A method to suppress the decrease in strength of a glass substrate and to suppress the scattering of fragments.

Abstract

The present invention aims to provide a new method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments. [Solution] A method to suppress the decrease in strength of the glass substrate and suppress the scattering of fragments.

Description

[Technical Field]

[0001] This invention relates to a method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments. [Background technology]

[0002] Patent Document 1 discloses the applicant's invention, a coating composition for electroless plating on a non-conductive substrate whose surface has been anionized, comprising (1) a composite of palladium particles and a dispersant, (2) a cationic surfactant, and (3) water. When a non-conductive substrate is pretreated for electroless plating using this coating composition, and then electroless plating is performed, the electroless plated product exhibits excellent adhesion between the non-conductive substrate and the plating, and the electroless plated product forms a plated product with a good appearance film.

[0003] In recent years, there has been much discussion about replacing conventional resin substrates with glass substrates in semiconductor packaging to reduce power consumption. Glass is suitable for larger and thinner substrates due to its excellent smoothness and dimensional stability, but it has the disadvantage of being brittle. In particular, glass substrates that have undergone conductive treatment such as plating or sputtering become brittle due to the difference in coefficient of thermal expansion between them and copper. Furthermore, in applications such as glass substrates and interposers, glass substrates with fine through-holes (TGV) are used, which further reduces the strength of the glass and makes it more brittle. Given this situation, methods such as forming a brittle sacrificial zone around the wiring area of ​​the glass substrate are being considered.

[0004] Patent Document 2 discloses a core substrate applicable to the manufacture of a semiconductor packaging substrate, wherein the core substrate is divided into a product area and a blank area, the product area is an area on which products to be used as substrates for discrete semiconductors are arranged, the blank area is the area excluding the product area, a protective area is arranged in the blank area, and the protective area is an area on which grooves (concaves) or vias are arranged. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 5819020 [Patent Document 2] Japanese Patent Publication No. 2024-25692 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a new method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments. [Means for solving the problem]

[0007] Generally, when a glass substrate is plated, its strength decreases compared to the unplated glass (or unplated glass after etching). Furthermore, if the glass substrate is partially damaged, the resulting fragments can come into contact with wiring, causing a short circuit.

[0008] As a result of diligent research, the inventors have developed a technology in which, by pre-treating a glass substrate with a coating composition containing (1) a resin having reactive ends and (2) a silane coupling agent, and then applying electroless plating, it is possible to suppress the decrease in strength of the plated glass substrate and suppress the scattering of fragments.

[0009] The present invention is particularly effective for glass substrates with microporous coatings (TGV).

[0010] In other words, the present invention includes the following pretreatment coating compositions for electroless plating and methods for producing electroless plated products.

[0011] Section 1. A method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments, (1) A step of applying a pretreatment coating composition to a glass substrate, (2) A step of subjecting the glass substrate coated with the pretreatment coating composition to contact with an aqueous solution containing a cationic surfactant to perform cationization treatment; (3) A step of subjecting the cationized glass substrate to contact with a palladium (Pd) colloid solution to impart palladium, and (4) A step of performing electroless plating on the glass substrate imparted with palladium (which) includes them in order, The pretreatment coating composition (1) contains a resin having reactive terminals, and (2) contains a silane coupling agent, The (2) silane coupling agent is a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; is a silane coupling agent having a butadiene skeleton and an alkoxysilyl group; and is at least one silane coupling agent selected from the group consisting of a silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group; Method.

[0012] Item 2. The method according to item 1, wherein the glass substrate is a glass substrate with micropores (Through Glass Vias: TGV).

[0013] Item 3. The step (1) (1) is a step of performing a polymerization reaction between the resin having reactive terminals and the (2) silane coupling agent after applying the pretreatment coating composition to the glass substrate, according to the method described in item 1.

[0014] Item 4. The pretreatment coating composition further (5) contains a solvent, according to the method described in item 1.

[0015] Item 5. The method according to item 1, wherein the resin having the (1) reactive terminal is at least one resin selected from the group consisting of an acetal resin, an epoxy resin, an ester resin, an acrylic resin, a urethane resin, a polyamide, a polyimide, a polyamideimide, a shellac resin, a urea resin, nitrocellulose, an alkyd resin, a petroleum resin, a rosin-based resin, a styrene / maleic acid resin, a silicone resin, a vinyl chloride-vinyl acetate copolymer, an acrylic monomer / oligomer, a polyolefin, a phenol resin, a polyarylate resin, and a butyral resin.

[0016] Item 6. The method according to item 1, wherein the resin having the (1) reactive terminal is at least one resin selected from the group consisting of a urethane resin, a polyimide, a polyamideimide, a polyamide, and an epoxy resin.

[0017] Item 7. The pretreatment coating composition further comprises (3) containing palladium (Pd) colloid, the method according to item 1.

[0018] Item 8. The method according to item 1, wherein the (5) solvent is at least one solvent selected from the group consisting of an aprotic polar solvent, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, and fluorinated solvents.

[0019] In the present invention, when electroless plating is performed on a glass substrate (particularly, a glass substrate with micropores (TGV)) using a specific pretreatment coating composition for electroless plating, it is possible to suppress a decrease in the strength of the plated glass substrate and suppress the scattering of fragments.

[0020] In the present invention, by first applying a pretreatment coating composition to a glass substrate and then performing plating, even when the glass substrate is subjected to a conductivity treatment, it is possible to maintain the strength of the glass and suppress the scattering of fragments.

Effects of the Invention

[0021] This invention provides a new method for suppressing the decrease in strength of a glass substrate and preventing the scattering of fragments.

[0022] The present invention makes it possible to suppress the decrease in strength of the plated glass substrate and suppress the scattering of fragments by pre-treating the glass substrate with a specific electroless plating pre-treatment coating composition, and then applying electroless plating. [Brief explanation of the drawing]

[0023] [Figure 1] This figure shows a method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments according to the present invention. [Modes for carrying out the invention]

[0024] The present invention will be described in detail below.

[0025] The embodiments illustrating the present invention are intended to provide a better understanding of the invention's intent and, unless otherwise specified, do not limit the scope of the invention.

[0026] In this specification, "contains" and "include" are concepts that encompass all of the following: "comprise," "consist essentially of," and "consist of."

[0027] In this specification, when a numerical range is indicated as "A to B", it means "greater than or equal to A and less than or equal to B".

[0028] In this specification, the notations "parts," "%," etc., are generally used.

[0029] In this specification, parts by mass, parts by weight, mass%, and weight% (wt%) are generally expressed.

[0030] The present invention encompasses a method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments.

[0031] [1] Method for manufacturing electroless plated products Figure 1 shows one embodiment of a method for suppressing the decrease in strength of the glass substrate of the present invention and suppressing the scattering of fragments.

[0032] The present invention provides a method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments, (1) A step of applying a pretreatment coating composition to a glass substrate, (2) A step of cationizing a glass substrate coated with the pretreatment coating composition by bringing it into contact with an aqueous solution containing a cationic surfactant. (3) A step of contacting the cationized glass substrate with a palladium (Pd) colloidal solution to impart palladium (Pd), and (4) The process includes sequentially performing electroless plating on the glass substrate to which the palladium (Pd) has been applied.

[0033] The aforementioned pretreatment paint composition, (1) Resins having reactive ends, and (2) Contains a silane coupling agent.

[0034] The silane coupling agent described in (2) above is Acid anhydride structure and silane coupling agents having alkoxysilyl groups; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group; and The silane coupling agent is at least one selected from the group consisting of a butadiene skeleton, an acid anhydride structure, and a silane coupling agent having an alkoxysilyl group.

[0035] The glass substrate is preferably a glass substrate with microporous holes (Through Glass Vias: TGV).

[0036] Step (1) is preferably, (1) The process involves applying a pretreatment coating composition to a glass substrate, followed by carrying out a polymerization reaction between the resin having the reactive ends (1) and the silane coupling agent (2).

[0037] In this invention, by pre-treating a glass substrate with a specific pre-treatment coating composition, and then applying electroless plating, it is possible to suppress the decrease in strength of the plated glass substrate and suppress the scattering of fragments.

[0038] Pretreatment paint composition The pretreatment coating composition is a coating composition that is applied (pretreated) to a glass substrate before electroless plating.

[0039] Pretreatment coating composition, (1) Resins having reactive ends, and (2) Contains a silane coupling agent.

[0040] (1) The resin having a reactive end is preferably at least one resin selected from the group consisting of acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, polyamide, polyimide, polyamideimide, shellac resin, urea resin, nitrated cotton, alkyd resin, petroleum resin, rosin-based resin, styrene / maleic acid resin, silicone resin, vinyl chloride-vinyl acetate copolymer, acrylic monomer / oligomer, polyolefin, phenolic resin, polyarylate resin, and butyral resin.

[0041] (1) The resin having reactive ends is preferably at least one resin selected from the group consisting of urethane resins, polyimide resins, polyamideimide resins, polyamides, and epoxy resins.

[0042] (2) Silane coupling agents are Acid anhydride structure and silane coupling agents having alkoxysilyl groups; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group; and The silane coupling agent is at least one selected from the group consisting of a butadiene skeleton, an acid anhydride structure, and a silane coupling agent having an alkoxysilyl group.

[0043] The pretreatment coating composition is preferably further, (3) Contains palladium (Pd) colloid.

[0044] The aforementioned pretreatment coating composition is preferably further, (5) Contains a solvent.

[0045] (5) The solvent is preferably at least one solvent selected from the group consisting of aprotic polar solvents, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, and fluorinated solvents.

[0046] (1) Resins having reactive ends The pretreatment coating composition contains (1) a resin having reactive ends.

[0047] The resin having reactive ends is preferably selected from the viewpoint of obtaining good reactivity for electroless plating, such as the viscosity of the pretreatment coating composition, the adhesion between the pretreatment coating composition and the substrate (glass, ceramic, etc.), and the conditions of the heat treatment (polymerization treatment).

[0048] The resin having reactive ends is preferably (5) dispersed or dissolved in a solvent.

[0049] Resins having reactive ends are preferably acetal resin (POM), epoxy resin, ester resin, acrylic resin, urethane resin, amide resin (PA, polyamide, nylon), imide resin (polyimide), amide-imide resin (PAI, polyamide-imide), shellac resin, urea resin, nitrated cotton, alkyd resin, petroleum resin, rosin-based resin, styrene / maleic acid resin, silicone resin, vinyl chloride-vinyl acetate copolymer, acrylic monomer / oligomer, olefin resin (polyolefin), phenolic resin, polyarylate resin, butyral resin, etc.

[0050] PVC-vinyl acetate copolymer (vinyl chloride-vinyl acetate modified resin) is a copolymer resin of vinyl chloride and vinyl acetate, etc.

[0051] The resin having reactive ends is more preferably a resin such as a urethane resin, polyimide, polyamide-imide, polyamide, or epoxy resin, and even more preferably an epoxy resin or polyamide.

[0052] Resins having reactive ends may be used individually or as a mixture (blend) of two or more types.

[0053] As an example of using two or more resins having reactive ends, a preferred example is a combination of a main component and a curing agent.

[0054] The main component is preferably a resin having reactive ends.

[0055] The curing agent is preferably an isocyanate (-N=C=O) compound, an epoxy (epoxy group) compound, a polyamide, a carbodiimide (-N=C=N-) compound, or a hexamethylenediamine.

[0056] (2) Silane coupling agent The pretreatment coating composition contains (2) a silane coupling agent.

[0057] Silane coupling agents are Acid anhydride structure and silane coupling agents having alkoxysilyl groups; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group; and The silane coupling agent is at least one selected from the group consisting of a butadiene skeleton, an acid anhydride structure, and a silane coupling agent having an alkoxysilyl group.

[0058] The silane coupling agent is more preferably a silane coupling agent that includes all of the butadiene skeleton, acid anhydride structure, and alkoxysilyl group.

[0059] The alkoxysilyl groups of the silane coupling agent can bond with the glass substrate, thereby improving the alkali resistance of the glass substrate.

[0060] The acid anhydride of the silane coupling agent can be incorporated into the reaction system of a resin having reactive ends, forming a strong bond with high crosslink density.

[0061] Since the silane coupling agent has a carboxyl terminus, it imparts adsorption properties of Pd colloid to the glass substrate.

[0062] The pretreatment coating composition adheres firmly to the glass substrate due to the presence of a silane coupling agent. Normally, to create a strong bond with glass material, it is necessary to form a hydrogen bond with an inorganic compound containing hydroxyl groups, and then to form a covalent bond by condensation at a high temperature of 500°C or higher.

[0063] The present invention makes it possible to suppress the decrease in strength of the plated glass substrate and suppress the scattering of fragments by pre-treating the glass substrate with a specific electroless plating pre-treatment coating composition, and then applying electroless plating.

[0064] By using the method of the present invention, which suppresses the decrease in strength of the glass substrate and suppresses the scattering of fragments, it is possible to form a highly adhesive plating at a low temperature of 150°C or less.

[0065] Examples of silane coupling agents having an acid anhydride structure and an alkoxysilyl group include compounds having the following structure (3-trimethoxysilylpropyl succinic anhydride).

[0066] For example, use Shin-Etsu Silicone X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd.

[0067] Me represents a methyl group.

[0068] [ka]

[0069] Silane coupling agents having a butadiene skeleton and an alkoxysilyl group include, for example, compounds (organosilanes) having the following structure.

[0070] For example, use Shin-Etsu Silicone X-12-1267B manufactured by Shin-Etsu Chemical Co., Ltd.

[0071] Me represents a methyl group. a and b are arbitrary integers.

[0072] [ka]

[0073] Silane coupling agents having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group include, for example, compounds (organosilanes) having the following structures.

[0074] For example, use Shin-Etsu Silicone X-12-1287A manufactured by Shin-Etsu Chemical Co., Ltd.

[0075] Me represents a methyl group. a, b, and c are arbitrary integers.

[0076] [ka]

[0077] These silane coupling agents may be used individually or in mixtures (blends) of two or more types.

[0078] (3) Palladium (Pd) colloid The pretreatment coating composition preferably contains (3) palladium (Pd) colloid.

[0079] The pretreatment coating composition contains palladium colloid (Pd colloid), which allows the Pd ions contained in the Pd colloid aqueous solution to be sufficiently adsorbed onto the glass substrate, enabling sufficient plating deposition. Preferably, the Pd colloid in the pretreatment coating composition is adjusted to contain about 0.001% to 0.1% by weight of Pd particles. After applying the pretreatment coating composition to the glass substrate, electroless plating can be performed to produce an electroless plated product.

[0080] Pd colloids can be made using a composite of palladium particles (Pd particles) and a dispersant (Pd composite).

[0081] Pd complexes can be prepared by the following method.

[0082] It can be prepared by reducing palladium ions (Pd ions) supplied from palladium compounds (Pd compounds) such as palladium chloride in a solvent with secondary or tertiary amines such as hydrazine hydrates, in the presence of a dispersant such as a polycarboxylic acid polymer.

[0083] Preferably, the dispersant is a polycarboxylic acid-based dispersant, a block copolymer-type polymer dispersant having a hydroxyl group, and / or a block copolymer-type polymer dispersant having a carboxyl group. Commercially available dispersants may also be used.

[0084] The polycarboxylic acid-based polymer dispersant is preferably an ammonium polycarboxylic acid salt, a sodium polycarboxylic acid salt, a triethylamine polycarboxylic acid salt, or a triethanolamine polycarboxylic acid salt. Examples of polycarboxylic acid-based polymer dispersants include Nopcosanto K, R, RFA, Nopcospers 44-C, SN Dispersant 5020, 5027, 5029, 5034, 5045, 5468 from Sunopco Co., Ltd., and Demol P, EP, Poise 520, 521, 530, 532A from Kao Corporation.

[0085] The block copolymer type polymer dispersant having a hydroxyl group is preferably a polyoxyethylene alkyl ether carboxylate, alkyl hydroxy ether carboxylate, etc. For example, the block copolymer type polymer dispersant having a hydroxyl group may be DISPERBYK190, 2010, etc., manufactured by BIC Chemie Japan Co., Ltd.

[0086] Preferably, block copolymer polymer dispersants containing carboxyl groups include acrylic acid-maleic acid copolymers, styrene-maleic acid copolymers, acrylic acid-sulfonic acid copolymers, etc. Examples of block copolymer polymer dispersants containing carboxyl groups include DISPERBYK180, 187, 191, 194 from BIC Chemie Japan Co., Ltd., and AQUALIC TL, GL, LS from Nippon Shokubai Co., Ltd.

[0087] These dispersants may be used individually or in a mixture (blend) of two or more types.

[0088] Among dispersants, a block copolymer type polymer dispersant having carboxyl groups is more preferably used.

[0089] Pd particles can be prepared by reducing Pd ions supplied from a Pd compound using a reducing agent in the presence of a dispersant.

[0090] The Pd compound that supplies Pd ions is preferably palladium chloride, palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium p-toluenesulfonate, palladium perchlorate, palladium benzenesulfonate, etc.

[0091] Pd compounds may be used individually or as a mixture (blend) of two or more.

[0092] The reducing agent is preferably a secondary or tertiary amine such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N,N-dimethylethanolamine, or diethanolamine.

[0093] The solvent used in the reduction is preferably solvent (5), such as water, aprotic polar solvents, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, 2-phenoxyethanol (ethylene glycol phenyl ether), etc.

[0094] The solvent may be used individually or as a mixture (blend) of two or more types.

[0095] A preferred method for reducing Pd ions involves first placing a dispersant and Pd ions in a solvent, and then adding a reducing agent to the solvent. This allows the Pd ions to come into contact with the reducing agent, thereby reducing the Pd ions.

[0096] It is thought that most Pd particles adhere to the outside of the dispersant. For example, if the shape of the Pd complex (the overall shape of the dispersant) is a densely packed sphere, it is thought that most of the Pd particles adhere to the surface (outside) of that sphere.

[0097] The weight ratio of Pd particles to dispersant in the Pd composite is preferably Pd particles:dispersant = 35:65 to 85:15, and more preferably Pd particles:dispersant = 50:50 to 75:25.

[0098] The average particle size of individual Pd particles is preferably about 2 nm to 10 nm.

[0099] The particle size of Pd particles is measured, for example, using a transmission electron microscope. The average particle size of individual Pd particles is calculated by randomly selecting 10 Pd particles, measuring the particle size of each Pd particle with a transmission electron microscope, and then averaging the results (number-based average diameter).

[0100] The structure of the Pd composite is preferably spherical.

[0101] The average particle size of the Pd composite is preferably about 10 nm to 300 nm, and more preferably about 10 nm to 100 nm.

[0102] The average particle size of the Pd composite is measured, for example, using a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (weight-based average diameter).

[0103] (4) Additives The pretreatment coating composition preferably contains additives such as (4) fillers and thickeners.

[0104] The filler is preferably silica (silica colloid), alumina, or the like.

[0105] The particle size of the filler is preferably such that it can maintain a dispersed state in the paint. The particle size of the filler is preferably about 1 nm to 500 nm, and more preferably about 5 nm to 100 nm. When the glass substrate has fine through-pores (TGV), a smaller particle size of the filler can prevent the blockage of the fine through-pores. In that case, the particle size of the filler is preferably 10 nm to 50 nm.

[0106] The thickening agent is preferably an inorganic thickening agent such as a smectite-type clay mineral, or an organic thickening agent such as a cellulose nanofiber.

[0107] (5) Solvent The pretreatment paint composition preferably contains (5) a solvent.

[0108] The solvent (dispersion solvent) has excellent affinity for (1) resins having reactive ends and (2) silane coupling agents, and (4) can disperse Pd colloids.

[0109] Preferably, the solvent used is an aprotic polar solvent such as N-methylpyrrolidone, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, or fluorinated solvents.

[0110] The solvent contained in the pretreatment coating composition preferably does not contain water.

[0111] The aprotic polar solvent is preferably an aprotic polar solvent such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc); dimethyl sulfoxide (DMSO); or γ-butyrolactone (GBL).

[0112] The alcohols are preferably methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol, diacetone alcohol, etc.

[0113] The ketones are preferably acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), cyclohexanone, isophorone, etc.

[0114] Glycol ethers are preferably ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, etc.

[0115] Aromatic carboxylic acid esters are preferably methyl benzoate, ethyl benzoate, methyl salicylate, etc.

[0116] Aromatic hydrocarbons are preferably toluene, xylene, tetrahydrofuran, etc.

[0117] Aliphatic hydrocarbons are preferably n-hexanes, n-heptanes, mineral spirits, etc.

[0118] Glycol ether esters are preferably methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl carbitol acetate, etc.

[0119] The alkanol esters are preferably ethyl acetate, butyl acetate, and the like.

[0120] The fluorine-based solvent is preferably 1,1,2,2,-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1-chloro-2,3,3-trifluoropropene, etc.

[0121] Preferably, the solvent is selected from the viewpoints of (1) affinity with the resin having reactive ends and (3) silane coupling agent contained in the pretreatment coating composition, (4) dispersibility of Pd colloid, viscosity of the pretreatment coating composition, evaporation rate, etc., and adhesion between the pretreatment coating composition and the glass substrate, so that electroless plating can be performed well.

[0122] Preferably, the solvent used is tetrahydrofuran, diacetone alcohol, ethylene glycol phenyl ether, propylene glycol phenyl ether, etc.

[0123] Preferably, a low-viscosity solvent is used. The low viscosity of the solvent makes it possible to uniformly apply the pretreatment coating composition to a glass substrate with a specific shape.

[0124] The viscosity of the solvent is preferably 1 cP (centipoise) or less, and more preferably 0.5 cP or less. Preferred solvents with a viscosity of 1 cP or less include methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, n-hexane, cyclohexane, toluene, ethyl acetate, etc. Preferred solvents with a viscosity of 0.5 cP or less include methanol, tetrahydrofuran, n-hexane, acetone, ethyl acetate, etc.

[0125] The solvent may be used individually or as a mixture (blend) of two or more types.

[0126] Mixing ratio of pre-treatment paint composition The content of each component in the pretreatment coating composition is not particularly limited, as long as it satisfies the effects of the present invention.

[0127] The content of (1) a resin having reactive ends (such as epoxy resin) in the pre-treated paint composition (solid content in the paint) is preferably about 0.1% to 10% by weight, more preferably about 0.5% to 5% by weight, and even more preferably about 1% to 4% by weight.

[0128] The content of (2) silane coupling agent in the pretreatment coating composition is preferably about 0.1% to 5% by weight, more preferably about 0.2% to 3% by weight, and even more preferably about 0.5% to 2% by weight.

[0129] The (3) Pd colloid in the pretreatment coating composition may or may not be included.

[0130] If the pre-treatment paint composition contains (3) Pd colloid, its content (solids in the paint) is preferably about 0.02% to 1% by weight, more preferably about 0.05% to 0.5% by weight, and even more preferably about 0.075% to 0.25% by weight.

[0131] The content of (4) additives (silica colloid, etc.) in the pre-treated paint composition (solid content in the paint) is preferably about 0.01% to 5% by weight, more preferably about 0.1% to 2.5% by weight, and even more preferably about 0.5% to 1.5% by weight.

[0132] The content of (5) solvent (such as diacetone alcohol) in the pretreatment coating composition is preferably about 80% to 99.9% by weight, more preferably about 85% to 99% by weight, and even more preferably about 90% to 98% by weight.

[0133] Method for manufacturing pre-treatment paint composition The pretreatment coating composition is preferably prepared by mixing (1) a resin having reactive ends and (2) a silane coupling agent in (5) a solvent, and additionally (3) a Pd colloid and (4) an additive. The mixing is preferably carried out in a closed system such as a rotary-orbit mixer or a ball mill to prevent the inclusion of water.

[0134] (Step 1) Step of applying a pretreatment coating composition to a glass substrate. The present invention provides a method for suppressing a decrease in the strength of a glass substrate and suppressing the scattering of fragments, which includes the step of (1) applying a pretreatment coating composition to the glass substrate.

[0135] First, a pretreatment coating composition is used to pre-treat the glass substrate, and then an electroless plating treatment is performed to form a plating on the glass substrate. This treatment allows an electroless plating film to be formed on the molded product.

[0136] Step (1) preferably involves applying a pretreatment coating composition to a glass substrate, and then carrying out a polymerization reaction between (1) a resin having reactive ends contained in the pretreatment coating composition and (2) a silane coupling agent contained in the pretreatment coating composition.

[0137] In the method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments of the present invention, if the pretreatment coating composition contains palladium (Pd) colloid, steps (2) and (3) below may be omitted.

[0138] After step (1), in step (2), the glass substrate coated with the pre-treatment coating composition is brought into contact with an aqueous solution containing a cationic surfactant to perform a cationization treatment.

[0139] After step (2), in step (3), the cationized glass substrate is brought into contact with a palladium (Pd) colloidal solution to impart palladium (Pd).

[0140] The substrate to be coated is a glass substrate.

[0141] The glass substrate is preferably a through-glass via (TGV) substrate. A through-glass via (TGV) substrate has micro-holes formed in various patterns on a thin glass substrate. Through-glass vias (TGV) substrates can be used in a wide range of fields, including circuit boards for 3D mounting of semiconductor packages, circuit boards for semiconductor packages, glass interposers, 3D glass IPDs, MEMS (Micro Electro Mechanical Systems, devices that integrate mechanical components, sensors, actuators, and electronic circuits on a single silicon substrate, glass substrate, organic material, etc., using microfabrication technology), and sensor devices.

[0142] By applying the pretreatment coating composition to the glass substrate, Pd ions can be sufficiently adsorbed onto the glass substrate, allowing for sufficient plating deposition.

[0143] The glass substrate may preferably contain inorganic materials such as glass, ceramic, low-temperature co-fired ceramic (LTCC), dielectric ceramic, silicon, graphite, or ferrite.

[0144] The glass is preferably alkali glass, alkali-free glass, diosilicate glass, soda-lime glass, quartz, etc.

[0145] Preferred ceramic materials include alumina, aluminum nitride, silicon nitride, silicon carbide, gallium nitride, macelite, and the like.

[0146] Preferably, the dielectric ceramic used is magnesium titanate, calcium titanate, barium titanate, strontium titanate, lithium titanate, zinc zirconate titanate, etc.

[0147] The glass substrate is preferably in the form of a plate (or film), a thread, or various shapes formed by a mold.

[0148] The glass substrate may contain clay minerals (e.g., talc, mica, etc.), inorganic fillers (e.g., carbon, calcium carbonate, titanium dioxide, etc.), rubber (e.g., ethylene-propylene copolymer), etc.

[0149] Depending on the glass substrate, the solvent and (1) the resin having reactive ends included in the pretreatment coating composition are appropriately selected.

[0150] The surface of the glass substrate may preferably be etched. The surface of the glass substrate may preferably be activated by corona treatment, plasma treatment, UV treatment, ozone treatment, etc. The surface of the glass substrate may preferably be cleaned by alkaline degreasing.

[0151] The surface of the glass substrate may be modified using a silane coupling agent or the like.

[0152] The silane coupling agent is preferably one having a functional group such as an epoxy group, an amino group, an acryloxy group, a methacryloxy group, or a vinyl group.

[0153] The silane coupling agent having an epoxy group is preferably 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc.

[0154] Preferably, silane coupling agents having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc.

[0155] The silane coupling agent having an acryloxy group is preferably 3-acryloxypropyltrimethoxysilane or the like.

[0156] The silane coupling agent having a methacryloxy group is preferably 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, etc.

[0157] The silane coupling agent having a vinyl group is preferably vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, etc.

[0158] The silane coupling agent may preferably include a silane coupling agent having a ureido group such as 3-ureidopropyltriethoxysilane, a silane coupling agent having a mercapto group such as 3-mercaptopropyltrimethoxysilane, or a silane coupling agent having an isocyanate group such as 3-isocyanatetopropyltriethoxysilane.

[0159] Among silane coupling agents used for surface treatment of glass substrates, a silane coupling agent having an amino group is particularly preferred.

[0160] The silane coupling agents may be used individually or in a mixture (blend) of two or more types.

[0161] Coating treatment By using a pre-treatment coating composition and performing coating, drying, and electroless plating treatments on a glass substrate, a plating can be formed on the glass substrate.

[0162] The method for applying the pretreatment coating composition to a glass substrate is preferably a coating method using a bar coater, gravure printing machine (gravure offset), flexographic printing machine, inkjet printing machine, dispenser, dipping, spray, spin coater, roll coater, reverse coater, screen printing machine, etc.

[0163] When pattern printing the pretreatment coating composition, inkjet printing or flexographic printing is preferred.

[0164] From the viewpoint of masking-free operation and production efficiency, the application method preferably employs gravure offset printing, pad printing, or a dispenser. Depending on the plating pattern, spray painting is preferably employed.

[0165] The viscosity of the pretreatment coating composition is adjusted according to the application method.

[0166] When the pretreatment coating composition is applied by gravure offset printing or pad printing, the viscosity of the pretreatment coating composition is preferably about 100 mPa·s to 1,000 mPa·s.

[0167] When the pretreatment coating composition is applied by flexographic printing, inkjet printing, dipping, or spraying, the viscosity of the pretreatment coating composition is preferably about 1 mPa·s to 10 mPa·s.

[0168] The film thickness of the pre-treatment coating composition before drying and heat treatment (polymerization) is appropriately selected depending on the intended use and depends on the viscosity of the pre-treatment coating composition. From the viewpoint of being able to apply the pre-treatment coating composition well and preventing dripping of the pre-treatment coating composition, the film thickness of the pre-treatment coating composition before drying and heat treatment (polymerization) is preferably about 1 μm to 100 μm, and more preferably about 2 μm to 20 μm.

[0169] Polymerization by heat treatment After applying the pretreatment coating composition to the glass substrate, the solvent contained in the pretreatment coating composition is evaporated and / or dried, and then a polymerization treatment is performed. Due to the polymerization treatment, a polymerization reaction occurs between (1) a resin having reactive ends contained in the pretreatment coating composition and (2) a silane coupling agent contained in the pretreatment coating composition.

[0170] After applying the pretreatment coating composition to the glass substrate, a drying treatment is preferably performed. The drying treatment efficiently removes unnecessary solvents during electroless plating and improves the adhesion between the coating film and the glass substrate, as well as the surface strength of the coating film. The drying temperature is preferably around 60°C to 400°C, and more preferably around 80°C to 150°C. The drying time is preferably around 6 seconds to 60 minutes, and more preferably around 10 minutes to 30 minutes, depending on the drying temperature.

[0171] The film thickness of the pre-treated coating composition after drying depends on the solid content concentration of the pre-treated coating composition. From the viewpoint of enabling efficient electroless plating (good reaction rate of electroless plating) and exhibiting good plating adhesion, the film thickness of the pre-treated coating composition after drying and heat treatment (polymerization treatment) is preferably about 0.05 μm to 20 μm, and more preferably 0.1 μm to 1 μm.

[0172] (Step 2) A step in which a glass substrate coated with a pre-treatment coating composition is brought into contact with an aqueous solution containing a cationic surfactant to perform a cationization treatment. The present invention provides a method for suppressing a decrease in the strength of a glass substrate and suppressing the scattering of fragments, which includes (2) a step of cationizing a glass substrate coated with a pretreatment coating composition by contacting it with an aqueous solution containing a cationic surfactant.

[0173] Cationic surfactants (cationic surfactants) are surfactants that dissociate in aqueous solutions to form organic cations. In aqueous solutions, they play a role in neutralizing the charge on the surface of a glass substrate coated with a pretreatment coating composition, thereby giving it a positive charge.

[0174] By bringing an aqueous solution containing a cationic surfactant into contact with a glass substrate coated with a pretreatment coating composition on its surface, the Pd composite contained in the subsequent Pd colloid aqueous solution is sufficiently adsorbed onto the glass substrate, allowing for sufficient plating deposition.

[0175] A cationic surfactant is dispersed in water to prepare a solution containing the dispersed cationic surfactant. The cationic surfactant is preferably a quaternary ammonium salt.

[0176] The molecular weight of the cationic surfactant is preferably around 300 to 1,000.

[0177] Cationic surfactants are preferably high molecular weight quaternary amine compounds such as polydiaminodimethylammonium salts, polydiallyldialkylammonium salts, and polyvinylpyridine quaternary salts, polyacrylamide, polyethyleneimine, and more preferably polydiallyldimethylammonium chloride, a copolymer of polydiallyldimethylammonium chloride / acrylamide, polyethyleneimine, and the like.

[0178] The amount of solvent used is not particularly limited, as long as it can ensure a uniform presence of the cationic surfactant. Preferably, 1 × 10 parts by weight of the solvent per 100 parts by weight of the cationic surfactant. 5 Weight part~1×10 8 It is approximately the weight of parts, more preferably 1 × 10 6 Weight part~1×107 It is approximately the weight of a part.

[0179] The cationic surfactant is preferably present in the solution at an amount of about 0.001% to 0.1% by weight. By bringing the glass substrate coated with the pretreatment coating composition into contact with an aqueous solution containing the cationic surfactant, the Pd particles contained in the pretreatment coating composition are sufficiently adsorbed onto the glass substrate, and the plating can be sufficiently deposited.

[0180] A glass substrate coated with a pretreatment coating composition is preferably immersed in a solution containing a dispersed cationic surfactant.

[0181] The liquid temperature is not particularly limited, but is preferably around 30°C to 60°C, and more preferably around 40°C to 50°C.

[0182] The immersion time in the solution is preferably 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes. After immersion, a water rinse is performed.

[0183] (Step 3) The cationized glass substrate is brought into contact with a palladium (Pd) colloidal solution to impart palladium (Pd) to it (coating process). The present invention provides a method for suppressing a decrease in the strength of a glass substrate and suppressing the scattering of fragments, which includes (3) a step of contacting a cationized glass substrate with a palladium (Pd) colloidal solution to impart palladium (Pd).

[0184] By contacting a cationized glass substrate with a Pd colloidal aqueous solution, the Pd particles contained in the Pd colloidal aqueous solution are sufficiently adsorbed onto the glass substrate, allowing for sufficient plating deposition.

[0185] Preferably, the Pd colloid aqueous solution contains about 0.001% to 0.1% by weight of Pd particles. Electroless plating can be performed on a glass substrate coated with the pretreatment coating composition to produce an electroless plated product.

[0186] It is preferable to immerse the glass substrate in an aqueous Pd colloid solution. The liquid temperature is not particularly limited, but is preferably around 30°C to 60°C, and more preferably around 40°C to 50°C. The immersion time in the solution is preferably around 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes. After the immersion treatment, the substrate is rinsed with water.

[0187] (Step 4) A process of electroless plating the glass substrate to which palladium (Pd) has been applied. The present invention provides a method for suppressing a decrease in the strength of a glass substrate and suppressing the scattering of fragments, which includes (4) a step of electroless plating a glass substrate to which palladium (Pd) has been applied. Through this step, a plating is formed on the glass substrate.

[0188] After washing the paint (pre-treatment paint composition) film with water, electroless plating is performed to form a plating on the glass substrate.

[0189] A glass substrate with a paint film formed on it comes into contact with a plating solution for depositing metal, and an electroless plating film is formed. The paint film formed after applying a pre-treatment paint composition, followed by cationization treatment, and then applying a Pd colloid aqueous solution exhibits good reactivity for electroless plating, and the resulting electroless plating film is uniform, with excellent adhesion and appearance.

[0190] In this invention, by pre-treating a glass substrate with a pre-treatment coating composition, and then applying electroless plating, it is possible to suppress the decrease in strength of the plated glass substrate and suppress the scattering of fragments.

[0191] The plating solution used is generally the same as that used for electroless plating. Preferably, the plating solution contains copper, gold, silver, nickel, palladium, platinum, etc. Preferably, the plating solution contains copper or nickel.

[0192] Plating conditions follow standard procedures. The paint film exhibits excellent reactivity for electroless plating, eliminating the need to increase the reducing agent or alkaline component concentrations in the plating solution. As a result, the plating solution has a longer lifespan.

[0193] When using an electroless copper plating bath in electroless plating, the processing temperature is preferably around 25°C to 65°C, and the processing time is preferably around 5 to 20 minutes. This electroless plating process forms a deposited film thickness of approximately 0.3 μm to 1.0 μm.

[0194] When using an electroless nickel-boron bath in electroless plating, the processing temperature is preferably around 55-70°C, and the deposition rate is preferably around 5 μm / hr (at 65°C).

[0195] When using an electroless nickel-phosphorus bath in electroless plating, the processing temperature is preferably around 30°C to 95°C, and the deposition rate is preferably around 3 μm / hr at a bath temperature of 30°C and around 10 μm / hr at 90°C.

[0196] The technique of forming a plating on a glass substrate using a pretreatment coating composition is preferably used for full-surface plating or pattern plating.

[0197] For decorative purposes, after electroless plating, a common process such as electrolytic copper plating, semi-bright nickel plating, bright nickel plating, or chromium plating is preferably used.

[0198] When using an electrolytic copper plating bath for decorative processing, the processing temperature is preferably around 20°C to 60°C, and the current density is preferably 1 A / m². 2 ~10A / m 2 The processing time is preferably about 10 to 60 minutes. This decorative treatment forms a precipitate film thickness of about 5 μm to 40 μm.

[0199] When using a semi-gloss nickel plating bath for decorative treatment, the treatment temperature is preferably around 45°C to 55°C, and the current density is preferably 1 A / m². 2 ~10A / m 2The degree is such that the processing time is preferably about 10 to 60 minutes. Due to this decorative treatment, a deposited film thickness of about 5 to 20 μm is achieved.

[0200] In the case of using a bright nickel plating bath for the decorative treatment, the processing temperature is preferably about 45°C to 55°C, and the current density is preferably 1 A / dm 2 ~10 A / dm 2 The degree is such that the processing time is preferably about 10 to 60 minutes. Due to this decorative treatment, a deposited film thickness of about 5 to 20 μm is achieved.

[0201] In the case of using a chromium plating bath for the decorative treatment, the processing temperature is preferably about 40°C to 60°C, and the current density is preferably 10 A / m 2 ~60 A / m 2 The degree is such that the processing time is preferably about 1 to 5 minutes. Due to this decorative treatment, a deposited film thickness of about 0.1 to 0.3 μm is achieved.

[0202] [2] Electroless plating film and molded product with the film applied According to the method for suppressing the decrease in the strength of the glass substrate of the present invention and suppressing the scattering of fragments, when electroless plating is performed on the glass substrate, plating with high adhesion can be formed at a low temperature of 150°C or lower.

[0203] The pretreatment paint composition of the present invention is applied to the glass substrate to form an ink film, and electroless plating is performed. The molded product (the object to be plated) with the electroless plating film has excellent adhesion of the plating film.

[0204] The glass substrate is preferably a through-glass via (TGV) substrate. A through-glass via (TGV) substrate has micro-holes formed in various patterns on a thin glass substrate. Through-glass vias (TGV) substrates can be used in a wide range of fields, including circuit boards for 3D mounting of semiconductor packages, circuit boards for semiconductor packages, glass interposers, 3D glass IPDs, MEMS (Micro Electro Mechanical Systems, devices that integrate mechanical components, sensors, actuators, and electronic circuits on a single silicon substrate, glass substrate, organic material, etc., using microfabrication technology), and sensor devices.

[0205] Using the pretreatment coating composition, electroless plating on a glass substrate exhibits high reactivity, excellent adhesion capable of withstanding multi-layer plating up to chromium plating, and excellent smoothness capable of withstanding decorative plating. In electroless plating, it is possible to suppress pattern spreading and perform partial plating with good results.

[0206] Glass substrates coated with electroless plating are used in electronic components such as printed circuit boards, flexible printed circuit boards (FPCs), transparent conductive films, electromagnetic shields, rigid substrates, antennas, snow melting heaters, RFID, and metasurface reflectors. It is particularly effective for plating glass and ceramic-based liquid crystal panels, thin film transistors (TFTs), interposers, semiconductor circuits, and MEMS.

[0207] The pretreatment coating composition can be effectively applied to substrates with a specific shape, such as glass or ceramic. Preferably, the substrates with a specific shape include TGV (through glass via), TSV (through silicon via), ceramic filters, silicon capacitors, and component-embedded substrates.

[0208] The pretreatment coating composition provides good adhesion to multiple materials, making it particularly effective for applications where the surface is composed of two or more glass substrates. Preferred applications for surfaces composed of two or more substrates include LTCC (Low Temperature Co-fired Ceramics) made of glass and ceramic, glass filler-containing resins such as FR-4, carbon filler-containing resins, build-up substrates consisting of a correlated insulating film and Cu bumps, and component-embedded substrates such as epoxy resin with molded ceramic components.

[0209] Using a pretreatment coating composition eliminates the need to increase the concentration of the reducing agent in electroless plating to improve its reactivity, nor does it require raising the reaction temperature of the electroless plating. Furthermore, it eliminates the need for etching processes using harmful substances and complicated catalyst application processes.

[0210] The reason why the pretreatment coating composition exhibits high reactivity in electroless plating and achieves good adhesion that can withstand multi-layer plating up to chromium plating is as follows:

[0211] The adhesion mechanism between the glass substrate and the pretreatment coating composition involves strong adhesion due to the bonding of alkoxysilyl groups contained in the pretreatment coating composition to the glass substrate. Furthermore, the organic molecules of the silane coupling agent (butadiene, acid anhydride groups, etc.) bond to the reactive ends of the resin, forming a coating film in which the silane coupling agent and resin are mixed. This coating film, composed of organic and inorganic materials, exhibits excellent stress-relieving properties between the glass substrate and the plating. In particular, the presence of butadiene groups in the silane coupling agent further enhances stress-relieving performance.

[0212] The surface of the glass substrate coated with the pretreatment coating composition readily adsorbs cationic surfactants, forming numerous ionic bonds. Pd colloids, having anionic functional groups such as carboxyl groups on their surface, bond strongly with cationic surfactants.

[0213] When metal ions in the electroless plating solution are reduced, numerous carboxyl groups are present on the surface of the glass substrate coated with the pretreatment coating composition. These carboxyl groups strongly bond with the metal deposited by the electroless plating. Numerous ionic bonds are formed between the glass substrate, the Pd colloid, and the plating film, providing strong adhesion.

[0214] In particular, the silane coupling agent can enhance the adsorption capacity of cationic surfactants by having acid anhydride groups contained in the pretreatment paint composition. [Examples]

[0215] The present invention will be specifically described below with reference to examples and reference examples.

[0216] The present invention is not limited to the following specific embodiments.

[0217] [1] A method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments. Referring to Figure 1, a method for suppressing the decrease in strength of the glass substrate in the embodiment and suppressing the scattering of fragments will be explained.

[0218] (1) Step of applying a pretreatment coating composition to a glass substrate. Preparation of pretreatment coating composition (1) Resin with reactive ends: Polyamide resin, solids content 20% by weight (wt%), 15 parts by weight (2) Silane coupling agent: 100% by weight (wt%) solids, 1 part by weight (4) Additives: Silica colloid, average particle size 12 nm, solid content 20% by weight (wt%), 5 parts by weight (5) Solvent: Diacetone alcohol, 79 parts by weight

[0219] [Table 1]

[0220] Glass substrate: Alkali glass, alkali-free glass, alumina, epoxy resin, polyphenylene ether (PPE)

[0221] Application process of pretreatment coating composition Immersion coating, lifting speed 100 mm / min, drying at 120°C for 60 minutes.

[0222] (2) A step of cationizing a glass substrate coated with a pretreatment coating composition by bringing it into contact with an aqueous solution containing a cationic surfactant. Preparation of cationization treatment solution-1 1 part by weight of an aqueous solution containing a cationic surfactant (Cleaner Conditioner XP2285, manufactured by Rohm & Haas) was added to 19 parts by weight of water. This was shaken and stirred to prepare cationization treatment solution-1 for electroless plating.

[0223] Preparation of cationization treatment solution-2 1 part by weight of an aqueous solution containing a cationic surfactant (Cleaner Conditioner MTE-1A, manufactured by Uemura Kogyo Co., Ltd.) was added to 19 parts by weight of water. This was shaken and stirred to prepare cationization treatment solution-2 for electroless plating.

[0224] (3) A step of imparting Pd to a cationized glass substrate by contacting it with a Pd colloid solution. (3) Pd colloid Preparation of Pd colloid aqueous solution 1 Preparation of a composite of palladium particles (Pd particles) and a dispersant. 944.5g of deionized water was placed in a 3L flask, and then 5.0g of palladium nitrate (Pd sulfate) was added to the deionized water and stirred. The Pd nitrate was dissolved in water to prepare an aqueous solution of Pd nitrate.

[0225] To this aqueous solution, 3.8 g of a block copolymer type polymer dispersant containing carboxyl groups (DISPERBYK194, manufactured by Bic Chemie Japan, non-volatile content 53 wt%) was added and dissolved in the aqueous solution.

[0226] This solution was heated to 42°C, and then 10.0 g of hydrazine monohydrate was added while stirring. Afterward, the solution was stirred at room temperature (23°C) for 1 hour. The temperature of the solution rose to 53°C after the addition of hydrazine monohydrate, but the temperature of the solution after 1 hour of stirring was 40°C.

[0227] This procedure reduced the palladium ions (Pd ions) in the aqueous solution. Using an ultrafiltration filter AHP-1010 (manufactured by Asahi Kasei Corporation), the reduced Pd complex-containing solution and the inorganic salt-containing solution were separated to obtain a Pd complex-containing solution (a complex of Pd particles and a dispersant).

[0228] To the Pd complex-containing solution obtained by this operation, an equal mass of deionized water was added to the separated inorganic salt-containing solution (Pd nitrate aqueous solution), and the separation operation was performed again using an ultrafiltration filter. This deionized water replenishment and separation operation was repeated five times.

[0229] The electrical conductivity of the Pd composite-containing solution obtained after this procedure was 28 μS·cm. -1 The electrical conductivity was 30 μS·cm. -1 The following results were obtained, confirming that the inorganic salts could be removed from this Pd composite-containing solution.

[0230] Regarding the obtained Pd complex-containing solution, TG / DTA analysis was performed to determine the Pd complex content. Based on the residual solids at 550°C, the Pd complex content was confirmed to be 1.0 wt%.

[0231] The average particle size of the Pd particles in the Pd composite-containing solution was in the range of 2 nm to 10 nm.

[0232] The mass ratio of Pd particles to dispersant in the Pd composite was Pd particles:dispersant = 75:25.

[0233] Two parts by weight of the composite of Pd particles and dispersant was added to 98 parts by weight of water. This was shaken and stirred to prepare a Pd colloidal aqueous solution.

[0234] Preparation of Pd colloid aqueous solution-2 Catalyst C-10 (Okuno Pharmaceutical Co., Ltd.), 32°C x 3 minutes Accelerator X (Okuno Pharmaceutical Co., Ltd.), 35℃ x 5 minutes

[0235] (4) Process of electroless plating the glass substrate to which Pd has been added. (1) Immerse in the plating pretreatment solution at 50 °C for 5 minutes (2) Immerse in Pd colloid aqueous solution - 1 at 40 °C for 3 minutes (3) Electroless Cu plating: Immerse in OPC Copper HFS (Okuno Pharmaceutical) at 40 °C for 10 minutes (5) Heat treatment: 120 °C for 30 minutes

[0236] [2] Evaluation of electroless plated products (1) Appearance after plating 〇 Evaluation: The plating is copper - colored, without peeling, and is an acceptable product. △ Evaluation: The plating has peeling and is an unacceptable product. × Evaluation: No deposition occurred, and it is an unacceptable product.

[0237] (2) Cross-cut test On the obtained copper - plated film, based on JIS K 5600 (Cross - cut method), cuts were made at 1 - mm intervals into 100 squares. Cellophane tape (Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.) was pasted on it, and the number of squares that did not peel off when the tape was peeled off was measured.

[0238] In the table, "100 / 100" indicates that none of the 100 squares peeled off.

[0239] In the table, "22 / 100" indicates that 22 squares did not peel off and the remaining 78 squares peeled off. [[ID=3​​​​​​​​​​

[0242] The maximum load was taken as the peel strength, and the adhesion was evaluated. ◎ Evaluation: The average peel strength is 5 N / cm or more, and it is an acceptable product. 〇 Evaluation: The average peel strength is 1 N / cm to 5 N / cm, and it is an acceptable product. × Evaluation: The average peel strength is 0 to 1 N / cm, and it is an unacceptable product.

[0243] comprehensive evaluation ◎ Evaluation: Appearance after plating is "〇", cross-cut test is "100 / 100", and average peel strength of plating is "5 N / cm or more". 〇 Evaluation: Appearance after plating is "〇", cross-cut test is "100 / 100", and average peel strength of plating is "1 N / cm to 5 N / cm".

[0244]

Table 2

[0245]

Table 3

[0246] (4) Measurement of glass strength As the glass substrate for strength measurement, alkali-free glass with the surface microcracks sufficiently etched with hydrofluoric acid was used. The size of the alkali-free glass was 80 mm × 80 mm × 0.4 mm t (thickness). A primer composition was applied onto the surface of the sufficiently etched alkali-free glass so as not to contact, and electroless Cu plating was performed.

[0247] The strength measurement was carried out by a ring-on-ring test. The plated alkali-free glass substrate was placed between the bottom ring and the top ring of a ring-on-ring mechanical test apparatus. The top ring and the bottom ring are made of stainless steel. The test is carried out at about 25°C in an environment with a relative humidity of 45% to 55%.

[0248] [Chemical formula]

[0249] (5) Measurement of glass fragment scattering As the glass substrate for strength measurement, an alkali-free glass was used. The size of the alkali-free glass was 50 mm × 50 mm × 0.7 mm t (thickness). A primer composition was applied to the surface of the alkali-free glass, and electroless Cu plating was performed.

[0250] For the measurement of fragment scattering, a square pyramid diamond indenter with a face angle of 90° at the tip was pressed into the center of the plated glass substrate at 3.0 kgf to 15 kgf, and the number N of fragments at the time of fracture was measured with a microscope having a magnification of 25 times.

[0251] [Table 4]

[0252] [Table 5]

[0253] In Example 11, when the glass substrate was pretreated using a specific electroless plating pretreatment paint composition and then electroless plating was performed, the plated glass substrate suppressed the decrease in the strength of the glass substrate and the scattering of fragments as compared with the glass that was electroless plated without applying the pretreatment paint composition of the comparative example.

[0254] [3] Industrial applicability In the present invention, when the glass substrate is pretreated using a specific electroless plating pretreatment paint composition and then electroless plating is performed, it is possible to suppress the decrease in the strength of the plated glass substrate and the scattering of fragments.

[0255] This invention provides a glass substrate that is less prone to breakage even when the glass is thinner and the through-holes are formed at a higher density, thereby enabling thinner substrates and improved transmission speeds through the through-holes.

Claims

1. A method for suppressing the decrease in strength of a glass substrate and suppressing the scattering of fragments, (1) A step of applying a pretreatment coating composition to a glass substrate, (2) A step of cationizing a glass substrate coated with the pretreatment coating composition by bringing it into contact with an aqueous solution containing a cationic surfactant. (3) A step of imparting palladium to the cationized glass substrate by contacting it with a palladium (Pd) colloidal solution, and (4) A step of electroless plating the glass substrate to which the palladium has been applied. It includes in order, The aforementioned pretreatment paint composition, (1) Resins having reactive ends, and (2) Contains a silane coupling agent, The silane coupling agent described in (2) above is Acid anhydride structure and silane coupling agents having alkoxysilyl groups; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group; and A silane coupling agent selected from the group consisting of a butadiene skeleton, an acid anhydride structure, and a silane coupling agent having an alkoxysilyl group; method.

2. The method according to claim 1, wherein the glass substrate is a glass substrate with micropors (TGV).

3. The above step (1) is, The method according to claim 1, comprising the steps of (1) applying a pretreatment coating composition to a glass substrate, and then carrying out a polymerization reaction between the (1) resin having reactive ends and the (2) silane coupling agent.

4. The aforementioned pretreatment coating composition, further, (5) The method according to claim 1, comprising a solvent.

5. The method according to claim 1, wherein the resin having a reactive end (1) is at least one resin selected from the group consisting of acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, polyamide, polyimide, polyamideimide, shellac resin, urea resin, nitrated cotton, alkyd resin, petroleum resin, rosin-based resin, styrene / maleic acid resin, silicone resin, vinyl chloride-vinyl acetate copolymer, acrylic monomer / oligomer, polyolefin, phenolic resin, polyarylate resin, and butyral resin.

6. The method according to claim 1, wherein the resin having the reactive end (1) is at least one resin selected from the group consisting of urethane resin, polyimide, polyamideimide, polyamide, and epoxy resin.

7. The aforementioned pretreatment coating composition, further, (3) The method according to claim 1, comprising palladium (Pd) colloid.

8. The method according to claim 1, wherein the (5) solvent is at least one solvent selected from the group consisting of aprotic polar solvents, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, and fluorinated solvents.

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