CN1777655A - Powder coating and process for the preparation of thin layers in the manufacture of printed circuit boards - Google Patents

Powder coating and process for the preparation of thin layers in the manufacture of printed circuit boards Download PDF

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Publication number
CN1777655A
CN1777655A CN 200480008105 CN200480008105A CN1777655A CN 1777655 A CN1777655 A CN 1777655A CN 200480008105 CN200480008105 CN 200480008105 CN 200480008105 A CN200480008105 A CN 200480008105A CN 1777655 A CN1777655 A CN 1777655A
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China
Prior art keywords
powder coating
characterised
method
substrate
coating
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CN 200480008105
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Chinese (zh)
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CN1777655B (en
Inventor
C·里克特
J·克雷斯
S·奇凯蒂
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阿托特希德国有限公司
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Priority to DE10313555.3 priority Critical
Priority to DE10313556.1 priority
Priority to DE2003113556 priority patent/DE10313556A1/en
Priority to DE2003113555 priority patent/DE10313555A1/en
Application filed by 阿托特希德国有限公司 filed Critical 阿托特希德国有限公司
Priority to PCT/EP2004/003001 priority patent/WO2004085550A2/en
Publication of CN1777655A publication Critical patent/CN1777655A/en
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Publication of CN1777655B publication Critical patent/CN1777655B/en

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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/46Manufacturing multilayer circuits
    • H05K3/4644Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03Powdery paints
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/46Manufacturing multilayer circuits
    • H05K3/4644Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H05K3/4655Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern by using a laminate characterized by the insulating layer
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03Conductive materials
    • H05K2201/0332Structure of the conductor
    • H05K2201/0335Layered conductors or foils
    • H05K2201/0358Resin coated copper [RCC]
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01Tools for processing; Objects used during processing
    • H05K2203/0147Carriers and holders
    • H05K2203/0156Temporary polymeric carrier or foil, e.g. for processing or transferring
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/06Lamination
    • H05K2203/066Transfer laminating of insulating material, e.g. resist as a whole layer, not as a pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/13Moulding and encapsulation; Deposition techniques; Protective layers
    • H05K2203/1333Deposition techniques, e.g. coating
    • H05K2203/1355Powder coating of insulating material
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/46Manufacturing multilayer circuits
    • H05K3/4644Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern

Abstract

The invention relates to a powder coating, a water dispersion liquid based on the powder coating and a preparing method, a method for preparing coating on a base, in particular to a method for preparing multilayered structure; no organic solvent is needed in the method.

Description

Be used to prepare the powder coating and the method for thin layer in the printed circuit board (PCB) manufacturing

The present invention relates to a kind of powder coating, its preparation method and a kind of method that particularly prepares coating in substrate on the printed circuit board (PCB).

The preparation of insulation layer itself is known, is that the sheet that several layers constitutes carries out by adopting dry film basically.

One of these layers be also not completely solidified still have the resin (B-stage) of reactive behavior.This layer is stable by carrier layer (for example copper, PET), opposite side protective cover (for example PE).The application carries out by this way: remove protective layer, remaining is laminated on the structurizing printed circuit board (PCB).In the situation of using the pet vector layer, peel off the pet vector layer after the thermofixation.In the scheme of this method, there is other resin layer between reactive resin layer (B-stage) and the carrier layer, this resin layer is completely solidified (C-stage).The advantage of this method is to the better control of the thickness of thin layer that insulate and for the better planning at the layer at the end of whole steps.

These dry films are described in Charles A.Harper, high-performance printed circuit board (PCB) (HighPerformance Printed Circuit Boards), and 1999, McGraw-Hill is in the 2nd chapter.Because the high reaction activity of resin layer, material must be in low temperature (<0 ℃) storage and transportation down, and this causes extra cost and needs appreciable logistics processing power.This layer prepares by liquid formulation is imposed on the carrier layer usually, and promptly this formulation is necessary can be as liquid dosage.Solvent discharge takes place when in addition, dry.

Aforesaid method has the shortcoming that only can add difficultly or can not add at all some filler.As a universal rule, coating must can stable dispersion in organic solvent.

Another shortcoming is the low storage stability of above-mentioned dry film and need stores at low temperatures and transport.

The object of the present invention is to provide a kind of powder coating, a kind of dispersion liquid, a kind of method for preparing this coating or dispersion liquid and a kind ofly particularly prepare shallow layer to prepare the method for printed circuit board (PCB) on the copper sheet in substrate based on this powder coating with these shortcomings.

All conceivable fillers all can be used in powder coating of the present invention and the method.

In addition, avoided with an organic solvent.

And using powder coating of the present invention or method to make in structurizing or non-structure substrate preparation have the thin insulating coating of improving performance becomes possibility.

The invention provides a kind of hardenable coatings, this coating is obtained by following steps:

(i) mix

(a) polymer binder, piperazine resin, cyanate or maleimide,

(b) solidifying agent or initiator,

(c) paint additive,

(d) nonessential filler,

(e) nonessential compatibilizing polymer,

With other nonessential component

(ii) gained mixture in the step (i) is melt extruded, and

(iii) grind and sieve the mixture of extruding.

According to preferred implementation of the present invention, powder coating has at least 20 ℃ second-order transition temperature in uncured attitude, and preferably at least 25 ℃, more preferably at least 30 ℃; Have at least 150 ℃ second-order transition temperature in cure states, preferably at least 160 ℃, more preferably at least 170 ℃.

In addition, the preferred polymers tackiness agent is to be solid Resins, epoxy under the room temperature on substantially.The second-order transition temperature of preferred this resin should be at least 25 ℃.

Preferred powder coating of the present invention can also comprise epoxy resin composition.Preferred this mixture has in uncured attitude>25 ℃ second-order transition temperature.Its molecular weight (number-average molecular weight) usually>600.

The suitable Resins, epoxy that is used to prepare powder coating of the present invention for example is described in Clayton A.May (editor), Resins, epoxy: chemistry and technology (Epoxy Resins:Chemistry andTechnology) the 2nd edition, Marcel Dekker Inc., New York is in 1988.

Be preferably based on the epoxy resin composition of dihydroxyphenyl propane and diglycidyl rthers of bisphenol-A.Epoxy equivalent (weight) weight>300g/ the equivalent of these resins.This resin for example is D.E.R.6508 (can obtain from DowChemicals).

Also can not necessarily add Resins, epoxy based on Bisphenol F and bisphenol S.

In addition, this mixture can comprise polyfunctional epoxy resin.The functionality of these resins>3.The example of this polyfunctional epoxy resin is cresol-novolac epoxy resin, phenol-novolac epoxy resin and contains the naphthols polyfunctional epoxy resin.

The example of aforementioned epoxy resins is: dihydroxyphenyl propane, as D.E.R.667-20, D.E.R.663UE, D.E.R.692H, D.E.R.692, D.E.R.662E, D.E.R.6508, D.E.R.642U-20 (can obtain) from Dow Chemicals; Cresol-novolac epoxy resin is as Araldite ECN 1299, Araldite ECN 1280 (Vantico), EOCN-103S, EOCN-104, NC-3000, EPPN201, EPPN-502H (Nippon Kayaku); Naphthols Resins, epoxy is as NC 7000-L (Nippon Kayaku); And brominated epoxy resin, as Araldite 8010 (Vantico), BREN-S (Nippon Kayaku), ESB-400T (Sumitomo) and Epikote 5051 (Resolution).In addition, can also use modified epoxy.This class modification is for example for using chain reaction terminator control molecular weight, so-called " high workability " resin; Prepare the side chain resin with the use polyfunctional monomer.

Particularly preferred powder coating of the present invention comprises as about 50-90 weight % epoxide of component (a) and about 5-20 weight % cyanate, as about 0.5-5 weight % Dyhard RU 100 and about 0.1-2 weight %2-phenylimidazole of component (b); For example about 85 weight % epoxide, 10 weight % cyanates, as about 2 weight % Dyhard RU 100s of solidifying agent with as about 1 weight %2-phenylimidazole of initiator.

As mentioned above, except Resins, epoxy, cyanate also can be used as polymer binder.In powder coating preparation of the present invention, they can use with monomeric form and with the form of oligopolymer or polymkeric substance.

Suitable cyanate is the difunctionality cyanate, as BADCy, Primaset Fluorocy, Primaset MethylCy; Or multifunctional cyanate ester, as Primaset BA-200, PrimasetPT60, Primaset CT90, Primaset PT30.Above-mentioned all difunctionalitys and multifunctional cyanate ester can be from Lonza, Basel, and Switzenland obtains.

Particularly preferred cyanate is BADCy and prepolymer (as Primaset BA-200) thereof.

Except cyanate, component (a) can also comprise the compound (piperazine resin) that contains 1-oxa--3-azepine-1,2,3,4-tetralin.In the preparation of powder coating of the present invention, these compounds are also used with monomeric form at the beginning.

Preferred piperazine resin is or by dihydroxyphenyl propane and aniline and formaldehyde reaction being obtained or by making 4, those resins that 4-diaminodiphenylmethane and phenol and formaldehyde reaction obtain.Other example can find in WO02/07655 and EP0 493 310 A1 and WO02/055603 and Japanese patent application JP2001-48536, JP2000-358578, JP2000-255897, JP2000-231515, JP2000-123496, JP1999-373382, JP1999-310113 and JP1999307512.Other example can be at Macromolecular Chemistry, Macromolecular Symposia (1993) 74 (the 4th flame proofing polymer meeting, 1992), find among 165-71, EP0493310 A1, EP0458740 A1, EP0458739 A2, EP0356379 A1 and the EP0178414 A1.

The maleimide itself that is used in the powder coating preparation of the present invention also is that the technician is known, is described in for example Shiow-Ching Lin, Eli M.Pearce, High-PerformanceThermosets, Carl Hanser Verlag is in Munich 1994, the 2 chapters.

Component in the resin combination of the present invention (b) comprises solidifying agent or initiator.This solidifying agent and initiator are originally known as the technician, comprise and have SA latent curing agent under the room temperature, for example: phenols curing agent obtains as D.E.H.90, D.E.H.87, D.E.H.85, D.E.H.84, D.E.H.82 (can from U.S. Dow Chemicals); The Dyhard RU 100 or derivatives thereof is as Dyhard OTB, DyhardUR200, Dyhard UR300, Dyhard UR500, Dygard 100, Dyhard 100S, Dyhard100 SF and Dyhard 100SH (can obtain from German Degussa); Dihydroxyphenyl propane; Acid anhydrides, as Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride, hexahydrophthalic anhydride, HET acid anhydrides, dodecenyl succinic anhydride, two rings [2.2.1] heptan-5-alkene-2, the 3-dicarboxylic anhydride; Aromatic series and fatty amine are as diamino diphenyl sulfone, diamino-diphenyl ether, diaminodiphenyl-methane or cyclosubstituted pentanoic, as Lonzacure M-DEA, Lonzacure M-DIPA, Lonzacure M-MIPA, Lonzacure DETDA 80 (above-mentioned all compounds are all from Lonza, Basel, Switzerland obtains).

Preferably, adopt Dyhard RU 100 or modification Dyhard RU 100.

In resin combination of the present invention, solidifying agent or initiator are to be lower than 10 weight %, and the amount that preferably is lower than 5 weight % is used (lower limit: about 0.1 weight %).

Preferred initiator is imidazoles and derivative thereof, as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, two (2-ethyl-4-methylimidazoles), 2-undecyl imidazole, 2,4-diamino-6 (2 '-methyl-imidazoles (1 ')) ethyl-s-triazine and 1-cyanoethyl-2-undecyl imidazole.In addition, can use the salt that generates by imidazoles and carboxylic acid.Other initiator is 1, and 8-diaza-two ring (5.4.0) undecylene (DBU) and boron-three halogen amine complex are as BF 3-amine.Other example can be Clayton A.May (editor), Resins, epoxy: chemistry and technology (Epoxy Resins:Chemistry and Technology) the 2nd edition, and Marcel Dekker Inc., New York finds in 1988.

Resin combination of the present invention further comprises the paint additive as component (c).These additives comprise flow control agent, degasifier and lubricant.These additives this as known to the technician.Exemplary be as flow control agent the butyl acrylate polymkeric substance, as the bitter almond oil camphor of degasifier and as the wax of lubricant.In addition, for example can adopt stablizer as paint additive.

Resin combination of the present invention is with common 0.1-10 weight %, and the amount of preferred 0.2-5 weight % comprises paint additive.

Paint additive also comprises adhesive accelerant.These promotor helping, provide the adhesion with the copper substrate.

Powder coating of the present invention can further comprise organic or mineral filler (d).

Use these coating to suit with the amount of 5-300 weight % in the powder coating of the present invention, preferred 10-200 weight %, more preferably 10-100 weight %.Described amount is existing for powder coating component (a) and (b) with (c) for the sum.

The example of organic coating is a fluoropolymer, as polytetrafluoroethylene (PTFE), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene multipolymer (E/TFE), tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride trimer (THV), gather (trifluorochloroethylene) (PCTFE), trifluorochloroethylene/ethylene copolymer (E/CTFE), gather (ethylene fluoride) (PVF), gather (vinylidene fluoride) (PVDF), perfluoroalkyl alkoxy copolymer (PFA), tetrafluoroethylene/perfluoro methyl ethylene ether copolymer (MFA), also has poly-(vinylchlorid) (PVC), polyphenylene oxide (PPO), polysulfones (PSU), polyphenylene ether sulfone (PES), polyphenylene ether sulfone (PPSU), polyphenylene sulfide (PPS), polyetherketone (PEK) and polyimide (PEI).

Particularly preferred organic filler is tetrafluoroethylene/hexafluoropropylene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE) and polyphenylene oxide (PPO).

In powder coating of the present invention, preferably can exist to add not fused exhausted organic filler in man-hour.In addition, the exhausted filler that can have fusion and be separated in when cooling performance.

Except organic filler, also can use mineral filler in the powder coating of the present invention.

This coating for example is fused silica, as Silbond 800 EST, Silbond 800 AST, Silbond 800 TST, Silbond 800 VST, Silbond 600 EST, Silbond 600 AST, Silbond 600 TST, Silbond 600 VST (can obtain from German Quarzwerke Frechen); Pyrogenic silica is as Aerosil 300 and Aerosil R 972; Precipitated silica is as Ultrasil360, Sipernat D 10, Sipernat 320 (can obtain from German Degussa); Calcined kaolin is as PoleStar (Imerys of Britain St Austell), Santintone (the Engelhard Corporation of New Jersey Iselin); Aluminum oxide; Magnesium oxide; Zirconium white; Pure aluminium silicate; Lime carbonate and barium sulfate, silica glass and kaolin are preferred filler.In addition, can mention pottery, especially those have the pottery of low or negative thermal expansion coefficient.

The advantage of powder coating of the present invention is can select to satisfy most a kind of of related request in order to optimize product performance from various fillers.Can be when for example, needing thus with given oxyethane modification.Even unmanageable filler also can be sneaked into without a doubt.Can adjust electrical characteristic such as specific inductivity (Dk), dielectric loss factor (tan δ), resistance to sparking, surface resistivity, volume resistance and mechanical characteristics such as flexural strength, shock strength, tensile strength and other material behavior such as thermal expansivity (CTE), flammable and other character when therefore, needing.Filler needn't dissolve in or stable dispersion in organic solvent.Thereby, can will before can not or only can be used for the material of order formation (SBU) as filler, for example above-mentioned organic filler difficultly.

The electrical characteristic of powder filler and coating prepared therefrom and mechanical characteristics can be used fillers affect and control.

Therefore, for example, can adopt filler, as PTFE, FEP and kaolin with low-k in order to prepare coating with corresponding low-k.

Can control other electrical characteristic with similar approach.

Can be comprised by the mechanical characteristics of fillers affect, especially the characteristic such as thermal expansivity, shock strength and tensile strength.

Following filler is particularly suitable for controlling thermal expansivity: silica glass, kaolin, lime carbonate and have the pottery of negative thermal expansion coefficient.

Flexural strength for example can be influenced by PPO or control.

According to a preferred embodiment of the present invention, the solidified powder coating x-, y-and-have<thermal expansivity (CTE) of 70ppm/ ℃ preferred<60ppm/ ℃ on the z direction.

According to another preferred embodiment of the present invention, the specific inductivity of cure states coating is<3.8, preferred<3.6.And the second-order transition temperature of preferred consolidation formulation is higher than 150 ℃, more preferably is higher than 160 ℃.

In addition, can be with fire retardant material as filler.When being heating, the example of these materials emits the inorganic materials of water, as aluminium hydroxide, for example can obtain with Martinal OL-104, Martinal OL-111 (the Martinswerk GmbH of German Bergheim) or Apyral 60D (Nabaltec of German Schwandorf), magnesium hydroxide for example can obtain with magnesium hydroxide 8814 (the Martinswerk GmbH of German Bergheim) or hydroxide Mg SIM 2.2 (ScheruhnIndustrie-Mineralien of German Hof); Organic phosphorus compound, as triphenylphosphate (TPP), Tritolyl Phosphate (TCP), tricresyl phosphate biphenyl ester (CDP), phosphine oxides is as Cyagrad And Reoflam 410, be dispersed in the red phosphorus of the form in the Resins, epoxy such as the red phosphorus such as the Exolit OP 930 (two kinds all can obtain from the ClariantGmbH of German Frankfurt) of Exolit RP650 or powder type; And ANTIMONY TRIOXIDE SB 203 99.8 PCT.

In addition, the combustibility of powder coating of the present invention can be paint additive influence and control by component (c).Thus, for example can mention phosphorous and contain nitrogen combustion inhibitor.

Powder coating of the present invention can not necessarily further contain compatibilizing polymer.This class compatibilizing polymer for example is two-or the multipolymer of three blocks, as styrene/butadiene/styrene or phenylethylene/butadiene/methyl methacrylate segmented copolymer (French Atofina).

And powder coating of the present invention can contain the conventional additives that is used in usually in the Resins, epoxy processing.

In the preparation of powder coating of the present invention, component (a) and (b), (c) and nonessential (d) and (e) at first by the dry grinding powdered.

So therebetween, in advance each component is mixed and extrude with the preparation masterbatch perhaps favourable.

Especially when some component is difficult to mix, must adopt this step.In advance these components are pre-mixed mutually then.This masterbatch also can be buied.For example in the situation of resin, for example can realize two kinds of mixed with resin.Especially when wherein a kind of resin has low second-order transition temperature, adopt this way.And, when certain component during, can adopt this step only with a small amount of use.

Aforementioned component or masterbatch are with dry state pre-mixing and grinding.Before the grinding, can not necessarily mixture be cooled off.

Mixing (and nonessential cooling) afterwards fully, when keeping powdered form, grinding this material, subsequently powder is being extruded with dry state.This extruding provides homogenizing fully and being committed step in the entire method of component.

After extruding, material is ground with dry state, material on the separation sieve, wherein suitable the employing is lower than 10 to 500 μ m and preferably is lower than sieve size in 100 mu m ranges, and this has guaranteed consistent particle size.Classified grinding machine such as Hosekawa MicroPul are particularly suitable for grinding.

Aforementioned melt extrude preferably carry out by this way: the transformation efficiency of reactive component is lower than 20%, preferably is lower than 10%.This reaction takes place owing to forming melt during extruding.Transforming degree is determined by heat analysis by the technician.Extruding parameter (being used to obtain this transforming degree) accordingly can be determined by simple experiment by the technician.They depend on the kind and the consumption of the type and the used component of forcing machine.For example, Buss can be total to kneader as forcing machine, aforementioned component is extruded therein.As mentioned above, subsequently with gains coolings and turn to small pieces.Final powder coating compositions preferably has the median size in 1-500 μ m, particularly the 10-100 mu m range.

Zhi Bei powder coating is used to prepare suprabasil coating according to the present invention thus, and this substrate is used for the manufacturing of printed circuit board (PCB) subsequently.

The present invention further provides a kind of method that in substrate, prepares coating, comprise following steps:

(i) powder coating of the present invention is imposed in the substrate,

(ii) with the powder coating fusion, and

(iii) with powder coating solidification.

In the method for the invention, preparation thin insulating coating, promptly thickness is the layer of about 5-500 μ m.Thereby method of the present invention can be used for the manufacturing of printed circuit board (PCB), particularly is used in the so-called order formation (sequential-build-up) (SBU).Other possible purposes intercepts in cover (the solder stop mask) device for being used in scolder, and all need prepare thin layer and be characterised in that in the process of having used filler that described filler is insoluble to or is refractory to usual vehicle under usual processing conditions to be used in other.

Available several different methods imposes on powder coating in the substrate.Thereby the coating of powder coating for example can be brushed by spraying, electromagnetism, the powder cloud cluster applies (powder cloud coating) or roller coat carries out.

For example can spray by corona discharge or tribo-charging.These methods are as well known to those skilled in the art.The preferred tribo-charging that adopts among the present invention.

In addition, in the method for the invention, can use roller coating powders coating.In this case, can powder be imposed in the substrate, handle with roller then with sieve.This roller can be to heat.

The unit describe that adopts electromagnetic brush technology is in WO96/15199.

Powder cloud cluster technology for example is described in Proceedings-International Conference inOrganic Coatings:Waterborne, High Solids, Powder Coatings, 23 Rd, Athens, June, 7-11,1997 (1997), 139-150, publisher: Institute of Materials Science, New Paltz, N.Y.; Journal f ü r Oberfl  chentechnik (1996), 36 (8), 34-36,39; Deutsche Forschungsgesellschaft f ü r Oberfl  chenbehandlung (2000), 44 (Pulverlack-Praxis), 95-100; Journal f ü r Oberfl  chentechnik (1998), 38 (2), among 14-18 and the WO97/47400.

In principle, following method is suitable for the powder coating fusion:

A) the band convection current or not with the stove of convection current in fusion,

B) ir radiation,

C) near-infrared radiation (NIR) and

D) induction and nonessential

E) use microwave-excitation.

In the inventive method, preferably carry out fusion with NIR.This method is described in WO99/47276, DE10109847, Kunststoffe (1999), and 89 (6), 62-64 and Journal f ü rOberfl  chentechnik (1998), 38 (2), among the 26-29.

Fusion step particularly important.During fusion, viscosity changes, i.e. powder elder generation fusion, and the viscosity of melt reduces.With after fixing, viscosity raises thus.Must this mode carry out this operation in the inventive method: the viscosity of melt begins low as much as possible, obtains good flowing subsequently and does not have bubble formation, thereby obtain non-porous film.

As seen the substantial advantage of the inventive method is at first fusion of coating, keeps and can flow, and therefore can be used for preparing multilayered structure.

The present invention further provides a kind of method for preparing multilayered structure, comprise following steps:

(i) powder coating of the present invention is imposed in the substrate,

(ii) with the powder coating fusion, with postcooling,

(iii) the stratum basale through applying is pressed onto on the printed circuit board (PCB), this circuit card can comprise the above layer of one deck,

(iv) solidify,

(v) each layer is connected with the preparation multilayered structure with substrate boring and perforation,

(vi) repeating step (i)-(v) not necessarily.

In this method, powder coating preferably uses aforesaid electromagnetic brush technology (EMB) to apply.Like this, can obtain the powder coated of homogeneous more and therefrom the bed thickness of homogeneous more.Preferably carry out fusion with the NIR method.Like this, obtain the atresia coating.

A key character of this method is only to be cured in (iv) in step, promptly after forming multilayered structure.Thus, importantly film remains flowable during the structure preparation.

The melted powder coating be solidificated in the extruding or lamination during carry out.Push or be laminated under vacuum and the pressure and carry out, relevant parameter is that the technician is known.For example, can use Lauffer pressing machine or Adara pressing machine.Adjust extrusion cycle to adapt to employed each material.

In the final step of this method,, carry out each layer and contact with the extruding of substrate for the preparation multilayered structure.

Typical substrates is copper sheet or polymer support sheet particularly.These substrates can further combine with the weaving or the nonwoven fabric of glass fibre or Kevlar.

When the utilization structure substrate, method of the present invention comprises following steps:

(i) powder coating of the present invention is imposed on the structured substrate,

(ii) the powder coating fusion is also solidified, with postcooling,

(iii) boring,

(iv) metallization,

(v) repeating step (i)-(v) not necessarily.

In this method, powder coating preferably uses aforesaid electromagnetic brush technology (EMB) to apply.Like this, can obtain the coating of homogeneous more and therefrom the bed thickness and the edges cover preferably of homogeneous more.

The present invention further provides a kind of method that in substrate, prepares coating, comprise following steps:

(i) with powder coating wet-milling of the present invention with the preparation dispersion liquid, not necessarily handle with other additive,

(ii) this dispersion liquid is imposed in the substrate, and

(iii) will be through the substrate thermal treatment of coating.

In the first step of the inventive method, prepare dispersion liquid from powder coating by adding water.The solid content of this dispersion liquid is generally 20-70 weight %, preferred 30-60 weight %.

In order to prepare dispersion liquid, powder and water are ground, not necessarily add other additive.Except the aforementioned additive that can use with the amount of 0.1-5 weight %, preferred 0.5-2.5 weight %, can add wetting agent, dispersion agent, defoamer and degasifier and flow control agent.

The example of this class wetting agent and dispersion agent is a high molecular weight block copolymer solution, and this multipolymer contains the group with pigment avidity, as Disperbyk 160,170 or 182; Acrylate copolymer, this multipolymer contains the group with pigment avidity, as Disperbyk 116; Alkylammonium salt solution is as Disperbyk 140; The salts solution or the polarity ester solution of unsaturated polyester amino amides and acid are as Anti Terra U or Disperbyk 101 (all are all from the Byk Chemie of German Wesel); With or without the multipolymer of the polycarboxylic acid polymkeric substance of polysiloxane, as Byk P 104 or Byk 220S; Fluorine-containing wetting agent is as Zonyl FSN or Zonyl FSH (all from DuPont) and nonionic surface active agent, as the Surfynol series product from the Air Product of Dutch Utrecht.

The example of defoamer and degasifier is for not containing the froth breaking polymkeric substance of organic silicone resin, as Byk 051; The solution of froth breaking polysiloxane or emulsion are as Byk 020 or Byk 067; Do not contain the froth breaking polymkeric substance of silicone and the solid of hydrophobizing agent, as Byk 011; The emulsion of paraffin base mineral oil and hydrophobic components and mixture are as Byk 033 or Byk 036 (all from German Wesel Byk Chemie).

The example of flow control agent is polyether-modified polydimethylsiloxane, as Byk 300 or Byk085; The modified dimethyl polysiloxane of hydroxyl-functional is as Byk 370; Polyether-modified polydimethylsiloxane is as Byk 345 and ionic and non-ionic type acrylate copolymer, as Byk 380.

Other example of additive can be in WO96/32452, WO96/37561, WO97/01609, WO97/17390, WO99/15593, EP0714958A2 and EP0044810A1.

Method of the present invention has the advantage that filler is arranged in coating particles, thereby, because filler has been incorporated in the water-fast coating particles, therefore do not divide.This is the special benefits of the inventive method: prior art is known when processing contains the solvent of formulation, or filling settlement, or must make it stable by carrying out special weighing, promptly occurs different packing densities in the formulation.

In the method for the invention, use soluble coating particles, this particle contains homodisperse filler therein, thereby does not produce concentration difference.

In order to obtain stable dispersion liquid, particle must have the median size less than 10 μ m, preferably less than 7 μ m.Particle diameter can be measured with the Coulter counter.

After imposing on dispersion liquid in the substrate, heat-treat (be used to remove dispersion medium and make the powder coating fusion).Thermal treatment can so be carried out: after imposing on dispersion liquid in the substrate that film is at first dry, and fusion, with after fixing.In addition, after imposing on dispersion liquid in the substrate, only carry out powder coating drying, fusion and solidified one step.

Preceding method is applicable to powder coating thermal treatment, particularly fusion.

In addition, the invention provides a kind of method for preparing multilayered structure, comprise following steps:

(i) with powder coating wet-milling of the present invention with the preparation dispersion liquid, not necessarily handle with other additive,

(ii) this dispersion liquid is imposed on the structured substrate,

Substrate thermal treatment that (iii) will be through applying,

(iv) boring, fusion and structure,

(v) not necessarily repeating step (ii) to (iv).

In a word, powder coating of the present invention and method of the present invention provide the possibility that need not any organic solvent and prepare coating in substrate especially printed circuit board (PCB).

With regard to industrial safety and thereby the ventilation system, waste treatment, the environmental protection requirement that produce are more and more stricter all the time and the expense of coming with these factors for, not using any organic solvent is an important aspect.

The main advantages of described method in industrial practice is that material to be coated is an one-component system, promptly tackiness agent (Resins, epoxy) and solidifying agent Already in actual composition suffered, just need not before applying, to mix.

Another advantage of comparing with dry film is the storage stability of room temperature transportation and storage.Term " storage-stable " is meant the nonreactive resin combination of component, and particularly the decline of heat release is no more than 10% composition (when storing down for 25 ℃) in about 3 months periods.

The present invention is described in further detail by following examples.

Embodiment 1

With 4444g D.E.R.6508 (Dow Chemicals) in stove in 110 ℃ of following fusions.Adding 1460g fusion Primaset BA-200 (Lonza) and 74g dihydroxyphenyl propane (Aldrich), 60gModarez and 12g bitter almond oil camphor (Aldrich) afterwards, with the mixture thorough mixing.After cooled with liquid nitrogen, material is ground and extrudes with dry state (the twin screw extruder EBVP:110-120 of OMC ℃, 500rpm).

Powder has 45 ℃ second-order transition temperature (DSC).

Repeating dry grinding and screening (100 μ m) afterwards, powder is imposed on the thick copper sheet of 32 μ m with EMB machine (Epping).After 160 ℃ of following fusions were more than 5 minutes, what the powder performance was splendid flowed.Film does not have bubble.

After 20 minutes, measuring insulating layer thickness is 45 μ m in 190 ℃ of following thermofixations.T g(DSC) be 172 ℃.

Embodiment 2

290g DER 6508,58g NC 7000-L, 58g BADCy, 11.7g DICY, 180g Silbond EST 800 and 0.6g phenylimidazole are mixed in the premix machine, extrude subsequently (the twin screw extruder EBVP:110-120 of OMC ℃, 500rpm).After dry grinding and the screening, measure the coefficient of expansion (CTE=55ppm, D with the part powder curing and with TMA k(1GHz)=3.6).

Embodiment 3

With 350g DER 6508,70g NC 7000-L, 202g Silbond EST 800 and 50gETFE ET 6235 thorough mixing in the premix machine, and under 260 ℃, extrude.This material is ground and screening, and mix with 70g Primaset BA-200,14g DICY, 0.7g phenylimidazole, 1.5g bitter almond oil camphor and 11.4g Modarez, under 130 ℃, extrude then (the twin screw extruder EBVP:110-120 of OMC ℃, 500rpm).Grind and screening after, on the copper sheet that powder is imposed on EMB machine (Epping) and 190 ℃ of curing down.D k(1GHz)=3.3。

Embodiment 4

Sieve with 100 μ m after the powder dry grinding of embodiment 1 is sieved.This powder of 250g and 374g softening water, 0.37g Surfynol 440,2.77g Disperbyk 185 and 4.16g defoamer Byk028 are stirred and mix.(Bachofen, Basel grind twice (abrasive material ZrO in CH) at DynoMill with this dispersion liquid 2, diameter 0.8mm; Wavelength width of a slit 0.3mm; Engine speed 10m/s).And then add the 124g powder, 0.185g Surfynol 440,0.277g Disperbyk 185,0.369g Byk 028 and 0.28g Aerosil R 972, and grind again twice as mentioned above.For making formed lather collapse, should slow stirring of the sticking material of height spend the night.The dispersion liquid that so obtains (more not thickness) is mixed with 0.28g Aerosil again, impose on to cover on the copper FR-4 thin slice and with scalpel then and solidify down at 190 ℃.(Isoscope, Fischer) measuring bed thickness is 45 μ m with the bed thickness metering facility.The smooth atresia of coating has 165 ℃ second-order transition temperature (T g).

Comparative Examples 1

43.7g D.E.R.6508 (Dow Chemicals) is dissolved among the 150ml MPA with 14.4g Primaset BA-200 (Lonza) and 0.73g dihydroxyphenyl propane (Aldrich), 0.59g Modarez and 0.12g bitter almond oil camphor (Aldrich).Add 5.5g poly-(tetrafluoroethylene) (Ausimont) after, white solid floats from the teeth outwards, thereby this mixture can not apply.

Comparative Examples 2

With the powder suspension of embodiment 3 in MPA.Material forms the bottom be deposited on container, can not impose on the thick substances on the copper sheet.

Claims (44)

1. hardenable coatings can be obtained by following steps:
(i) mix
(a) polymer binder, piperazine resin, cyanate or maleimide,
(b) solidifying agent or initiator,
(c) paint additive,
(d) nonessential filler,
(e) nonessential compatibilizing polymer,
With other nonessential component
(ii) gained mixture in the step (i) is melt extruded and
(iii) grind and sieve the mixture of extruding.
2. the powder coating of claim 1 is characterised in that it has at least 20 ℃ in uncured attitude, preferably at least 25 ℃, and more preferably at least 30 ℃ second-order transition temperature; Have at least 150 ℃ in cure states, preferably at least 160 ℃, more preferably at least 170 ℃ second-order transition temperature.
3. the powder coating of claim 1 is characterised in that polymer binder is a solid epoxy.
4. claim 1 or 3 powder coating are characterised in that component (a) comprises the mixture of the Resins, epoxy of the second-order transition temperature with at least 20 ℃.
5. claim 1,3 or 4 powder coating are characterised in that Resins, epoxy is selected from the standard solid Resins, epoxy based on dihydroxyphenyl propane and diglycidyl rthers of bisphenol-A.
6. the powder coating of claim 5 is characterised in that the epoxy equivalent (weight) weight>300g/ equivalent of Resins, epoxy.
7. the powder coating of claim 1 is characterised in that Resins, epoxy comprises polyfunctional epoxy resin or polyfunctional epoxy resin mixture.
8. the powder coating of claim 7 is characterised in that polyfunctional epoxy resin is selected from cresol-novolac epoxy resin, phenol-novolac epoxy resin and contains the naphthols polyfunctional epoxy resin.
9. the powder coating of claim 1 is characterised in that cyanate is selected from difunctionality and multifunctional cyanate ester.
10. the powder coating of claim 1 is characterised in that maleimide is selected from difunctionality or multifunctional maleimide, is preferably based on aromatic diamine; The piperazine resin is selected from difunctionality or multifunctional piperazine resin.
11. the powder coating of claim 1 is characterised in that solidifying agent is selected from phenols curing agent, dihydroxyphenyl propane, Dyhard RU 100 or modification Dyhard RU 100, acid anhydrides, aromatic series and fatty amine or cyclosubstituted diamines.
12. the powder coating of claim 11 is characterised in that solidifying agent is Dyhard RU 100 or modification Dyhard RU 100.
13. claim 1,11 or 12 powder coating are characterised in that it with 0.1-10 weight %, the amount of preferred 0.5-5 weight % contains solidifying agent or initiator.
14. the powder coating of claim 1 is characterised in that its amount with 0.1-10 weight % contains paint additive.
15. the powder coating of claim 1 is characterised in that based on component (a) and (b) and (c), it is with 5-300 weight %, preferred 10-200 weight %, more preferably the amount of 10-100 weight % contains filler.
16. the powder coating of claim 1 or 15 is characterised in that filler is mineral filler.
17. the powder coating of claim 16 is characterised in that filler is fused silica or kaolin.
18. the powder coating of claim 16 or 17 is characterised in that filler has less than 30 μ m, preferably less than 20 μ m, is more preferably less than the median size of 10 μ m.
19. the powder coating of claim 1 or 15 is characterised in that not fused organic filler when filler is the processing powder coating.
20. the powder coating of claim 1 or 15 is characterised in that filler is processing fusion and show the organic filler that is separated when cooling during powder coating.
21. the powder coating of claim 1 or 15 is characterised in that filler is polyphenylene ether or fluorizated thermoplastic material, especially poly-(tetrafluoroethylene) (PTFE), Tefzel (ETFE) or tetrafluoroethylene/hexafluoropropylene copolymer.
22. the powder coating of claim 1 is characterised in that its cure states has<70ppm/ ℃, preferred<60ppm/ ℃ thermal expansivity on x-, y-and z-direction.
23. the powder coating of claim 1, the specific inductivity that is characterised in that its cure states is<3.8, preferred<3.6.
24. the powder coating of claim 1 is characterised in that it is stable in storage, wherein when when storing three months down for 25 ℃, its heat release descends and is no more than 10%.
25. the powder coating of claim 1 is characterised in that it comprises as about 50-90 weight % epoxide of component (a) and about 5-20 weight % cyanate, as about 0.5-5 weight % Dyhard RU 100 and about 0.1-2 weight %2-phenylimidazole of component (b).
26. the method for the curable powder coating of preparation claim 1 is characterised in that following steps:
(i) with component (a) and (b), (c) and nonessential (d) and (e) mixing,
(ii) gained mixture in the step (i) is melt extruded, and
(iii) extrusioning mixture is ground and screening.
27. the method for claim 26 is characterised in that with (a) and (b), (c), (d) and (e) two or more are as the masterbatch in the step (i).
28. the method for claim 26 or 27, be characterised in that step (ii) so carries out: the transformation efficiency of active ingredient is lower than 20%, preferably is lower than 10%.
29. in substrate, prepare the method for coating, comprise following steps:
(i) with the powder coating wet-milling of one of claim 1-25 with the preparation dispersion liquid, not necessarily carry out with other additive,
(ii) this dispersion liquid is imposed in the substrate, and
(iii) will be through the substrate thermal treatment of coating.
30. the method for claim 29 is characterised in that the thermal treatment during step is (iii) so carried out: after imposing on dispersion liquid in the substrate, film is at first dry, and fusion again is with after fixing.
31. the method for claim 29 is characterised in that will so carry out through the substrate thermal treatment that applies during step (iii): after imposing on dispersion liquid in the substrate, only carry out powder coating drying, fusion and solidified one step.
32. prepare the method for multilayered structure, comprise following steps:
(i) with the powder coating wet-milling of one of claim 1-25 with the preparation dispersion liquid, not necessarily carry out with other additive,
(ii) this dispersion liquid is imposed on the structured substrate,
Substrate thermal treatment that (iii) will be through applying,
(iv) hole and metallize,
(v) not necessarily repeating step is (ii) and (iv).
33. each method among the claim 29-32 is characterised in that substrate is copper sheet, polymer support sheet, structurizing printed circuit board (PCB) or its sandwich layer.
34. the method for claim 33 is characterised in that carrier-pellet combines with the weaving or the nonwoven fabric of glass fibre or Kevlar.
35. the method for claim 29 or 32 is characterised in that defoamer, wetting agent, biocide, rheologic additive or flow control agent as additive.
36. the method for claim 29 or 32 is characterised in that thermal treatment or solidifies and carries out like this:
A) the band convection current or not with the stove of convection current in fusion,
B) ir radiation,
C) near-infrared radiation (MR)
D) induction, or
E) use microwave-excitation.
37. in substrate, prepare the method for coating, comprise following steps:
(i) powder coating with one of claim 1-25 imposes in the substrate,
(ii) with the powder coating fusion, and
(iii) with powder coating solidification.
38. prepare the method for multilayered structure, comprise following steps:
(i) powder coating with one of claim 1-25 imposes in the substrate,
(ii) with the powder coating fusion, with postcooling,
(iii) the stratum basale through applying is pressed onto on the printed circuit board (PCB), this circuit card can comprise the above layer of one deck,
(iv) solidify,
(v) each layer being holed with substrate and run through is connected with the preparation multilayered structure,
(vi) repeating step (i)-(v) not necessarily.
39. the method for claim 37 or 38 is characterised in that substrate is copper sheet or polymer support sheet.
40. the method for claim 39 is characterised in that carrier-pellet combines with the weaving or the nonwoven fabric of glass fibre or Kevlar.
41. prepare the method for multilayered structure, comprise following steps:
(i) powder coating with one of claim 1-25 imposes on the structured substrate,
(ii) the powder coating fusion is also solidified, with postcooling,
(iii) boring,
(iv) metallization,
(v) repeating step (i)-(v) not necessarily.
42. each method among the claim 37-41 is characterised in that the coating of powder coating is undertaken by spraying, electromagnetism brushing, the coating of powder cloud cluster or roller coat.
43. the method for claim 42 is characterised in that spraying undertaken by corona charging or triboelectric charging.
44. the method for one of claim 37-41 is characterised in that fusion carries out as follows:
A) the band convection current or not with the stove of convection current in fusion,
B) ir radiation,
C) near-infrared radiation (NIR)
D) induction, or
E) use microwave-excitation.
CN 200480008105 2003-03-26 2004-03-22 Powder coating and process for the preparation of thin layers in the manufacture of printed circuit boards CN1777655B (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE10313555.3 2003-03-26
DE10313556.1 2003-03-26
DE2003113556 DE10313556A1 (en) 2003-03-26 2003-03-26 Curable powder coating useful in manufacture of printed circuit boards is obtained by mixing polymeric binder, oxazine resin, cyanate ester or maleimide, hardener or initiator and coating additive; melt extruding; and milling and sieving
DE2003113555 DE10313555A1 (en) 2003-03-26 2003-03-26 Curable powder coating useful in manufacture of printed circuit boards is obtained by mixing polymeric binder, oxazine resin, cyanate ester or maleimide, hardener or initiator and coating additive; melt extruding; and milling and sieving
PCT/EP2004/003001 WO2004085550A2 (en) 2003-03-26 2004-03-22 Powder coating and process for the preparation of thin layers in the manufacture of printed circuit boards

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040803A (en) * 2009-10-14 2011-05-04 住友电木株式会社 Epoxy resin composition, prepreg, metal-clad laminate, printed wiring board and semiconductor device
CN103571160A (en) * 2012-07-31 2014-02-12 三星电机株式会社 Epoxy resin composition for printed circuit board, insulting film, prepreg and multilayer printed circuit board
TWI504327B (en) * 2010-05-10 2015-10-11 Denki Kagaku Kogyo Kk Manufacturing method of metal base substrate and electronic circuit board
CN107141896A (en) * 2017-05-17 2017-09-08 合肥绿洁环保科技有限公司 A kind of fluoro coatings of environmental protection

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860557A (en) * 1971-01-18 1975-01-14 Beatrice Foods Co Electrostatic method of applying multilayer coating and product produced thereby
US5290882A (en) * 1991-08-13 1994-03-01 Shin-Etsu Chemical Co., Ltd. Thermosetting resin compositions
DE4306102A1 (en) * 1993-02-27 1994-09-01 Basf Lacke & Farben Powder coatings based on polyesters containing carboxyl groups and suitable crosslinking agents as well as processes for coating metal sheets
DE4322437C1 (en) * 1993-07-06 1995-03-30 Basf Lacke & Farben Powder coating, process for the external coating of metal pipes and use of the powder coating for single-layer external coating of metal pipes
CA2187820C (en) * 1994-04-13 2000-05-30 Chun-Tzer Chou Thermosetting powder coating compositions
DE4427225A1 (en) * 1994-08-01 1996-02-08 Bayer Ag Hardener for powder coating binders
BR9608453A (en) * 1995-05-19 1999-01-05 Basf Coatings Ag Aqueous powder dispersion for coating
CN1084364C (en) * 1997-03-17 2002-05-08 姜祖斌 Thermosetting luminescent powder coating material and production thereof
DE19711225A1 (en) * 1997-03-18 1998-09-24 Huels Chemische Werke Ag Isocyanate group containing polymer mixture
DE19933095A1 (en) * 1999-07-15 2001-01-18 Herberts Gmbh & Co Kg Coating powder for coating plastic, wood and MDF materials consists of heat-cured resin and hardener, thermoplastic resin powder, inorganic filler and additives and-or pigments
US6437045B1 (en) * 1999-11-10 2002-08-20 Vantico Inc. Powder coating of carboxyl polyester or (poly)methacrylate and cycloaliphatic polyepoxide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040803A (en) * 2009-10-14 2011-05-04 住友电木株式会社 Epoxy resin composition, prepreg, metal-clad laminate, printed wiring board and semiconductor device
CN102040803B (en) * 2009-10-14 2014-07-16 住友电木株式会社 Epoxy resin composition, prepreg, metal-clad laminate, printed wiring board and semiconductor device
TWI504327B (en) * 2010-05-10 2015-10-11 Denki Kagaku Kogyo Kk Manufacturing method of metal base substrate and electronic circuit board
CN103571160A (en) * 2012-07-31 2014-02-12 三星电机株式会社 Epoxy resin composition for printed circuit board, insulting film, prepreg and multilayer printed circuit board
CN107141896A (en) * 2017-05-17 2017-09-08 合肥绿洁环保科技有限公司 A kind of fluoro coatings of environmental protection

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