TWI631193B - Moisture-proof and insulating coating material and uses thereof - Google Patents

Abstract

The present invention provides a moisture-proof insulating coating comprising a block copolymer or a hydride resin (A) thereof, an adhesive resin (B), a solvent (C), and an epoxy having the formula (1) Compound (D). The moisture-proof insulating coating according to the present invention has the advantage of long-term insulation reliability. The present invention also provides a moisture-proof insulating film, a method of manufacturing the same, an electronic component including the moisture-proof insulating film, and a method of manufacturing the same.

Description

Moisture-proof insulating coating and its application

The invention provides a moisture-proof insulating coating for electronic parts and an electronic component for performing moisture-proof insulation treatment using the moisture-proof insulating coating and a manufacturing method thereof. In particular, it provides a moisture-proof insulating coating for electronic parts with long-term insulation reliability.

With the advancement of technology, electronic components are gradually becoming more miniaturized and multi-functional, and the design of circuits in the electronic components is becoming more and more complicated. At this time, insulation and moisture resistance become important factors affecting the service life of electronic components. Accordingly, the industry generally forms a coating layer outside the electronic component to achieve protection against moisture, dust, gas, and insulation.

Japanese Laid-Open Patent Publication No. 2006-16531 discloses a moisture-proof insulating coating comprising 10 to 40 parts by weight of a thermoplastic resin, 1 to 20 parts by weight of a hydrazine-based resin, and 50 to 90 parts by weight of a solvent. The coating layer formed by the coating has good moisture-proof insulation. However, the coating film formed by the coating after coating has the problem of poor long-term insulation reliability, resulting in easy formation of electrons after prolonged use. The damage of components cannot be accepted by the industry.

Therefore, how to improve the long-term insulation reliability while meeting the requirements of the current industry is an object of diligent research in the technical field to which the present invention pertains.

The present invention utilizes a component which provides a special block copolymer or a hydride resin thereof and an epoxy compound to obtain a moisture-proof insulating coating which is excellent in long-term insulation reliability.

Accordingly, the present invention provides a moisture-proof insulating coating comprising: a block copolymer or a hydride resin (A) comprising a skeleton comprising at least two vinyl aromatic polymer blocks and at least one a conjugated diene polymer block; an adhesive resin (B); a solvent (C); and an epoxy compound (D) represented by the formula (1);

In the formula (1): E ¹ , E ² and E ³ each independently represent an organic group represented by the formula (2), an organic group represented by the formula (3) or an organic group represented by the formula (4), wherein At least one of E ¹ , E ² and E ³ is an organic group represented by the formula (2) or an organic group represented by (3); and R ¹ , R ² and R ³ each independently represent a C ₂ group which may have a branch a C ₆ alkyl group or a branched C ₂ to C ₆ oxyalkylene group;

Wherein R ⁴ represents a hydrogen atom or a methyl group.

The present invention also provides a method of producing a moisture-proof insulating film comprising coating a carrier with the aforementioned moisture-proof insulating coating.

The present invention further provides a moisture-proof insulating film which is produced by the above-described method for producing a moisture-proof insulating film.

The present invention further provides an electronic component comprising the aforementioned moisture-proof insulating film.

The present invention further provides a method of manufacturing an electronic component comprising a moisture-proof insulating film provided by the method comprising the foregoing.

The present invention provides a moisture-proof insulating coating comprising: a block copolymer or a hydride resin (A) comprising a skeleton comprising at least two vinyl aromatic polymer blocks and at least one conjugate a diene polymer block; an adhesive resin (B); a solvent (C); and an epoxy compound (D) represented by the formula (1);

In the formula (1): E ¹ , E ² and E ³ each independently represent an organic group represented by the formula (2), an organic group represented by the formula (3) or an organic group represented by the formula (4), wherein At least one of E ¹ , E ² and E ³ is an organic group represented by the formula (2) or an organic group represented by (3); and R ¹ , R ² and R ³ each independently represent a C ₂ group which may have a branch a C ₆ alkyl group or a branched C ₂ to C ₆ oxyalkylene group;

Wherein R ⁴ represents a hydrogen atom or a methyl group.

The block copolymer or the hydride resin (A) thereof according to the present invention comprises a skeleton comprising at least two vinyl aromatic polymer blocks and at least one conjugated diene polymer block.

Preferably, the vinyl aromatic polymer block is obtained by polymerization of a vinyl aromatic monomer. The vinyl aromatic mono system is selected from one or more of the following compounds: (1) unsubstituted or alkyl substituted styrene compounds: for example, styrene, 2-methylstyrene, 3-methyl Styrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 2,4-dimethylstyrene, α-methylstyrene, α-methyl-4 -methylstyrene or the like; (2) a styrene compound substituted with a halogen: for example, 2-chlorostyrene, 4-chlorostyrene, or the like.

Preferably, the conjugated diene polymer block is obtained by polymerization of a conjugated diene monomer. The conjugated diene single system is selected from one or more of the following Compound: 1,3-butadiene, 2-methyl-1,3-butadiene, 2-methyl-1,3-isoprene, 2,3-dimethyl-1,3- Butadiene, 1,3-pentadiene, 1,3-hexadiene.

In a specific embodiment of the present invention, the method for synthesizing the block copolymer or the hydride resin (A) thereof comprises the steps of: (1) a polymerization reaction, respectively, the ethylene-based aromatic monomer and the conjugate The diene monomer is dissolved in an organic solvent, followed by addition of a polymerization initiator to carry out an anionic polymerization reaction to form a block copolymer precursor; and (2) a hydrogenation reaction, which blocks the block copolymer precursor The hydrogenation reaction is carried out in the presence of a hydrogenation catalyst to obtain the block copolymer of the present invention or its hydride resin (A). Here are the explanations:

(1) Polymerization: When preparing the block copolymer or the hydride resin (A) thereof, preferably, the vinyl aromatic monomer and/or the conjugated diene monomer may be diluted with an organic solvent, respectively. At appropriate concentrations, mixing and polymerization are carried out. In a particular embodiment of the invention, the diluted concentration is 25 wt%.

Preferably, the organic solvent is selected from the group consisting of (1) aliphatic compounds such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, etc.; (2) alicyclic Class of compounds: for example, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, methylcycloheptane, etc.; or (3) a combination of the above. Further, an aromatic compound such as benzene, toluene, xylene or ethylbenzene may be used without affecting the polymerization reaction.

The polymerization initiator is not particularly limited, and an organic alkali metal compound which is conventionally used can be usually used. The organic alkali metal compound includes, but is not limited to, an aliphatic alkali metal compound, an aromatic alkali metal compound, an organic amine base metal compound, and the like. Preferably, the polymerization initiator is selected from the group consisting of C ₁ to C ₂₀ aliphatic lithium compounds, C ₆ to C ₂₀ aromatic lithium compounds, C ₁ to C ₂₀ aliphatic sodium compounds, and C ₆ to C ₂₀ aromatics. A sodium compound, a C ₁ to C ₂₀ aliphatic potassium compound, a C ₆ to C ₂₀ aromatic potassium compound, or a combination thereof.

The C ₁ to C ₂₀ aliphatic lithium compound includes, but is not limited to, n-propyl lithium, n-butyl lithium, second butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl dilithium, Isoprenyl dilithium. The C ₆ to C ₂₀ aromatic lithium compound includes, but is not limited to, a reaction product of diisopropenylbenzene and a second butyllithium, or divinylbenzene, a second butyllithium, and a small amount of 1,3-butadiene. The reaction product or the like. Further, an organic alkali metal compound disclosed in the specification of U.S. Patent No. 5,708,092, the specification of the U.S. Patent No. 2,241,239, and the specification of U.S. Patent No. 5,527,753, etc., may be used. The above polymerization initiators may be used singly or in combination of two or more.

Preferably, the polymerization temperature ranges from 10 ° C to 150 ° C; more preferably, the polymerization temperature ranges from 40 ° C to 120 ° C. The polymerization time is adjusted depending on the polymerization temperature. Preferably, the polymerization time ranges from 10 hours; more preferably, the polymerization time ranges from 0.5 hours to 5 hours. Preferably, the polymerization reaction environment is in an environment of an inert gas such as nitrogen. The polymerization reaction pressure range is not particularly limited as long as the ethylene-based aromatic monomer, the conjugated diene monomer, and the solvent are maintained within a pressure range required for the liquid in the polymerization reaction temperature range. Just fine. Further, it is necessary to pay attention to the fact that impurities which inactivate the polymerization initiator and the living polymer are not mixed in the polymerization reaction, for example, water, oxygen, carbonic acid gas or the like is not mixed.

(2) Hydrogenation reaction: The hydrogenation catalyst is not particularly limited and may be conventionally used, such as (1) a hydrogenation catalyst in which a metal is placed in a porous inorganic substance; (2) an organic acid salt or a transition metal a salt, a Ziegler type hydrogenation catalyst which reacts with a reducing agent, (3) an organometallic compound, (4) an organic metal complex, and the like.

The hydrogenation catalyst includes, but is not limited to, (1) a hydrogenation catalyst supporting a metal such as Ni, Pt, Pd or Ru in carbon, cerium oxide, aluminum oxide, diatomaceous earth or the like; (2) using Ni, Co, Fe, An organic acid salt such as Cr or a transition metal salt such as acetoacetate or a Ziegler hydrogenation catalyst which reacts with a reducing agent such as organoaluminum; (3) an organometallic compound such as Ti, Ru, Rh or Zr; (4) Ti, Ruthenium, Rh, Zr and other organic metal complexes. Hydrogenation The chemical agent can also be disclosed in Japanese Patent Publication No. Sho 42-8704, Japanese Patent Publication No. Sho 43-6636, Japanese Patent Publication No. Sho-63-4841, Japanese Patent Laid-Open No. Hei 1-37970, and Japanese Patent No. The hydrogenation catalyst in the Japanese Patent Publication No. Hei 2-9041, Japanese Patent Publication No. Hei 2-9041. The above hydrogenation catalyst is preferably an organometallic complex of titanocene, an organometallic compound having a reducing property, or a combination of the above.

As the organometallic complex of the titanocene, a complex compound disclosed in Japanese Laid-Open Patent Publication No. Hei 8-109219 can be used. The organometallic complex of the titanocene may, for example, be a complex having at least one ligand, and the ligand has a dicyclopentadienyl titanium dichloride, a monopentamethylcyclopentadienyl titanium trichloride. a (substituted) cyclopentadiene skeleton, a fluorenyl skeleton or a fluorenyl skeleton. The reducing organometallic compound includes, but is not limited to, an organic alkali metal compound such as organolithium, an organomagnesium compound, an organoaluminum compound, an organoboron compound, or an organozinc compound.

Preferably, the hydrogenation reaction temperature ranges from 0 ° C to 200 ° C; more preferably, the hydrogenation reaction temperature ranges from 30 ° C to 150 ° C. Preferably, the hydrogenation reaction pressure ranges from 0.1 MPa to 15 MPa; more preferably, the hydrogenation reaction pressure ranges from 0.2 MPa to 10 MPa; more preferably, the hydrogenation reaction pressure ranges from 0.3 MPa to 7 MPa. Preferably, the hydrogenation reaction time ranges from 3 minutes to 10 hours; more preferably, the hydrogenation reaction time ranges from 10 minutes to 5 hours. The hydrogenation reaction can also be carried out by a batch process, a continuous process, or any of the combinations.

The hydrogenation rate of the hydrogenated conjugated diene polymer block of the present invention can be controlled by the hydrogenation reaction temperature, the hydrogenation reaction pressure, the hydrogenation reaction time, the amount of hydrogen used, and the type of hydrogenation reaction, and is not specified. The limit.

Preferably, the block copolymer or its hydride resin (A) has a number average molecular weight ranging from 10,000 to 200,000; more preferably, from 15,000 to 150,000; more preferably from 18,000 to 100,000. When the block copolymer or its hydride resin has a number average molecular weight of 10,000 to 200,000, a long-term insulation reliability is obtained. coating.

The moisture-proof insulating coating according to the present invention comprises an adhesive resin (B) to improve the long-term insulation reliability of the moisture-proof insulating coating to electronic parts such as glass, semiconductor wafers or printed circuit boards.

In a preferred embodiment of the present invention, the adhesive resin (B) comprises a petroleum resin, a rosin resin or a fluorene resin. These materials are readily soluble in solvents.

The petroleum resin is preferably an aliphatic petroleum resin, a petroleum resin, an aromatic hydrocarbon, an alicyclic petroleum resin, an aliphatic/aromatic copolymer petroleum resin, and a hydrogenated petroleum resin thereof.

Commercially available products such as "ARKON P" and "ARKON M" (the above are trade names) manufactured by Arakawa Chemical Industries Co., Ltd., "escorez" (trade name) manufactured by Toei Petrochemical Co., Ltd., Mitsui Chemicals Co., Ltd., and Mitsui Chemicals Co., Ltd. "Hi-rez" (trade name) manufactured by Chemical Co., Ltd., "Quintone" (trade name) manufactured by Japan ZEON Co., Ltd., "wingtak" (trade name) manufactured by Goodyear Co., Ltd., and "startak" (product name) manufactured by Dainippon Ink Chemical Industry Co., Ltd. ) "Tohopetorosin" (trade name) manufactured by Toei Petrochemical Co., Ltd., "W120" (trade name) manufactured by Yingqun Chemical Co., Ltd., "takace" (trade name) manufactured by Mitsui Chemicals Co., Ltd., and "FTR" manufactured by Mitsui Chemicals Co., Ltd. ("FTR") Product name).

The rosin-based resin is preferably rosin and a derivative thereof and a rosin-modified resin, and the source thereof may be natural rosin and polymerized rosin. In a specific embodiment of the present invention, the rosin-based resin is, for example, an esterified rosin such as pentaerythritolester rosin or glycerine ester rosin, or a hydrogen additive thereof. Commercial products such as "rosin gum", "wood rosin", "ester gum A", "ester glue H", "PENSEL A", "PENSEL C" ("Piso") can also be used. The above is the product name), and "pentalin A", "fooraru AX", "fooraru 85", "fooraru 105" and "pentalin C" (the above are trade names) manufactured by Physicochemical Hercules.

The lanthanide resin is preferably a ruthenium, a phenolic phenol resin and a hydrogenated resin thereof. For commercial products, for example, "picolight S" manufactured by Physicochemical Hercules, "picolight A" (above), and "YS resin", "YS Polyster-T" and "Clearon" manufactured by YASUHARA CHEMICAL Co., Ltd. Product name).

In a preferred embodiment of the present invention, a commercially available adhesive resin (B) such as KE311, KE604, P100, P125, P140, M100, M115, M135, A100, S100, 101, 102 is used. (produced by Arakawa Chemical Co., Ltd.), YSTO125 resin, TR105, CREARON P125, CREARON M115, CREARON K110, CREARON K4090, RESIN U130, RESIN T145, RESIN T160, YST0125 (manufactured by Anyuan Chemical Co., Ltd.).

The softening point of the adhesive resin (B) is not particularly limited, and is preferably from 100 ° C to 150 ° C as measured by the ring and ball method, more preferably from 110 ° C to 140 ° C. When the softening point of the adhesive resin is between 100 ° C and 150 ° C, when the moisture-proof insulating coating is applied to electronic parts such as glass, semiconductor wafers or printed circuit boards, it has better long-term insulation reliability.

The adhesive resin (B) is used in an amount of 15 to 150 parts by weight, preferably 20 to 125 parts by weight, based on 100 parts by weight of the block copolymer or the hydride resin (A) thereof, more preferably It is 25 to 100 parts by weight. When the adhesive resin (B) is not used, there is a disadvantage that the long-term insulation reliability is poor.

The moisture-proof insulating coating according to the present invention comprises a solvent (C) selected from the conditions of drying the moisture-proof insulating coating at room temperature, preferably, the solvent (C) is, for example, acetone or methyl. a ketone solvent of ethyl ketone; an aromatic hydrocarbon solvent such as toluene or xylene; an aliphatic solvent such as cyclohexane, methylcyclohexane or ethylcyclohexane; such as ethyl acetate, butyl acetate or acetic acid An ester solvent of isopropyl ester; an alcohol solvent such as ethanol or butanol; such as paraffin oil, naphthalene oil, mineral turpentine, naphtha or other petroleum-based solvent. On the other hand, the solvent (C) preferably has a boiling point of 70 ° C to 140 ° C, and when the boiling point of the solvent (C) is between 70 ° C and 140 ° C, when the moisture-proof insulating coating is applied to, for example, a glass or a semiconductor wafer. or When electronic components such as printed circuit boards are printed, workability problems such as peeling of the insulating film and insufficient drying are less likely to occur.

The solvent (C) is used in an amount of 150 to 1,500 parts by weight, preferably 175 to 1250 parts by weight, more preferably 200, based on 100 parts by weight of the block copolymer or its hydride resin (A). Up to 1000 parts by weight.

The moisture-proof insulating coating according to the present invention comprises the epoxy compound (D) represented by the formula (1):

In the formula (1): E ¹ , E ² and E ³ each independently represent an organic group represented by the formula (2), an organic group represented by the formula (3) or an organic group represented by the formula (4), wherein At least one of E ¹ , E ² and E ³ is an organic group represented by the formula (2) or an organic group represented by (3); and R ¹ , R ² and R ³ each independently represent a C ₂ group which may have a branch a C ₆ alkyl group or a branched C ₂ to C ₆ oxyalkylene group;

Wherein R ⁴ represents a hydrogen atom or a methyl group.

Specific examples of the C ₂ to C ₆ alkylene group which may have a branched chain include an exoethyl group, an exopropyl group, an exoisopropyl group, a cyclopropyl group, an exobutyl group, an exobutyl group, and a second group. Base, extended tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cis-pentyl, 1-methyl-exetylene, 2-methyl - n-butyl, 3-methyl-exetylene, 1,1-dimethyl-extension, 1,2-dimethyl-extension, 2,2-dimethyl-extension, 1-ethyl-extended propyl, cyclopentyl, 1-methyl-cyclopentene, 2-methyl-cyclopentene, 3-methyl-cyclopentene, 1,2-dimethyl Base-extended cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, exocyclohexyl, 1-methyl-extension Pentyl, 2-methyl-exetylpentyl, 3-methyl-exetylpentyl, 4-methyl-exetylpentyl, 1,1-dimethyl-extended butyl, 1,2-dimethyl- Stretching butyl, 1,3-dimethyl-extended butyl, 2,2-dimethyl-extended butyl, 2,3-dimethyl-extended butyl, 3,3-dimethyl-extension , 1-ethyl-extended butyl, 2-ethyl-exetylene, 1,1,2-trimethyl-extension 1,2,2-Trimethyl-extended propyl, 1-ethyl-1-methyl-extended propyl, 1-ethyl-2-methyl-extended propyl, Cyclohexyl, 1-methyl Base-extension cyclopentyl, 2-methyl-cyclopentylene, 3-methyl-cyclopentyl, 1-ethyl-cyclopentene, 2-ethyl-cyclopentene, 3-ethyl Base-cyclopentene butyl, 1,2-dimethyl-cyclopentene butyl, 1,3-dimethyl-cyclopentene butyl, 2,2-dimethyl-cyclopentene butyl, 2,3- Dimethyl-cyclopentene butyl, 2,4-dimethyl-cyclopentene butyl, 3,3-dimethyl-cyclopentene butyl, 1-n-propyl-cyclopropyl, 2-n-propyl Base-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3- Trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-extension Cyclopropyl, 2-ethyl-2-methyl-cyclopropyl or 2-ethyl-3-methyl-cyclopropyl, and the like. Preferred is a C ₂ to C ₄ alkylene group.

Specific examples of the branched C ₂ to C ₆ oxyalkylene group include an oxy-ethyl group, an oxy-n-propyl group, an oxy-extension isopropyl group, an oxy-cyclopropyl group, an oxy-n-butyl group, and an oxygen group. Stretching isobutyl, oxy-terminated second butyl, oxy-t-butyl butyl, oxy-cyclobutyl, oxy 1-methyl-cyclopropyl, oxy 2-methyl-cyclopropyl, oxygen Base n-pentyl, oxy 1-methyl-exetylene, oxy 2-methyl-exetylene, oxy 3-methyl-exetylene, oxy 1,1-dimethyl-extension 1,1-dimethyl-extended propyl, oxy 2,2-dimethyl-extended propyl, oxy 1-ethyl-extended propyl, oxycyclopentyl, oxy 1 -Methyl-cyclopentene butyl, oxy 2-methyl-cyclopentene butyl, oxy 3-methyl-cyclopentene butyl, oxy 1,2-dimethyl-cyclopropyl, oxy 2,3-Dimethyl-cyclopropyl, oxy 1-ethyl-cyclopropyl, oxy 2-ethyl-cyclopropyl, oxy-n-hexyl, oxy 1-methyl-extension Pentyl, oxy 2-methyl-exetylpentyl, oxy 3-methyl-exetylpentyl, oxy 4-methyl-exetylpentyl, oxy 1,1-dimethyl-exetylene, Oxy 1,2-dimethyl - butyl butyl, oxy 1,3-dimethyl-extended butyl, oxy 2,2-dimethyl-extended butyl, oxy 2,3-dimethyl-extended butyl, oxy 3 ,3-dimethyl-extended n-butyl, oxy 1-ethyl-extended butyl, oxy 2-ethyl-extended butyl, oxy 1,1,2-trimethyl-extended propyl, oxygen 1,2,2-trimethyl-extended propyl, oxy 1-ethyl-1-methyl-extended propyl, oxy 1-ethyl-2-methyl-extended propyl, oxy ring Hexyl, oxy 1-methyl-cyclopentylene, oxy 2-methyl-cyclopentylene, oxy 3-methyl-cyclopentyl, oxy 1-ethyl-cyclopentene, Oxy 2-ethyl-cyclopentene butyl, oxy 3-ethyl-cyclopentene butyl, oxy 1,2-dimethyl-cyclopentene butyl, oxy 1,3-dimethyl-extension Cyclobutyl, oxy 2,2-dimethyl-cyclopentene butyl, oxy 2,3-dimethyl-cyclopentene butyl, oxy 2,4-dimethyl-cyclopentene butyl, oxygen 3,3-dimethyl-cyclo-cyclobutyl, oxy 1-n-propyl-cyclopropyl, oxy 2-n-propyl-cyclopropyl, oxy 1-isopropyl-extension ring Propyl, oxy 2-isopropyl-cyclopropyl, oxy 1,2,2-trimethyl-cyclopropyl, oxy 1,2,3-trimethyl-cyclopropyl, Oxygen 2,2,3- Methyl-cyclopropyl, oxy 1-ethyl-2-methyl-cyclopropyl, oxy 2-ethyl-1-methyl-cyclopropyl, oxy 2-ethyl-2 -Methyl-cyclopropyl or oxy 2-ethyl-3-methyl-cyclopropyl propyl and the like. Preferably, the oxy group extends to an ethyl group or an oxy group extends to an isopropyl group.

The organic group represented by the above formula (2) accounts for 67 to 100 mol%, preferably 90 to 100 mol%, of the total number of moles of E ¹ , E ² and E ³ .

In the formula (1), when E ¹ , E ² and E ³ each independently represent an organic group represented by the formula (2), R ¹ , R ² and R ³ preferably each independently represent a branch. a C ₂ to C ₆ alkylene group or a branched C ₂ to C ₆ alkyloxy group; when E ¹ , E ² and E ³ each independently represent an organic group represented by the formula (3), R ¹ , R ² and R ³ preferably each independently represent a C ₂ to C ₆ alkylene group having a branched chain.

Preferably, R ¹ , R ² and R ³ are a C ₂ to C ₄ alkylene group; more preferably a C ₂ to C ₃ alkylene group (e.g., an extended ethyl group, an n-extended propyl group).

Preferably, E ¹ , E ² and E ³ are an organic group represented by the formula (2).

Preferably, R ⁴ is a hydrogen atom.

When R ¹ , R ² and R ³ are a C ₂ to C ₄ alkylene group, a moisture-proof insulating coating having a long-term insulation reliability can be obtained.

Specific examples of the epoxy compound represented by the above formula (1) may include, but are not limited to, the compounds represented by the following formulas (1-1) to (1-13):

In one embodiment of the present invention, the epoxy compound represented by the formula (1), which is a compound represented by the formula (1-1), can be obtained by the following reaction:

The above reaction uses sodium hydroxide to convert isocyanuric acid to isocyanuric acid sodium salt. The reaction can be carried out in an aqueous solvent at a reaction temperature of 0 to 100 ° C for 1 to 10 hours. Next, the sodium isocyanurate is reacted with a halogenated alkene to obtain an ene substituted isocyanuric acid. The reaction can be carried out in a solvent such as DMF (dimethylformamide) at a reaction temperature of 0 to 150 ° C for 1 to 10 hours. In the above reaction formula, X represents a halogen atom, and monohalogene or monochloroolefin can be used as the halogenated alkene. Next, the olefin-substituted isocyanuric acid is oxidized with a peracid to obtain an epoxy compound, and specific examples of the peracid are m-chloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid, and the like. It can be carried out in a solvent such as dichloromethane or toluene at a reaction temperature of 0 to 110 ° C for 1 to 10 hours. The compounds of the above formula (1-2), formula (1-5), formula (1-6), formula (1-9) and formula (1-10) are synthesized in the same manner as described above, and there is no other difference here. Narration.

In another embodiment of the present invention, the epoxy compound represented by the formula (1), which is a compound represented by the formula (1-3), can be obtained by the following reaction:

The above reaction is carried out by reacting a hydroxyalkyl isocyanurate with a halogenated propylene oxide (epihalohydrin) to obtain a tris(alkyloxyglycidyl) isocyanurate. The hydroxyalkyl isocyanurate is, for example, but not limited to, hydroxyethyl isocyanurate or the like. In another aspect, the halogenated propylene oxide is, for example but not limited to, epichlorohydrin, epibromohydrin, and the like. The reaction can be carried out in a solvent such as dioxane using boron trifluoride or tin chloride as a catalyst at a reaction temperature of from 0 to 100 ° C for from 1 to 10 hours. The compounds of the above formula (1-4), formula (1-7), formula (1-8), formula (!-11), and formula (1-12) are synthesized in the same manner as described above, and Let me repeat.

In a specific example of the present invention, when E ¹ , E ² and E ³ are an organic group represented by the formula (3), the epoxy compound represented by the formula (1) according to the present invention is as defined in the formula (1-13). The compounds shown are synthesized in the same manner as described above, as follows:

The above reaction converts an alcohol to a halogenated olefin with a halocarbon. The reaction can be carried out in a solvent such as dichloromethane at a reaction temperature of 0 to 100 ° C for 1 to 10 hours. On the other hand, isocyanuric acid can be converted to isocyanuric acid sodium salt by means of sodium hydroxide. The reaction can be carried out in an aqueous solvent at a reaction temperature of 0 to 100 ° C for 1 to 10 hours to further react an isocyanurate sodium salt with a halogenated olefin to obtain an olefin-substituted isocyanuric acid. The reaction can be carried out in a solvent such as DMF (dimethylformamide) at a reaction temperature of 0 to 150 ° C for 1 to 10 hours. In the above formula, X represents a halogen atom, and a monobromoolefin or a monochloroolefin may be used as the halogenated olefin. Next, the olefin-substituted isocyanuric acid is oxidized with a peracid to obtain an epoxy compound, and specific examples of the peracid are chloroperbenzoic acid, peracetic acid, and hydrogen peroxide-tungstic acid. The reaction can be carried out in a solvent such as dichloromethane or toluene at a reaction temperature of 0 to 110 ° C for 1 to 10 hours.

The epoxy compound (D) represented by the above formula (1) may be used singly or in combination of plural kinds.

Preferably, the epoxy compound (D) represented by the formula (1) may be of the formula (1-1). A compound represented by (1-2), (1-5), (1-6), (1-9), (1-10) or (1-13).

The epoxy compound (D) represented by the formula (1) is used in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the block copolymer or the hydride resin (A) thereof, preferably 0.1 to 8 parts by weight, more preferably 0.1 to 5 parts by weight. When the epoxy compound (D) represented by the formula (1) is not used, there is a disadvantage that the long-term insulation reliability is poor.

The moisture-proof insulating coating according to the present invention may preferably further comprise an additive (E) such as a filler, a modifier, an antifoaming agent, a colorant, an adhesive or the like. Wherein the filler is, for example, cerium oxide, magnesium oxide, aluminum hydroxide, aluminum oxide, aluminum nitride, boron nitride or calcium carbonate, preferably a fine powder; a modifier such as manganese naphthenate or the like, such as A salt metal of manganese octylate; an antifoaming agent such as eucalyptus oil, fluoro oil or other known polycarboxylic acid polymer; coloring agents such as inorganic pigments, organic pigments, organic dyes and the like.

The organic pigment according to the invention comprises a black pigment. The black pigment suitable for use in the present invention is preferably a black pigment having heat resistance, light resistance and solvent resistance.

Specific examples of the aforementioned black pigment include black organic pigments such as perylene black, lactam black, cyanine black, and aniline black; Among the pigments such as green, purple, yellow, cyanine, and magenta, two or more pigments are selected and mixed to form a nearly blackened mixed color organic pigment; carbon black And a light-shielding material such as chromium oxide, iron oxide, titanium black or graphite, wherein the carbon black may include, but not limited to, CIpigment black 7, etc., and the carbon black is specifically manufactured by a product such as Mitsubishi Chemical. (trade names MA100, MA230, MA8, #970, #1000, #2350, #2650). The above-mentioned black pigments can be generally used singly or in combination of plural kinds.

In a preferred embodiment of the present invention, the method for producing a moisture-proof insulating coating of the present invention comprises the aforementioned block copolymer or a hydride resin (A) thereof, an adhesive resin (B), and a formula (1) The epoxy compound (D) and the additive (E) shown are uniformly dispersed in The solvent (C) is stirred in a stirrer for 3 to 24 hours until the solid portion is dissolved and mixed to form a liquid moisture-proof insulating coating. Generally, the viscosity of the moisture-proof insulating coating is adjusted according to the properties of coating property, volatility, etc., which are generally known to those skilled in the art, when the viscosity of the moisture-proof insulating coating is between 0.1 and 30 Pa‧ In the case of S, the moisture-proof insulating coating has better coating characteristics. Preferably, the moisture-proof insulating coating has a viscosity of 0.1 to 20 Pa·s, and more preferably, the moisture-proof insulating coating has a viscosity of 0.1 to 10 Pa. ‧S.

The present invention also provides a method of producing a moisture-proof insulating film comprising coating a carrier with the aforementioned moisture-proof insulating coating.

Preferably, the carrier is an electronic component.

The present invention further provides a moisture-proof insulating film which is produced by the above-described method for producing a moisture-proof insulating film.

The present invention further provides an electronic component comprising the aforementioned moisture-proof insulating film.

The present invention further provides a method of manufacturing an electronic component comprising a moisture-proof insulating film provided by the method comprising the foregoing.

According to the present invention, an electronic component suitable for the moisture-proof insulating coating of the moisture-proof insulating coating includes, but is not limited to, a circuit substrate on which a microprocessor, a transistor, a capacitor, a resistor, a relay, a transformer, or the like is mounted, and the circuit substrate has a wire (lead wire), wire harness (wire harness) and other configurations that require moisture-proof insulation treatment.

The method for treating an electronic component with a moisture-proof insulating coating according to the present invention can be applied to a conventional coating method such as a dipping method, a brush coating method, a spray coating method, or a mechanical dispensing method. The coating method. In a preferred embodiment of the present invention, after the electronic component is coated, the coating film is dried at a temperature of 20 ° C to 80 ° C to obtain the electronic component of the present invention.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

<Preparation of Block Copolymer Resin (A)>

In the following synthesis examples, the hydrogenation catalyst is prepared by adding a dried, purified 1 liter of cyclohexane to a nitrogen-containing reaction vessel and adding 100 millimolar of bis(η5-cyclopentadiene). Titanium dichloride was further added with a solution of 200 mmol of trimethylaluminum in n-hexane while stirring well to obtain a reaction liquid. The above reaction solution was allowed to react at room temperature for about three days, and the obtained product was a hydrogenation catalyst.

<Synthesis Example 1>

Under a nitrogen atmosphere, a cyclohexane solution containing 10 parts by weight of styrene, a cyclohexane solution containing 1.3 parts by weight of n-butyllithium, and 0.05 part by weight of tetramethylethylenediamine [None] a randomizer is placed in an autoclave having a stirrer and polymerized at a temperature of 70 ° C for 20 minutes; then, 20 parts by weight of styrene and 50 parts by weight of 1 are contained in 50 minutes. A cyclohexane solution of 3-butadiene was added to the autoclave, and polymerization was carried out at 70 ° C for 5 minutes. Next, a cyclohexane solution containing 10 parts by weight of 1,3-butadiene was further added, and polymerization was further carried out at 70 ° C for 5 minutes. Next, a cyclohexane solution containing 10 parts by weight of styrene was further added, and polymerization was further carried out at 70 ° C for 25 minutes. After the reaction, the reaction solution containing the block copolymer precursor was added to the above hydrogenation catalyst. And hydrogen gas, wherein the hydrogenation catalyst content is 100 ppm, the hydrogen gas usage is 1.1 parts by weight, the hydrogenation operation pressure is 0.7 MPa, the hydrogenation reaction time is 1 hour, and the hydrogenation reaction temperature is 100 parts by weight of the block copolymer precursor. The hydrogenation reaction was carried out at 65 °C. Thereafter, methanol and 0.3 parts by weight of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (relative to 100 parts by weight of the block copolymer precursor) were added. The solvent removal treatment was carried out to obtain a block copolymer resin (A-1) having a number average molecular weight of 66,000 and a hydrogenation ratio of 50%.

<Synthesis Examples 2 to 9>

Synthesis Examples 2 to 9 were prepared in the same manner as in Synthesis Example 1. The polymer or its hydride resin differs in that the ethylene-based aromatic monomer, the conjugated diene monomer, the amount of hydrogen used, and the hydrogenation reaction conditions are as shown in Table 1.

<moisture-proof insulating coating> <Example 1>

100 parts by weight of the block copolymer obtained in the above Synthesis Example or its hydride resin (A-1), 15 parts by weight of the adhesive resin (B-1), and 0.05 part by weight of the formula (1) The epoxy compound (D-1) and 0.4 parts by weight of the additive (E-1) are added to 150 parts by weight of the solvent (C-1), and stirred in a stirrer for 16 hours until the solid portion is dissolved and mixed, and then prepared. A moisture-proof insulating coating was obtained, which was evaluated by the following measurement evaluation methods, and the results are shown in Table 2.

<Examples 2 to 10>

The manufacturing method of the first embodiment is different from the block copolymer or the hydride resin (A), the adhesive resin (B), the solvent (C), and the epoxy compound represented by the formula (1) ( D) and the type and amount of the additive (E), the formulation and evaluation results are shown in Table 2.

<Comparative Examples 1 to 5>

The manufacturing method of the first embodiment is different from the block copolymer or the hydride resin (A), the adhesive resin (B), the solvent (C), and the epoxy compound represented by the formula (1) ( D) and the type and amount of the additive (E), the formulation and evaluation results are shown in Table 3.

D-2 type (1-2)

D-3 type (1-3)

D-4 type (1-5)

D-5 type (1-8)

D-6 type (1-11)

D-7 type (1-13)

D'-1 1,3,5-triglycidyl isocyanurate (1,3,5-triglycidyl isocyanurate) 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate

D'-2 (3',4'-epoxycyclohexylmethyl 3,4-epoxy cyclohexane carboxylate) 1,4-cyclohexanedimethanol diglycidyl ether

D'-3 (1,4-cyclohexane dimethanol diglycidylether)

E-1 fluoro oil

E-2 oil oil (silicon oil, Shin-Etsu Chemical, KF-96-3000CS)

E-3 C.I.pigment black 7

Evaluation method: <Long-term insulation reliability>

On the patterned electrode formed on the glass substrate, a comb-shaped ITO line having a line/space of 40 μm/10 μm was formed, and 100 μm thick of the composition of the example or the comparative example was applied to the electrode, and the mixture was allowed to stand at room temperature. It was allowed to stand for 10 minutes and then dried at 70 ° C for 1.5 hours.

Next, the glass substrate was subjected to a bias of 10 V under conditions of 60 ° C and a humidity of 90% RH to carry out a temperature and humidity stability test (manufactured by IMV, model MIGRATION TESTER MODEL MIG-8600), and the above temperature and humidity were 500. The hourly test measures the impedance value (R) and evaluates it based on the following criteria:

◎: 1.0×10 ¹² Ω≦R

○: 1.0 × 10 ¹⁰ Ω ≦ R < 1.0 × 10 ¹² Ω

△: 1.0 × 10 ⁸ Ω ≦ R < 1.0 × 10 ¹⁰ Ω

×: R < 1.0 × 10 ⁸ Ω.

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (9)

A moisture-proof insulating coating comprising: a block copolymer or a hydride resin (A) comprising a skeleton comprising at least two ethylene-based aromatic polymer blocks and at least one conjugated diene system a polymer block; an adhesive resin (B); a solvent (C); and an epoxy compound (D) having the formula (1); In the formula (1): E ¹ , E ² and E ³ each independently represent an organic group represented by the formula (2), an organic group represented by the formula (3) or an organic group represented by the formula (4), wherein At least one of E ¹ , E ² and E ³ is an organic group represented by the formula (2) or an organic group represented by (3); and R ¹ , R ² and R ³ each independently represent a C ₂ group which may have a branch a C ₆ alkyl group or a branched C ₂ to C ₆ oxyalkylene group; Wherein R ⁴ represents a hydrogen atom or a methyl group; and the amount of the adhesive resin (B) used is 15 to 150 parts by weight based on 100 parts by weight of the block copolymer or the hydride resin (A) thereof; The solvent (C) is used in an amount of from 150 to 1,500 parts by weight; and the epoxy compound (D) represented by the formula (1) is used in an amount of from 0.1 to 10 parts by weight. The moisture-proof insulating coating according to claim 1, wherein, in the formula (1), R ¹ , R ² and R ³ each independently represent a C ₂ to C ₄ alkylene group. The moisture-proof insulating coating according to claim 1, wherein the block copolymer or the hydride resin (A) has a number average molecular weight of 10,000 to 200,000. The moisture-proof insulating coating according to claim 1, wherein the adhesive resin (B) is selected from the group consisting of a petroleum resin, a rosin resin, and a lanthanum resin. A method for producing a moisture-proof insulating film, comprising coating a carrier with the moisture-proof insulating coating according to any one of claims 1 to 4 The method of claim 5, wherein the carrier is an electronic component. A moisture-proof insulating film produced by the method of claim 5 or 6. An electronic component comprising the moisture-proof insulating film according to claim 7. A method of manufacturing an electronic component comprising a moisture-proof insulating film, the method comprising coating a carrier with the moisture-proof insulating coating according to any one of claims 1 to 4 to provide the moisture-proof insulating film.