WO2005015309A2 - Composition durcissable au rayonnement, a developpement alcalin - Google Patents

Composition durcissable au rayonnement, a developpement alcalin Download PDF

Info

Publication number
WO2005015309A2
WO2005015309A2 PCT/EP2004/007731 EP2004007731W WO2005015309A2 WO 2005015309 A2 WO2005015309 A2 WO 2005015309A2 EP 2004007731 W EP2004007731 W EP 2004007731W WO 2005015309 A2 WO2005015309 A2 WO 2005015309A2
Authority
WO
WIPO (PCT)
Prior art keywords
compound
meth
acrylate
epoxy
alkyl
Prior art date
Application number
PCT/EP2004/007731
Other languages
English (en)
Other versions
WO2005015309A3 (fr
Inventor
Kong Chin Chew
Original Assignee
Cytec Surface Specialties, 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 Cytec Surface Specialties, S.A. filed Critical Cytec Surface Specialties, S.A.
Publication of WO2005015309A2 publication Critical patent/WO2005015309A2/fr
Publication of WO2005015309A3 publication Critical patent/WO2005015309A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/141—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
    • C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • This invention relates to radiation curable composition which can be used as alkali-developable photosensitive or photoimageable materials for the fabrication of articles such as printed circuit boards and liquid crystal displays.
  • the radiation curable compositions used as alkali-developable photosensitive materials are removable by aqueous alkaline solution when they are not cured by radiation.
  • the alkali-developable photosensitive materials can be utilized as photoimageable etching resist or plating resist inks in formation of circuit pattern, as photoimageable solder mask to protect circuit pattern on printed circuit board, or as photoresist ink in preparation of color filters for liquid crystal display.
  • printed circuit boards are fabricated by applying a radiation curable coating to the copper surface of the board.
  • a negative film of the desired circuit image is then applied to the curable coating and the film is exposed to a UV light source.
  • the printed circuit board is washed in an aqueous alkaline solution to remove the coating areas that were not exposed to the UV light source.
  • the board is then etched to remove the uncoated copper regions.
  • Other imaging techniques may be used. In addition to this use for forming printed circuit boards, these techniques can be used to form other surfaces such as printing plate surfaces.
  • radiation curable compositions are often termed photo-resist compositions.
  • US Patent 5002977 teaches the synthesis of a radiation curable polymer made from the reaction of an acrylic binder based on methyl methacrylate, and methacrylic acid further reacted with a cycloaliphatic unsaturated epoxy, 3,4- epoxycyclohexyl methyl (meth)acrylate.
  • This polymer in liquid photoimageable solder mask gives coatings that are excellent in tack-free property before cure, and high photosensitivity.
  • a main disadvantage with this material is the excessive brittleness.
  • US Patent 4943516 teaches the synthesis of a radiation curable polymer made from the reaction of an epoxy resin such as epoxy cresol novolak with (meth)acrylic acid. This material is then further reacted with a cyclic anhydride such as 1 ,2,3,6-tetrahydrophthalic anhydride to provide acid functionality to the epoxy (meth)acrylate.
  • a radiation curable polymer made from the reaction of an epoxy resin such as epoxy cresol novolak with (meth)acrylic acid. This material is then further reacted with a cyclic anhydride such as 1 ,2,3,6-tetrahydrophthalic anhydride to provide acid functionality to the epoxy (meth)acrylate.
  • a cyclic anhydride such as 1 ,2,3,6-tetrahydrophthalic anhydride
  • US Patent 5858618 also teaches a technique similar to US4943516. The difference is that instead of reacting the epoxy novolak with (meth)acrylic acid, it is reacted with a (meth)acrylated half-ester, which is a product of a cyclic anhydride with a hydroxy-group containing (meth)acrylate. This material is also known to have similar performance as the product of US4943516.
  • WO 9800759 attempts to address the issue of the brittleness of the material taught in US5002977 by blending it with the novolak-based material taught in US4943516. However, the resulting material is still quite brittle.
  • JP2000143579 attempts to solve the problem of brittleness by using as additive a material prepared from a dianhydride reacted with 2 equivalents of a
  • JP 2000297137 and JP 07092674 teach a photoimageable composition based on the product of an epoxy acrylate with a dianhydride.
  • the process based on this composition can take a long time to completion if the epoxy acrylate is used in only slight equivalent excess to the dianhydride, in order to synthesize a high molecular weight copolymer.
  • the present invention aims to find an improved process and an improved radiation curable polymer that overcomes these problems.
  • the invention provides a radiation curable polymer. This polymer is generally described as dianhydride-polyol extended epoxy acrylate bearing carboxylic groups, as represented by Formula ( ⁇ ) below;
  • the radiation curable polymer is derived by reacting Compound (I), Compound (II), and Compound (III), optionally further reacting with Compound (IV) and Compound (V);
  • (I) is derived from compound (I-a) and/or Compound (I-b) which is reacted with Compound (II) through the hydroxyl groups of Compound (I-a) and/or (I-b);
  • Compound (I-a) Compound (I-b) B designates -CH2- or o — H 2 C — O— C E— C-0 — F— X designates H or -CH3; Y designates a compound derived from polyols of Compound (III);
  • R represents an optionally substituted organo moiety which links the two anhydride groups on Compound (II), such that each anhydride group forms a five-membered cyclic structure with two atoms on R,
  • Z designates -H or
  • the radiation curable polymer according to the invention permits to solve the above-mentioned problems, including brittleness.
  • the invention provides a process for producing a radiation-curable polymer comprising : (i) reacting together compounds (I), (II) and (III) optionally in the presence of solvent or multifunctional (meth)acrylate diluting monomer or mixture of both, polymerization catalyst and inhibitors, generally at 95 to 100°C between 5-20 hours wherein: - compound (I) has at least 2 secondary hydroxyl groups and at least 2 (meth)acrylate groups and is of formula (I-a) and/or (I-b): - compound (II) is a dianhydride compound of formula:
  • ⁇ R represents an optionally substituted organo moiety which links the two anhydride groups, such that each anhydride group forms a five-membered cyclic structure with two atoms on R, - compound (III) is a polyol with at least 2 primary hydroxyl groups,
  • the radiation curable polymer according to this invention is useful in alkali- developable photosensitive formulation for the fabrication of printed circuit boards or flat panel displays.
  • the invention provides a radiation curable and/or alkali developable photosensitive and/or thermosetting formulation comprising; 50 to 100 parts by weight of radiation curable polymer of Formula ( ⁇ ), 0 to100 parts of COOH- functional- acrylic polymer, 0 to 100 parts of COOH-functional acrylated acrylic polymers, 0 to 50 parts of multifunctional monomers, 1-20 parts of photo- polymerization initiators, 1-20 parts of pigments or dyes, and 0-50 parts of epoxy- group containing resin.
  • the alkali-developable radiation curable polymer of Formula ( ⁇ ) is further described as having structural unit (m) and (n) at a ratio of (m/n) between 1/99 to 90/10, described as the following
  • the radiation curable polymer is derived by reacting Compound (I), Compound (II), and Compound (III), optionally further reacting with Compound (IV) and Compound (V);
  • (I) is derived from compound (I-a) and/or Compound (I-b) which is reacted with Compound (II) through the hydroxyl groups of Compound (I-a) and/or (i-b);
  • Compound (I-b) B designates -CH2-- or o o II II — H 2 C — O — C E— C-0 F—
  • X designates H or -CH3;
  • Y designates a compound derived from diols of Compound (III);
  • R represents an optionally substituted organo moiety which links the two anhydride groups of Compound (II), such that each anhydride group forms a five-membered cyclic structure with two atoms on R,
  • Z designates -H or
  • the reaction can be conducted as follows: first reacting compound (I), compound (II) and compound (III), along with solvent, polymerization catalyst, and inhibitors in a reaction flask at 95-100 degree Celsius between 5 to 20 hours. The mixture is continuously stirred while maintaining temperature between 95 to 100 degrees Celsius, until more than 95% of all the anhydride groups are reacted to the hydroxyl groups. Then the final mixture is post-stabilized with hydroquinone or its derivatives to improve shelf stability of the final products.
  • the radiation curable polymer of Formula ( ⁇ ) generally has theoretical molecular weight ranging from 1000 to 150,000 based on weight-average molecular weight as measured by Gel Permeation Chromatography. The range of final acid number is preferably between 50 and 200 mg KOH/gm.
  • Compound (I) is preferably selected from di(meth)acrylate compounds having at least 2 secondary hydroxyl groups which are described below by
  • A is selected from one of the following:
  • D is derived from C8-C20 fatty acids, poly(butadiene), poly(butadiene- acrylonitrile).
  • B is-CH2— or: o o II II -H 2 C — O — C — E— C-0 — F— such that E is a structure preferably derived from acid anhydrides based on maleic, succinic, glutaric, phthalic, tetrahydrophthalic, alkyl substituted tetrahydrophthalic, endomethylene tetrahydrophthalic, hexahydrophthalic, rnethyl- hexahydrophthalic anhydrides, but not limited to these;
  • F is a structure derived from hydroxyl-functional (meth)acrylates preferably based on alkyl, alkyl ether, alkyl ester, alkyl ester ether, and cycloalkyl, wherein the alkyl is C2-C20;
  • X is H or -CH3.
  • Compound (I) is preferably a bisphenol-A epoxy acrylate.
  • Compound (II) is preferably selected from dianhydrides based on pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, 4,4'- bisphenol-A dianhydride, biphenyltetracarboxylic acid dianhydride, biphenylether tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofurfuryl)-3-methyl-3- cyclohexane-1 ,2-dicarboxylic acid dianhydride, 1 ,4,5,8-naphthalene tetracarboxylic dianhydride, and 3,4,9,10-perylene tetracarboxylic dianhydride.
  • Preferred compound (II) is pyromellitic dianhydride.
  • Compound (III) is selected from polyol with at least two primary hydroxyl groups such as, for example, polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol, poly(tetrahydrofuran) diol, poly(tetramethylene glygol) diol, 1 ,4-cyclohexanedimethanol, diol of poly(1 ,4-cycIohexanedimethanol) and diol of poly(alkylene carbonate), tricyclodecane dimethanol, diol of poly(tricyclodecane dimethanol) and diol of poly(alkylene carbonate), diol of poIy(alkylene glycol) and diol of poly(isophthalic acid), bisphenol-A, hydrogenated bisphenol-A, and alkoxylated bisphenol-A, poly(urethane) diol
  • compound (IV) In order to obtain complete reaction of the dianhydrides, very small amount of mono alcohol, compound (IV), can be added to the reaction product of (I), (II), and (111).
  • the range of compound (IV) added to the mixture is generally between 0 and 10 % by weight of the final product.
  • Compound (IV) can be selected from mono-functional alcohol such as alkyl alcohols of C2-C20 and methoxy alkyl alcohols of C2-C20.
  • compound (IV) is methoxy propanol.
  • Compound (IV) also can be selected from any (meth)acrylate compound containing a primary or secondary hydroxyl group.
  • Such compound can be any hydroxyl alkyl (meth)acrylates with alkyl group of C2-C20.
  • Example of hydroxyl alkyl (meth)acrylates are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate.
  • the reaction product of compound (I), (II), and (III), and optionally with (IV) can be further reacted with epoxy-containing unsaturated compound (V) to adjust the acid number.
  • the range of compound (V) to be added is preferably from 0.1 to 0.8 epoxy equivalent to each equivalent of carboxylic acid. Preferred amount of compound (V) is not more than 0.50 epoxy equivalent to each equivalent of carboxylic acid.
  • Compound (V) is preferably selected from the fallowings;
  • G can be absent, or -(C2-C10 aikyl)-O--, or
  • a radiation curable polymer according to the invention can be prepared in solvents or in multifunctional (meth)acrylate diluting monomers, or in a mixture of both.
  • Type of solvents recommended to use must not contain any hydroxyl group which can react with the dianhydride compounds.
  • Organic solvents that could be used effectively includes ketones such as methyl ethyl ketone, methyl iso-butyl ketone or cyclohexanone; aromatic hydrocarbons such as toluene, xylene; esters such as ethyl acetate and butyl acetate; and esters of glycol ethers such as cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol methyl ether acetate.
  • the organic solvent is preferred to be highly compatible with the extended epoxy acrylate of Formula ( ⁇ ).
  • Multifunctional (meth)acrylate diluting monomers can be selected from any (meth)acrylate containing monomers containing from 1 to 10 (meth)acrylate groups derived from any alcohols or polyols of C2-C50.
  • the reaction between anhydride and hydroxyl group can be catalyzed by inorganic alkaline salts such as sodium carbonate, lithium carbonate, sodium hydroxide; organometallic salts such as lithium octanoate, dibutyltin oxide, and dibutyltin dilaurate, or basic organic compounds such as tertiary amines like ethylmorpholine, triethylamine, and phosphines like tri-phenyl phosphine.
  • inorganic alkaline salts such as sodium carbonate, lithium carbonate, sodium hydroxide
  • organometallic salts such as lithium octanoate, dibutyltin oxide, and dibutyltin dilaurate
  • basic organic compounds such as tertiary amines like ethylmorpholine, triethylamine, and phosphines like tri-phenyl phosphine.
  • Thermal polymerization of the (meth)acrylate unsaturation can be suppressed by adding thermal polymerization inhibitors based on quinones such as hydroquinones, methyl ether of hydroquinone, and ditertiobutyl hydroquinone; organometallic stabilizers based on phosphorus such as triphenyl phosphite, tris(nonylphenyl) phosphine; organo-antimony such as triphenyl antimony; and phenothiazine. These inhibitors are used for retarding thermal polymerization of the (meth)acrylate unsaturation in presence of oxygen. These stabilizers can be added to the extended epoxy acrylate during the preparation step, or after the completion of the preparation to improve the shelf-life of the final product.
  • thermal polymerization inhibitors based on quinones such as hydroquinones, methyl ether of hydroquinone, and ditertiobutyl hydroquinone
  • organometallic stabilizers based on phosphorus such
  • Carboxylic functional acrylic polymers suitable for the alkali-developable photosensitive formulation can be selected from any acrylic copolymer prepared from carboxylic group bearing (meth)acrylate such as (meth)acrylic acid, dimer of
  • carboxyl functional polymers can also be obtained from the partial esterification of maleic anhydride copolymers selected from styrene-maleic anhydride copolymers, alkylene-maleic anhydride copolymer, and poly(butadiene)- maleic anhydride copolymer with mono-alcohols. Opening of the anhydride groups by the monoalcohols formed pendant carboxylic groups on these copolymers.
  • carboxyl-functional acrylic polymers preferably have weighted average molecular weight between 5000 and 200,000; acid number between 50 and 250 mg KOH/gm; and glass transition temperature higher than 60 degree Celsius.
  • Carboxyl-functional acrylated acrylic polymers can be prepared via solution polymerization of (meth)acrylate monomers selected from any of these (meth)acrylic acid, alkyl (meth)acrylate, styrene and its derivatives, hydroxyl- containing (meth)acrylates, vinyl ether, butadiene, and vinyl acetate. This resulted in carboxylic functional acrylic copolymer which is then further reacted to epoxy- containing unsaturated (meth)acrylate such as glycidyl methacrylate or 3,4- epoxycyclohexyl methyl acrylate. Particular example is unsaturated acrylic polymer as described in US Patent 5,002,977. Furthermore, polymers prepared by partial esterification of styrene-maleic anhydride and hydroxyl (meth)acrylates could be used in the alkali-developable photosensitive formulation.
  • Multifunctional (meth)acrylate monomers or (meth)acrylate diluents are useful for adjusting the ink viscosity and increasing the photo-resist compositions.
  • Typical multifunctional (meth)acrylates or (meth)acrylate diluents are hydroxyethyl (meth)acrylate, hydroxypropyl acrylate and methacrylate, trimethylolpropane triacrylate and trimethacrylate, pentaerythritol triacrylate and tetraacrylate, dipentaerythritol hexaacrylate, and any mixtures of these.
  • Suitable photo-initiators for photo-resist application include 2-benzyl-2-N,N- dimethylamino-1-(4-morpholinophenyl)-1-butanone commercially available as Irgacure 369 and 2-methyl-1-(4-methylthiophenyl)-2-morpholino propan-1-one commercially available as Irgacure 907. These photo-initiators are typically used in combination with thioxanthone sensitisers such as 2,4-diethylthioxanthone, 2- and 4-isopropylthioxanthone, and 2- and 4-chlorothioxanthone.
  • thioxanthone sensitisers such as 2,4-diethylthioxanthone, 2- and 4-isopropylthioxanthone, and 2- and 4-chlorothioxanthone.
  • Typical pigments used in the formulation are organic pigments such as phthalocyanines, quinacridones, dioxazines, isoindolinones, perinones, anthraquinones, and their mixtures.
  • organic pigments such as phthalocyanines, quinacridones, dioxazines, isoindolinones, perinones, anthraquinones, and their mixtures.
  • Inorganic pigments such as iron oxide, cobalt- based pigments, manganese-based pigments, ultramarine, Prussian blue, cobalt blue, cerulean blue, viridian, emerald green, cobalt green and their mixtures are also used in the formulation.
  • Epoxy-group containing resins are necessary in formulation for solder mask or color filter resist.
  • Suitable epox -containing resins are bisphenol-A epoxy and its polymer with bisphenol-A, cycloaliphatic epoxy, epoxy phenol novolak, epoxy cresol novolak, triglycidyl of isocyanurate, triglycidyl ether of trimethylolpropane, bisphenol-A novolak, and epoxy containing (meth)acrylate.
  • organic solvents can be required to adjust the viscosity of the photo-resist ink for different applications. These solvents can be used alone or in any combination. Suitable organic solvents include butyl cellosolve, butyl cellosolve acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol and diethyl ether.
  • a monomer is a polymerisable compound with a low molecular weight (e.g. ⁇ 1000 g/mol).
  • An oligomer is a polymerizable compound of intermediate molecular weight, higher than a monomer.
  • the molecular weight of an oligomer is comprised between about 250 and about 4,000 daltons.
  • a monomer is generally a substantially monodisperse compound whereas an oligomer or a polymer is a polydisperse mixture of compounds.
  • a polydisperse mixture of compounds prepared by a polymerisation method is a polymer.
  • a polymer precursor is an oligomer or a polymer which can be (further) polymerized.
  • Curable resin as well as curable polymer refer to polymer or polymer precursor having at least ethylenically unsaturated group that can be polymerized i.e. cured.
  • a composition is a mixture of compounds.
  • a formulation is a mixture of compounds containing ingredients able to react together upon exposure to radiation.
  • the polymerisation of polymerisable compounds may be achieved by thermal curing or irradiation, irradiation curing being often called radiation curing.
  • An irradiation curing can be done for example by using ultraviolet radiation and/or ionising radiation, such as gamma rays, X-rays or an electron beam.
  • Radiation curing can be a free radical polymerization initiated by any free radical initiator, preferably a photochemical initiator.
  • Radiation-curable polymer precursors can be acrylated oligomers or monomers i.e. compound containing radiation-curable acrylate functionalities.
  • Certain moieties, species, groups, repeat units, compounds, oligomers, polymers, materials, mixtures, compositions and/or formulations which comprise some or all of the invention as described herein may exist as one or more stereoisomers (such as enantiomers, diastereoisomers, geometric isomers, tautomers and/or conformers), salts, zwitterions, complexes (such as chelates, clathrates, crown compounds, cyptands / cryptades, inclusion compounds, intercalation compounds, interstitial compounds, ligand complexes, non-stoichiometric complexes, organometallic complexes, ⁇ -adducts, solvates and/or hydrates); isotopically substituted forms, polymeric configurations [such as homo or copolymers, random,
  • star and/or side branched polymers such as those of the type described in WO 93/17060
  • hyperbranched polymers and/or dendritic macromolecules such as those of the type described in WO 93/17060
  • cross-linked and/or networked polymers polymers obtainable from di and/or tri-valent repeat units, dendrimers, polymers of different tacticity (e.g. isotactic, syndiotactic or atactic polymers)]; polymorphs [ such as interstitial forms, crystalline forms, amorphous forms, phases and/or solid solutions] combinations thereof where possible and/or mixtures thereof.
  • the present invention comprises all such forms which are effective.
  • Fomrez 55-112 neopentyl glycol-adipic acid polyester diol, hydroxyl number 112 mgKOH/g, commercially available from Crompton Chemicals
  • Ebecryl (Trade Mark) 3700 (bisphenol A diglycidyl ether diacrylate commercially available from UCB Surface Specialties) were charged into a reaction vessel. 400g methoxy propyl acetate, 0.7g hydroquinone and 0.7g methyl ether hydroquinone were subsequently added. The mixture was heated to 96°C and 1g 4-ethylmorpholine was added. Lastly, 130g pyromellitic dianhydride was charged. The mixture was stirred and maintained at this temperature for 11h, after which 0.1 g hydroquinone and 0.1 g methyl ether hydroquinone were added. Final acid value of the mixture was 124 mgKOH/g. This material is designated as Resin
  • Resin A can be schematically described as in Formula (2) based on reaction scheme of pyromellitic dianhydride, bisphenol-A epoxy acrylate and polyester diol (based on neopentyl glycol and adipic acid)
  • Resin A 335.8g of Resin A, 13.4g of 4-hydroxybutyl acrylate glycidyl ether, 0.35g AMC-2, 0.25g hydroquinone and 0.25g methylether hydroquinone were charged into a flask and heated to 96°C. The mixture was stirred at this temperature for 6h. The final acid value of this material is 90 mgKOH/g. This material is designated as Resin B. Mole equivalent of Compound (V) to COOH-group of Resin A: Resin B is 0.15: 1.00.
  • Comparative example 1 As a comparison, in a separate synthesis, 211.4 g Eb3700 was charged into a reaction vessel (no diol added). 200g methoxy propyl acetate, 0.25g triphenyl antimony and 0.25g hydroquinone were subsequently added. The mixture was heated to 96°C and 0.5g 4-ethylmorpholine was added. Lastly, 87.6g pyromellitic dianhydride was charged. The mixture was stirred and maintained at this temperature. After 7h, the partial acid value was 151 mgKOH/g while the total acid value was 170mgKOH/g. One hour later, the total acid value has only decreased to 168mgKOH/g, indicative of a very slow reaction. After 10 hours of heating, gelling of the mixture occurred.
  • Resin A and Resin B are evaluated in formulation containing Cyclomer-P ACA250.
  • the formulations comprising a photoinitiator are applied onto a steel panel using bar coater, and dried in the oven at 80 degrees Celsius to evaporate the solvent.
  • the final coating thickness after drying is between 10-15 microns.
  • the coated steel is exposed to UV source of Fe-doped metal halide for 60 seconds, through a glass in a vacuum condition. Intensity of the UV source at the coating surface is approximately 10 mW/cm 2 .
  • Time to tack-free is measured by first placing the coated steel panel in the oven at 80 degrees Celsius, and taken out at 5 minutes increment. Tackiness of coating is measured by pressing a finger onto the coating. The coating is considered tack-free when there is no finger mark is left on the coating after pressing the finger onto the coating. Coating with shorter time to tack-free has the better tack-free property.
  • Hardness test is conducted by scratching the coating using pencils ranging from HB to 9H:
  • a high resistance to cracks in reverse impact resistance test and/or in deformation resistance test indicates a low brittleness of the coating.
  • an epoxy novolak (meth)acrylate prepared by reaction of epoxy cresol novolak, carboxyl-functional acrylonitrile butadiene and methacrylic acid; then further reacted to tetrahydrophthalic anhydride) as Comparative 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Emergency Medicine (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne un polymère durcissable au rayonnement, sous la forme d'acrylate d'époxy à extension dianhydride-polyol porteur de groupes carboxyliques, de formule (?) ci-après, utile dans les formulations photosensibles à développement alcalin, pour la fabrication de cartes imprimées ou d'afficheurs à écran plat.
PCT/EP2004/007731 2003-07-17 2004-07-13 Composition durcissable au rayonnement, a developpement alcalin WO2005015309A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI20032693 2003-07-17
MYPI20032693 2003-07-17

Publications (2)

Publication Number Publication Date
WO2005015309A2 true WO2005015309A2 (fr) 2005-02-17
WO2005015309A3 WO2005015309A3 (fr) 2005-04-21

Family

ID=34132412

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/007731 WO2005015309A2 (fr) 2003-07-17 2004-07-13 Composition durcissable au rayonnement, a developpement alcalin

Country Status (1)

Country Link
WO (1) WO2005015309A2 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007146209A2 (fr) * 2006-06-09 2007-12-21 Dentsply International Inc. Compositions photopolymérisables comprenant un nouvel accélérateur aminé pour une stabilité améliorée des couleurs et une contrainte de polymérisation réduite
WO2010071700A1 (fr) * 2008-12-18 2010-06-24 Dow Global Technologies Inc. Procédé de séparation d'un sel solide dans des solutions de résine époxy
CN102952511A (zh) * 2011-08-16 2013-03-06 通用电气公司 环氧树脂封装和层压粘合剂及其制备方法
JP2014206727A (ja) * 2013-03-21 2014-10-30 新日鉄住金化学株式会社 絶縁膜用感光性樹脂組成物及び硬化物
CN105399935A (zh) * 2015-11-16 2016-03-16 孝感市易生新材料有限公司 可降解光固化树脂预聚体及制备方法、光固化树脂及制备方法
CN109627423A (zh) * 2018-12-07 2019-04-16 湖南普瑞迪新材料有限公司 柔性链改性环氧丙烯酸酯树脂及其制备方法
CN109689725A (zh) * 2016-11-21 2019-04-26 协立化学产业株式会社 电子装置用树脂组合物
CN110951047A (zh) * 2019-11-22 2020-04-03 张家港康得新光电材料有限公司 改性环氧丙烯酸酯树脂及其制备方法
CN111040387A (zh) * 2019-12-28 2020-04-21 广东生益科技股份有限公司 一种无卤树脂组合物及包含其的挠性覆铜板
CN113061218A (zh) * 2019-12-16 2021-07-02 固安鼎材科技有限公司 一种光敏树脂及其制备方法和应用
EP3901189A4 (fr) * 2018-12-21 2022-09-14 Wanhua Chemical Group Co., Ltd. Dispersant stable et son application permettant la préparation de polyols copolymères
CN116082914A (zh) * 2022-11-24 2023-05-09 厦门恒坤新材料科技股份有限公司 一种有机抗反射涂层组合物及其制备方法和图案形成方法
WO2024113130A1 (fr) * 2022-11-29 2024-06-06 上纬创新育成股份有限公司 Oligomère contenant du carbonate, son procédé de préparation et produit durci

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923523A (en) * 1972-09-29 1975-12-02 Nippon Oil Seal Ind Co Ltd Photocurable composition and a method of preparing same
US5009982A (en) * 1985-04-19 1991-04-23 Taiyo Ink Manufacturing Co., Ltd. Resist ink composition
EP0646845A1 (fr) * 1992-06-19 1995-04-05 Nippon Steel Corporation Filtre couleur, resine et materiau destine a sa fabrication
US5576399A (en) * 1993-07-02 1996-11-19 Ciba-Geigy Corporation Epoxy acrylates
JP2000327758A (ja) * 1999-05-25 2000-11-28 Nippon Kayaku Co Ltd 不飽和基含有ポリカルボン酸樹脂、樹脂組成物及びその硬化物
JP2002275237A (ja) * 2001-03-16 2002-09-25 Nippon Kayaku Co Ltd 樹脂組成物、ソルダーレジスト樹脂組成物及びこれらの硬化物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923523A (en) * 1972-09-29 1975-12-02 Nippon Oil Seal Ind Co Ltd Photocurable composition and a method of preparing same
US5009982A (en) * 1985-04-19 1991-04-23 Taiyo Ink Manufacturing Co., Ltd. Resist ink composition
US5009982B1 (en) * 1985-04-19 1994-03-15 Taiyo Ink Manufacturing Co.,Ltd. Resist ink composition
EP0646845A1 (fr) * 1992-06-19 1995-04-05 Nippon Steel Corporation Filtre couleur, resine et materiau destine a sa fabrication
US5576399A (en) * 1993-07-02 1996-11-19 Ciba-Geigy Corporation Epoxy acrylates
JP2000327758A (ja) * 1999-05-25 2000-11-28 Nippon Kayaku Co Ltd 不飽和基含有ポリカルボン酸樹脂、樹脂組成物及びその硬化物
JP2002275237A (ja) * 2001-03-16 2002-09-25 Nippon Kayaku Co Ltd 樹脂組成物、ソルダーレジスト樹脂組成物及びこれらの硬化物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 14, 5 March 2001 (2001-03-05) & JP 2000 327758 A (NIPPON KAYAKU CO LTD), 28 November 2000 (2000-11-28) *
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 01, 14 January 2003 (2003-01-14) & JP 2002 275237 A (NIPPON KAYAKU CO LTD), 25 September 2002 (2002-09-25) *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007146209A3 (fr) * 2006-06-09 2008-03-13 Dentsply Int Inc Compositions photopolymérisables comprenant un nouvel accélérateur aminé pour une stabilité améliorée des couleurs et une contrainte de polymérisation réduite
WO2007146209A2 (fr) * 2006-06-09 2007-12-21 Dentsply International Inc. Compositions photopolymérisables comprenant un nouvel accélérateur aminé pour une stabilité améliorée des couleurs et une contrainte de polymérisation réduite
WO2010071700A1 (fr) * 2008-12-18 2010-06-24 Dow Global Technologies Inc. Procédé de séparation d'un sel solide dans des solutions de résine époxy
US8829212B2 (en) 2008-12-18 2014-09-09 Dow Global Technologies Llc Method of separating solid salt from epoxy resin solutions
CN102952511A (zh) * 2011-08-16 2013-03-06 通用电气公司 环氧树脂封装和层压粘合剂及其制备方法
JP2014206727A (ja) * 2013-03-21 2014-10-30 新日鉄住金化学株式会社 絶縁膜用感光性樹脂組成物及び硬化物
CN105399935A (zh) * 2015-11-16 2016-03-16 孝感市易生新材料有限公司 可降解光固化树脂预聚体及制备方法、光固化树脂及制备方法
CN109689725B (zh) * 2016-11-21 2020-07-14 协立化学产业株式会社 电子装置用树脂组合物
CN109689725A (zh) * 2016-11-21 2019-04-26 协立化学产业株式会社 电子装置用树脂组合物
CN109627423A (zh) * 2018-12-07 2019-04-16 湖南普瑞迪新材料有限公司 柔性链改性环氧丙烯酸酯树脂及其制备方法
EP3901189A4 (fr) * 2018-12-21 2022-09-14 Wanhua Chemical Group Co., Ltd. Dispersant stable et son application permettant la préparation de polyols copolymères
US11945775B2 (en) 2018-12-21 2024-04-02 Wanhua Chemical Group Co., Ltd. Stable dispersant and application thereof in preparing copolymer polyols
CN110951047B (zh) * 2019-11-22 2022-06-10 张家港康得新光电材料有限公司 改性环氧丙烯酸酯树脂及其制备方法
CN110951047A (zh) * 2019-11-22 2020-04-03 张家港康得新光电材料有限公司 改性环氧丙烯酸酯树脂及其制备方法
CN113061218A (zh) * 2019-12-16 2021-07-02 固安鼎材科技有限公司 一种光敏树脂及其制备方法和应用
CN113061218B (zh) * 2019-12-16 2023-11-03 固安鼎材科技有限公司 一种光敏树脂及其制备方法和应用
CN111040387A (zh) * 2019-12-28 2020-04-21 广东生益科技股份有限公司 一种无卤树脂组合物及包含其的挠性覆铜板
CN111040387B (zh) * 2019-12-28 2022-06-03 广东生益科技股份有限公司 一种无卤树脂组合物及包含其的挠性覆铜板
CN116082914A (zh) * 2022-11-24 2023-05-09 厦门恒坤新材料科技股份有限公司 一种有机抗反射涂层组合物及其制备方法和图案形成方法
CN116082914B (zh) * 2022-11-24 2024-04-30 厦门恒坤新材料科技股份有限公司 一种有机抗反射涂层组合物及其制备方法和图案形成方法
WO2024113130A1 (fr) * 2022-11-29 2024-06-06 上纬创新育成股份有限公司 Oligomère contenant du carbonate, son procédé de préparation et produit durci

Also Published As

Publication number Publication date
WO2005015309A3 (fr) 2005-04-21

Similar Documents

Publication Publication Date Title
US4239866A (en) Curable coating composition
EP0235704B1 (fr) Acrylates lactones terminés par un groupe carboxylique
WO2010117056A1 (fr) Résine photodurcissable et composition de résine photodurcissable
WO2005015309A2 (fr) Composition durcissable au rayonnement, a developpement alcalin
JP3543409B2 (ja) 活性エネルギ−線硬化型エポキシアクリレ−ト樹脂組成物
JPH0231118B2 (ja) Kokaseikooteingunyuyonasoseibutsu
US4618635A (en) Coating compositions prepared from lactone-acrylate adduct, polyol and isocyanate
US6063898A (en) Compounds, polymers of them, processes for the preparation of both, and compositions containing the compounds
US5973034A (en) (Oxide or sulfide) powder epoxy (meth) acrylate w/glass and/or metal
WO2008056750A1 (fr) Composition de résine photosensible
JPH0987346A (ja) エネルギ−線硬化型エポキシアクリレ−ト樹脂組成物
US20030175615A1 (en) Photocurable resin composition
US4144283A (en) Curable coating compositions
KR930001852B1 (ko) 내구성 패턴 형성용부재
KR20170046126A (ko) 반응성 폴리에스테르 화합물, 그것을 이용한 활성 에너지선 경화형 수지 조성물
KR100633793B1 (ko) 불포화모노카본산 에스테르화합물, 그 제조방법 및 활성에너지선 경화성 조성물
JP4978787B2 (ja) 感光性樹脂組成物及び新規酸基含有ビニルエステル樹脂
JP2990398B2 (ja) 感光性組成物
JPWO2002090418A1 (ja) 不飽和基含有多分岐化合物、それを含有する硬化性組成物及びその硬化物
GB1583412A (en) Curable coating compositions comprising vinylurethanes
JP5222156B2 (ja) カルボキシレート樹脂及びそれを含有する樹脂組成物
US20040039100A1 (en) Radiation curable compositions
WO2003095506A1 (fr) Compositions durcissables par rayonnement
JP3158619B2 (ja) 光硬化性樹脂組成物
JP4043884B2 (ja) 水性光重合性樹脂組成物の製造方法及び水性光重合性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase