, ceramics, glass, and a synthetic resin. The electroless plating pretreatment method according to 1.   The pretreatment method according to claim 3 or 4 is applied to the object to be plated, and further selected from the group consisting of copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium, tungsten, platinum, rhodium and ruthenium. The manufacturing method of the electroless-plating film which forms an electroless-plating film by electroless-plating the 1 type, or 2 or more types of component by which it is carried out.