WO2002085962A1 - Composition durcissable par rayonnement amelioree - Google Patents

Composition durcissable par rayonnement amelioree Download PDF

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Publication number
WO2002085962A1
WO2002085962A1 PCT/EP2002/004456 EP0204456W WO02085962A1 WO 2002085962 A1 WO2002085962 A1 WO 2002085962A1 EP 0204456 W EP0204456 W EP 0204456W WO 02085962 A1 WO02085962 A1 WO 02085962A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
amido
composition
reacting
Prior art date
Application number
PCT/EP2002/004456
Other languages
English (en)
Inventor
Mohd Nor Azmi Alias
Kris Verschueren
Original Assignee
Ucb, S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ucb, S.A. filed Critical Ucb, S.A.
Publication of WO2002085962A1 publication Critical patent/WO2002085962A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to a radiation curable composition containing amide linkages and its utility in resistant inks for the fabrication of printed circuit boards.
  • the present invention in its preferred embodiments has two aspects, the first aspect relating to a composition specific for UV etch resist composition and the second aspect relating to composition for UV solder mask application.
  • a first aspect of the invention is directed to the use of radiation curable composition containing amido (NHCO) linkage for UV etch resist application to impart good hardness, and alkaline solubility in the alkaline stripping solution.
  • the second aspect of the invention is directed to the use of radiation curable composition containing amido (NHCO) linkage for UV solder mask application to impart good adhesion to Cu, Ni and Au.
  • the said composition also provides good chemical resistance to various fluxes used during the soldering processes in the printed circuit board fabrication.
  • the present invention is directed towards a radiation curable composition containing amido (NHCO) linkage the use for which includes:
  • adhesion promoters based on (meth)acrylated phosphoric acid are widely known in the formulation of UV solder masks. These adhesion promoters are highly acidic and can lead to detrimental effect to the properties of the solder mask such as poor resistance to chemicals used in printed circuit board processes.
  • the applicant also founds that UV solder mask containing these type of adhesion promoters is susceptible to blistering or total delamination during the Sn/Pb soldering processes when water-based fluxes are used prior to the soldering processes. Due to increasing environmental concerns water-based fluxes are rapidly replacing solvent-based fluxes (or No- clean fluxes based containing solvent).
  • Flux is a component used in the soldering process of electronic product. It is known that there are many different types of fluxes in the market such as rosin-based flux, low volatile-organic-content flux, and water-based flux. These fluxes typically contains active ingredients such as halides, amines, and organic acids to help removing the oxides and contaminants on the metallic Cu surface prior to Sn/Pb soldering process. Typically ink supplier deigns the solder mask specific to a particular type of flux, and when the end-user requires using different types of fluxes, they'll encounter problems during the soldering process. Blisters or total delamination of the solder mask can be one of the dramatic problems due to flux and solder mask incompatibility. Therefore, an ink formulation that can be used with various types of fluxes would be an advantage to the end user. UV solder mask composition with good resistance to Sn/Pb soldering with different types of fluxes are disclosed in this invention.
  • a further aspect of the present invention is directed towards providing a UV etch resist composition with good surface hardness, excellent acid etching resistance and good alkaline solubility in the 3-5% NaOH stripping solution.
  • Typical formulations of UV etch resist utilized acid functional monoacrylate to provide resistance to the acidic etching solution and solubility in the alkaline stripping solution.
  • Use of monofunctional (meth)acrylate will lead to slow cure speed and the resultant UV curable resist could only achieve pencil hardness as high as H. This lead to sticking of the resist to the back of another board when many boards are stacked together after the UV curing step in waiting for the wet processes.
  • a radiation curable composition including at least one amide (- NH(CO)-) linkage and at least one (meth)acrylate functionality.
  • the amide linkage is contained within the internal structure of the (meth)acrylate.
  • One method for the production of said curable composition comprises:
  • the curable formulation of the present invention has particular application when secondary processes such as stripping of the temporary coating or resist is required such as in the etching resist application. This however does not compromise the adhesion of the said composition to the substrate to be protected, hardness of the coating containing the said composition, and chemical resistance in various chemicals.
  • a further application for the curable formulation of the present invention is for use in UV solder mask with good resistance to different fluxes used in the soldering processes.
  • the principal embodiment of the present invention relates to a radiation curable composition based on amide-containing (meth)acrylate which contains at least one amide, -NH(CO)-, linkage and at least one (meth)acrylate functionality.
  • the amide linkage is preferred to be in the internal structure of the (meth)acrylate, as generally described below in I and II:
  • R1 and R2 can be alkyl, aryl, arylalkyl or cycloalkyl.
  • R is alkyl
  • difunctional amido (meth)acrylate (III) is as the following:
  • Examples of monofunctional amide-containing (meth)acrylate are those containing at least one amide linkage and at least one (meth)acrylate functionality.
  • Preferred amido (meth)acrylates are those prepared from reaction of gamma-butyrolactone and alkylamine, alkanolamine or alkyl diamine to produce amido alcohols, and the amido alcohols are further reacted with methyl (meth)acrylate by transesterification to produce amido (meth)acrylate and a side product of mono alcohol which may be distilled under vacuum.
  • the second embodiment of the present invention relates to radiation curable composition with utility as a UV etching resist formulation.
  • the said composition contains the amido (meth)acrylates I, or II or III, in combination with (meth)acrylate half ester generally described in IV:
  • R alkyl, alkene, cycloalkyl, aryl
  • the (meth)acrylate half ester described in IV is based on partial esterification of acid anhydride with hydroxyl (meth)acrylates.
  • acid anhydrides are succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride but not limited to these only.
  • hydroxyl (meth)acrylates are 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate, but not limited to these only.
  • the UV etching resist formulation useful in the invention typically contains 60 wt% of (meth)acrylate oligomer, 30-40 wt% of inert fillers, 0.5-1% of phthalocyanin blue pigment, 1-5% of various additives such as slip agent, flow additives and thickening agent, and final 3-5% of photoinitiators.
  • the (meth)acrylate oligomer must contain both the (Meth)acrylate Half Ester IV, and Amido (meth)acrylate at a ratio of 1 :1 to 4:1.
  • Inert fillers can be micronized talc which typically contains silica, alumina and magnesia, or barium sulfate or clay.
  • Typical photoinitiators can be the type of benzophenone, benzyl dimethyl ketol, or ethyl anthraquinone and any mixture thereof but not limited to this.
  • a third embodiment of the present invention relates to a radiation curable composition for utility in the UV solder mask formulation.
  • the UV solder mask composition useful in this invention contains Epoxy (meth)acrylate - V, and optionally, the amido (meth)acrylates or Urethane (meth)acrylate - VI .
  • a preferred epoxy (meth)acrylate is based on reaction of 1 epoxy equivalent from bisphenol-A epoxy (or diglycidyl ether of bisphenol-A) with 0.90- 1.05 equivalent of acrylic or methacrylic acid and simultaneously with 0.01 - 0.10 equivalent of diacid from carboxyl terminated acrylonitrile butadiene (such as commercially available as Hycar CTBN1300Z13 from BF Goodrich).
  • Example of this type of epoxy (meth)acrylate is Ebecryl 3604 from UCB Chemicals.
  • Another preferred epoxy (meth)acrylate is based on reaction of 1 epoxy equivalent from epoxy phenol novolac (commercially available as EPN1179 or EPN1180 from Ciba Specialty Chemicals or DEN431 or DEN438 from Dow Chemicals) with 0.90-1.05 equivalent of acrylic or methacrylic acid and simultaneously with 0.01 - 0.10 equivalent of diacid from carboxyl terminated acrylonitrile butadiene (such as commercially available as Hycar CTBN1300X13 from BF Goodrich).
  • Epoxy cresol novolac such as ECN1280, and ECN1299 from Ciba Specialty Chemicals can be used to replace the epoxy phenol novolac partially or completely.
  • mixture of 0.05-0.50 epoxy equivalent from diglycidyl ether of bisphenol-A and 0.50-0.95 epoxy equivalent from epoxy phenol novolac can be used in the preparation of the epoxy (meth)acrylate.
  • Preferred monofunctional amido (meth)acrylates are:
  • Urethane (meth)acrylate useful in this invention contains at least one (meth)acrylate function.
  • Example of monofunctional urethane (meth)acrylate is a reaction product of n-butyl isocyanate with hydroxyl functional (meth)acrylate like 2-HEA, HEMA, HPA or HPMA or mixture thereof.
  • Example of multifunctional urethane methacrylate is those derived from reaction of polyester or polyether diols or triols with diisocyanates and/or triisocyanates, and later capped with hydroxyl functional (meth)acrylates containing 1 to 5 (meth)acrylate functions.
  • Typical diisocyanates are toluene diisocyanates, isophorone diisocyanate, hexamethylene diisocyanates and many more but not limited to these.
  • Typical composition useful for UV solder mask contains 60-80 wt% epoxy (meth)acrylate, 5-20% amido (meth)acrylate, 5-20% of diluting (meth)acrylate monomers, 10-30 % of inert fillers, 1-2% of phthalocyanin green pigment, 1-5% of additives such as slip agent, flow additives and thickening additives, 0-3% adhesion promoter and 2-5% of photoinitiators.
  • the amido (meth)acrylate can be replaced partially or completely with urethane (meth)acrylate of 1 -5 (meth)acrylate functionality per molecule of the urethane (meth)acrylate.
  • Example 1 Amido acrylate I
  • Butyl-amine is dissolved in dioxane and the mixture heated 70 °C.
  • 4.54 mole of butyrolactone is added drop-wise during 2 hours. Stirring is continued for 9 hours at 110 °C.
  • the reaction mixture is cooled to 80°C and the dioxane distilled under vacuum. At the end traces of dioxane and butyrolactone are removed by distillation under high vacuum.
  • the column was topped by a varying reflux head to remove the methanol/methyl acrylate mixture.
  • the reaction was considered to be complete when the refractive index of the distillate indicated it to be pure methyl acrylate.
  • (Meth)acrylate half ester I is prepared by charging 1 mole of hexahydrophthalic anhydride into a 3-neck glass vessel and heated to 60°C under agitation. 0.95 mole of 2-hydroethyl acrylate, 500 ppm hydroquinone, 500 ppm triphenyl stibene and 1000 ppm dilithium carbonate are added to the vessel. The mass is allowed to exotherm to 110°C, and once exotherm completed the mass is hold at this temperature for 2-4 hours. Then 0.05 mole of HEMA is added and the mixture is hold at 110°C for 2-4 hours until all the anhydride is completely opened. This is indicated when the acid value reached the theoretical value of 207 mg KOH/gm.
  • Methacrylate half ester II is prepared similar to the process above except that all the 1.00 mole of hexahydrophthalic anhydride is reacted to 1.00 mole of hydroxyethyl methacrylate.
  • Blends of (meth)acrylate half ester and amido (meth)acrylate were evaluated for UV etching resist ink formulation as described in the table I below (all composition is described in parts per hundred resin).
  • the formulation is applied onto a clean Cu board using a 120T mesh screen with a circuit pattern. Thickness of the applied resist is approximately 10- 12 ⁇ m.
  • the dosage applied for curing is approximately 750 mJ/cm 2 .
  • the pencil hardness is evaluated immediately after UV cure using pencils of HB to 9H. Coating hardness of minimum 2H is preferred.
  • the board with cured resist is etched in 35% FeCI 3 solution at 30°C for 5 minutes to etch the unprotected Cu.
  • the resist must not be attacked by the acid solution during this process.
  • the resist is stripped in 5% NaOH solution at 30°C.
  • the resist must be stripped in at least 20 seconds. Resist that completely dissolved in the solution is preferred. Flakes that dissolved after few hours in the NaOH solution is also sometime preferred. Hard flakes that do not dissolved after few hours is less preferred.
  • amido acrylates are evaluated for solder mask application.
  • Cu laminated board is first prepared for the ink application by cleaning with dilute acid such as 5-10% HCI or H 2 S0 , then rinsed with water and final cleaning with solvent such as acetone or isopropanol. The cleaned board is oven-dried to remove the residual solvent.
  • a Ni-plated board is also prepared in a similar manner.
  • the prepared ink is applied onto the cleaned Cu or Ni-plated board using a patterned screen with 70-90T mesh at 45 degrees angle. This would typically gives a wet film of 20-30 microns.
  • the applied ink is cured under a medium pressure Hg vapor lamp with lamp power of 80 watts/cm at a conveyor speed of 3-4 m/minute. This would typically require 3-4 passes with a total UV dosage of 1500-2000 mJ/cm2.
  • the cured ink is tested for adhesion with a cross cut pattern, hardness with HB to 9H pencils, and soldering resistance.
  • Soldering resistance is tested by first spraying the flux onto the Cu board with UV solder mask, then board is baked at 170°C for 15 seconds to activate the flux. Then the board is dipped in molten Sn/Pb solder at 260°C for a maximum of 50 minutes. The solder mask is tested for cross cut adhesion.
  • the following example describes the utility of urethane (meth)acrylate for adhesion to Ni plated boards, and provide good soldering resistance using different fluxes.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne une composition durcissable par rayonnement destinée à être utilisée comme formulation de réserve de gravure UV, cette composition comprenant : a) un amido (méth)-acrylate en combinaison avec b) un (méth)acrylate demi-ester. L'invention concerne également des compositions pour formulation de masque de soudure UV, ces compositions comprenant : i) un époxy (méth)acrylate et ii) un amido- méth)acrylate. Ces compositions peuvent procurer une adhésion à des métaux difficiles tels que le cuivre, le nickel et l'or.
PCT/EP2002/004456 2001-04-24 2002-04-23 Composition durcissable par rayonnement amelioree WO2002085962A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI20011906 2001-04-24
MYPI20011906 2001-04-24

Publications (1)

Publication Number Publication Date
WO2002085962A1 true WO2002085962A1 (fr) 2002-10-31

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104817656A (zh) * 2015-04-01 2015-08-05 苏州瑞红电子化学品有限公司 一种聚氨酯丙烯酸酯共聚物及其光刻胶组合物
EP2920809A4 (fr) * 2012-11-14 2015-11-11 Sun Chemical Corp Compositions et processus pour une fabrication de cellules solaires passivées par l'arrière
JP2016161666A (ja) * 2015-02-27 2016-09-05 日立化成株式会社 感光性樹脂組成物、感光性エレメント及びガラス基板の加工方法
JP2021028699A (ja) * 2019-08-09 2021-02-25 味の素株式会社 感光性樹脂組成物、感光性樹脂組成物の硬化物、樹脂シート、プリント配線板及び半導体装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849321A (en) * 1985-06-20 1989-07-18 M&T Chemicals Inc. UV curable compositions for making improved solder mask coatings
US4874799A (en) * 1985-05-17 1989-10-17 M&T Chemicals Inc. Aqueous akaline developable, UV curable urethane acrylate compounds and compositions useful for forming liquid 100 percent solids, solvent-free solder mask coatings
US4956264A (en) * 1985-11-15 1990-09-11 Hoechst Aktiengesellschaft Radiation-polymerizable mixture
EP0970945A1 (fr) * 1998-07-06 2000-01-12 Dsm N.V. Esters d'acide acrylique contenant des groupes hydroxyalkylamides durcissables par irradiation
JP2000281634A (ja) * 1999-03-30 2000-10-10 Kohjin Co Ltd 新規なアミド（メタ）アクリレート化合物及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4874799A (en) * 1985-05-17 1989-10-17 M&T Chemicals Inc. Aqueous akaline developable, UV curable urethane acrylate compounds and compositions useful for forming liquid 100 percent solids, solvent-free solder mask coatings
US4849321A (en) * 1985-06-20 1989-07-18 M&T Chemicals Inc. UV curable compositions for making improved solder mask coatings
US4956264A (en) * 1985-11-15 1990-09-11 Hoechst Aktiengesellschaft Radiation-polymerizable mixture
EP0970945A1 (fr) * 1998-07-06 2000-01-12 Dsm N.V. Esters d'acide acrylique contenant des groupes hydroxyalkylamides durcissables par irradiation
JP2000281634A (ja) * 1999-03-30 2000-10-10 Kohjin Co Ltd 新規なアミド（メタ）アクリレート化合物及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 0105, Derwent World Patents Index; AN 2001-034819, XP002212408 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2920809A4 (fr) * 2012-11-14 2015-11-11 Sun Chemical Corp Compositions et processus pour une fabrication de cellules solaires passivées par l'arrière
US9882082B2 (en) 2012-11-14 2018-01-30 Sun Chemical Corporation Compositions and processes for fabrication of rear passivated solar cells
JP2016161666A (ja) * 2015-02-27 2016-09-05 日立化成株式会社 感光性樹脂組成物、感光性エレメント及びガラス基板の加工方法
CN104817656A (zh) * 2015-04-01 2015-08-05 苏州瑞红电子化学品有限公司 一种聚氨酯丙烯酸酯共聚物及其光刻胶组合物
JP2021028699A (ja) * 2019-08-09 2021-02-25 味の素株式会社 感光性樹脂組成物、感光性樹脂組成物の硬化物、樹脂シート、プリント配線板及び半導体装置
JP7363182B2 (ja) 2019-08-09 2023-10-18 味の素株式会社 感光性樹脂組成物、感光性樹脂組成物の硬化物、樹脂シート、プリント配線板及び半導体装置

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