• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    The present invention relates to a method of forming a metal pattern on a substrate, the method comprising the following steps: polysilane, a photosensitive radical generator, an oxidizing agent, an alkoxy group, dissolved in an organic solvent and having a weight average molecular weight of 10,000 or more Applying a photosensitive resin composition containing a silicon compound and an organic solvent to a substrate to form a photosensitive layer; Selectively exposing the photosensitive layer to form a latent image portion associated with the metal pattern; Adsorbing a metal or metal colloid having a low standard electrode potential to a latent image by contacting a photosensitive layer with a liquid containing a salt of a metal having a low standard electrode potential or a metal colloid with a metal; And contacting the photosensitive layer with an electroless plating solution to adsorb a metal film having a high standard electrode potential to a latent image on which a metal having a low standard electrode potential or a metal colloid is adsorbed to form a metal pattern.
    公开号:KR20030085569A
    申请号:KR10-2003-7012407
    申请日:2002-03-20
    公开日:2003-11-05
    发明作者:쯔시마히로시
    申请人:닛뽕 뻬인또 가부시키가이샤；
    IPC主号:
    专利说明:

    Method of Forming Metal Pattern {METHOD FOR FORMING METAL PATTERN}
    [2] Polysilanes are very interesting polymers because they have metallic and electron delocalization due to the presence of silicon compared to carbon, and also have high heat resistance and excellent thin film formation properties. Polysilane doped with iodine or ferric chloride is used to make highly conductive materials. Studies on the use of polysilanes are actively conducted to develop photoresists capable of forming fine patterns with high precision (for example, Japanese Patent Laid-Open Publications Hei 6-291273 and Hei 7-114188).
    [3] Japanese Patent Laid-Open No. Hei 5-72694 proposes a method for manufacturing a semiconductor integrated circuit using polysilane. This method uses a polysilane film or a polysilane film doped with iodine as the conductive layer. Moreover, the siloxane layer converted from polysilane by irradiation is used as an insulating layer.
    [4] However, when the semiconductor integrated circuit obtained by the above method is applied to an electronic material, problems arise due to insufficient conductivity of the polysilane conductive portion and ease of corrosion of iodine. Also, when exposed to moisture, polysilanes readily change to siloxanes, so their use as conductive materials is usually insufficient to ensure the reliability required for electronic materials.
    [5] Japanese Patent Laid-Open No. Sho 57-11339 discloses a method of forming a metal image by contacting a metal salt solution after exposing a compound having a Si-Si bond. This method utilizes the reduction of the metal salt solution that occurs when a compound having a Si—Si bond is in contact with the metal solution, ie, forms a metal layer in the unexposed portion.
    [6] Japanese Patent Laid-Open No. Hei 10-326957 discloses a method of forming a metal pattern by irradiating a film of polysilane acid alone, doping the exposed area with a palladium salt, and performing an electroless plating catalyzed by the palladium salt. have.
    [7] Polysilane membranes are usually highly crystalline, hard and brittle. Therefore, the above method has a problem in that a practical metal pattern cannot be formed by forming a metal pattern having poor adhesion.
    [1] The present invention relates to a method of forming a metal pattern using polysilane, and more particularly to a method of forming a metal pattern applicable to circuit boards and other applications used in the fields of electrical, electronic and communication.
    [18] BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing explaining the method of forming the metal pattern of this invention.
    [19] Best Mode for Carrying Out the Invention
    [20] BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing explaining the formation method of the metal pattern of this invention.
    [21] As shown in Fig. 1 (a), the photosensitive resin composition of the present invention is first applied onto the substrate 1 to form the photosensitive layer 2.
    [22] As shown in FIG. 1B, a mask 3 is disposed on the photosensitive layer 2, ultraviolet light 4 is irradiated to the photosensitive layer 2 through the mask 3, and the photosensitive layer 2 is selectively exposed. The mask 3 is patterned so that the area | region corresponding to the metal pattern formed later may be exposed. Therefore, the region of the photosensitive layer 2 corresponding to the metal pattern formed later is exposed to form the latent image portion 2a. Here, a photosensitive layer is selectively exposed using a mask. However, the present invention is not limited to this. For example, laser light can be selectively exposed by scanning.
    [23] In the latent image portion 2a, the polysilane is irradiated with ultraviolet light in the presence of oxygen. This cleaves the Si-Si bonds to produce Si-OH groups (silanol groups). As a result, the resin of the latent flaw part 2a changes its characteristic from nonpolar to polar, and becomes hydrophilic.
    [24] Next, as shown in Fig. 1 (c), a liquid containing a metal salt having a low standard electrode potential, for example, a liquid containing a palladium salt, is brought into contact with the photosensitive layer 2 to adsorb palladium to the latent image portion 2a. Let's do it. When contacted with the hydrophilized latent portion 2a, the palladium salt is reduced to produce metallic particles of palladium which are subsequently adsorbed. On the other hand, metallic particles of such palladium are not produced in regions other than the latent flaw portion 2a in which the palladium salt can be easily removed by washing. Therefore, palladium can be adsorbed only in the latent image part 2a.
    [25] As shown in Fig. 1 (d), the electroless plating solution is brought into contact with the photosensitive layer 2 to deposit the metal film 5 on the latent image portion 2a on which palladium is adsorbed. When the electroless plating liquid contacts the palladium adsorption latent portion 2a, the metal present in the plating liquid is separated and deposited as if the metallic particles of palladium act as a catalytic nucleus. As a result, the metal film 5 is selectively deposited on the latent image portion 2a. Since the latent image portion 2a is formed corresponding to the shape of the metal pattern to be formed, a metal pattern in the shape of the deposited metal film 5 is formed.
    [26] Now, the photosensitive resin composition used in the present invention, a liquid containing a salt or colloid of a metal having a low standard electrode potential (hereinafter, a "metal salt containing liquid") and an electroless plating solution will be described.
    [27] (Photosensitive resin composition)
    [28] The photosensitive resin composition used in the present invention contains a polysilane, a photosensitive radical generator, an oxidizing agent, an alkoxy-containing silicone compound (hereinafter referred to as a "silicon compound") and an organic solvent dissolved in an organic solvent and having a weight average molecular weight of 10,000 or more. . These compounds are described below.
    [29] (Polysilane)
    [30] Networked and linear polysilanes can be used in the present invention. Considering the mechanical strength as the photosensitive material, it is preferable to use polysilane on the network. Networked and linear polysilanes are distinguished from each other by the bonding state of the Si atoms contained in the polysilane. Polysilane on a network is a polysilane containing Si atoms whose number of bonds (bond count) couple | bonded with an adjacent Si atom is three or four. On the other hand, the linear polysilane contains Si atoms in which the number of bonds bonded to adjacent Si atoms is two. Since Si usually has a valence of 4, Si atoms having a bond number of 3 or more among Si atoms present in the polysilane are bonded not only to hydrocarbon groups, alkoxy groups or hydrogen atoms, but also to adjacent Si atoms. Preferred hydrocarbon groups are aliphatic hydrocarbon groups of 1 to 10 carbon atoms which may be substituted by halogen, or aromatic hydrocarbon groups of 6 to 14 carbon atoms.
    [31] Specific examples of aliphatic hydrocarbon groups include chain hydrocarbon groups such as methyl, propyl, butyl, hexyl, octyl, decyl, trifluoropropyl and nonafluorohexyl groups; And cycloaliphatic hydrocarbon groups such as cyclohexyl and methylcyclohexyl groups.
    [32] Specific examples of aromatic hydrocarbon groups are phenyl, p-tolyl, bi (phenyl) and anthracyl groups. The alkoxy group may have 1 to 8 carbon atoms. Examples of such alkoxy groups are methoxy, ethoxy, phenoxy and octyloxy groups. In view of easy synthesis, methyl and phenyl groups are particularly preferred among these.
    [33] In the case of the network polysilane, it is preferable to contain 2 to 50% of the Si atoms having 3 or 4 bonds with adjacent Si atoms based on the total number of Si atoms present in the network polysilane. This value can be determined by nuclear magnetic resonance spectrum measurement of silicon.
    [34] The polysilanes herein also include mixtures of networked and linear polysilanes. In that case, the content of the Si atom is calculated as the average value of the content of the network polysilane and the linear polysilane.
    [35] The polysilanes used in the present invention may be produced by polycondensation reactions that occur when the halogenated silane compound in an organic solvent such as n-decane or toluene is heated to 80 ° C. or higher in the presence of an alkali metal such as sodium.
    [36] The polysilane on the network is obtained by a polycondensation reaction, which occurs when the halosilane mixture containing, for example, an organotrihalosilane compound, a tetrahalosilane compound and a diorganodihalosilane compound is heated, wherein The non-halosilane and tetrahalosilane compounds are present in an amount of at least 2 mol% and less than 50 mol% based on the total amount of the halosilane mixture. Here, the organotrihalosilane compound serves as a source of Si atoms having 3 bonds with adjacent Si atoms, and the tetrahalosilane compound as a source of Si atoms having 4 bonds with adjacent Si atoms. Play a role. Network structures can be identified by ultraviolet absorption spectra or nuclear magnetic resonance spectra of silicon.
    [37] Straight chain polysilanes can be prepared by the same reactions used to prepare networked polysilanes, but use plural or singular diorganodichlorosilanes.
    [38] Preferably, each halogen atom of the organotrihalosilane compound, tetrahalosilane compound and diorganodihalosilane compound used as a raw material of polysilane is a chlorine atom. In addition to such halogen atoms, organotrihalosilanes and diorganodihalosilane compounds have substituents, examples of which include the above hydrocarbon and alkoxy groups and hydrogen atoms.
    [39] These networked and linear polysilanes are not particularly limited as long as they are dissolved in an organic solvent and have a weight average molecular weight of 10,000 or more. In view of the usefulness as the photosensitive material, the polysilane used in the present invention is preferably dissolved in a volatile organic solvent. Examples of such organic solvents include hydrocarbons having 5 to 12 carbon atoms, halogenated hydrocarbons and ether solvents.
    [40] Examples of hydrocarbon-based organic solvents are pentane, hexane, heptane, cyclohexane, n-decane, n-dodecane, benzene, toluene, xylene and methoxybenzene. Examples of halogenated hydrocarbon-based organic solvents are carbon tetrachloride, chloroform, 1,2-dichloroethane, dichloro-methane and chlorobenzene. Examples of ether-based organic solvents are diethyl ether, dibutyl ether and tetrahydrofuran.
    [41] The polysilane used in the present invention has a weight average molecular weight of 10,000 or more. If the weight average molecular weight is less than 10,000, the polysilane has insufficient membrane properties such as chemical resistance and heat resistance. The polysilane preferably has a weight average molecular weight of 10,000 to 50,000, more preferably 15,000 to 30,000.
    [42] (Photosensitive radical generator and oxidant)
    [43] The photosensitive radical generator used in the present invention is not particularly limited as long as it can generate halogen radicals upon irradiation. Examples of such photosensitive radical generators include 2,4,6-tris (trihalomethyl) -l, 3,5-triazine, and derivatives thereof substituted at the 2 or 4 position thereof; Phthalimidetrihalomethane sulfonate, and derivatives thereof having substituents attached to the benzene ring thereof; Naphthalimidetrihalomethane sulfonate and its derivatives having substituents attached to the benzene ring thereof and the like. Substituents of these compounds are aliphatic and aromatic hydrocarbon groups which may have substituents.
    [44] The oxidant used in the present invention is not particularly limited as long as it can be an oxygen source. Examples of oxidants are peroxides, amine oxides and phosphine oxides.
    [45] Trichlorotriazine-based photosensitive radical generators and peroxide oxidants are components of particularly preferred combinations of photosensitive radical generators and oxidants.
    [46] The purpose of adding a photosensitive radical generator is to achieve effective cleavage of Si-Si bonds by halogen radicals when the polysilane is decomposed by light irradiation. The purpose of adding the oxidant is to easily insert oxygen into the Si bond after cleavage.
    [47] Soluble dyes such as coumarin, cyanine or merocyanine dyes are added to promote the generation of halogen radicals by photoexcitation of the dyes. The addition of soluble dyes also improves the sensitivity of the polysilanes to light.
    [48] (Silicon compound)
    [49] The silicone compound used in the present invention is a silicone compound containing two or more alkoxy groups per molecule. Preference is given to using silicone compounds having the structure represented by the following general formula:
    [50]
    [51] (In the meal,
    [52] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with halogen or glycidyl group, and having 6 to 12 carbon atoms which may be substituted with halogen. An aromatic hydrocarbon group and a functional group selected from the group consisting of alkoxy groups having 1 to 8 carbon atoms, which may be the same or different, provided that the silicon compound contains at least two of said alkoxy groups per molecule;
    [53] m and n are both integers, where m + n ≥ 1).
    [54] Specific examples of aliphatic hydrocarbon groups which may be selected for the above substituents R 1 to R 6 are chain hydrocarbon groups such as methyl, propyl, butyl, hexyl, octyl, decyl, trifluoropropyl and glycidyloxypropyl groups. ; And cycloaliphatic hydrocarbon groups such as cyclohexyl and methylcyclohexyl groups. Specific examples of aromatic hydrocarbon groups are phenyl, p-tolyl and biphenyl groups. Examples of alkoxy groups are methoxy, ethoxy, phenoxy, octyloxy and ter-butoxy groups.
    [55] The kind of R 1 to R 6 and the values of m and n are not very important, and therefore the silicone compound is not particularly limited as long as it is compatible with polysilane and organic solvent. As far as compatibility is concerned, the silicone compounds preferably have the same hydrocarbon groups as contained in the polysilanes used. For example, when using a phenylmethyl type polysilane, it is preferable to use a phenylmethyl type or diphenyl type silicone compound.
    [56] In the silicone compound used in the present invention, at least two of R 1 to R 6 in the molecule are an alkoxy group having 1 to 8 carbon atoms. Since it contains two or more alkoxy groups per molecule, the silicone compound serves as a crosslinking agent for the polysilane. Such silicone compounds will be described as methylphenylmethoxy silicones and phenylmethoxy silicones, each having 15 to 35% by weight of alkoxy groups.
    [57] The silicone compound used in the present invention preferably has a weight average molecular weight of 10,000 or less, more preferably 3,000 or less. If the weight average molecular weight of the silicone compound is too high, compatibility with the polysilane is lowered, and as a result, the film becomes nonuniform and the sensitivity is lowered.
    [58] (Organic solvent)
    [59] The organic solvent contained in the photosensitive resin composition of this invention is not specifically limited as long as it can melt | dissolve polysilane. Specifically, organic solvents exemplified in the description of the polysilane can be used.
    [60] (Formulation of Photosensitive Resin Composition)
    [61] The photosensitive resin composition used for this invention contains 1-30 weight part photosensitive radical generator, 1-30 weight part oxidizing agent, and 5-100 weight part silicone compound based on 100 weight part polysilane. When added, the soluble dye is preferably present in an amount of 1 to 20 parts by weight based on 100 parts by weight of polysilane. The organic solvent is preferably incorporated at a concentration of 20 to 99% by weight, based on the total weight of the composition.
    [62] Silicone compounds act as crosslinking agents for polysilanes, increase the solubility of polysilanes in organic solvents, and function as compatibilizers of polysilanes with photosensitive radical generators and oxidants. Thus, with the use of silicone compounds, the composition may contain higher amounts of photosensitive radical generators and oxidants.
    [63] (Application method of the photosensitive resin composition)
    [64] The coating method of the photosensitive resin composition is not specifically limited. The photosensitive layer can be formed by various coating methods including a spin coating method, a dipping method, a casting method, a vacuum deposition method, and an LB method (Langmuir-Blodgett method). It is especially preferable to use the spin coating method which develops the photosensitive resin composition on a board | substrate, and rotates and apply | coats a board | substrate at high speed.
    [65] In the case of forming the photosensitive layer using the spin coating method, preferred organic solvents used in the photosensitive resin composition include aromatic hydrocarbons such as benzene, toluene and xylene and ethers such as tetrahydrofuran and dibutyl ether. The organic solvent is preferably used in an amount which keeps the solid concentration within 1 to 20% by weight, that is, an amount that keeps the organic solvent content within 80 to 99% by weight.
    [66] The photosensitive layer is preferably deposited on the substrate to a thickness of 0.01 to 1,000 mu m, more preferably 0.1 to 50 mu m.
    [67] (Exposure of Photosensitive Layer)
    [68] It is preferable to use ultraviolet rays to irradiate the photosensitive layer. Useful sources of ultraviolet light include continuous spectrum light sources such as hydrogen discharge tubes, rare gas discharge tubes, tungsten lamps and halogen lamps; And discrete spectral light sources such as various lasers and mercury lamps. Useful lasers include He-Cd lasers, Ar lasers, YAG lasers and excimer lasers. Among these, it is preferable to use a mercury lamp as a light source because it is inexpensive and easy to handle.
    [69] Preferably, as a light source, ultraviolet-ray which has a wavelength of 250-400 nm corresponding to the sigma-σ * absorption range of polysilane is preferable. The irradiation amount is preferably 0.1 to 10 J / cm 2 , more preferably 0.1 to 1 J / cm 2 per 1 μm of the photosensitive layer.
    [70] (Board)
    [71] The substrate is not particularly limited and may be selected from various substrates according to a specific use. Examples of useful substrates include insulator substrates such as quartz glass and ceramics, semiconductor substrates such as silicon, and conductor substrates such as aluminum.
    [72] (Metal Salt Containing Liquid)
    [73] The metal salt containing liquid of this invention is a solution containing the salt or colloid of the metal with low standard electrode potential. The metal salt-containing liquid is not particularly limited as long as it contains metal salts useful for pretreatment of the electroless plating solution. Usually, solutions containing precious metals such as gold, silver, platinum or palladium are often used in the form of metal salts. These metal salt-containing liquids serve as a catalyst imparting agent and are readily available at low cost. Often, solutions containing silver or palladium salts are often used as catalysts. The metal salt compound can usually be represented in the form of AZ n (n is the valence of A and A is the metal). Z is exemplified by halogen atoms such as Cl, Br or I, acetate, trifluoroacetate, acetylacetonate, carbonate, perchlorate, nitrate, sulfonate, oxide and the like. Examples of palladium salt compounds include PdCl 2 , PdBr 2 , PdI 2 , Pd (OCOCH 3 ) 2 , Pd (OCOCF 3 ) 2 , PdSO 4 , Pd (N0 3 ) 2 and PdO.
    [74] The metal colloid-containing solution is, for example, a colloidal solution of a noble metal disclosed in Japanese Patent Laid-Open No. Hei 11-80647.
    [75] The metal salt-containing liquid is a solution in which the metal salt or metal colloid is dissolved or dispersed. Preferably, solvents are used which dissolve or disperse the metal salts or metal colloids but do not dissolve the polysilane. Since the solubility of the polysilane varies depending on the type of side chain group, the degree of polymerization, and the like, it is difficult to clearly specify a suitable solvent, but it is usually preferable to use the following: water; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate; Alcohols such as methanol and ethanol; Aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide and hexamethylphosphoric triamide; Nitromethane; Acetonitrile and the like. If polysilane is used in the form of phenylmethylpolysilane, it is particularly preferred to use alcohols such as methanol. The solvent is used to such an extent that the concentration of the palladium salt is preferably maintained within 0.1 to 20% by weight, more preferably 1 to 10% by weight.
    [76] Preferably, the substrate having the photosensitive layer is impregnated with the metal salt containing liquid to bring the photosensitive layer on the substrate into contact with the metal salt containing liquid. Although deposition time is not specifically limited, For example, it may be about 1 second-about 10 minutes. After the deposition, drying is usually carried out at a temperature of 10 ° C. to 200 ° C. under room temperature or reduced pressure.
    [77] As described above, the exposed portion on which the latent image is formed is hydrophilized due to generation of silanol groups. Therefore, in this part, the metal salt is reduced to metallic particles for adsorption. In order to promote the reduction of the metal salt to metallic particles, the liquid temperature can be raised to 40 to 200 ° C when the metal salt-containing liquid is in contact with the photosensitive layer.
    [78] In the case of a metal colloid, a metal colloid is adsorbed to an exposure part in the form as it is.
    [79] The metal salt-containing liquid may further contain ions of at least one metal in addition to the metal. An example of another metal is tin. These metals are precipitated and adsorbed in the form of alloy particles if alloyable with the metal.
    [80] (Electroless plating solution)
    [81] For example, it is preferable to use an electroless plating solution containing metal ions of copper, nickel, palladium, gold, platinum or rhodium. Electroless plating solutions usually contain water-soluble metal salts of any of the above metals, reducing agents such as sodium hypophosphite, hydrazine or sodium boron hydride and complexing agents such as sodium acetate, phenylenediamine or potassium sodium tartrate. Usually, such an electroless plating solution can be easily obtained that is commercially available at low cost.
    [82] As a method of contacting a photosensitive layer with an electroless plating liquid, it is preferable to impregnate a photosensitive layer holding board | substrate in the same way as the contact with said metal salt containing liquid, ie, an electroless plating liquid. When the electroless plating solution is brought into contact with the photosensitive layer, the liquid is preferably maintained at a temperature of 15 to 120 ° C, more preferably 25 to 85 ° C. The contact time is, for example, in the range of 1 minute to 16 hours, preferably about 10 to 60 minutes.
    [83] The thickness of the metal film formed by the electroless liquid varies depending on the intended use, but is preferably about 0.01 to 100 µm and even more about 0.1 to 20 µm.
    [84] According to the present invention, an excellent adhesive metal pattern can be easily formed on a substrate.
    [85] The invention is explained in more detail by the following examples. The following examples merely illustrate examples of the invention but are not intended to limit the invention. It can change suitably and can implement in the range of this invention.
    [86] (Manufacture example 1)
    [87] (Production of Polysilane)
    [88] 400 ml of toluene and 13.3 g of sodium were charged into a 1,000 ml flask equipped with a stirrer. The flask contents were raised to 111 ° C. in a UV cut yellow room and then stirred at high speed to finely disperse sodium in toluene. 42.1 g of phenylmethyl-dichlorosilane and 4.1 g of tetrachlorosilane were added to the dispersion, followed by stirring to polymerize. Thereafter, ethanol was added to the obtained reaction mixture to deactivate excess sodium. Then the mixture was washed with water and separated. The introduction of the separated organic layer into ethanol precipitated polysilane. The obtained crude polysilane was precipitated three times with ethanol to obtain a polymethylphenylsilane on the network having a weight average molecular weight of 11,600.
    [89] (Example 1)
    [90] 100 parts by weight of the network polysilane obtained in Preparation Example 1, 50 parts by weight of TSR-165 (molecular weight 930 methylphenylmethoxy silicone resin, methoxy group content: 15% by weight, as silicone compound) of Toshiba Silicone Co., Ltd. Product), 10 parts by weight of TAZ-110 [2,4-bis (trichloromethyl) -6- (p-methoxyphenyl-vinyl) -1,3,5-triazine, Midori Kagaku Co as a photosensitive radical generator ., Ltd. Products], and 15 parts by weight of BTTB [3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, NOF Corp. Product] was dissolved in 1215 parts by weight of toluene to obtain a photosensitive resin composition. This photosensitive resin composition was apply | coated to the glass substrate by 20 micrometers in thickness by the spin coater, and it dried in oven at 120 degreeC for 10 minutes, and formed the photosensitive layer on the glass substrate.
    [91] Then, a photomask was disposed on the photosensitive layer, and a 500 W mercury lamp was used to irradiate ultraviolet rays having a wavelength of 365 nm through the photomask with a light quantity of 500 mJ / cm 2 to expose the photosensitive layer in a predetermined pattern. A latent image of a metal circuit pattern was formed.
    [92] The photosensitive layer was immersed with the substrate in a 5 wt% ethanol solution of palladium chloride for 5 minutes, then taken out of the solution, washed with ethanol and dried at 100 ° C. for 10 minutes. As a result, palladium was adsorbed on the latent portion of the metal circuit pattern.
    [93] Thereafter, the photosensitive layer was immersed with the substrate in an electroless plating solution consisting of 20 g nickel chloride, 10 g sodium hypophosphite, 30 g sodium acetate, and 1,000 g water at 23 ° C. for 30 minutes.
    [94] As a result, a metal film made of nickel was deposited on the latent portion of the metal circuit pattern to form a metal circuit pattern. The thickness of the metal film was 2 m.
    [95] The photosensitive layer in which the metal circuit pattern was formed was washed with pure water, and then dried at 150 ° C. for 30 minutes. The conductivity of the formed metal circuit pattern was measured to be 7 × 10 3 S / cm. The adhesive force of the part of a metal circuit pattern was evaluated by the measurement of peeling strength. The peeling strength was 0.7 kgf / cm or more, and the outstanding adhesiveness of the metal circuit pattern was confirmed.
    [96] (Comparative Example 1)
    [97] 150 parts by weight of a networked polysilane obtained in Preparation Example 1, 10 parts by weight of TAZ-110 as a photosensitive radical generator and 15 parts by weight of BTTB as an oxidant were dissolved in 1215 parts by weight of toluene to thereby contain a photosensitive resin composition containing no silicone compound. Obtained. In the procedure of Example 1, a photosensitive layer was formed on an organic substrate using the photosensitive resin composition, and a metal circuit pattern was formed on the photosensitive layer.
    [98] The conductivity of the formed metal circuit pattern was measured to be 6 x 10 3 S / cm. The adhesive force of the part of a metal circuit pattern was evaluated by the measurement of peeling strength. The peeling strength was 0.1 kgf / cm or less, and the metal circuit pattern of the comparative example 1 was inferior in adhesiveness to the metal circuit pattern of Example 1.
    [99] (Example 2)
    [100] A photosensitive resin composition was prepared and applied onto a substrate according to the procedure of Example 1 to form a photosensitive layer. This photosensitive layer was exposed to ultraviolet rays in the same manner as in Example 1 to form a latent image of a metal circuit pattern.
    [101] The photosensitive layer which formed the latent image of the metal circuit pattern was immersed with the board | substrate in the 5 weight% ethanol solution of palladium chloride for 5 minutes, and after immersion, it was wash | cleaned with ethanol and dried at 100 degreeC for 10 minutes.
    [102] This obtained the photosensitive layer by which palladium tin was adsorbed on the latent image part.
    [103] Thereafter, the photosensitive layer was immersed with the substrate in an electroless plating solution consisting of 10 g of copper sulfate, 5 g of 37% formalin, 5 g of sodium hydroxide, and 1,000 g of water at 23 ° C. for 30 minutes. As a result, a metal film made of copper was deposited on the latent image portion of the photosensitive layer to form a metal circuit pattern. The thickness of the metal film was 2 m.
    [104] The photosensitive layer in which the metal circuit pattern was formed was washed with pure water, and then dried at 150 ° C. for 30 minutes. The conductivity of the formed metal circuit pattern was measured to be 7 × 10 5 S / cm. The adhesion of the metal circuit pattern was evaluated by the measurement of the peel strength. The peeling strength was 0.9 kgf / cm or more, and confirmed the outstanding adhesiveness of a metal circuit pattern.
    [105] In the above embodiment, the metal circuit pattern has been described as an example of the metal pattern. However, the present invention is not limited to the formation of a metal pattern for circuit use. The present invention can also be applied to the formation of metal patterns for uses other than circuits.
    [8] An object of the present invention is to provide a method of forming a metal pattern capable of forming a metal pattern excellent in adhesion in a simple process.
    [9] The method of the present invention is a method of forming a metal pattern on a substrate, characterized by comprising the following steps: polysilane, photosensitive radical generator, oxidizing agent, alkoxy-containing silicone, dissolved in an organic solvent and having a weight average molecular weight of 10,000 or more Applying a photosensitive resin composition containing a compound and an organic solvent to a substrate to form a photosensitive layer; Selectively exposing the photosensitive layer to form a latent image portion associated with the metal pattern; Adsorbing a metal or metal colloid having a low standard electrode potential to a latent image by contacting a photosensitive layer with a liquid containing a salt of a metal having a low standard electrode potential or a colloid of a metal; And forming a metal pattern by contacting the photosensitive layer with an electroless plating solution to deposit a metal film with a high standard electrode potential on a latent image on which a metal with a low standard electrode potential or a metal colloid is adsorbed.
    [10] The photosensitive resin composition used for this invention contains an alkoxy containing silicone compound. This alkoxy-containing silicone compound contains two or more alkoxy groups per molecule. When heated, the alkoxy groups decompose to produce Si-OH groups (silanol groups). Since this silanol group reacts with the polysilane, the alkoxy-containing compound can be crosslinked with the polysilane by heating the coating film, thereby improving the adhesion of the coating film. Therefore, the metal pattern adsorbed on the photosensitive layer by electroless plating according to the present invention has excellent adhesion to the photosensitive layer which is the lower layer. Therefore, according to the present invention, it is possible to form a metal pattern with excellent fineness and high adhesion, and therefore, a metal pattern which can be widely applied in the fields of electricity, electronics, and communication can be manufactured in a low cost and simple process. have.
    [11] In order to promote the crosslinking reaction of the silicone compound and polysilane, it is preferable to heat the photosensitive layer on which the metal pattern is formed after forming the metal pattern by electroless plating. At this time, heating temperature becomes like this. Preferably it is about 150-250 degreeC. Although heating time is 5 minutes-60 minutes normally, it can adjust suitably according to heating temperature.
    [12] In the present invention, particularly preferred for use as an alkoxy containing compound are silicone compounds having a structure represented by the following general formula:
    [13]
    [14] (In the meal,
    [15] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with halogen or glycidyl group, and having 6 to 12 carbon atoms which may be substituted with halogen. An aromatic hydrocarbon group and a functional group selected from the group consisting of alkoxy groups having 1 to 8 carbon atoms, which may be the same or different, provided that the silicon compound contains at least two of said alkoxy groups per molecule;
    [16] m and n are both integers, where m + n ≥ 1).
    [17] The electroless plating solution used in the present invention preferably contains metal ions of, for example, copper, nickel, platinum, gold, palladium or rhodium, and forms a metal film when adsorbed.
    [106] According to the method for forming a metal pattern of the present invention, it is possible to form a high adhesion metal pattern in an inexpensive and simple process. Thus, the present invention can be used to form metal patterns in various applications, such as small heating elements, battery electrodes, solar cells, sensors, integrated circuits, and casings for small motors. Thus, the present invention is useful for the formation of metal patterns for a wide range of applications in the fields of electrical, electronics and communication.
    权利要求:
    Claims (5)
    [1" claim-type="Currently amended] A method of forming a metal pattern on a substrate, the method comprising the following steps:
    Forming a photosensitive layer by applying a photosensitive resin composition containing a polysilane, a photosensitive radical generator, an oxidizing agent, an alkoxy-containing silicone compound and an organic solvent, dissolved in an organic solvent and having a weight average molecular weight of 10,000 or more;
    Selectively exposing the photosensitive layer to form a latent image portion associated with a metal pattern; Adsorbing a metal or metal colloid having a low standard electrode potential to the latent image portion by contacting a photosensitive layer with a liquid containing a salt of a metal having a low standard electrode potential or a colloid of metal; And
    A step of forming a metal pattern by contacting a photosensitive layer with an electroless plating solution to deposit a metal film having a high standard electrode potential on a latent image where a metal having a low standard electrode potential or a metal colloid is adsorbed.
    [2" claim-type="Currently amended] The method of claim 1, wherein the alkoxy-containing silicone compound is a silicone compound having a structure represented by the following general formula:

    (In the meal,
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with halogen or glycidyl group, and having 6 to 12 carbon atoms which may be substituted with halogen. An aromatic hydrocarbon group and a functional group selected from the group consisting of alkoxy groups having 1 to 8 carbon atoms, which may be the same or different, provided that the silicon compound contains at least two of said alkoxy groups per molecule;
    m and n are both integers, where m + n ≥ 1).
    [3" claim-type="Currently amended] The method according to claim 1 or 2, wherein the electroless plating solution contains metal ions of copper, nickel, palladium, gold, platinum or rhodium, which form a metal film upon deposition.
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3, wherein the metal having a low standard electrode potential is gold, silver, platinum or palladium.
    [5" claim-type="Currently amended] 4. The method of any one of claims 1 to 3, wherein the metal having a low standard electrode potential is palladium.
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    同族专利:
    公开号 | 公开日
    EP1375699A1|2004-01-02|
    US20040081762A1|2004-04-29|
    WO2002077321A1|2002-10-03|
    TW535476B|2003-06-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-03-26|Priority to JPJP-P-2001-00088156
    2001-03-26|Priority to JP2001088156
    2002-03-20|Application filed by 닛뽕 뻬인또 가부시키가이샤
    2002-03-20|Priority to PCT/JP2002/002632
    2003-11-05|Publication of KR20030085569A
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2001-00088156|2001-03-26|
    JP2001088156|2001-03-26|
    PCT/JP2002/002632|WO2002077321A1|2001-03-26|2002-03-20|Method for forming metal pattern|
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