CN101535896B - Photosensitive resin composition, cured product thereof, and method for producing photosensitive resin - Google Patents

Photosensitive resin composition, cured product thereof, and method for producing photosensitive resin Download PDF

Info

Publication number
CN101535896B
CN101535896B CN2007800409539A CN200780040953A CN101535896B CN 101535896 B CN101535896 B CN 101535896B CN 2007800409539 A CN2007800409539 A CN 2007800409539A CN 200780040953 A CN200780040953 A CN 200780040953A CN 101535896 B CN101535896 B CN 101535896B
Authority
CN
China
Prior art keywords
compound
methyl
carboxylic
acid
group
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.)
Expired - Fee Related
Application number
CN2007800409539A
Other languages
Chinese (zh)
Other versions
CN101535896A (en
Inventor
秦野望
清水格
东比吕子
石川崇
松泽孝洋
小林英宣
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.)
Toyo Ink Mfg Co Ltd
Original Assignee
Toyo Ink Mfg Co Ltd
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 Toyo Ink Mfg Co Ltd filed Critical Toyo Ink Mfg Co Ltd
Publication of CN101535896A publication Critical patent/CN101535896A/en
Application granted granted Critical
Publication of CN101535896B publication Critical patent/CN101535896B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/674—Unsaturated compounds containing the unsaturation at least partially in a cyclic ring having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Abstract

Disclosed is a photosensitive resin composition containing a carboxyl group-containing photosensitive urethane resin (A), a photopolymerization initiator (B) and a photosensitive ethylenically unsaturated group-containing compound (C). This photosensitive resin composition is characterized in that the carboxyl group-containing photosensitive urethane resin (A) is a resin obtained by reacting a hydroxy group in a hydroxy group-containing urethane prepolymer (c) with an acid anhydride group in an acid anhydride group-containing compound (d). The hydroxy group-containing urethane prepolymer (c) is obtained by reacting a carboxyl group in a carboxyl group-containing urethane prepolymer (a), which is obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxy groups in a molecule and a diisocyanate compound (g) as essential ingredients, with an epoxy group or an oxethane group in a compound (b) having an epoxy group or an oxethane group and an ethylenically unsaturated group. This photosensitive resin composition is excellent in sensitivity to an active energy ray and enables to form a fine pattern. A cured coating film of the photosensitive resin composition is excellent in flexibility, insulating property, adhesion, solder heat resistance, coating film resistance and flame retardance, and is thus suitably used for a photosolder resist.

Description

The preparation method of photosensitive polymer combination and solidfied material thereof and photoresist
Technical field
The present invention relates to the photosensitive polymer combination that contains carboxylic photonasty urethane resin useful in printed wiring board etc. and the preparation method of solidfied material and above-mentioned photoresist thereof.More particularly; Relate to as flexible printed circuit board excellently with useful development property such as solder resist (solder resist), platedresist, multilayer printed wiring board-use interlayer electrically insulating material, photonasty optical waveguide, its cured coating film provides the photosensitive polymer combination that contains specific carboxylic photonasty urethane resin of excellent in curing things such as adhesiveness, flexibility (bendability), soldering thermotolerance, chemical reagent resistance, electrical insulating property and the preparation method of solidfied material and above-mentioned photoresist thereof.Further, the photonasty resistance solder paste China ink (solder resist ink) and the dry-film type photonasty solder resist that relate to fire-retardantization of height that contains above-mentioned photosensitive polymer combination.
Background technology
Be formed in the soldering step of carrying out when wiring (circuit) pattern on the substrate does not receive external environment influence or is installed in electronic component on the printed wiring board surface in protection; In order to protect the non-cohesive scolding tin of unnecessary portions, the protective seam that will be called as overlayer or soldering mask covers on the printed wiring board.The protective seam that particularly wiring pattern that is formed on the polyimide film that is called as flexible printed circuit board is used requires adhesiveness, flexibility, folding resistance with polyimide.
In the past; Use protective seam as flexible printed circuit board; After exist making the polyimide film stamping-out that the mould that meets pattern will be called as covering layer film, the type of using bonding agent to paste; Thermohardening type printing inks through serigraphy coating etc., but owing to become more meticulous along with high density, the height of advances in electronic technology in recent years are to studying with resistance solder paste China ink or dry-film type solder resist that high precision more forms the ultraviolet hardening photoresist type of pattern.
Usually use photic solder resist for flexible printed circuit board; When utilizing the photic solder resist that in the past in rigid substrates is used, used, though obtain the pattern precision, filming after existence is solidified is hard; With the poor adhesion of polyimide, can not get problems such as sufficient flexibility, bendability, folding resistance.
Thus, as having flexible photic solder resist, a lot of motions have been proposed in recent years.For example, the resist ink composite (patent documentation 1) that contains the resin that the epoxy resin that on main chain, has the bisphenol-A skeleton and monocarboxylic addition compound product that contains unsaturated group and succinic anhydride reaction obtain is disclosed.Though excellences such as said composition development property, light sensitivity, adhesiveness, thermotolerance still exist flexible, the inadequate problem of folding resistance.In addition; As photosensitive heat curing voltinism composition; Secondary hydroxyl and the reaction product of saturated or unsaturated multi-anhydride, the secondary hydroxyl of this generation and (patent documentations 2) such as reaction product that contain the isocyanate compound of unsaturated group through the esterification generation of cresols phenolic varnish type epoxy compound and unsaturated monocarboxylic acid have been proposed.Though their adhesivenesses, soldering thermotolerance, the patience of filming are very excellent, still there are flexible, the inadequate problem of folding resistance.
In addition, proposed to contain polymkeric substance that the monomer copolymerization that (methyl) acrylic acid and (methyl) acrylic ester is obtained photonasty composition (patent documentation 3) as adhesive ingredients.Though their development property, distinguishing excellence when being used for the flexible printed circuit board purposes, can not get sufficient adhesiveness, flexibility, folding resistance.
In addition; Proposed to make the multi-anhydride reaction that has 2 anhydride group in polyol compound and the molecule; What preparation had ester bond that half esterization derives in the main chain contains the carboxyl polyester polyvalent alcohol; Make this contain carboxyl polyester polyvalent alcohol and polyisocyanate compounds reaction; Obtain carboxylic polyurethane prepolymer, the photosensitive polymer combination that contains carboxylic urethane oligomer (patent documentation 4) that (methyl) acrylate reactions of having 1 epoxy radicals in a part and the molecule of the carboxyl in this polyurethane prepolymer is obtained.Though they obtain flexibility; But owing to have the ester bond of deriving in the main chain through the half esterization of multi-anhydride; Be at high temperature to produce chemically unsettled structures such as dehydration, main chain easy fracture; Because carboxyl directly is connected with main chain, the motility of carboxyl is suppressed, so insufficient aspect development property or various film patience and soldering thermotolerance in addition.
In addition, the photosensitive polymer combination (patent documentation 5) that is added with phosphorus type flame retardant is disclosed.They carry out fire-retardantization in order to reduce the load to environment through using halogen-free flame retardants.But; In order to utilize halogen-free flame retardants to give sufficient anti-flammability, be necessary to add a large amount of fire retardants, owing to this reason; The remarkable reduction of the distinguishing of the tens μ m levels that require in recent years etc.; The anti-flammability rerum natura in addition that resist is required reduces, so for the rerum natura that has concurrently beyond anti-flammability and the anti-flammability, be inadequate.
As stated; In the prior art; Do not obtain having concurrently as flexible printed circuit board with sufficient flexibility, the folding resistance of protective seam requirement with can realize development property, the soldering thermotolerance of patterns of high precision, and can satisfy resin combination and solidfied material thereof as whole various rerum naturas such as the essential electrical insulating property of circuit protecting layer, chemical reagent resistance, anti-flammabilitys.
For printed wiring board, in order to improve miniaturization and, communication speed, require high precision, densification as portable instrument, for the flexible printed circuit board of the bend that is mainly used in instrument, connecting portion periphery, this trend is identical.Can know by this background; Flexible printed circuit board is increased with the requirement of protective seam day by day; When require keeping to realize development property that the height of resist pattern becomes more meticulous and the flexibility higher, folding resistance, satisfy the performance of soldering thermotolerance, substrate adhesiveness, high-insulativity, the patience of filming, anti-flammability etc. than requirement in the past.When utilizing now commercially available photic solder resist, can not fully satisfy these requirements.
Patent documentation 1: No. 3281473 communique of Jap.P.
Patent documentation 2: No. 2707495 communique of Jap.P.
Patent documentation 3: TOHKEMY 2004-279479 communique
Patent documentation 4: TOHKEMY 2001-159815 communique
Patent documentation 5: TOHKEMY 2006-251715 communique
Summary of the invention
The objective of the invention is to; Provide excellent for the photonasty of active energy beam; Can form fine pattern through developing with dilute alkaline aqueous solution; And, be suitable for the photosensitive polymer combination and the solidfied material thereof of photic solder resist, and the preparation method of photoresist through excellences such as the flexibility of later solidifying the cured coating film that (post cure) step obtains, insulativity, adhesiveness, soldering thermotolerance, the patience of filming, anti-flammabilitys.
The inventor furthers investigate in order to address the above problem, and the result finds that the photosensitive polymer combination that contains specific carboxylic photonasty urethane resin (A) has solved the problems referred to above, thereby has accomplished the present invention.
That is, the present invention's the 1st scheme relates to photosensitive polymer combination, and this photosensitive polymer combination contains the compound (C) that carboxylic photonasty urethane resin (A), Photoepolymerizationinitiater initiater (B) and photonasty contain the ethylenic unsaturated group, it is characterized in that:
Carboxylic photonasty urethane resin (A) is the resin that obtains through following reaction,
Through obtaining carboxylic polyurethane prepolymer (a) as must composition reacting with the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and diisocyanate cpd (g),
Through making the carboxyl in the above-mentioned carboxylic polyurethane prepolymer (a) that obtains react the polyurethane prepolymer (c) that obtains hydroxyl with the epoxy radicals or the oxa-cyclobutyl that have in the compound (b) of epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group,
Make the anhydride group reaction in hydroxyl and the compound (d) that contains anhydride group in the polyurethane prepolymer (c) of the above-mentioned hydroxyl that obtains.
In addition, the 2nd scheme relates to the photosensitive polymer combination of the 1st scheme, wherein, further contains Thermocurable compound (D).
In addition, the 3rd scheme relates to the photosensitive polymer combination of the 2nd scheme, wherein, further contains heat curing auxiliary agent (E).
In addition, the 4th scheme relates to the photosensitive polymer combination of the 1st～3 any scheme, and wherein, the acid number of carboxylic photonasty urethane resin (A) is 10～200mgKOH/g.
In addition, the 5th scheme relates to the photosensitive polymer combination of the 1st～4 any scheme, and wherein, the ethylenic unsaturated group equivalent of carboxylic photonasty urethane resin (A) is 200～3000g/eq.
In addition, the 6th scheme relates to the photosensitive polymer combination of the 1st～5 any scheme, and wherein, the weight-average molecular weight of carboxylic photonasty urethane resin (A) is 1000～100000.
In addition, the 7th scheme relates to the photosensitive polymer combination of the 2nd～6 any scheme, and wherein, Thermocurable compound (D) is the compound (k) with 2 above epoxy radicals or oxa-cyclobutyl.
In addition, the 8th scheme relates to solidfied material, and it is the photosensitive polymer combination of the 1st～7 any scheme to be solidified form.
In addition, the 9th scheme relates to photonasty resistance solder paste China ink, contains the photosensitive polymer combination and the fire retardant of the 1st～7 any scheme.
Further, the 10th scheme relates to dry-film type photonasty solder resist, contains the photosensitive polymer combination and the fire retardant of the 1st～7 any scheme.
Further, the 11st scheme relates to the preparation method of carboxylic photonasty urethane resin, the method is characterized in that, comprising:
With the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and diisocyanate cpd (g) as must reacting the first step that obtains carboxylic polyurethane prepolymer (a) by composition,
Make above-mentioned carboxylic polyurethane prepolymer (a) and compound (b) react second step of the polyurethane prepolymer (c) obtain hydroxyl with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group, and
Make the polyurethane prepolymer (c) of above-mentioned hydroxyl and the third step of compound (d) reaction that contains anhydride group.
Through the present invention; Can provide excellent for the photonasty of active energy beam; Can form fine pattern through developing with dilute alkaline aqueous solution; And, be suitable for the photosensitive polymer combination and the solidfied material thereof of photic solder resist, and the preparation method of photoresist through excellences such as the flexibility of later solidifying the cured coating film that (post cure) step obtains, insulativity, adhesiveness, soldering thermotolerance, the patience of filming, anti-flammabilitys.
Photosensitive polymer combination of the present invention can be suitable as flexible printed circuit board and use solder resist; The photosensitive cover lay film; Platedresist; Wiring plate is used the interlayer electrically insulating material, the photonasty optical waveguide, and on the polyethylene terephthalate film printed silver stick with paste or conductive ink such as carbon paste, form circuit the flexible printing substrate with the overlayer resist etc.
Embodiment
The carboxylic urethane oligomer of record in above-mentioned patent documentation 4; As stated, contain the ester bond that the half esterization of carrying out through multi-anhydride is derived in the main chain, with respect to this; Photosensitive polymer combination of the present invention has following characteristic: owing to do not have the ester bond that this half esterization is derived in the main chain; Main chain is chemically stable, thus the various patience excellences of filming of the cured coating film that obtains, even be exposed to the situation under the hot conditions such as scolder bath; Also the excellent thermotolerance of performance is brought into play the distinctive adhesiveness of urethane resin, flexibility simultaneously.In addition; The carboxylic photonasty urethane resin of the present invention (A) even under the few situation of carboxyl-content, also shows very excellent development property through having photonasty group and carboxyl on the side chain; In addition; These side chain functionalities since with directly compare with the situation of main chain bonding, reactive fully, so can bring into play photo-curable, distinguishing and the patience of filming of excellence.Below photosensitive polymer combination of the present invention is carried out bright specifically.
At first, describe for carboxylic photonasty urethane resin of the present invention (A).Carboxylic photonasty urethane resin of the present invention (A) can obtain as follows: with respect to 1 mole of the carboxyl in the carboxylic polyurethane prepolymer (a); After making epoxy radicals or oxa-cyclobutyl in the compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group preferably carry out the polyurethane prepolymer (c) of prepared in reaction hydroxyl with 0.1 mole～1.0 moles ratio, more preferably 0.30 mole～0.95 mole ratio; With respect to 1 mole of the hydroxyl in the polyurethane prepolymer (c) of above-mentioned hydroxyl, anhydride group in the compound (d) that contains anhydride group is preferably reacted with 0.1 mole～1.0 moles ratio, more preferably 0.3 mole～0.95 mole ratio obtain carboxylic photonasty urethane resin of the present invention (A).
Above-mentioned mol ratio is the reaction mol ratio, and the consumption of each parent material is can be with the amount of above-mentioned molar ratio reaction.Therefore; For example; Sometimes with respect to 1 mole of the carboxyl in " carboxylic polyurethane prepolymer (a) ", the amount that epoxy radicals in " compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group " or oxa-cyclobutyl are 0.1～1.2 mole makes, and above-mentioned " carboxylic polyurethane prepolymer (a) reacts with above-mentioned " compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group ".In addition, it is same as described above to relate to the meaning of the record of reacting mol ratio in this instructions.
Wherein, With respect to the carboxyl in the carboxylic polyurethane prepolymer (a); When making ratio that epoxy radicals or oxa-cyclobutyl in the compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group react less than 0.1 mole; The amount of the unsaturated group in the carboxylic photonasty urethane resin (A) that finally obtains reduces, and photosensitive polymer combination is difficult to obtain required photonasty.
And, with respect to 1 mole of the carboxyl in the carboxylic polyurethane prepolymer (a), can not make epoxy radicals or oxa-cyclobutyl in the compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group to react greater than 1.0 moles amount.
Further; With respect to 1 mole of the hydroxyl in the polyurethane prepolymer (c) of above-mentioned hydroxyl; When making ratio that the anhydride group in the compound (d) that contains anhydride group reacts less than 0.1 mole, the ratio that imports carboxyl reduces, and photosensitive polymer combination is difficult to obtain required development property.
And, with respect to 1 mole of the hydroxyl in the polyurethane prepolymer (c) of above-mentioned hydroxyl, can not make anhydride group in the compound (d) that contains anhydride group to react greater than 1.0 moles amount.
Carboxylic polyurethane prepolymer (a) is through preparing the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and diisocyanate cpd (g) as must composition reacting.Further; As required composition, can suitably use the isocyanate compound (i) and the amines (j) that have 1 or 3 above NCO in the compound (h) [but above-mentioned " polymer polyatomic alcohol (e) " and above-mentioned " carboxylic acid compound (f) that has 2 hydroxyls in the molecule " except], molecule of hydroxyl.
Among the present invention; When synthesizing carboxylic polyurethane prepolymer (a); The ratio that this initiation material reacts; For the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and the compound (h) and the amines (j) of the hydroxyl that adds as required; Preferably with the hydroxyl that contains in them with amino when adding up to 1 mole, 0.5 mole～1.00 moles the ratio of adding up to that has contained NCO in the isocyanate compound (i) of 1 or 3 above NCO in diisocyanate cpd (g) and the molecule reacts, and more preferably reacts with 0.70 mole～0.95 mole ratio.NCO is during less than 0.50 mole, and the decrease in molecular weight of carboxylic polyurethane prepolymer (a) is difficult to obtain required film patience or system film property.In addition, NCO is during greater than 1.00 moles, and remaining NCO remains in the system, is prone to and in the subsequent reaction step, produces the problem that gelation takes place in accessory substance or the reaction.
In addition; This moment is for the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and the compound (h) and the amines (j) of the hydroxyl that adds as required, is that the ratio of 5～200mgKOH/g adds the carboxylic acid compound (f) that has 2 hydroxyls in the molecule (more preferably 10～180mgKOH/g) with the acid number of the carboxylic polyurethane prepolymer (a) that finally obtains preferably.
The polymer polyatomic alcohol that uses among the present invention (e) is the compound that contains 2 above hydroxyls, and is to be preferably 500～50000 compound through the weight-average molecular weight that gel permeation chromatography (below be also referred to as " GPC ") is measured the polystyrene conversion that obtains.And, in this instructions, only otherwise specify that weight-average molecular weight refers to the weight-average molecular weight of measuring the polystyrene conversion that obtains through GPC.Among the present invention; As polymer polyatomic alcohol (e); Can enumerate the polyether glycol class such as segmented copolymer or random copolymers of segmented copolymer or random copolymers, polytetramethylene glycol, tetramethylene glycol and the neopentyl glycol of polyethylene oxide, polypropyleneoxide, ethylene oxide/propylene oxide
The condensation product of polyprotonic acids such as polyvalent alcohol or polyether glycol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, hexane diacid, m-phthalic acid is the polyester polyols alcohols,
Through the reaction of dibasic alcohol or bis-phenol and carbonic ester, the perhaps polycarbonate polyol class that in the presence of alkali, obtains of dibasic alcohol or bis-phenol with phosgene reaction etc.,
Polyvalent alcohols such as polybutadiene polyvalent alcohols such as caprolactone modification polyvalent alcohols such as caprolactone modification polytetramethylene polyvalent alcohol, polyolefins polyvalent alcohol, hydrogenated butadiene polymer polyvalent alcohol, type siloxane polyvalent alcohol.Among the present invention, these polymer polyatomic alcohols (e) can only use a kind of separately or and with multiple.
Wherein, Polyether glycol classes such as the segmented copolymer of polytetramethylene glycol, tetramethylene glycol and neopentyl glycol or random copolymers; Because the flexibility of skeleton, hydrolytic resistance, water wettability excellence; Be used for when of the present invention, the flexibility of filming, chemical reagent resistance, development property etc. are excellent and preferred especially.
" carboxylic acid compound (f) that has 2 hydroxyls in the molecule " that uses among the present invention is the compound that has 2 hydroxyls in the molecule and (be preferably 1～3) more than 1 carboxyl; And be that weight-average molecular weight is preferably 90～1000 compound; For example can enumerate; Dimethylolpropionic acid, dihydromethyl propionic acid and their derivant (caprolactone addition product, ethylene oxide adduct, propylene oxide adduct etc.), 3-hydroxyl salicylic acid, 4-hydroxyl salicylic acid, 5-hydroxyl salicylic acid, 2-carboxyl-1,4 cyclohexane dimethanol etc.
Wherein, dimethylolpropionic acid, dihydromethyl propionic acid are considered preferred in the present invention from the carboxyl concentration aspect that can increase the resin.In addition, caprolactone addition product, ethylene oxide adduct, propylene oxide adduct etc. can be used for improving the flexibility of filming owing to can reduce the amount of the ammonia ester bond in the carboxylic polyurethane prepolymer (a).Further, aromatic compounds such as hydroxyl salicylic acid can be used for improving the thermotolerance of filming.
So, among the present invention, these carboxylic acid compounds (f) can suitably be selected use according to purpose or purposes, can only use a kind of separately or and with multiple.
As the diisocyanate cpd that uses among the present invention (g), can enumerate carbon number for example and be 4～50 aromatic diisocyanates, aliphatic diisocyanate, aromatic-aliphatic diisocyanate, alicyclic diisocyanate etc.
As aromatic diisocyanates, for example can enumerate, 1,3-phenylene vulcabond, 4; 4 '-diphenyl diisocyanate, 1,4-phenylene vulcabond, 4,4 '-methyl diphenylene diisocyanate, 2,4-benzal diisocyanate, 2; 6-benzal diisocyanate, 4,4 '-toluidine diisocyanate, 2,4; 6-triisocyanate base toluene, 1,3,5-triisocyanate base benzene, DADI, 4; 4 '-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate etc.
As aliphatic diisocyanate; Can enumerate for example trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1; 2-trimethylene diisocyanate, 2,3-butylidene diisocyanate, 1,3-butylidene diisocyanate, ten dimethylene diisocyanates, 2; 4,4-trimethyl hexamethylene diisocyanate etc.
As the aromatic-aliphatic diisocyanate, for example can enumerate ω; ω '-diisocyanate based-1,3-dimethyl benzene, ω, ω '-diisocyanate based-1; 4-dimethyl benzene, ω, ω '-diisocyanate based-1,4-diethylbenzene, 1; 4-tetramethylbenzene dimethyl diisocyanate, 1,3-tetramethylbenzene dimethyl diisocyanate etc.
As alicyclic diisocyanate, for example can enumerate 3-isocyanates ylmethyl-3; 5,5-3-methyl cyclohexanol based isocyanate [another name: IPDI], 1,3-cyclopentane diisocyanate, 1; 3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2; 6-cyclohexane diisocyanate, 4; 4 '-methylene two (cyclohexyl isocyanate), 1,3-two (isocyanates ylmethyl) cyclohexane, 1,4-two (isocyanates ylmethyl) cyclohexane etc.
Among the present invention; When improving the thermotolerance of purpose photosensitive polymer combination; Preferred aromatic diisocyanates or the aromatic-aliphatic diisocyanate of using when improving the flexibility of purpose photosensitive polymer combination, preferably uses aliphatic diisocyanate or alicyclic diisocyanate.Among the present invention, these diisocyanate cpds (g) can suitably be selected use according to purpose or purposes, in addition, can only use a kind of separately or and with multiple.
The compound of the hydroxyl that uses among the present invention (h) is the compound with 1 above hydroxyl; And be the compound except compound that belongs to above-mentioned " polymer polyatomic alcohol (e) " and the compound that belongs to above-mentioned " carboxylic acid compound (f) that has 2 hydroxyls in the molecule "; As its representative example; For example can enumerate; The monohydroxy alcohol compound (h1) that has 1 hydroxyl in the molecule has 2 hydroxyls in the molecule and the weight-average molecular weight that do not have a carboxyl is 50～499 dibasic alcohol (h2), has 3 above hydroxyls, weight-average molecular weight in the molecule and be 50～499 polyol compound (h3).They can have the functional group beyond hydroxyl and the hydroxyl concurrently.In addition, can use separately or and with multiple.
As the monohydroxy alcohol compound (h1) that in molecule, has 1 hydroxyl, for example can enumerate, aliphatic monobasic alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, the tert-butyl alcohol, lauryl alcohol, stearyl alcohol,
Alicyclic monohydroxy alcohol such as cyclohexanol,
Phenmethylol, fluorenol, phenol, methoxyl quinone aromatics monohydroxy alcohols such as (メ ト キ ノ Application),
As the monohydroxy alcohol compound that has the functional group beyond the hydroxyl concurrently; Can enumerate the carboxylic acid compound of hydroxyls such as 12-hydroxy stearic acid; (methyl) acrylic acid 2-hydroxy methacrylate (" acrylic acid 2-hydroxy methacrylate " and " 2-hydroxyethyl methacrylate " is referred to as " (methyl) acrylic acid 2-hydroxy methacrylate ", below identical.), (methyl) acrylate compounds of hydroxyl such as (methyl) acrylic acid 4-hydroxyl butyl ester, the epoxy compound of hydroxyls such as diglycidyl, the heterocycle butane compound of hydroxyls such as oxa-cyclobutanol.
In addition, can enumerate the polypropylene glycol of the polyglycol of a terminal methoxy groupization, a terminal methoxy groupization, be the oligomeric monohydroxy alcohols such as caprolactone addition polymer of initiating agent with the monohydroxy alcohol.
Among the present invention; When using these monohydroxy alcohol compounds, because can be, when thinking synthetic low-molecular-weight carboxylic polyurethane prepolymer (a) etc. with the polymerization end-capped of the carboxylic polyurethane prepolymer (a) that obtains; When being necessary to adjust molecular weight, can be fit to use.In addition; When use has the compound of hydroxyl of the functional group beyond the hydroxyl concurrently; Owing to can import the functional group beyond the hydroxyl, when being necessary that end to carboxylic polyurethane prepolymer (a) carries out modification, can be fit to use at the end of carboxylic polyurethane prepolymer (a).Among the present invention,, then preferably use lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxy stearic acid, epoxy prapanol, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 4-hydroxyl butyl ester etc. if consider the reactivity or the polymerization Control of hydroxyl.
The weight-average molecular weight that does not have carboxyl as having 2 hydroxyls in the molecule is 50～499 diatomic alcohol compounds (h2), for example can enumerate monoethylene glycol, diethylene glycol, triethylene glycol, TEG, propylene glycol, DPG, butylene glycol, 1; 3-butylene glycol, 1,4-butylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 1; 6-hexanediol, neopentyl glycol, 1; Glycols such as 9-nonanediol, hydrogenated bisphenol A, 1,4 cyclohexane dimethanol, the spiroglycol
Quinhydrones, 1,3-dihydroxy benzenes, 1, aromatic diol classes such as 2-dihydroxy benzenes, bis-phenol, two phenoxetol fluorenes, bisphenol fluorene, xylenol fluorenes,
N, N-two (2-hydroxypropyl) aniline, N, N-two (2-hydroxyethyl) aniline, N; N-two (2-hydroxyethyl) methyl amine, N, N-two (2-hydroxyethyl) propyl group amine, N, N-two (2-hydroxyethyl) butylamine, N; N-two (2-hydroxyethyl) hexyl amine, N, N-two (2-hydroxyethyl) octyl amine, N, N-two (2-hydroxyethyl) benzyl amine, N; The diatomic alcohol compounds of tertiary-amino-containings such as N-two (2-hydroxyethyl) cyclo-hexylamine
Can enumerate in addition sulfur atom-containing for example dibasic alcohol, contain the dibasic alcohol of bromine atoms etc.Among the present invention, these dibasic alcohol (h2) can only use a kind of separately or and with multiple.Among the present invention, through use N, the diatomic alcohol compounds of tertiary-amino-containings such as N-two (2-hydroxypropyl) aniline, the cohesiveness of filming increases, and can under the state that keeps flexibility, form more firm the filming of excellence of patience, so preferred.
As having 3 above hydroxyls, weight-average molecular weight in the molecule is 50～499 polyol compound (h3), for example can enumerate trimethylolethane, gathers trimethylolethane, trimethylolpropane, gathers trimethylolpropane, pentaerythrite, polypentaerythritol, sorbierite, sweet mellow wine, arabite, xylitol, galactitol, glycerine etc.Among the present invention, when using these polyvalent alcohols (h3), because can be so that the cross-linking density of solidfied material, the patience of raising cured coating film can improve in a part of branch of the carboxylic polyurethane prepolymer (a) that arrives.Therefore, in the present invention,, can use as required in order further to improve the patience of cured coating film.In these polyol compounds (h3), consider preferred trimethylolpropane or the pentaerythrite of using from reaction control aspect.
As " isocyanate compound (i) that has 1 or 3 above NCO in the molecule " that use among the present invention; Specifically; As the monofunctional isocyanates that has 1 NCO in 1 molecule; Can enumerate (methyl) acryloxy ethyl isocyanate, 1; 1-two [(methyl) acryloyl-oxy ylmethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanates, (methyl) acryloyl group isocyanates, isopropenyl-α, α-Er Jiajibianji isocyanates etc.Also can use 1; The diisocyanate based hexane of 6-, two isocyanic acid isophorone esters, two isocyanic acids 4; 4 '-diphenyl methane, gather methyl diphenylene diisocyanate, xylylene diisocyanate, 2; 4-two isocyanic acid benzal esters, toluene-2,4-diisocyanate, 2; 4-toluene-2,4-diisocyanate, two isocyanic acid hexa-methylene esters, two isocyanic acid 4-methyl-metaphenylene esters, naphthalene diisocyanate, to phenylene vulcabond, tetramethylbenzene dimethyl diisocyanate, cyclohexyl-methane diisocyanate, hydrogenation of benzene dimethyl diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2; 2; 4-trimethyl hexamethylene diisocyanate, 2; 4,4-trimethyl hexamethylene diisocyanate, a tetramethylbenzene dimethyl diisocyanate, to diisocyanate cpds such as tetramethylbenzene dimethyl diisocyanate, dimer acid diisocyanate and the vinyl monomer that contains hydroxyl, carboxyl, amide group with etc. mole react the compound that obtains as isocyanate compound.
In addition; As the polyfunctional isocyanate who has 3 above NCOs in 1 molecule; For example can enumerate; Aliphatic polymeric isocyanate such as aromatic polyisocyanate, LTI, aromatic-aliphatic polyisocyanate, alicyclic polymeric isocyanate etc., the biuret compounds that can enumerate the trimethylolpropane addition product of above-mentioned diisocyanate (g), obtain with water reaction, trimer with isocyanurate ring.
Among the present invention; When wanting to reduce the unreacted hydroxyl of the end that remains in carboxylic polyurethane prepolymer (a); For with end-capped; The preferred monofunctional isocyanates that has 1 NCO in 1 molecule of using; In addition, when making carboxylic polyurethane prepolymer (a) branch, preferably use the polyfunctional isocyanate who has 3 above NCOs in 1 molecule in order to improve patience of filming of obtaining through filming of obtaining of photocuring or through photocuring or heat curing by photosensitive polymer combination of the present invention etc.Among the present invention, these isocyanate compounds can suitably be selected use according to purpose or purposes, in addition, can only use a kind of separately or and with multiple.
Further, among the present invention, when synthetic carboxylic polyurethane prepolymer (a), the amines (j) as required composition is reacted.Amines (j) alleged among the present invention refers to the compound that has at least 1 primary amino radical or secondary amino group in the molecule.
As amines of the present invention (j); For example can enumerate; Monoamine compounds such as propyl group amine, hexyl amine, cyclo-hexylamine, benzyl amine, 2-DEHA, octyl amine, lauryl amine, aniline, ethylenediamine, propane diamine, trimethylene diamines, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, trien, diethylene triamine, triamido propane, 2,2; Aliphatic polyamines such as 4-trimethylhexamethylenediamine, tolylene diamine, hydrazine, piperazine; IPD, dicyclohexyl methyl hydride-4, alicyclic ring polyamines such as 4 '-diamines, and aromatic polyamine such as phenylenediamine, xylylene diamines.
In addition; Can enumerate the diamine compound such as polypropyleneoxide, polysiloxane diamine, polybutadiene diamines of polyethylene oxide, the two terminal amino group modifications of two terminal amino group modifications; Monoamine compounds such as the polypropyleneoxide of the polyethylene oxide of a terminal amino group modification, a terminal amino group modification, polysiloxane monoamine, polybutadiene monoamine, polymer-type polyamine compounds such as polyethyleneimine, PAH.
In addition, as amines (j), can enumerate through make in the compound with primary amino radical primary amino radical with contain that (methyl) in (methyl) acrylate-based compound is acrylate-based to carry out Michael addition reaction, be modified as the amines that secondary amino group obtains.When using this compound,, can in carboxylic polyurethane prepolymer (a), import polar functional group through studying to containing (methyl) acrylate-based compound.For example, the primary amino radical of the acrylate-based and IPD through making acrylic acid 4-hydroxyl butyl ester carries out Michael addition, and synthetic diamines with secondary amino group with its raw material as urethane resin of the present invention, can import hydroxyl in resin.
In addition, as amines of the present invention (j), also can use amines with amino functional group in addition.For example can enumerate; 2-hydroxyethyl ethylenediamine, N-(2-hydroxyethyl) propane diamine, (2-hydroxyethyl propylidene) diamines, (two 2-hydroxyethyl ethylidene) diamines, (two-2-hydroxyethyl propylidene) diamines, (2-hydroxypropyl ethylidene) diamines, (two-2-hydroxypropyl ethylidene) diamines etc. have two amines of hydroxyl, and the carboxyl of dimer acid is converted into dimerization diamines that amino obtains and has polyoxy alkylene glycol diamines of propoxyl group amine etc. at two ends.
Among the present invention, these amines (j) can only use a kind of separately or also with multiple, can suitably select to use or make up use monoamine, diamines, polyamines according to purpose or purposes.
During for example synthetic carboxylic polyurethane prepolymer (a), through and use monoamine compound, can reduce the amount of residual isocyanate base, can be with end-capped, thereby molecular weight easy to control.In addition, through using diamine compound, can prolong polymer chain, thereby can obtain high molecular weight polymers.Further, through using polyamine compounds, can make final cohesiveness, the patience of filming that improves of polymer chain branch.
As the method that makes amines (j) reaction; Can enumerate with polymer polyatomic alcohol (e) wait other raw material add simultaneously the back, with the method for diisocyanate cpd (g) [and as required further with isocyanate compound (i)] reaction, in advance the terminal polyurethane chain of synthesizing isocyanate, prolong chain, obtain containing the method etc. of the carboxylic polyurethane prepolymer (a) of urea key thus to wherein dripping or adding amines (j) then.Among the present invention, when so making amines (j) reaction,, can form more excellent the filming of thermotolerance, permanance, so can use amines (j) as required because the cohesiveness of the carboxylic photonasty urethane resin (A) that obtains improves.
Among the present invention,, can under known condition, carry out the qualification especially of synthesis condition of carboxylic polyurethane prepolymer (a).
For example; Polymer polyatomic alcohol (e), carboxylic acid compound (f) and solvent [and compound (h) of the hydroxyl that uses as required] are joined in the flask, under stream of nitrogen gas, in 20～120 ℃ of heating down, stirring; After making its uniform dissolution thus; Drop into diisocyanate cpd (g) [and the isocyanate compound (i) that uses as required], 50～150 ℃ of heating down, can obtain carboxylic polyurethane prepolymer (a) thus when stirring.At this moment, also can use the ammonia esterification catalysts such as compound of organo-tin compound, tertiary-amino-containing as required.
In addition, also can drop into diisocyanate cpd (g) before, polymer polyatomic alcohol (e), carboxylic acid compound (f) and the solvent that will join in advance in the flask are heating more than 100 ℃, are stirring, with a part of desolventizing of solvent.This operation is normally carried out in order to remove intrasystem moisture (processed); Through this operation; Make diisocyanate cpd (g) when reacting; Because NCO inactivation that water caused is inhibited, finally obtain having more carboxylic polyurethane prepolymer (a) near the physics value of theoretical value.
Then, among the present invention, make carboxylic polyurethane prepolymer (a) and compound (b) reaction with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group, the polyurethane prepolymer (c) of synthetic hydroxyl.
Among the present invention; As the ratio that makes carboxylic polyurethane prepolymer (a) with compound (b) reaction with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group; As stated; With respect to 1 mole of the carboxyl in the carboxylic polyurethane prepolymer (a), epoxy radicals or oxa-cyclobutyl in the compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group are preferably reacted with 0.1 mole～1.0 moles, more preferably 0.3 mole～0.95 mole ratio.
Wherein, With respect to the carboxyl in the carboxylic polyurethane prepolymer (a); When making ratio that epoxy radicals or oxa-cyclobutyl in the compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group react less than 0.1 mole; Because the unsaturated group amount in the carboxylic photonasty urethane resin (A) that finally obtains reduces, so photosensitive polymer combination is difficult to obtain required photonasty.
The preferred carbon number of " compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group " that uses among the present invention is 6～50 compound; For example can enumerate; (methyl) acrylic acid glycidyl esters, cinnamic acid glycidyl esters, (methyl) acrylic acid 4-hydroxyl butyl ester glycidyl ether, glycidyl allyl ether, (methyl) acrylic acid 2; 3-epoxy-2-methyl propyl ester, (methyl) acrylic acid (3; The 4-epoxycyclohexyl) methyl esters, 4-vinyl-1-cyclohexene-1; 2-epoxide, 1; 3-butadiene monoepoxide, (methyl) acrylic acid oxa-cyclobutyl ester, cinnamic acid oxa-cyclobutyl ester or pentaerythritol triacrylate etc. make the hydroxyl and the chloropropylene oxide of the multifunctional acrylic monomer of hydroxyl react the monoepoxide that contains the polyfunctional acrylic ester base that obtains; Or be modified as the monoepoxide that contains the polyfunctional acrylic ester base of residual 1 epoxy radicals in acrylate-based average 1 molecule that obtains with acrylic acid etc. through major part with the epoxy radicals of phenol novolak type epoxy resin; Has the monoepoxide that contains the polyfunctional acrylic ester base that the part reaction of epoxy radicals of the compound of 2 above epoxy radicals obtains etc. in carboxyl through making carboxylic polyfunctional acrylic monomer and the molecule; Through making the carboxyl reaction in these epoxy radicals or oxa-cyclobutyl and the polyurethane prepolymer (a), obtain the polyurethane prepolymer (c) of hydroxyl.Among the present invention, the compound (b) with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group can only use a kind of separately or and with multiple.
Wherein, (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid 4-hydroxyl butyl ester glycidyl ether etc.; Since in the present invention with carboxylic polyurethane prepolymer (a) in carboxyl reactive fully; The photonasty of the photosensitive polymer combination that obtains in addition is very excellent, so preferred especially.
In addition, among the present invention, can " do not have the ethylenic unsaturated group and with epoxy radicals or oxa-cyclobutyl compound (o) " and " compound (b) " and usefulness with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group yet.It is 6～50 compound that " do not have the ethylenic unsaturated group and with epoxy radicals or oxa-cyclobutyl compound (o) " that can use as required among the present invention is preferably carbon number; For example can enumerate; Styrene oxide, phenylglycidyl ether, o-phenyl phenol glycidyl ether, p-phenyl phenol glycidyl ether, cinnamic acid glycidyl esters, methyl glycidyl ether, butyl glycidyl base ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, diglycidyl, N-glycidyl phthalimide, 1; 3-dibromo phenyl glycidyl ether, CELLOXIDE 2000 (DAICEL CHEMICAL INDUSTRIES, LTD. preparation), oxa-cyclobutanol etc.
Among the present invention; Through these " not being had the compound (o) that the ethylenic unsaturated group has epoxy radicals or oxa-cyclobutyl " and " compound (b) " and usefulness with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group; Can in wideer scope, control, so preferably suitably use according to purpose or purposes to the photonasty of carboxylic photonasty urethane resin of the present invention (A).
Qualification especially of reaction conditions when making carboxyl in the carboxylic polyurethane prepolymer (a) with the epoxy radicals or the reaction of oxa-cyclobutyl that have in the compound (b) of epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group can be carried out under known condition.For example; Carboxylic polyurethane prepolymer (a), compound (b) [and " do not have the ethylenic unsaturated group and with epoxy radicals or oxa-cyclobutyl compound (o) " of using as required] and solvent with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group are joined in the flask; Under oxygen flow; Under 50～150 ℃, heat when stirring, obtain the polyurethane prepolymer (c) of hydroxyl thus.At this moment, the compound that preferably adds tertiary-amino-containings such as triethylamine or dimethyl benzyl amine in addition, adds the polymerization inhibitor of quinhydrones, methoxyl quinone ethylenic unsaturated groups such as (methoquinone) as catalyzer.As the addition of catalyzer, with respect to (a) and total amount (b), preferably add 0.1～10 weight %, as the addition of suppressant, preferably add 0.05～10 weight %.
Further, the invention is characterized in, when the carboxylic photonasty urethane resin of preparation (A), make the polyurethane prepolymer (c) and compound (d) reaction that contains anhydride group of hydroxyl.The compound of the compound that contains anhydride group (d) that uses among the present invention for having anhydride group through the hydroxyl reaction in the polyurethane prepolymer (c) that makes its anhydride group and hydroxyl, obtains the carboxyl photonasty urethane resin (A) that contains of the present invention.
Among the present invention; Make the polyurethane prepolymer (c) of hydroxyl be with the ratio that the compound (d) that contains anhydride group reacts; With respect to 1 mole of the hydroxyl in the polyurethane prepolymer (c) of above-mentioned hydroxyl, the anhydride group in the compound (d) that contains anhydride group is reacted with 0.1 mole～1.0 moles ratio.
With respect to 1 mole of the hydroxyl in the polyurethane prepolymer (c) of above-mentioned hydroxyl; When making ratio that the anhydride group in the compound (d) that contains anhydride group reacts less than 0.1 mole; The ratio that imports the excellent carboxyl of curable and development property reduces, and is difficult to obtain required development property.
The compound that contains anhydride group (d) that uses among the present invention is preferably that to have 1 or 2 acid anhydrides, carbon numbers in the molecule be 4～50 compound; For example can enumerate, anhydride phthalic acid, trimellitic anhydride, methyl tetrahydrochysene anhydride phthalic acid, methyl ENB dicarboxylic acid anhydride (acid of メ チ Le Ha ィ ミ ッ Network), six hydrogen anhydride phthalic acids, tetrahydrochysene anhydride phthalic acid, methyl pentahydro-anhydride phthalic acid, methyl three hydrogen anhydride phthalic acids, trialkyl tetrahydrochysene anhydride phthalic acid, methylcyclohexene dicarboxylic acid anhydride, HET acid acid anhydride, tetrabromophthalic anhydride etc. have the compound that contains anhydride group of alicyclic structure or aromatic ring structure.As other the compound that contains anhydride group (d), can enumerate succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl group succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, heptyl maleic anhydride, hexyl maleic anhydride, octyl group maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, butyl glutamic acid acid anhydride, hexyl glutamic acid acid anhydride, heptyl glutamic acid acid anhydride, octyl group glutamic acid acid anhydride, decyl glutamic acid acid anhydride, dodecyl glutamic acid acid anhydride etc.Among the present invention, the compound (d) that contains anhydride group can only use a kind of separately or and with multiple.
Wherein, patience is very excellent because development property, the pattern of the photosensitive polymer combination that obtains in the present invention become second nature and film for succinic anhydride, tetrahydrochysene anhydride phthalic acid etc., so preferred especially.
Reaction conditions when the hydroxyl in the polyurethane prepolymer (c) that makes hydroxyl is reacted with the anhydride group in the compound (d) that contains anhydride group does not limit especially, can under known condition, carry out.For example, the polyurethane prepolymer (c) of hydroxyl and the compound (d) and the solvent that contain anhydride group are joined in the flask, under Oxygen Flow, under 50～150 ℃, heat when stirring, obtain carboxylic photonasty urethane resin (A) thus.At this moment, the compound that preferably adds tertiary-amino-containings such as triethylamine or dimethyl benzyl amine at this moment, with respect to the polyurethane prepolymer (c) and the total amount that contains the compound (d) of anhydride group of hydroxyl, preferably adds 0.1～10 weight % as catalyzer.
The acid number of carboxylic photonasty urethane resin of the present invention (A) is preferably 10～200mgKOH/g, more preferably 30～150mgKOH/g.During less than 10mgKOH/g, might be difficult to development property fully at acid number, for example, when developing the desire dissolving remove the part of filming might residual filming as residue.In addition, when acid number surpassed 200mgKOH/g, the dissolubility of filming in developer solution improved, even carries out photocuring and desire also to dissolve as the residual part of pattern, and pattern form might variation.
The ethylenic unsaturated group equivalent of the carboxylic photonasty urethane resin of the present invention (A) is preferably 200～3000g/eq, more preferably 300～2000g/eq.Ethylenic unsaturated group equivalent is during less than 200g/eq, and light sensitivity might be too high, and the desire dissolving is removed the part of filming also by photocuring when developing, and might can not get good pattern form.When ethylenic unsaturated group equivalent surpassed 3000g/eq, light sensitivity might be low excessively, and the part of desiring photocuring is not fully solidified, and therefore pattern dissolved when developing might can not get good pattern form.
Alleged " equivalent of ethylenic unsaturated group " is the theoretical value that the raw-material weight that used when synthetic by resin is calculated among the present invention; It is the value that weight resin is obtained divided by the ethylenic unsaturated group quantity that exists in the resin; The weight resin that is equivalent to per 1 mole of ethylenic unsaturated group, the i.e. inverse of ethylenic unsaturated group concentration.
The weight-average molecular weight of carboxylic photonasty urethane resin of the present invention (A) is preferably 1000～100000, and more preferably 3000～60000.Weight-average molecular weight might can not get sufficient soldering thermotolerance and flexibility less than 1000 o'clock.In addition, weight-average molecular weight surpasses at 100000 o'clock, though the soldering excellent heat resistance, the possible variation of development property, in addition, viscosity during coating or operability might become problem.
Carboxylic photonasty urethane resin (A) pass through preparation method provided by the invention, comprising:
With the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and diisocyanate cpd (g) as must reacting the first step that obtains carboxylic polyurethane prepolymer (a) by composition,
Make the carboxylic polyurethane prepolymer (a) that obtains in the first step and compound (b) react second step of the polyurethane prepolymer (c) that obtains hydroxyl with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group, and
Make the polyurethane prepolymer (c) of the hydroxyl that obtains in second step and the third step of compound (d) reaction that contains anhydride group.
As the reaction conditions of first step, preferably heating under the temperature of room temperature～180 ℃, stir and react, also can use catalysts as required.As the reaction conditions of second step, preferably in the presence of oxygen, heating under 50～150 ℃ temperature, stirring are reacted, and also can use the polymerization inhibitor of catalysts and ethylenic unsaturated group as required.In addition, as the reaction conditions of third step, preferably with second step likewise; In the presence of oxygen; React 50～150 ℃ of heating down, stirrings, after second step finishes, also can newly append the polymerization inhibitor of suitable catalysts and ethylenic unsaturated group as required.
In addition; When in first step, preparing carboxylic polyurethane prepolymer (a); With the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and diisocyanate cpd (g) as must reacting by composition, but also can be further with as the compound (h) of the above-mentioned hydroxyl of composition arbitrarily, as the above-mentioned isocyanate compound (i) of composition arbitrarily, react as the above-mentioned amines (j) of composition arbitrarily.
In addition, the solvent that uses when synthesizing above-mentioned carboxylic photonasty urethane resin (A) can suitably be selected according to final use, dissolubility of reactants.For example, when final use is dry-film type photonasty solder resist, in the dry film manufacturing step,, preferably use lower boiling solvent owing to be necessary to make solvent rapid draing.As the low boiling point solvent of this moment, can enumerate methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol etc.In addition, when final use is liquid solder resist, in the printing ink preparation process; Because if consider filling material or pigment etc. with the mixing process of roller; Or, then be necessary to do one's utmost to suppress the volatilization of solvent, so preferably use high boiling solvent as the preservation stability of printing ink.As the high boiling solvent of this moment, can enumerate carbitol acetate ester, acetate methoxyl propyl ester, cyclohexanone, DIBK etc.
Among the present invention, these solvents can only use a kind of as required separately or also with multiple, in addition, can in course of reaction, carry out adding other novel solvent behind desolventizing or the desolventizing.
Photosensitive polymer combination of the present invention contains above-mentioned carboxylic photonasty urethane resin (A), Photoepolymerizationinitiater initiater (B) and photonasty ethylenically unsaturated compounds (C).
Photoepolymerizationinitiater initiater (B) is in order photosensitive compounds to be solidified and to add.As Photoepolymerizationinitiater initiater; So long as have the Photoepolymerizationinitiater initiater that can cause the function of vinyl polymerization through optical excitation; Then do not limit especially, for example can use mono-carbonylation compound, dicarbonyl compound, acetophenone compound, benzoin ether compound, oxidation acylphosphanes compound, aminocarboxyl compound etc.
Specifically, as the mono-carbonylation compound, can enumerate benzophenone, 4-methyl-benzophenone, 2,4; 6-tri-methyl benzophenone, methyl o-benzoyl yl benzoic acid ester, 4-phenyl benzophenone, 4-(4-aminomethyl phenyl sulfenyl) phenyl-toluene (ェ ネ タ ノ Application), 3, and 3 '-dimethyl-4-methoxy benzophenone, 4-(1,3-acryloyl group-1; 4,7,10; 13-five oxo tridecyls) benzophenone, 3,3 ', 4; 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 4-benzoyl-N, N, ammonium chloride, 2-hydroxyl-3-(4-benzoyl-phenoxy group)-N between the N-trimethylbenzene; N, N-trimethyl-1-propane amine hydrochlorate, 4-benzoyl-N, bromic acid ammonium, 2-/4-isopropyl thioxanthone, 2 between N-dimethyl-n-[2-(1-oxo-2-propenyloxy group ethyl)]; 4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones, 2-hydroxyl-3-(3,4-dimethyl-9-oxo-9H-thioxanthones-2-base oxygen base)-N; N, and N-trimethyl-1-propane amine hydrochlorate, benzoyl methylene-3-methyl naphtho-(1,2-d) thiazoline etc.
As dicarbonyl compound, can enumerate 1,7,7-trimethyl-two ring [2.1.1] heptane-2,3-diketone, benzil (ベ Application ザ ィ Le), 2-EAQ, 9,10-phenanthrenequione, methyl-alpha-oxo-phenylacetate, 4-phenyl benzil etc.
As acetophenone compound; Can enumerate 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl) 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl) 2-hydroxyl-two-2-methyl isophthalic acid-phenyl-propane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styryl propane-1-ketone polymer, diethoxy acetophenone, dibutoxy acetophenone, 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone, 2; 2-diethoxy-1; 2-diphenylethane-1-ketone, 2-methyl isophthalic acid-[4-(methyl sulfenyl) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino-phenyl) butane-1-ketone, 1-phenyl-1,2-propane diketone-2-(adjacent ethoxy carbonyl) oxime, 3,6-two (2-methyl-2-morpholino-acetonyl)-9-butyl carbazole etc.
As the benzoin ether compound, can enumerate benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether etc.
As oxidation acylphosphanes compound, can enumerate oxidation 2,4,6-trimethylbenzoyl diphenylphosphine, oxidation 4-n-pro-pyl phenyl-two (2,6-dichloro-benzoyl base) phosphine etc.
As aminocarboxyl compound; Can enumerate methyl-4-(dimethylamino) benzoic ether, ethyl-4-(dimethylamino) benzoic ether, 2-n-butoxy ethyl-4-(dimethylamino) benzoic ether, isopentyl-4-(dimethylamino) benzoic ether, 2-(dimethylamino) ethylamino benzonitrile acid esters, 4; 4 '-two-4-dimethylamino benzophenone, 4; 4 '-two-4-diethylamino benzophenone, 2,5 '-two-(4-diethylamino benzal) cyclopentanone etc.
Wherein, among the present invention, 2-methyl isophthalic acid-[4-(methyl sulfenyl) phenyl]-2-morpholino propane-1-ketone and thioxanthene ketone are made up when using, because cheapness and photonasty are very excellent, so preferred especially.
They are not limited to above-claimed cpd, as long as have the ability through the active energy beam initiated polymerization, then can be any compound.They can use separately or and usefulness, consumption is not limited especially, amount to 100 weight portions with respect to the dry weight of carboxylic photonasty urethane resin (A), preferably add 1～20 weight portion.In addition, also can add known organic amine as sensitizer.
The compound (C) that then photonasty of the present invention is contained the ethylenic unsaturated group describes.Compound (C) is the conventional photosensitive compounds that is engaged in usually in the photonasty resistance solder paste China ink etc., in structure, has the ethylenic unsaturated double-bond.Among the present invention, the photosensitive compounds in the regulation of being not included in the photosensitive compounds that can these are conventional above-mentioned " carboxylic urethane resin (A) " contains the compound (C) of ethylenic unsaturated group as photonasty.The compound (C) that contains the ethylenic unsaturated group as the photonasty that can use in the present invention; So long as have the ethylenic unsaturated double-bond in the structure and be not included in the compound in the regulation of above-mentioned " carboxylic urethane resin (A) "; Then do not limit especially; For example can enumerate, alkyls (methyl) acrylic ester, alkylene glycol class (methyl) acrylic ester, have carboxyl and ethylenic unsaturated group compound [but except the compound that comprises in the regulation of above-mentioned carboxylic urethane resin (A)], have (methyl) acrylate compounds of hydroxyl, nitrogenous (methyl) acrylate compounds etc.In addition, can use simple function, polyfunctional compound suitably.Consider from photo-curable, the aspect of being coated with property firmly of filming, be preferably polyfunctional compound.
Further enumerate following example particularly; As alkyls (methyl) acrylic ester; There are (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) 2-EHA, (methyl) acrylic acid heptyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid myristyl ester, (methyl) acrylic acid pentadecyl ester, (methyl) acrylic acid cetyl ester, (methyl) acrylic acid heptadecyl ester, (methyl) acrylic acid stearyl, (methyl) acrylic acid nonadecyl ester, (methyl) acrylic acid eicosyl ester, (methyl) acrylic acid heneicosyl ester, (methyl) acrylic acid docosyl ester etc. to have (methyl) alkyl acrylate that carbon number is 1～22 alkyl; In order to regulate polarity chron, (methyl) alkyl acrylate that preferably have carbon number and be 2～10, further preferred carbon number is 2～8 alkyl.
In addition; As alkylene glycol class (methyl) acrylic ester; Can enumerate for example diethylene glycol list (methyl) acrylic ester, triethylene glycol list (methyl) acrylic ester, TEG list (methyl) acrylic ester, six glycol monomethyls (methyl) acrylic ester, polyethyleneglycol (methyl) acrylic ester, DPG list (methyl) acrylic ester, tripropylene glycol list (methyl) acrylic ester, four propylene glycol list (methyl) acrylic ester, single (methyl) acrylic ester of polytetramethylene glycol etc.
End has hydroxyl and has the list of polyoxyalkylene chain (methyl) acrylic ester etc.,
Methoxyl monoethylene glycol (methyl) acrylic ester; Methoxyl diethylene glycol (methyl) acrylic ester; Methoxyl triethylene glycol (methyl) acrylic ester; Methoxyl TEG (methyl) acrylic ester; Ethoxy TEG (methyl) acrylic ester; Propoxyl group TEG (methyl) acrylic ester; N-butoxy TEG (methyl) acrylic ester; N-pentyloxy TEG (methyl) acrylic ester; Tripropylene glycol (methyl) acrylic ester; Four propylene glycol (methyl) acrylic ester; Methoxyl tripropylene glycol (methyl) acrylic ester; Methoxyl four propylene glycol (methyl) acrylic ester; Ethoxy four propylene glycol (methyl) acrylic ester; Propoxyl group four propylene glycol (methyl) acrylic ester; N-butoxy four propylene glycol (methyl) acrylic ester; N-pentyloxy four propylene glycol (methyl) acrylic ester; Polytetramethylene glycol (methyl) acrylic ester; Methoxyl polytetramethylene glycol (methyl) acrylic ester; Methoxy poly (ethylene glycol) (methyl) acrylic ester; Ethoxy polyglycol (methyl) acrylic ester; End has alkoxy and has the list of polyoxyalkylene chain (methyl) acrylic ester etc.
Ends such as phenoxy group diethylene glycol (methyl) acrylic ester, phenoxy group monoethylene glycol (methyl) acrylic ester, phenoxy group triethylene glycol (methyl) acrylic ester, phenoxy group TEG (methyl) acrylic ester, phenoxy group six monoethylene glycol (methyl) acrylic ester, phenoxy group polyglycol (methyl) acrylic ester, phenoxy group four propylene glycol (methyl) acrylic ester have polyoxyalkylene class (methyl) acrylic ester of phenoxy group or aryloxy group etc.
In addition; As the compound except the carboxylic urethane resin (A) with carboxyl and ethylenic unsaturated group; Can enumerate maleic acid, fumaric acid, itaconic acid, citraconic acid or their alkyl or alkenyl monoesters, phthalic acid β-(methyl) acryloxy ethyl monoesters, m-phthalic acid β-(methyl) acryloxy ethyl monoesters, terephthalic acid (TPA) β-(methyl) acryloxy ethyl monoesters, succinic acid β-(methyl) acryloxy ethyl monoesters, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid etc.
In addition; As compound, can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, glycerine list (methyl) acrylic ester, 4-hydroxyl vinyl benzene etc. with hydroxyl and ethylenic unsaturated group.
In addition; As compound with nitrogen-atoms and ethylenic unsaturated group; Can enumerate (methyl) acrylic amide, N-methylol (methyl) acrylic amide, N-methoxy-(methyl) acrylic amide, N-ethoxyl methyl-(methyl) acrylic amide, N-propoxyl group methyl-(methyl) acrylic amide, N-butoxymethyl-(methyl) acrylic amide, N-amoxy methyl-monohydroxyalkyl group (methyl) acrylic amides such as (methyl) acrylic amide; N; N-two (methylol) acrylic amide, N-methylol-N-methoxy (methyl) acrylic amide, N; N-two (methoxy) acrylic amide, N-ethoxyl methyl-N-methoxy Methacrylamide, N; N-two (ethoxyl methyl) acrylic amide, N-ethoxyl methyl-N-propoxyl group methyl acrylic amide, N; N-two (propoxyl group methyl) acrylic amide, N-butoxymethyl-N-(propoxyl group methyl) Methacrylamide, N; N-two (butoxymethyl) acrylic amide, N-butoxymethyl-N-(methoxy) Methacrylamide, N; Acrylic amide unsaturated compounds such as dihydroxyalkyl (methyl) acrylic amide such as N-two (amoxy methyl) acrylic amide, N-methoxy-N-(amoxy methyl) Methacrylamide, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid Methylethyl amino ethyl ester, dimethylamino styrene, diethylamino styrene etc. have the unsaturated compound of dialkyl amido, and have the Cl as gegenion -, Br -, I -Deng halogen ion or QSO 3-The quaternary ammonium salt of the unsaturated compound that contains dialkyl amido of (Q: carbon number is 1～12 alkyl).
Further; As other unsaturated compound; Can enumerate (methyl) acrylic acid perfluoro-methyl methyl esters; (methyl) acrylic acid perfluor ethyl methyl esters; (methyl) acrylic acid 2-perfluoro butyl ethyl ester; (methyl) acrylic acid 2-perfluoro hexyl ethyl ester; (methyl) acrylic acid 2-perfluoro capryl ethyl ester; The different nonyl ethyl ester of (methyl) acrylic acid 2-perfluor; (methyl) acrylic acid 2-perfluor nonyl ethyl ester; (methyl) acrylic acid 2-perfluor decyl ethyl ester; (methyl) acrylic acid perfluoro propyl propyl ester; (methyl) acrylic acid perfluoro capryl propyl ester; (methyl) acrylic acid perfluoro capryl pentyl ester; (methyl) acrylic acid perfluoro capryl undecyl ester etc. has (methyl) acrylic acid perfluoroalkyl alkyl esters that carbon number is 1～20 perfluoroalkyl
Perfluoroalkyls such as perfluorobutyl ethylene, perfluoro hexyl ethene, perfluoro capryl ethene, perfluor decyl ethylene, alkylene base class etc. contain the vinyl monomer class of perfluoroalkyl,
Vinyl trichlorosilane, vinyl three ('beta '-methoxy ethoxy) silane, VTES, γ-(methyl) acryloxy propyl trimethoxy silicane etc. contain the vinyl compound and the derivatives class thereof of alkoxysilyl,
(methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy cyclohexyl etc. contain (methyl) acrylic ester of glycidyl etc., can from these groups, suitably select a kind to use.
In addition,, can use vinyl acetate, vinyl butyrate, propionate, vinyl caproate, sad vinyl acetate, vinyl laurate, palmitic acid vinyl acetate, stearic acid vinyl ester etc. as the fatty acid vinyl ester compounds,
As the alkyl vinyl ether compound, can use butyl vinyl ether, ethyl vinyl ether etc.,
As the alpha-olefin compound, can use 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene etc.,
As vinyl compound; Can use allyl compounds such as allyl acetate, allyl alcohol, allyl benzene, cyaniding allyl; Vinyl cyanide, vinyl cyclohexane, ethenyl methyl ketone, styrene, AMS, 2-methyl styrene, chlorostyrene etc.
As acetylene compound, can use acetylene, acetylenylbenzene, ethinyl toluene, 1-ethinyl-1-cyclohexanol etc.
Then carry out bright specifically to polyfunctional compound with the ethylenic unsaturated group more than 2.
At first, have in the compound of ethylenic unsaturated group, can enumerate the aliphatic category compound.Specifically; Can enumerate 1; Ammediol two (methyl) acrylic ester, 1; 4-butylene glycol two (methyl) acrylic ester, 1; 6-hexanediol two (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, two (acryloxy neopentyl glycol) adipate, two (methacryloxy neopentyl glycol) adipate, chloropropylene oxide modification 1,6-hexanediol two (methyl) acrylic ester: Japanese chemical drug system KAYARADR-167, hydroxy new pentane acid neopentyl glycol two (methyl) acrylic ester, caprolactone modification hydroxy new pentane acid neopentyl glycol two (methyl) acrylic ester: alkyl type (methyl) acrylic ester, ethylene glycol bisthioglycolate (methyl) acrylic ester, diethylene glycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, TEG two (methyl) acrylic ester, polyglycol two (methyl) acrylic ester, chloropropylene oxide modification ethylene glycol bisthioglycolate (methyl) acrylic ester such as Japanese chemical drug system KAYARAD HX series: long rapids industry DenacolDA (M)-811, chloropropylene oxide modification diethylene glycol two (methyl) acrylic ester: long rapids industry DenacolDA (M)-851, propylene glycol two (methyl) acrylic ester, DPG two (methyl) acrylic ester, tripropylene glycol two (methyl) acrylic ester, four propylene glycol two (methyl) acrylic ester, polypropylene glycol two (methyl) acrylic ester, chloropropylene oxide modification propylene glycol two (methyl) acrylic ester: long rapids industry DenacolDA alkylene glycol type (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, two (trimethylolpropane) three (methyl) acrylic ester, neopentyl glycol modification trimethylolpropane two (methyl) acrylic ester such as (M)-911: Japanese chemical drug system KAYARAD R-604, oxirane modification trimethylolpropane tris (methyl) acrylic ester: SARTOMER SR-454, epoxy pronane modification trimethylolpropane tris (methyl) acrylic ester; Japan chemical drug system TPA-310, chloropropylene oxide modification trimethylolpropane tris (methyl) acrylic ester: grow rapids industry DA trimethylolpropane type (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, stearic acid modified pentaerythrite two (methyl) acrylic ester such as (M)-321: East Asia is synthesized ARONIX M-233, dipentaerythritol six (methyl) acrylic ester, dipentaerythritol monohydroxy five (methyl) acrylic ester, alkyl-modified dipentaerythritol and is gathered (methyl) esters of acrylic acid: Japanese chemical drug system KAYARAD D-310; 320; 330 grades, caprolactone modification dipentaerythritol gather (methyl) esters of acrylic acid: Japanese chemical drug system KAYARAD DPCA-20; 30; 60,120 type such as pentaerythrite such as grade (methyl) acrylic ester, glycerine two (methyl) acrylic ester, chloropropylene oxide modified glycerol three (methyl) acrylic ester: glycerol type (methyl) acrylic ester, two cyclopentyl two (methyl) acrylic ester, three cyclopentyl two (methyl) acrylic ester, cyclohexyl two (methyl) acrylic ester, methoxylation cyclohexyl two (methyl) acrylic ester such as long rapids industry Denacol DA (M)-314, triglycerin two (methyl) acrylic ester: ester ring type (methyl) acrylic ester such as adret state basic policy PLUPCAM-200, three (acryloxy ethyl) isocyanuric acid ester: isocyanuric acid ester type (methyl) acrylic ester such as ARONIX M-315, three (methacryloxyethyl) isocyanuric acid ester, caprolactone modification three (acryloxy ethyl) isocyanuric acid ester, caprolactone modification three (methacryloxyethyl) isocyanuric acid ester etc. are synthesized in East Asia.
In compound, can enumerate the aromatic species compound with ethylenic unsaturated group.For example can enumerate; Quinhydrones, resorcinol, catechol, 1,2,3,-thrihydroxy-benzene, bisphenol-A two (methyl) acrylic ester, [" oxirane (epoxypropane) " refers to " oxirane " or " epoxypropane " to oxirane (epoxypropane) modified bisphenol A two (methyl) acrylic ester; Below identical], Bisphenol F two (methyl) acrylic ester, oxirane (epoxypropane) modified bisphenol F two (methyl) acrylic ester, bisphenol S two (methyl) acrylic ester, oxirane (epoxypropane) modified bisphenol S two (methyl) acrylic ester, chloropropylene oxide modification phthalic acid two (methyl) acrylic ester etc. have (methyl) acrylate compounds of aryl, tetrachlorobisphenol S oxirane (epoxypropane) modification two (methyl) acrylic ester, tetrabromo-bisphenol s oxirane (epoxypropane) modification two (methyl) acrylic ester etc. has phenylethylene and (methyl) acrylate compounds of the substituted aryl of halogen atom with the atomic weight more than the chlorine atom etc.
Further, consider, can suitably multifunctional (methyl) esters of acrylic acids such as urethane (methyl) acrylic ester, epoxy radicals (methyl) acrylic ester, polyester (methyl) acrylic ester be used as compound (C) from coating strength, mar resistance aspect.Epoxy radicals (methyl) acrylic ester is through the epoxy radicals esterification of (methyl) acrylic acid with epoxy resin; And functional group's (methyl) acroleic acid esterification formed, (methyl) acrylic acid addition product of bisphenol A type epoxy resin, (methyl) acrylic acid addition product of phenolic resin varnish type epoxy resin etc. are arranged.Urethane (methyl) acrylic ester; Urethane (methyl) acrylic ester that diisocyanate is obtained with (methyl) esters of acrylic acid reaction with hydroxyl is for example arranged, make the reaction under the excessive condition of NCO of polyvalent alcohol and polyisocyanate obtain containing NCO polyurethane prepolymer, this polyurethane prepolymer that contains NCO and (methyl) esters of acrylic acid with hydroxyl are reacted and urethane (methyl) acrylic ester that obtains.Perhaps also can through make the reaction under the excessive condition of hydroxyl of polyvalent alcohol and polyisocyanate obtain hydroxyl polyurethane prepolymer, the polyurethane prepolymer of this hydroxyl is reacted with (methyl) esters of acrylic acid with NCO obtain.
As commercially available article, can enumerate following example.
Toagosei Co., Ltd's system: ARONIX M-400, ARONIX M-402, ARONIXM-310, ARONIX M-408, ARONIX M-450, ARONIX M-7100, ARONIXM-8030, ARONIX M-8060,
Osaka Organic Chemical Industry Co., Ltd.'s system: VISCOAT#400,
Chemical drug SARTOMER Co., Ltd. system: SR-295,
DAICEL UCB Co., Ltd. system: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,
Xin Zhong village chemical industry Co., Ltd. system: NK Ester A-TMMT, NK O1igoEA-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6, NK Oligo U-4HA, NK Oligo U-6HA, NK Oligo U-324A
BASF society system: Laromer EA81,
Sannopco Co., Ltd. system: Photomer 3016,
Arakawa Chemical Industries, Ltd.'s system: BEAMSET 371, BEAMSET 575, BEAMSET 577, BEAMSET 700, BEAMSET 710,
Root is attend Industrial Co., Ltd's system: Artregin UN-3320HA, Artregin UN-3320HB, Artregin UN-3320HC, Artregin UN-3320HS, Artregin UN-9000H, ArtreginUN-901T, Artregin HDP, Artregin HDP-3, Artregin H61
The Nippon Synthetic Chemical Industry Co., Ltd's system: purple light UV-7600B, purple light UV-7610B, purple light UV-7620EA, purple light UV-7630B, purple light UV-1400B, purple light UV-1700B, purple light UV-6300B,
Kyoeisha Chemical Co., Ltd.'s system: LIGHT-ACRYLATE PE-4A, LIGHT-ACRYLATE DPE-6A, UA-306H, UA-306T, UA-306I,
Nippon Kayaku K. K's system: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330, SR-35 etc.
As stated; The compound (C) that photonasty contains the ethylenic unsaturated group is engaged in the photonasty resistance solder paste China ink etc. usually; For example known carboxylic compound improves the development property or the Thermocurable of composition, and the adhesiveness of the compound of hydroxyl raising composition and base material or development property etc.Therefore; Among the present invention; Contain the compound (C) of ethylenic unsaturated group as photonasty, carboxylic compound [except the compound that still, comprises in the regulation of above-mentioned carboxylic urethane resin (A)] is preferred for improving in the situation of development property or Thermocurable of composition; In addition, the compound of hydroxyl is preferred for improving in the situation of adhesiveness or development property of composition and base material.In addition, the polyfunctional compound with 2 above ethylenic unsaturated groups can be used for improving the light sensitivity of composition or the situation of distinguishing, and the aromatic species unsaturated compound is preferred for improving thermotolerance, the control refractive index of filming.Further, oligomeric (methyl) such as urethane (methyl) acrylic ester, epoxy radicals (methyl) acrylic ester acrylic ester is preferred for improving the intensity or the scratch property aspect of filming.
In addition; When containing oxirane addition structure in the molecule or dibasic alcohol modification (methyl) acrylic ester (for example, Toagosei Co., Ltd system ARONIX M-310, the system SR-355 of Nippon Kayaku K. K etc.) because water wettability is high, and viscosity is low; In the present invention; Through using these compounds, can obtain the very excellent photosensitive polymer combination of development property, distinguishing, so preferred especially.
Above-mentioned photonasty contains the consumption of the compound (C) of ethylenic unsaturated group, with respect to carboxylic photonasty urethane resin (A) 100 weight portions, is preferably 0.1～300 weight portion, and more preferably 0.5～200 weight portion further is preferably 5～100 weight portions.The compound (C) that photonasty contains the ethylenic unsaturated group uses for photonasty or the distinguishing of adjusting photosensitive polymer combination.During less than 0.1 weight portion, the photonasty of photosensitive polymer combination might be insufficient, if surpass 300 weight portions, then bendability might have problems.
Photosensitive polymer combination of the present invention is except above-mentioned carboxylic photonasty urethane resin (A), Photoepolymerizationinitiater initiater (B), above-mentioned photonasty ethylenically unsaturated compounds (C); Preferably further contain Thermocurable compound (D), further preferably contain Thermocurable compound (D) and heat curing auxiliary agent (E).
(D) describes to the Thermocurable compound.Thermocurable compound (D) if having more than 2 can with the functional group of contained functional group reactions in the carboxylic photonasty urethane resin (A), then do not limit especially.Among the present invention, as with the functional group of Thermocurable compound (D) reaction, be preferably hydroxyl and carboxyl in the carboxylic photonasty urethane resin (A).
As have at least 2 can with the Thermocurable compound (D) of the functional group of hydroxyl reaction, can enumerate polyisocyanate compounds, amino resins, phenol resin, polyfunctional poly carboxylic acid anhydrides.
Polyisocyanate compounds gets final product qualification especially so long as have the compound of a plurality of NCOs in the molecule.As the example of polyisocyanate compounds, can enumerate the addition product etc. of biuret compounds or isocyanurate compound and these polyisocyanate compounds and known polyether glycol or polyester polyol, acrylic polyol, polybutadiene polyol, the polyisoprene polyvalent alcohol etc. of addition product, these polyisocyanate compounds of polyisocyanate compounds such as benzal diisocyanate, hexamethylene diisocyanate, IPDI, xylylene diisocyanate, hydrogenation of benzene dimethyl diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, tetramethylbenzene dimethyl diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate and polyol compounds such as these polyisocyanate compounds and trimethylolpropane.
As amino resins, phenol resin, additive compound or its that can enumerate compound such as urea, melamine, benzoguanamine, phenol, cresols class, bisphenols and formaldehyde be condensation product partly.
The polyfunctional poly carboxylic acid anhydrides can be enumerated polybasic acid anhydride classes such as tetracarboxylic dianhydride, hexacarboxylic acid three acid anhydrides, hexacarboxylic acid dianhydride, maleic anhydride copolymer resins etc. as long as for having 2 above acid anhydrides' compound, just do not limit especially.In addition, the poly carboxylic acid, polycarboxylate, poly carboxylic acid half ester etc. that can be in reaction form acid anhydride through dehydration are also contained among the present invention's alleged " compound with 2 above acid anhydrides ".
Further following for example concrete; As the tetracarboxylic dianhydride; Can enumerate pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, hydroxyl (oxy) two phthalic acid dianhydrides, diphenyl sulfone tetracarboxylic dianhydride, diphenylsulfide tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride, perylenetetracarboxylic dianhydride, naphthalene tetracarboxylic acid dianhydride, New Japan Chem Co., Ltd's system " RIKACID TMTA-C ", " RIKACID MTA-10 ", " RIKACID MTA-15 ", " RIKACID TMEG series ", " RIKACID TDA " etc.
As the maleic anhydride copolymer resins; Nippon Paper Chemicals Co., Ltd.'s system), maleic anhydride co-polypropylene acid resin etc. can enumerate the abundant SHELLAC of fork of SARTOMER corporate system SMA resin series, Co., Ltd. and make phenylethylene-maleic anhydride copolymer resinses such as made GSM series, alpha-olefins such as styryl phenyl-maleic anhydride copolymer resins, polyvinyl-maleic anhydride-maleic anhydride copolymer resins, DAICEL chemical industry Co., Ltd. system " VEMA " (multipolymer of methyl vinyl ether and maleic anhydride), the acrylic acid modified polyolefin of maleic anhydride (" AUROREN is serial ":.
As have at least 2 can with the heat curing composition (D) of the functional group of carboxyl reaction; Can enumerate, have compound (k), polyfunctional vinyl ether compound, high-molecular-weight poly carbodiimide class, aziridine cpd of epoxy radicals or oxa-cyclobutyl more than 2 etc.Wherein, the compound (k) that has epoxy radicals or an oxa-cyclobutyl more than 2 aspect the permanance of curing rate and solidfied material very preferably.
Have the compound (k) of epoxy radicals or oxa-cyclobutyl more than 2 so long as the epoxy radicals or the compound of oxa-cyclobutyl that in molecule, have more than 2 get final product, do not limit especially.As compound (k); As compound with epoxy radicals; Specifically; For example can enumerate; Ethylene glycol bisthioglycolate glycidyl ether, polyglycol diglycidyl ether, 1; The poly epihydric alcohol base ether of disclosed dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, monoethylene glycol-chloropropylene oxide addition product, pentaerythrite poly epihydric alcohol base ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, quinhydrones diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane poly epihydric alcohol base ether, hexahydrobenzene dioctyl phthalate diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether, N in the poly epihydric alcohol base ether of 6-hexanediol diglycidyl ether, bisphenol-A-chloropropylene oxide type epoxy resin, Bisphenol F-chloropropylene oxide type epoxy resin, xenol-chloropropylene oxide type epoxy resin, glycerine-chloropropylene oxide addition product, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, the TOHKEMY 2001-240654 communique; N; N '; N '-four glycidyl group m-xylene diamine, 1; 3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N-diglycidylaniline, N; The excellent epoxy compound of disclosed flexibility in N-diglycidyl toluidine, TOHKEMY 2004-156024 communique, TOHKEMY 2004-315595 communique, the TOHKEMY 2004-323777 communique, or the epoxy compound of structure shown in following formula (1)～(3) etc.
(formula 1)
Figure G2007800409539D00271
(formula 2)
Figure G2007800409539D00272
(formula 3)
Figure G2007800409539D00281
In addition; As compound (k); As compound, specifically, for example can enumerate with oxa-cyclobutyl; The carboxylate of etherate, (2-ethyl-2-oxa-cyclobutyl) ethanol and the polybasic carboxylic acid compound of carboxylate, (2-ethyl-2-oxa-cyclobutyl) ethanol and the phenol novolac resin of 4,4 '-two [(3-ethyl-3-oxa-cyclobutyl) methoxy] biphenyl, (2-ethyl-2-oxa-cyclobutyl) ethanol and terephthalic acid (TPA) etc.
Epoxy compound as the epoxy compound of compound (k), particularly aliphatic category or TOHKEMY 2004-156024 communique, TOHKEMY 2004-315595 communique, the record of TOHKEMY 2004-323777 communique is preferred because the flexibility of cured coating film is excellent.In addition; Dicyclopentadiene-type epoxy compound of putting down in writing in the TOHKEMY 2001-240654 communique or phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, biphenyl-chloropropylene oxide type epoxy resin, 4; The carboxylates of 4 '-two [(3-ethyl-3-oxa-cyclobutyl) methoxy] biphenyl, (2-ethyl-2-oxa-cyclobutyl) ethanol and terephthalic acid (TPA) etc. in the present invention; Be excellent aspect the cured coating film permanance of representative at Thermocurable with hydroscopicity or thermotolerance, so preferred.
Concrete example as the polyfunctional vinyl ether compound; Can enumerate ethylene glycol bisthioglycolate vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, TEG divinyl ether, pentaerythrite divinyl ether, propylene glycol divinyl ether, DPG divinyl ether, tripropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1; 4-butylene glycol divinyl ether, 1; 6-hexanediol divinyl ether, glycerine divinyl ether, trimethylolpropane divinyl ether, 1; 4-dihydroxy cyclohexane divinyl ether, 1,4-dihydroxy methylcyclohexane divinyl ether, quinhydrones divinyl ether, oxirane modification quinhydrones divinyl ether, oxirane modification resorcinol divinyl ether, oxirane modified bisphenol A divinyl ether, oxirane modified bisphenol S divinyl ether, glycerine trivinyl ether, sorbierite tetrem alkene ether, trimethylolpropane tris vinyl ether, pentaerythrite trivinyl ether, pentaerythrite tetrem alkene ether, dipentaerythritol six vinyl ether, dipentaerythritol polyvingl ether, two (trimethylolpropane) tetrem alkene ether, two (trimethylolpropane) polyvingl ether etc.
As high-molecular-weight poly carbodiimide class, can enumerate the Carbodilite series of Misshin Spinning Co., Ltd.Wherein, the compatibility of Carbodilite V-01, V-03, V-05, V-07, V-09 and organic solvent is excellent, so preferred.
As aziridine cpd, for example can enumerate, 2,2 '-dihydroxy methyl butanol three [3-(1-'-aziridino) propionic ester], 4,4 '-two (ethylidene imino group carbonylamino) diphenyl methane etc.
As other Thermocurable compound (D); So long as the compounds through being heating and curing such as benzoxazine compound, benzocyclobutene compound, maleimide compound, Na Dike acid imide (Na ジ ィ ミ De) compound, allyl Na Dike imide compound, melamine compound, guanamines compound, block isocyanate compound can use effectively.These have the optical polymerism group, can with the functional group of carboxyl reaction, can with the compound of the functional group of hydroxyl reaction owing to can improve the thermotolerance of filming after the curing especially, can more effectively use.
These Thermocurable compounds (D) can only use a kind of or and with two or more.The consumption of Thermocurable compound (D) can determine on the basis of the purposes of considering photosensitive polymer combination etc.; Do not limit especially; But with respect to carboxylic photonasty urethane resin (A) 100 weight portions; More preferably 0.1 weight portion～100 weight portions further are preferably 0.5 weight portion～80 weight portions.Thus, owing to can the cross-linking density of photosensitive polymer combination be adjusted to suitable value, can further improve the various rerum naturas of photosensitive polymer combination.If the consumption of Thermocurable compound (D) is less than 0.1 weight portion, the cross-linking density of filming after then being heating and curing is low excessively, and cohesiveness or permanance might be insufficient.In addition, if this consumption surpasses 100 weight portions, the cross-linking density after then being heating and curing is too high, the bendability that the result films, the flexible reduction, and the warpage of substrate is variation significantly.
Then heat curing auxiliary agent (E) is described.When alleged heat curing auxiliary agent is illustrated in heat curing among the present invention directly or catalytic ground help the compound of curing reaction.
Heat curing auxiliary agent (E) is suitably selected according to the Thermocurable compound (D) that uses.In addition, carboxylic photonasty urethane resin (A) can suitably be selected according to Thermocurable compound (D) that uses or heat curing auxiliary agent (E) with the condition of cure of Thermocurable compound (D).
As heat curing auxiliary agent (E), can enumerate for example triethylamine, tri-butylamine, benzyl dimethyl amine, 2,4, tertiary amines and its esters such as 6-three (dimethylaminomethyl) phenol, N methyl piperazine,
Glyoxal ethyline, 2-phenylimidazole, 2-undecyl imidazole, 2-ethyl-4-methylimidazole, 1-cyano ethyl-glyoxal ethyline, 2,4-dicyano-6-[glyoxal ethyline base-1]-ethyl-imidazoles and its esters such as S-triazine,
1,5-diazabicylo [5,4,0]-7-undecane, 1,5-diazabicylo [4,3,0]-5-nonene, 1, diazabicylo compounds such as 4-diazabicylo [2,2,2] octane,
Phosphine classes such as tributylphosphine, triphenylphosphine, three (Dimethoxyphenyl) phosphine, three (hydroxypropyl) phosphine, three (cyano ethyl) phosphine,
Phosphonium salt classes such as tetraphenylphosphoniphenolate tetraphenyl borate salts, methyl San Ding Ji Phosphonium tetraphenyl borate salts, methyl tricyano Yi Ji Phosphonium tetraphenyl borate salts,
In addition, directly help the compound of curing reaction, can enumerate dicyandiamide, carboxylic acid hydrazides etc. as catalytic and itself.As carboxylic acid hydrazides, can enumerate succinic acid hydrazides, hexane diacid hydrazides etc.
Among the present invention, when using epoxy compound, as heat curing auxiliary agent (E) as Thermocurable compound (D); If use dicyandiamide, carboxylic acid hydrazides, imidazoles, diazabicylo compounds; Then owing to more effectively carry out the heat curing reaction, the patience of filming is excellent, so preferred.
In addition, among the present invention, the consumption of heat curing auxiliary agent (E) with respect to carboxylic photonasty urethane resin (A) 100 weight portions, is preferably 0.1～10 weight portion, further is preferably 0.5～8 weight portion.If consumption then can not be brought into play the effect of sufficient as the heat curing auxiliary agent less than 0.1 weight portion, cohesiveness of finally filming or permanance might be insufficient.In addition, this consumption remains in the system more than the then remaining heat curing auxiliary agent of 10 weight portions, exists to ooze out or the situation of the various rerum natura variation of filming such as insulativity variation.
Photosensitive polymer combination of the present invention can contain compound (C) resin in addition that above-mentioned carboxylic photonasty urethane resin (A) or photonasty contain the ethylenic unsaturated group as required.Contain compound (C) resin in addition of ethylenic unsaturated group as carboxylic photonasty urethane resin (A) or photonasty, can enumerate acrylic resin, vibrin, urethane resin, urea resin, polyurethane urea resin, epoxy resin, polyamide, polyimide resin etc.They consider from development property aspect preferably to contain carboxyl, in addition, preferably contain the compatibility excellence of the compound (C) of ethylenic unsaturated group with carboxylic photonasty urethane resin (A) or photonasty.Among the present invention, when containing in addition resin of compound (C) that carboxylic photonasty urethane resin (A) or photonasty contains the ethylenic unsaturated group, can separately or and use with multiple.
In addition; In photosensitive polymer combination of the present invention; In the scope of not damaging purpose, can further add solvent as any composition, dyestuff, pigment, fire retardant, anti-oxidant, polymerization inhibitor, levelling agent, NMF, viscosity modifier, antiseptic, antiseptic, antistatic agent, antiblocking agent, ultraviolet light absorber, infrared absorbent, electromagnetic wave shielding agent, filling agent etc.When particularly in the electronic material purposes, being used in the parts (printed wiring board bonding agent, supporting substrate etc.) that possibly form high heat of the direct-connected insulating element of circuit (for example circuit protection film, overlayer, interlayer dielectic etc.) or circuit periphery, preferably and use fire retardant.
As fire retardant; Can enumerate for example phosphoric acid salt compound or Quadrafos compounds such as melamine phosphate, polyphosphoric acid melamine, phosphoguanidine, polyphosphoric acid guanidine, ammonium phosphate, APP, phosphoamide ammonium, polyphosphoric acid acid amides ammonium, phosphorylated amino formic ether, polyphosphoric acid carbamate; Phosphorus type flame retardants such as red phosphorus, organophosphorus compounds, phosphonitrile (ホ ス Off ァ ゼ Application) compound, phosphinic acid compounds, phosphinic compounds, phosphine oxide compound, positive phosphine compound, phosphamide compound; Compound in triazine class such as melamine, melam, melem, mellon, melamine cyanurate; Nitrogen based flame retardants such as cyanogen urea acid compound, isocyanuric acid compound, triazole class compounds, tetrazole compound, diazo-compounds, urea; Silicon such as silicone compounds or silane compound based flame retardant; Halogen based flame retardants such as low molecule halide-containing such as halogenation bisphenol-A, halogenation epoxy compound, benzene halide oxo-compound, halogenation oligomer or polymkeric substance; Metal hydroxides such as hydrate of aluminium, magnesium hydroxide, zirconium hydroxide, baryta hydrate, calcium hydroxide, mineral-type fire retardants such as tin oxide, aluminium oxide, magnesium oxide, zirconia, zinc paste, molybdena, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, lime carbonate, barium carbonate, Firebrake ZB, hydrated glass etc.Among the present invention; If consider the influence of talking about in recent years to environment; Then preferably use non-halogen based flame retardants such as phosphorus type flame retardant or nitrogen based flame retardant; Wherein, preferred use through with photosensitive polymer combination of the present invention and usefulness, aspect anti-flammability, have more resultful phosphazene compound, phosphine compound, polyphosphoric acid melamine, APP, melamine cyanurate etc.Among the present invention, these fire retardants can separately or and use with multiple.
Photosensitive polymer combination of the present invention and solidfied material thereof can be suitable for comprising that filming that photocuring, alkali develop, solidify the back forms in the purposes of step owing to have the excellent characteristic of alkali-developable.Further, because soldering thermotolerance, the patience of filming are excellent and flexible simultaneously, bendability is also excellent, particularly can be suitable for flexible printed circuit board with in resistance solder paste China ink or the photonasty coverlay purposes.
Photosensitive polymer combination of the present invention can be coated on metal as base material, pottery, glass, plastics, timber, the slabstone etc., does not limit especially.Specifically, as the kind of plastics, can enumerate polyester, polyolefin, polycarbonate, polystyrene, polymethylmethacrylate, tri acetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin etc.In addition,, can enumerate diaphragm, plate-like panel, lens shape, disc-shape, fibrous material, not limit especially as the base material shape.
Photosensitive polymer combination of the present invention can solidify to form solidfied material through known radiation-curing method; As active energy beam; Can use the visible light of electron ray, ultraviolet ray, 400～500nm, the radiographic source of the electron ray of irradiation can use thermionic emission rifle, field emission rifle etc.In addition, the radiographic source (light source) of the visible light of ultraviolet ray and 400～500nm for example can use high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, gallium lamp, xenon lamp, carbon arc lamp etc.Specifically, from being that pointolite, brightness constancy aspect are considered, use ultrahigh pressure mercury lamp, xenon-mercury lamp, metal halide lamp mostly.The active energy beam amount of irradiation can suitably be set in 5～2000mJ/cm 2Scope in, but be preferably manageable 50～1000mJ/cm on the engineering 2Scope.In addition, these active energy beams can and be used with the heat that realizes through infrared ray, far infrared, hot blast, high-frequency heating.
Photosensitive polymer combination of the present invention is during as photic solder resist, can be to be dissolved in the liquid etching resisting ink that forms in the solvent or to make solvent seasoning in advance and the form of the dry-film type resist that obtains is used.
During as liquid etching resisting ink; After photosensitive polymer combination of the present invention can be coated on the base material; Make solvent evaporates through nature or force drying, carry out radiation curing then, also can be after coating radiation curing; Carry out nature or force drying then, but preferably carry out carrying out radiation curing after nature or the force drying.In addition, during for liquid etching resisting ink, do not accomplish during before the coating on the base material preserving step, application step etc.; In operation; The preferred volatilization that does not produce solvent is so the diluting solvent when solvent that uses when synthetic as resin or preparation printing ink is preferably high boiling solvent.Especially preferably use carbitol acetate ester, methoxy propyl yl acetate, cyclohexanone, DIBK etc.In addition, under the situation of liquid etching resisting ink, exist and to consider storage stability or operability, preserve hardening agent in advance in addition, the 2 liquid types that use of mixed curing agent as required before coating.The present invention also can separate preservation etc. with these compositions composition in addition with Photoepolymerizationinitiater initiater (B), Thermocurable compound (D), heat curing auxiliary agent (E) as required, uses with the form of 2 liquid types.
On the other hand, during as the dry-film type resist, at first on release property good film base materials such as diffusion barrier, after coating is dissolved in the photosensitive composite in the solvent, make solvent seasoning, make the dry-film type resist thus.At this moment, as the solvent that uses, since different with above-mentioned liquid etching resisting ink, be necessary to make solvent seasoning at short notice fully, so be preferably low boiling point solvent.Especially preferably use methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol etc.For the dry film of on diffusion barrier, making, fit be formed on copper circuit on the polyimide etc. after, carry out lamination or vacuum lamination, carry out thus bubble etc. remove and with the driving fit of circuit.After this applying step, there is the situation of carrying out radiation curing through diffusion barrier, or contacts the situation that developing pattern carries out radiation curing behind the peel separation film.When the contact developing pattern carries out radiation curing,, therefore,, require the stickability of dry coating few as the dry-film type resist if, then might pollute developing pattern because dry film has stickability.Photosensitive polymer combination of the present invention can serviceably be used as the dry-film type resist owing to can reduce stickability as required.
Further, photosensitive polymer combination of the present invention is after carrying out radiation curing, and the formation pattern that develops carries out heat curing and solidifies as the back, forms excellent the filming of patience thus.Back cured was preferably carried out under 100 ℃～200 ℃ 30 minutes～2 hours.In addition, in order further to improve the patience of filming, can, the back shine active energy beam as required after solidifying.Through solidify back irradiation active energy beam in the back, can further improve soldering thermotolerance etc.
Embodiment
Below through embodiment the present invention is explained more specifically, but below embodiment interest field of the present invention is not carried out any qualification.And, " part " expression " weight portion " among the embodiment.
The condition determination of GPC is described below.
< mensuration of weight-average molecular weight (Mw) >
The mensuration of Mw is used the eastern ソ system GPC (gel permeation chromatography) " HPC-8020 " of one Co., Ltd..GPC is that (THF: the material tetrahydrofuran) carries out the liquid chromatography of separation and quantitative according to the difference of its molecular dimension with being dissolved in solvent.In the mensuration among the present invention; Chromatographic column is that (Showa Denko K. K's system: the GPC chromatographic column is used in express-analysis: 6mmID * 150mm size) 2 of series connection are used with " LF-604 "; Under the condition of 40 ℃ of flow 0.6ml/min, chromatogram column temperature, carry out, the decision of weight-average molecular weight (Mw) is carried out through polystyrene conversion.
[preparation example 1]
In four neck flasks, add 156 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 129 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 13000, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 98mgKOH/g.
Then; Stop in this flask, to import nitrogen from nitrogen ingress pipe; Switch to the importing dry air; Drop into 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 14800, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 8mgKOH/g.
Then in this flask, drop into 63 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.Then, in this solution, add cyclohexanone, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 863g/eq, polystyrene conversion is 15400, the acid number of the actual resin solid composition that records is 73mgKOH/g.
[preparation example 2]
In four neck flasks, add 4 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 201 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 296 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 8900, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 152mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Drop into 193 parts of methyl propenoic acid glycidyl base esters, 7 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.4 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 9600, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 1mgKOH/g.
Then in this flask, drop into 136 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 611g/eq, polystyrene conversion is 11020, the acid number of the actual resin solid composition that records is 92mgKOH/g.
[preparation example 3]
In four neck flasks, add 318 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 46 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, add 136 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 19800, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 35mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Drop into 44 parts of methyl propenoic acid glycidyl base esters, 5 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 22000, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 3mgKOH/g.
Then in this flask, drop into 31 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 1846g/eq, polystyrene conversion is 23100, the acid number of the actual resin solid composition that records is 30mgKOH/g.
[preparation example 4]
In four neck flasks, add 140 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 115 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 244 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 48900, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 87mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Drop into 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 52200, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 5mgKOH/g.
Then in this flask, drop into 78 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.Then, in this solution, add cyclohexanone, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 884g/eq, polystyrene conversion is 54000, the acid number of the actual resin solid composition that records is 68mgKOH/g.
[preparation example 5]
In four neck flasks, add 164 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 135 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 202 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 3900, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 102mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add 103 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 4600, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 17mgKOH/g.
Then in this flask, drop into 65 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 920g/eq, polystyrene conversion is 5100, the acid number of the actual resin solid composition that records is 71mgKOH/g.
[preparation example 6]
In four neck flasks, add 156 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 129 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 13000, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 98mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Drop into when stirring 4-hydroxybutyl acrylic ester glycidyl ether (Nippon Kasei Chemical Company's system: 4-HBAGE) 156 parts, 7 parts of dimethyl benzyl amines and as 0.3 part of the quinhydrones of polymerization inhibitor, under 90 ℃ state, reacted 8 hours.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 16500, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 9mgKOH/g.
Then in this flask, drop into 70 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.Then, in this solution, add cyclohexanone, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 931g/eq, polystyrene conversion is 18800, the acid number of the actual resin solid composition that records is 65mgKOH/g.
[preparation example 7]
In four neck flasks, add polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g) 156 parts, 129 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system), as 375 parts of the cyclohexanone of solvent with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 13000, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 98mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 14800, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 8mgKOH/g.
Then in this flask, drop into tetrahydrochysene anhydride phthalic acid (New Japan Chem Co., Ltd's system: RIKACID TH) 107 parts, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 920g/eq, polystyrene conversion is 16500, the acid number of the actual resin solid composition that records is 62mgKOH/g.
[preparation example 8]
In four neck flasks, add 156 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 129 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 13000, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 98mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add when stirring 55 parts of methyl propenoic acid glycidyl base esters, 4-hydroxybutyl acrylic ester glycidyl ether (Nippon Kasei Chemical Company's system: 4-HBAGE) 78 parts, 7 parts of dimethyl benzyl amines and as 0.3 part of the quinhydrones of polymerization inhibitor, under 90 ℃ state, reacted 8 hours.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 16900, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 7mgKOH/g.
Then in this flask, drop into 72 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 885g/eq, polystyrene conversion is 17300, the acid number of the actual resin solid composition that records is 68mgKOH/g.
[preparation example 9]
In four neck flasks, add 156 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 129 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 13000, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 98mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 14800, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 8mgKOH/g.
Then in this flask, add the tetrahydrochysene anhydride phthalic acid (New Japan Chem Co., Ltd's system: RIKACID TH) 53 parts with 35 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 840g/eq, polystyrene conversion is 17100, the acid number of the actual resin solid composition that records is 72mgKOH/g.
[preparation example 10]
In four neck flasks, add 156 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 128 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then, in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 14100, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 97mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add 133 parts of methacrylic acid oxa-cyclobutyl esters, 6 parts of dimethyl benzyl amines when stirring and as 0.3 part of the quinhydrones of polymerization inhibitor, 95 ℃ of reactions 16 hours down.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 15100, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 7mgKOH/g.
Then in this flask, drop into 70 parts of succinic anhydrides, in the dry air atmosphere, reaction is 6 hours when under 90 ℃, stirring.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 901g/eq, polystyrene conversion is 16300, the acid number of the actual resin solid composition that records is 69mgKOH/g.
[preparation example 11]
In four neck flasks, add PCDL (Kuraray Polyol C-1090: the Kuraray of Co., Ltd. system: hydroxyl value=112mgKOH/g, Mw=1002) 156 parts, 129 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system), as 375 parts of the cyclohexanone of solvent with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 23100, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 100mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 24600, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 7mgKOH/g.
Then in this flask, drop into 63 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 870g/eq, polystyrene conversion is 25500, the acid number of the actual resin solid composition that records is 70mgKOH/g.
[preparation example 12]
In four neck flasks, add 156 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 129 parts of dihydromethyl propionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into 215 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 18700, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 102mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 20200, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 6mgKOH/g.
Then in this flask, drop into 63 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 851g/eq, polystyrene conversion is 22600, the acid number of the actual resin solid composition that records is 74mgKOH/g.
[preparation example 13]
In four neck flasks, add 156 parts of polytetramethylene glycol (PTG1000sn: protect native ケ paddy KCC system: hydroxyl value=110mgKOH/g, Mw=1020), 129 parts of dimethylolpropionic acids (Nippon Kasei Chemical Company's system) with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, as 375 parts of the cyclohexanone of solvent; Under stream of nitrogen gas; Be warming up to 60 ℃ when stirring, make its uniform dissolution.Then in this flask, drop into m-xylene group diisocyanate (Mitsui Chemicals Polyurethane Co., Ltd. system) 215 parts, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 24500, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 99mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Drop into 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 26300, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 11mgKOH/g.
Then in this flask, drop into 63 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the carboxylic photonasty urethane resin through this preparation example preparation is that the weight-average molecular weight of 858g/eq, polystyrene conversion is 27400, the acid number of the actual resin solid composition that records is 67mgKOH/g.
The rerum natura of the carboxylic photonasty urethane resin that obtains in the preparation example 1～13 is as shown in table 1.
Figure G2007800409539D00431
1) PTG1000sn... protects native ケ paddy KCC system: polytetramethylene glycol
2) DMBA... Nippon Kasei Chemical Company system: dimethylolpropionic acid
3) IPDI... IPDI
4) GMA... methyl propenoic acid glycidyl base ester
5) SA... succinic anhydride
6) 4HBAGE...4-hydroxybutyl acrylic ester glycidyl ether
7) TH... tetrahydrochysene anhydride phthalic acid
8) OXMA... methacrylic acid oxa-cyclobutyl ester
9) Kuraray of C-1090... Co., Ltd. system: PCDL
10) DMPA... Nippon Kasei Chemical Company system: dihydromethyl propionic acid
11) XDI... Mitsui Chemicals Polyurethane Co., Ltd. system: m-xylene group diisocyanate
[preparation example 14]
In four neck flasks, drop into epoxide equivalent and be 650 with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, softening point is that 81.1 ℃, melt viscosity (150 ℃) are 925 parts of 371 parts of bisphenol A type epoxy resins, chloropropylene oxides, 463 parts of the dimethyl sulfoxide (DMSO)s of 12.5 pools; After making its uniform dissolution, under agitation added 52.8 parts of 98.5% sodium hydrate aqueous solutions down at 70 ℃ with 100 minutes.After the interpolation, further reacted 3 hours down at 70 ℃.Then; More than half part that excessive unreacted chloropropylene oxide and dimethyl sulfoxide (DMSO) are removed in distillation under reduced pressure; The reaction product that will contain by-product salt and dimethyl sulfoxide (DMSO) is dissolved in 750 parts of the methyl isobutyl ketones, further adds 10 parts of 30% sodium hydrate aqueous solutions, 70 ℃ of reactions 1 hour down.After reaction finished, water carried out 2 washings for 200 parts.After the oil and water separation, reclaim methyl isobutyl ketone, obtain epoxide equivalent and be 287, water-disintegrable chlorinity is 0.07%, softening point is that 64.2 ℃, melt viscosity (150 ℃) are 340 parts of the epoxy resin of 7.1 pools from oil reservoir distillation.
287 parts of this epoxy resin are put in another four neck flasks with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer; Further add 72 parts in acrylic acid, 0.3 part of methylnaphthohydroquinone, 194 parts of cyclohexanone; Under 90 ℃, heat, stir, the solubilizing reaction potpourri.Then, reactant liquor is cooled to 60 ℃, adds 1.7 parts of triphenylphosphines, under oxygen, reacted about 32 hours, the reactant that to obtain the actual acid number that records be 1mgKOH/g at 100 ℃ times.To wherein adding 78 parts of succinic anhydrides, 42 parts of cyclohexanone, reacted about 6 hours down at 95 ℃ then, obtaining main framing is the carboxylic photoresist of bisphenol A type epoxy resin.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the bisphenol A type epoxy resin through this preparation example preparation is 450g/eq, and the weight-average molecular weight of polystyrene conversion is 7400, the acid number of the actual resin solid composition that records is 100mgKOH/g.
[preparation example 15]
In four neck flasks with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer, adding epoxide equivalent is cresols phenolic resin varnish type epoxy resin (Toto Kasei KK's system: YDCN-702) 330 parts of 218g/eq; At 90～100 ℃ of following heating and meltings, stir.Add 120 parts in acrylic acid, 0.6 part of quinhydrones, 5 parts of dimethyl benzyl amines then, in the presence of oxygen, be warming up to 115 ℃ when stirring, reacted 12 hours.In this flask, drop into 400 parts of cyclohexanone then, be heated to 70 ℃ and make its dissolving.Drop into 81 parts of succinic anhydrides then, be warming up to 95 ℃, stir, reacted 8 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature, obtaining main framing is the carboxylic photoresist of cresols novolaks skeleton.Then, in this solution, add cyclohexanone, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the anhydride modified cresols novolac resin through this preparation example preparation is that the weight-average molecular weight of 319g/eq, polystyrene conversion is 11000, the acid number of the actual resin solid composition that records is 85mgKOH/g.
[preparation example 16]
On four neck flasks, tap funnel is set, in flask, adds 400 parts of cyclohexanone, under nitrogen atmosphere gas, be warming up to 90 ℃ when stirring with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer.In another container, add 15 parts of methacrylic acids, 30 parts of methyl methacrylates, 30 parts of butyl methacrylates, 25 parts of benzyl methacrylates, 20 parts of azoisobutyronitriles, 100 parts of cyclohexanone, stirring, uniform dissolution as polymerization initiator.This monomer solution is joined in the tap funnel that is arranged on the flask, make flask under nitrogen atmosphere gas, be added drop-wise in the flask with 2 hours monomer solutions when under 90 ℃, stirring tap funnel.After dripping end, under 90 ℃ state, continue to stir, drip and finish after 2 hours, the input azoisobutyronitrile is 0.5 part in flask.After 1 hour, in flask, drop into 0.5 part of azoisobutyronitrile once more, further continue to stir 2 hours.Then, the cooling flask stops reaction.Take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 18700, the acid number of resin solid composition is the carboxylic acrylic polymer of 98mgKOH/g.
Stop then importing nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Drop into 111 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and as 0.3 part of the quinhydrones of polymerization inhibitor, 90 ℃ of reactions 8 hours down.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 19900, the acid number of the actual resin solid composition that records is the acrylic polymer of the hydroxyl of 5mgKOH/g.
Then in this flask, drop into 63 parts of succinic anhydrides, in the dry air atmosphere, further reacted 6 hours when under 90 ℃, stirring.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature, obtaining main framing is the carboxylic photoresist of acryl resin.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the acryl resin through this preparation example preparation is that the weight-average molecular weight of 863g/eq, polystyrene conversion is 22000, the acid number of the actual resin solid composition that records is 70mgKOH/g.
[preparation example 17]
In four neck flasks, add polytetramethylene glycol (PTG850: protect native ケ paddy KCC system: hydroxyl value=129mgKOH/g) 212 parts, 75 parts of monoethylene glycol, 159 parts of PMA acid anhydrides (DAICEL chemical industry Co., Ltd. system), 2 parts of dimethyl benzyl amines, as 375 parts of the cyclohexanone of solvent with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer; Under stream of nitrogen gas; Stirred 10 hours down at 100 ℃ when stirring, carry out the reaction of half esterization.Then in this flask, drop into 54 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 15200, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 170mgKOH/g.
Then; Stop to import nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Drop into 110 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After the cooling, take a sample on a small quantity, obtaining main framing is the carboxylic photonasty urethane resin of anhydride modified polyurethane skeleton.In this solution, add cyclohexanone then, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the anhydride modified urethane resin through this preparation example preparation is that the weight-average molecular weight of 896g/eq, polystyrene conversion is 18800, the acid number of the actual resin solid composition that records is 72mgKOH/g.
[preparation example 18]
In four neck flasks, add polytetramethylene glycol (PTG850: protect native ケ paddy KCC system: hydroxyl value=129mgKOH/g) 218 parts, 47 parts of monoethylene glycol, 125 parts of PMA acid anhydrides (DAICEL chemical industry Co., Ltd. system), 2 parts of dimethyl benzyl amines, as 375 parts of the cyclohexanone of solvent with stirring machine, backflow cooling tube, nitrogen ingress pipe, ingress pipe, thermometer; Under stream of nitrogen gas; Stirred 10 hours down at 100 ℃ when stirring, carry out the reaction of half esterization.Then, in this flask, drop into 111 parts of IPDIs, stirred 8 hours down, carry out the urethane reaction at 90 ℃.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 17000, the acid number of the actual resin solid composition that records is the carboxylic polyurethane prepolymer of 110mgKOH/g.
Then; Stop to import nitrogen from nitrogen ingress pipe to this flask; Switch to the importing dry air; Add 131 parts of methyl propenoic acid glycidyl base esters, 6 parts of dimethyl benzyl amines when stirring and, under 90 ℃ state, reacted 8 hours as 0.3 part of the quinhydrones of polymerization inhibitor.After reaction finishes, take a sample on a small quantity, the weight-average molecular weight that obtains polystyrene conversion is 19200, the acid number of the actual resin solid composition that records is the polyurethane prepolymer of the hydroxyl of 4mgKOH/g.
Then in this flask, add 74 parts of succinic anhydrides, in the dry air atmosphere, under 90 ℃ state, further reacted 6 hours.Measure the absorption disappearance of affirmation anhydride group through FT-IR after, be cooled to room temperature, obtaining main framing is the carboxylic urethane resin of anhydride modified urethane resin.Then, in this solution, add cyclohexanone, being adjusted to solid constituent is 50.0%.The ethylenic unsaturated group equivalent of the resin solid composition of the anhydride modified urethane resin through this preparation example preparation is that the weight-average molecular weight of 765g/eq, polystyrene conversion is 21400, the acid number of the actual resin solid composition that records is 67mgKOH/g.
Resin for obtaining in the preparation example 14～18 gathers rerum natura as shown in table 2.
[table 2]
Preparation example 14 Preparation example 15 Preparation example 16 Preparation example 17 Preparation example 18
Main framing Bisphenol type epoxy Anhydride modified cresols novolaks Acrylic acid Anhydride modified polyurethane Anhydride modified polyurethane
Weight-average molecular weight 7400 11000 22000 18800 21400
The actual acid number that records (mgKOH/g) 100 85 70 72 67
Ethylenic unsaturated group equivalent (g/eq) 450 319 863 896 765
[embodiment 1]
With 100.0 parts of resin varnishs (solution of carboxylic polyurethane prepolymer) that obtain in the preparation example 1, as the IRGACURE-907 of Photoepolymerizationinitiater initiater (the special KCC of Chiba system: 2-methyl isophthalic acid-[4-(methyl sulfenyl) phenyl]-2-morpholino-1-propane) 2.5 parts, as DETX-S (Nippon Kayaku K. K's system: 2 of Photoepolymerizationinitiater initiater; The 4-diethyl thioxanthone) 0.25 part, (Nippon Kayaku K. K's system: two (trimethylolpropane) tetraacrylate) 22.5 parts of uniform dissolution and mixing prepare photosensitive polymer combination of the present invention to contain the SR-355 of the compound of ethylenic unsaturated group as photonasty.
[embodiment 2～13]
For the resin varnish that obtains in the preparation example 2～13, by cooperating with embodiment 1 identical ratio, preparation contains the photosensitive polymer combination of each resin.
[comparative example 1～5]
For the resin varnish that obtains in the preparation example 14～18, by cooperating with embodiment 1 identical ratio, preparation contains the photosensitive polymer combination of each resin.
< estimating 1 >
For the photosensitive polymer combination that obtains, estimate as follows.
[manufacturing of sample A]
The photosensitive polymer combination that obtains is coated on polyimide film, and (Kapton 100H: Dong Li-Dupont Kabushiki Kaisha's system: making dry film thickness 25 μ m thickness) is 20 μ m, and the hot-air drier that utilizes 80 ℃ is cooled to room temperature after dry 30 minutes.With it as sample A.
[manufacturing of sample B]
To sample A, use ultraviolet exposure apparatus according (Ushio Electric Co., Ltd system: " UVC-2534/1MNLC3-AA08 ", 120W/cm metal halide lamp, 1 lamp) irradiation accumulation light quantity to be 300mJ/cm 2Ultraviolet ray after, utilize 150 ℃ hot-air drier heat curing (then solidify) 1 hour.The cured film that obtains is cooled to room temperature.With it as sample B.
[manufacturing of sample C]
Make 21 grades of (Kodak corporate system) driving fits of ladder type board (step tablet) on sample A, the ultraviolet exposure apparatus according irradiation accumulation light quantity that the ultraviolet exposure apparatus according of using when utilizing with the manufacturing sample B is identical is 150mJ/cm 2Ultraviolet ray make public.With it as sample C.
And ladder type board refers to and makes optical concentration with 21 grades of films that raise successively and carry out shading, if with its driving fit on test is filmed, irradiates light on the film develops then, the distinguishing of then filming corresponding to test, the progression of peeling off of filming changes.The index of the distinguishing of filming as evaluation test thus.
[adhering evaluation]
According to JIS K5400,, on cured coating film,, carry out disbonded test through Scotch tape (registered trademark) with 100 cuttings of the latticed manufacturing of the chessboard of 1mm * 1mm part for sample B.Observe the state of peeling off of the latticed cutting part of chessboard, estimate by following benchmark.
Zero ... do not have and peel off
△ ... peeling off below 20% of the latticed cutting part of chessboard
* ... peeling off more than 21% of the latticed cutting part of chessboard
[evaluation of bendability]
With the cured coating film face serves as the outside with crooked 180 degree of sample B, the state of filming at this moment by following benchmark evaluation.
Zero ... face is not seen crackle (slight crack)
△ ... the rarely seen minority crackle of face
* ... film splits, face can clearly be seen crackle
[evaluation of development property]
For sample C, use 1% aqueous sodium carbonate, with 2Kg/cm 2Spray press to develop 60 seconds.With the progression through the developer solution swelling of filming as swelling progression, with the progression through the clean flushing of developer solution of filming as peeling off progression.It is low more to peel off progression, and then developing powder is fast more, and development property is more excellent.Use this to peel off progression, judge development property by following benchmark.
Zero ... peel off progression≤10
△ ... peel off progression=11～15
* ... peel off progression >=16
[evaluation of distinguishing]
Swelling sum of series for the evaluation through development property is confirmed is peeled off progression, through following formula try to achieve differentiate differential.
[differentiating differential]=[peeling off progression]-[swelling progression]
Differentiate differential more for a short time, then form in the step at the pattern of reality, can form distincter pattern, distinguishing is more excellent.Use should be differentiated differential, judged distinguishing by following benchmark.
Zero ... differentiate differential≤2
△ ... differentiate differential=3～5
* ... differentiate differential >=6
< estimating 1 result >
The result of evaluation 1 is as shown in table 3.
[table 3]
Adhesiveness Bendability Development property Distinguishing
Embodiment 1 ○ ○ ○ ○
Embodiment 2 ○ ○ ○ ○
Embodiment 3 ○ ○ ○ ○
Embodiment 4 ○ ○ ○ ○
Embodiment 5 ○ ○ ○ ○
Embodiment 6 ○ ○ ○ ○
Embodiment 7 ○ ○ ○ ○
Embodiment 8 ○ ○ ○ ○
Embodiment 9 ○ ○ ○ ○
Embodiment 10 ○ ○ ○ ○
Embodiment 11 ○ ○ ○ ○
Embodiment 12 ○ ○ ○ ○
Embodiment 13 ○ ○ ○ ○
Comparative example 1 × × ○ ○
Comparative example 2 × × ○ ○
Comparative example 3 × △ △ ×
Comparative example 4 ○ △ × △
Comparative example 5 ○ ○ △ ×
Result by estimating 1 can know that in the prior art (comparative example 1～5), development property, the distinguishing of the sample of adhesiveness, bendability excellence are poor, and on the contrary, adhesiveness, the bendability of the sample of development property, distinguishing excellence are poor.On the other hand, in the resin combination of the present invention (embodiment 1～13), adhesiveness, bendability, development property, each rerum natura of distinguishing all balance are excellent well.
[embodiment 14]
With 100.0 parts of resin varnishs (solution of carboxylic polyurethane prepolymer) that obtain in the preparation example 1, as 2-methyl isophthalic acid-[4-(methyl sulfenyl) the phenyl]-2-morpholino-1-propane of Photoepolymerizationinitiater initiater (IRGACURE-907: the special KCC of Chiba system) 2.5 parts, as 2 of Photoepolymerizationinitiater initiater; 4-diethyl thioxanthone (DETX-S: Nippon Kayaku K. K's system) 0.25 part, contain two (trimethylolpropane) tetraacrylate (SR-355: Nippon Kayaku K. K's system) 7.5 parts, as 15.0 parts of uniform dissolution of hydrogenated bisphenol A diglycidyl ether (Denacol EX-252:Nagasechemtex Co., Ltd. system) of heat curing composition and mix, prepare photosensitive polymer combination of the present invention of the compound of ethylenic unsaturated group as photonasty.
[embodiment 15～26]
For the resin varnish that obtains in the preparation example 2～13, by cooperating with embodiment 14 identical ratios, preparation contains the photosensitive polymer combination of each resin.
[comparative example 6～10]
For the resin varnish that obtains in the preparation example 14～18, by cooperating with embodiment 14 identical ratios, preparation contains the photosensitive polymer combination of each resin.
< estimating 2 >
For the photosensitive polymer combination that obtains, estimate as follows.
[manufacturing of sample D]
Through processing, obtain dry coating with the identical method of manufacturing of estimating 1 sample A.With it as sample D.
[manufacturing of sample E]
Use sample D to substitute sample A,, obtain cured film through processing with the identical method of manufacturing of the sample B of evaluation 1.With it as sample E.
[manufacturing of sample F]
Use sample D to substitute sample A,, obtain cured film through processing with the identical method of manufacturing of the sample C of evaluation 1.With it as sample F.
[manufacturing of sample G]
The photosensitive polymer combination that obtains is coated on to make dry film thickness on the thick polyethylene terephthalate of 38 μ m (below be labeled as " the PET ") diffusion barrier be 20 μ m, the hot-air drier that utilizes 80 ℃ is cooled to room temperature after dry 30 minutes.The ultraviolet exposure apparatus according irradiation accumulation light quantity that the ultraviolet exposure apparatus according of using when then, utilization is made with the sample B that estimates 1. is identical is 300mJ/cm 2Ultraviolet ray after, utilize 150 ℃ hot-air drier heat curing (then solidify) 1 hour.The cured film that obtains is cooled to room temperature, peels off cured coating film from diffusion barrier.With it as sample G.
[referring to touch adhesive evaluation]
For sample D, through referring to touch following evaluation stickability.
Zero ... do not have fingerprint fully
△ ... a little fingerprint occurs
* ... fingerprint occurs obviously
[adhering evaluation]
Use sample E to substitute sample B, likewise carry out adhering test, estimate with evaluation 1.
[evaluation of bendability]
Use sample E to substitute sample B, likewise carry out the test of bendability, estimate with evaluation 1.
[evaluation of development property]
Use sample F to substitute sample C,, estimate according to following benchmark with evaluation 1 test of development property likewise.
Zero ... peel off progression≤7
△ ... peel off progression=8～14
* ... peel off progression >=15
[evaluation of distinguishing]
Likewise carry out the evaluation of distinguishing with evaluation 1 according to following benchmark.
Zero ... differentiate differential≤3
△ ... differentiate differential=4～7
* ... differentiate differential >=8
[evaluation of solvent resistance]
Sample E at room temperature is immersed in the isopropyl alcohol 30 minutes.After confirming that outward appearance is not unusual, utilize adhesive tape [Scotch tape (registered trademark)] to carry out disbonded test, estimate by following benchmark.
Zero ... appearance of film is no abnormal, do not have and expand or peel off
△ ... the end of filming (border of coated portion and polyimide base material) has a little and peel off
* ... filmed and expanded or peel off
[acid proof evaluation]
Sample E at room temperature is immersed in 10% aqueous hydrochloric acid solution 30 minutes.After confirming that outward appearance is not unusual, utilize adhesive tape [Scotch tape (registered trademark)] to carry out disbonded test, estimate by following benchmark.
Zero ... appearance of film is no abnormal, do not expand or peel off
△ ... the end (border of coated portion and polyimide base material) to film is the center has and expands a little or peel off
* ... filmed and expanded or peel off
[evaluation of substrate warp]
Sample E is cut into the square of 5cm * 5cm, cured coating film is faced up, under 25 ℃, the condition of humidity 50%, on smooth platform, left standstill 12 hours.For the sample after leaving standstill, measure foursquare four jiaos of height from table flotation, calculate its mean value, estimate according to following benchmark.The warpage of the more little then sample of this value is few more, representes good more.
Zero ... below the 5mm
△...6mm～10mm
* ... more than the 11mm
[flexible evaluation]
With crooked 180 degree of sample G, same section is spent to opposition side also bending 180.Judge the membrane stage that is coated with of this moment by following benchmark.
Zero ... face is not seen crackle (slight crack)
△ ... face is only seen crackle slightly
* ... film splits, face can clearly be seen crackle
< evaluation result >
The result of evaluation 2 is as shown in table 4.
[table 4]
Refer to touch viscosity Adhesiveness Bendability Development property Distinguishing Chemical reagent resistance Acid resistance Substrate warp Flexible
Embodiment 14 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 15 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 16 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 17 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 18 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 19 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 20 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 21 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 22 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 23 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 24 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 25 ○ ○ ○ ○ ○ ○ ○ ○ ○
Embodiment 26 ○ ○ ○ ○ ○ ○ ○ ○ ○
Comparative example 6 ○ △ × ○ ○ ○ △ × ×
Comparative example 7 ○ × × ○ ○ ○ ○ × ×
Comparative example 8 △ × △ △ × ○ △ × △
Comparative example 9 △ ○ △ × △ × × ○ ○
Comparative example 10 × ○ ○ △ × × × △ ○
Result by estimating 2 can know, resin combination of the present invention (embodiment 14～26) with estimate 1 likewise, not only adhesiveness, bendability, development property are excellent, and because the stickability of dry coating is few, processability is also excellent.Further, have patience and the substrate warp or the flexible softness of filming concurrently, have the performance that prior art utilized (comparative example 6～10) can not obtain.
[embodiment 27]
With 105 parts of resin varnishs (solution of carboxylic polyurethane prepolymer) that obtain in the preparation example 1, as 2-methyl isophthalic acid-[4-(methyl sulfenyl) the phenyl]-2-morpholino-1-propane of Photoepolymerizationinitiater initiater (IRGACURE-907: the special KCC of Chiba system) 6 parts, as 2 of Photoepolymerizationinitiater initiater; 4-diethyl thioxanthone (DETX-S: Nippon Kayaku K. K's system) 1 part, contain trimethylolpropane PO modification triacrylate (the ARONIX M-310: Toagosei Co., Ltd's system) 8 parts, of the compound of ethylenic unsaturated group as photonasty as the dicyclopentadiene-type epoxy of heat curing composition (HP7200: Dainippon Ink and Chemicals, Inc's system) 21 parts, as the dicyandiamide of heat curing auxiliary agent (DICY7: monosodium glutamate Off ァ ィ Application テ Network ノ Co., Ltd. system) 1 part, as the hydrophobic silica particulate of adjuvant (R812: Japanese AEROSIL Co., Ltd. system) 8 parts, 2 parts of cooperations of green paste (green pigment/material resin (phenol resin)/solvent (the acetate card is finished alcohol ester)=28/12/60); It is mixing to utilize triple-roller mill to carry out, and prepares photonasty resistance solder paste China ink of the present invention.
[embodiment 28～39]
For the resin varnish that obtains in the preparation example 2～13, by cooperating with embodiment 27 identical ratios, preparation contains the resistance solder paste China ink of each resin.
[comparative example 11～15]
For the resin varnish that obtains in the preparation example 14～18, by cooperating with embodiment 27 identical ratios, preparation contains the resistance solder paste China ink of each resin.
[embodiment 40]
With 105 parts of resin varnishs (solution of carboxylic polyurethane prepolymer) that obtain in the preparation example 1, as 2-methyl isophthalic acid-[4-(methyl sulfenyl) the phenyl]-2-morpholino-1-propane of Photoepolymerizationinitiater initiater (IRGACURE-907: the special KCC of Chiba system) 6 parts, as 2 of Photoepolymerizationinitiater initiater; 4-diethyl thioxanthone (DETX-S: Nippon Kayaku K. K's system) 1 part, contain trimethylolpropane PO modification triacrylate (the ARONIX M-310: Toagosei Co., Ltd's system) 8 parts, of the compound of ethylenic unsaturated group as photonasty as the flexibility epoxy resin of heat curing composition (EPICLON EXA-4850-150: Dainippon Ink and Chemicals, Inc's system) 25 parts, as the dicyandiamide of heat curing auxiliary agent (DICY7: monosodium glutamate Off ァ ィ Application テ Network ノ Co., Ltd. system) 1 part, as the hydrophobic silica particulate of adjuvant (R812: Japanese AEROSIL Co., Ltd. system) 8 parts, 2 parts of green pastes (green pigment/material resin (phenol resin)/solvent (the acetate card is finished alcohol ester)=28/12/60) and 8 parts of phosphazene flame retardants (SPB-100: Otsuka Chemical Co., Ltd system), polyphosphoric acid melamine (PHOSMEL-100: Nissan Chemical Ind Ltd's system) 8 parts, melamine cyanurate fire retardant (STABIACE MC-5S: Sakai Chemical Industry Co., Ltd.'s system) 8 parts of cooperations; It is mixing to utilize triple-roller mill to carry out, and prepares photonasty resistance solder paste China ink of the present invention.
[embodiment 40～52]
For the resin varnish that obtains in the preparation example 2～13, by cooperating with embodiment 40 identical ratios, preparation contains the photonasty resistance solder paste China ink of each resin.
[comparative example 16～20]
For the resin varnish that obtains in the preparation example 14～18, by cooperating with embodiment 40 identical ratios, preparation contains the photonasty resistance solder paste China ink of each resin.
< estimating 3 >
For the photonasty resistance solder paste China ink that obtains, estimate as follows.
[manufacturing of sample H]
On the release surface of one side having been carried out the thick separation PET film of 38 μ m that fissility handles, it is 20 μ m that the photonasty resistance solder paste China ink that obtains in coating embodiment 21～40, the comparative example 11～20 makes dried thickness, utilizes 80 ℃ dry 20 minutes of heated-air drying.Then, fit, make the dry-film type photonasty solder resist of the photosensitive polymer combination that the two sides clips with the PET film through the PET film that the photosensitive polymer combination face on this film and 25 μ m are thick.
Then; By this dry film peel separation PET film; The copper-clad surface that is exposed to surperficial photosensitive polymer combination face and copper laminate (copper laminate that roughened obtains being carried out on the copper surface through etching) is fitted, utilize vacuum laminator (60 ℃, 0.2MPa=2Kg/cm 2) carry out driving fit.Then, make and to have the resist pattern minus film driving fit of [φ 70 μ m holes, 21 grades of ladders, solid line/space=100/60 (μ m/ μ m)] from the PET film, use ultraviolet exposure apparatus according (ORC makes made EXM-1201F, short-arc lamp) irradiation ultraviolet radiation (400mJ/cm 2).Peel off the PET film then, use 1% aqueous sodium carbonate, at 2Kg/cm 2Spray depress and developed 60 seconds.Then, utilize 150 ℃ air drier to be heating and curing perparation of specimen H 1 hour.
[evaluation of solvent resistance]
Use sample H to substitute sample E, likewise carry out the test of solvent resistance, estimate with evaluation 2.
[acid proof evaluation]
Use sample H to substitute sample E, likewise carry out acid proof test, estimate with evaluation 2.
[evaluation of development property]
Use sample H to substitute sample C,, judge by following benchmark with evaluation 1 test of development property likewise.
Zero ... peel off progression≤5
△ ... peel off progression=6～10
* ... peel off progression >=11
[evaluation of distinguishing]
For sample H, utilize magnifier to observe φ 70 μ m hole portions, the mensuration resist layer is developed and the diameter of copper surface exposed portions serve (perforate part), judges distinguishing according to following benchmark.The diameter in this hole is more near 70 μ m, and then pattern forms more exactly, and distinguishing is more excellent.
Zero ... more than the diameter 60 μ m
△ ... diameter 40 μ m～59 μ m
* ... below the diameter 39 μ m
[the stable on heating evaluation of soldering]
(Co., Ltd.'s ASAHI chemical research is made: SPEEDY FLUX P-550-5), dipping is 10 seconds in 260 ℃ scolder baths (JIS C 6481) for coating rosin based flux on sample H.This as 1 circulation, is repeated 2 circulations, be described below the state of filming is judged.
Zero ... appearance of film is no abnormal, also do not expand or peel off.
△ ... be coated with membrane portions and exist expand or peel off.
* ... the existence of all filming is expanded or is peeled off.
[manufacturing of sample I]
The photonasty that obtains in embodiment 27～52, the comparative example 11～20 resistance solder paste China ink is coated on to make dry film thickness on the thick separation PET film of 38 μ m be 20 μ m, utilizes 80 ℃ dry 20 minutes of hot-air drier.The ultraviolet exposure apparatus according irradiation accumulation light quantity that the ultraviolet exposure apparatus according of using when then, utilization is made with the sample H that estimates 3 is identical is 400mJ/cm 2Ultraviolet ray after, utilize 150 ℃ hot-air drier heat curing 1 hour.The cured film that obtains is cooled to room temperature, peels off cured coating film from diffusion barrier.With it as sample I.
[flexible evaluation]
The identical ground of evaluation with estimating 2 flexibility carries out flexibility test to sample I, estimates.
[manufacturing of sample J]
For the photonasty resistance solder paste China ink that obtains in the embodiment that contains fire retardant 40～52, the comparative example 16～20; Except in the manufacturing step of sample H, not using minus film and the irradiation ultraviolet radiation (blanket exposure) with resist pattern; Through likewise carrying out perparation of specimen J with the manufacturing of sample H.
[evaluation of anti-flammability]
For sample J, carry out the evaluation of anti-flammability according to UL Subject94V method, according to following benchmark judged result.
○...VTM-0
△...VTM-1
* ... below the VTM-2 (comprising perfect combustion etc.)
< evaluation result >
The result of evaluation 3 is shown in table 5 and table 6.
[table 5]
Chemical reagent resistance Acid resistance Development property Distinguishing The soldering thermotolerance Flexible
Embodiment 27 ○ ○ ○ ○ ○ ○
Embodiment 28 ○ ○ ○ ○ ○ ○
Embodiment 29 ○ ○ ○ ○ ○ ○
Embodiment 30 ○ ○ ○ ○ ○ ○
Embodiment 31 ○ ○ ○ ○ ○ ○
Embodiment 32 ○ ○ ○ ○ ○ ○
Embodiment 33 ○ ○ ○ ○ ○ ○
Embodiment 34 ○ ○ ○ ○ ○ ○
Embodiment 35 ○ ○ ○ ○ ○ ○
Embodiment 36 ○ ○ ○ ○ ○ ○
Embodiment 37 ○ ○ ○ ○ ○ ○
Embodiment 38 ○ ○ ○ ○ ○ ○
Embodiment 39 ○ ○ ○ ○ ○ ○
Comparative example 11 ○ △ ○ ○ ○ ×
Comparative example 12 ○ ○ ○ △ ○ ×
Comparative example 13 ○ △ △ × △ △
Comparative example 14 × × × △ × ○
Comparative example 15 × × × × × ○
Result by table 5 can know, in the comparative example 11,12 (prior art), though the patience of filming, development property, excellent heat resistance can not satisfy the most important rerum natura flexibility as the flexible insulating protective film that in flexible printed circuit board etc., uses.In addition, in the comparative example 13～15 (prior art), for flexible excellent, and the result of the patience of filming, development property difference.On the other hand, photosensitive polymer combination of the present invention (embodiment 27～39) can satisfy as essential whole these rerum naturas of flexible insulating protective layer with high level.
The of the present invention carboxylic photonasty urethane resin that does not particularly have the ester skeleton of the half ester origin of carrying out in the main chain through acid anhydrides; Because main chain is chemically stable; Compare with comparative example 14, the comparative example 15 of identical polyurethane main framing; Have under the excellent especially patience of filming of maintenance, stable on heating state, can bring into play the characteristic of the distinctive adhesiveness of urethane resin, flexibility.In addition; Carboxylic photonasty urethane resin of the present invention even contain the carboxyl amount after a little while, also shows very excellent development property owing on side chain, have photonasty group and carboxyl; In addition; These side chain functionalities since with directly compare with the situation of main chain bonding, reactive fully, can bring into play the distinguishing of excellence and the patience of filming.
[table 6]
Chemical reagent resistance Acid resistance Development property Distinguishing The soldering thermotolerance Flexible Anti-flammability
Embodiment 40 ○ ○ ○ ○ ○ ○ ○
Embodiment 41 ○ ○ ○ ○ ○ ○ ○
Embodiment 42 ○ ○ ○ ○ ○ ○ ○
Embodiment 43 ○ ○ ○ ○ ○ ○ ○
Embodiment 44 ○ ○ ○ ○ ○ ○ ○
Embodiment 45 ○ ○ ○ ○ ○ ○ ○
Embodiment 46 ○ ○ ○ ○ ○ ○ ○
Embodiment 47 ○ ○ ○ ○ ○ ○ ○
Embodiment 48 ○ ○ ○ ○ ○ ○ ○
Embodiment 49 ○ ○ ○ ○ ○ ○ ○
Embodiment 50 ○ ○ ○ ○ ○ ○ ○
Embodiment 51 ○ ○ ○ ○ ○ ○ ○
Embodiment 52 ○ ○ ○ ○ ○ ○ ○
Comparative example 16 △ × × △ △ ○ △
Comparative example 17 ○ △ △ × × △ △
Comparative example 18 △ × × × × △ ○
Comparative example 19 × × × × × ○ ○
Comparative example 20 × × × × × ○ ○
Result by table 6 can know; Owing to add fire retardant; Prior art (comparative example 16～20) reduces as the rerum natura of resist on the whole, but photosensitive polymer combination of the present invention (embodiment 40～52) can have anti-flammability and other rerum natura as resist concurrently.This is because through carboxylic photonasty urethane resin of the present invention; As stated; On side chain, have reactive photonasty group and carboxyl fully; Even when existing fire retardant etc. significantly to hinder development property and photosensitive main cause, also can bring into play very excellent development property, photonasty, can keep distinguishing or the state of the patience of filming under show anti-flammability.
More than, describing the present invention according to specific mode, the distortion that still it will be apparent to those skilled in the art that, improvement are also within the scope of the invention.

Claims (8)

1. photosensitive polymer combination, said composition contains the compound (C) that carboxylic photonasty urethane resin (A), Photoepolymerizationinitiater initiater (B) and photonasty contain the ethylenic unsaturated group, it is characterized in that:
Carboxylic photonasty urethane resin (A) is the resin that generates through following reaction,
Through obtaining carboxylic polyurethane prepolymer (a) as must composition reacting with the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and diisocyanate cpd (g),
Through making the carboxyl in the above-mentioned carboxylic polyurethane prepolymer (a) that obtains react the polyurethane prepolymer (c) that obtains hydroxyl with the epoxy radicals or the oxa-cyclobutyl that have in the compound (b) of epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group,
Make the anhydride group reaction in hydroxyl and the compound (d) that contains anhydride group in the polyurethane prepolymer (c) of the above-mentioned hydroxyl that obtains, wherein,
The acid number of carboxylic photonasty urethane resin (A) is 10～200mgKOH/g,
The ethylenic unsaturated group equivalent of carboxylic photonasty urethane resin (A) is 200～3000g/eq,
The weight-average molecular weight of carboxylic photonasty urethane resin (A) is 1000～100000.
2. photosensitive polymer combination as claimed in claim 1 wherein, further contains Thermocurable compound (D).
3. photosensitive polymer combination as claimed in claim 2 wherein, further contains heat curing auxiliary agent (E).
4. photosensitive polymer combination as claimed in claim 2, wherein, Thermocurable compound (D) is the compound (k) with 2 above epoxy radicals or oxa-cyclobutyl.
5. solidfied material, it solidifies the described photosensitive polymer combination of claim 1 and forms.
6. photonasty resistance solder paste China ink contains described photosensitive polymer combination of claim 1 and fire retardant.
7. dry-film type photonasty solder resist contains described photosensitive polymer combination of claim 1 and fire retardant.
8. the preparation method of carboxylic photonasty urethane resin is characterized in that, comprising:
With the carboxylic acid compound (f) that has 2 hydroxyls in polymer polyatomic alcohol (e), the molecule and diisocyanate cpd (g) as must reacting the first step that obtains carboxylic polyurethane prepolymer (a) by composition,
Make said carboxylic polyurethane prepolymer (a) and compound (b) react second step of the polyurethane prepolymer (c) obtain hydroxyl with epoxy radicals or oxa-cyclobutyl and ethylenic unsaturated group, and
Make the polyurethane prepolymer (c) of said hydroxyl and the third step of compound (d) reaction that contains anhydride group,
The acid number of said carboxylic photonasty urethane resin is 10～200mgKOH/g,
The ethylenic unsaturated group equivalent of said carboxylic photonasty urethane resin is 200～3000g/eq,
The weight-average molecular weight of said carboxylic photonasty urethane resin is 1000～100000.
CN2007800409539A 2006-11-02 2007-11-02 Photosensitive resin composition, cured product thereof, and method for producing photosensitive resin Expired - Fee Related CN101535896B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP298361/2006 2006-11-02
JP2006298361 2006-11-02
JP252808/2007 2007-09-28
JP2007252808 2007-09-28
PCT/JP2007/071373 WO2008053985A1 (en) 2006-11-02 2007-11-02 Photosensitive resin composition, cured product thereof, and method for producing photosensitive resin

Publications (2)

Publication Number Publication Date
CN101535896A CN101535896A (en) 2009-09-16
CN101535896B true CN101535896B (en) 2012-06-13

Family

ID=39344324

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800409539A Expired - Fee Related CN101535896B (en) 2006-11-02 2007-11-02 Photosensitive resin composition, cured product thereof, and method for producing photosensitive resin

Country Status (5)

Country Link
JP (1) JP5298855B2 (en)
KR (1) KR101536366B1 (en)
CN (1) CN101535896B (en)
TW (1) TWI432897B (en)
WO (1) WO2008053985A1 (en)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI375866B (en) * 2008-01-22 2012-11-01 Agi Corp Radiation curable and developable polyurethane and radiation curable and developable photoresist composition containing the same
KR100965189B1 (en) * 2007-10-11 2010-06-24 주식회사 엘지화학 Fluorene-based polymer having urethane group and preparation method thereof, and negative photosensitive resin composition containing the fluorene-based polymer
JP5049175B2 (en) * 2008-03-25 2012-10-17 株式会社カネカ Novel photosensitive resin composition, photosensitive resin composition solution obtained therefrom, photosensitive film, insulating film, and printed wiring board with insulating film
JP5285355B2 (en) * 2008-08-27 2013-09-11 アイカ工業株式会社 Resin composition and molded product
JP5617177B2 (en) * 2009-03-27 2014-11-05 東洋インキＳｃホールディングス株式会社 Coloring composition for color filter and color filter
JP5099851B2 (en) * 2009-04-27 2012-12-19 太陽ホールディングス株式会社 Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them
KR101361753B1 (en) * 2010-03-22 2014-02-12 주식회사 엘지화학 Photo-curable and thermo-curable resin composition, and dry film solder resist
JP5624794B2 (en) * 2010-04-19 2014-11-12 東京応化工業株式会社 Negative photosensitive resin composition, photosensitive dry film, and light receiving device
JP5471966B2 (en) * 2010-08-17 2014-04-16 Ｊｓｒ株式会社 Photosensitive adhesive composition, laminate or solid-state image sensor manufacturing method using the composition, and solid-state image sensor
JP6028360B2 (en) * 2011-06-29 2016-11-16 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and cured product thereof, and method for producing photosensitive resin
WO2013011873A1 (en) * 2011-07-20 2013-01-24 株式会社カネカ Novel conductive layer integrated fpc
CN103926791B (en) * 2013-01-15 2016-11-16 太阳油墨制造株式会社 Hardening resin composition, its dry film and solidfied material and use their printed circuit board (PCB)
CN103969951A (en) * 2013-01-30 2014-08-06 太阳油墨制造株式会社 Conducting Resin Composition And Conducting Circuit
CN103616800B (en) * 2013-10-21 2016-08-10 溧阳市东大技术转移中心有限公司 Photo-curing resin combination
JP5835416B2 (en) * 2014-06-25 2015-12-24 日立化成株式会社 Photosensitive resin composition, photosensitive film, and method for forming resist pattern
WO2016068254A1 (en) * 2014-10-30 2016-05-06 昭和電工株式会社 Hydroxyl-containing polyurethane resin, polyurethane resin and urethane (meth)acrylate resin using hydroxyl-containing polyurethane resin as starting material, production methods for these resins, overcoat composition, and uv-curable resin composition
JP6912494B2 (en) 2016-11-18 2021-08-04 株式会社有沢製作所 Photosensitive resin composition, solder resist film using the photosensitive resin composition, flexible printed wiring board and image display device
CN110268325B (en) * 2017-02-07 2023-06-06 株式会社有泽制作所 Photosensitive resin composition, and solder resist film and flexible printed wiring board using same
WO2018146821A1 (en) * 2017-02-07 2018-08-16 株式会社有沢製作所 Photosensitive resin composition, solder resist film using said photosensitive resin composition, flexible printed wiring board, and image display device
JP2018203820A (en) * 2017-05-31 2018-12-27 凸版印刷株式会社 Aqueous urethane resin dispersion, and film and sheet using same
CN111247216A (en) * 2017-10-20 2020-06-05 株式会社Lg化学 Ink composition
JP2019211540A (en) * 2018-05-31 2019-12-12 太陽インキ製造株式会社 Photocurable thermosetting resin composition for forming optical waveguide, and cured product thereof and optical waveguide, and optoelectronic hybrid substrate, waveguide-type light splitter, and optical module including optical waveguide
JP7348177B2 (en) * 2018-06-29 2023-09-20 株式会社カネカ Resist composition for pattern printing and pattern forming method
CN109100918B (en) * 2018-07-25 2020-08-04 深圳市华星光电技术有限公司 Photosensitive resin composition and preparation method and application thereof
JP7203577B2 (en) * 2018-11-13 2023-01-13 株式会社Adeka Curable resin composition
TWI662014B (en) * 2019-01-02 2019-06-11 Daxin Materials Corporation Oligomer, photosensitive resin composition, photospacer and coating including the same
DE102019100769A1 (en) * 2019-01-14 2020-07-16 Voestalpine Stahl Gmbh Phosphate-based paint coating with good resistance to alkaline stamping aids
CN111072962B (en) * 2019-12-20 2022-11-04 上海维凯光电新材料有限公司 Synthesis and application of photosensitive polyimide for high-temperature-resistant optical fiber coating
JP7441528B2 (en) * 2021-08-30 2024-03-01 互応化学工業株式会社 glue

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02296819A (en) * 1989-05-10 1990-12-07 Hitachi Maxell Ltd Polyurethane resin and its production
JP4503199B2 (en) * 2001-04-12 2010-07-14 岡本化学工業株式会社 Photosensitive composition for photosensitive lithographic printing plate
JP2003122001A (en) * 2001-10-15 2003-04-25 Nippon Kayaku Co Ltd Photosensitive resin, photosensitive resin composition using the same, and its hardened product
JP3523857B2 (en) * 2001-12-25 2004-04-26 昭和高分子株式会社 Photosensitive resin and photosensitive resist ink composition
KR100725432B1 (en) * 2003-03-06 2007-06-07 닛뽄 가야쿠 가부시키가이샤 Photosensitive resin composition and curing product thereof
JP2005048143A (en) * 2003-07-31 2005-02-24 Fuji Photo Film Co Ltd Polymerizable composition
BRPI0413182A (en) * 2003-08-07 2006-10-03 Huntsman Adv Mat Switzerland linear polyurethane, composition, molding, material, process for the production of welding mask over a printed circuit, and, use of composition
JP2007002030A (en) * 2005-06-21 2007-01-11 Fujifilm Holdings Corp Elastomer, photosensitive solder resist composition, photosensitive solder resist film, permanent pattern, and method for forming the same

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
JP平2-296819A 1990.12.07
JP特开2002-311579A 2002.10.23
JP特开2003-122001A 2003.04.25
JP特开2003-192760A 2003.07.09
JP特开2005-48143A 2005.02.24
说明书第0011-0017段.

Also Published As

Publication number Publication date
JPWO2008053985A1 (en) 2010-02-25
CN101535896A (en) 2009-09-16
TWI432897B (en) 2014-04-01
TW200844657A (en) 2008-11-16
KR20090082264A (en) 2009-07-29
JP5298855B2 (en) 2013-09-25
KR101536366B1 (en) 2015-07-13
WO2008053985A1 (en) 2008-05-08

Similar Documents

Publication Publication Date Title
CN101535896B (en) Photosensitive resin composition, cured product thereof, and method for producing photosensitive resin
CN103098561B (en) The manufacture method of stiffener integral type flexible printing substrate and stiffener integral type flexible printing substrate
CN1755524B (en) Phototonus thermosetting resin composition and printing plug board coating with resist and its manufacturing method
CN105705525B (en) Use in printed circuit board curing composition, cured coating film and printed circuit board (PCB) using it
KR100525984B1 (en) Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, resist pattern and substrate having the resist pattern laminated thereon
JP5319132B2 (en) Photocurable / thermosetting resin composition and cured product thereof
JP2010117452A (en) Photosensitive flame retardant resin composition
CN104010815A (en) Dry film, printed wiring board using same, method for producing printed wiring board, and flip chip mounting substrate
US7910631B2 (en) Photosensitive resin composition and flexible printed wiring circuit board having insulative cover layer formed of photosensitive resin composition
CN108350203B (en) Black resin composition, polyimide with black resin cured film, and method for producing same
KR20120060938A (en) Photo-sensitive resin composition, dry film solder resist, and circuit board
KR20140018117A (en) Photo-curable and thermo-curable resin composition, and dry film solder resist
JP4623890B2 (en) Photosensitive composition, cured product thereof and printed wiring board using the same
JP2009271290A (en) Photosensitive resin composition for rigid printed wiring board
CN108701657A (en) The wafer-class encapsulation of curable resin constituent and fan-out-type
CN101872124B (en) Photosensitive resin composition, flexible circuit board employing the same, and circuit board production method
JP5493347B2 (en) Flame retardant resin composition
TWI761412B (en) Curable composition, main agent and curing agent, dry film, cured product, and printed wiring board
JP2002014466A (en) Photosensitive resin composition
JP2013182174A (en) Photosensitive resin composition
TW525039B (en) Photoimageable composition containing flexible oligomer
KR101785706B1 (en) Photo-curable and thermo-curable resin composition, and dry film solder resist
CN114945611A (en) Curable composition, dry film thereof, and cured product thereof
TWI789483B (en) Photocurable resin composition, cured film, adhesive sheet, photosensitive film, printed wiring board, and image display device
JP6603442B1 (en) Curable resin composition, dry film and cured product thereof, and printed wiring board

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120613

Termination date: 20211102

CF01 Termination of patent right due to non-payment of annual fee