WO2012053483A1 - 防湿絶縁材料 - Google Patents
防湿絶縁材料 Download PDFInfo
- Publication number
- WO2012053483A1 WO2012053483A1 PCT/JP2011/073846 JP2011073846W WO2012053483A1 WO 2012053483 A1 WO2012053483 A1 WO 2012053483A1 JP 2011073846 W JP2011073846 W JP 2011073846W WO 2012053483 A1 WO2012053483 A1 WO 2012053483A1
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- WO
- WIPO (PCT)
- Prior art keywords
- moisture
- insulating material
- proof insulating
- solvent
- styrene
- Prior art date
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- 0 C*CCNC(C)(*)* Chemical compound C*CCNC(C)(*)* 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N CC(C)(C)c1cc(C)cc(C(C)(C)C)c1O Chemical compound CC(C)(C)c1cc(C)cc(C(C)(C)C)c1O NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0133—Elastomeric or compliant polymer
Definitions
- the present invention relates to a moisture-proof insulating material for an electronic component excellent in workability and quick drying property, and an electronic component insulated by the moisture-proof insulating material.
- coating with an insulating film is performed for the purpose of protecting exposed metal parts such as mounting circuit boards and electrodes from moisture, dust, corrosive gas, and the like.
- This coating material includes types such as an ultraviolet curable type, a moisture curable type, and a solvent dry type, and acrylic resin, silicone resin, styrene block copolymer resin, and the like are used, respectively.
- Moisture-curing coating materials are excellent in moisture resistance of silicone resin itself, but have moisture permeability, so there is a problem that a thick coating material must be applied to protect the metal of circuits and electrodes. is there.
- UV curable coating materials are widely used because they can be cured in a short time and have excellent productivity.
- an ultraviolet curable coating material for example, a urethane-modified acrylate compound derived from a polyolefin polyol described in Patent Document 1 or a polycarbonate polyol described in Patent Document 2 is known.
- Patent Document 3 discloses a composition comprising a styrene-based thermoplastic elastomer, a tackifier, and toluene.
- a highly toxic solvent such as toluene.
- Patent Documents 4 and 5 disclose a composition comprising a styrene-based thermoplastic elastomer, a tackifier, a silane coupling agent, and ethylcyclohexane.
- a solvent containing ethylcyclohexane as a main component if the solid content concentration is increased in order to increase the drying property, the viscosity of the composition increases, and as a result, workability (ie, potting performance) decreases.
- the solvent-drying coating material does not involve a curing reaction, the necessary physical properties must be expressed only by coating and drying, and the molecular weight of the resin must be increased. However, as the molecular weight of the resin increases, the viscosity of the coating material increases and workability decreases. Alternatively, if the coating material is diluted to ensure workability, the thickness of the coating film after application / drying may be reduced, resulting in inferior moisture resistance. Since it took a long time, there was a problem that productivity decreased.
- the solvent-drying type coating material be transferred to the next process in about 3 minutes after application, and quick drying is required.
- drying is too fast, problems such as clogging of the syringe tip at the time of potting occur, and therefore an appropriate drying property is required.
- an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or more and less than 110 ° C. in a solvent-drying coating material containing a styrene-based thermoplastic elastomer.
- a solvent-drying coating material containing a styrene-based thermoplastic elastomer By using it as a main component of the solvent, it has been found that an excellent moisture-proof insulating film having a low viscosity and a sufficient solid content concentration and exhibiting quick drying properties can be obtained, and the present invention has been completed.
- the present invention (I) is a moisture-proof insulating material containing a styrenic thermoplastic elastomer, a tackifier, and a solvent, wherein the solvent has an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C. It is a moisture-proof insulating material characterized by including.
- the present invention (II) is an electronic component that has been insulated using the moisture-proof insulating material described in the present invention (I).
- a moisture-proof insulating material including a styrene-based thermoplastic elastomer, a tackifier, and a solvent, wherein the solvent includes an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C.
- the solvent includes an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C.
- Moisture-proof insulating material [2] The moisture-proof insulating material according to [1], wherein the solvent further includes an aliphatic hydrocarbon solvent having a boiling point of 110 ° C. or higher and lower than 140 ° C.
- the moisture-proof insulating material contained in the moisture-proof insulating material to the aliphatic hydrocarbon solvent having a boiling point of 110 ° C. or higher and lower than 140 ° C. is 50:50.
- the total amount of the styrene-based thermoplastic elastomer and the tackifier is 20 to 40% by mass and the total amount of the solvent is 60 to 80% by mass with respect to the total mass of the moisture-proof insulating material.
- the moisture-proof insulating material as described in 1.
- the styrenic thermoplastic elastomer is selected from the group consisting of a styrene-butadiene block copolymer elastomer, a styrene-isoprene block copolymer elastomer, a styrene-ethylene / butylene block copolymer elastomer, and a styrene-ethylene / propylene block copolymer elastomer.
- the moisture-proof insulating material according to any one of [1] to [6], which is at least one selected.
- the content of structural units derived from styrene contained in the styrenic thermoplastic elastomer is 15 to 50% by mass based on the total amount of the styrenic thermoplastic elastomer [1] to [7]
- the moisture-proof insulating material of the present invention (I) has a low viscosity and a sufficient solid content, and is excellent in workability, adhesion to a substrate, moisture-proof, and insulation reliability. By processing, it is possible to obtain a highly moisture-proof and insulated electronic component.
- the present invention will be specifically described below. First, the moisture-proof insulating material of the present invention (I) will be described.
- the present invention (I) is a moisture-proof insulating material containing a styrene thermoplastic elastomer, a tackifier, and a solvent, and the solvent contains an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C.
- thermoplastic elastomer described in the present specification is flowable by heating and can be molded in the same manner as ordinary thermoplastics, and exhibits rubber elasticity (that is, remarkable elastic recovery) at room temperature. This is a high-molecular compound with properties. Details are described in “Edition Committee for Physicochemical Dictionary”, “All about Thermoplastic Elastomers”, first edition, first edition, published by Industrial Research Co., Ltd., December 20, 2003. ing.
- thermoplastic elastomer described in the present specification means a thermoplastic elastomer having a structural unit derived from styrene in the molecular structure.
- the styrene thermoplastic elastomer used for the moisture-proof insulating material of the present invention (I) is excellent in moisture resistance and insulation reliability.
- styrenic thermoplastic elastomers include styrene-butadiene block copolymer elastomers, styrene-isoprene block copolymer elastomers, styrene-ethylene / butylene block copolymer elastomers, styrene-ethylene / propylene block copolymer elastomers, and the like. it can.
- styrenic thermoplastic elastomers include D1101, D1102, D1155, DKX405, DKX410, DKX415, D1192, D1161, D1171, G1652, and G1730 (above, Kraton Polymer Co., Ltd.), Tufprene (registered trademark) A TUFPRENE (registered trademark) 125, TUFPRENE (registered trademark) 126S, TUFTEC (registered trademark) H1141, TUFTECH (registered trademark) H1041, TUFTECH (registered trademark) H1043, TUFTEC (registered trademark) H1052, (above, Asahi Kasei Chemicals Corporation Manufactured). These can be used alone or in combination of two or more.
- the content of structural units derived from styrene contained in the styrene-based thermoplastic elastomer is preferably 15 to 50% by mass, more preferably 18 to 45% by mass, based on the total amount of the styrene-based thermoplastic elastomer. More preferably, it is 19 to 43% by mass.
- the content of the structural unit derived from styrene contained in the styrene-based thermoplastic elastomer is less than 15% by mass with respect to the total amount of the styrene-based thermoplastic elastomer, the cohesive force of the elastomer may be insufficient, which is preferable. That's not true.
- the tackifier used in the present invention is a substance that is added to a polymer compound typified by an elastomer having rubber elasticity to give an adhesive function.
- the molecular weight is much smaller and is generally a compound in an oligomer region having a molecular weight of several hundred to several thousand, and has a property of not exhibiting rubber elasticity by itself in a glass state at room temperature.
- tackifier a petroleum resin tackifier, a terpene resin tackifier, a rosin resin tackifier, a coumarone indene resin tackifier, a styrene resin tackifier, or the like can be generally used.
- Examples of petroleum resin tackifiers include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and hydrogenated products thereof. Of the modified product.
- the synthetic petroleum resin may be C5 or C9.
- terpene resin tackifier examples include ⁇ -pinene resin, ⁇ -pinene resin, terpene-phenol resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. Many of these terpene resins are resins having no polar group.
- Rosin resin tackifiers include rosins such as gum rosin, tall oil rosin, wood rosin; hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin such as maleated rosin; rosin glycerin ester, hydrogenated rosin ester, water Examples thereof include rosin esters such as rosin glycerol ester. These rosin resins have polar groups.
- tackifiers petroleum resin tackifiers and terpene resin tackifiers are preferred. Furthermore, a petroleum resin tackifier is preferable. These tackifiers can be used alone or in combination of two or more.
- the total blending amount of the styrene-based thermoplastic elastomer and the tackifier is 20 to 40% by mass, preferably 23, based on the total mass of the moisture-proof insulating material. Is 35% by mass, more preferably 25-33% by mass. If the total amount of the styrene-based thermoplastic elastomer and the tackifier is less than 20% by mass with respect to the total mass of the moisture-proof insulating material, the thickness of the coating material becomes thin, and sufficient moisture-proof properties and film strength can be obtained. There may not be.
- the blending ratio of the styrenic thermoplastic elastomer and the tackifier is in the range of 2: 1 to 10: 1, preferably in the range of 2.5: 1 to 9.5: 1, by mass ratio.
- the range is preferably 3: 1 to 9: 1. If the blending ratio of the styrene-based thermoplastic elastomer and the tackifier is greater than 10: 1 by mass ratio, it may not be possible to develop a sufficient adhesion function, which is not preferable. On the other hand, if the blending ratio of the styrene-based thermoplastic elastomer and the tackifier is less than 2: 1 by mass ratio, the tensile (breaking) strength of the coating after application and drying may be significantly reduced.
- the moisture-proof insulating material of the present invention (I) contains an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C. as an essential component.
- the boiling point refers to the boiling point at 1 atmosphere.
- the aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C. include n-heptane (boiling point 98.4 ° C.), cyclohexane (boiling point 80.7 ° C.), methylcyclohexane (boiling point 101.1 ° C.). Etc. Of these, preferred are cyclohexane and methylcyclohexane. Most preferred is methylcyclohexane.
- the moisture-proof insulating material of the present invention (I) further includes an aliphatic hydrocarbon solvent having a boiling point of 110 ° C. or higher and lower than 140 ° C.
- an aliphatic hydrocarbon solvent having a boiling point of 110 ° C. or higher and lower than 140 ° C examples of the aliphatic hydrocarbon solvent having a boiling point of 110 ° C. or higher and lower than 140 ° C.
- n-octane (boiling point 125.7 ° C.), cis-1,2-dimethylcyclohexane (boiling point 129.7 ° C.), cis- 1,3-dimethylcyclohexane (boiling point 120.1 ° C.), cis-1,4-dimethylcyclohexane (boiling point 124.3 ° C.), trans-1,2-dimethylcyclohexane (boiling point 123.4 ° C.), trans-1, Examples thereof include 3-dimethylcyclohexane (boiling point 124.5 ° C.), trans-1,4-dimethylcyclohexane (boiling point 119.4 ° C.), ethylcyclohexane (boiling point 132 ° C.), and the like.
- cis-1,2-dimethylcyclohexane preferred are cis-1,2-dimethylcyclohexane, cis-1,3-dimethylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,2-dimethylcyclohexane, trans-1, 3-Dimethylcyclohexane, trans-1,4-dimethylcyclohexane, and ethylcyclohexane.
- ethylcyclohexane is most preferable.
- these solvents include hydrocarbon solvents having an alicyclic structure such as decahydronaphthalene, acetate esters such as n-propyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, isopropyl acetate, and ethyl acetate.
- Solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether, alcohol solvents such as ethanol, 1-propanol, 2-propanol, acetone, methyl ethyl ketone, Examples thereof include ketone solvents such as methyl isobutyl ketone and petroleum naphtha.
- the boiling point is desirably 140 ° C.
- Acetate solvents such as isopropyl acetate, ethyl acetate, and n-propyl acetate are preferred, and n-propyl acetate, isobutyl acetate, t-butyl acetate, and n-butyl acetate are more preferred.
- the total amount of the solvent containing an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C. is preferably 60 to 80% by mass, more preferably 67 to 77% by mass, based on the total mass of the moisture-proof insulating material. %, More preferably 70 to 75% by mass.
- the ratio of the aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or higher and lower than 110 ° C. to the total solvent is preferably 50 to 100% by mass.
- an aliphatic hydrocarbon solvent having a boiling point of 110 ° C. or more and less than 140 ° C. is used in combination, an aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or more and less than 110 ° C. and a boiling point of 110 ° C. or more and less than 140 ° C. are used.
- the ratio of the total amount of the aliphatic hydrocarbon solvent to the total solvent is preferably 60 to 100% by mass.
- the blending ratio is 50 by mass. : 50 to 95: 5, preferably 65:35 to 95: 5.
- the blending ratio of the aliphatic hydrocarbon solvent having a boiling point of 80 ° C. or more and less than 110 ° C. and the aliphatic hydrocarbon solvent having a boiling point of 110 ° C. or more and less than 140 ° C. is greater than 95: 5 by mass ratio, In the case of a composition having a high thermoplastic elastomer concentration, drying is too fast, the syringe of the dispenser may be clogged, and the coating solution may have spinnability, which is not preferable.
- the moisture-proof insulating material of the present invention has a viscosity at 25 ° C. of preferably 1.5 Pa ⁇ s or less, more preferably 1.1 Pa ⁇ s or less, and still more preferably 1. 0 Pa ⁇ s or less. Since it is generally applied using a dispenser, the pressure at the time of application increases when the viscosity at 25 ° C. of the moisture-proof insulating material is higher than 1.5 Pa ⁇ s in consideration of the pressure of the dispenser at the time of application. When the moisture-proof insulating material is applied by a dispenser, the spread after the application is suppressed, and as a result, the thickness after drying may be unnecessarily thick. It is not preferable.
- the viscosity described in the present specification is a value measured at 25 ° C. and a rotation speed of 20 rpm using a DV-II + Pro viscometer small sample adapter (spindle model number: SC4-31) manufactured by Brookfield.
- additives such as a leveling agent, an antifoaming agent, an antioxidant, a coloring agent, and a silane coupling agent can be used as necessary.
- the leveling agent is not particularly limited as long as it is a material having a function of improving the leveling property of the coating film surface when added.
- polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, and the like can be used. These may be used alone or in combination of two or more. 0.01 to 3 parts by mass can be added to 100 parts by mass of the moisture-proof insulating material of the present invention (I).
- the amount is less than 0.01 part by mass, the effect of adding the leveling agent may not be exhibited.
- the amount is more than 3 parts by mass, the surface of the coating film may become sticky or the insulating properties may be deteriorated depending on the type of the leveling agent used.
- the antifoaming agent is not particularly limited as long as it has an action of eliminating or suppressing bubbles generated or remaining when the moisture-proof insulating material of the present invention (I) is applied.
- antifoaming agents used in the moisture-proof insulating material of the present invention (I) include known antifoaming agents such as silicone oils, fluorine-containing compounds, polycarboxylic acid compounds, polybutadiene compounds, and acetylenic diol compounds. .
- Silicone defoaming agents such as Toray Dow Corning Co., Ltd., Dappo SN-348 (manufactured by San Nopco), Dappo SN-354 (manufactured by San Nopco), Dappo SN-368 (manufactured by San Nopco), Acetylene such as acrylic polymer antifoaming agents such as Disparon 230HF (manufactured by Enomoto Kasei Co., Ltd.), Surfinol DF-110D (manufactured by Nissin Chemical Industry Co., Ltd.), Surfynol DF-37 (manufactured by Nissin Chemical Industry Co., Ltd.) Diol-based antifoaming agent, FA-630 (Shin-Etsu Chemical) Business Co., Ltd.), a fluorine-containing silicone-based anti-foaming agent such as, etc.
- Dappo SN-348 manufactured by San Nopco
- Dappo SN-354
- the moisture-proof insulating material of the present invention can be mentioned. These may be used alone or in combination of two or more. Usually, 0.001 to 5 parts by mass can be added to 100 parts by mass of the moisture-proof insulating material of the present invention (I). If the amount is less than 0.01 parts by mass, the effect of adding the antifoaming agent may not be exhibited. On the other hand, when the amount is more than 5 parts by mass, the surface of the coating film may become sticky or the insulating properties may be deteriorated depending on the type of antifoaming agent used.
- the colorant used in the moisture-proof insulating material of the present invention (I) is preferably an oil-soluble dye.
- Specific examples include, for example, OIL BLACK860 (manufactured by Orient Chemical Industry Co., Ltd.), OIL BLACK 803 (Orient Chemical Industry Co., Ltd.).
- OIL BLUE 2N made by Orient Chemical Co., Ltd.
- OIL BLUE 630 made by Orient Chemical Co., Ltd.
- SOT Black made by Hodogaya Chemical Co., Ltd.
- the added amount of these dyes can be 0.01 to 5 parts by mass with respect to 100 parts by mass of the moisture-proof insulating material of the present invention (I).
- an antioxidant can be used and is preferable.
- the antioxidant is not particularly limited as long as it is a compound capable of preventing thermal deterioration and discoloration of the moisture-proof insulating material of the present invention (I).
- a phenol-based antioxidant can be used.
- examples of phenolic antioxidants include compounds represented by the following formulas (1) to (11).
- a silane coupling agent can be used when a strong adhesion to a glass or metal oxide of a coating film formed by applying the moisture-proof insulating material of the present invention (I) is required.
- a silane coupling agent is an organosilicon compound having a functional group reactively bonded to an organic material and a functional group reactively bonded to an inorganic material in the molecule, and generally has a structure as shown in the following formula (12). Indicated.
- Y is a functional group reactively bonded to an organic material, and representative examples thereof include a vinyl group, an epoxy group, an amino group, a substituted amino group, a (meth) acryloyl group, a mercapto group, and the like.
- X is a functional group that reacts with an inorganic material and is hydrolyzed by water or moisture to produce silanol. This silanol reacts with the inorganic material.
- Representative examples of X include an alkoxy group, an acetoxy group, a chlorochlorine atom, and the like.
- R 1 is a divalent organic group, and R 2 represents an alkyl group.
- a represents an integer of 1 to 3
- silane coupling agent examples include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, p-styryltrimethoxysilane, p -Styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldi Toxisilane, 3-methacryloyloxyprop
- silane coupling agents preferred are N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N -(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propyl Amino group-containing silane coupling agents such as amines and N-phenyl-3-aminopropyltrimethoxysilane, mercapto group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, 3- Acryloyloxypropyltriethoxys
- Examples of commercially available products include KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.), KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KBE-903 (stock of Shin-Etsu Chemical Co., Ltd.). Company-made), Z-6062 (manufactured by Toray Dow Corning Co., Ltd.), Z-6023 (manufactured by Toray Dow Corning Co., Ltd.), and the like. These can be used alone or in combination of two or more.
- the amount of the silane coupling agent is 0.1 to 10 with respect to 100 parts by mass of the styrene thermoplastic elastomer.
- the amount is preferably part by mass, and more preferably 0.5 to 8 parts by mass.
- the present invention (II) is an electronic component that is insulated using the moisture-proof insulating material of the present invention (I).
- electronic components include microcomputers, transistors, capacitors, resistors, relays, transformers, etc., and mounting circuit boards on which these are mounted, and lead wires, harnesses, and film substrates that are joined to these electronic components. Etc. can also be included.
- the signal input part of flat panel display panels such as a liquid crystal display panel, a plasma display panel, an organic electroluminescent panel, and a field emission display panel, are also mentioned as an electronic component.
- the moisture-proof insulating material of the present invention (I) can be preferably used in IC peripheral parts such as display boards for electronic parts, panel bonding parts, and the like.
- the electronic component of the present invention (II) is manufactured by insulating the electronic component using a moisture-proof insulating material.
- a specific method for producing the electronic component of the present invention (II) first, the above-described moisture-proof insulating material is applied to the electronic component by a generally known method such as dipping, brushing, spraying, or drawing.
- the electronic component can be obtained by applying to the substrate and evaporating the organic solvent contained in the moisture-proof insulating material and drying the coating film.
- Example 1 25 g of D1155 (made by Kraton Polymer Co., Ltd., styrene content 40% by mass) as a styrene-butadiene block copolymer elastomer, and Quinton (registered trademark) D100 (aliphatic-aromatic copolymer petroleum resin made by Nippon Zeon Co., Ltd.) as a tackifier 6.1 g, 53.3 g of methylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd .: trade name: Suwaclean MCH) as a solvent, and 26.7 g of ethylcyclohexane (trade name: Maruzen Petrochemical Co., Ltd .: trade name: Suwaclean ECH) are mixed and blended. It was set as the thing D1. The viscosity of the formulation D1 at 25 ° C. was 0.85 Pa ⁇ s.
- Example 2 22.5 g of D1155 (made by Kraton Polymer Co., Ltd., styrene content 40% by mass) as a styrene-butadiene block copolymer elastomer, 5.5 g of Quinton (registered trademark) D100 (made by Nippon Zeon Co., Ltd.) as a tackifier, and methylcyclohexane as a solvent (Made by Maruzen Petrochemical Co., Ltd., trade name: Swaclean MCH), 42 g of ethylcyclohexane (Made by Maruzen Petrochemical Co., Ltd., trade name: Swaclean ECH), n-butyl acetate (Kyowa Hakko Chemical Co., Ltd., trade name: butyl acetate) -P) 8 g was mixed to make Formulation D2.
- the viscosity of the formulation D2 at 25 ° C. was 0.64 Pa ⁇ s.
- Example 3 22.5 g of D1155 (manufactured by Kraton Polymer Co., Ltd., styrene content 40 mass%) as a styrene-butadiene block copolymer elastomer, 3.0 g of Quinton (registered trademark) D100 (manufactured by Nippon Zeon Co., Ltd.) and Imabe (registered trademark) as a tackifier ) S-110 (manufactured by Idemitsu Kosan Co., Ltd., 2.5 g of dicyclopentadiene / aromatic copolymer hydrogenated petroleum resin mainly composed of C5 fraction), methylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd.) Name: Swaclean MCH (42 g), ethylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd., trade name: Swaclean ECH) 22 g, and n-butyl
- Example 4 22.5 g of D1161 (manufactured by Kraton Polymer, styrene content 15% by mass) as a styrene-isoprene block copolymer elastomer, 5.5 g of Quinton (registered trademark) D100 (manufactured by ZEON Corporation) as a tackifier, and methylcyclohexane as a solvent (Product name: Maruzen Petrochemical Co., Ltd., trade name: Suwaclean MCH) 36.0 g, Ethylcyclohexane (Product name: Maruzen Petrochemical Co., Ltd .: trade name: Suwaclean ECH), n-butyl acetate (Kyowa Hakko Chemical Co., Ltd.) (Name: butyl acetate-P) was mixed to obtain a formulation D4. The viscosity of the formulation D4 at 25 ° C. was 1.20 Pa ⁇ s.
- Example 5 25 g of D1155 (made by Kraton Polymer, styrene content 40% by mass) as a styrene-butadiene block copolymer elastomer, 6.1 g of Quinton (registered trademark) D100 (made by Nippon Zeon Co., Ltd.) as a tackifier, and methylcyclohexane (Maruzen as a solvent) 98.5 g of Petrochemical Co., Ltd. trade name: Swaclean MCH) was mixed to prepare a compound D5. The viscosity of the formulation D5 at 25 ° C. was 0.30 Pa ⁇ s.
- Comparative Example 1 20 g of D1161 (manufactured by Kraton Polymer Co., Ltd., styrene content 15% by mass) as a styrene-isoprene block copolymer elastomer, and Imabe (registered trademark) P-100 (manufactured by Idemitsu Kosan Co., Ltd., based on C5 fraction as a tackifier) Hydrogenated petroleum resin of dicyclopentadiene / aromatic copolymer system, P grade has a hydrogenation (hydrogenation) rate higher than S grade) 10 g, N-2- (aminoethyl) -3 as silane coupling agent -Compound 1 was prepared by mixing 1 g of aminopropylmethyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and 70 g of ethylcyclohexane (trade name: Suwaclean ECH, manufactured by
- Comparative Example 2 20 g of G1652 (manufactured by Kraton Polymer, styrene content 30% by mass) and 20 g of styrene-butadiene block copolymer elastomer D1101 (manufactured by Kraton Polymer, 31% by mass of styrene) as a styrene-ethylene / butylene block copolymer elastomer, tackifier 10 g of I-MAB (registered trademark) P-100 (manufactured by Idemitsu Kosan Co., Ltd., dicyclopentadiene / aromatic copolymer hydrogenated petroleum resin mainly containing C5 fraction), N-2- as a silane coupling agent 1 g of (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and 70 g of e
- Comparative Example 3 25 g of D1155 (made by Kraton Polymer Co., Ltd., styrene content 40% by mass) as a styrene-butadiene block copolymer elastomer, and Quinton (registered trademark) D100 (aliphatic-aromatic copolymer petroleum resin made by Nippon Zeon Co., Ltd.) as a tackifier 6.1 g and 80 g of ethylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd., trade name: SWACLEAN ECH) as a solvent were mixed to obtain a formulation E3. The viscosity of the formulation E3 at 25 ° C. was 0.88 Pa ⁇ s.
- Comparative Example 4 22.5 g of D1155 (made by Kraton Polymer Co., Ltd., styrene content 40% by mass) as a styrene-butadiene block copolymer elastomer, 5.5 g of Quinton (registered trademark) D100 (made by Nippon Zeon Co., Ltd.), and ethylcyclohexane as a solvent (Maruzen Petrochemical Co., Ltd., trade name: Swaclean ECH) 64 g and n-butyl acetate (Kyowa Hakko Chemical Co., Ltd., trade name: butyl acetate-P) 8 g were mixed to obtain a blend E4. The viscosity in 25 degreeC of the compound E4 was 0.66 Pa.s.
- Comparative Example 5 22.5 g of D1155 (manufactured by Kraton Polymer Co., Ltd., styrene content 40 mass%) as a styrene-butadiene block copolymer elastomer, 3.0 g of Quinton (registered trademark) D100 (manufactured by Nippon Zeon Co., Ltd.) and Imabe (registered trademark) as a tackifier ) S-110 (manufactured by Idemitsu Kosan Co., Ltd., 2.5 g of dicyclopentadiene / aromatic copolymer hydrogenated petroleum resin mainly containing C5 fraction), ethylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd.) Name: Swaclean ECH) 64 g and n-butyl acetate (trade name: butyl acetate-P, manufactured by Kyowa Hakko Chemical Co., Ltd.) 8 g were mixed to obtain
- Comparative Example 6 22.5 g of D1161 (manufactured by Kraton Polymer, styrene content: 15% by mass) as a styrene-isoprene block copolymer elastomer, 5.5 g of Quinton (registered trademark) D100 (manufactured by ZEON Corporation) as a tackifier, and ethylcyclohexane as a solvent (Maruzen Petrochemical Co., Ltd., trade name: Swaclean ECH) 67 g and n-butyl acetate (Kyowa Hakko Chemical Co., Ltd., trade name: butyl acetate-P) were mixed to obtain a formulation E6.
- the viscosity in 25 degreeC of the compound E6 was 1.22 Pa.s.
- Comparative Example 7 25 g of D1155 (made by Kraton Polymer Co., Ltd., styrene content 40% by mass) as a styrene-butadiene block copolymer elastomer, 6.1 g of Quinton (registered trademark) D100 (made by Nippon Zeon Co., Ltd.) as a tackifier, and ethylcyclohexane (Maruzen) as a solvent 98.5 g of Petrochemical Co., Ltd. trade name: SWACLEAN ECH) was mixed to prepare a compound E7. The viscosity in 25 degreeC of the compound E7 was 0.32 Pa.s.
- the viscosity was measured by the following method. Using a sample of 10 mL, using a viscometer (manufactured by Brookfield, model: DV-II + Pro), using a small sample adapter and a spindle of model number C4-31, at a temperature of 25.0 ° C. and a rotation speed of 20 rpm The value when the viscosity became almost constant was measured.
- tack free time was evaluated by the following method.
- Formulations D1 to D5 and Formulations E1 and E3 to E7 were applied on a glass using a dispenser so that the thickness after drying was about 130 ⁇ m. After coating, the coating surface was checked for stickiness every 30 seconds. It was confirmed by finger touch. The first time when stickiness disappeared was defined as tack-free time.
- the tack free time is an index of quick drying property, and the shorter the free time, the better.
- the formulation E2 was too high in viscosity and could not be applied with a dispenser.
- the adhesive force is fixed to a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE) so that the cured film peeled off from the glass plate forms an angle of 90 degrees, and the initial distance between chucks is 2.5 cm.
- the 90-degree peel strength was measured at 23 ° C. at a speed of 50 mm / min. The results are shown in Tables 1 and 2.
- “X” in “peelability” means that the cured film was cut during measurement of 90-degree peel strength
- ⁇ in “peelability” means 90-degree peel strength. It means that the cured film could be peeled off without being cut during the measurement.
- a certain level of adhesion is necessary to maintain moisture resistance and insulation reliability, but if there is a defect in the LCD panel pre-shipment inspection, the glass panel will be reused (the flexible wiring board will be discarded).
- the film can be peeled off without breaking the coating film.
- the board (henceforth a "polyimide film sticking epoxy resin board") which bonded the surface in which this compound of polyimide film was not apply
- the epoxy resin board containing glass cloth with the double-sided adhesive tape was produced.
- the adhesive force is fixed to a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE) so that the cured film peeled off from the polyimide resin-attached epoxy resin plate forms an angle of 90 degrees.
- peel strength was determined by measuring 90 ° at a speed of 50 mm / min at 23 ° C. and 2.5 cm. The results are shown in Tables 1 and 2.
- X in “peelability” means that the cured film was cut during measurement of 90-degree peel strength
- ⁇ in “peelability” means 90-degree peel strength. It means that the cured film could be peeled off without being cut during the measurement.
- a self-supporting film was formed by recoating the compounds D1 to D5 and the compounds E1 and E3 to E7 on a Teflon (registered trademark) plate using a bar coater so that the thickness after drying was about 130 ⁇ m. Produced. Using a moisture permeable cup jig (manufactured by Tester Sangyo Co., Ltd.), the moisture permeability of these free-standing films was measured in accordance with JIS Z0208. The results are shown in Tables 1 and 2. The test conditions for moisture permeability were a temperature of 40 ° C., a humidity of 90% RH, and 24 hours.
- a substrate having a fine comb pattern shape described in JPCA-ET01, manufactured by etching a flexible copper-clad laminate (manufactured by Sumitomo Metal Mining Co., Ltd., grade name: Esperflex, copper thickness: 8 ⁇ m, polyimide thickness: 38 ⁇ m) (Copper wiring width / copper wiring width 15 ⁇ m / 15 ⁇ m)
- a flexible wiring board having been subjected to tin plating was applied with the compounds D1 to D5, E1, and E3 to E7 so that the thickness after drying was 100 ⁇ m. After being kept at room temperature for 10 minutes, it was dried at 70 ° C. for 1.5 hours.
- composition D1 to D5, E1, and E3 to E7 were each dried to a thickness of 100 ⁇ m on a patterned electrode in which a comb-shaped ITO wiring having a line / space of 40 ⁇ m / 10 ⁇ m was formed on a glass substrate. After coating and holding at room temperature for 10 minutes, it was dried at 70 ° C. for 1.5 hours. Using this test piece, a bias voltage of 30 V was applied, and a constant temperature and humidity test under the conditions of a temperature of 85 ° C. and a humidity of 85% RH was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV). Tables 1 and 2 show the resistance values at the initial start of the temperature and humidity test and at 1000 hours after the start.
- the compounds D1 to D5 are excellent in drying property, adhesion to a glass substrate, and long-term insulation reliability, and have a viscosity of 1.5 Pa ⁇ s or less (in particular, D1 to D5). It can be seen that the viscosity of D3 and D5 is as low as less than 1.0 Pa ⁇ s.
- the compound E2 has high viscosity and poor handling properties, and the compounds E1, E3 to E7 are inferior in drying speed, and the composition of the present invention is a moisture-proof insulating material to be applied using a dispenser. It turns out that it is suitable for.
- the moisture-proof insulating material of the present invention is a composition that can exhibit low viscosity and quick drying properties, and by coating with this moisture-proof insulating material, it is possible to obtain an electronic component that is highly moisture-proof and insulated.
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Abstract
Description
本発明(II)は、本発明(I)に記載の防湿絶縁材料を用いて絶縁処理された電子部品である。
[1] スチレン系熱可塑性エラストマー、粘着付与剤、および溶媒を含む防湿絶縁材料であって、前記溶媒が80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒を含むことを特徴とする防湿絶縁材料。
[2] 前記溶媒が、さらに110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒を含むことを特徴とする[1]に記載の防湿絶縁材料。
[3] 防湿絶縁材料中に含まれる80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒と110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒の質量比が50:50~95:5の範囲であることを特徴とする[2]に記載の防湿絶縁材料。
[4] 80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒が、シクロヘキサンおよび/またはメチルシクロヘキサンであることを特徴とする[1]~[3]のいずれかに記載の防湿絶縁材料。
[5] 110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒が、cis-1,2-ジメチルシクロヘキサン、cis-1,3-ジメチルシクロヘキサン、cis-1,4-ジメチルシクロヘキサン、trans-1,2-ジメチルシクロヘキサン、trans-1,3-ジメチルシクロヘキサン、trans-1,4-ジメチルシクロヘキサンおよびエチルシクロヘキサンからなる群から選ばれる少なくとも1種であることを特徴とする[2]~[4]のいずれかに記載の防湿絶縁材料。
[6] 防湿絶縁材料の総質量に対して、スチレン系熱可塑性エラストマーと粘着付与剤の総量が20~40質量%であり、溶媒の総量が60~80質量%であり、防湿絶縁材料中に含まれるスチレン系熱可塑性エラストマーと粘着付与剤の質量比が2:1~10:1の範囲であり、防湿絶縁材料中に含まれる80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒が、溶媒の総量に対して50質量%以上であり、さらに、防湿絶縁材料の25℃での粘度が1.5Pa・s以下であることを特徴とする[1]~[5]のいずれかに記載の防湿絶縁材料。
[7] スチレン系熱可塑性エラストマーが、スチレン-ブタジエンブロック共重合エラストマー、スチレン-イソプレンブロック共重合エラストマー、スチレン-エチレン/ブチレンブロック共重合エラストマー、およびスチレン-エチレン/プロピレンブロック共重合エラストマーからなる群から選ばれる少なくとも1種であることを特徴とする[1]~[6]のいずれかに記載の防湿絶縁材料。
[8] スチレン系熱可塑性エラストマー中に含まれるスチレン由来の構造単位の含量が、スチレン系熱可塑性エラストマーの総量に対して15~50質量%であることを特徴とする[1]~[7]のいずれかに記載の防湿絶縁材料。
[9] 粘着付与剤が、石油系樹脂粘着付与剤であることを特徴とする[1]~[8]のいずれかに記載の防湿絶縁材料。
[10] [1]~[9]のいずれかに記載の防湿絶縁材料を用いて絶縁処理された電子部品。
まず、本発明(I)の防湿絶縁材料について説明する。
本発明(I)は、スチレン系熱可塑性エラストマー、粘着付与剤、および溶媒を含む防湿絶縁材料であって、前記溶媒が80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒を含むことを特徴とする防湿絶縁材料である。
これらの粘着付与剤は、それぞれ単独で、あるいは2種以上を組み合わせて使用することができる。
スチレン系熱可塑性エラストマーと粘着付与剤の配合比率が、質量比で、10:1より大きくなると、十分な粘着機能を発現することができない場合があり好ましくない。また、スチレン系熱可塑性エラストマーと粘着付与剤の配合比率が、質量比で、2:1より小さくなると、塗布乾燥後の皮膜の引張(破断)強度が、著しく低下してしまうことがある。その結果、不具合が発生した部品を除去して再度新たな部品を接合し直すというリペア工程の際に行われる防湿絶縁皮膜を引き剥がして除去する際に、防湿絶縁皮膜が切断されて1枚ものの膜として除去できなくなる場合が生じてしまい、好ましくない。
80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒としては、例えば、n-ヘプタン(沸点98.4℃)、シクロヘキサン(沸点80.7℃)、メチルシクロヘキサン(沸点101.1℃)等を挙げることができる。これらの中で、好ましいものとしては、シクロヘキサン、メチルシクロヘキサンである。最も好ましいものとしては、メチルシクロヘキサンである。
110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒としては、例えば、n-オクタン(沸点125.7℃)、cis-1,2-ジメチルシクロヘキサン(沸点129.7℃)、cis-1,3-ジメチルシクロヘキサン(沸点120.1℃)、cis-1,4-ジメチルシクロヘキサン(沸点124.3℃)、trans-1,2-ジメチルシクロヘキサン(沸点123.4℃)、trans-1,3-ジメチルシクロヘキサン(沸点124.5℃)、trans-1,4-ジメチルシクロヘキサン(沸点119.4℃)、エチルシクロヘキサン(沸点132℃)等を挙げることができる。これらの中で、好ましいものとしては、cis-1,2-ジメチルシクロヘキサン、cis-1,3-ジメチルシクロヘキサン、cis-1,4-ジメチルシクロヘキサン、trans-1,2-ジメチルシクロヘキサン、trans-1,3-ジメチルシクロヘキサン、trans-1,4-ジメチルシクロヘキサン、エチルシクロヘキサンであり、入手の容易さを考慮すると、エチルシクロヘキサンが最も好ましい。
80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒の全溶媒に占める割合は、50~100質量%が好ましい。
また110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒を併用する場合には、80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒と110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒との合計量の全溶媒に占める割合は、60~100質量%が好ましい。
酸化防止剤としては、本発明(I)の防湿絶縁材料の熱劣化や変色を防止する作用のある化合物であれば特に制限は無く、例えば、フェノール系酸化防止剤等を使用することができる。
フェノール系酸化防止剤としては、例えば、下記式(1)~式(11)のような化合物を挙げることができる。
シランカップリング剤とは、分子内に有機材料と反応結合する官能基、および無機材料と反応結合する官能基を同時に有する有機ケイ素化合物で、一般的にその構造は下記式(12)のように示される。
また、液晶ディスプレイパネル、プラズマディスプレイパネル、有機エレクトロルミネッセンスパネル、フィールドエミッションディスプレイパネル等のフラットパネルディスプレイパネルの信号入力部等も、電子部品として挙げられる。特に、電子部品用ディスプレイ用基板等のIC周辺部やパネル張り合わせ部等に、本発明(I)の防湿絶縁材料を好ましく使用できる。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)25g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製脂肪族-芳香族共重合系石油樹脂)6.1g、溶媒としてメチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンMCH)53.3g、エチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)26.7gを混合し、配合物D1とした。
配合物D1の25℃での粘度は、0.85Pa・sであった。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)22.5g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)5.5g、溶媒としてメチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンMCH)42g、エチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)22g、酢酸n-ブチル(協和発酵ケミカル株式会社製 商品名:酢酸ブチル-P)8gを混合し、配合物D2とした。
配合物D2の25℃での粘度は、0.64Pa・sであった。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)22.5g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)3.0gおよびアイマーブ(登録商標)S-110(出光興産株式会社製、C5留分を主成分とするジシクロペンタジエン/芳香族共重合系の水添石油樹脂)2.5g、溶媒としてメチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンMCH)42g、エチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)22g、酢酸n-ブチル(協和発酵ケミカル株式会社製 商品名:酢酸ブチル-P)8gを混合し、配合物D3とした。
配合物D3の25℃での粘度は、0.66Pa・sであった。
スチレン-イソプレンブロック共重合エラストマーとしてD1161(クレイトンポリマー社製,スチレン含量15質量%)22.5g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)5.5g、溶媒としてメチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンMCH)36.0g、エチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)31.0g、酢酸n-ブチル(協和発酵ケミカル株式会社製 商品名:酢酸ブチル-P)5gを混合し、配合物D4とした。
配合物D4の25℃での粘度は、1.20Pa・sであった。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)25g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)6.1g、溶媒としてメチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンMCH)98.5gを混合し、配合物D5とした。
配合物D5の25℃での粘度は、0.30Pa・sであった。
スチレン-イソプレンブロック共重合エラストマーとしてD1161(クレイトンポリマー社製,スチレン含量15質量%)20g、粘着付与剤としてアイマーブ(登録商標)P-100(出光興産株式会社製、C5留分を主成分とするジシクロペンタジエン/芳香族共重合系の水添石油樹脂、PグレードはSグレードよりも水素化(水添)率が高いグレード)10g、シランカップリング剤としてN-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン(信越化学工業株式会社製 商品名:KBM-602)1g、溶媒としてエチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)70gを混合し、配合物E1とした。
配合物E1の25℃での粘度は、1.11Pa・sであった。
スチレン-エチレン/ブチレンブロック共重合エラストマーとしてG1652(クレイトンポリマー社製,スチレン含量30質量%)20gおよびスチレン-ブタジエンブロック共重合エラストマーD1101(クレイトンポリマー社製,スチレン含量31質量%)20g、粘着付与剤としてアイマーブ(登録商標)P-100(出光興産株式会社製、C5留分を主成分とするジシクロペンタジエン/芳香族共重合系の水添石油樹脂)10g、シランカップリング剤としてN-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン(信越化学工業株式会社製 商品名:KBM-602)1g、溶媒としてエチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)70gを混合し、配合物E2とした。
配合物E2の25℃での粘度は高すぎて、前記の粘度測定条件で測定することができなかった。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)25g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製脂肪族-芳香族共重合系石油樹脂)6.1g、溶媒としてエチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)80gを混合し、配合物E3とした。
配合物E3の25℃での粘度は、0.88Pa・sであった。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)22.5g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)5.5g、溶媒としてエチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)64g、酢酸n-ブチル(協和発酵ケミカル株式会社製 商品名:酢酸ブチル-P)8gを混合し、配合物E4とした。
配合物E4の25℃での粘度は、0.66Pa・sであった。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)22.5g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)3.0gおよびアイマーブ(登録商標)S-110(出光興産株式会社製、C5留分を主成分とするジシクロペンタジエン/芳香族共重合系の水添石油樹脂)2.5g、溶媒としてエチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)64g、酢酸n-ブチル(協和発酵ケミカル株式会社製 商品名:酢酸ブチル-P)8gを混合し、配合物E5とした。
配合物E5の25℃での粘度は、0.68Pa・sであった。
スチレン-イソプレンブロック共重合エラストマーとしてD1161(クレイトンポリマー社製,スチレン含量15質量%)22.5g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)5.5g、溶媒としてエチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)67g、酢酸n-ブチル(協和発酵ケミカル株式会社製 商品名:酢酸ブチル-P)5gを混合し、配合物E6とした。
配合物E6の25℃での粘度は、1.22Pa・sであった。
スチレン-ブタジエンブロック共重合エラストマーとしてD1155(クレイトンポリマー社製,スチレン含量40質量%)25g、粘着付与剤としてクイントン(登録商標)D100(日本ゼオン株式会社製)6.1g、溶媒としてエチルシクロヘキサン(丸善石油化学株式会社製 商品名:スワクリーンECH)98.5gを混合し、配合物E7とした。
配合物E7の25℃での粘度は、0.32Pa・sであった。
上記の組成により調製した配合物D1~D5およびE1、E3~E7の特性を、以下に示す方法により評価した。結果を表1および表2に示す。
粘度は以下の方法により測定した。
試料10mLを使用して、粘度計(Brookfield社製、型式:DV-II+Pro)を用いて、少量サンプルアダプターおよび型番C4-31のスピンドルを使用し、温度25.0℃、回転数20rpmの条件で粘度がほぼ一定になったときの値を測定した。
タックフリータイムは以下の方法により評価した。
配合物D1~D5および配合物E1、E3~E7をそれぞれガラス上に乾燥後の厚みが約130μmになるようにディスペンサーを用いて塗布し、塗布後、塗膜表面のべたつきの有無を30秒ごとに指触により確認した。べたつきが無くなった最初の時間をタックフリータイムとした。
タックフリータイムは速乾燥性の指標であり、短いほど好ましい。
なお、配合物E2は、粘度が高すぎて、ディスペンサーでの塗布ができなかった。
ガラスへの密着性は以下の方法により評価した。
配合物D1~D5および配合物E1、E3~E7を、それぞれガラス上に乾燥後の厚みが130μmになるよう塗布し、室温で10分間保持した後に、70℃で0.5時間乾燥した後、室温で12時間放置した。これらの塗膜について、評価試験用の硬化膜の一端のみを剥離して、幅2.5mmの接着力測定用試験片を作製した。接着力は、ガラス板と剥離した硬化フィルムが90度の角度を成すように引張り試験機(株式会社島津製作所製、EZ Test/CE)に固定し、最初のチャック間距離を2.5cmとし、23℃において50mm/minの速度で90度引き剥がし強さを測定して求めた。結果を表1および表2に示す。
また、「引き剥がし性」における×印とは、90度引き剥がし強さの測定中に硬化膜が切れたことを意味し、「引き剥がし性」における○印とは、90度引き剥がし強さの測定中に硬化膜が切れずに剥離できたことを意味する。
ある程度の密着性は、防湿性、絶縁信頼性を維持するために必要であるが、LCDパネルの出荷前検査で不良がある場合には、ガラスパネルは再利用したい(フレキシブル配線板は捨てる)ので、引き剥がしたいときには、塗膜が切れることなくきれいに引き剥がしを行えることが好ましい。
ポリイミドフィルムへの密着性は以下の方法により評価した。
配合物D1~D5および配合物E1、E3~E7を、それぞれポリイミドフィルム(商品名:カプトン(登録商標)150EN、東レ・デュポン株式会社製)上に乾燥後の厚みが130μmになるよう塗布し、室温で10分間保持した後に、70℃で0.5時間乾燥した後、室温で12時間放置した。その後、このポリイミドフィルムの配合物が塗布されていない面とガラスクロス入りエポキシ樹脂板を両面接着テープで貼り合わせた板(以下、「ポリイミドフィルム貼り付けエポキシ樹脂板」と記す。)を作製した。これらの塗膜について、評価試験用の硬化膜の一端のみを剥離して、幅2.5mmの接着力測定用試験片を作製した。接着力は、ポリイミドフィルム貼り付けエポキシ樹脂板と剥離した硬化フィルムが90度の角度を成すように引張り試験機(株式会社島津製作所製、EZ Test/CE)に固定し、最初のチャック間距離を2.5cmとし、23℃において50mm/minの速度で90度引き剥がし強さを測定して求めた。結果を表1および表2に示す。
また、「引き剥がし性」における×印とは、90度引き剥がし強さの測定中に硬化膜が切れたことを意味し、「引き剥がし性」における○印とは、90度引き剥がし強さの測定中に硬化膜が切れずに剥離できたことを意味する。
配合物D1~D5および配合物E1、E3~E7を、それぞれテフロン(登録商標)板上に乾燥後の厚みが約130μmになるように、バーコーターを用いて、重ね塗りすることにより自立膜を作製した。
透湿カップ治具(テスター産業株式会社製)を使用して、これらの自立膜の透湿度を、JIS Z0208に準拠して測定した。その結果を表1および表2に記す。
なお、透湿度の試験条件は、温度40℃、湿度90%RH、24時間とした。
フレキシブル銅張り積層板(住友金属鉱山株式会社製、グレード名:エスパーフレックス、銅厚:8μm、ポリイミド厚:38μm)をエッチングして製造した、JPCA-ET01に記載の微細くし形パターン形状の基板(銅配線幅/銅配線間幅=15μm/15μm)に錫メッキ処理を施したフレキシブル配線板に、配合物D1~D5およびE1、E3~E7を、それぞれ乾燥後の厚みが100μmになるよう塗布し、室温で10分間保持した後に、70℃で1.5時間乾燥した。
この試験片を用いて、バイアス電圧30Vを印加し、温度85℃、湿度85%RHの条件での温湿度定常試験を、MIGRATION TESTER MODEL MIG-8600(IMV社製)を用いて行った。上記温湿度定常試験をスタートしてから1000時間後の抵抗値を表1および表2に記す。
ガラス基板上にライン/スペースが40μm/10μmである櫛形パターン形状のITO配線を形成したパターン電極上に、配合物D1~D5およびE1、E3~E7を、それぞれ乾燥後の厚みが100μmになるよう塗布し、室温で10分間保持した後に、70℃で1.5時間乾燥した。
この試験片を用いて、バイアス電圧30Vを印加し、温度85℃、湿度85%RHの条件での温湿度定常試験を、MIGRATION TESTER MODEL MIG-8600(IMV社製)を用いて行った。上記温湿度定常試験をスタート初期およびスタートしてから1000時間後の抵抗値を表1および表2に記す。
Claims (10)
- スチレン系熱可塑性エラストマー、粘着付与剤、および溶媒を含む防湿絶縁材料であって、前記溶媒が80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒を含むことを特徴とする防湿絶縁材料。
- 前記溶媒が、さらに110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒を含むことを特徴とする請求項1に記載の防湿絶縁材料。
- 防湿絶縁材料中に含まれる80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒と110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒の質量比が50:50~95:5の範囲であることを特徴とする請求項2に記載の防湿絶縁材料。
- 80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒が、シクロヘキサンおよび/またはメチルシクロヘキサンであることを特徴とする請求項1~3のいずれか1項に記載の防湿絶縁材料。
- 110℃以上140℃未満の沸点を有する脂肪族炭化水素系溶媒が、cis-1,2-ジメチルシクロヘキサン、cis-1,3-ジメチルシクロヘキサン、cis-1,4-ジメチルシクロヘキサン、trans-1,2-ジメチルシクロヘキサン、trans-1,3-ジメチルシクロヘキサン、trans-1,4-ジメチルシクロヘキサンおよびエチルシクロヘキサンからなる群から選ばれる少なくとも1種であることを特徴とする請求項2~4のいずれか1項に記載の防湿絶縁材料。
- 防湿絶縁材料の総質量に対して、スチレン系熱可塑性エラストマーと粘着付与剤の総量が20~40質量%であり、溶媒の総量が60~80質量%であり、防湿絶縁材料中に含まれるスチレン系熱可塑性エラストマーと粘着付与剤の質量比が2:1~10:1の範囲であり、防湿絶縁材料中に含まれる80℃以上110℃未満の沸点を有する脂肪族炭化水素系溶媒が、溶媒の総量に対して50質量%以上であり、さらに、防湿絶縁材料の25℃での粘度が1.5Pa・s以下であることを特徴とする請求項1~5のいずれか1項に記載の防湿絶縁材料。
- スチレン系熱可塑性エラストマーが、スチレン-ブタジエンブロック共重合エラストマー、スチレン-イソプレンブロック共重合エラストマー、スチレン-エチレン/ブチレンブロック共重合エラストマー、およびスチレン-エチレン/プロピレンブロック共重合エラストマーからなる群から選ばれる少なくとも1種であることを特徴とする請求項1~6のいずれか1項に記載の防湿絶縁材料。
- スチレン系熱可塑性エラストマー中に含まれるスチレン由来の構造単位の含量が、スチレン系熱可塑性エラストマーの総量に対して15~50質量%であることを特徴とする請求項1~7のいずれか1項に記載の防湿絶縁材料。
- 粘着付与剤が、石油系樹脂粘着付与剤であることを特徴とする請求項1~8のいずれか1項に記載の防湿絶縁材料。
- 請求項1~9のいずれか1項に記載の防湿絶縁材料を用いて絶縁処理された電子部品。
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- 2011-10-17 KR KR1020127033830A patent/KR101587510B1/ko not_active IP Right Cessation
- 2011-10-17 WO PCT/JP2011/073846 patent/WO2012053483A1/ja active Application Filing
- 2011-10-17 SG SG2013020557A patent/SG189028A1/en unknown
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WO2022054583A1 (ja) * | 2020-09-11 | 2022-03-17 | 日本ゼオン株式会社 | コーティング溶液 |
Also Published As
Publication number | Publication date |
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KR20130021416A (ko) | 2013-03-05 |
CA2814138A1 (en) | 2012-04-26 |
TW201233747A (en) | 2012-08-16 |
JPWO2012053483A1 (ja) | 2014-02-24 |
CN103068914A (zh) | 2013-04-24 |
CN103068914B (zh) | 2015-07-01 |
KR101587510B1 (ko) | 2016-01-21 |
SG189028A1 (en) | 2013-05-31 |
US20130178578A1 (en) | 2013-07-11 |
JP5791623B2 (ja) | 2015-10-07 |
TWI487759B (zh) | 2015-06-11 |
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