TW201035374A - Electroless tin or tin alloy plating solution and electronic element foemed with tin or tin alloy film by using electroless tin or tin alloy plating solution - Google Patents

Abstract

The present invention provides an electroless tin or tin alloy plating solution capable of forming a plating film having a good solder wettability and a reliable bonding ability with substrate and solder, and having less bleeding of the plating solution into the interface of cover-lay film or solder resist and copper or copper alloy. The electroless tin or tin alloy plating solution contains at least a tin salt, a complexing agent and an acid, and further contains an azole compound or an azine compound having at least three nitrogen atoms in the ring.

Description

201035374 VI. Description of the invention: [Technical field to which the invention pertains] ^About the electroless tin or tin alloy ore coating (in the present invention, ..., electrolytic tin coating or tin alloy plating solution) and using the plating The coating liquid forms a tin or tin alloy quilt member. [Prior Art] Electroless tin Ο 〇 ' ' is widely used as a tin bond treatment method for flexible printed substrates. In recent years, due to the trend of lead-free, electroless tin ore coating The program is an exaggerated and eye-catching approach to the final surface treatment of rigid printed substrates. However, Bu & ττ

, electroless tin plating solution, in general, due to pH - this is more than two temperatures (50 ° C or more) will be impregnated in the plating solution, / spears in the printed substrate Then, the tin plating solution penetrates into the interface between the copper and the protective film (cover lay; filin). In the rigid printed substrate, the tin-bell coating is incorporated into the interface between the copper and the solder-resist layer, and the solder resist layer is caused. The problem of floating or forming a local battery to dissolve the copper in the portion. In order to solve such a problem, a method of forming a solder resist layer on a wiring substrate to which a mineral coating is applied is generally employed. However, since this method also forms a plating film for a portion which does not require plating treatment, the manufacturing cost is increased and it is not suitable. Further, Patent Document 1 discloses a method for suppressing penetration of a plating solution into a copper-preservative layer by performing an oxidation treatment by a chromate or an organic compound in forming a solder resist layer, but this method is also There is a problem of rising manufacturing costs due to the increase in steps. On the other hand, it is generally known that a four-degree sitting compound or a two-dimensional sitting material 321709 3 201035374 can be used as an anti-corrosion agent or a rust preventive agent. For example, Patent Documents 2 and 3 disclose metal anti-surplus agents or rust inhibitors containing a tetraindole compound or a salt thereof. Further, Patent Documents 4 to 6 describe a surface treatment agent containing a tetraπ-seat compound or a benzotriazine sitting compound. These surface treatment agents are microetched for their purpose, and contain an acid or an oxidizing agent to thicken the surface. Although such a corrosion inhibitor or surface treatment agent employs a tetrazole compound or a benzotriazole compound, it exhibits a property different from that of a tin or tin alloy plating solution. [Prior Art Document] [Patent Document] Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Japanese Patent Laid-Open No. Hei. No. Hei. No. 2,092, 281, Japanese Patent No. 2,021, 281, Japanese Patent No. 3141145 [Problem to be Solved by the Invention] An object of the present invention is to provide a plating solution that penetrates a protective film or a solder resist layer. The interface with copper or copper alloy is small, and it is possible to form an electroless tin or tin alloy forging solution of a plating film which has good wettability of the solder and good joint reliability between the substrate and the flux. [Means for Solving the Problems] As a result of intensive research on the above-mentioned problems, the present inventors have found that, as in the electroless tin and tin alloy plating solution, a specific azole compound (azol e 321709 201035374 compound) or D well compound (azine) is contained. Compound) 'The fact that the above problems can be solved, finally completed the present invention. That is, the present invention is as follows. (1) An electroless tin or tin alloy plating solution containing at least a tin salt, a binder, an acid electroless tin or a tin alloy plating solution, wherein a compound containing three or more nitrogen atoms in the ring is contained Or bismuth compound. (2) The electroless tin or tin alloy plating solution according to the above (1), wherein the electroless tin or tin alloy ore coating liquid contains a triterpenoid compound represented by the following general formula (A) or (B) :

(匕 to R3 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, an alkoxy group having a carbon number of 10 or less, or a halogen atom, a trans group, a thiol group, an amine C) group, or a lower alkane. a substituted amino group, a hydroxy lower alkyl-substituted amine group, a thiol-substituted group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, a carboxyl group Or either a halogen atom or a hydrogen atom). (3) The electroless tin or tin alloy plating solution according to the above (1), wherein the electroless tin or tin alloy plating solution contains the benzotriazole compound represented by the following general formula (C): 321709 201035374

(R4 to R8 represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkoxy group having a carbon number of 10 or less, or substituted by an IS atom, a hydroxyl group, a carboxyl group, an amine group or a lower alkyl group; a group substituted with an amine group, a hydroxy lower alkyl-substituted amine group, or a fluorenyl group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, a carboxyl group, or Any of a halogen atom or a hydrogen atom). (4) The electroless tin or tin alloy plating solution according to the above (1), wherein the electroless tin or tin alloy plating solution contains the fourth general formula (D). Sitting compound:

(Rg, Rio represents a decyl group of 10 or less, an alkenyl 'alkynyl group, an aryl group, an aralkyl group, an alkoxy group, or the like, or substituted by an ifi atom, a hydroxyl group, a carboxyl group, an amine group, or a lower alkyl group. a group substituted with an amine group, a hydroxy lower alkyl-substituted amine group, or a fluorenyl group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, a carboxyl group, or Any of a halogen atom or a hydrogen atom). (5) The electroless tin or tin alloy plating solution according to the above (1), wherein the electroless tin or tin alloy plating solution contains the tetrasal compound represented by the following general formula (E) in 6 321 709 201035374 : (E) R12 Rll / \

(Rn, Ri2 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a D aralkyl group, an alkoxy group having a carbon number of 10 or less, or is substituted by a halogen atom, a hydroxyl group, a carboxyl group, an amine group, or a lower alkyl group. An amine group, a group substituted with an amine group substituted with a lower alkyl group, or a group substituted with a thio group, or an amine group, a lower alkyl group-substituted amine group, a hydroxy lower alkyl group-substituted amine group, a thiol group, a hydroxyl group, a carboxyl group, Or a halogen atom or a hydrogen atom, and Rl3 represents a single bond, or an alkylene group having at least 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a halogen atom. Any one of a hydroxyl group, a carboxyl group, an amine group, a fluorenyl group, an azo group, a thio group, a disulfide group, or a azo group, a thio group or a dithiol group. (6) The electroless tin or tin alloy plating solution according to the above (1), wherein the electroless tin or tin alloy key solution contains the three-till compound represented by the following general formula (F): (F)

14

R15 (r14 to r16 represents an alkyl group, an alkenyl group, an alkynyl group, an aromatic 7 321709 201035374 group, an aralkyl group, an alkoxy group having a carbon number of 10 or less, or such a iodin atom, a hydroxyl group, a carboxyl group, an amine group, or a lower group. An alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol-substituted group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a fluorenyl group, a hydroxyl group , a carboxyl group, or any of a halogen atom or a hydrogen atom). (7) An electronic component in the electroless tin or tin alloy plating solution according to any one of (1) to (6) above, wherein the impregnated surface has a copper or copper alloy pattern, and is formed at least The electronic component of the resin composition on the copper or copper alloy pattern forms an electronic component of the tin or tin alloy coating, and the electroless tin or tin alloy plating solution penetrates into the interface of the copper or copper alloy and the resin composition to a depth of 30 //m or less. (8) The electronic component according to the above (7), wherein the electronic component is a printed circuit board. (9) The electronic component according to the above (7), wherein the electronic component is a TAB (Tape Aut (10) Bonded Bond) film carrier. (10) The electronic component according to the above (7), wherein the electronic component is a wafer substrate. [Effects of the Invention] The electroless tin or tin alloy plating solution of the present invention is used for the final surface treatment of a flexible substrate or a rigid printed substrate, and the plating solution penetrates into the protective film or the solder resist layer and the copper or copper alloy interface. In a few cases, the problem of floating of the protective film or the solder resist layer and formation of a local battery to dissolve the copper or copper alloy in the portion can be solved. Further, it is possible to form a plating film having a good wettability of the flux and a good bonding reliability between the substrate and the flux 8321709 201035374. [Embodiment] The electroless tin plating solution or the tin alloy plating solution of the present invention contains at least a tin salt, a coupling agent, and an acid in the key solution, and contains three or more azole compounds containing a nitrogen atom in the ring. Or cultivated compounds. In the case of an azole compound or a π well compound containing three or more nitrogen atoms in the ring, it is preferred that the ring contains a nitrogen atom of three or four azole compounds or a ruthenium complex, and examples thereof include a triazole compound and a benzo compound. The triazole compound, the tetrazole compound, the three-till compound, and the like are particularly preferably the following three general formulas (A) and (B). The compound, the benzotriazole compound represented by the general formula (C), the tetrazole compound represented by the general formula (1)), (E), and the tri-farming compound represented by the general formula (F).

(Ri to Rs represents an alkyl group, a mercapto group, an alkynyl group, an aryl group, an aralkyl group, an alkoxy group having a carbon number of 1 Å or less, or substituted by a halogen atom, a hydroxyl group, a carboxyl group, an amine group or a lower alkyl group; a group substituted with an amine group, a hydroxy lower alkyl-substituted amine group, or a fluorenyl group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, a carboxyl group, or a halogen Any of an atom or a hydrogen atom). 321709 9 201035374 (c) R 〇 R4

Rs (R4 to R8 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkoxy group having a carbon number of 10 or less, or substituted by a halogen atom, a hydroxyl group, a carboxyl group, an amine group or a lower alkyl group; a group substituted with an amine group, a hydroxy lower alkyl-substituted amine group, or a fluorenyl group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, a carboxyl group, or Any of a halogen atom or a hydrogen atom).

(RpRi. represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, an alkoxy group having a carbon number of 10 or less, or an amine group substituted by a halogen atom, a hydroxyl group, a carboxyl group, an amine group or a lower alkyl group. a group substituted with a hydroxy-lower alkyl-substituted amine group or a fluorenyl group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, a carboxyl group, or a halogen Any of an atom or a hydrogen atom). 10 321709 201035374 (E)

(Rn, R12, (4) number of alkyl, keto, alkynyl aralkyl, alkoxy, or such surface ~ θ base, low minus substituted amine, = atom, thiol, fluorenyl Any one of the amine groups, or a lower-molecular amine group, a lower-based alkyl group, a lower alkyl group, a lower alkyl group-substituted amine group, a sub-nitrogen atom, And; =, the base, the slow base, or the dentinogen of the extension of the base, the extension of the alkenyl, the alkyne, from the opposite of the (four) auxiliaries, secret, county, 2 base, extension technology, or Any of these dithio groups - the county group, the H azo group, the thio group, the divalent group -). Cut azo, thio, disulfide (F)

α" to Rl6, the number of carbon to the lower, the thin, the base, the base, the Fang, the alkoxy, or the (tetra) atom, the base, the slow, the amine, the low minus a material, a low-alcohol-substituted amine, a sulphide-substituent-substituted amino group, a lower-substituted amino group, an amine substituted with a lower alkyl group, a recorded, a carboxy group, or 321709 11 201035374 Any one of a halogen atom and a hydrogen atom). In the above-mentioned general formulae (1) to (F), Ri to &, the heart to the number ίο or less, the second one of the lower alkyl group, the alkenyl group and the s ' is preferably a carbon number. The solder base and the block of 2 to 4 are preferably a phenyl group, and an aromatic yarn is preferably a node group. Calcination: Preferably, the number of carbon atoms is from 1 to 4. These silk, women's base, ^ base,. The aryl group, the aryl group, and the silk group may be substituted by an amine group substituted with a halogen atom, a (four), a silk, a group, a lower group, or a group substituted with a lower group. Further, ^, ^ to ^, 'other acceptable amine groups, lower alkyl substituted amine groups, hydroxy lower alkyl substituted amine groups, mercapto groups, hydroxyl groups, carboxyl groups, or halogen atoms, hydrogen atoms, Etc. =, preferably a hydroxyl group, a mercapto group, an amine group, a lower alkyl group substituted amine group, a mercapto group, or a hydrogen atom. The lower alkyl group substituted with a lower alkyl group and the lower alkyl group substituted with a hydroxy lower alkyl group are preferably an alkyl group of 1 to 4. In R1S, the alkylene group having a carbon number of 10 or less is preferably a lower alkylene group having a carbon number of from 4 to 4, an alkenyl group having an alkyl group of 1 or less and an alkylene group, preferably a carbon number. 2 to 4 of an alkenyl group and an alkynyl group, and a aryl group having a carbon number of 1 Å or less, preferably a stearyl group, and a arylene group having a carbon number of 10 or less, preferably a benzylidene group. . Any of an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group, which may be a halogen atom, a hydroxyl group, a carboxyl group, an amine group, a thiol group, an azo group, a thio group or a monothio group. Replaced by. Further, in the case of Rls, a divalent group of a single bond, an azo group, a thio group or a disulfide group may be mentioned, and among these, a divalent group of a single bond, an azo group or a disulfide group is preferable. In the case of the compound represented by the above general formula (A), it is preferably 321709 12 201035374 1H-1, 2, 3-triazole, 5-mercapto-1H-1, 2,3-triazole, 5-amino group. _1H-1, 2, 3-three β sit and so on. The compound represented by the above general formula (Β) is preferably 1Η-1,2,4-triazole, 3-mercapto 2,4-triazole, 3-amino-1H-1,2, 4- Triazole, 3-amino-5-mercapto-1H-1, 2,4-triazole, and the like. In the case of the compound represented by the above general formula (C), it is preferably benzotriazole, 5-mercapto-1H-benzotriazole, acenamylbenzotriazole, or hydroxybenzox-3-oxime: I-[n,n-bis(hydroxyethyl)aminomethyl]tolyltriazole or the like. In the case of the compound represented by the above general formula (D), it is preferably iH-tetrazole, 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-phenyl-5-fluorenyl group. 1H_ Four zeros wait. The compound represented by the above general formula (E) is preferably bistetrazole, 5,5-methylenebis-1H-tetrazole, 5,5,-azobis-1H-tetrazole, 5, 5-Azobis-1-methyl-tetrazole, 5,5'-dithiotetrazole, and the like. The hydrazine may be a compound represented by the above general formula (F), preferably 1' 3' 5-trimized, 2-amino-4 ethoxymethyl 6-methylamino- 1 - 3, 5 - 3 Plowing, 2, 4-=amino-6-phenyl], 3, 5_ triterpene, melamine (five), etc. In the ring liquid, three or more kinds of wow compounds or ruthenium compounds may be used in the ring, and two or more kinds may be used in the recording liquid. In the bell liquid, it is preferable to contain 〇. G1 to · g/ Liter, better for & If it does not reach 0, Glg / liter, the accounting shows (four) characteristics. Moreover, 舜P makes it more than 3 GGg/fill, and it is not beneficial to increase the loss of the coating due to the flash. · Also used for the tin salt, the wrong agent, the acid, and other constituents of the bell coating 321709 13 201035374 For the well-known person. As the tin salt, any soluble tin salt can be used, and tin oxide, chloride, sulfate, and organic hydrogenate can be used. In the case of tin alloy plating, a metal salt capable of forming an alloy with tin is used. For the metal salt, an oxide of a metal such as silver, lead, copper, cobalt, nickel, zinc, ruthenium, iridium or indium may be used. Chloride, sulfate, and organic sulfonate. The organic sulfonic acid of the above organic sulfonate may, for example, be methane sul fonic acid, ethinoic acid, decyl tartaric acid, ethanol-refluoric acid, benzoic acid, naphthalene acid Wait. The tin salt concentration at the time of tin plating is preferably from 1 to 200 g/liter, more preferably from 2 to 100 g/liter, in terms of metal concentration. 009至90质量份,优选优选为0. 009至90质量份, The 001 to 99. 9 parts by mass, particularly preferably from 0. 009 to 90 parts by mass, with respect to 1 part by mass of the tin salt. The total of the tin salt and the metal salt capable of forming an alloy with tin is preferably from 1 to 200 g/liter, more preferably from 2 to 100 g/liter, based on the metal concentration of tin. The binder may be placed on the base metal such as copper or copper alloy to form a mis-ion, and it is preferred to use the following (1) to (3) tongs alone or in combination. (1) Thiourea and 1, 3-dimercaptothiourea, trimethylthiourea, diethylthiourea (for example, 1,3-diethyl-2-thiourea), hydrazine, hydrazine '-Diisopropylthiourea, allylthiourea, acetylthiourea, ethylthiourea, 1,3-diphenylthiourea, thiourea dioxide, thiosemicarbazide 14 321709 201035374 Equal sulfur gland derivatives. (2) Ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetic acid disodium salt (EDTA · 2Na), hydroxyethyl ethylenediamine triacetic acid (HEDTA), diethylenetriamine pentaacetic acid (DTPA), three Ethylene triamine hexaacetic acid (TTHA), ethylenediaminetetrapropionic acid, ethylenediaminetetrakis (methylenephosphoric acid), diamethylenetriamine penta (methylene phosphate), and the like. (3) Nitrogen triacetic acid (1111:1^1〇1:1^&〇61:1〇3(:1(1,1^8), iminodiacetic acid (IDA) , iminodipropionate (IDP), amine tris (phosphinium phosphate), amine tris (methylene phosphate) pentasodium salt, benzylamine, 2-naphthylamine, isobutylamine, Isoamylamine, methyldiamine, ethylenediamine, tetradecyldiamine, pentadecyldiamine, hexamethylenediamine, diethylenetriamine, tetraamethyleneamine, pentaethylene Amine, heptaerythritol, cinnamyl amine, p-methoxy cinnamylamine, etc. The amount of the above-mentioned complexing agent is generally 5 to 300 g / liter. For the acid, it can be used: burnt stone yellow Acid (alkane sulfonic acid), C) alkanol sulfonic acid, organic retinic acid such as aromatic acid; or organic acid such as aliphatic carboxylic acid; inorganic acid such as sulfuric acid, hydrochloric acid or fluoroboric acid. Examples thereof include a repeating acid, a vinyl acid, a 1-propofuronic acid, a 1-butanesulfonic acid, etc. Examples of the alkanolsulfonic acid include 2-hydroxyethane-1-sulfonic acid, and 2 - Hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid 1-hydroxypropane-2-sulfonic acid, etc. The aromatic sulfonic acid may, for example, be benzenesulfonic acid or naphthalenesulfonic acid, and these may be substituted by a hydroxyl group, a halogen, an alkyl group, a carboxyl group or the like. : phenolsulfonic acid, naphtholsulfonic acid, etc. Examples of the aliphatic carboxylic acid include carboxylic acids having 1 to 6 carbon atoms such as acetic acid, propionic acid, n-butyric acid, and citric acid. 15 321709 201035374 Concentrations of such acids It is preferably from 1 to 30 g/liter, more preferably from 5 to 200 g/liter. Other components include a surfactant, an antioxidant, etc. The surfactant can be used to make the precipitated crystal fine and uniform. Further, when the tin alloy plating is applied, the potential difference between the tin and the alloy component metal element having a large difference in oxidation-reduction potential can be exhibited to stabilize the alloy composition property. Various non-ionic, anionic, cationic, and amphoteric surfactants are used. Examples of the nonionic surfactant include ethylene oxide and/or propylene oxide of 2 to 300 moles and the following compounds. Addition polymerization, etc.: polyalkylene glycol C1 to C20 alkanol, phenol, naphthol, bisphenols, C1 to C25 alkylphenol, arylalkylphenol, C1 to C25 alkyl naphthol, C1 to C25 alkoxy phosphate (salt), sorbitol An anhydride ester, a C1 to C22 aliphatic decylamine, etc. Examples of the anionic surfactant include an alkyl sulfate, a polyoxyethylidene ether sulfate, and a polyoxyethylene ethyl phenyl ether sulfate. Salt, alkyl benzoate, alkyl naphthylate, etc. Examples of the cationic surfactant include monoalkylamines, dialkylamines, trialkylamines, and dimercaptos. An alkyl ammonium salt, a tridecyl alkyl ammonium salt or the like. The amphoteric surfactant may, for example, be a carboxybetaine, a sulfo-sweet, a 13-million beet test, an aminocarboxylic acid or the like. The concentration of the surfactant is preferably from 0.01 to 10 g/liter, more preferably from 0.05 to 5 g/liter. 16 321709 201035374 Antioxidant, for the purpose of preventing the oxidation of tin, for example, hypophosphorous acid or its salt, ascorbic acid or its salt, hydroquinone, resorcinol, resorcinol Trisphenol (phl〇r〇glucin〇1), cresolsulfonic acid or a salt thereof, phenolsulfonic acid or a salt thereof, hydroquinone or a salt thereof, hydrazine or the like. The concentration of the antioxidant is preferably from 1 to 2 g/liter. The electroless tin plating solution or the tin alloy plating solution aqueous solution of the present invention has a plating temperature of preferably 5 to 9 (TC, more preferably 30 to 8 Torr). If it is less than 30 ° C, The deposition rate of the plating film is low, and even if it exceeds 9 (rc, precipitation of tin occurs, and the decomposition of the bath or the like is exhibited. The method of coating the electroless tin or tin alloy plating solution of the present invention is used. As long as the material is covered in the mineral coating, the treatment time is preferably 10 to 36,000 seconds, more preferably 6 to 30,000 seconds. If it is less than 1 second, the film forming property is obtained. It is low and does not show good characteristics. Even if it exceeds 36,000 seconds, there is no benefit because the deposition rate of the tin film is considerably reduced. The film thickness of the obtained tin plating film or tin alloy plating film. Preferably, it is OH to 5# m, more preferably 〇. 3 to m. Examples of the plated material include a printed circuit board, a ΤΑβ film-loaded θθ circular substrate, a connector, and a lead frame. An electronic component such as ruthenium or the like, preferably having a copper or copper alloy pattern on the surface and formed in steel and copper A resin composition of a pattern. If a copper or steel alloy® case of an electronic component is laminated on a substrate or a carrier, the resin composition may be formed not only on the copper or copper alloy pattern but also on itself. It is preferable that at least a copper or copper alloy pattern is formed with a resin composition on a substrate or a film of a carrier of 321709 17 201035374, and an interface exists between copper or a copper alloy and a resin composition. For example, a copper or copper alloy layer is provided on a surface of a substrate such as a glass epoxy resin or a paper phenolic resin, and after etching to form a copper or copper alloy pattern, the substrate is provided on a substrate containing at least a copper or copper alloy pattern. a rigid printed substrate of the solder resist layer; or a copper or copper alloy layer on the surface of the polyimide or PET (polyethylene terephthalate) film, and after etching to form a copper or copper alloy pattern, A flexible printed circuit board or the like having a protective film or the like laminated on a substrate containing at least a copper or copper alloy pattern. The resin composition is preferably a protective film or a fresh-keeping layer itself, as a surface treatment thereof. In order to use the electroless tin or tin alloy ore coating of the present invention, the resin composition such as the solder resist layer or the protective film is not particularly limited and can be suitably used. For the copper or copper alloy layer provided on the above substrate, For those formed by well-known methods, the metal forming the copper alloy may be exemplified by nickel, complex, zinc, tin, silver, wrinkle, magnesium, chin, iron, ming, fierce, drill, wrong, wrong, Recording, money, indium, shixi, shixi, etc. The electroless tin or tin plating solution of the present invention is such that the plating penetration protective film or the solder resist layer has less interface with copper or copper alloy, so that the penetration depth is not reached. 30 / im, can solve the problem of the floating of the protective film or the solder resist layer, and the formation of a partial battery to cause the copper or copper alloy to be dissolved in the portion. Moreover, the obtained tin or tin alloy film is made into a flux wettable Good properties and reliable bonding with the flux 18 321709 201035374 Excellent coating of the film. [Examples] The examples are enumerated below to explain the present invention in more detail. [Examples 1 to 23 and Comparative Examples 1 to 2] As a material to be plated, copper was adhered to a glass epoxy substrate, and a pattern was formed by etching, and then formed on a substrate containing at least a copper pattern. The general printed wiring board of the solder layer (PSR4000SP19, solar ink) was plated as follows. Plating step Acid degreasing

I Wash 3 times i Soft etching (sodium persulfate) i 〇 Wash 3 times

I Electroless tin plating or tin alloy plating Water washing and drying Electroless tin or tin alloy plating liquid is carried out by using the iron coating liquid described in Table 1 under the impregnation conditions of 7 ° C C 1 l min. Further, 1-[N,N-bis(hydroxyethyl)aminomethyl]tolyltriazole used in Example 10 is 4-methyl-1-[N,N-bis(hydroxyl) A mixture of 4:6 of aryl 321709 19 201035374 hydrazino] benzodiazepine and 5-methyl], bis(hydroxyethyl)aminomethyl]benzotriazole. & It is evaluated by the following "It's covered". The results are shown in Table 1. (Thickness) Using a fluorescent x-ray thickness gauge (SII, SFT-3200), the film thickness at 7 (TCx 10 minutes of impregnation conditions was measured. (State of solder resist layer) & electroless 钖 or 钖After the alloy bond is applied, the printed circuit board is formed by using an epoxy resin. In order to observe a cross section of a region including the portion where the electroless tin plating is in contact with the anti-fresh layer, the polishing is performed to prepare a printing base. The vapor deposition was carried out as a plating solution of the copper interface for observation by a scanning electron microscope. For example, the treatment was carried out by SEM observation on the solder resist layer and evaluated as follows. ◦: The recording liquid penetrates into the solder mask/copper interface 30" △. Plating solution / into the anti-layer 〆 copper interface more than 3 〇, and 2 〇〇 ρ or less. X: The mineral coating penetrates into the F square weld layer/steel interface over 200 //m. Alternatively, the portion of the ' _ layer at the time of completion of the plating is peeled off from the copper. (flux wettability) Reflow soldering (refi〇w) 3 times in a reflow oven at a peak temperature of 250 ° C under a nitrogen atmosphere, using M705-GRN-360-K2-V ( As a solder paste, a metal mask with a thickness of 200//m was used to evaluate the wettability of the solder of 20 321 709 201035374. 〇: After reflowing 3 times, the solder paste was completely applied to a 5x5 mm pad and then reflowed. More than 95% of the pad area was covered by the solder paste. △: After the reflowing was performed three times, the fresh paste was applied to the 5x5 mm pad and the reflow was performed. As a result, 80% or more of the pad area was less than 95% of which was covered by the solder paste. X: After the zinc was returned three times, the solder paste was applied to the 5x5 mm lining and the reflow was performed. As a result, less than 80% of the pad area was covered by the solder paste. ❹ 21 321709 201035374 5 ang CM 3 〇δ S s 〇〇o ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ^*· 〇〇o ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο <·- o oo oo S 8 〇〇o ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Μ 1 1 1 1 1 1 1 1 1 1 1 1 oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo 1 oo 1 1 1 oo 1 1 1 1 1 1 1 1 1 1 〇o ΙΑ ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο So SV·· 8 S ^*· 〇ΙΟ o ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο - + «! B- «ί 6-series « /-Ν 〇I _ 屮VX Μ Ο K| evT SC w4 »»i CO ••4 T 6- f , 丨1 Λ Ξ 1 铯J, “ 1 1 令 CvT mmrn ν·Ν f Hi IS 1 tt ,丨1 *> Λ Molybdenum Λ ¥ 1 ΙΛ 铯Λ ¥ Ι<1 ®- Β- <4 隹/-Ν ο ¥ 2S a£ i_l 1 « Μ ψ ψ 上ψ^< S- ψ Β •1 «< 铤ιη ¥ S 香5 δ- ! «έ 1 ίη ΙίΓ Ten ε SS Lf5 ιτί 香 Hi 丄CO ··< 隹«έ Ml glucoside &quot I tn CO •Ν 1 蚪i 1 Ί evT «4: * «Ε a: 22 321709 201035374 ο 实施 Example 1 CO o Ο 8 Vi· ο § 〇〇〇ioo ο ο ο ο ο ο ο ο ο ο ο ο ο 1 0.59 | 〇< 芑ο Ο ο ο δ 〇〇〇1 0.0Q1 1 oo ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Oo ο ο ο ο ο ο ο ο ο T S S SS SS SS SS SS SS SS SS SS 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ο ο ο ο ο ο ο ο 1.0 1.0 1.0 1.0 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. · 〇〇〇ooo ο ο ο ο ο ο ο ο ο ο ο ο 9 - 二 二 二 - - - - 9 - 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 ο ο ο 1 1.08 〇〇«D s ο ο ο ο 〇〇〇ooo ο ο ο ο ο ο ο ο ο ι ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ι ο 1. oo 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo ο ο ο ο ο Μ> ο ο ο ο ο ο 1 1.09 0 〇 composition and its concentration (g/L) f sulfonic acid kick (in terms of Sn2+) + a «f 6- 1 methanesulfonate ι 1 thiourea I 1 Phosphoric Acid Pin 1 1 Polyethylene Diacetate (Molecular Dong loooo) 1 1 1丨 Bu 1,2,3-Tri 1 | 5-Methyl-11Μ, 2,3-三喳'ί1 CO 1 4 铤Ik | 1丨丨-1,2,4-triazole, i Λ «NM 1 4 'Ί ca •M 1 benzotriwas 1 5-pinyl-11 benzotrim 1 1-aminobenzotrizole • ft 'Ί »- Γ—Ί ¢- ^•Ν 0 ¥ 1 •«Η 1 5-A Base-11-tetrazole 1 5-amino-1Η-四峻1 phenyl-5-»yl-ΠΙ-tetrazine 1 联四哇1 gr fe-1 M 1 In in 1 5,5,- Disulfide-111-tetraguanoside til ιό CO ««Η 1 Trimeric amide camp = Hi 1 ΙΛ «Γ 4 1 >1 1 Weld-proof layer 1 Freshness wettability 23 321709 201035374 [Table 1 -3 ] Composition and concentration comparison Example 1 2 Tin methane sulfonate (calculated as Sn 2+ ) 20 20 Silver methacrylate (as Ag + ) 0 0. 1 Methanesulfonic acid 100 100 Sulfur gland 100 100 Sodium hypophosphite 30 30 Ethylene glycol (molecular weight 10,000) 1 1 1H-1,2,3-triazole 0 0 5-mercapto-1H-1,2,3-triazole 0 0 5-amino-1H-1,2 , 3-triazole 0 0 1H-1, 2, 4-triazole 0 0 3-mercapto-1H-1,2,4-triazole 0 0 3-amino 2, 4-tri. Sitting 0 0 benzotriazole 0 0 5-methyl-1H-benzotriazole 0 0 1-aminobenzotriazole 0 0 1-[N,N-bis(hydroxyethyl)aminoindenyl]甲基基三唑0 0 5-曱-ΙΗ-四〇坐0 0 5-amino-1H-four 0 sitting 0 0 1-phenyl-5-weiki-1^_四〇坐0 0 Squatting 0 0 5, 5'-azobis-1-methyltetrazole 0 0 5,5'-dithio-1H-tetrazole 0 0 1,3,5-three tillage 0 0 melamine 0 0 2 , 4-diamino-6-phenyl-1,3,5-trioxin 0 0 film thickness (// m) 1. 08 0. 98 state of solder resist layer XX flux wettability 〇〇 [pattern Brief description] No [Main component symbol description] No 24 321709

Claims (1)

201035374 VII. Patent application scope: 1. An electroless tin or tin alloy plating solution, which contains at least tin salt, a wrong agent, an acid-free electroless tin or tin alloy plating solution, wherein the ring contains 3 An azole compound or a cultivating compound of the above nitrogen atom. 2. The electroless tin or tin alloy plating solution according to the first aspect of the patent application, wherein the electroless tin or tin alloy clock solution contains the triterpenoid compound represented by the following general formula (A) or (B): (Ri to R3 represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, an alkoxy group having a carbon number of 10 or less, or an amine substituted by a halogen atom, a hydroxyl group, a carboxyl group, an amine group or a lower alkyl group; a group substituted with a hydroxyl lower alkyl group substituted with an amine group or a fluorenyl group, or an amine group, a lower alkyl group-substituted amine group, a hydroxy lower alkyl group-substituted amine group, a decyl group, a hydroxyl group, a slow group, or Any of a halogen atom or a hydrogen atom). 3. The electroless tin or tin alloy plating solution according to the first aspect of the patent application, wherein the electroless tin or tin alloy plating solution contains the benzotrisamine compound represented by the following general formula (C): 25 321709 201035374 (c) A aryl (= represents a decyl group, an alkenyl group, an alkynyl group, an oxy group having a carbon number of 10 or less or an amine substituted by a halogen atom, a transatom group, an amine group, a substituted filament, or a substituted domain group) Or an amine group, a lower alkyl group, a soil, a hydroxy group lower alkyl group-substituted amine group, a fluorenyl group, a hydroxyl group, a ruthenium group, or an i atom or a hydrogen atom). For example, the electroless tin or tin alloy ore coating of the item i of the patent scope, wherein the electroless tin or tin alloy coating contains the tetra-salt compound represented by the following formula (D): (h, R! represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, an alkoxy group having a carbon number of 1 Å or less, or a halogen atom, a hydroxyl group, a carboxyl group, an amine group or a lower alkyl group; a substituted amino group, a hydroxy lower alkyl substituted amine group, a thiol group substituted with any one, or an amine group, a lower alkyl group substituted amine group, a hydroxy lower alkyl group substituted amine group, a thiol group, a hydroxyl group, a carboxyl group 'or ii atom or hydrogen atom). 26 321709 201035374 5. The electroless tin or tin alloy plating solution according to claim 1, wherein the electroless tin or tin alloy plating solution contains the tetradentate compound represented by the following general formula (E): (Rn and R12 represent an alkyl group, an alkenyl group, an alkynyl group, an anthranyl group, an aryl group, an alkoxy group having a carbon number of 10 or less, or a halogen atom, a trans group, a carboxyl group, an amine group or a lower alkyl group; a group substituted with an amine group, a hydroxy lower alkyl-substituted amine group, or a fluorenyl group, or an amine group, a lower alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, a thiol group, Or a halogen atom or a hydrogen atom, and Rl3 represents a single bond, or an alkylene group having at least 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a halogen atom. Any one of a hydroxyl group, a carboxyl group, a decyl group, a fluorenyl group, an azo group, a thio group or a disulfide group, or a azo group, a thio group or a disulfide group; 6. The electroless tin or tin alloy plating solution according to claim 1, wherein the electroless tin or tin alloy plating solution contains the triterpenoid compound represented by the following general formula (F): 27 321709 201035374 (^ to - represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, an alkoxy group having a carbon number of 10 or less, or such a dentate atom, a hydroxyl group, a aryl group, an amine group, or a lower order An alkyl-substituted amine group, a hydroxy lower alkyl-substituted amine group, a lining-substituted group, or an amine group, a lower-grade substituted amino group, a hydroxy lower alkyl-substituted amine group, a thiol group, a hydroxyl group, Carboxyl group, or any of a dentate atom or a hydrogen atom). 9. 10. An electronic component which is impregnated with an electronic component having a copper or copper alloy pattern on its surface and at least a resin composition formed on the copper or copper alloy pattern in the first to sixth items of the patent application scope In the middle of the project - the benefit of electrolytic tin or tin alloy ore coating, and the formation of tin or tin alloy coating electronic components, the aforementioned electroless tin or tin alloy ore coating the thickness of the copper or steel and resin composition interface 30 or less. The electronic component of claim 7, wherein the printed circuit board is a printed circuit board. The tweezers member The electronic component of the seventh application of the patent application is a TAB thin carrier. The electronic component is the electronic component of the seventh aspect of the patent application, wherein the electronic component is a wafer substrate. 321709 28 201035374 IV. Designated representative map: There is no schema in this case (1) The representative representative map of this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: This case is not represented by the chemical formula 321709 201035374 State WW Order e,:: Correction | Antioxidant 'System In order to prevent the oxidation of tin, you can take two ~ tea factory f such as: hypophosphorous acid or its salt, ascorbic acid (ascorbic ac illusion or its salt, hydrogen xi Kun, resorcinol, benzophenone) (phior〇giucin〇i), indophenolsulfonic acid or a salt thereof, phenolsulfonic acid or a salt thereof, hydroquinonesulfonic acid or a salt thereof, hydrazine, etc. The concentration of the antioxidant is preferably 1 to 2 Torr. g/liter. The electroless tin plating solution or the tin alloy plating solution aqueous solution of the present invention, and the plating bath temperature is preferably 5 to 9 (TC, more preferably 30 to 80 t. If less than 30 ° C In this case, the deposition rate of the plating film is low, and even if it exceeds 9 〇〇c, there is a drawback that tin precipitates and the bath is decomposed. The plating method of the electroless tin or tin alloy plating liquid of the present invention is employed. And s, as long as the plated material is immersed in the plating solution. Preferably, it is 10 to 36,000 seconds, more preferably 60 to 3000 () seconds. If it is less than 10 seconds, the film formation property is low and the good characteristics are not exhibited. Even if it exceeds 36,000 seconds, it is also due to tin. The filming speed of the film is considerably reduced, and there is no benefit. The film thickness of the obtained tin plating film or tin alloy plating film is preferably 〇〇1 to 5/zm', more preferably 〇. 3 to 3#m. Examples of the plated material include a printed circuit board, a ΤΑβ film carrier, a wafer substrate, a connector, and a lead frame. The electronic components preferably have a surface. a copper or copper alloy pattern, and a resin composition formed by a square, copper, and copper alloy pattern. When a copper or copper alloy pattern of an electronic component is laminated on a substrate or a film, the resin composition is not limited It may be formed on a copper or copper alloy pattern, or may be formed on a substrate or film of the carrier of the patent application No. 98, s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s a resin composition is formed on the copper alloy pattern, and Or an interface between the copper alloy and the resin composition. Examples of the electronic member include a steel or a copper alloy layer formed on a surface of a substrate such as a glass epoxy resin or a paper phenolic resin, and formed by engraving. a copper or copper alloy pattern, a rigid printed substrate provided with a solder resist layer on a substrate containing at least a copper or copper alloy pattern; or copper on a surface of a polyimide or ρΕτ (polyethylene terephthalate) film Or a copper alloy layer, and after forming a copper or copper alloy pattern by a money, a flexible printed circuit board or the like having a protective film or the like is applied to a substrate containing at least a copper or copper alloy pattern. For the composition of the tree and the moon, it is preferably a protective film or a solder resist layer. As the 'surface treatment', it is preferred to use the electroless tin or tin alloy of the present invention, the beta layer or the film. The composition is not particularly limited and can be well known. The copper or copper alloy layer on the substrate may be formed by a circumferential process, and examples of the metal forming the copper alloy include nickel, chromium, zinc, tin, silver, and antimony. Magnesium, titanium, iron, Shao, Meng, recorded, lead, wrong, bismuth, antimony, indium, selenium, tellurium and so on. u 卩 无 解 解 解 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或The floating of the warm film or the solder resist layer, and the formation of the local battery 2:: the problem of the dissolution of the steel or steel alloy of the knife. Further, the obtained tin or tin alloy film is made into a hair dryer 1 and has a good wettability and a reliable bond with the flux. 18 321 709 Revision