TWI512062B - Moisture-proof and insulating coating material and uses thereof - Google Patents

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 good weather resistance uniformity.

With the advancement of technology, electronic components are gradually becoming more and 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-proof have become important factors affecting the service life of electronic components. Accordingly, a coating layer is formed on the outside of the electronic component to achieve protection against moisture, dust, gas, and insulation.

Japanese Laid-Open Patent Publication No. 2005-132966 discloses an insulating coating comprising a methacrylic resin, a polyolefin resin or a polyurethane resin, and a solvent butyl acetate. This coating is mainly used to solve the environmental problems caused by the use of highly toxic solvents.

Japanese Laid-Open Patent Publication No. 2005-126456 discloses a moisture-proof insulating coating which is composed of 10 to 40 parts by weight of a thermoplastic resin such as an ABA type styrenic block copolymer or a hydride thereof, 1 to 20 It is composed of a part by weight of an adhesive resin and 50 to 90 parts by weight of a solvent, and a naphthenic coupling agent is selectively added. In the patent publication, after the conventional coating is applied to an electronic product and formed into a coating film, the electronic product is prevented from being infiltrated by the water at the interface between the coating film and the electronic product in the subsequent high temperature and high humidity environment. Poor wetness question.

However, the above composition still does not meet the current requirements for moisture resistance in the industry. Therefore, Japanese Laid-Open Patent Publication No. 2008-189763 further discloses an insulating coating which is composed of an ABA type styrenic block copolymer and/or a hydride thereof. It is composed of an adhesive resin and 50 to 150 parts by weight of a solvent to improve the above-mentioned problem of poor moisture resistance. However, the coating film after the coating described in the above patent has a problem that the weathering uniformity is poor, and the electronic component is easily damaged after prolonged use.

Therefore, how to simultaneously improve the weathering uniformity while achieving the requirements of the current industry is an object of diligent research in the technical field to which the present invention pertains.

The invention utilizes a component which provides a special segment of the copolymer resin and a special compound to obtain a weatherproof uniformity moisture-proof insulating coating.

Accordingly, the present invention provides a moisture-proof insulating coating comprising: at least one block copolymer 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 a modified polyoxyalkylene (D); a compound (D) having a structure represented by the formula (I)

In the formula (I), the A ₁ groups each independently represent a fluorinated alkyl group having a carbon number of 1 to 4, the A ₂ groups each independently represent a methyl group or an ethyl group, and m represents an integer of 2 to 100.

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: at least one block copolymer resin (A) comprising a skeleton comprising at least two vinyl aromatic polymer blocks and at least one conjugated diene a polymer block; an adhesive resin (B); a solvent (C); and a modified polyoxyalkylene (D); a compound (D) having a structure represented by the formula (I)

In the formula (I), the A ₁ groups each independently represent a fluorinated alkyl group having a carbon number of 1 to 4, the A ₂ groups each independently represent a methyl group or an ethyl group, and m represents an integer of 2 to 100.

The at least one block copolymer resin (A) according to the present invention comprises a skeleton comprising at least two vinyl aromatic polymer blocks and at least one hydrogenated 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 compound: styrene, 2-methyl Styrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 2,4-dimethylstyrene, α-methylstyrene, Α-methyl-4-methylstyrene or the like; (2) styrene compound substituted by halogen: 2-chlorostyrene, 4-chlorostyrene, and 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, and the like.

In a specific embodiment of the present invention, the method for synthesizing the at least one block copolymer resin (A) comprises the steps of: (1) a polymerization reaction, respectively, the ethylene-based aromatic monomer and the conjugated diene The 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 at least one block copolymer resin (A) of the present invention. Here are the explanations:

(1) Polymerization:

When the at least one block copolymer resin (A) is prepared, preferably, the vinyl aromatic monomer and/or the conjugated diene monomer may be diluted with an organic solvent to an appropriate concentration, and then mixed. And polymerization. In a particular embodiment of the invention, the concentration of the dilution is 25 wt%.

Preferably, the organic solvent is selected from the group consisting of (1) aliphatic compounds: n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, etc.; (2) alicyclic Compound: 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 gathering The starting agent is selected from the group consisting of C1 to C20 aliphatic lithium compounds, C6 to C20 aromatic lithium compounds, C1 to C20 aliphatic sodium compounds, C6 to C20 aromatic sodium compounds, C1 to C20 aliphatic potassium compounds, C6 to C20 aromatic potassium compound, or a combination of these.

The C1 to C20 aliphatic lithium compound includes, but is not limited to, n-propyl lithium, n-butyl lithium, second butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprene Dienyldilithium. The C6 to C20 aromatic lithium compound includes, but is not limited to, a reaction product of diisopropenylbenzene and a second butyllithium, or a reaction of divinylbenzene, a second butyllithium and a small amount of 1,3-butadiene Product, etc. 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 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, 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 determined by hydrogenation reaction temperature, hydrogenation reaction pressure, hydrogenation reaction time, hydrogen usage, and hydrogenation. There are no specific restrictions on the manner in which the type of reaction is regulated.

The hydrogenation ratio of the hydrogenated conjugated diene polymer block according to the present invention is from 50 to 100 mol%, preferably, the hydrogenation ratio of the hydrogenated conjugated diene polymer block is From 60 to 100 mol%; more preferably, the hydrogenated conjugated diene polymer block has a hydrogenation ratio of from 70 to 100 mol%.

When the hydrogenation ratio of the conjugated diene polymer is from 50 to 100 mol%, weather resistance uniformity is preferred.

Preferably, the at least one block copolymer 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 resin has a number average molecular weight of 10,000 to 200,000, a moisture-proof insulating coating having better weather resistance uniformity 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 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 Tokay Petrochemical Co., Ltd., "takace" (trade name) manufactured by Mitsui Chemicals Co., Ltd., and "FTR" (trade name) manufactured by Mitsui Chemicals Co., Ltd., etc.

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 invention, the rosin resin For example, esterified rosin such as pentaerythritolester rosin and glycerine ester rosin, and hydrogen additives 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 is not particularly limited, and is preferably from 100 ° C to 150 ° C, more preferably from 110 ° C to 140 ° C, measured by the ring and ball method. When the softening point of the adhesive resin is between 100 ° C and 150 ° C, the moisture-proof insulating coating is preferably used when applied to electronic parts such as glass, semiconductor wafers or printed circuit boards.

According to the invention, the amount of the adhesive resin to be used is preferably 100 parts by weight based on the amount of the block copolymer resin (A), and the adhesive resin (B) is used in an amount of 20 to 200 parts by weight, preferably 25 to 160 parts by weight, more preferably 30 to 120 parts by weight.

The moisture-proof insulating coating according to the present invention comprises a solvent (C), and the solvent (C) is selected in consideration of the conditions for drying the moisture-proof insulating coating at room temperature. Preferably, the solvent (C) is, for example, acetone or methyl ethyl. a ketone solvent; an aromatic hydrocarbon solvent such as toluene or xylene; such as cyclohexane; An aliphatic solvent of methylcyclohexane or ethylcyclohexane; an ester solvent such as ethyl acetate, butyl acetate or isopropyl acetate; an alcohol solvent such as ethanol or butanol; such as paraffin oil, naphthalene oil , mineral turpentine, naphtha or other petroleum based solvents. On the other hand, the solvent (C) preferably has a boiling point of 70 ° C to 140 ° C, and when the solvent (C) has a boiling point of 70 ° C to 140 ° C, when the moisture-proof insulating coating is applied to, for example, glass, 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.

According to the present invention, the content of the solvent (C) is preferably 100 parts by weight based on the amount of the block copolymer resin (A), and the solvent (C) is used in an amount of 200 to 2000 parts by weight, preferably 250 to 1600 parts by weight, more preferably 300 to 1200 parts by weight.

The compound (D) having the structure represented by the following formula (I) according to the present invention

In the formula (I), the A ₁ groups each independently represent a fluorinated alkyl group having a carbon number of 1 to 4, the A ₂ groups each independently represent a methyl group or an ethyl group, and m represents an integer of 2 to 100.

The compound (D) having a structure represented by the formula (I) may include, but is not limited to, a fluorine-based surfactant having a hydroxyl group. Preferred are compounds having a fluorinated alkyl group having 1 to 4 carbon atoms and at least two hydroxyl groups.

Further, in the above formula (I), in order to enhance the effect of the moisture-proof insulating coating, A ₁ preferably represents a perfluoroalkyl group having a carbon number of 1 to 4. Preferably, A ₁ may be CF ₃ CH ₂ -, CF ₃ CH ₂ CH ₂ -, CF ₃ CF ₂ CH ₂ -, CF ₃ CF ₂ CH ₂ CH ₂ -, CF ₃ CF ₂ CF ₂ CH ₂ -, CF ₃ CF ₂ CF ₂ CH ₂ CH ₂ -, CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ - or CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -.

If m represents an integer of from 2 to 100, the weather resistance uniformity of the prepared moisture-proof insulating coating is preferred. Preferably, m can represent an integer from 3 to 70. More preferably, m may represent an integer from 4 to 40.

A specific example of the compound (D) having a structure represented by the formula (I) may be manufactured by OMNOVA, model PF-636 (wherein A ₁ represents CF ₃ CH ₂ -, A ₂ represents a methyl group, and m represents 6). ), PF-6320 (wherein A ₁ represents CF ₃ CH ₂ -, A ₂ represents a methyl group, and m represents 20), PF-656 (wherein A ₁ represents CF ₃ CF ₂ CH ₂ -, and A ₂ represents a methyl group, And m represents a product of 6), PF-6520 (wherein A ₁ represents CF ₃ CF ₂ CH ₂ -, A ₂ represents a methyl group, and m represents 20). The aforementioned compound (D) having a structure represented by the formula (I) may be used singly or in combination of plural kinds.

According to the present invention, the compound (D) having a structure represented by the formula (I) is preferably used in an amount of 100 parts by weight based on the block copolymer resin (A), which has the formula (I) The compound (D) of the structure shown is used in an amount of from 0.3 to 3 parts by weight, preferably from 0.3 to 2.5 parts by weight, more preferably from 0.4 to 2 parts by weight.

If the moisture-proof insulating coating material of the present invention does not contain the compound (D) having a structure as shown in the formula (I), the weather-resistant uniformity of the obtained moisture-proof insulating coating material is not good.

In a preferred embodiment of the present invention, the moisture-proof insulating coating according to the present invention further comprises a modified polyoxyalkylene (E) having the structure of the formula (II);

In the formula (II), n represents an integer of 10 to 200; preferably 20 to 120; p represents an integer of 0 to 9; preferably 2 to 3; and q represents an integer of 3 to 9; preferably 3 to 5.

Commercial products of the modified polyoxane (E) having the structure of the formula (II) such as KF-6001, KF-6002, KF-6003 (above manufactured by Shin-Etsu Chemical Co., Ltd.), SF8427, BY-16 -005, BY-16-006, BY-16-007, BY-16-008 (above, manufactured by Dow Corning Toray Silicone Co., Ltd.).

According to the present invention, the content of the modified polyoxyalkylene (E) having the structure of the formula (II) is preferably 100 parts by weight based on the amount of the block copolymer resin (A) used, and the modified polyoxane ( D) is used in an amount of 0.1 to 1 part by weight, preferably 0.13 to 0.9 part by weight, more preferably 0.15 to 0.8 part by weight. Quantities.

When the modified polyoxyalkylene (E) having the structure of the formula (II) is used, the weathering uniformity can be further improved.

The moisture-proof insulating coating according to the present invention preferably further contains an additive (F) 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 manufactured by a product such as Mitsubishi Chemical Corporation (trade name: 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 according to the present invention comprises the block copolymer resin (A) and the adhesive resin (B) having the formula (I). The structural compound (D), the modified polyoxane (E) having the structure of the formula (II), and the additive (F) are uniformly dispersed in the solvent (C), and stirred in a stirrer for 3 to 24 hours to a solid form. The parts are dissolved and mixed to form a liquid moisture-proof insulating coating. Generally, the viscosity of the moisture-proof insulating coating is based on the coating property and volatilization of those having ordinary knowledge in the technical field to which the present invention pertains. Adjusted for properties such as sex, when the moisture-proof insulating coating has a viscosity of 0.1 to 30 Pa. When 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, 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.

<Synthesis Example>

<Preparation of Block Copolymer Resin (A)>

In the following synthesis examples, the hydrogenation catalyst is prepared in the following manner: One liter of cyclohexane which has been dried and purified is added to the vessel, and 100 millimolar of bis(η5-cyclopentadiene) titanium dichloride is added, and while stirring, three additional 200 millimoles are added. A solution of methyl aluminum in n-hexane to obtain a reaction solution. 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 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 rate of 50%.

<Synthesis Examples 2 to 9>

Synthesis Examples 2 to 9 The block copolymer resins (A-2 to A-9) were prepared in the same manner as in Synthesis Example 1, except that the vinyl aromatic monomer and the conjugated diene were changed. The amount of the monomer used, the amount of hydrogen used, and the hydrogenation reaction conditions are shown in Table 1.

S styrene polymer block

B Butadiene Polymer Block

S/B copolymer block of styrene and butadiene

<moisture-proof insulating coating>

<Example 1>

100 parts by weight of the block copolymer resin (A-1) obtained in the above Synthesis Example, 20 parts by weight of the adhesive resin (B-1) shown in Table 2, and a compound having a structure represented by the formula (I) D-1) 0.3 parts by weight, 0.4 parts by weight of the additive (F-1), 200 parts by weight of a solvent (C-1), and stirred in a stirrer for 16 hours until the solid portion is dissolved and mixed, and then prepared to prevent moisture The insulating coating material was evaluated by the following measurement evaluation methods, and the results are shown in Table 2.

<Examples 2 to 11>

The manufacturing method of the first embodiment is different from that of the block copolymer resin (A), Adhesive resin (B), compound (D) having a structure represented by formula (I), solvent (C), modified polyoxyalkylene (E) having a structure of formula (II) and additive (F) The type and amount of use, 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 resin (A), the adhesive resin (B), the compound (D) having the structure represented by the formula (I), the solvent (C), The type and amount of the modified polyoxane (E) having the structure of the formula (II) and the additive (F) are shown in Table 3.

Evaluation method:

Weathering uniformity

Apply a 100mm x 100mm coating on a rectangular glass substrate of 100mm x 100mm with a dispenser (ES-300SR), and let it stand for 120 minutes. The film was cut into 10 10 mm x 100 mm coatings with a knife, and then placed in a constant temperature and humidity machine (manufactured by Terchy, model MHE-408RL) at a temperature of 40 ° C and a humidity of 90% for 20 hours, and the direction of the vertical substrate was 10 cm / For the speed of s, 10 coating films were respectively pulled up, and the number of tearing and no breakage of each coating film was calculated, and evaluated according to the following criteria:

◎: 10≧ completed tearing without breaking the number>8

○: 8≧ completed tearing without breaking number>5

△: 5≧ complete tearing without breaking number> 2

×: 2≧ completed tearing without breaking the number ≧0

B-1 KE311 Arakawa Chemical Co., Ltd.)

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

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

C-1 cyclohexane

C-2 methylcyclohexane

C-3 ethylcyclohexane

D-1 PF-636 (manufactured by OMNOVA)

D-2 PF-6320 (manufactured by OMNOVA)

D-3 PF-656 (manufactured by OMNOVA)

D-4 PF-6520 (manufactured by OMNOVA)

E-1 SF8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.)

E-2 KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)

E-3 BY-16-005 (manufactured by Dow Corning Toray Silicone Co., Ltd.)

F-1 fluoro oil

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

F-3 C.I.pigment black 7

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

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

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

C-1 cyclohexane

C-2 methylcyclohexane

C-3 ethylcyclohexane

D-1 PF-636 (manufactured by OMNOVA)

D-2 PF-6320 (manufactured by OMNOVA)

D-3 PF-656 (manufactured by OMNOVA)

D-4 PF-6520 (manufactured by OMNOVA)

E-1 SF8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.)

E-2 KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)

E-3 BY-16-005 (manufactured by Dow Coming Toray Silicone Co., Ltd.) Made)

F-1 fluoro oil

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

F-3 C.I.pigment black 7

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 (11)

A moisture-proof insulating coating comprising: at least one block copolymer 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 compound (D) having a structure as shown in formula (I) In the formula (I), the A ₁ groups each independently represent a fluorinated alkyl group having a carbon number of 1 to 4, the A ₂ groups each independently represent a methyl group or an ethyl group, and m represents an integer of 2 to 100. The moisture-proof insulating coating according to claim 1, wherein the conjugated diene polymer block has a hydrogenation ratio of from 50 to 100 mol%. The moisture-proof insulating coating according to claim 1, wherein the adhesive resin (B) is used in an amount of 20 to 200 parts by weight based on 100 parts by weight of the block copolymer resin (A); C) is used in an amount of from 200 to 2000 parts by weight; and the compound (D) having a structure represented by the formula (I) is used in an amount of from 0.3 to 3 parts by weight. The moisture-proof insulating coating according to claim 1, wherein the moisture-proof insulating coating further comprises a modified polyoxyalkylene (E) having the structure of the formula (II); n represents an integer of 10 to 200; p represents an integer of 0 to 9; and q represents an integer of 3 to 9. The moisture-proof insulating coating according to claim 4, wherein the amount of the modified polyoxane (E) having the structure of the formula (II) is used based on 100 parts by weight of the block copolymer resin (A). It is 0.1 to 1 part by weight. The moisture-proof insulating coating according to claim 1, wherein the block copolymer resin (A) has a number average molecular weight of from 10,000 to 200,000. A method of producing a moisture-proof insulating film comprising coating a carrier with the moisture-proof insulating coating according to any one of claims 1 to 6. The method of claim 7, wherein the carrier is an electronic component. A moisture-proof insulating film produced by the method according to claim 7 or 8. An electronic component comprising the moisture-proof insulating film according to claim 9. 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 6 to provide the moisture-proof insulating film.