CN1219687A - Photoimageable compositions containing photopolymerizable urethane oligomers and low Tg binder polymers - Google Patents

Photoimageable compositions containing photopolymerizable urethane oligomers and low Tg binder polymers Download PDF

Info

Publication number
CN1219687A
CN1219687A CN98123055A CN98123055A CN1219687A CN 1219687 A CN1219687 A CN 1219687A CN 98123055 A CN98123055 A CN 98123055A CN 98123055 A CN98123055 A CN 98123055A CN 1219687 A CN1219687 A CN 1219687A
Authority
CN
China
Prior art keywords
weight
general assembly
photoimageable composition
count
photoimageable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN98123055A
Other languages
Chinese (zh)
Inventor
R·巴尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Morton Corp
Nichigo Morton Co Ltd
Original Assignee
Nihon Morton Corp
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 Nihon Morton Corp filed Critical Nihon Morton Corp
Publication of CN1219687A publication Critical patent/CN1219687A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

In a negative acting photoimageable composition comprising an acid functional binder polymer having a Tg between about 60 and about 90.degree.C, photopolymerizable .alpha.,.beta.-ethylenically unsaturated compounds, and photoinitiator, at least a portion of the photopolyme rizable compounds are isocyanate trimers having tri-.alpha.,.beta.-ethylenically unsaturated functionality and a weight average molecular weight of at least about 1000.

Description

The Photoimageable composition that contains photopolymerizable urethane oligomers and low Tg binder
The present invention relates to be used for making the negative-type Photoimageable composition of the photosensitive resist agent of printed circuit board (PCB) as those.Photoimageable composition adopts the low binder polymer of glass temperature, and contains the oligourethane of photopolymerization, to the photopolymerization component of small part be this oligomer.
The present invention relates to the negative-type Photoimageable composition that can in alkaline aqueous solution, develop.The present invention is particularly suited for as key light imaging resist, makes the composition of solder mask etc. but also be suitable for use as to harden.
All kinds of Photoimageable compositions are existing to be described.The solvent of this based composition that the present invention relates to is A) binder polymer; B) α of photopolymerization, β-ethylene linkage unsaturated compound and C) the photoinitiator chemistry system.Binder polymer A) enough acid functional groups (normally carboxylic acid functional) is arranged, make it dissolve in the alkaline aqueous solution, thereby photopolymerisable compositions can be developed in alkaline aqueous solution.
When Photoimageable composition of the present invention applied with dry film, it had special advantage.These dry films comprise the supporting sheet (as polyethylene terephthalate) of relative stiffness, the composition layer and the diaphragm (as polyethylene film) of Photoimageable usually.These dry films can expect that volume provides.In the time of on being applied to printed circuit board (PCB) (normally copper facing/glass fibre-epoxy resin board) blank, film is removed, Photoimageable composition is pressed onto on the blank layer by layer, remove supporting sheet then with heat and pressure.
The cold flow (edge fusion) that a FAQs of dry film photosensitive resist agent composition is the film of reel form and add man-hour film and the cohesive of base material between balance.Being used for improving fusible typical prior art, to remedy method be that the low polymkeric substance of glass temperature is mixed with the composition that contains the multi-functional polymerisable monomer of high-load.Improving the fusible while, these compositions have also promoted not wish the cold flow that produces, and can make the storage life of dry film shorten (can make storage life usually less than 1 month).Attempting to increase storage life then can make cohesive relatively poor or make flexible the reduction usually.
Overall purpose of the present invention provides a kind of Photoimageable composition that is suitable for use as the photosensitive resist agent that is used for making printed circuit board (PCB), and said composition has T gThe good cohesive that low polymer is given, but the cold flow of minimum degree, good storage life and good flexibility had.
The negative-type Photoimageable composition comprises: A) in A), B) and C) general assembly (TW) be about the organic polymer bonding agent of 29-69% (weight), this bonding agent has enough acid functional groups that Photoimageable composition can be developed in alkaline aqueous solution, its glass temperature (T g) between about 60-90 ℃, be good with about 80-90 ℃; B) about 30-60% (weight) (in A), B) and general assembly (TW) C)) but the component of addition polymerization, B component) comprise the compound that the on-gaseous ethylenically unsaturated compounds maybe can form polymkeric substance by the chain growth polyaddition reaction that free radical causes; And C) about 0.5-15% (weight) (in A), B) and general assembly (TW) C)) the generation free radical organic system to radiation sensitive, this system can activate by actinic radiation, but to cause the substance B of addition polymerization) the chain growth polyaddition reaction.According to the present invention, B component) include three-α, the isocyanate trimerization body B ' of the unsaturated functionality of β-ethylene linkage), tripolymer B ') content be about A), B) and the C) 2-30% of general assembly (TW) (weight); Its surplus of B (promptly being up to A), B) and C) 57% (weight) of general assembly (TW), preferably be at least about 5% (weight)) for containing other α, the B of β-ethylene linkage unsaturated monomer ".In addition, composition of the present invention should contain the 1-8% that has an appointment (weight) (in A), B) and general assembly (TW) C)) dibenzoate plasticiser D), be good with about 2-6% (weight).
In this article, unless refer else, all percentage number averages are percent by weight.In this article, think component A) (binder polymer), B component) (photopolymerization compound) and component C) total amount of (photoinitiator chemistry system) equals 100% (weight), other component (as plastifier) is then according to 100 parts of A), B) and C) calculate umber.Except that referring else, the molecular weight of polymkeric substance and oligomer is weight-average molecular weight (M w).
The Photoimageable composition that the present invention relates to can develop in alkaline aqueous solution, so it has very big acid functionality.These Photoimageable compositions contain adhesive A usually), the acid functionality of this bonding agent normally acid number is at least about 80, being at least about 100 for good, about 150 or more mostly be better, reach as high as about 250.Acid functional group is carboxylic acid functional normally, but also for example can comprise, sulfonic acid functionality or phosphoric acid functional group.The weight-average molecular weight of the binder polymer of Photoimageable composition is usually about 40, and 000-200 is between 000, being good at least about 80,000.
Polymkeric substance obtains from acid functional monomer and non-acid functional monomer's potpourri usually.Some object lessons of suitable acid functional monomer are acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, 2-acrylamido-2-methyl propane sulfonic acid, 2-hydroxyethyl acryloyl group phosphate, 2-hydroxypropyl acryloyl group phosphate, 2-hydroxyl-α-acryloyl group phosphate etc.One or more of available these acid functional monomers are made binder polymer.
The acid functional monomer can with non-acid functional monomer's copolymerization, thereby provide required acid number, these non-acid functional monomers' example is acrylic acid ester class, as methyl acrylate, methyl methacrylate, hydroxy-ethyl acrylate, butyl methacrylate, 2-ethyl hexyl acrylate, methacrylic acid 2-ethoxy ethyl ester, tert-butyl acrylate, n-butyl acrylate, 2-EHA, the just own ester of acrylic acid, 1,5-pentanediol diacrylate, acrylic acid N, N-diethyl amino ethyl ester, glycol diacrylate, 1, the ammediol diacrylate, the decanediol diacrylate, the decanediol dimethylacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dihydroxy methylpropane diacrylate, the glycerine diacrylate, tri (propylene glycol) diacrylate, glycerol tri-acrylate, 2,2-two (right-hydroxyphenyl)-propane dimethylacrylate, triethylene glycol diacrylate, polyoxy ethyl-2-2-two (to hydroxyphenyl)-propane dimethylacrylate, triethylene glycol dimethacrylate, the polyoxyethyl propyl trimethylolpropane triacrylate, ethylene glycol dimethacrylate, butanediol dimethylacrylate, 1, the ammediol dimethylacrylate, 1,2,4-butantriol trimethyl acrylic ester, 2,2,4-trimethyl-1,3-pentanediol dimethylacrylate, pentaerythritol acrylate trimethyl, 1-phenylethylene-1, the 2-dimethylacrylate, pentaerythrite tetramethyl acrylate, trimethylol-propane trimethacrylate, 1,5-pentanediol dimethylacrylate and 1,4-benzenediol dimethylacrylate; The styrene of styrene and replacement is as 2-methyl styrene and vinyltoluene; And vinyl acetate, as vinyl acrylate and metering system vinyl acetate.
The T of acrylic polymer gDepend on content of monomer to a great extent.Usually, the monomer (as just own ester of n-butyl acrylate, acrylic acid and 2-EHA) that provides the hydrocarbon chain of certain-length at the alcohol moiety of acrylate part or esterification can reduce T gTherefore, by suitably selecting to be used for forming the monomer of binder polymer, just can obtain required T g
The example that the Photoimageable composition of these polymkeric substance and these polymkeric substance of employing is arranged in following United States Patent (USP): 3,953,309,4,003,877,4,610,951 and 4,695,527, it is for referencial use that the description in these patents all is incorporated into this paper.
Account for the photopolymerization B component) the isocyanate trimerization body B ' of acrylate-functional of the Photoimageable of a part (or whole in some instances)) (" oligourethane ") have following general formula:
Figure A9812305500051
Wherein R is-(CH 2) p-NH-COO-(CHY-CHY-O) m-CO-CX=CH 2, wherein X is H or CH 3, Y is H, CH 3Or C 2H 5, p is the integer between the 1-36, m is the integer between 1-14.These tripolymers are described to some extent at European patent application EP 0 738 927 A2.When with low T gCombination of polymers when using, the weight-average molecular weight of carbamate should be at least about 1000, the highlyest is about 10,000.By the photo polymerizable component (being oligourethane) and low T that adopts higher molecular weight gThe combination of binder polymer can obtain satisfied cold flow and storage life, and low T gBinder polymer make and can not have a negative impact cohesive and flexibility.On directly perceived, adopt the photopolymerization component of higher molecular weight to have a negative impact, because reduce for the mole of monomer content of molar basis to cohesive.But surprisingly, adopted oligourethane according to the present invention after, just can obtain to adopt low T gWhole advantages of binder polymer.
The photopolymerization B component) (consumption is about the 0-30% (weight) of Photoimageable composition to its surplus, in A), B) and C) general assembly (TW)) be B "); normally the alkene class is undersaturated for it; α especially; the undersaturated monomer of β-ethylene linkage, dimer or short chain oligomer; it comprises monofunctional compound and α, the unsaturated functionality of β-ethylene linkage are 2 or bigger compound.Suitable photopolymerization compound includes, but are not limited to, the above-mentioned monomer that is suitable for forming binder polymer, the especially acid-functionalized compound of right and wrong.
For in the polyreaction that is exposed to trigger monomer under the actinic radiation, Photoimageable composition contains the photoinitiator chemistry system.Suitable light trigger comprises, for example 9-phenylacridine, benzoin ether, benzil ketals, acetophenone, benzophenone and the compound relevant with amine.Equally, U.S. Patent No. 5,217, the suitable 9-phenylacridine homolog of describing in 845 also is useful light trigger, it is for referencial use that the description of this patent is incorporated into this paper.
According to preferred embodiment of the present invention,, can further improve the flexibility of this paper by adopting the combination of dibenzoate plasticiser and isocyanate trimerization body.This combination also provides fine rule cohesive and good stripping.General formula according to dibenzoate plasticiser of the present invention is:
C 6H 5-COO-[R] n-R '-C 6H 5, wherein R is-CHX-CHX-O-, wherein one or more X are H or an X is CH 3, another is H; N is 1 to 10, and R ' is-CH 2-CH (CH 3)-OOC-,-CH 2-CH 2-OOC-or-OC-.The instantiation of suitable dibenzoate includes, but are not limited to, dibenzoic acid dipropylene glycol ester, diethylene glycol dibenzoate, polypropylene glycol dibenzoate and polyethylene glycol dibenzoate.Dibenzoate plasticiser D) consumption is A), B) and C) about 1-8% (weight) of general assembly (TW), usually between about 2-6% (weight).
Compare with the plastifier of other test, dibenzoate makes and covers intensity and be significantly improved.Combine being combined to form and the copper surface fine rule of good bond (fine line) (less than 75 microns) resist sidewalls (sidewall) more of dibenzoate plasticiser and isocyanate trimerization body with the flexibility of improving.The adding that it is believed that dibenzoate has given prescription lower glass transition temperature (T g).Lower T gFlowability when making lamination is better, the copper surface of more fitting.This character is particular importance for the copper surface that indentation or scratch are arranged.Because the applying of dibenzoic acid ester composition and copper is good more, the photosensitive resist agent surface area that contacts with the copper surface is just big more.This makes that the tendency that combines with copper surface chemical is big more, thereby has improved bond properties.Because dibenzoate can not be incorporated in the skeleton of acrylic monomers system of exposure, so mixing of dibenzoic acid ester compounds will be reduced the overall shrinkage of composition.This contraction reduces and may produce less stress at copper/photosensitive resist agent interface, thereby has improved cohesive.If adopt the 9-phenylacridine as initiating agent, should be specifically noted that make shrink less because the cross-linking density that this initiating agent produces is higher.
In addition, Photoimageable composition can contain various annexing ingredients known in the art, comprises other polymkeric substance (can be used to realize the final sclerosis cured polymer of solder mask as those), dyestuff, stabilizing agent, softening agent, filling agent etc.
The processing of Photoimageable composition is carried out with conventional method.In typical method, Photoimageable composition layer that will make from fluid composition or photopolymer layer transfer printing acquisition is applied on the copper surface of copper facing plate.Make the Photoimageable composition layer be subjected to actinic radiation by suitable wiring diagram (artwork).The actinic radiation exposure makes the monomer polymerization in the exposure area, thereby forms the cross-linked structure of anti-developer.Then, composition is developed in the alkaline aqueous solution (as 1% sodium carbonate liquor) of dilution.The hydroxy-acid group of alkaline solution and binder polymer forms salt, thereby makes binder polymer solvable and can remove.After development, with etchant copper is removed from those have removed the zone of resist, thereby formed P.e.c..With suitable stripping agent the resist of remnants is removed then.
To the present invention be described in more detail by specific embodiment now.
Embodiment A (comparative example) and Embodiment B (embodiment of the invention)
Preparation Photoimageable composition A and B shown in the according to the form below 1, every kind of prescription adopts T gBe 85 ℃ acryloid cement polymkeric substance:
The variation of table 1-solvent and monomer
Component Prescription A monomer Prescription B oligomer
Acrylic polymers (23% methacrylic acid, 66% methyl methacrylate, 11% butyl acrylate) 40.0 gram 40.0 gram
Isocyanuric acid carbamate trimethyl acrylic ester ?????- 20.0 gram
Tetraethylene glycol diacrylate 10.0 gram 10.0 gram
The trimethylolpropane triacrylate of ethoxylation (3 moles) 20.0 gram ??-
The 9-phenylacridine 0.2 gram 0.2 gram
Dibenzoic acid dipropylene glycol ester 2.0 gram 2.0 gram
The Mi Xile ethyl ketone 0.09 gram 0.09 gram
Nitrated azo dyes (Furon Navy) 0.075 gram 0.075 gram
Methylnaphthohydroquinone 0.045 gram 0.045 gram
Triphenhlmethane dye (Flexoblue 680) 0.025 gram 0.025 gram
Composition was at 7: 1 2-butanone: preparation is into about containing 50% solid in the 2-propyl alcohol.With solution coat on the polyester film of 80 lattice bases of biaxial orienting and be dried to residual solvent and be about 1% or lower.Under 110 ℃, 2 meters/minute and 3 bar pressures mixture layer through applying is being pressed onto on the 1oz./FR-4/1oz. copper facing compound substance that machinery cleaned with the hot roll lamination machine then.
Make the material behind the lamination on the UV printing machine, come imaging then, to obtain through Stouffer  21 phase step type wedge (about 20mJ/cm by the suitable exposure tool (phototool) that exposure is regulated 2) the copper exponent number (copper step) that records is 7.Make in the 1% single sodium carbonate hydrate solution of flat board at 29 ℃ of exposure with the conveyorization spray development machine under about 26psi then and develop, the adjusting residence time makes the spraying halt occur in the 40%-50% place (unless refering in particular in addition) of developing room (chamber) length in concrete example, uses tap water and deionized water hydro-peening for several times then.
In the conveyorization etching machine of a plurality of nozzles is housed, carry out etching with 2N cupric chloride/hydrochloric acid solutions of 48 ℃.In the conveyorization stripping device of a plurality of nozzles is arranged, in 54 ℃ 3% sodium hydroxide solution, peel off the photosensitive resist agent after imaging, development and etching on the etched plate then, use the tap water hydro-peening then.
Processing result according to each embodiment of above-mentioned whole steps is described in all its bearings, and these the results are shown in the following table 2.Table 2 changes monomer to cold flow, cohesive and flexible effect
Component Thickness The spraying halt time 1 Film viscosity Cross-hatching adhesion 2 Cover intensity 3 Cold flow 4 The stripping time 5 The fine rule cohesive 6
Prescription A 38 microns 20 seconds Moderate 75% is complete 500 grams Seriously 55 seconds 45 microns
Prescription B 38 microns 19 seconds Slightly 90% is complete 750 grams Slightly 53 seconds 40 microns
Annotate 1-and be dissolved in 30 ℃ of 1%Na fully at resist 2CO 3When middle, the record spraying halt time.
The photosensitive resist agent several of notes 2-after the instrument of " thin blade-like " cuts development in one direction cuts on 90 ° of directions of last time cutting then.This test is used to measure fragility and adhesion.The percentage of record is the percentage (100% for best) of the integrality of the resist that stays after all blade cuts.Being exposed to Stouffer21 copper exponent number is 7, and the spraying halt is at 25% place of developing room.Developer solution is 30 ℃ 1%Na 2CO 3
Annotate 3-and the photosensitive resist agent is laminated to 0.25 inch both sides, hole.Then resist is shone and develop that (being exposed to Stouffer21 copper exponent number is 7, and the spraying halt is at 25% place of developing room.Developer solution is 30 ℃ 1%Na 2CO 3).Pressing resist to measure the flexibility that this " covers " resist on the hole with circular probe on the stress ga(u)ge then.With gram is to make the thing required power of breaking that covers under the unit record.
Annotate 4-and measure cold flow by distortion (deformulation) (tangerine peel) degree of observation resist after at room temperature 14 days.
It is 7 that notes 5-is exposed to Stouffer21 copper exponent number with resist, and the spraying halt is at 25% place of developing room.Developer solution is 30 ℃ 1%Na 2CO 3Come the etching resist with 130 cupric chloride then.After etching, peel off the photosensitive resist agent with 130 3%NaOH, and with second being the unit record time.
Annotating 6-fine rule cohesive measures after development.It is with the bonding residual extra fine wire bar of 400 micron pitch.Being exposed to Stouffer21 copper exponent number is 7, and the spraying halt is at 25% place of developing room.Developer solution is 30 ℃ 1%Na 2CO 3

Claims (5)

1. Photoimageable composition comprises:
A) with A), B) and C) general assembly (TW) count the organic polymer bonding agent of 29-69% weight, this bonding agent has enough acid functional groups that described Photoimageable composition can be developed in alkaline aqueous solution, described binder polymer A) T gBetween 60-90 ℃,
B) with A), B) and general assembly (TW) C) count the α that comprises of 30-60% weight, but the addition polymerization component of β-ethylene linkage unsaturated compound, described B component) comprise
Three-α is arranged, and the weight-average molecular weight of the unsaturated functionality of β-ethylene linkage is at least 1000 isocyanate trimerization body B '), described tripolymer B ') content be A), B) and C) general assembly (TW) 2-30% weight and
With A), B) and C) general assembly (TW) count other α of 0-57% weight, β-ethylene linkage unsaturated compound and
C) with A), B) and general assembly (TW) C) count the generation free radical organic system to radiation sensitive of 0.5-15% weight.
2. Photoimageable composition according to claim 1, wherein the content of B ") is at least A), B) and C) general assembly (TW) 5%.
3. Photoimageable composition according to claim 1, wherein said generation free radical system C) comprise the 9-phenylacridine.
4. Photoimageable composition according to claim 1 wherein further comprises with A), B) and general assembly (TW) C) count dibenzoate plasticiser into 1-8% weight.
5. Photoimageable composition according to claim 1, the T of wherein said binder polymer gBetween 80-90 ℃.
CN98123055A 1997-12-01 1998-12-01 Photoimageable compositions containing photopolymerizable urethane oligomers and low Tg binder polymers Pending CN1219687A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98068697A 1997-12-01 1997-12-01
US08/980,686 1997-12-01

Publications (1)

Publication Number Publication Date
CN1219687A true CN1219687A (en) 1999-06-16

Family

ID=25527772

Family Applications (1)

Application Number Title Priority Date Filing Date
CN98123055A Pending CN1219687A (en) 1997-12-01 1998-12-01 Photoimageable compositions containing photopolymerizable urethane oligomers and low Tg binder polymers

Country Status (7)

Country Link
JP (1) JPH11231528A (en)
KR (1) KR19990062605A (en)
CN (1) CN1219687A (en)
AU (2) AU700263B1 (en)
CA (1) CA2254684A1 (en)
IL (1) IL126889A0 (en)
SG (1) SG79240A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007101863A (en) * 2005-10-04 2007-04-19 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57108122A (en) * 1980-12-25 1982-07-06 Dainippon Ink & Chem Inc Novel molding material
US4610951A (en) * 1983-06-06 1986-09-09 Dynachem Corporation Process of using a flexible, fast processing photopolymerizable composition
DE3412992A1 (en) * 1984-04-06 1985-10-24 Hoechst Ag, 6230 Frankfurt BY RADIATION POLYMERIZABLE MIXTURE AND METHOD FOR APPLYING MARKINGS TO A SOLDER STOP PRESIS LAYER
US5288589A (en) * 1992-12-03 1994-02-22 Mckeever Mark R Aqueous processable, multilayer, photoimageable permanent coatings for printed circuits
US5362605A (en) * 1993-05-10 1994-11-08 W. R. Grace & Co.-Conn. Photosensitive polymer composition for flexographic printing plates processable in aqueous media
TW424172B (en) * 1995-04-19 2001-03-01 Hitachi Chemical Co Ltd Photosensitive resin composition and photosensitive element using the same

Also Published As

Publication number Publication date
AU706730B1 (en) 1999-06-24
JPH11231528A (en) 1999-08-27
AU700263B1 (en) 1998-12-24
SG79240A1 (en) 2001-03-20
IL126889A0 (en) 1999-09-22
CA2254684A1 (en) 1999-06-01
KR19990062605A (en) 1999-07-26

Similar Documents

Publication Publication Date Title
KR19990077957A (en) Photoimageable compositions having improved stripping properties in aqueous alkaline solutions
TW557412B (en) Photoimageable compositions
US4353978A (en) Polymeric binders for aqueous processable photopolymer compositions
CN1109926C (en) Photoimageable composition containing photopolymerizable urethane oligomers and dibenzoate plasticizers
CN1103066C (en) Photoimageable composition having improved flexibility, adhesion and stripping characteristics
CN1232990A (en) Photoimageable compositions having hydrophilic binder polymers and hydrophilic monomers
JP2002023349A (en) Photosensitive resin relief printing plate material
KR19990088586A (en) Photoimageable composition having improved flexibility
JP2004212805A (en) Photopolymerizable resin composition
CN1219687A (en) Photoimageable compositions containing photopolymerizable urethane oligomers and low Tg binder polymers
JP2719799B2 (en) Photosensitive resin composition
JP2818768B2 (en) Crosslinkable curable resin composition
CN1218918A (en) Photoimageable compositions for improved adhesion and processing times
JP2821547B2 (en) Crosslinkable curable resin composition
JPH11174667A (en) Photopolymerized resin composition and layered product
JP3997753B2 (en) Photosensitive resin composition
JP4065065B2 (en) Photosensitive resin composition for photoresist
JPH10198033A (en) Photopolymerizable composition and its use
JPH06202325A (en) Photopolymerizable composition
JPS62208044A (en) Novel photopolymerizable laminate
JPH10111565A (en) Novel photopolymerizable resin laminated body
JPH11218907A (en) Photopolymerizable resin composition and laminate

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication