TW201700649A - Moisture-proof and insulating coating material and uses thereof - Google Patents

Abstract

The invention relates a moisture-proof and insulating coating material comprising a block copolymer or hydrogenated copolymer thereof (A), an adhesive resin (B), a solvent (C) and a polysiloxane (D) having an epoxy group. The moisture-proof and insulating coating material according to the invention has good long-term insulating reliability. A moisture-proof and insulating coating film and a method for producing the same and an electrical device comprising the moisture-proof and insulating coating film and a method for producing the same are also provided in the invention.

Description

Moisture-proof insulating coating and its application

The present invention relates to a moisture-proof insulating coating for an electronic component and an electronic component and a method of manufacturing the same using the moisture-proof insulating coating. 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 group-containing polyoxyalkylene to obtain a moisture-proof insulating coating 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 Conjugated diene polymer block; adhesive resin (B); solvent (C); and epoxy group-containing polyoxyalkylene (D).

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); An epoxy group-containing polyoxyalkylene (D).

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 system is selected from one or more of the following compounds: 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), preferably, the vinyl aromatic monomer and/or the conjugated diene monomer may be diluted with an organic solvent to an appropriate concentration, respectively. Mixing and polymerization are carried out. In a specific embodiment of the invention, the The concentration after release was 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 pressure range is not It is particularly limited that the ethylene-based aromatic monomer, the conjugated diene monomer, and the solvent can be maintained in a pressure range required for the liquid in the polymerization reaction temperature range. 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 used in a conventional manner, 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 salt, which is reacted with a reducing agent. Ziegler type hydrogenation catalyst; (3) organometallic compound; (4) organometallic complex.

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. The above-mentioned hydrogenation catalyst 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. The hydrogenation catalyst in Japanese Patent Publication No. Hei. No. 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, or an organic A boron compound, or an organic zinc compound or the like.

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 moisture-proof insulating coating having a long-term insulation reliability can be obtained.

The moisture-proof insulating coating according to the present invention comprises an adhesive resin (B) to improve the adhesion 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 can be used for the petroleum-based resin according to the present invention, for example, "ARKON P" and "ARKON M" manufactured by Arakawa Chemical Industries Co., Ltd. (the above are trade names), "Escorez" (trade name) manufactured by Toei Petrochemical Co., Ltd., "Hi-rez" (trade name) manufactured by Mitsui Chemicals Co., Ltd., "Quintone" (trade name) manufactured by Japan ZEON Co., Ltd., "wingtak" (trade name) manufactured by Goodyear Co., Ltd. "startak" (trade name) manufactured by Dainippon Ink and Chemicals Co., Ltd., "tohopetorosin" (trade name) manufactured by Tohoku Petrochemical Co., Ltd., "W120" (trade name) manufactured by British Chemicals Co., Ltd., and "takace" manufactured by Mitsui Chemicals Co., Ltd. (trade name), and "FTR" (trade name) manufactured by Mitsui Chemicals Co., Ltd.

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 trade name), and "pentalin A", "fooraru AX", "fooraru 85", "fooraru 105" and "pentalin C" (the above are trade names) manufactured by Physicochemical Hercules.

The oxime resin is preferably a ruthenium resin, a phenol resin, or a hydrogenated resin thereof, and a commercial product such as "picolight S" manufactured by Physicochemical Hercules, "picolight A" (above), and YASUHARA CHEMICAL Co., Ltd. "YS resin", "YS Polyster-T" and "Clearon" (the above are trade names).

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 adhesion The softening point of the resin is between 100 ° C and 150 ° C. When this 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.

According to the invention, the amount of the adhesive resin (B) to be used is preferably 100 parts by weight based on the amount of the block copolymer or the hydride resin (A), and the amount of the adhesive resin (B) is 15 to 150 parts by weight, preferably 20 to 125 parts by weight, more preferably 25 to 100 parts by weight.

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. When an electronic component such as a printed circuit board is printed, it is less likely to cause workability problems such as peeling of the insulating film and insufficient drying.

According to the present invention, the content of the solvent (C) is preferably 100 parts by weight based on the block copolymer or the hydride resin (A), and the solvent (C) is used in an amount of 150 to 1500 parts by weight. It is preferably 175 to 1250 parts by weight, more preferably 200 to 1000 parts by weight.

The moisture-proof insulating coating according to the present invention comprises an epoxy group-containing polyoxyalkylene (D) which can be self-polymerized from an epoxy group-containing decane compound (d-1). Condensed; or by copolymerization of the epoxy group-containing decane compound (d-1) with other decane compound (d-2).

The epoxy group-containing group which the epoxy group-containing decane compound (d-1) has is, for example, a glycidyl group or a glycidyloxy group. Group), epoxycyclohexyl group or oxetanyl group.

Specifically, the epoxy group-containing group is selected from the group consisting of groups represented by formula (1), formula (2), and formula (3):

In the formula (1), A represents an oxygen atom or a single bond; h represents an integer of 1 to 3; i represents an integer of 0 to 6; wherein, when i is 0, A is a single bond;

In the formula (2), j represents an integer from 0 to 6;

In the formula (3), B represents an alkylene group having 2 to 6 carbon atoms; and R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The epoxy group-containing group preferably includes at least a group represented by the formula (1-1), a group represented by the formula (2-1), and a group represented by the formula (3-1). One.

The epoxy group-containing group is preferably selected from the group consisting of the groups represented by the formulas (2) and (3), and a moisture-proof insulating coating having a long-term insulation reliability is obtained.

Specific examples of the epoxy group-containing decane compound (d-1) include 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 3-(N-allyl-N-shrinkage Glyceryl)aminopropyltrimethoxydecane, 3-glycidyloxypropyltrimethoxydecane, 3-glycidyloxypropyltriethoxydecane, 3-glycidyl ether propylmethyldi Methoxydecane, 3-glycidyl ether propyl methyl diethoxy decane, 3-glycidyl ether propyl dimethyl methoxy decane, 3-glycidyl ether propyl dimethyl ethoxylate Base decane, 2-glycidyl ether ethyl trimethoxy decane, 2-glycidyl ether ethyl triethoxy decane, 2-glycidyl ether ethyl methyl dimethoxy decane, 2-glycidol Ethyl ethyl methyl diethoxy decane, 2-glycidyl ether ethyl dimethyl methoxy decane, 2-glycidyl ether ethyl dimethyl ethoxy decane, 4-glycidyl ether Butyl trimethoxy decane, 4-glycidyl ether butyl triethoxy decane, 4-glycidyl ether butyl methyl dimethoxy decane, 4-glycidyl ether butyl methyl diethoxy decane, 4 - shrink Glyceryl ether butyl dimethyl methoxy decane, 4-glycidyl ether butyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 2- (3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propane Triethoxy decane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltrimethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy) Propyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propylmethyldimethoxydecane or ((3-ethyl-3-epoxypropane) Methoxy)propane dimethyl methoxy decane, or a combination of the above compounds.

Specific examples of the epoxy group-containing decane compound (d-1) preferably include 3-condensation Glycidyl ether propyl trimethoxy decane, 2-glycidyl ether ethyl trimethoxy decane, 4-glycidyl ether butyl trimethoxy decane, 2-(3,4-epoxycyclohexyl) Trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltrimethoxydecane ((3-Ethyl-3-epoxypropenyl)methoxy)propyltriethoxydecane or a combination of the above compounds.

The total amount of the epoxy group-containing decane compound (d-1) and the other decane compound (d-2) is 1.00 mol, and the epoxy group-containing decane compound (d-1) is used in an amount of 0.20. To 1.00 moles, preferably from 0.30 to 0.95 moles, more preferably from 0.40 to 0.90 moles. When the epoxy group-containing decane compound (d-1) is used in an amount of the above ratio, a moisture-proof insulating coating which is excellent in long-term insulation reliability can be obtained.

The other decane compound (d-2) is, for example, a compound having one ruthenium atom. The compound having one ruthenium atom includes a decane compound having four hydrolyzable groups, a decane compound having three hydrolyzable groups, a decane compound having two hydrolyzable groups, and a decane having one hydrolyzable group. a compound, or a combination thereof.

Specific examples of the decane compound having 4 hydrolyzable groups include tetrachlorodecane, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane. , four second butoxydecane, or a combination of the above compounds.

Specific examples of the decane compound having three hydrolyzable groups include trichlorodecane, trimethoxy decane, triethoxy decane, fluorotrichloro decane, fluorotrimethoxy decane, fluorotriethoxy decane, and methyl three. Chlorodecane, methyltrimethoxydecane, methyltriethoxydecane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-( Trifluoromethyl)ethyltriethoxydecane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane, decylmethyltrichlorodecane, 3-mercaptopropyltrichloride Decane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane,phenyltrichlorodecane,phenyltrimethoxy A decyl alkane, a phenyl triethoxy decane, or a combination of the above compounds.

Specific examples of the decane compound having two hydrolyzable groups include methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, dimethyl dichloro decane, and dimethyl dimethoxy group. Decane, dimethyldiethoxydecane, methyl[2-(perfluoro-n-octyl)ethyl]dichlorodecane, methyl[2-(perfluoro-n-octyl)ethyl]dimethoxydecane 3-巯propylmethyldichlorodecane, 3-mercaptopropylmethyldimethoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, or a combination of the above compounds.

Specific examples of the decane compound having one hydrolyzable group include chlorodimethyl decane, methoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, and methoxy three. Methyl decane, chloromethyl diphenyl decane, methoxymethyl diphenyl decane, or a combination of the above compounds.

Specific examples of the commercially available product of the other decane compound (d-2) include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, and X-21-5843. X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X- 22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40- 2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (manufactured by Shin-Etsu Chemical Co., Ltd.); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (manufactured by Toray Dow Corning); FZ3711, FZ3722 (manufactured by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS- S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51 DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by JNC); MS51, MS56 (manufactured by Mitsubishi Chemical Corporation); and partial condensation of GR100, GR650, GR908, GR950 (made by Showa Denko) Things.

The other decane compound (d-2) is preferably tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethyl ethane. Oxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, dimethyldimethoxydecane , dimethyldiethoxy decane, or a combination of the above compounds.

The total amount of the epoxy group-containing decane compound (d-1) and other decane compound (d-2) is 1.00 mol, and the other decane compound (d-2) is used in an amount of 0 to 0.80 mol. Preferably, it is from 0.05 to 0.70 moles, more preferably from 0.10 to 0.60 moles.

The polycondensation reaction for forming the epoxy group-containing polyoxyalkylene (D) can be carried out by a general method, for example, by adding an organic solvent, water or optionally further adding a catalyst to the above decane compound or a mixture thereof, followed by using The oil bath or the like is heated at 50 ° C to 150 ° C, preferably for a period of from 0.5 hours to 120 hours. While heating, the mixture may be stirred or placed under reflux. Further, in the course of heating and stirring, if necessary, hydrolysis by-products (for example, alcohols such as methanol and ethanol) and condensation by-products (for example, water) may be removed by distillation.

The above organic solvent is not particularly limited and may be the same as or different from the solvent (C) contained in the moisture-proof insulating coating of the present invention.

Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; ketone compounds such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone. Ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; ethylene glycol dimethyl ether, An ether compound such as ethylene glycol diethyl ether, tetrahydrofuran or dioxane; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl An alcohol compound such as ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or propylene glycol mono-n-propyl ether, or a combination of the above organic solvents .

The above organic solvents may be used singly or in combination of two or more.

The organic solvent is preferably used in an amount of 10 to 1200 parts by weight, more preferably 30 to 1,000 parts by weight, based on 100 parts by weight of all of the decane compound.

The water-based group is preferably used in an amount of from 0.5 to 100 moles, more preferably from 1 to 30 moles, based on 1 mole of the hydrolyzable group of all the decane compounds.

The catalyst is not particularly limited, and preferably, the catalyst is selected from the group consisting of an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, or a combination thereof.

Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic acid anhydride, or a combination thereof.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.

Specific examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperididine, pyrrolidine, pyrrole, etc.; triethylamine, three Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc.; An amine or the like, or a combination of the above compounds.

The amount of the catalyst to be used varies depending on the reaction conditions such as the type and temperature, and can be appropriately set, for example, 1 mol based on all the decane compound, and the catalyst is added in an amount of 0.01 to 5 mol, preferably 0.03 to 3 moles, more preferably 0.05 to 1 mole.

From the viewpoint of stability, after completion of the polycondensation reaction, it is preferred to wash the organic solvent layer fractionated from the reaction liquid with water. In the case of performing the cleaning, it is preferred to use a water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like. The cleaning can be carried out until the water layer after washing becomes neutral, and then the organic solvent layer is anhydrous as needed. After drying with a desiccant such as calcium sulfate or molecular sieves, the organic solvent is removed to obtain an epoxy group-containing polyoxyalkylene (D).

The epoxy group-containing polyoxyalkylene (D) of the present invention has a weight average molecular weight of from 1,000 to 10,000, preferably from 1,200 to 8,000, as measured by gel permeation chromatography. Good for 1,500 to 5,000. When the weight average molecular weight of the epoxy group-containing polyoxyalkylene (D) is within the above range, the long-term insulation reliability of the obtained moisture-proof insulating coating is better.

The epoxy group-containing polyoxyalkylene oxide (D) is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 8 based on 100 parts by weight of the block copolymer or the hydride resin (A) thereof. Part by weight, and more preferably 0.1 to 5 parts by weight. When the epoxy group-containing polyoxyalkylene (D) 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 preferably further comprises 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 foregoing black pigment include black organic pigments such as perylene black, cyanine black, and aniline black; and red, blue, green, purple, yellow, and cyanine. Among the pigments such as (cyanine) and magenta (magenta), two or more pigments are selected and mixed to form a nearly blackened mixed color organic pigment; carbon black, chromium oxide, iron oxide, titanium black (titanium black), a light-shielding material such as graphite, wherein the carbon black may include, but not limited to, CIpigment black 7, etc., and the carbon black is specifically a commercial product (trade name) manufactured by Mitsubishi Chemical Corporation. 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 an epoxy group-containing compound. The polyoxyalkylene (D) and the additive (E) are uniformly dispersed in the solvent (C), and stirred in a stirrer for 3 to 24 hours until the solid portions are 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, or a spray coating method. A coating method such as a method or a mechanical dispensing 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 [ A randomizer is placed in an autoclave with a stirrer and polymerized at a temperature of 70 ° C for 20 minutes, and then 20 parts by weight of styrene and 50 parts by weight of the mixture 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) were added. a block copolymer precursor), which is subjected to a solvent removal treatment to obtain a block copolymer resin (A-1) having a number average molecular weight of 66,000 and a hydrogenation ratio. 50%.

<Synthesis Examples 2 to 9>

Synthesis Examples 2 to 9 The block copolymer or a hydride resin thereof was prepared in the same manner as in Synthesis Example 1, except that the vinyl aromatic monomer, the conjugated diene monomer, and the hydrogen were changed. The amount used and the hydrogenation reaction conditions are shown in Table 1.

<Preparation of epoxy group-containing polyoxyalkylene (D)> <Synthesis Example D-1>

A stirrer, a condenser, and a thermometer were placed on a three-necked flask having a volume of 500 ml. Then, in a three-necked flask, 1.00 mol of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (hereinafter abbreviated as EECTS) and 2000 g of methyl isobutyl ketone (hereinafter referred to as ETC) were added. MIBK), 500g of propylene glycol monomethyl ether (hereinafter referred to as PGME) and 20g of triethylamine (hereinafter referred to as TEA), and add 180g in 30 minutes while stirring at room temperature. Ionic water. Next, the three-necked flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and then the oil bath was heated to 95 ° C in 30 minutes. When the internal temperature of the solution reached 80 ° C, stirring was continued for 3 hours. . After the completion of the reaction, the organic layer was taken out, and the organic layer was washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and polyoxyalkylene (B-1) was obtained.

<Synthesis Examples D-2 to D-10 and D'-1>

Synthesis Examples D-2 to D-10 and D'-1 were prepared in the same manner as in Synthesis Example D-1, except that the epoxy group-containing group was changed. The amount of the decane compound, other decane compound, solvent, catalyst used, reaction temperature, and polycondensation time are shown in Table 2.

DMDMS dimethyldimethoxy silane

PTMS phenyltrimethoxy silane

PTES phenyltriethoxy silane

PGME propylene glycol monomethyl ether

MIBK methyl isobutyl ketone

H ₂ O water (water)

TEA triethylamine

<moisture-proof insulating coating> <Example 1>

100 parts by weight of the block copolymer obtained by the above Synthesis Example or its hydride resin (A-1), 15 parts by weight of the adhesive resin (B-1), and 0.1 weight of the epoxy group-containing polyoxyalkylene (D). 0.4 parts by weight of the additive (E-1), 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 to obtain a moisture-proof insulating coating, which is moisture-proof. The insulating coating was evaluated by the following measurement evaluation methods, and the results are shown in Table 3.

<Examples 2 to 13>

The manufacturing method of the first embodiment is different from the block copolymer or its hydride resin (A), the adhesive resin (B), the solvent (C), and the epoxy group-containing polyoxyalkylene (D). The type and amount of the additive (E), the formulation and evaluation results are shown in Table 3.

<Comparative Examples 1 to 6>

The manufacturing method of the first embodiment is different from the block copolymer or its hydride resin (A), the adhesive resin (B), the solvent (C), and the epoxy group-containing polyoxyalkylene (D). The type and amount of the additive (E), the formulation and evaluation results are shown in Table 4.

In Tables 3 and 4:

B-1 KE311 (produced by Arakawa Chemical Co., Ltd.)

B-2 YSTO125 resin (produced by Anyuan Chemical Co., Ltd.)

B-3 TR105 (produced by Anyuan Chemical Co., Ltd.)

C-1 cyclohexane

C-2 methylcyclohexane

C-3 ethylcyclohexane

D'-2 alkoxy-terminated polyoxyalkylene having a weight average molecular weight of 20,000 (Manufactured by GE Toshiba Organic Co., Ltd. under the trade name XR31-B2733)

D'-3 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane)

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.

The test piece was subjected to a temperature and humidity stability test (Model MIGRATION TESTER MODEL MIG-8600, manufactured by IMV, Inc.) under the conditions of 60 ° C and a humidity of 90% RH for a temperature and humidity test for 500 hours. , measure the impedance value (R) and evaluate it according to 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 (12)

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 Polymer block; adhesive resin (B); solvent (C); and epoxy group-containing polyoxyalkylene (D). The moisture-proof insulating coating according to claim 1, wherein the epoxy group of the epoxy group-containing polyoxyalkylene (D) is selected from the group consisting of formula (1), formula (2) and formula (3). a group of groups; In the formula (1), A represents an oxygen atom or a single bond; h represents an integer of 1 to 3; i represents an integer of 0 to 6; wherein, when i is 0, A is a single bond; In the formula (2), j represents an integer from 0 to 6; In the formula (3), B represents an alkylene group having 2 to 6 carbon atoms; and R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The moisture-proof insulating coating according to claim 2, wherein the epoxy group of the epoxy group-containing polyoxyalkylene (D) is selected from the group consisting of groups represented by formula (2) and formula (3) ; In the formula (2), j represents an integer from 0 to 6; In the formula (3), B represents an alkylene group having 2 to 6 carbon atoms; and R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 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 used in an amount of 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 group-containing polyoxyalkylene (D) is used in an amount of from 0.1 to 10 parts by weight. The moisture-proof insulating coating according to claim 1, wherein the epoxy group-containing polyoxyalkylene (D) has a weight average molecular weight of 1,000 to 10,000. 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 7 The method of claim 8, wherein the carrier is an electronic component. A moisture-proof insulating film produced by the method of claim 8 or 9. An electronic component comprising the moisture-proof insulating film according to claim 10. A method of manufacturing an electronic component, the electronic component comprising a moisture-proof insulating film, The method comprises coating a carrier with a moisture-proof insulating coating according to any one of claims 1 to 7 to provide the moisture-proof insulating film.