US20050075459A1 - Non-sticky water-based conformal coating material - Google Patents
Non-sticky water-based conformal coating material Download PDFInfo
- Publication number
- US20050075459A1 US20050075459A1 US10/954,273 US95427304A US2005075459A1 US 20050075459 A1 US20050075459 A1 US 20050075459A1 US 95427304 A US95427304 A US 95427304A US 2005075459 A1 US2005075459 A1 US 2005075459A1
- Authority
- US
- United States
- Prior art keywords
- acrylic resin
- coating material
- parts
- acrylate
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 27
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 28
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 238000004581 coalescence Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 18
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- -1 alkoxy acrylate Chemical compound 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- URYHQMZOXSKGRF-UHFFFAOYSA-N 2-(cyclopenten-1-yloxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CCCC1 URYHQMZOXSKGRF-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- UACBZRBYLSMNGV-UHFFFAOYSA-N 3-ethoxypropyl prop-2-enoate Chemical compound CCOCCCOC(=O)C=C UACBZRBYLSMNGV-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- H05K3/284—Applying non-metallic protective coatings for encapsulating mounted components
Definitions
- the present invention relates to a conformal coating material (hereinafter referred to as coating material) that forms an insulating moisture-proof membrane, in which cracking and peeling from the substrate tend not to occur and which does not apply excessive stress to the lead pin of electronic parts.
- coating material a conformal coating material that forms an insulating moisture-proof membrane, in which cracking and peeling from the substrate tend not to occur and which does not apply excessive stress to the lead pin of electronic parts.
- circuit boards loaded with electronic parts have come to be used in household electric products and automobiles. Also, solvent coating materials having moisture resistance and insulating properties have come to be applied, in order to protect circuit boards from sudden temperature change, humidity, water and dust.
- water-based coating materials that do not contain a solvent have been considered.
- coating materials contain 5 to 10% of a solvent.
- Young's modulus when the Young's modulus is low, the membrane remains sticky and problems occur, such as adhesion of dirt and blocking when handling.
- coating materials having less stickiness are not sufficient, as these have large Young's modulus and apply large load to the substrate. As a result, peeling of solder and deformation of the lead pin may occur, due to expansion and contraction of the membrane caused by increase and decrease in the environmental temperature.
- the present invention aims to provide a non-sticky water-based coating material that solves the above problems and forms a membrane having favorable adhesive properties, moisture resistance and insulating properties.
- Tg hard resin having high glass transition temperature
- the present invention relates to a non-sticky water-based conformal coating material comprising a resin wherein a flexible acrylic resin having glass transition temperature of at most 0° C. is the main chain and a vinyl polymer having a glass transition temperature of at least 20° C. is grafted to the flexible acrylic resin; the content of the vinyl polymer being 10 to 70% by weight based on the flexible acrylic resin.
- the coating material of the present invention is a conformal coating material that is applied to the face of a circuit board that is loaded with electronic parts, which comes into contact with the outside environment.
- conformal coating refers to a coating for providing moisture resistance and insulation of a circuit board.
- the coating material can be formed into a film at room temperature without using a coalescence, because the acrylic resin that composes the main chain has low Tg of at most 0° C. Also, the coating material does not cause peeling of solder and deformation of the lead pin of the substrate due to expansion and contraction when heating or cooling, as the membrane obtained therefrom is flexible and has low Young's modulus and small contraction stress after being formed into a film.
- the upper limit of Tg of the above acrylic resin is 0° C., preferably ⁇ 5° C. and the lower limit is preferably ⁇ 55° C., more preferably ⁇ 35° C. When Tg is higher than 0° C., film-forming properties are poor and flexibility decreases when applied under low temperatures.
- a coating material obtained by graft polymerizing monomers that form a vinyl polymer (hard resin) having high Tg of at least 20° C. and excellent water resistance does not have the surface stickiness of flexible resin, does not collect dust and exhibits excellent moisture resistance.
- the upper limit of Tg of the above vinyl polymer is preferably 150° C., more preferably 120° C. and the lower limit is 20° C., preferably 50° C.
- Tg is lower than 20° C., controlling the stickiness of the membrane surface is difficult and dust may adhere.
- the non-sticky water-based coating material of the present invention is obtained by first, polymerizing the flexible acrylic monomer in a water-based medium and then, graft polymerizing a monomer that forms hard resin with the flexible acrylic resin, in an amount that is suitable depending on the composition of the acrylic resin.
- the non-sticky water-based coating material can be formed into a film at room temperature without using a coalescence and the film obtained therefrom is flexible, has low Young's modulus and is excellent in insulating properties and moisture resistance. Usually, when stickiness is improved, that is stickiness is decreased, the Young's modulus becomes extremely high and high stress is applied to solder of the substrate and lead pins.
- polymers of at least one kind of alkyl acrylate or alkoxy acrylate or copolymers composed mainly of these monomers, to which other acrylate or vinyl monomers having high Tg, within the range that Tg is at most 0° C., are copolymerized, can be used.
- Examples of the other acrylate or vinyl monomer having high Tg are methyl methacrylate, ethyl methacrylate, butyl methacrylate, tertial butyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate and butoxyethyl methacrylate.
- Tg at most 0° C.
- acrylate containing an unsaturated group can be used, such as dicyclopentenyl (meth)acrylate, cyclopentenyloxyethyl (meth)acrylate and dihydrodicyclopentenyl (meth)acrylate.
- dicyclopentenyl (meth)acrylate cyclopentenyloxyethyl (meth)acrylate
- dihydrodicyclopentenyl (meth)acrylate dicyclopentenyloxyethyl (meth)acrylate
- cyclopentenyloxyethyl acrylate is preferable.
- the amount of the grafting agent is preferably 1 to 10% by weight based on the flexible acrylic resin.
- the amount of the grafting agent is less than 1% by weight based on the flexible acrylic resin, the number of graft sites is too small and stickiness may remain.
- the amount is more than 10% by weight, the properties of the membrane tend to degrade.
- Examples of the monomer that graft polymerizes with the flexible acrylic resin and forms hard resin are styrene, ⁇ -methylstyrene, methyl methacrylate, butyl methacrylate, tertial butyl methacrylate, acrylonitirile, methacrylonitrile, cyclohexyl methacrylate and cyclohexylacrylate. Of these, in view of water resistance, weather resistance and thermal discoloring resistance, styrene is preferable.
- the content of hard resin is 10 to 70% by weight based on the flexible acrylic resin and can be suitably selected within the above range, according to the composition of the flexible acrylic resin and hard resin which are to be combined. More preferably, the content is 20 to 50% by weight. When the content is less than 10% by weight, surface stickiness remains and when the content is more than 70% by weight, film-forming properties are poor and cracks tend to develop in the membrane surface.
- aqueous azo compounds can be used, such as V-30, V-50, VA-545, VA546, VA041 and VA-044 (all available from Wako Pure Chemical Industries, Ltd.). From the viewpoint of reactivity and storage stability, V-50 is preferable.
- a surfactant When conducting polymerization, a surfactant is used.
- the surfactant common surfactants such as polyoxyethylene alkyl ether, polyoxyethylene styrenated phenyl ether and polyoxyethylene polyoxypropylene block polymer can be used.
- a reactive surfactant is preferable.
- ADEKA REASOAP ER-10, ER-20, ER-30 and ER-40 are preferable.
- the conformal coating material of the present invention can contain other components such as water, a defoaming agent, a thickener and a leveling agent.
- ADEKA REASOAP ER-20 20 parts by weight (hereinafter referred to as parts) of ADEKA REASOAP ER-20 (available from Asahi Denka Co., Ltd.), 150 parts of butyl acrylate, 150 parts of butyl methacrylate, 16 parts of cyclopentenyloxyethyl acrylate, 2 parts of acrylic acid, 1 part of V-50 (available from Wako Pure Chemical Industries, Inc.) and 200 parts of deionized water were processed in a homomixer to obtain an emulsion.
- parts 20 parts by weight (hereinafter referred to as parts) of ADEKA REASOAP ER-20 (available from Asahi Denka Co., Ltd.), 150 parts of butyl acrylate, 150 parts of butyl methacrylate, 16 parts of cyclopentenyloxyethyl acrylate, 2 parts of acrylic acid, 1 part of V-50 (available from Wako Pure Chemical Industries, Inc.) and 200 parts of deionized water were
- a colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 120 minutes.
- the Tg of the obtained acrylic resin was ⁇ 19° C.
- the temperature was maintained at 80° C.
- 0.2 part of V-50 was added and reaction was conducted while dropping 80 parts of styrene over 60 minutes.
- the temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 34.8 parts of deionized water to obtain a graft copolymer.
- the styrene resin content of the obtained graft copolymer was 25.2% by weight based on the acrylic resin.
- the Tg of polystyrene was 100° C.
- a colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 120 minutes.
- the Tg of the obtained acrylic resin was ⁇ 19° C.
- the temperature was maintained at 80° C. Then, 0.2 part of V-50 was added and reaction was conducted while dropping 40 parts of styrene over 60 minutes. The temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 34.8 parts of deionized water to obtain a graft copolymer.
- the styrene resin content of the obtained graft copolymer was 12.6% by weight based on the acrylic resin.
- a colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 120 minutes.
- the Tg of the obtained acrylic resin was ⁇ 19° C.
- the temperature was maintained at 80° C. Then, 0.2 part of V-50 was added and reaction was conducted while dropping 160 parts of styrene over 60 minutes. The temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 34.8 parts of deionized water to obtain a graft copolymer.
- the styrene resin content of the obtained graft copolymer was 50.3% by weight based on the acrylic resin.
- ADEKA REASOAP ER-20 20 parts of ADEKA REASOAP ER-20, 150 parts of butyl acrylate, 150 parts of butyl methacrylate, 80 parts of styrene, 16 parts of cyclopentenyloxyethyl acrylate, 2 parts of acrylic acid, 1 part of V-50 and 200 parts of deionized water were processed in a homomixer to obtain an emulsion.
- a colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 150 minutes. The temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 30 parts of deionized water to obtain a random copolymer.
- the cured membranes obtained using the above copolymers were evaluated in the following manner. Unless indicated otherwise, measurement was conducted under an environment of 23° C. and 50% RH.
- the coating material was tested in the range of ⁇ 10 to 50° C. by a temperature gradient testing machine (made by Tester Sangyo Co., Ltd.) and the minimum temperature at which a normal film is formed was measured.
- the sample was applied by an applicator to prepare a film having thickness of 80 to 90 ⁇ m.
- Tensile strength, elongation and Young's modulus of a die-cut specimen were measured using an all-purpose tensile and compression testing machine (made by Minebea Co., Ltd.), under the conditions of pulling speed rate of 100 mm/minute for tensile strength and elongation and 1 mm/minute for Young's modulus.
- the sample was applied to JIS II model comb-type substrate and after drying for 30 minutes at 90° C., the insulation resistance was measured by applying DC.100 V using a high-resistance tester (made by Yokogawa Hewlett Packard, Ltd.).
- the sample was applied to JIS II model comb-type substrate and dried for 30 minutes at 90° C.
- the specimen was placed in a constant temperature and humidity chamber (atmosphere inside chamber: 85° C., 85 to 90% RH) and after 168 hours, the insulation resistance was measured by applying DC.100 V using a high-insulation measuring machine (made by Yokogawa Hewlett Packard, Ltd.).
- the sample was flow-coated on a glass board and dried for 30 minutes at 90° C. to obtain a membrane.
- the membrane was evaluated by touch as ⁇ when the membrane did not feel sticky, ⁇ when the membrane felt somewhat sticky but was not largely distorted and X when the membrane felt sticky.
- the membrane formed on the JIS II model comb-type substrate was tested by the 1 mm spacing cross-cut test method (according o JIS K5600-5-6) and the number of remaining squares that were not flaked was represented in a number value. The number of squares that were cut was 100.
- the coating material of the present invention can be formed into a film at room temperature without using a coalescence, does not contain a solvent and forms a membrane having flexibility, low Young's modulus, favorable adhesive properties, moisture resistance and insulating properties.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The present invention provides a non-sticky water-based coating material, which can be formed into a film at room temperature without using a coalescence, does not contain a solvent and forms a membrane having flexibility, low Young's modulus, favorable adhesive properties, moisture resistance and insulating properties. Specifically, the present invention relates to a non-sticky water-based conformal coating material comprising a resin wherein a flexible acrylic resin having glass transition temperature of at most 0° C. is the main chain and a vinyl polymer having a glass transition temperature of at least 20° C. is grafted to the flexible acrylic resin; the content of the vinyl polymer being 10 to 70% by weight based on the flexible acrylic resin.
Description
- The present invention relates to a conformal coating material (hereinafter referred to as coating material) that forms an insulating moisture-proof membrane, in which cracking and peeling from the substrate tend not to occur and which does not apply excessive stress to the lead pin of electronic parts.
- Due to widespread use of computers, circuit boards loaded with electronic parts have come to be used in household electric products and automobiles. Also, solvent coating materials having moisture resistance and insulating properties have come to be applied, in order to protect circuit boards from sudden temperature change, humidity, water and dust.
- In recent years, along with increase in social awareness regarding environmental problems, a coating material has been developed, in which ethyl acetate, methyl acetate and butyl acetate are used instead of aromatic hydrocarbon solvents such as toluene and xylene, which are high in toxicity (see JP-A-2002-146266). However, this coating material lets out a great deal of solvent when applied and therefore, has many problems such as danger of fire, foul odor generated by the evaporated solvent and health management of workers to poisoning. Furthermore, depending on the locational conditions of the working area, measures against the Foul Smell Control Law may become necessary.
- Also, water-based coating materials that do not contain a solvent have been considered. However, because film-forming properties and durability of the coating film are not sufficient, at present, coating materials contain 5 to 10% of a solvent. In such water-based coating materials containing a solvent, when the Young's modulus is low, the membrane remains sticky and problems occur, such as adhesion of dirt and blocking when handling. Also, coating materials having less stickiness are not sufficient, as these have large Young's modulus and apply large load to the substrate. As a result, peeling of solder and deformation of the lead pin may occur, due to expansion and contraction of the membrane caused by increase and decrease in the environmental temperature.
- The present invention aims to provide a non-sticky water-based coating material that solves the above problems and forms a membrane having favorable adhesive properties, moisture resistance and insulating properties.
- As a result of intensive studies to solve the above problems, by grafting a hard resin having high glass transition temperature (hereinafter referred to as Tg) to an acrylic resin main chain having low Tg and high flexibility, a non-sticky water-based coating material, which does not contain a solvent and has small Young's modulus and large insulation resistance, has been successfully developed.
- That is, the present invention relates to a non-sticky water-based conformal coating material comprising a resin wherein a flexible acrylic resin having glass transition temperature of at most 0° C. is the main chain and a vinyl polymer having a glass transition temperature of at least 20° C. is grafted to the flexible acrylic resin; the content of the vinyl polymer being 10 to 70% by weight based on the flexible acrylic resin.
- The coating material of the present invention is a conformal coating material that is applied to the face of a circuit board that is loaded with electronic parts, which comes into contact with the outside environment. Herein, conformal coating refers to a coating for providing moisture resistance and insulation of a circuit board.
- The coating material can be formed into a film at room temperature without using a coalescence, because the acrylic resin that composes the main chain has low Tg of at most 0° C. Also, the coating material does not cause peeling of solder and deformation of the lead pin of the substrate due to expansion and contraction when heating or cooling, as the membrane obtained therefrom is flexible and has low Young's modulus and small contraction stress after being formed into a film. The upper limit of Tg of the above acrylic resin is 0° C., preferably −5° C. and the lower limit is preferably −55° C., more preferably −35° C. When Tg is higher than 0° C., film-forming properties are poor and flexibility decreases when applied under low temperatures.
- Also, a coating material obtained by graft polymerizing monomers that form a vinyl polymer (hard resin) having high Tg of at least 20° C. and excellent water resistance does not have the surface stickiness of flexible resin, does not collect dust and exhibits excellent moisture resistance.
- The upper limit of Tg of the above vinyl polymer is preferably 150° C., more preferably 120° C. and the lower limit is 20° C., preferably 50° C. When Tg is lower than 20° C., controlling the stickiness of the membrane surface is difficult and dust may adhere.
- The non-sticky water-based coating material of the present invention is obtained by first, polymerizing the flexible acrylic monomer in a water-based medium and then, graft polymerizing a monomer that forms hard resin with the flexible acrylic resin, in an amount that is suitable depending on the composition of the acrylic resin. The non-sticky water-based coating material can be formed into a film at room temperature without using a coalescence and the film obtained therefrom is flexible, has low Young's modulus and is excellent in insulating properties and moisture resistance. Usually, when stickiness is improved, that is stickiness is decreased, the Young's modulus becomes extremely high and high stress is applied to solder of the substrate and lead pins.
- As the flexible acrylic resin, polymers of at least one kind of alkyl acrylate or alkoxy acrylate or copolymers composed mainly of these monomers, to which other acrylate or vinyl monomers having high Tg, within the range that Tg is at most 0° C., are copolymerized, can be used. Specific examples are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, isobutyl acrylate, isomyristyl acrylate, lauryl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate and ethoxypropyl acrylate. Examples of the other acrylate or vinyl monomer having high Tg are methyl methacrylate, ethyl methacrylate, butyl methacrylate, tertial butyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate and butoxyethyl methacrylate. Of these, from the viewpoints of reactivity, storage stability and weather resistance, a system in which alkyl acrylate is the main component and alkyl methacrylate is added, with Tg of at most 0° C., is preferable.
- As a grafting agent, acrylate containing an unsaturated group can be used, such as dicyclopentenyl (meth)acrylate, cyclopentenyloxyethyl (meth)acrylate and dihydrodicyclopentenyl (meth)acrylate. Of these, in view of reactivity and graft efficiency, cyclopentenyloxyethyl acrylate is preferable.
- The amount of the grafting agent is preferably 1 to 10% by weight based on the flexible acrylic resin. When the amount of the grafting agent is less than 1% by weight based on the flexible acrylic resin, the number of graft sites is too small and stickiness may remain. When the amount is more than 10% by weight, the properties of the membrane tend to degrade.
- Examples of the monomer that graft polymerizes with the flexible acrylic resin and forms hard resin are styrene, α-methylstyrene, methyl methacrylate, butyl methacrylate, tertial butyl methacrylate, acrylonitirile, methacrylonitrile, cyclohexyl methacrylate and cyclohexylacrylate. Of these, in view of water resistance, weather resistance and thermal discoloring resistance, styrene is preferable.
- The content of hard resin is 10 to 70% by weight based on the flexible acrylic resin and can be suitably selected within the above range, according to the composition of the flexible acrylic resin and hard resin which are to be combined. More preferably, the content is 20 to 50% by weight. When the content is less than 10% by weight, surface stickiness remains and when the content is more than 70% by weight, film-forming properties are poor and cracks tend to develop in the membrane surface.
- As the polymerization initiator, aqueous azo compounds can be used, such as V-30, V-50, VA-545, VA546, VA041 and VA-044 (all available from Wako Pure Chemical Industries, Ltd.). From the viewpoint of reactivity and storage stability, V-50 is preferable.
- When conducting polymerization, a surfactant is used. As the surfactant, common surfactants such as polyoxyethylene alkyl ether, polyoxyethylene styrenated phenyl ether and polyoxyethylene polyoxypropylene block polymer can be used. However, from the viewpoint that water resistance is excellent and the surfactant does not bleed to the membrane surface, a reactive surfactant is preferable. Particularly, in view of polymerization stability and thermal discoloring resistance, ADEKA REASOAP ER-10, ER-20, ER-30 and ER-40 (all available from Asahi Denka Co., Ltd.) are preferable.
- Besides the acrylic resin to which vinyl polymers are grafted, the conformal coating material of the present invention can contain other components such as water, a defoaming agent, a thickener and a leveling agent.
- Hereinafter, the coating material of the present invention is explained by means of Examples.
- 20 parts by weight (hereinafter referred to as parts) of ADEKA REASOAP ER-20 (available from Asahi Denka Co., Ltd.), 150 parts of butyl acrylate, 150 parts of butyl methacrylate, 16 parts of cyclopentenyloxyethyl acrylate, 2 parts of acrylic acid, 1 part of V-50 (available from Wako Pure Chemical Industries, Inc.) and 200 parts of deionized water were processed in a homomixer to obtain an emulsion.
- A colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 120 minutes. The Tg of the obtained acrylic resin was −19° C.
- For 30 minutes after dropping, the temperature was maintained at 80° C. Then, 0.2 part of V-50 was added and reaction was conducted while dropping 80 parts of styrene over 60 minutes. The temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 34.8 parts of deionized water to obtain a graft copolymer. The styrene resin content of the obtained graft copolymer was 25.2% by weight based on the acrylic resin. The Tg of polystyrene was 100° C.
- 20 parts of ADEKA REASOAP ER-20, 150 parts of butyl acrylate, 150 parts of butyl methacrylate, 16 parts of cyclopentenyloxyethyl acrylate, 2 parts of acrylic acid, 1 part of V-50 and 200 parts of deionized water were processed in a homomixer to obtain an emulsion.
- A colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 120 minutes. The Tg of the obtained acrylic resin was −19° C.
- For 30 minutes after dropping, the temperature was maintained at 80° C. Then, 0.2 part of V-50 was added and reaction was conducted while dropping 40 parts of styrene over 60 minutes. The temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 34.8 parts of deionized water to obtain a graft copolymer. The styrene resin content of the obtained graft copolymer was 12.6% by weight based on the acrylic resin.
- 20 parts of ADEKA REASOAP ER-20, 150 parts of butyl acrylate, 150 parts of butyl methacrylate, 16 parts of cyclopentenyloxyethyl acrylate, 2 parts of acrylic acid, 1 part of V-50 and 200 parts of deionized water were processed in a homomixer to obtain an emulsion.
- A colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 120 minutes. The Tg of the obtained acrylic resin was −19° C.
- For 30 minutes after dropping, the temperature was maintained at 80° C. Then, 0.2 part of V-50 was added and reaction was conducted while dropping 160 parts of styrene over 60 minutes. The temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 34.8 parts of deionized water to obtain a graft copolymer. The styrene resin content of the obtained graft copolymer was 50.3% by weight based on the acrylic resin.
- 20 parts of ADEKA REASOAP ER-20, 150 parts of butyl acrylate, 150 parts of butyl methacrylate, 80 parts of styrene, 16 parts of cyclopentenyloxyethyl acrylate, 2 parts of acrylic acid, 1 part of V-50 and 200 parts of deionized water were processed in a homomixer to obtain an emulsion.
- A colben was charged with 350 parts of deionized water and after the temperature was adjusted to 70° C., 10% of the above emulsion was added to start the reaction. Thereafter, the temperature was adjusted to 80° C. and the rest of the emulsion was dropped over 150 minutes. The temperature was maintained at 80° C. for 60 minutes to finish the reaction and after cooling, the pH was adjusted with 1 part of 28% ammonium water and 30 parts of deionized water to obtain a random copolymer.
- The cured membranes obtained using the above copolymers were evaluated in the following manner. Unless indicated otherwise, measurement was conducted under an environment of 23° C. and 50% RH.
- (1) Film-Forming Temperature
- The coating material was tested in the range of −10 to 50° C. by a temperature gradient testing machine (made by Tester Sangyo Co., Ltd.) and the minimum temperature at which a normal film is formed was measured.
- (2) Tensile Strength, Elongation and Young's Modulus
- The sample was applied by an applicator to prepare a film having thickness of 80 to 90 μm. Tensile strength, elongation and Young's modulus of a die-cut specimen were measured using an all-purpose tensile and compression testing machine (made by Minebea Co., Ltd.), under the conditions of pulling speed rate of 100 mm/minute for tensile strength and elongation and 1 mm/minute for Young's modulus.
- (3) Insulation Resistance
- The sample was applied to JIS II model comb-type substrate and after drying for 30 minutes at 90° C., the insulation resistance was measured by applying DC.100 V using a high-resistance tester (made by Yokogawa Hewlett Packard, Ltd.).
- (4) Insulating Properties in High Temperature and High Humidity
- The sample was applied to JIS II model comb-type substrate and dried for 30 minutes at 90° C. The specimen was placed in a constant temperature and humidity chamber (atmosphere inside chamber: 85° C., 85 to 90% RH) and after 168 hours, the insulation resistance was measured by applying DC.100 V using a high-insulation measuring machine (made by Yokogawa Hewlett Packard, Ltd.).
- (5) Non-Stickiness
- The sample was flow-coated on a glass board and dried for 30 minutes at 90° C. to obtain a membrane. The membrane was evaluated by touch as ο when the membrane did not feel sticky, Δ when the membrane felt somewhat sticky but was not largely distorted and X when the membrane felt sticky.
- (6) Adhesive Properties
- The membrane formed on the JIS II model comb-type substrate was tested by the 1 mm spacing cross-cut test method (according o JIS K5600-5-6) and the number of remaining squares that were not flaked was represented in a number value. The number of squares that were cut was 100.
- The evaluation results are shown in Table 1.
TABLE 1 Com. Ex. 1 Ex. 2 Ex. 3 Ex. 1 Film-forming <0 <0 <0 <0 temperature (° C.) Tensile strength (MPa) 5.6 1.8 7.6 7.8 Elongation (%) 385 520 285 360 Non-stickiness ◯ Δ ◯ X Insulating properties (Ω) 1.9 × 1011 2.6 × 1011 2.7 × 1011 7.0 × 1010 Insulating properties in 5.8 × 109 2.6 × 109 5.4 × 109 1.1 × 109 high humidity (Ω) Young's modulus (MPa) 1.2 0.4 20.2 17.6 Adhesive properties 100/100 100/100 100/100 100/100 - The resin of Comparative Example 1 obtained by random polymerization, in which the hard resin was not grafted to the flexible acrylic resin main chain by two-step polymerization, tends to exhibit stickiness, although the composition is the same, and also, the Young's modulus tends to be high.
- The coating material of the present invention can be formed into a film at room temperature without using a coalescence, does not contain a solvent and forms a membrane having flexibility, low Young's modulus, favorable adhesive properties, moisture resistance and insulating properties.
Claims (1)
1. A non-sticky water-based conformal coating material comprising a resin wherein a flexible acrylic resin having glass transition temperature of at most 0° C. is the main chain and a vinyl polymer having a glass transition temperature of at least 20° C. is grafted to said flexible acrylic resin;
the content of said vinyl polymer being 10 to 70% by weight based on said flexible acrylic resin.
Priority Applications (1)
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US11/399,468 US7642325B2 (en) | 2003-10-03 | 2006-04-07 | Non-sticky water-based conformal coating material |
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JP2003-345953 | 2003-10-03 | ||
JP2003345953A JP4733919B2 (en) | 2003-10-03 | 2003-10-03 | Non-adhesive aqueous conformal coating material |
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US11/399,468 Division US7642325B2 (en) | 2003-10-03 | 2006-04-07 | Non-sticky water-based conformal coating material |
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US10/954,273 Abandoned US20050075459A1 (en) | 2003-10-03 | 2004-10-01 | Non-sticky water-based conformal coating material |
US11/399,468 Expired - Fee Related US7642325B2 (en) | 2003-10-03 | 2006-04-07 | Non-sticky water-based conformal coating material |
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US11/399,468 Expired - Fee Related US7642325B2 (en) | 2003-10-03 | 2006-04-07 | Non-sticky water-based conformal coating material |
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JP (1) | JP4733919B2 (en) |
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WO2014009408A1 (en) * | 2012-07-11 | 2014-01-16 | Omnova Solutions | Rheological agent, preparation methods and uses thereof |
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JP4923291B2 (en) * | 2005-12-02 | 2012-04-25 | ソマール株式会社 | Water-based moisture-proof insulation coating agent |
WO2012115011A1 (en) * | 2011-02-25 | 2012-08-30 | 昭和電工株式会社 | Moistureproof insulation material |
CN102595771B (en) * | 2012-01-11 | 2015-07-01 | 深圳创维数字技术有限公司 | Paper base printing circuit board with protective layer and preparation method thereof |
CN114630018A (en) * | 2020-12-14 | 2022-06-14 | 晋城三赢精密电子有限公司 | Lens module and electronic device |
WO2023200993A1 (en) * | 2022-04-13 | 2023-10-19 | Actnano, Inc. | Conformal coating with low volatile organic compound content |
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- 2004-10-08 CN CN200410080721.4A patent/CN1613932B/en not_active Expired - Fee Related
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WO2014009408A1 (en) * | 2012-07-11 | 2014-01-16 | Omnova Solutions | Rheological agent, preparation methods and uses thereof |
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JP2005112919A (en) | 2005-04-28 |
US20060178479A1 (en) | 2006-08-10 |
CN1613932A (en) | 2005-05-11 |
JP4733919B2 (en) | 2011-07-27 |
US7642325B2 (en) | 2010-01-05 |
CN1613932B (en) | 2011-10-19 |
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