WO2017108510A1 - Procédé de revêtement de cartes à circuit imprimé - Google Patents

Procédé de revêtement de cartes à circuit imprimé Download PDF

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WO2017108510A1
WO2017108510A1 PCT/EP2016/080879 EP2016080879W WO2017108510A1 WO 2017108510 A1 WO2017108510 A1 WO 2017108510A1 EP 2016080879 W EP2016080879 W EP 2016080879W WO 2017108510 A1 WO2017108510 A1 WO 2017108510A1
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group
polymer
formulation
formula
chain
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PCT/EP2016/080879
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Antonio Russo
Milan Wilhelm KRUMBE
Michael Dornbusch
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2017108510A1 publication Critical patent/WO2017108510A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

Definitions

  • the present invention relates to a method for coating printed circuit boards and to printed circuit boards obtained with such method.
  • PCBs are supports used for connecting together different electronic components of an electronic circuit through conductive tracks, pads or other features etched from copper sheets laminated onto a non-conductive substrate.
  • PCBs are used in a variety of environments and often exposed to different agents conditions, like moisture, salts, chemicals and temperature changes, which can sometimes be harsh and, therefore, cause corrosion or damages or malfunctioning of the circuitry.
  • a "conformal coating” i.e. a thin polymeric film (typically 25 - 250 ⁇ thick) which perfectly adheres to and follows the shape of, the circuit's components.
  • conformal coatings are acryclic polymers, epoxy polymers, polyurethanes, silicones fluorinated and non-fluorinated poly-para-xylylenes and amorphous fluoropolymers.
  • the polymer materials can be dissolved in an organic solvent or in water, optionally in combination with other additives, in order to provide solvent-based or water-based coating formulations.
  • the choice of the coating formulation depends on the application method of the same to the circuit, said method comprising curing and drying. Usually, conformal coatings are applied by air drying (at room temperature or with heating) or by UV curing, the latter being preferred when speed of application is required.
  • acrylic polymers also referred to in the filed as "acrylic
  • resins are chosen when ease of re-work, simple drying, good moisture resistance, high fluorescence value and ease of viscosity adjustment are required.
  • compositions for conformal coatings may include, in addition to the
  • polymer material and solvent or water, other ingredients which promote drying and curing (e.g. UV-curing agents) or improve one or more properties of the finished coating.
  • other ingredients which promote drying and curing e.g. UV-curing agents
  • improve one or more properties of the finished coating e.g. UV-curing agents
  • EP 2093243 A SAMSUNG ELECTRONICS CO., LTD. 8/26/2009
  • compositions comprising a functional or non-functional
  • PFPE perfluoropolyether
  • PFPE-miscible polymer for inhibiting or preventing oxide film formation on electronic components, especially those made of copper, aluminium, iron and molybdenum.
  • the functional PFPE comprise end groups selected from silanol, chlorosilane, carboxylic acid, alcohol, amine and phosphoric acid and derivatives thereof.
  • PFPE-miscible polymers are typically selected from the group consisting of polyvinyl alcohol, polyvinyl chloride, polyacrylic amide, polyethylene glycol, polyethylene oxide,
  • compositions typically include water and are applied to the substrate by UV curing, therefore, they contain a UV-curing agent as additive.
  • Preferred substrates onto which the compositions are applied are wiring pads of memory and processing microdevices, optical sensors, heat sinks for display devices, wirings and electrodes of Organic Thin Film Transistors, electrodes of display devices, and wirings and electrodes of battery devices.
  • DE 102008012895 A (ROBERT BOSCH GMBH) 9/10/2009 discloses fluorinated or partially fluorinated anti-corrosion gels for electronic or microelectronic devices which comprise a PFPE derivative which may comprise hydroxy, alkoxy, trialkoxysilane, amino, carboxyl, thiol, cyanate, isocyanate, isothiocyanate, phosphate, carboxamide or polyether alcohol groups.
  • This document does not disclose gels which contain another polymer selected from acryclic polymers, epoxy polymers, polyurethanes, silicones fluorinated and non-fluorinated poly-para-xylylenes.
  • (per)fluoropolyether polymers can be mixed with acrylic polymers, organic solvents and, optionally, other ingredients, to provide solvent-based conformal coatings formulations able to form conformal coatings which are improved in terms of one or more of hydrophobicity, chemical resistance and conductivity and which can be applied to printed circuit boards with conventional methods.
  • the present invention relates to a method [method (M)] for coating a printed circuit board (PCB), said method comprising the following steps:
  • the invention further relates to a PCB obtained by coating a PCB with method (M) as defined above and to specific formulations (F) for performing said method.
  • brackets "( )" before and after symbols or numbers identifying compounds or formulae e.g. "polymer (P1 )", “polymer (P2)”, etc .
  • P1 polymer
  • P2 polymer
  • said parentheses could also be omitted;
  • functional group has its general meaning as intended in organic chemistry and it encompasses atoms or combination of atoms bonded to the carbon skeleton of chain (R P f), either directly or by means of a bridging moiety and which confers to polymer (P1 ) specific chemical properties and reactivity.
  • functional groups are those comprising one or more heteroatoms other than fluorine, said atoms being independently selected from O, S, N, P, Si and mixtures thereof.
  • aromatic denotes any mono- or polynuclear cyclic group (or moiety) having a number of ⁇ electrons equal to 4n+2, wherein n is 0 or any positive integer;
  • aromatic group (or moiety) can be an aryl or an arylene group (or moiety);
  • PFPE perfluoropolyether and PFPEs
  • an "aryl group” is a hydrocarbon monovalent group consisting of one core composed of one benzenic ring or of a plurality of benzenic rings fused together by sharing two or more neighboring ring carbon atoms, and of one end.
  • Non limitative examples of aryl groups are phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, triphenylyl, pyrenyl, and perylenyl groups.
  • the end of an aryl group is a free electron of a carbon atom contained in a (or the) benzenic ring of the aryl group, wherein an hydrogen atom linked to said carbon atom has been removed.
  • the end of an aryl group is capable of forming a linkage with another chemical group;
  • an "arylene group” is a hydrocarbon divalent group consisting of one core composed of one benzenic ring or of a plurality of benzenic rings fused together by sharing two or more neighboring ring carbon atoms, and of two ends.
  • arylene groups are phenylenes, naphthylenes, anthrylenes, phenanthrylenes, tetracenylenes,
  • triphenylylenes pyrenylenes, and perylenylenes.
  • An end of an arylene group is a free electron of a carbon atom contained in a (or the) benzenic ring of the arylene group, wherein an hydrogen atom linked to said carbon atom has been removed.
  • Each end of an arylene group is capable of forming a linkage with another chemical group.
  • the polymer (P1 ) is a functional (per)fluoropolyether, that is to say a polymer comprising at least one fully or partially fluorinated polyoxyalkylene chain [chain (R P f)] having at least two ends, in which at least one end bears an end group [end group (E)] comprising at least one functional group [functional group (G)].
  • the PFPE polymer (P1 ) comprises one fully or partially fluorinated polyoxyalkylene chain (R P f) having two ends, in which and at least one end bears a group (E) comprising at least one functional (G).
  • group (G) is at least one hydroxyl group [group (G1 )] or at least one ⁇ , ⁇ -unsaturated carbonyl group [group (G2)].
  • the other end of chain (R P f) can also bear an end group (E) comprising at least one functional group (G) as defined above or can bear a non-functional fluorinated alkyl group .
  • chain (R P f) of polymer (P1 ) is a chain of formula: -O-D- (CFX # )zi-O(Rf)(CFX#)z2-D-O- wherein:
  • z1 and z2, equal or different from each other, are equal to or higher than 1 , preferably from 1 to 10, more preferably from 1 to 3;
  • X # equal or different from each other, is -F or -CF3,
  • both X are -F;
  • D is a divalent straight or branched aliphatic radical comprising from 1 to 20, more preferably from 1 to 6 and even more preferably from 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms.
  • each X is F and each D is methylene, ethylene or -CH(CF3)-.
  • each X is fluorine and each D is methylene.
  • chain (Rf) is a fully or partially fluorinated chain comprising,
  • repeating units R° preferably consisting of, repeating units R°, said repeating units being independently selected from the group consisting of:
  • chain (Rf) complies with the following formula:
  • - X 1 is independently selected from -F and -CF3,
  • - X 2 , X 3 are independently -F, -CF3, with the proviso that at least one of X is -F;
  • g1 +g2+g3+g4 is in the range from 2 to 300, preferably from 2 to 100; should at least two of g1 , g2, g3 and g4 be different from zero, the different recurring units are generally statistically distributed along the chain.
  • chain (Rf) is selected from chains of formula:
  • - a1 and a2 are independently integers ⁇ 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10;
  • b1 , b2, b3, b4, are independently integers ⁇ 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably b1 is 0, b2, b3, b4 are > 0, with the ratio b4/(b2+b3) being >1 ;
  • cw 1 or 2; d , c2, and c3 are independently integers ⁇ 0 chosen so that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably c1 , c2 and c3 are all > 0, with the ratio c3/(c1 +c2) being generally lower than 0.2;
  • d is an integer > 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000;
  • chain (Rf) complies with formula (Rf-lll) here below:
  • - a1 and a2 are integers > 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000, with the ratio a1/a2 being generally comprised between 0.1 and 10, more preferably between 0.2 and 5.
  • PFPE polymers (P1 ) comply with general formula (P1 ) here below:
  • - E is an end group as defined above or a non-functional fluorinated alkyl group.
  • group E comprises from 1 to 3 functional groups (G).
  • PFPE polymer (P1 ) comprises a chain (R P f) having at least two ends, wherein at least one end bears an end group (E) comprising at least one hydroxyl group (G-1 ) [end group (E-1 )].
  • This PFPE polymer (P1 ) will be herein after also referred to as "PFPE alcohol(s) (P1 )".
  • Preferred PFPE alcohols (P1 ) are those wherein at least one end bears one end group (E-1 ) comprising one hydroxyl group (G-1 ).
  • Preferred groups (E-1 ) comprising one hydroxyl group (G-1 ) are those complying with formula (E-1A):
  • - J is independently selected from hydrogen, straight or branched alkyl and aryl, preferably from hydrogen, methyl, ethyl, ethyl and phenyl; more preferably, J is hydrogen and
  • - j is 0 or a positive number ranging from 1 to 50, more preferably from 1 to 15 and even more preferably from 4 to 7.
  • Preferred PFPE alcohols (P1 ) comply with general formula (P1 -A):
  • - X is as defined above, preferably F;
  • - T is a non-functional group selected from -CF3, -C2F5 and -C3F7, or a functional group of formula -(CFX)-CH 2 O[CH 2 CH(J)O]j-H in which X, J and j are as defined above.
  • each [CH 2 CH(J)O] unit can be equal to or different from one another; when j is equal to or higher than 2 and the units are different, they can be arranged randomly.
  • polymers (P1 -A) are those comprising [CH 2 CH(J)O] units arranged to form moieties complying with the following formulae (RM) - (RMII):
  • - j1 and j2 are equal to or higher than 1 , with the proviso that j1 +j2 is not higher than 50.
  • J is hydrogen and j ranges from 4 to 7.
  • chain (Rf) complies with formula (Rf-lll) as defined above.
  • Preferred polymers (P1-A) are those wherein T is -(CFX)-
  • bifunctional polymers P1 -A
  • X F
  • J hydrogen
  • j ranges from 4 to 7.
  • monofunctional polymers P1 -A
  • PFPEs PFPEs wherein both ends of the polymer chain bear non-functional groups as defined above.
  • the expression "bifunctional polymers (P1 -A)" identifies PFPE alcohols (P1 -A) having an average functionality (F), i.e. an average number of -OH groups per polymer molecule, at least equal to 1.80, more preferably at least equal to 1.85 and still more preferably at least equal to 1.94.
  • Functionality (F) can be calculated by means of 1 H-NMR and 19 F-NMR analyses according to methods known in the art, for example following the teaching of US 5910614 (AUSIMONT SPA) .
  • PFPE alcohols are known in the art.
  • polymers (P1 -A) in which chain (Rf) complies with formula (Rf-lll), j is 0 and T is - CF2CH2OH are available on the market from Solvay Specialty Polymers Italy S.p.A. with trademark Fomblin ®
  • Polymers (P1 -A) in which j is an integer ranging from 1 to 50 can be advantageously manufactured according to the method disclosed in WO 2014/090649 (SOLVAY SPECIALTY POLYMERS ITALY SPA) .
  • This polymer (P1 ) will be herein after referred to as acrylic polymer (P1 ).
  • Such acrylic polymer (P1 ) preferably complies with formula (P1 -B):
  • - T is -(CFX)-CH 2 O[CH 2 CH(J)O]j-E* or a group selected from -CF 3 , -C2F5
  • Preferred groups E* are those complying with formulae (E * 1 ) - (E * 3) here below:
  • RH is H or a C1 -C6 alkyl group
  • R A is selected from the group consisting of:
  • R B being a divalent group selected from the group
  • cycloaliphatic group C6-Ci 4 aromatic or alkylaromatic group.
  • group E* complies with formula (E * 1 ), as defined above; preferably, in formula (E * 1 ), RH is hydrogen or methyl.
  • chain (Rf) complies with formula (Rf-lll) as defined above.
  • Such polymers (P1 -B) can be manufactured according to known methods by reaction of polymers (P1), preferably polymers (P1 -A) as defined above, with an ⁇ , ⁇ unsaturated carbonyl halide.
  • Suitable examples of ⁇ , ⁇ -unsaturated carbonyl halides are compounds having the following general formulae:
  • X is halogen atom, preferably CI, and
  • RH and R A have the same meaning defined above.
  • Preferred ⁇ , ⁇ -unsaturated carbonyl compounds are for example acryloyi chloride, methacryloyl chloride and the like.
  • group E * is a group ( ⁇ * ') comprising two or three two or three groups (G2) as defined above.
  • group E * comprises a hydrocarbon moiety [moiety (U)] optionally comprising oxygen and/or nitrogen atoms and/or (hetero)cycloalkylene groups, said moiety having two or three bonding sites for the carbonyl group of group (G2).
  • optional oxygen atoms can be ethereal oxygen atoms or can form oxygen-containing groups such as carbonyl, ester and carbonate groups; the nitrogen atoms can be comprised as primary, secondary or tertiary amino groups or, together with oxygen and/or nitrogen atoms, can form groups like amido, urea or urethane groups.
  • moiety (U) comprises urethane groups.
  • the optional oxygen atoms can be ethereal oxygen atoms or can form oxygen-containing groups such as carbonyl, ester and carbonate groups; the nitrogen atoms can be comprised as primary, secondary or tertiary amino groups or, together with oxygen and/or nitrogen atoms, can form groups like amido, urea or urethane groups.
  • moiety (U) comprises urethane groups.
  • the optional oxygen atoms can be ethereal oxygen atoms or can form oxygen-containing groups such as carbonyl, ester and carbonate groups; the nitrogen atoms can be comprised as primary, secondary
  • cycloalkylene groups in moiety (U) are typically C5-C10 cycloalkylene rings, optionally substituted with one of more straight or branched alkyl groups, preferably straight or branched C1 -C3 alkyl groups; when the cycloalkylene groups comprise heteroatoms, said heteroatoms are preferably one or more oxygen and/or nitrogen atoms, wherein oxygen atoms can be ethereal oxygen atoms or can form oxygen-containing groups such as carbonyl, ester and carbonate groups; the nitrogen atoms can be comprised as primary, secondary or tertiary amino groups or, together with oxygen and/or nitrogen atoms, can form groups like amido, urea or urethane groups.
  • a preferred moiety (U) complies with formula (U-1 ) here below:
  • R U 1 A is a straight or branched C2-C10 hydrocarbon chain and each R u1 b , equal to or different from one another, is a C2-C10 hydrocarbon group
  • the * represents the bonding site to the right side oxygen atom in the -CH2O[CH2CH(J)O]j- moiety of polymer (P1-B)
  • the # represents the bonding site to the carbonyl group of group (G2).
  • RH is as defined above, preferably hydrogen or methyl and the * is as defined above.
  • Preferred examples of polymers (P1 -B) comprise a chain (Rf-lll) as defined above and groups (E * 'ui) as defined above wherein RH is hydrogen of methyl.
  • a convenient example of such polymers (P1 -B) is available from Solvay Specialty Polymers Italy S.p.A. as Fluorolink ® MT 70 and complies with general formula:
  • Rf is a chain (Rf-lll) as defined above and
  • - T' is a non-functional group selected from -CF3, -C2F5 and -CsF 7 or a group of formula (Tui):
  • R U 1 B and RH are as defined above according to methods known in the art.
  • R U2A is a straight or branched C2-C10 hydrocarbon group, optionally comprising one or more oxygen and/or nitrogen atoms and/or
  • each R U2B is a C2-C10
  • Preferred moieties (U2) are those in which R U2A is a straight or branched C2-C10 hydrocarbon group comprising (hetero)cycloalkylene groups.
  • Preferred examples of polymers (P1 -B) comprise a chain (Rf-lll) as defined above and groups (E*'u2) as defined above wherein RH is hydrogen of methyl and R U2b is an ethylene moiety (-CH2CH2-).
  • Rf is a chain of formula (Rf-lll) as defined above;
  • - R U2b is an ethylene moiety (-CH2CH2-);
  • T is a group of formula (Tu2):
  • This polymer is available from Solvay Specialty Polymers Italy S.p.A. as Fluorolink ® AD 1700 in solution with ethylacetate and butylacetate (70%wt polymer in a 1 : 1 wt. mixture of ethylacetate and butylacetate).
  • polymer (P1 -B) is Fluorolink ® AD 1700 PFPE.
  • Polymers (P1 -B) in which group ( ⁇ * ') is a group (E*'u2) as defined above can be conveniently obtained by reaction of a PFPE alcohol (P1 -A) as defined above, preferably a bifunctional PFPE alcohol (P1 -A) with a isocyanate of formula (I s ):
  • R U2a , R U2b and RH are as defined above according to methods know in the art.
  • PFPE polymer (P1) can be used at concentrations ranging from 0.1 % to 20% wt with respect to the weight of formulation (F), preferably at concentrations ranging from 0.1 to 6% wt, more preferably at concentrations ranging from 0.1 %wt to 5% wt.
  • the polymer (P2) is the polymer (P2)
  • an acrylic polymer (P2) is a
  • an acrylic polymer (P2) comprising acrylic acid moieties or methacrylic acid moieties does not comprise acrylic polymers (P2).
  • Reactive derivatives preferably include halides and esters.
  • ⁇ , ⁇ -unsaturated carboxylic acids and reactive derivatives thereof include, but are not limited to, acrylic acid, acryloyl chloride, methyl acrylate, ethyl acrylate, ethyl acryloyl chloride, butyl acrylate, ieri-butyl acrylate, ethyl methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl 2-ethyl acrylate, 2-ethylacryloyl chloride, 2- ethylhexyl acrylate, ethyl 2-propyl acrylate, 2-(trimethylsilylmethyl)acrylate, hexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, isobutyl acrylate.
  • the acrylic polymer (P2) can optionally comprise reactive functional groups able to undergo cross-linking reactions in the presence of a cross- linker (or cross-linking agent).
  • a cross- linker or cross-linking agent
  • such acrylic polymers (P2) will be selected in particular when formulation (F) is hardened by curing (thermal curing or UV-curing).
  • Such polymers (P2) can be obtained either by polymerizing ⁇ , ⁇ -unsaturated carboxylic acids or derivatives thereof comprising such functional groups or by polymerizing such acids in the presence of non-acid monomers comprising such functional groups.
  • acrylic polymers (P2) comprising reactive functional groups are acrylic polyols.
  • polymer (P2) in method (M) according to the present invention, can be used in amounts typically up to 40%wt with respect to formulation (F), advantageously from 15% to 40%wt with respect to formulation (F).
  • a person skilled in the art will be able to select the kind and amount of polymer (P2) according to the specific method whereby formulation (F) is applied to the PCB.
  • an organic solvent is a non-polar or polar aprotic aliphatic or aromatic solvent or a mixture thereof.
  • the solvent is an aromatic solvent selected from one or more of toluene, xylene and naphthalene or an aliphatic solvent selected from a ketone or an ester or a mixture thereof, whererein the term "ester” is intended to include also esters of (poly)oxylakylene alcohols.
  • suitable ketones are methylethylketone (MEK), methylisobutylketone (MIBK ).
  • ester examples include ethyl acetate, butyl acetate, isobutyl acetate, 2-ethoxy ethylacetate, 2-methoxy propylacetate, 2- methoxy-1 -methylethyl acetate, ethyleneglycol diacetate, butyleneglycol diacetatepolyoxyethylene monoethyl-ether acetate, polyoxyethylene monobutylether acetate, polyoxy butylene mono-ethyl-ether acetate, polyoxy-butylene monobutylether acetate, polyoxyethylene diacetate, polyoxybutylene-diacetate.
  • the solvent is butyl acetate or 2-methoxy- 1-methylethyl acetate.
  • the solvent can be used in amounts ranging from 15% to 90%wt, advantageously ranging from 15% to 50%wt with respect to the weight of formulation (F).
  • Formulations (F) can include optional ingredients conventionally used in conformal coating formulations; advantageously, in formulations (F) the optional ingredients are selected from cross-linkers, such as
  • the overall amount of the optional additional ingredients can range from 0.01 % to 50% wt based on the total weight of formulation (F).
  • each additional ingredients can be used in amounts ranging from 0.01 % to 8 wt.%, preferably from 0.01 to 5 wt.% based on the total weight of formulation (F).
  • a coating on a PCB (also designated as conformal coating) is made through a method (M) which comprises:
  • formulation (F) does not comprise additional
  • formulation (F) comprises at least one additional ingredient which is a cross-linker and polymer (P2) comprises functional groups able to react with the cross-linker, thereby allowing hardening of the coating.
  • This kind of formulation is commonly referred to as "2K" formulation.
  • Step (c) can be carried out according to conventional methods, including brushing, spraying and dipping, or by selective coating via a robot.
  • Step (d) can be carried out according to conventional methods.
  • formulation (F) does not contain a cross-linker and step d) is carried out by air drying, at room temperature or in an oven;
  • formulation (F) contains a cross-linker and step d) is carried out by curing.
  • formulation (F) and whether drying or curing the formulation on the PCB according to the specific need. Typically, drying is carried out by air drying, but UV-curing shall be preferred when speed is required.
  • n 7 and a1 and a2 are integers as defined above, selected in such a way that the average number molecular weight is 2,200 (in the following, "PFPE P1 -A1 or P1-A1 );
  • n is 4.7 and a1 and a2 are integers as defined above, selected in such a way that the average number molecular weight is 2,000 (in the following, "PFPE P1 -A2 or P1-A2);
  • Fluorolink ® AD 1700 PFPE, PFPEs (P1 -A1 ) and (P1 -A2) were manufactured from PFPE diols of formula:
  • Fluorolink ® AD 1700 PFPE is available on the market from Solvay
  • the selected PFPE polymer (P1 ) was mixed with a commercially available acrylic polymer (P2) and butyl acetate, while for the obtainment of 2K formulations, the selected polymer (P1 ) was mixed with a commercially available acrylic polymer (P2), a cross-linker and 2-methoxy-1 -methyl acetate.
  • the contact angle versus water was determined according to DIN/ ISO 55660.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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Abstract

Un procédé de revêtement d'une carte à circuit imprimé qui comprend l'utilisation d'une formulation à base de solvant comprenant des polymères (per)fluoropolyéther fonctionnels et des polymères acryliques est décrit. Des cartes à circuit imprimé fabriquées au moyen de ce procédé sont également décrites.
PCT/EP2016/080879 2015-12-23 2016-12-14 Procédé de revêtement de cartes à circuit imprimé WO2017108510A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP15202545.8 2015-12-23
EP15202545 2015-12-23
EP16163628 2016-04-04
EP16163628.7 2016-04-04

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WO2017108510A1 true WO2017108510A1 (fr) 2017-06-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1411073A1 (fr) * 2001-06-27 2004-04-21 Daikin Industries, Ltd. Composition d'agent de traitement de surface et procede de fabrication associe
EP2093243A1 (fr) * 2008-02-01 2009-08-26 Samsung Electronics Co., Ltd. Composition, film anti-oxydant l'incluant, composant électronique incluant le film anti-oxydant, et procédés de formation du film anti-oxydant et composant électronique
US7718264B2 (en) * 2005-03-23 2010-05-18 3M Innovative Properties Company Perfluoropolyether urethane additives having (meth)acryl groups and hard coats
US20140044932A1 (en) * 2012-08-09 2014-02-13 3M Innovative Properties Company Photocurable compositions
WO2015056731A1 (fr) * 2013-10-18 2015-04-23 旭硝子株式会社 Composé contenant du fluor, composition permettant d'obtenir une couche de revêtement dur et objet comportant une couche de revêtement dur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1411073A1 (fr) * 2001-06-27 2004-04-21 Daikin Industries, Ltd. Composition d'agent de traitement de surface et procede de fabrication associe
US7718264B2 (en) * 2005-03-23 2010-05-18 3M Innovative Properties Company Perfluoropolyether urethane additives having (meth)acryl groups and hard coats
EP2093243A1 (fr) * 2008-02-01 2009-08-26 Samsung Electronics Co., Ltd. Composition, film anti-oxydant l'incluant, composant électronique incluant le film anti-oxydant, et procédés de formation du film anti-oxydant et composant électronique
US20140044932A1 (en) * 2012-08-09 2014-02-13 3M Innovative Properties Company Photocurable compositions
WO2015056731A1 (fr) * 2013-10-18 2015-04-23 旭硝子株式会社 Composé contenant du fluor, composition permettant d'obtenir une couche de revêtement dur et objet comportant une couche de revêtement dur

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