JP5855363B2 - Organosilicon compound and electroless plating pretreatment method using the organosilicon compound - Google Patents

Description

  The product of the present invention relates to a novel organosilicon compound and a pretreatment method for electroless plating using the organosilicon compound.

  Electroless plating is a method of forming a film on the surface of an object to be plated (hereinafter also referred to as a substrate) selected from glass, synthetic resin, noble metal, etc. by using a reducing agent without using electricity. That is. However, when performing electroless plating, if the surface of the object to be plated is directly plated, the adhesion may be weak when the film is formed, and plating may be insufficient.

  Therefore, conventionally, for the purpose of improving the adhesion between the object to be plated and the deposited plating film, electroless plating has been performed after pretreatment of the object to be plated. At that time, it is generally known to use an organosilicon compound as a pretreatment agent.

  For example, Patent Document 1 discloses a plating method that can improve adhesion between a glass substrate that is difficult to be plated and a plating film of an electroless plating layer by using a silane coupling agent as a pretreatment agent. doing. Patent Document 2 discloses a metal surface treatment agent using an imidazole silane compound that is excellent in heat resistance and has a high rust-preventing action on the metal surface. Patent Document 3 discloses a silver plating method using an azole-based silane coupling agent.

Japanese Examined Patent Publication No.59-52701 Japanese Patent Publication No. 7-68256 JP 2002-47573 A

  However, the organosilicon compound (silane coupling agent) disclosed in Patent Documents 1 to 3 as a pretreatment agent for the object to be plated cannot be said to have sufficient adhesive force, and depends on the type of object to be plated. No desired performance is obtained, and development of an organosilicon compound useful as a silane coupling agent that can function more effectively when used as a pretreatment agent for an object to be plated is desired. Furthermore, from the viewpoint of environmental conservation on a global scale in recent years, it is desired to develop a treatment agent with less environmental load even for a pretreatment agent used in a pretreatment method for electroless plating.

  Accordingly, an object of the present invention is to provide an organosilicon compound that exhibits good adhesion to metal plating and that can effectively function as a water-based silane coupling agent that is simple and has a low environmental impact. Furthermore, the object of the present invention is to develop an aqueous silane coupling agent useful as a pretreatment agent for the object to be plated, thereby improving the adhesion between the object to be plated and the metal plating when electroless plating is applied. Another object of the present invention is to provide a pretreatment method for electroless plating that can be applied to various objects to be plated.

（上記式（１）中、Ａは窒素原子を含む炭素数３〜７の複素環基を表し、Ｚ¹は、直接結合を表すか又は炭素原子数１〜１０のアルキレン基を表す。）

（上記式（３）中、Ｒ³は炭素原子数１〜１２の炭化水素基を表し、Ｒ⁴は、−ＮＨ₂、−ＮＣＯ、イミダゾリル基又はトリアゾリル基を表し、Ｚ²は炭化水素数１〜１０のアルキレン基を表し、かつ、該アルキレン基は、−ＮＨ−、−Ｏ−又は−Ｓ−で中断されていてもよい。）
Thus, as a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention provides at least one polycarboxylic acid selected from the group consisting of a compound represented by the following general formula (1) and tetracarboxylic dianhydride, tetracarboxylic dianhydride, and tricarboxylic dianhydride. An intermediate product, which is a reaction product with an acid anhydride, is further reacted with a compound represented by the following general formula (3) to obtain an intermediate product, and the final product obtained by polymerizing the obtained intermediate product between molecules Provided is an organosilicon compound characterized by being a product.

(In the above formula (1), A represents a heterocyclic group having 3 to 7 carbon atoms including a nitrogen atom, Z ¹ represents or alkylene group having 1 to 10 carbon atoms represents a direct bond.)

(In the above formula (3), R ³ represents a hydrocarbon group having 1 to 12 carbon atoms, R ⁴ represents —NH ₂ , —NCO, imidazolyl group or triazolyl group, and Z ² represents 1 hydrocarbon group. Represents an alkylene group of 10 to 10, and the alkylene group may be interrupted by -NH-, -O-, or -S-).

  As another embodiment, the present invention provides, as another embodiment, a pretreatment method for electroless plating, in which pretreatment is performed on the object to be plated with the organosilicon compound when electroless plating is performed on the object to be plated. I will provide a.

  ADVANTAGE OF THE INVENTION According to this invention, the organosilicon compound which exhibits the favorable adhesiveness with metal plating, and can function effectively as a water-based silane coupling agent with simple and little environmental impact is provided. Furthermore, according to the present invention, by using the aqueous silane coupling agent as a pretreatment agent for the object to be plated, the adhesion between the object to be plated and the metal plating can be improved when electroless plating is performed. An electroless plating pretreatment method applicable to various objects to be plated is provided.

  The present invention will be described in detail with reference to preferred embodiments of the present invention. The organosilicon compound of the present invention is a compound represented by the following general formula (1) and at least one kind of polycarboxylic acid selected from tetracarboxylic dianhydride, tetracarboxylic dianhydride and tricarboxylic dianhydride. An intermediate obtained by reacting a carboxylic acid anhydride is obtained, and further obtained by reacting the intermediate with a compound represented by the following general formula (3). Hereinafter, each component will be described.

（上記式（１）中、Ａは窒素原子を含む炭素数３〜７の複素環基を表し、Ｚ¹は、直接結合を表すか又は炭素原子数１〜１０のアルキレン基を表す。）

（上記式（３）中、Ｒ³は炭素原子数１〜１２の炭化水素基を表し、Ｒ⁴は、−ＮＨ₂、−ＮＣＯ、イミダゾリル基又はトリアゾリル基を表し、Ｚ²は炭化水素数１〜１０のアルキレン基を表し、かつ、該アルキレン基は、−ＮＨ−、−Ｏ−又は−Ｓ−で中断されていてもよい。）

(In the above formula (1), A represents a heterocyclic group having 3 to 7 carbon atoms including a nitrogen atom, Z ¹ represents or alkylene group having 1 to 10 carbon atoms represents a direct bond.)

(In the above formula (3), R ³ represents a hydrocarbon group having 1 to 12 carbon atoms, R ⁴ represents —NH ₂ , —NCO, imidazolyl group or triazolyl group, and Z ² represents 1 hydrocarbon group. Represents an alkylene group of 10 to 10, and the alkylene group may be interrupted by -NH-, -O-, or -S-).

[Compound represented by general formula (1)]
First, the compound represented by the general formula (1) will be described.
In the compound represented by the general formula (1) (hereinafter sometimes simply referred to as “compound of the general formula (1)”), A represents a C 3-7 heterocyclic group containing a nitrogen atom. . The nitrogen-containing aromatic ring that can be used for A is not particularly limited as long as it is an aromatic ring in which at least one nitrogen is present in the ring. For example, pyrrolyl group, imidazolyl group, imioxazolyl group, pyridinyl group, pyrazolyl group, pyrazinyl group, indolyl group, indazol group, oxazolidine group, isoxazolidine group, thiazolyl group, isothiazolyl group, triazolyl group, triazinyl group, benzoxazolyl group , An indolyl group, an isoindolyl group, a furazanyl group, and the like. Among these nitrogen-containing aromatic rings, when used in a plating pretreatment method, the adhesion between the object to be plated and the metal plating can be further improved, so that the azole group pyrrolyl group, pyrazolyl group, imidazolyl Group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, and a furazanyl group are preferable. Furthermore, an imidazolyl group or a triazolyl group is more preferable. These nitrogen-containing heterocycles may have one or two or more substituents in the ring. However, depending on the type of the substituent, water solubility may be deteriorated, so care must be taken.

Moreover, Z < ¹ > in the said General formula (1) represents a direct bond in the state without a coupling group, or represents a C1-C10 alkylene group. According to the study by the present inventors, when Z ¹ is an alkylene group having 11 or more carbon atoms, the water solubility of the organosilicon compound as the final product may deteriorate. Examples of the alkylene group that can be used as Z ¹ 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, and an octylene group. In order to improve the water solubility of the organosilicon compound of the present invention, it is preferable that Z ¹ is a direct bond or an alkylene group having 1 to 7 carbon atoms. In particular, Z ¹ is more preferably a direct bond or an alkylene group having 1 to 5 carbon atoms.

  Specific examples of the compound represented by the general formula (1) that satisfies the above requirements include 1- (3-aminopropyl) imidazole, 4-amino-1,2,4-triazole, 3-amino-1H, for example. -1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, 1- (3-aminopropyl) -2-methylimidazole, 1- (3-aminopropyl)- Examples include 2-ethyl-4-methylimidazole, 1-aminopropyl-2,4,5-tributylimidazole, 1-aminoethyl-4-hexylimidazole, 1-aminobutyl-2,5-dimethylimidazole.

[Polycarboxylic anhydride]
Next, the polycarboxylic acid anhydride used when reacting with the compound represented by the general formula (1) to obtain an intermediate will be described.
The polycarboxylic acid anhydride is an acid anhydride dehydrated in the molecule from the polycarboxylic acid. In the present invention, the polycarboxylic acid anhydride is selected from tetracarboxylic acid monoanhydride, tetracarboxylic acid dianhydride, and tricarboxylic acid monoanhydride. At least one polycarboxylic acid anhydride is used. These carboxylic anhydrides may form a ring in the molecular structure, and may have an aromatic ring. Hereinafter, in the present specification, “polycarboxylic acid” means tetracarboxylic acid or tricarboxylic acid, and “polycarboxylic acid anhydride” means an acid anhydride dehydrated from the above polycarboxylic acid within the molecule. Means.

（上記式（２）中、Ｒ¹およびＲ²は結合して酸無水物を形成する基を表すか、或いは、Ｒ¹およびＲ²のうちの一方が−ＣＯＯＨ基を、他方が水素原子、炭素原子数１〜１２の炭化水素基および−ＣＯＯＨ基から選ばれるいずれかの基を表し、Ｘは、−ＣＯ−、−Ｏ−、−ＳＯ₂−又は窒素原子で中断されてもよい炭素原子数１〜２０の炭化水素基を表す。） The polycarboxylic acid anhydride used in the present invention is a compound represented by the following general formula (2) among the above-mentioned polycarboxylic acid anhydrides (hereinafter sometimes simply referred to as “compound of general formula (2)”). Preferably there is.

(In the above formula (2), R ¹ and R ² represent a group which is bonded to form an acid anhydride, or one of R ¹ and R ² is a —COOH group, the other is a hydrogen atom, It represents any group selected from a hydrocarbon group having 1 to 12 carbon atoms and a —COOH group, and X is a carbon atom which may be interrupted by —CO—, —O—, —SO ₂ — or a nitrogen atom. Represents a hydrocarbon group of formula 1-20.)

Examples of the hydrocarbon group having 1 to 12 carbon atoms that can be used for R ¹ and R ² in the general formula (2) include the following alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups. It is done.

  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, isoheptyl group. 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 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 group, cyclopentyl group, cycloheptyl group, methylcyclopentyl group, methylcyclohexyl group, methylcycloheptyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, methylcyclopentenyl group, methylcyclohexenyl group. Group, methylcycloheptenyl group and the like.

  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.

Further, R ¹ and R ² in the general formula (2) may be —COOH, and R ¹ and R ² may be linked to form a ring as an acid anhydride. In particular, R ¹ and R ² are preferably —COOH or linked to form a ring as an acid anhydride. Furthermore, since it is highly reactive with the general formula (1) and the organosilicon compound of the present invention can be produced in a short time, it is more preferable that R ¹ and R ² form a ring as an acid anhydride.

X in the general formula (2) is —CO—, —O—, —SO ₂ —, a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by a nitrogen atom, and forms a ring. It may have an aromatic ring. More preferably, it is a hydrocarbon group having 1 to 10 carbon atoms. X is not particularly limited as long as the above conditions are satisfied. However, when the organosilicon compound of the present invention is used for pretreatment of the object to be plated during electroless plating, the adhesion strength after plating is improved. (B-1) to (B-18) exemplified in Among these, (B-1) to (B-5) are more preferable, and (B-1), (B-3), (B-4) or (B-5) is more preferable.

  Examples of the tetracarboxylic monoanhydride and tetracarboxylic dianhydride represented by the general formula (2) that are suitable as a material for forming the organosilicon compound of the present invention include, for example, the compounds (C-1) listed below. The monoanhydride or dianhydride formed by dehydrating the tetracarboxylic acid of (C-18) is mentioned.

Moreover, as a preferable specific example of the tricarboxylic acid monoanhydride represented by General formula (2) suitable for the formation material of the organosilicon compound of the present invention, the following (C-19) to (C-22) A monoanhydride formed by dehydrating tricarboxylic acid can be mentioned.

  Specific examples of the compound represented by the general formula (2) suitable for the material for forming the organosilicon compound of the present invention include the following. That is, for example, meso-butane 1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane-tetracarboxylic dianhydride, bicyclo [2.2.2] oct- 7-ene-2,3,5,6-tetracarboxylic dianhydride, trimellitic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, 1,2,3,4 Cyclopentane-tetracarboxylic dianhydride, cis-aconitic acid anhydride, ethylenediaminetetraacetic acid dianhydride, diethylenetriaminepentaacetic acid dianhydride, diglycolic acid anhydride, benzophenone-3,3 ', 4,4'-tetra Carboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, 1,4,5,8-naphthalene teto Dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride can be suitably used.

[Compound represented by formula (3)]
Next, the compound represented by the following general formula (3) used for the material for forming the organosilicon compound of the present invention will be described. The organosilicon compound of the present invention is obtained by reacting an intermediate obtained by reacting the compound of the above general formula (1) with a polycarboxylic acid anhydride, further represented by the following general formula (3): And a final product obtained by reacting with a “compound of general formula (3)” in some cases.

R ³ in the general formula (3) represents a hydrocarbon group having 1 to 12 carbon atoms. For example, an alkyl group or alkenyl exemplified in the description of R ¹ and R ^{2 in} the general formula (2) Groups, cycloalkyl groups, aryl groups and the like can be used. Among these, because of high water solubility, R ³ in the general formula (3) is more preferably an alkyl group having 1 to 6 carbon atoms, further a methyl group or an ethyl group are preferable, and most preferably a methyl group.

R ⁴ in the general formula (3) is a reaction product of the compound of the general formula (1) and the polycarboxylic acid anhydride, which is reacted with the compound of the general formula (3) as described below. Preferred substituents vary depending on the structure of the intermediate.
(I) When the intermediate is a reaction product of a compound of the general formula (1) and tetracarboxylic dianhydride and there is an anhydride skeleton as a residue, R ⁴ in the general formula (3) is It is preferably —NH ₂ or imidazolyl group.
(Ii) The intermediate is a reaction product of a compound of general formula (1) and tetracarboxylic dianhydride, tricarboxylic acid monoanhydride or tetracarboxylic acid monoanhydride, and an anhydride skeleton as a residue. If not, R ⁴ in the general formula (3) is preferably —NCO.

Z ² in the general formula (3) represents an alkylene group having 1 to 10 hydrocarbons, and the alkylene group may be interrupted by —NH—, —O—, or —S—. . Examples of such Z ² include the alkylene groups exemplified as Z ¹ in the general formula (1). Since the water solubility of the product of the present invention is good, 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 the compound represented by the general formula (3) include, for example, 3-aminopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanato. Propyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane , 3-mercapto B pills trimethoxysilane, and 3-mercaptopropyl triethoxy silane.

[Production method]
Next, the manufacturing method of the organosilicon compound of this invention is demonstrated.
The manufacturing method of the organosilicon compound of this invention is not specifically limited, It can manufacture by the following well-known methods. First, an intermediate is obtained by the following method. For example, in a solution in which a polycarboxylic anhydride (hereinafter sometimes referred to as component (B)) is dissolved in a solvent, a compound of general formula (1) (hereinafter sometimes referred to as component (A)) is used as a solvent. The dissolved solution is added dropwise at 0 to 25 ° C., and after completion of the addition, the solution is stirred at 5 to 40 ° C. for 0.5 to 10 hours to obtain an intermediate. Next, without purifying the obtained intermediate, the intermediate is reacted with the compound represented by the general formula (3) by a method such as the following (I) or (II). The organosilicon compound of the present invention, which is the object, is obtained.

(I) When R ⁴ in the general formula (3) is —NH ₂ , an imidazolyl group or a triazolyl group, the compound of the general formula (3) (hereinafter sometimes referred to as “component (C)”) is dissolved in a solvent. The resulting organosilicon compound of the present invention is obtained by dropping at 0 to 25 ° C. and stirring at 5 to 40 ° C. for 0.1 to 5 hours after completion of the dropping.
(II) When R ⁴ in the general formula (3) is —NCO, a solution obtained by dissolving the compound of the general formula (3) in a solvent is dropped at 30 to 80 ° C., and after completion of the dropping, 30 to 80 ° C. The organosilicon compound of the present invention is obtained by stirring for 0.5 to 6 hours.

In the reaction product (intermediate) obtained as described above, a preferable reaction ratio between the compound of the general formula (1) and the polycarboxylic acid anhydride is R ^{4 in} the structure of the compound of the general formula (3). It depends on the group that can be taken.
(I) When R ⁴ is —NH ₂ , an imidazolyl group or a triazolyl group, the number of moles of the compound represented by the general formula (1) / the number of moles of the polycarboxylic acid = 1.5 / 1 to 1 / 1.5 Is preferred. The molar ratio is more preferably 1.2 / 1 to 1 / 1.2, and still more preferably 1.1 / 1 to 1 / 1.1.
(Ii) When R ⁴ is —NCO Number of moles of compound represented by general formula (1) / (number of moles of polycarboxylic acid × number of acid anhydrides in one molecule) = 1.5 / 1 to 1/1 .5 is preferred. The molar ratio is more preferably 1.2 / 1 to 1 / 1.2, and still more preferably 1.1 / 1 to 1 / 1.1.
In addition, the ratio of the intermediate obtained as described above to the compound of the general formula (3) in the final product is preferably as follows. That is, the ratio of the compound of the general formula (1) used for the formation of the intermediate and the compound of the general formula (3) to be reacted with the intermediate is preferably as follows. Specifically, the ratio of the compound of the general formula (1) to the compound of the general formula (3) is a molar ratio: the compound of the general formula (1) / the compound of the general formula (3) = 1.5 / 1. It is preferable to be configured to be ~ 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2, and 1.1 / 1 to 1 / 1.1. More preferably, it is configured as follows.

  Although it does not specifically limit as a solvent used by each above-mentioned reaction, It is preferable that it is an aprotic polar solvent. 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 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 particularly preferable to use NMP.

Specific production examples of the organosilicon compound of the present invention will be described below as Method 1 to Method 3 with a schematic diagram of the reaction.
<Method 1>
In Method 1, the component (A) and the dianhydride of the tetracarboxylic acid of the component (B) are reacted at a molar ratio of 1: 1 to obtain an intermediate (S). The component (A) and the component (B) In the reaction at a molar ratio of 1: 1, the acid anhydride moiety of the component (B) and the amine moiety of the component (A) react to form an intermediate (S). When the compound [component (C)] in which R ⁴ in the general formula (3) is an amino group reacts with the intermediate (S), an acid anhydride moiety of the intermediate (S); and (C) The amino group site of the component reacts to form an amide bond, yielding intermediate (S2). And as shown below, the organosilicon compound which is the product of the present invention is obtained by removing R ³ OH from the —Si (OR ³ ) ₃ group of the obtained intermediate (S2) and polymerizing between molecules. can get. The outline of the reaction in Method 1 described above is shown below.

<Method 2>
In Method 2, the component (A) and the dianhydride of the tetracarboxylic acid of the component (B) are reacted at a molar ratio of 2: 1 to obtain an intermediate (T), but the component (A) and the component (B) In the reaction at a molar ratio of 2: 1, the acid anhydride moiety of the component (B) and the amine moiety of the component (A) react to form an intermediate (T). When the compound [(C) component] in which R ⁴ in the general formula (3) is an isocyanate group reacts with the intermediate (T), the -COOH moiety of the intermediate (T), (C) The isocyanate site of the component reacts to form an amide bond with the release of carbon dioxide, and an intermediate (T2) is obtained. This intermediate (T2) becomes a positional isomer depending on the structure of the intermediate (T). Then, as shown below, the organosilicon compound of the present invention is obtained by de-R ³ OH from the —Si (OR ³ ) ₃ group of the obtained intermediate (T2) and polymerizing between molecules. . The outline of the reaction is shown below.

<Method 3>
In Method 3, the component (A) and the monocarboxylic anhydride of the tetracarboxylic acid of the component (B) are reacted at a molar ratio of 1: 1 to obtain an intermediate (U), but the component (A) and the component (B) In the reaction at a molar ratio of 1: 1, the acid anhydride moiety of the component (B) and the amine moiety of the component (A) react to form an intermediate (U). When the compound [(C) component] in which R ⁴ in the general formula (3) is an isocyanate group reacts with the intermediate (U), the carboxylic acid moiety of the intermediate (U), and (C) The component isocyanate site reacts to form an amide bond, yielding intermediate (U2). When the intermediate (U) has a plurality of reaction sites, the intermediate (U2) is obtained as a mixture of isomers. Further, the intermediate (U2) becomes a regioisomer due to the structure of the intermediate (U). Then, as shown below, the organosilicon compound of the present invention is obtained by de-R ³ OH removal from the —Si (OR ³ ) ₃ group of the obtained intermediate (U2) and polymerization between molecules. . The outline of the reaction is shown below.

  The use of the organosilicon compound of the present invention is not particularly limited. For example, it is necessary to improve the adhesion between different materials such as inorganic-inorganic materials, inorganic-organic materials, and inorganic-inorganic organic composite materials. In addition, it can be used for modification of inorganic, organic and inorganic-organic composite materials, rust prevention of metals, and the like.

  Specific processes to which the organosilicon compound of the present invention that can function as a silane coupling agent can be applied include the following. For example, the organosilicon compound of the present invention can be produced by electroless plating, electrolytic plating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), or organometallic decomposition (MOD). , Fine particle coating, printing, and other various inorganic and organic materials can be used for coating, coating and film formation. Specifically, for example, brush coating, roller coating, spraying, electrodeposition, static It is useful to use the organosilicon compound of the present invention as a silane coupling agent in applications where adhesion is required between the deposited layer and the substrate (deposited body) by operations such as electricity and immersion. In particular, the organosilicon compound of the present invention is useful as a pretreatment agent for electroless plating as described below.

  A pretreatment method for electroless plating, which is another embodiment of the present invention, will be described. The method is characterized in that, when electroless plating is performed on the object to be plated, the object to be plated is pretreated with the organosilicon compound of the present invention described above. At least one of the organosilicon compounds of the present invention may be used as it is, but it is a solvent selected from water, alcohols such as methanol and ethanol, acetone, ethyl acetate, toluene, dimethylformamide, dimethyl sulfoxide and the like. It is simple and preferable to apply the solution by diluting it to 0.001 to 20% by mass and immersing the metal in this solution. In addition, although the organosilicon compound of this invention may be used independently, you may use it in the state with which several organosilicon compounds mixed.

  The temperature and immersion time when the object to be plated is immersed in a solution in which the organosilicon compound of the present invention is dissolved in the solvent as described above are not particularly limited. For example, it is preferably performed at 20 ° C. to 60 ° C., The immersion is preferably performed for 0.1 minute to 5 minutes, and more preferably for 0.1 minute to 3 minutes.

  Moreover, the concentration of the organosilicon compound in the solution in which the organosilicon compound of the present invention is dissolved is not particularly limited, but it is preferably diluted to 0.01% by mass to 5% by mass. It is more preferable to set it as 5 mass%-1.5 mass%. The organosilicon compound of the present invention may be used by dissolving it in a solvent as described above alone, or a plurality of organosilicon compounds may be dissolved in a solvent as described above and used as a mixture solution.

  In the pretreatment method of the present invention, for example, when the electroless plating is performed on the object to be plated by the specific means using the organosilicon compound of the present invention, the object to be plated is pretreated. Thereafter, a metal layer is plated on the object to be plated to form a deposited layer. In this way, by pre-treating with the organosilicon compound of the present invention, when a plated layer is subsequently formed by metal plating on the object to be plated, the —OH group in the structure of the organosilicon compound of the present invention is formed. Since highly hydrophilic functional groups and azole moieties such as high polarity are easily coordinated to metal atoms, adhesion between the substrate and the deposited layer can be improved.

  The object to be plated used in the pretreatment method of the present invention is not particularly limited, but for example, metals such as copper, silver, gold, zinc, nickel, tin, cobalt, and chromium, and those metals such as stainless steel. Alloy, polysiloxane polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polystyrene, acrylonitrile butadiene styrene, polycarbonate, polyhexamethylene adipamide, norbornene resin, nitro Cellulose, urethane resin, phenol resin, urea resin, melamine resin, amide resin, acrylic resin, epoxy resin, acrylonitrile butadiene rubber, silicone rubber and other synthetic resins, glass, silica, alumina, zirconia, nitride nitride Ceramics such as elemental, 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, copper, silver, gold, zinc, nickel, tin, cobalt, chromium, stainless steel, ceramics, and synthetic resins are preferred because of the high effect of improving adhesion after electroless plating, and copper, aluminum, stainless steel, and glass are more preferred. Glass is more preferable. 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. In addition, even if the to-be-plated body mentioned above is roughened, it does not need to be roughened.

  The electroless plating solution used for plating after pre-treating the object to be plated in the pretreatment method of the present invention can be a known one, and the metal that can be used for the plating solution is not particularly limited. For example, copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium, tungsten, platinum, rhodium, or ruthenium may be used, and these may be used in combination of two or more.

  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.

  The build-up method in semiconductor manufacturing using electroless plating is usually built up by alternately stacking insulating layers and conductor layers on the core layer made by plating through-hole method to form a multilayer power distribution layer. This is a method for forming a substrate, and is characterized in that a fine wiring pattern can be accommodated at a high density as compared with a conventional bonded printed circuit board. Although the manufacturing method of a buildup board | substrate is not specifically limited, For example, after performing an etching process with the chromic acid-sulfuric acid aqueous solution etc. for the purpose of roughening with respect to the to-be-plated body (board | substrate) which carried out soft etching first, to be plated For the purpose of improving the adhesion between the body and the deposited layer, the object to be plated is immersed in an aqueous solution containing the coupling agent using the organosilicon compound of the present invention. Then, a catalyst is provided using an aqueous solution containing a metal compound such as a palladium compound as a pre-dip. Thereafter, a method of performing electroless plating and subsequently performing electrolytic plating is well known.

  EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated further in detail, this invention is not limited by these Examples. In the following examples and the like, “%” is based on mass unless otherwise specified.

  As the compound of the general formula (1) defined in the present invention [component (A)], the compound of general formula (2) [component (B)] and the compound of general formula (3) [component (C)], respectively The following compounds were used.

(A) Component A-1: 1- (3-Aminopropyl) imidazole A-2: 4-amino-1,2,4-triazole A-3: 3-amino-1H-1,2,4-triazole A -4: 3-amino-5-methylthio-1H-1,2,4-triazole (B) component B-1: meso-butane 1,2,3,4-tetracarboxylic dianhydride B-2: 1 , 2,3,4-Cyclopentane-tetracarboxylic dianhydride B-3: Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride B- 4: Trimellitic anhydride B-5: Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (C) component C-1: 3-aminopropyltrimethoxysilane C-2: 3-isocyanato Propyltrimethoxysilane C-3: 3-isocyanatopropi Lutriethoxysilane

<Synthesis of organosilicon compounds>
In the following Production Example 1-1, a synthesis example of the organosilicon compound of the present invention is shown.
[Production Example 1-1] Compound No. 1 Synthesis of Compound No. 1 1 was synthesized as follows.
In NMP (51.17 g), meso-butane 1,2,3,4-tetracarboxylic dianhydride (5.94 g, 0.03 mol), which is a compound of B-1, was dissolved at 45 ° C. Thereafter, the mixture was cooled to 25 ° C., and a 1- (3-aminopropyl) imidazole (3.76 g, 0.03 mol) / NMP (3.76 g) solution, which is a compound of A-1, was dropped at the same temperature over 5 minutes. did. After completion of dropping, the mixture was stirred at 25 ° C. for 30 minutes. After stirring, a solution of 3-aminopropyltrimethoxysilane (5.38 g, 0.03 mol) / NMP (5.38 g), which is a compound of C-1, was added dropwise at 25 ° C. over 5 minutes. After completion of the dropwise addition, the mixture was stirred at 25 ° C. for 30 minutes, the disappearance of 3-aminopropyltrimethoxysilane was confirmed by gas chromatography (hereinafter abbreviated as GC), and the reaction was completed. 1 was obtained.

[Production Examples 1-2 to 1-3] Compound No. 2 and compound no. In the same manner as in Production Method 1-1 described above, each compound was used according to the ratio in Table 1 to obtain Compound No. 2 and compound no. 3 were synthesized respectively.

[Production Example 1-4] Compound No. Synthesis of Compound No. 4 4 was synthesized as follows.
Trimellitic anhydride (5.76 g, 0.03 mol), which is a compound of B-4, was dissolved in NMP (47.52 g) at 25 ° C. While cooling to 20 ° C. in a water bath, a 1- (3-aminopropyl) imidazole (3.76 g, 0.03 mol) / NMP (3.76 g) solution, which is a compound of A-1, was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 30 minutes and heated to 60 ° C. Then, 3-isocyanatopropyltrimethoxysilane (6.16 g, 0.03 mol) / NMP (6.16 g) solution, which is a compound of C-2, was dropped over 5 minutes. After completion of the dropwise addition, the temperature was raised to 95 ° C. and stirred for 2 hours. After confirming disappearance of 3-isocyanatopropyltrimethoxysilane by GC, the reaction was terminated. 4 was obtained.

[Production Examples 1-5 to 1-10] Compound No. 5-Compound No. 5 In the same manner as in the above production method 1-4, each compound was used in accordance with the ratio in Table 1, respectively. 5-Compound No. 5 Ten compounds were synthesized.

Compound no. 1-No. The weight (mass) average molecular weight of 10 was measured under the following conditions, and the results are shown in Table 1.
(Molecular weight measurement conditions)
Molecular weight measuring apparatus: GPC-101 manufactured by Shodex
Column: GPC KD-806M manufactured by Shodex
Molecular weight marker: Standard polystyrene (0.2 g / L)

Each of the following commercially available or synthesized compounds was compared with Comparative Compound No. 1-No. 8 and used for comparison.
Comparative Compound No. 1: 3-aminopropyltrimethoxysilane Comparative compound No. 1 2: 3-aminopropyltriethoxysilane Comparative compound No. 2 3: 3- (2-Aminoethylamino) propyltrimethoxysilane Comparative Compound No. 4: N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole Comparative compound no. 5: 3-ureidopropyltriethoxysilane Comparative compound No. 5 6: 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane Comparative Compound No. 7: 3-mercaptopropyltrimethoxysilane Comparative Compound No. 8: According to the description in paragraph [0022] of JP-B-7-68256, synthesis was performed as in Comparative Production Example 1-1 below.

[Comparative Production Example 1-1] (Comparative Compound No. 8)
3.4 g (0.05 mol) of imidazole was melted at 95 ° C., and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise over 30 minutes while stirring in an argon atmosphere. After completion of dropping, the reaction was further carried out at a temperature of 95 ° C. for 1 hour.

<Pretreatment method using organosilicon compound>
The pretreatment of electroless plating was performed using the organosilicon compound of the present example obtained above and the comparative compound for comparison, and then electroless plating was performed. At that time, the following three types of evaluation substrates (90 mm × 50 mm × 0.4 mm) having different materials were used as the objects to be plated.
D-1: FR-4 (Ra≈1.3 μm, copper-clad laminate made by Panasonic Electric Works Co., removed by etching)
D-2: Glass (soda lime glass)
D-3: Stainless steel (SUS304)

[Production method 2-1]
Compound No. of Example 1-No. 10 and comparative compound no. 1-No. 500 ml of each aqueous solution containing 8 organosilicon compounds at a concentration of 1% by mass was prepared. Evaluation board | substrates D-1 to D-3 were each immersed in each prepared aqueous solution for 5 minutes at 40 degreeC. After immersion, pre-dip (25 ° C, 1 minute), activation (35 ° C, 5 minutes), water washing (25 ° C, 1 minute), reduction (30 ° C, 5 minutes), water washing (25 ° C, 1 minute) It carried out in order and performed the pretreatment of electroless plating.

  Next, evaluation substrates D-1 to D-3 that were pretreated as described above and evaluation substrates D-1 to D-3 that were not pretreated were used as shown in Table 5, respectively. According to the manufacturing method 3-1 to manufacturing method 3-4, electroless plating and subsequent electrolytic plating were performed to plate on the substrate.

[Production method 3-1]
A commercially available electroless copper plating solution (manufactured by Atotech, product name: MSK-DK) was used, and the plating bath was adjusted to 32 ° C. In the plating bath, the substrate pretreated by the production method 2-1 or the substrate not subjected to pretreatment was immersed, stirred for 20 minutes under air stirring, and electrolessly plated. The plating thickness at that time is 1 μm. This was washed with water (25 ° C., 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 (25 ° C., 1 minute), and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product.

[Production Method 3-2]
An electroless nickel bath containing the components shown in Table 2 below is prepared, the temperature of the bath is adjusted to 60 ° C., and a substrate pretreated by the above production method 2-1 or a substrate not pretreated Was immersed, stirred for 2 hours under air stirring, and electrolessly plated. The plating thickness at that time is 8.3 μm. This was washed with water (25 ° C., 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 (25 ° C., 1 minute), and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product.

[Production Method 3-3]
An electroless tin bath containing the components shown in Table 3 below is prepared, the temperature of the bath is adjusted to 80 ° C., and a substrate pretreated by the above production method 2-1 or a substrate not pretreated Was immersed, stirred for 2 hours under air stirring, and electrolessly plated. The plating thickness at that time is 0.8 μm. This was washed with water (25 ° C., 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 tin plating, washed with water (25 ° C., 1 minute), and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product.

[Production Method 3-4]
An electroless silver bath containing the components shown in Table 4 below is prepared, the temperature of the bath is adjusted to 25 ° C., and a substrate pretreated by the above production method 2-1 or a substrate not subjected to pretreatment And 10% aqueous glucose solution was added dropwise over 7 minutes while stirring the bath. After completion of dropping, the mixture was stirred for 30 minutes and subjected to electroless plating. The plating thickness at that time is 0.6 μm. This was washed with water (25 ° C., 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 is formed on the electroless silver plating, and then washed with water (25 ° C., 1 minute), and then dried at 180 ° C. for 30 minutes in a thermostatic bath. Obtained.

[Examples 4-1 to 4-15, Comparative Examples 4-1 to 4-18]
About each board | substrate plated by each manufacturing method of above-described manufacture example 3-1 to manufacture example 3-4, peel strength was measured on condition of the following, and the result was put together in Table 5 and shown. In addition, it turns out that the to-be-plated body (evaluation board | substrate) and electroplating film | membrane after electrolytic plating are hard to peel, and an adhesiveness is so high that the numerical value of peel strength is high.

Measuring device: Use of desktop testing machine EZ-S manufactured by Shimadzu Corporation ・ Peel speed: 50 mm / min
・ Sample size: 5mm width

  Since the organosilicon compound provided in the present invention functions effectively as a water-based silane coupling agent with a low environmental load, the deposited layer and the substrate can be applied by operations such as brush coating, roller coating, spraying, electrodeposition, electrostatic, immersion, etc. By applying it to various uses that require close adhesion to the (deposited body), it is possible to achieve good film adhesion. For this reason, the organosilicon compound of the present invention can be produced by electroless plating, electrolytic plating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), organometallic decomposition (MOD). ), Fine particle coating, printing, and other various inorganic and organic materials can be applied / coated / formed to improve film adhesion, and its wide use is expected.

Claims (8)

Reaction of a compound represented by the following general formula (1) with at least one polycarboxylic anhydride selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic dianhydride and tricarboxylic dianhydride The product intermediate is further reacted with a compound represented by the following general formula (3) to obtain an intermediate , which is a final product obtained by polymerizing the obtained intermediate between molecules. An organosilicon compound.

(In the above formula (1), A represents a heterocyclic group having 3 to 7 carbon atoms including a nitrogen atom, Z ¹ represents or alkylene group having 1 to 10 carbon atoms represents a direct bond.)

(In the above formula (3), R ³ represents a hydrocarbon group having 1 to 12 carbon atoms, R ⁴ represents —NH ₂ , —NCO, imidazolyl group or triazolyl group, and Z ² represents 1 hydrocarbon group. Represents an alkylene group of 10 to 10, and the alkylene group may be interrupted by -NH-, -O-, or -S-). The organosilicon compound according to claim 1, wherein the polycarboxylic acid anhydride is a compound represented by the following general formula (2).

(In the above formula (2), R ¹ and R ² represent a group which is bonded to form an acid anhydride, or one of R ¹ and R ² is a —COOH group, the other is a hydrogen atom, It represents any group selected from a hydrocarbon group having 1 to 12 carbon atoms and a —COOH group, and X is a carbon atom which may be interrupted by —CO—, —O—, —SO ₂ — or a nitrogen atom. Represents a hydrocarbon group of formula 1-20.) The organosilicon compound according to claim 2, wherein X represents any one selected from the following general formulas (B-1) to (B-5).

  The organosilicon compound according to claim 1, wherein A is an azole group. The reaction ratio between the compound represented by the general formula (1) and the polycarboxylic acid anhydride in the reaction product as the intermediate is represented by the general formula (3) to be reacted with the reaction product. It is determined as follows by R ^{4 in} the structure of the compound,
(I) When R ⁴ in the general formula (3) is —NH ₂ , an imidazolyl group or a triazolyl group, the number of moles of the compound represented by the general formula (1) / the number of moles of polycarboxylic acid = 1. 5/1-1 / 1.5,
(Ii) When R ⁴ in the general formula (3) is —NCO,
Number of moles of compound represented by general formula (1) / (number of moles of polycarboxylic acid × number of acid anhydrides in one molecule) = 1.5 / 1 to 1 / 1.5,
And the ratio of the compound represented by the general formula (1) and the compound represented by the general formula (3) in the final product is a molar ratio of the compound represented by the general formula (1) / general The compound represented by Formula (3) = 1.5 / 1 to 1 / 1.5. The organosilicon compound according to any one of claims 1 to 4.   A pretreatment method for electroless plating, wherein when the electroless plating is performed on the object to be plated, the object to be plated is pretreated with the organosilicon compound according to any one of claims 1 to 5. .   The metal of the plating solution used for the electroless plating is one or two selected from the group consisting of copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium, tungsten, platinum, rhodium and ruthenium The pretreatment method for electroless plating according to claim 6, which is as described 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, and a synthetic resin. Pretreatment method of electroless plating.