CN103649831A - Photosensitive resin composition, and photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed substrate using same - Google Patents

Photosensitive resin composition, and photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed substrate using same Download PDF

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Publication number
CN103649831A
CN103649831A CN201280034051.5A CN201280034051A CN103649831A CN 103649831 A CN103649831 A CN 103649831A CN 201280034051 A CN201280034051 A CN 201280034051A CN 103649831 A CN103649831 A CN 103649831A
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general formula
group
photosensitive polymer
unsaturated group
polymer combination
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Inventor
有冈大辅
林利明
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Fujifilm Corp
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Fujifilm Corp
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    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Abstract

Provided is a photosensitive resin composition comprising at least one each of an acid-modified resin containing ethylenic unsaturated groups, an inorganic filler, an ion scavenger of an inorganic compound having at least one metal selected from Zr, Bi, and Sb, a radical polymerizable monomer, a photopolymerization initiator, and a heat crosslinking agent, wherein the inorganic filler content accounts for at least 20 vol% of the total nonvolatile component content of the photosensitive resin composition, as well as a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed substrate.

Description

Photosensitive polymer combination and the photosensitive film, photonasty laminate, permanent pattern forming method and the printed base plate that use it
Technical field
The present invention relates to a kind of can be suitably for the photosensitive polymer combination of solder resist (solder resist) etc. and photosensitive film, photonasty laminate, permanent pattern forming method and the printed base plate that uses it.
Background technology
Previously, when forming the permanent pattern of solder resist etc., used photosensitive film, described photosensitive film is to form photographic layer and form by being coated with silicon dioxide dispersive composition and being dried on supporter always.Method such as the known following methods of the permanent pattern of formation solder resist etc. etc.: form laminate forming lamination photosensitive film on the matrixes such as copper foil laminates of permanent pattern, photographic layer to this laminate exposes, after this exposure, photographic layer developed and form pattern, carry out cure process etc., form thus permanent pattern thereafter.
Recently, be accompanied by the miniaturization of element, just in the exploitation of the solder resist of the axis of thrust/gap (Line/Space, L/S) little conductor package substrate etc.Therefore,, in order to improve resistance to impact, insulativity, require to fill inorganic filler with high fill-ratio.
Recently propose, for make solder resist and the solder resist that while suppressing cold cycling produce consistent with the linear expansion coefficient of substrate of substrate that becomes solder resist be full of cracks generation or peel off the inorganic filler (with reference to patent documentation 1) that barium (Ba), magnesium (Mg) or the aluminium (Al) that the refractive index that contains 25 volume %～40 volume % with respect to the nonvolatile component total amount of photosensitive polymer combination is 1.50～1.65 is.Propose in addition, the shape level and smooth (smooth) of the internal face when making thermal cycle test patience, storage stability, formation passage (via), is used and through silane coupling agent, has carried out surface-treated spherical silicon dioxide and be used as inorganic filler (with reference to patent documentation 2).
On the other hand, the known specific ion adsorbent (with reference to patent documentation 3～patent documentation 5) that uses in photosensitive composite.
Yet for the photosensitive polymer combination for solder resist etc. or photosensitive film etc., if photographic layer is filled to inorganic filler with high fill-ratio, melting viscosity uprises, transfer printing, developability reduce.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2011-75923 communique
Patent documentation 2: Japanese Patent Laid-Open 2011-95731 communique
Patent documentation 3: Japanese Patent Laid-Open 2000-159859 communique
Patent documentation 4: Japanese Patent Laid-Open 2009-186510 communique
Patent documentation 5: Japanese patent laid-open 11-288090 communique
Summary of the invention
Problem of the present invention is to provide a kind of photosensitive polymer combination, even if it contains inorganic filler with high density, the dispersion stabilization of inorganic filler is also excellent, and resolution is good and development residue also still less, can obtain all excellent high performance cured films of insulativity, thermotolerance, resistance to plating.And then problem of the present invention is to provide a kind of photonasty laminate, permanent pattern forming method and printed base plate that uses described photosensitive polymer combination.
The inventor etc. have carried out making great efforts research repeatedly, found that, described problem of the present invention can utilize following means to solve.
That is, as follows by the means that solve described problem of the present invention.
< 1 > photosensitive polymer combination, contain at least respectively the resin containing ethene unsaturated group for a kind of sour modification, inorganic filler, ion capturing agent, free radical polymerization monomer, photopolymerization initiator and thermal cross-linking agent, and described photosensitive polymer combination is characterised in that: the content of the described inorganic filler in the nonvolatile component cumulative volume of described photosensitive polymer combination is more than 20 volume %, and described ion capturing agent for containing zirconium (Zr) in constituting atom, the mineral compound of at least one of bismuth (Bi) or antimony (Sb).
The photosensitive polymer combination that < 2 > record according to described < 1 >, is characterized in that: described ion capturing agent is the mineral compound being selected from basic zirconium phosphate, wolframic acid zirconium, molybdic acid zirconium, selenic acid zirconium, telluric acid zirconium, bismuth oxide, bismuth titanates, bismuth nitrate, bismuth salicylate, waltherite, antimony pentoxide, antimony oxide, phosphorus metaantimmonic acid, metaantimmonic acid zirconium and metaantimmonic acid titanium.
The photosensitive polymer combination that < 3 > record according to described < 1 > or < 2 >, is characterized in that: contain at least one mineral compound that contains Zr in constituting atom and mineral compound that at least one contains Bi in constituting atom as described ion capturing agent.
< 4 > are according to photosensitive polymer combination that in described < 1 > to < 3 >, any one is recorded, it is characterized in that containing macromolecule dispersing agent, described macromolecule dispersing agent has the group with the surface interaction of inorganic filler, and does not have ethene unsaturated group.
The photosensitive polymer combination that < 5 > record according to described < 4 >, is characterized in that: described spreading agent is the spreading agent with basic group or acidic-group.
The photosensitive polymer combination that < 6 > record according to described < 4 > or < 5 >, is characterized in that: described spreading agent has one-level amino or secondary is amino.
< 7 >, according to the photosensitive polymer combination that in described < 4 > to < 6 >, any one is recorded, is characterized in that: described spreading agent has grafted chain.
< 8 >, according to the photosensitive polymer combination that in described < 4 > to < 7 >, any one is recorded, is characterized in that: the amine value of described spreading agent is more than 0.65mmol/g.
< 9 >, according to the photosensitive polymer combination that in described < 4 > to < 8 >, any one is recorded, is characterized in that: the acid number of described spreading agent is more than 0.1mmol/g.
< 10 >, according to the photosensitive polymer combination that in described < 1 > to < 9 >, any one is recorded, is characterized in that: described inorganic filler contains silicon in constituting atom.
< 11 >, according to the photosensitive polymer combination that in described < 1 > to < 10 >, any one is recorded, is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin.
< 12 > are according to photosensitive polymer combination that in described < 1 > to < 11 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and arbitrary structure with following general formula (1)～general formula (3)
[changing 1]
Figure BDA0000454732150000031
In general formula (1)～general formula (3), R 1～R 11represent independently respectively hydrogen atom or any monovalent organic radical group; X and Y represent independently respectively oxygen atom, sulphur atom or-N (R 12)-; Here, R 12represent hydrogen atom or any monovalent organic radical group; Z represents oxygen atom, sulphur atom ,-N (R 13)-maybe can have substituent phenylene; Here, R 13represent hydrogen atom or any monovalent organic radical group.
< 13 > are according to photosensitive polymer combination that in described < 1 > to < 12 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and aromatic series part shared ratio in described resin is more than 30 quality %.
< 14 > are according to photosensitive polymer combination that in described < 1 > to < 13 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and there is the represented part-structure of following general formula (UB)
[changing 2]
General formula (UB)
Figure BDA0000454732150000041
In general formula (UB), X l1represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-, R u1～R u8represent independently respectively hydrogen atom or substituting group.
< 15 > are according to photosensitive polymer combination that in described < 1 > to < 14 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and there is the represented part-structure of following general formula (UB), aromatic series part shared ratio in described resin of described general formula (UB) is more than 30 quality %
[changing 3]
General formula (UB)
Figure BDA0000454732150000042
In general formula (UB), X l1represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-, R u1～R u8represent independently respectively hydrogen atom or substituting group.
The photosensitive polymer combination that < 16 > record according to described < 14 > or < 15 >, it is characterized in that: in described general formula (UB), R u1～R u8be hydrogen atom.
< 17 > are according to photosensitive polymer combination that in described < 1 > to < 16 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and there is the represented part-structure of following general formula (UNCO)
[changing 4]
General formula (UNCO)
Figure BDA0000454732150000051
In general formula (UNCO), X l1represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-; R u1～R u8represent independently respectively hydrogen atom or substituting group.
The photosensitive polymer combination that < 18 > record according to described < 17 >, is characterized in that: in described general formula (UNCO), and R u1～R u8be hydrogen atom, and X l1for-CH 2-.
The photosensitive polymer combination that < 19 > record according to described < 17 > or < 18 >, is characterized in that: the aromatic series part of described general formula (UNCO) is more than 30 quality % described sour modification containing shared ratio in the polyurethane resin of ethene unsaturated group.
< 20 > are according to photosensitive polymer combination that in described < 1 > to < 19 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and there is the represented part-structure of following general formula (UE1)
[changing 5]
General formula (UE1)
Figure BDA0000454732150000052
In general formula (UE1), L uErepresent bivalence linking base, described bivalence linking base in the key of main chain containing-NHC (=O) O-or-OC (=O) NH-, and there is an ethene unsaturated group or containing the group of ethene unsaturated group as substituting group.
< 21 > are according to photosensitive polymer combination that in described < 1 > to < 20 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and there is the represented part-structure of following general formula (G1)
[changing 6]
General formula (G1)
Figure BDA0000454732150000061
In general formula (G1), R 1～R 3represent independently respectively hydrogen atom or any monovalent organic radical group; A represents the organic residue of divalence; X represent oxygen atom, sulphur atom or-N (R 12)-, R 12represent hydrogen atom or any monovalent organic radical group.
< 22 > are according to photosensitive polymer combination that in described < 1 > to < 21 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has the represented part-structure of following general formula (U1).
[changing 7]
General formula (U1)
Figure BDA0000454732150000062
In general formula (U1), L u1represent not contain the bivalence linking base of ethene unsaturated group and carboxyl.
< 23 > are according to photosensitive polymer combination that in described < 1 > to < 22 >, any one is recorded, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has carboxylic group in polymer ends.
< 24 >, according to the photosensitive polymer combination that in described < 1 > to < 23 >, any one is recorded, is characterized in that: the ethene unsaturated group equivalent of the resin containing ethene unsaturated group of described sour modification is more than 1.00mmol/g.
< 25 > photosensitive film, is characterized in that: the photographic layer on supporter with the photosensitive polymer combination of recording containing any one in good grounds described < 1 > to < 24 >.
< 26 > photonasty laminate, is characterized in that: it is that the photographic layer on matrix with the photosensitive polymer combination of recording containing any one in good grounds described < 1 > to < 24 > forms.
< 27 > permanent pattern forming method, is characterized in that at least comprising: to utilizing, according to the formed photographic layer of photosensitive polymer combination that in described < 1 > to < 24 >, any one is recorded, expose.
< 28 > printed base plate, is characterized in that: it is to utilize the permanent pattern forming method of recording according to described < 27 > to form permanent pattern to form.
According to the present invention, a kind of photosensitive polymer combination, photosensitive film, photonasty laminate, permanent pattern forming method and printed base plate can be provided, described photosensitive polymer combination can make inorganic filler stablize and disperse with high density, be particularly suitable for solder resist etc., can obtain the high performance cured film of the minimizing of development residue or insulativity, flatness, resolution, thermotolerance and developability or transfer printing excellence.
Described and other features of the present invention and advantage will be according to following records and more cheer and bright.
Embodiment
(photosensitive polymer combination)
Photosensitive polymer combination of the present invention (below also referred to as photosensitive composite or composition) is for containing at least respectively the composition for a kind of resin, inorganic filler, ion capturing agent, free radical polymerization monomer, photopolymerization initiator and thermal cross-linking agent containing ethene unsaturated group of sour modification.Photosensitive polymer combination of the present invention can contain spreading agent, elastic body (elastomer) and then other compositions optionally.
The resin containing ethene unsaturated group of sour modification of the present invention is at least having the resin of the sour modification of ethene unsaturated group, and the resin containing ethene unsaturated group of this sour modification can be enumerated following resin.
1) polyurethane resin
2) (methyl) acrylic resin
3) polyether resin
4) phenolic varnish type resin
5) vibrin
6) polyamide or polyimide resin
Wherein, 3) polyether resin and 4) phenolic varnish type resin is the resin by epoxy resin gained.In addition, 2) (methyl) acrylic resin is the general name of the resin that comprises acrylic resin and metha crylic resin.In this instructions, by described 1) resin containing ethene unsaturated group of sour modification is in addition referred to as the non-polyurethane resin containing ethene unsaturated group of sour modification.
In the present invention, the resin containing ethene unsaturated group of sour modification used is acid modified resin, and this sour acidic group can be enumerated carboxyl, sulfo group, phosphate (phospho group), preferably carboxyl.
In addition, ethene unsaturated group can be any group, preferably the represented group of aftermentioned general formula (1)～general formula (3), the more preferably represented group of aftermentioned general formula (1).
Described 1) resin resin in resin～6), preferably 1)～4), particularly preferably 1).
First, the polyurethane resin containing ethene unsaturated group of sour modification is elaborated.
The polyurethane resin > > containing ethene unsaturated group of < < acid modification
There is no particular restriction for the polyurethane resin containing ethene unsaturated group of acid modification, can suitably select according to object, in the present invention, particularly preferably is the sour modification polyurethane resin that contains ethene unsaturated link on side chain.In the present invention, so-called side chain, refer to from form polyurethane resin main chain atom chain top set or be replaced in the atom that forms main chain and the chain linking, what is called contains ethene unsaturated group at side chain, refer to and in this side chain, contain ethene unsaturated group, or ethene unsaturated group is directly replaced on the atom that forms main chain.For example,, only by HOCH 2cH=CHCH 2the glycol of OH and OCN (CH 2) 6the polyurethane resin of the reaction gained of NCO contains ethene unsaturated group on main chain.In addition, utilize the compound containing ethene unsaturated group, the part through end-blocking of polymer ends is not side chain.
In addition, so-called ethene unsaturated group, refers to the group containing ethylenic linkage consuming in the mensuration of bromine number or iodine number, not represents the aromatic group that benzene is such.Ethene unsaturated group preferably can have substituent vinyl.
Below, the preferred content of preferred molecular weight, acid number and ethene unsaturated group equivalent and the photosensitive polymer combination of the polyurethane resin containing ethene unsaturated group of the sour modification of using in the present invention is described.
< < molecular weight > >
There is no particular restriction for the quality mean molecular weight containing the polyurethane resin of ethene unsaturated group of acid modification, can suitably select according to object quality mean molecular weight preferably 3,000～60,000, more preferably 3,000～50,000, particularly preferably 4,000～30,000.In the situation that photosensitive polymer combination of the present invention is used for to photonasty solder resist, if quality mean molecular weight is this kind of scope, the excellent dispersion of inorganic filler, crack resistance and thermotolerance are also excellent, and alkaline-based developer is excellent to the developability of non-image portion.
In addition,, if quality mean molecular weight is too small, the sufficient low elastic modulus in the time of sometimes cannot obtaining the high temperature of cured film, if quality mean molecular weight is excessive, is coated with adaptive and developability is deteriorated sometimes.
Here, described quality mean molecular weight for example can be used efficient gel permeation chromatography (Gel Permeation Chromatography, GPC) (Japan Cao Da incorporated company manufactures device, HLC-802A), by the tetrahydrofuran (Tetrahydrofuran of 0.5 quality %, THF) solution is as sample solution, tubing string is to use a TSKgel HZM-M, and inject the sample of 200 μ L, utilize described THF solution carry out molten from, at 25 ℃, utilize RI-detector or ultraviolet ray (Ultraviolet, UV) detecting device (detection wavelength is 254nm) is measured, according to the molecular weight distribution curve of proofreading and correct through polystyrene standard, obtain quality mean molecular weight.
< < acid number > >
There is no particular restriction for the acid number of the polyurethane resin containing ethene unsaturated group of acid modification, can suitably select according to object, preferred 20mgKOH/g～120mgKOH/g, more preferably 30mgKOH/g～110mgKOH/g, particularly preferably 35mgKOH/g～100mgKOH/g.If acid number is too low, developability becomes insufficient sometimes, otherwise if acid number is too high, developing powder is too high sometimes, so be difficult to control, develops.
Here, acid number is for example to measure according to Japanese Industrial Standards (Japanese Industrial Standards, JIS) K0070.In addition,, in the undissolved situation of sample, use dioxan or tetrahydrofuran etc. as solvent.In addition solid constituent (nonvolatile component) acid number that, acid number is described resin.
< < ethene unsaturated group equivalent > >
There is no particular restriction for the ethene unsaturated group equivalent of the polyurethane resin containing ethene unsaturated group of acid modification, can suitably select according to object, preferred 0.05mmol/g～3.0mmol/g, more preferably 0.5mmol/g～2.7mmol/g, and then preferred 0.75mmol/g～2.5mmol/g, particularly preferably 1.00mmol/g above (preferably 1.00mmol/g～2.5mmol/g).If ethene unsaturated group equivalent is too small, the poor heat resistance of cured film sometimes.
Here, ethene unsaturated group equivalent for example can be obtained by measuring bromine number.Described bromine number for example can be measured according to JIS K2605.
In addition, ethene unsaturated group equivalent is representative is here vinyl equivalent, is by the bromine (Br to mensuration resin 100g addition of gained in described bromine number 2) grams (gBr 2/ 100g) convert the bromine (Br of addition on every 1g resin to 2) the value of molal quantity gained.
The containing ratio > > of < < aromatic series part
In the present invention, the polyurethane resin containing ethene unsaturated group of acid modification preferably aromatic series part shared ratio in this polyurethane resin is more than 30 quality %, more preferably 30 quality %～60 quality %, and then preferably 33 quality %～55 quality %, particularly preferably 35% quality %～50 quality %.If aromatic series part shared ratio in polyurethane resin is too low, the lower hardness of the film after sclerosis sometimes.
Here, aromatic term refers to the such aromatic habitual concept of definition in the strange Advanced Organic Chemistry of the < < horse of document, particularly Jie Ruimaqi (Jerry MARCH) (MARCH'S Advanced Organic Chemistry) > > (the 5th edition, after John Wei Li father and son (John Wiley and Sons), 2001,37 pages).So-called aromatic series, preferably demonstrates aromatic series by hydrocarbon ring and heterocycle, in the present invention, and more preferably hydrocarbon ring.
The quality of described aromatic series part of the present invention refers to the gross mass of the hydrogen atom of bonding on the atom of the skeleton that forms aromatic rings and this atom.In addition, at 2 aromatic rings warp-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-situation of C (=O)-link under, refer to the gross mass of the quality that adds this linking portion.
The field that the situation that so-called 2 aromatic rings link through described concatenating group is for example phenyl ring at 2 aromatic rings, refers to and X represented by following general formula (UB) l1for-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-situation.In addition R, u1～R u8for hydrogen atom or substituting group.
[changing 8]
General formula (UB)
Figure BDA0000454732150000101
For example,, (A) in situation, due to the X of linking part l1for-CH (CH 3)-, therefore adds this-CH (CH 3)-quality.Otherwise, (B) in situation, the X of linking part l1for-C (=O)-O-, it does not meet described X l1regulation, therefore its quality is not added to aromatic series part qualitatively.In addition,, except described concatenating group, the substituting group being replaced on aromatic rings is not added to aromatic series part qualitatively.
Therefore, about the quality of the aromatic series part of (A) situation, the carbon atom of a phenyl ring part is that 6, hydrogen atom are 3, and the carbon atom of linking part is that 2, hydrogen atom are 4, and the carbon atom of another phenyl ring part is that 6, hydrogen atom are 3.As a result, it is that 14, hydrogen atom are the part of 10 that the part of considering as the quality of aromatic series part becomes carbon atom.
On the other hand, (B) in situation, due to do not add-C (=O)-O-part, it is that 12, hydrogen atom are the part of 6 that the part of therefore considering as the quality of aromatic series part becomes carbon atom.
The aromatic series part containing in the polyurethane resin of ethene unsaturated group of acid modification preferably at least has the represented part-structure of described general formula (UB), wherein R preferably u1～R u8be hydrogen atom, and X preferably l1for-CH 2-.
In addition, the containing ratio of the represented part-structure (part-structure of aromatic series part mentioned above) of the described general formula (UB) containing in the polyurethane resin of ethene unsaturated group of sour modification be more than 30 quality % situation more preferably.
The situation of the part-structure that the represented more preferably following general formula of part-structure (UNCO) of this general formula (UB) is represented.
Below, to preferably there is the sour modification polyurethane resin of ethene unsaturated link in the present invention on side chain, describe.
There is no particular restriction on side chain, to have the sour modification polyurethane resin of ethene unsaturated link, can be according to object and suitably select, for example can enumerate at least one the sour modification polyurethane resin having in the represented functional group of following general formula (1)～general formula (3) on its side chain.
[changing 9]
Figure BDA0000454732150000111
In general formula (1)～general formula (3), R 1～R 11represent independently respectively hydrogen atom or any monovalent organic radical group.Here, any monovalent organic radical group can enumerate: halogen atom, alkyl, thiazolinyl, alkynyl, naphthenic base, cycloalkenyl group, aryl, heterocyclic radical, alkoxy, aryloxy group, alkylthio group, arylthio, amino, alkyl amino, arylamino, acyl amino, sulfoamido, alkyl sulphonyl or aryl sulfonyl, alkyl sulphinyl or aryl sulfonyl kia, alkoxy carbonyl, aryloxycarbonyl, acyl group, acyloxy, carbamyl, sulfamoyl, hydroxyl, sulfydryl, cyano group, nitro, carboxyl, sulfo group, urea groups, carbamate groups etc., these groups also can be further replace through the substituting group of these groups.In addition, each following group or the group of any monovalent organic radical in each general formula or substituting group also can be enumerated same group.
R 1preferably hydrogen atom maybe can have substituent alkyl, wherein, and from the high aspect of free radical reaction, more preferably hydrogen atom, methyl.In addition, R 2, R 3, R 4～R 8, R 10and R 11preferred hydrogen atom, halogen atom, amino, carboxyl, alkoxy carbonyl, sulfo group, nitro, cyano group, can there is substituent alkyl, can there is substituent aryl, can there is substituent alkoxy, can there is substituent aryloxy group, can there is substituent alkyl amino, can there is substituent arylamino, can there is substituent alkyl sulphonyl, can there is substituent aryl sulfonyl, wherein, from the high aspect of free radical reaction, more preferably hydrogen atom, carboxyl, alkoxy carbonyl, can there is substituent alkyl, can there is substituent aryl.
R 9preferably hydrogen atom maybe can have substituent alkyl, wherein, and from the high aspect of free radical reaction, more preferably hydrogen atom, methyl.
X and Y represent independently respectively oxygen atom, sulphur atom or-N (R 12)-, R 12represent hydrogen atom or any monovalent organic radical group.R 12preferably can there is substituent alkyl, wherein, from the high aspect of free radical reaction, more preferably hydrogen atom, methyl, ethyl, isopropyl.
Z represents oxygen atom, sulphur atom ,-N (R 13)-maybe can have substituent phenylene.R 13represent hydrogen atom or any monovalent organic radical group.R 13preferably can there is substituent alkyl, wherein, from the high aspect of free radical reaction, more preferably methyl, ethyl, isopropyl.
Here; there is no particular restriction for the substituting group that described each group can have (can have the substituting group having in substituent alkyl etc.); can suitably select according to object; for example can enumerate the group of enumerating in described any monovalent organic radical group, preferably halogen atom, alkyl, thiazolinyl, alkynyl, aryl, alkoxy, aryloxy group, alkylthio group, arylthio, amino, alkyl amino, arylamino, acyl amino, carbamyl, alkoxy carbonyl, alkyl sulphonyl, aryl sulfonyl, carboxyl, sulfo group, nitro, cyano group.
In the represented group of general formula (1)～general formula (3), the represented group of preferred formula (1), from the aspect of crosslinked cured film formative, the preferably R in general formula (1) 1for methyl and R 2and R 3for the group of hydrogen atom, the R in general formula (1) 1～R 3be the group of hydrogen atom, the styryl that the Z in general formula (3) is phenylene, the more preferably R in general formula (1) 1for methyl and R 2and R 3for the group of hydrogen atom, the R in general formula (1) 1～R 3be the group of hydrogen atom, from having formative and the original conservatory aspect of crosslinked cured film concurrently, particularly preferably be the R in general formula (1) 1for methyl and R 2and R 3group for hydrogen atom.Here, the preferred oxygen atom of X in general formula (1), wherein, ethene unsaturated group preferable methyl acryloxy or acryloxy, most preferable acryloxy.
In order to import ethene unsaturated group on side chain, there is following methods: (i) the method that obtains polyurethane resin by the polyreaction with there is the compound of ethene unsaturated group in diisocyanate cpd or diol compound; And (ii) make carboxylic polycarbamate, react with the compound in molecule with epoxy radicals and ethene unsaturated group and obtain the method for polyurethane resin.
Below, by the polyurethane resin by (i) method gained also referred to as polyurethane resin (i), by the polyurethane resin by (ii) method gained also referred to as polyurethane resin (ii).In addition, the so-called polyurethane resin at side chain with ethene unsaturated link, comprise polyurethane resin (i) with polyurethane resin (ii) both.
In the present invention, preferably by the polyurethane resin of (i) method gained (i).
-polyurethane resin (i)-
Polyurethane resin be by diisocyanate cpd and diol compound (compound at least with 2 hydroxyls) react synthesize, polyurethane resin be (i) using the represented diisocyanate cpd of at least one following general formula (4), with the polyurethane resin of the represented structural unit of the reaction product of the represented diol compound of at least one following general formula (5) as basic framework.
OCN-X 0-NCO ... general formula (4)
HO-Y 0-OH ... general formula (5)
In general formula (4) and general formula (5), X 0and Y 0represent independently respectively the organic residue of divalence.
As long as the diol compound that the represented diisocyanate cpd of described general formula (4) or described general formula (5) are represented at least any has at least one in the represented group of described general formula (1)～general formula (3), be created on side chain and imported the polyurethane resin of the represented group of described general formula (1)～general formula (3) as the reaction product of this diisocyanate cpd and this diol compound.According to the method, the situation compared to replacing, import required side chain after reaction at polyurethane resin generates, can more easily be manufactured on the polyurethane resin that has imported the represented group of described general formula (1)～general formula (3) on side chain.
There is no particular restriction for the represented diisocyanate cpd of described general formula (4), can be according to object and suitably select, such as enumerating: make triisocyanate compound and the product etc. that there is the monofunctional alcohol of unsaturated group or the amines of simple function 1 equivalent and carry out addition reaction gained.
There is no particular restriction for described triisocyanate compound, can be according to object and suitably select, and such as enumerating the compound recorded in paragraph [the 0034]～paragraph [0035] of Japanese Patent Laid-Open 2005-250438 communique etc.
Described have the monofunctional alcohol of unsaturated group or the amines of described simple function there is no particular restriction, can be according to object and suitably select, such as enumerating the compound recorded in paragraph [the 0037]～paragraph [0040] of Japanese Patent Laid-Open 2005-250438 communique etc.
Use contains diisocyanate cpd in the method for diisocyanate cpd of ethene unsaturated group on side chain, and there is no particular restriction, can suitably select according to object, can enumerate: can be by making triisocyanate compound and thering is the monofunctional alcohol of unsaturated group or the amines of simple function 1 equivalent carries out the diisocyanate cpd that addition reaction obtains, such as the compound that contains unsaturated group on side chain of recording in paragraph [the 0042]～paragraph [0049] of Japanese Patent Laid-Open 2005-250438 communique etc.
For polyurethane resin (i), from improve with polymerizable composition, polymerizable composition the compatibility of other compositions, improve the viewpoint of storage stability, the diisocyanate cpd beyond the diisocyanate cpd that contains ethene unsaturated group described in also can making carries out copolymerization.
There is no particular restriction for the described diisocyanate cpd that carries out copolymerization, can suitably select according to object, and be for example the represented diisocyanate cpd of following general formula (6).
OCN-L 1-NCO ... general formula (6)
In general formula (6), L 1expression can have substituent divalence aliphatics or aromatic hydrocarbyl.L 1optionally also can there is other functional groups that do not react with isocyanate group, for example ester group, carbamate groups, amide group, urea groups.
There is no particular restriction for the represented diisocyanate cpd of described general formula (6), can suitably select according to object, for example can enumerate: 2,4-toluene diisocyanate, 2, the dipolymer of 4-toluene diisocyanate, 2,6-toluene diisocyanate, P-xylene diisocyanate, m xylene diisocyanate, 4,4'-methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl diphenyl-4, the aromatic diisocyanate compounds as 4'-diisocyanate etc.; Hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, from aliphatic diisocyanate compounds such as amino acid diisocyanate, dimer acid diisocyanates; Isophorone diisocyanate, 4,4'-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1, the alicyclic diisocyanate compounds such as 3-(isocyanates methyl) cyclohexane; Addition product of 1 mole of 1,3-BDO and 2 moles of toluene diisocyanates etc. is as diisocyanate cpd of the reactant of glycol and diisocyanate etc.
The represented diisocyanate cpd (the particularly represented diisocyanate cpd of general formula (6)) of general formula (4) or general formula (6) is use variety classes capable of being combined also, from improving the aspect of folding resistance, preferably at least one is aromatic diisocyanate cpd.Aromatic diisocyanate cpd for example preferably has the diisocyanate cpd of the skeleton of bisphenol A-type, Bisphenol F type, biphenyl type, naphthalene type, luxuriant and rich with fragrance type or anthracene type, the diisocyanate cpd more preferably with the skeleton of bisphenol A-type or Bisphenol F type, most preferably has the diisocyanate cpd of Bisphenol F type skeleton.
These various types of skeletons are represented by following general formula.
[changing 10]
Figure BDA0000454732150000151
In described skeleton, R a, R brepresent independently respectively substituting group, the alkyl that the preferred carbon number of substituting group is 2～5.L 1and l 2represent independently respectively 0～4 integer.L 1and l 2preferably 0 or 1.L 3represent 0～6 integer.L 4represent 0～8 integer.L 3preferably 0～2, l 4preferably 0 or 2.Work as l 1～l 4be 2 when above, a plurality of R a, R bcan be mutually the same also can be different.
From suppressing the warpage sclerosis, improve the viewpoint of folding resistance, described diisocyanate cpd is more preferably by aromatic diisocyanate cpd and the combination of aliphatic diisocyanate cpd.Aromatic diisocyanate cpd for example preferably has the diisocyanate cpd of the skeleton of bisphenol A-type, Bisphenol F type, biphenyl type, naphthalene type, luxuriant and rich with fragrance type or anthracene type, more preferably has the diisocyanate cpd of the skeleton of bisphenol A-type or Bisphenol F type.Aliphatic diisocyanate cpd for example preferably hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, from amino acid diisocyanate, dimer acid diisocyanate, more preferably hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate.
Described diisocyanate cpd is the represented compound of following general formula (UB1) particularly preferably, thereby the polyurethane resin of gained has the part-structure of general formula (UNCO).
[changing 11]
Figure BDA0000454732150000161
In general formula (UB1) and general formula (UNCO), X l1represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-, R u1～R u8represent independently respectively hydrogen atom or substituting group.
There is no particular restriction for the represented diol compound of described general formula (5), can suitably select according to object, such as enumerating PTMEG compound, polyester-diol compound, PCDL compound etc.
Here, on the side chain of polyurethane resin, import the method for ethene unsaturated group except method mentioned above, preferably following methods: use the diol compound that contains ethene unsaturated group on side chain to be used as manufacturing the raw material of polyurethane resin.The described diol compound that contains ethene unsaturated group at side chain for example can be the such commercially available product of trimethylolpropane monoallyl ether, also can be following compound: the compound of manufacturing that reacts by compounds such as halogenation diol compound, three alcoholic compounds, aminodiol compounds with compounds such as the carboxylic acid that contains unsaturated group, acyl chlorides compound, isocyanates, alcohol, amine, mercaptan, halogenated alkyl compounds.
The represented compound of the preferred following general formula of this diol compound that contains ethene unsaturated group (UE), thus the represented part-structure of following general formula (UE1) in polyurethane resin, there is.
[changing 12]
Figure BDA0000454732150000171
In general formula (UE), general formula (UE1), L uErepresent bivalence linking base, this bivalence linking base in the key of main chain containing-NHC (=O) O-or-OC (=O) NH-, and on side chain, there is an ethene unsaturated group.
L uEpreferably will be in the shortest marriage chain of 2 hydroxyls (HO yl) bonding containing aromatic rings, aliphatic divalent group that more preferably can contain in the shortest marriage chain-O-,-S-, and then preferably aliphatic divalent group, particularly preferably alkylidene.In addition, by the carbon number in the shortest marriage chain of 2 hydroxyls (HO yl) bonding preferably 2～12, more preferably 2～6, and then preferably 2～4, most preferably 2.L uEbivalence linking base there is an ethene unsaturated group as substituting group, in addition, also can there is the not substituting group of ethene unsaturated group, this substituting group can be enumerated the R of described general formula (1)～general formula (3) 1～R 11in any monovalent organic radical group that enumerates.
In the present invention, in the situation that be the represented group of described general formula (1) containing the group of ethene unsaturated group, preferably at L uEmain chain on to there is the alkoxy carbonyl of hydroxyl or acyl group, be not bonded to the situation on α position or β position.
The represented compound of the preferred following general formula of compound (UE-1)～general formula (UE-6) that general formula (UE) is represented.In addition, the represented compound of following general formula (UE-7) is preferred compound except the represented compound of described general formula (UE).
[changing 13]
Figure BDA0000454732150000181
In general formula (UE-1)～general formula (UE-7), E 1represent singly-bound or bivalence linking base (the organic residue of divalence), E 2represent singly-bound or-CH 2-bivalence linking base in addition.A represents bivalence linking base.Q represents arbitrary group of described general formula (1)～general formula (3).E 1, E 2bivalence linking base for example can enumerate :-O-,-S-,-OCH (CH 2-Q) CH 2-,-CO 2-CH 2-,-OCH 2c (CH 2-Q) 2cH 2-,-O-CONHCH 2cH 2-,-OC (=O)-,-CONHCH 2cH 2-,-CH 2c (CH 2-Q) 2cH 2-,-CH 2-,-NHCONHCH 2cH 2-,-NHCH (CH 2-Q) CH 2-,-NCH (CH 2-Q) CH 2-,-NHCH 2c (CH 2-Q) 2cH 2-,-NH-CH (CH 2-Q) CH 2-,-C (=O)-,-CO 2-CH 2cH 2-,-CO 2-CH 2cH 2cH 2-etc.In addition, Q represents arbitrary group of general formula (1)～general formula (3) here.
These concrete compounds can be enumerated the compound of recording in paragraph " the 0057 "～paragraph " 0060 " of Japanese Patent Laid-Open 2005-250438 communique.
In the represented compound of described general formula (UE-1)～general formula (UE-7), the represented compound of preferred described general formula (UE-1)～general formula (UE-6), the more preferably represented compound of described general formula (UE-6).In addition, in the represented compound of general formula (UE-6), the represented compound of following general formula (G) particularly preferably.In addition, the represented compound of general formula (G) becomes the represented part-structure of following general formula (G1) in polyurethane resin.
[changing 14]
Figure BDA0000454732150000191
In general formula (G), general formula (G1), R 1～R 3represent independently respectively hydrogen atom or any monovalent organic radical group, A represents the organic residue of divalence, X represent oxygen atom, sulphur atom or-N (R 12)-, R 12represent hydrogen atom or any monovalent organic radical group.
In addition the R in described general formula (G), general formula (G1), 1～R 3and the R in X and described general formula (1) 1～R 3and X is identical meanings, preferred aspects is also identical in addition.
The represented compound of general formula (G) can be enumerated the compound of recording in paragraph [the 0064]～paragraph [0066] of Japanese Patent Laid-Open 2005-250438 communique, is preferred in the present invention.
It is generally acknowledged, by use, derive from the polyurethane resin of the represented diol compound of described general formula (G), can be by the inhibition to the superfluous molecular motion of the main polymer chain being caused by the large secondary alcohol of steric hindrance, reach layer by the raising of film strength.
Polyurethane resin of the present invention is (i) sour modification, and the definition of the sour modification here represents that the polymkeric substance of this polyurethane resin has acidic group.There is no particular restriction for the acidic group here, can enumerate carboxyl, sulfo group etc.From the viewpoint of developability, preferably there is carboxyl.Preferably by carrying out sour modification with the diol compound with carboxyl at synthetic polyurethane resin (i) time.The described diol compound with carboxyl for example comprises the compound shown in following general formula (17)～general formula (19).
[changing 15]
Figure BDA0000454732150000201
In general formula (17)～general formula (19), R 15for example, as long as represent that hydrogen atom maybe can have substituting group and (comprise cyano group, nitro ,-F ,-Cl ,-the Br ,-halogen atoms such as I ,-CONH 2,-COOR 16,-OR 16,-NHCONHR 16,-NHCOOR 16,-NHCOR 16,-OCONHR 16(R here, 16represent the alkyl of carbon number 1～10 or the aralkyl of carbon number 7～15) etc. each group) alkyl, aralkyl, aryl, alkoxy, aryloxy group, there is no particular restriction, can be according to object and suitably select, the preferred aryl of 6～15 of alkyl, the carbon numbers of 1～8 of hydrogen atoms, carbon number.
In general formula (17)～general formula (19), L 9, L 10, L 11can distinguish identical also can be different, need only the divalence aliphatics or the aromatic hydrocarbyl that represent singly-bound, can there is substituting group (for example preferred alkyl, aralkyl, aryl, alkoxy, halogen atom), there is no particular restriction, can suitably select according to object, the preferred arlydene of 6～15 of alkylidene, the carbon numbers of 1～20 of carbon numbers, the more preferably alkylidene of 1～8 of carbon numbers.In addition, optionally also can be at described L 9～L 11in there are other functional groups that do not react with isocyanate group, for example can there is carbonyl, ester group, carbamate groups, amide group, urea groups, ether.In addition, also can be by described R 15, L 9, L 10, L 11in 2 or 3 form ring.
In general formula (18), Ar is as long as represent to have substituent trivalent aromatic hydrocarbyl, and there is no particular restriction, can suitably select according to object the aromatic series base that preferred carbon number is 6～15.
There is no particular restriction for the represented diol compound with carboxyl of described general formula (17)～general formula (19), can suitably select according to object, for example can enumerate: 3,5-dihydroxy-benzoic acid, 2, two (hydroxymethyl) propionic acid, 2 of 2-, two (2-hydroxyethyl) propionic acid, 2 of 2-, two (3-hydroxypropyl) propionic acid of 2-, two (hydroxymethyl) acetic acid, two (4-hydroxy phenyl) acetic acid, 2, two (hydroxymethyl) butyric acid, 4 of 2-, two (4-hydroxy phenyl) valeric acids of 4-, tartrate, N, N-dihydroxyethylglycin, N, two (2-the hydroxyethyl)-3-carboxyl-propionamides of N-etc.These compounds can be used, or two or more may be used separately.
There is no particular restriction to have the diol compound of carboxyl, can suitably select according to object, such as enumerating the compound recorded in the paragraph [0047] of Japanese Patent Laid-Open 2007-2030 communique etc.
By there being this carboxyl, can give to polyurethane resin the characteristics such as hydrogen bonding and alkali-soluble, therefore preferably.By importing like this carboxyl, acid number can be adjusted in the present invention as above in preferred scope.
By there being this carboxyl, can give to polyurethane resin the characteristics such as hydrogen bonding and alkali-soluble, therefore preferably.By importing like this carboxyl, acid number can be adjusted in the present invention as above in preferred scope.
In addition, while synthesizing the polyurethane resin that contains ethene unsaturated link on side chain, except described diol compound, also can be used together the compound that utilizes diol compound to make tetracarboxylic dianhydride's open loop gained.
There is no particular restriction to utilize diol compound to make the compound of described tetracarboxylic dianhydride's open loop gained, can be according to object and suitably select, such as enumerating the compound recorded in paragraph [the 0095]～paragraph [0101] of Japanese Patent Laid-Open 2005-250438 communique etc.
For polyurethane resin (i), for example the compatibility of other compositions from raising and polymerizable composition, polymerizable composition is, improve the viewpoint of storage stability, can make the diol compound copolymerization except the described diol compound that contains the diol compound of ethene unsaturated group or contain carboxyl on side chain, in the present invention, particularly preferably be and make this diol compound copolymerization.
There is no particular restriction for this diol compound, can be according to object and suitably select, such as enumerating: low molecular diol compound or as the polycarbonate compound of the PTMEG compound of polymer diol compound, polyester-diol compound, PCDL compound, Meta-dihydroxybenzene etc.
This diol compound means as following general formula (U), if group enters polyurethane resin, is represented by the represented part-structure of following general formula (U1).
[changing 16]
Figure BDA0000454732150000211
In general formula (U) and general formula (U1), L u1represent not contain the bivalence linking base of ethene unsaturated group and carboxyl.
L u1for example can enumerate alkylidene, arlydene, divalent heterocycle, this alkylidene also can contain in the chain of alkylidene-O-,-OCOO-, phenylene, carbon-to-carbon double bond, carbon-to-carbon triple bond ,-OCO-Z 1-COO-(Z 1represent alkylidene, alkenylene, arlydene).
In the represented diol compound of general formula (U), the low molecular diol compound compound that preferably quality mean molecular weight is less than 400, such as enumerating the compound recorded in the paragraph [0048] of Japanese Patent Laid-Open 2007-2030 communique etc.
In the present invention, preferred polymers diol compound, below will describe in detail.
-polymer diol compound-
There is no particular restriction for described polymer diol compound, can suitably select according to object, such as enumerating: PTMEG classes such as the segmented copolymer of the segmented copolymer of polyglycol, polypropylene glycol, polyethylene oxide, polypropyleneoxide, ethylene oxide/propylene oxide or random copolymers, polytetramethylene glycol, tetramethylene glycol and neopentyl glycol or random copolymerss; Polyester-diol class as the condensation product of the polyprotonic acids such as polyvalent alcohol or PTMEG and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, hexane diacid, terephthalic acid (TPA), m-phthalic acid; Reacting or making phosgene (phosgene) act on the PCDL class of the gained such as reaction of glycol or bis-phenol under the existence of alkali by glycol or bis-phenol and carbonic ester; Polybutadiene based polymer glycol, the silicone-based polymer diols etc. such as the caprolactone modification polymer diols such as caprolactone modification polytetramethylene glycol, polyolefin polymer diol, hydrogenated butadiene polymer glycol.These compounds can be used separately, or and with two or more.
In addition, in the present invention in preferred compound or part-structure, the L in described general formula (U), general formula (U1) u1for-(CH 2cH 2o)n u1cH 2cH 2-,-[CH 2cH (CH 3) O] n u1-CH 2cH (CH 3)-,-(CH2CH2CH2O) nU1-CH2CH2CH2-,-[(CH 2) n u2-OC (=O)-(CH 2) n u3-C (=O) O] n u4-O (CH 2) n u2-or-[(CH 2) n u5-OC (=O) O] n u6-(CH 2) n u7-.Here, n u1～n u7represent independently respectively more than 1 number.N u1～n u7the preferred number below 1000, more preferably below 500, and then the preferred number below 100.
In addition, the also preferred represented diol compound of aftermentioned general formula (III-1)～general formula (III-6) of the represented compound of general formula (U).
There is no particular restriction for described PTMEG compound, can be according to object and suitably select, and such as enumerating the compound recorded in paragraph [the 0068]～paragraph [0076] of Japanese Patent Laid-Open 2005-250438 communique etc.
There is no particular restriction for described polyester-diol compound, can suitably select according to object, such as enumerating: the compound of recording in the No.1～No.8 in the paragraph of Japanese Patent Laid-Open 2005-250438 communique [0077]～paragraph [0079], paragraph [0083]～paragraph [0085] and No.13～No.18 etc.
There is no particular restriction for described PCDL compound, can be according to object and suitably select, such as enumerating the compound recorded in paragraph [the 0080]～paragraph [0081] of Japanese Patent Laid-Open 2005-250438 communique and the No.9～No.12 in paragraph [0084] etc.
In addition, except described diol compound, also can be used together and there is the substituent diol compound not reacting with isocyanate group.
Described have the substituent diol compound not reacting with isocyanate group there is no particular restriction, can be according to object and suitably select, such as enumerating the compound recorded in paragraph [the 0087]～paragraph [0088] of Japanese Patent Laid-Open 2005-250438 communique etc.
The quality mean molecular weight of this polymer diol compound preferably 400～8,000, more preferably 500～5,000, and then preferably 600～3,000, particularly preferably 800～2,000.If quality mean molecular weight is less than 400, sometimes cannot fully obtain folding resistance, if quality mean molecular weight surpasses 8,000, the glass transition temperature (Tg) of the polyurethane resin of gained is too low, therefore insulating reliability reduces sometimes.
Here, quality mean molecular weight for example can be used efficient GPC device, and (Japan Cao Da incorporated company manufactures, HLC-802A), using the THF solution of 0.5 quality % as sample solution, tubing string is to use a TSKgel HZM-M, and inject the sample of 200 μ L, utilize described THF solution carry out molten from, at 25 ℃, utilize RI-detector or UV detecting device (detection wavelength is 254nm) to measure.
Acid modification containing in the polyurethane resin of ethene unsaturated group, the quality ratio of the part-structure that described general formula (U1) is represented preferably 10%～60%, more preferably 20%～60%, and then preferably 25%～55%, and then more preferably 30%～50%.If described quality ratio is less than 10%, be sometimes difficult to suppress the warpage after sclerosis, if described quality ratio surpasses 60%, the sensitivity of photo-hardening excessively reduces and resolution deteriorates sometimes.
In addition, the polyurethane resin that contains ethene unsaturated link on side chain using in the present invention also can suitably be used the resin on polymer ends, main chain with unsaturated group.By there is unsaturated group on polymer ends, main chain, and have between the polyurethane resin that further contains ethene unsaturated link at photosensitive polymer combination and on side chain or on side chain between the polyurethane resin of ethene unsaturated link, improve cross-linking reaction, thereby photo-hardening thing intensity increases.Here, from easily causing the aspect of cross-linking reaction, unsaturated group particularly preferably is has carbon-to-carbon double bond.
The method that imports unsaturated group in polymer ends has method shown below.; as long as in the operation that the remaining isocyanate group that utilizes polymer ends in the synthesis procedure of the described polyurethane resin that contains ethene unsaturated link on side chain and alcohols or amine etc. are processed, use has the alcohols of unsaturated group or amine etc.This compound specifically can be enumerated the compound identical with the exemplary compounds of above enumerating as having the monofunctional alcohol of unsaturated group or the amines of simple function.
In addition, calm import volume easy to control and can increase import volume, viewpoint that in addition cross-linking reaction efficiency improves, is directed into unsaturated group on polymer lateral chain, to be better than being directed into polymer ends.
There is no particular restriction for the unsaturated bonding base of ethene importing; can suitably select according to object; aspect from crosslinked cured film formative; preferable methyl acryloyl group, acryloyl group, styryl; more preferably methacryl, acryloyl group; from having formative and original conservatory aspect, the particularly preferably methacryl of crosslinked cured film concurrently.
In addition; there is no particular restriction for the import volume of methacryl; can suitably select according to object; preferred 0.05mmol/g～the 3.0mmol/g of ethene unsaturated group equivalent; more preferably 0.5mmol/g～2.7mmol/g; and then preferred 0.75mmol/g～2.5mmol/g, particularly preferably 1.00mmol/g above (preferably 1.00mmol/g～2.5mmol/g).
The method that imports unsaturated group on main chain has and will in main chain direction, have the diol compound of unsaturated group for the synthesis of the method for polyurethane resin.There is no particular restriction for the described diol compound in main chain direction with unsaturated group, can suitably select according to object, such as enumerating: cis-2-butene-Isosorbide-5-Nitrae-glycol, trans-2-butene-Isosorbide-5-Nitrae-glycol, polybutadiene diol etc.
In the present invention, aspect from alkaline-based developer to the developability excellence of non-image portion, the sour modification polyurethane resin that contains ethene unsaturated link on side chain using in the present invention also can be used the resin at the end of main polymer chain with at least 1 carboxyl suitably.End at main polymer chain has at least 1 carboxyl, preferably has 2 above, 5 following carboxyls, and the aspect from developability excellence, fine pattern formative, particularly preferably is and has 2 carboxyls.
In addition, the end of the main chain of described polyurethane resin has 2 carboxyls, preferably at single end, has at least 1 carboxyl, also can have at least 1 carboxyl at two ends.
Preferably the end at the main chain of described polyurethane resin has the represented structure of following general formula (AD).
General formula (AD)
-L 100-(COOH) n
In general formula (AD), L 100the organic coupling chain that represents (n+1) valency, n represents more than 1 integer, preferably 1～5, particularly preferably 2.
L 100represented organic concatenating group is to comprise to be more than onely selected from the atom in carbon atom, hydrogen atom, oxygen atom, nitrogen-atoms and sulphur atom and to form, and specifically, forms L 100the atomicity of the main framing of represented organic concatenating group preferably 1～30, more preferably 1～25, and then preferably 1～20, particularly preferably 1～10.
In addition, so-called described " main framing of organic concatenating group ", refer to be only used for atom or atomic group that the main chain of described polyurethane resin and end COOH are linked, in the situation that having many to link path, refer to atom or the atomic group in the path that atomicity that formation used is minimum.
There is no particular restriction at the end of the main chain of described polyurethane resin, to import the method for at least 1 carboxyl, can be according to object and suitably select, such as enumerating: use the carboxylic acid compound with at least 1 carboxyl to be used as manufacturing the method etc. of the raw material of polyurethane resin.
Described carboxylic acid compound can be enumerated: have 1 carboxyl monocarboxylic acid compound, have 2 carboxyls dicarboxylic acid compound, have 3 carboxyls tricarboxylic acids compound, have 4 carboxyls tetracarboxylic compound, there is the pentacarboxylic acid compound of 5 carboxyls etc.In these compounds, from the aspect of developability excellence, fine pattern formative, particularly preferably there is the dicarboxylic acid compound of 2 carboxyls.
As long as described carboxylic acid compound has at least 1 carboxyl, there is no particular restriction, can suitably select according to object, and suitable is the represented compound of following general formula (ADH).
General formula (ADH)
H-O-L 200-Y 100-L 100-(COOH)n
In general formula (ADH), L 100and n represents the implication identical with described general formula (AD).Y 100represent atom more than divalence.L 200represent that singly-bound maybe can have substituent alkylidene.
Y 100divalence more than atom such as enumerating oxygen atom, nitrogen-atoms, carbon atom, silicon atom etc.In these, particularly preferably nitrogen-atoms, carbon atom.Here, so-called Y 100represented atom is more than divalence, refers at least Y 100there is end-COOH via L 100and L 200and 2 associative keys of bonding, Y 100also can have more hydrogen atom or substituting group.
Can import to Y 100on substituting group can enumerate: comprise the substituting group that is selected from the atom in hydrogen atom, oxygen atom, sulphur atom, nitrogen-atoms and halogen atom and forms.In these substituting groups, the alkyl of preferred carbon number 1～50, the more preferably alkyl of carbon number 1～40, the particularly preferably alkyl of carbon number 1～30.
L 200the alkylidene of the preferred carbon number 1～20 of alkylidene, the more preferably alkylidene of carbon number 2～10.Can import to substituting group on described alkylidene such as enumerating: halogen atom (F ,-Br ,-Cl ,-I), can there is substituent alkyl etc.
There is no particular restriction for the represented carboxylic acid compound of described general formula (ADH), can be according to object and suitably select, and such as the reactant etc. that can enumerate lactic acid, malic acid, hydroxycaproic acid, citric acid, diol compound and acid anhydrides.These compounds can be used separately, also can be used together two or more.In these compounds, malic acid particularly preferably.
The polyurethane resin using in the present invention concrete example is (i) such as enumerating the polymkeric substance of the P-1～P-31 shown in paragraph [the 0293]～paragraph [0310] of Japanese Patent Laid-Open 2005-250438 communique etc.In these polymkeric substance, the P-27 shown in preferred paragraph [0308] and paragraph [0309] and the polymkeric substance of P-28.
The polyurethane resin that contains ethene unsaturated link on side chain using in the present invention is to synthesize in the following manner: described diisocyanate cpd and diol compound are added to well-known catalyzer corresponding to reactivity active and separately in non-protonic solvent, and heat.For the synthesis of diisocyanate and the mol ratio (M of diol compound a: M b) there is no particular restriction, can suitably select according to object, preferably 1:1～1.2:1, by utilizing alcohols or amine etc. to process, can carry out with the final not form of remaining isocyanate group the product of the required physical property such as synthetic molecular weight or viscosity.
The polyurethane resin that contains ethene unsaturated link on side chain using in the present invention has the carboxylic acid of 2 hydroxyls in particularly preferably being and making diisocyanate cpd mentioned above and have (methyl) acrylate compounds, molecule of 2 hydroxyls in molecule as diol compound and polymer diol compound mentioned above reacts and obtains, in addition, preferably make the represented compound reaction with 1 hydroxyl and carboxyl of general formula (ADH) and obtain.
-polyurethane resin (ii)-
Polyurethane resin is (ii) carboxylic polycarbamate to be reacted and the polyurethane resin that obtains with the compound in molecule with epoxy radicals and ethene unsaturated group.
Polyurethane resin be (ii) make to using diisocyanate and carboxylic glycol as carboxylic polyurethane resin that must composition, react with the compound in molecule with epoxy radicals and ethene unsaturated group and the polyurethane resin that obtains.According to object, the low-molecular-weight diol that also can add quality mean molecular weight as diol component and be low-molecular-weight diol below 300 or quality mean molecular weight and be and be more than 500 is used as copolymerization composition.
By using polyurethane resin (ii), excellent with stable dispersiveness, crack resistance or the resistance to impact of inorganic filler, so thermotolerance, humidity resistance, adhesion, mechanical property, electrical characteristics improve.
In addition, described polyurethane resin (ii) also can be following reactant: using can have substituent divalence aliphatics and aromatic hydrocarbon diisocyanate, with any and the carboxylic glycol with COOH base and 2 OH bases via C atom and the N atom reactant as essential composition, and react with the compound in molecule via-COO-key with epoxy radicals and ethene unsaturated group the compound obtaining for the reactant that makes gained.
In addition, described polyurethane resin (ii) also can be following reactant: using the represented diisocyanate of following general formula (1), be selected from polyurethane resin mentioned above (i) at least one in the represented carboxylic diol compound of general formula (17)～general formula (19) of explanation as essential composition, and the reactant of at least one depending on object and with being selected from following general formula (III-1)～general formula (III-6) in the represented quality mean molecular weight macromolecule diol in 800～3,000 scope; And be the reactant that makes gained, the compound that reacts gained with the compound that contains epoxy radicals and ethene unsaturated group in the represented molecule of following general formula (IV-1)～general formula (IV-16).
OCN-R1-NCO general formula (1)
In general formula (1), R 1expression can have divalence aliphatics or the aromatic alkyl of substituting group (for example preferred alkyl, aralkyl, aryl, alkoxy and halogen atom any).R 1optionally also can there are other functional groups that do not react with isocyanate group, for example any of ester group, carbamate groups, amide group, urea groups.
[changing 17]
Figure BDA0000454732150000281
In general formula (III-1)～general formula (III-3), R 7～R 11represent independently respectively divalence aliphatics or aromatic alkyl.R 7, R 9, R 10and R 11the arlydene of 6～15 of the alkylidene of 2～20 of preferred carbon numbers or carbon numbers respectively, the more preferably arlydene of 6～10 of the alkylidene of 2～10 of carbon numbers or carbon numbers.R 8the arlydene that represents 6～15 of the alkylidene of 1～20 of carbon numbers or carbon numbers, the more preferably arlydene of 6～10 of the alkylidene of 1～10 of carbon numbers or carbon numbers.In addition, R 7～R 11in also can there are other functional groups that do not react with isocyanate group, such as ether, carbonyl, ester group, cyano group, alkylene, carbamate groups, amide group, urea groups or halogen atom etc.
In general formula (III-4), R 12represent hydrogen atom, alkyl, aryl, aralkyl, cyano group or halogen atom.Preferably aralkyl, cyano group or the halogen atom of 7～15 of aryl, the carbon numbers of 6～15 of alkyl, the carbon numbers of 1～10 of hydrogen atoms, carbon number, the more preferably aryl of 6～10 of the alkyl of 1～6 of hydrogen atoms, carbon number and carbon numbers.In addition, R 12in also can there are other functional groups that do not react with isocyanate group, such as alkoxy, carbonyl, alkylene, ester group or halogen atom etc.M represents 2～4 integer.
In general formula (III-5), R 13represent aryl or cyano group, aryl or cyano group that preferred carbon number is 6～10.
In addition, in described general formula (III-1)～general formula (III-6), n 1, n 2, n 3, n 4, n 5, n 7, n 8and n 9represent respectively more than 2 numbers, preferably 2～100 number.In described general formula (III-5), n 6represent more than 0 or 2 numbers, preferably 0 or 2～100 number.
[changing 18]
Figure BDA0000454732150000291
[changing 19]
Figure BDA0000454732150000301
In general formula (IV-1)～general formula (IV-16), R 14represent hydrogen atom or methyl, R 15the alkylidene that represents carbon number 1～10, R 16the alkyl that represents carbon number 1～10.P represents 0 or 1～10 number.
In addition,, in the situation that carboxylic polycarbamate is reacted with the compound in molecule with epoxy radicals or oxetanyl, become have-CO in the part-structure of X, Y or Z and the link of polycarbamate main chain 2the structure of-(hydroxyl or acyloxy are replaced in the aliphatic group forming on β position or γ position)-(*).Here, in (*) side, there is the part-structure of general formula (1)～general formula (3).
In addition, described polyurethane resin (ii) also can further make not carboxylic low molecular weight diols as the 5th composition and copolymerization, this low molecular weight diols compound is that (III-6) is represented by described general formula (III-1)～general formula, and quality mean molecular weight is below 500.This not carboxylic low molecular weight diols can not make alkali dissolubility reduce, can fully guarantee in addition to add in the scope of elastic modulus of cured film.
Described low molecular weight diols compound is such as enumerating the compound recorded in the paragraph [0048] of Japanese Patent Laid-Open 2007-2030 communique etc.
Described polyurethane resin is (ii) specially suitable is that acid number is the alkali-soluble photocrosslinking reaction polyurethane resin of 20mgKOH/g～120mgKOH/g, this alkali-soluble photocrosslinking reaction polyurethane resin is compound and the following reactant reaction gained that further makes to have in any represented molecule of general formula (IV-1)～general formula (IV-16) 1 epoxy radicals and at least 1 (methyl) acrylic, described reactant is with the represented diisocyanate of described general formula (1), and be selected from least one in the represented carboxylic glycol of general formula mentioned above (17)～general formula (19) as essential composition, and the quality mean molecular weight represented depending on object and with being selected from general formula (III-1)～general formula (III-6) is 800～3, at least one in macromolecule diol in 000 scope, or the represented quality mean molecular weight of general formula (III-1)～general formula (III-6) is the reactant of the not carboxylic low molecular weight diols below 500.
In addition, described polyurethane resin (ii) in, also preferably replace the represented compound of described general formula (III-1)～general formula (III-6) and use or use in the lump polyurethane resin mentioned above (i) in the represented diol compound of general formula (U) of explanation, the quality ratio of the part-structure that the described general formula (U1) containing in the polyurethane resin of ethene unsaturated group of sour modification is represented is identical with polyurethane resin mentioned above situation (i).
These macromolecular compounds can be used, or two or more may be used separately.
In addition, polyurethane resin (ii) in, also preferably at the end of main polymer chain, there is at least 1 carboxyl, to obtain and (i) identical effect of polyurethane resin, preferably polyurethane resin (i) in end-capped method or the represented group of general formula (A) of main polymer chain as explanation, preferable range is also (i) identical with polyurethane resin.
Described polyurethane resin (ii) for example can be enumerated: by the U1～U4 shown in the paragraph of Japanese Patent Laid-Open 2007-2030 communique [0314]～paragraph [0315], conduct in the polymkeric substance of U6～U11 is containing the glycidyl acrylate of the compound of epoxy radicals and vinyl, change glycidyl methacrylate into, acrylic acid-3, 4-epoxycyclohexyl methyl esters (trade name: plug Crow horse (Cyclomer) A400, the chemical incorporated company of Daicel (Daicel) manufactures), methacrylic acid-3, 4-epoxycyclohexyl methyl esters (trade name: plug Crow horse (Cyclomer) M400, the manufacture of Daicel chemistry incorporated company) polymkeric substance forming etc.
-make synthetic method (ii) of carboxylic polycarbamate reacts gained polyurethane resin with the compound in molecule with epoxy radicals and ethene unsaturated group-
About described polyurethane resin synthetic method (ii), come in the following manner to synthesize polyurethane resin (ii): described diisocyanate cpd and diol compound are added to well-known catalyzer corresponding to reactivity active and separately in non-protonic solvent, and heat.The diisocyanate using and the preferred 0.8:1～1.2:1 of the mol ratio of diol compound, the in the situation that of the remaining isocyanate group of polymer ends, by processing with alcohols or amine etc., and synthesize polyurethane resin (ii) with the final not form of remaining isocyanate group.
The content > > of the polyurethane resin containing ethene unsaturated group of < < acid modification
Photosensitive polymer combination of the present invention except sour modification containing the polyurethane resin of ethene unsaturated group, also can be used together alkali-soluble macromolecule, this alkali-soluble macromolecule comprises the polyurethane resin with the structure different from the polyurethane resin containing ethene unsaturated group of sour modification.For example, can be together with the described polyurethane resin that contains ethene unsaturated link on side chain and and be used in the polyurethane resin that contains aromatic series base on main chain and/or side chain.
There is no particular restriction for the content of the polyurethane resin containing ethene unsaturated group of the sour modification in the solid constituent of photosensitive polymer combination of the present invention, can suitably select according to object, preferred 5 quality %～80 quality %, more preferably 20 quality %～75 quality %, particularly preferably 30 quality %～70 quality %.
If described content is too low, sometimes cannot keep folding resistance good, otherwise if described too high levels, thermotolerance is impaired sometimes.If described content in described scope, have concurrently good folding resistance and stable on heating aspect favourable.
(methyl) acrylic resin > > that < < contains acidic group and ethene unsaturated group
The preferred carboxyl of acidic group, the preferred acryloyl group of ethene unsaturated group, methacryl, allyl, vinyl ether group, ethenylphenyl.
Aspect from excellent heat resistance, (methyl) acrylic resin that contains acidic group and ethene unsaturated group is following modified copolymer (being sometimes referred to as below " modified copolymer ") preferably, and described modified copolymer is the compound that makes to contain epoxy radicals and ethene unsaturated group in molecule, obtains with a part of acid-base reaction of multipolymer (being sometimes referred to as below " multipolymer ") by (methyl) acrylate and the compound gained that contains ethene unsaturated group and contain at least 1 acidic group.In addition, as described above, so-called (methyl) acrylate, refers to acrylate and/or methacrylate.
Below, the raw material of described each reaction is illustrated.
-(methyl) acrylate-
Described (methyl) acrylate is such as enumerating: (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate; (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, own Inner ester modified (methyl) acrylic acid-2-hydroxyl ethyl ester etc. have (methyl) esters of acrylic acid of hydroxyl; (methyl) esters of acrylic acids such as (methyl) benzyl acrylate, methoxyl diethylene glycol (methyl) acrylate, ethoxy diethylene glycol (methyl) acrylate, different octyloxy diethylene glycol (methyl) acrylate, phenoxy group triethylene glycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate etc.In these (methyl) acrylate, from the aspect of low water absorbable, preferred (methyl) benzyl acrylate.
-contain ethene unsaturated group and contain at least 1 acidic group compound-
The described compound that contains ethene unsaturated group and contain at least 1 acidic group is such as enumerating: acrylic acid, methacrylic acid, vinylphenol, between ethene unsaturated group and carboxyl through modification unsaturated monocarboxylic of chain elongation etc.
Here, modification unsaturated monocarboxylic is such as enumerating: (methyl) senecioate-carboxyl ethyl ester, 2-acryloxy ethyl succinic acid, 2-acryloxy ethyl phthalic acid, 2-acryloxy ethyl hexahydrophthalic acid, interior ester modified etc. the unsaturated monocarboxylic with ester bond, have the modification unsaturated monocarboxylic of ehter bond etc.
These compounds can be used, or two or more may be used separately.
Except described compound, also can be further with (methyl) acrylate and/or (methyl) acrylic acid copolymerization in further carry out copolymerization with the monomer that contains ethene unsaturated group.This monomer can be enumerated: the styrene that (methyl) acrylamide, (methyl) vinyl cyanide, styrene, sulfo group or carboxyl substituted form on phenyl ring, vinyl chloride, vinyl acetate, ethene, butadiene etc.
Specifically, described interior ester modified unsaturated monocarboxylic is for example for to carry out the interior ester modified compound forming to (methyl) acrylic acid, and can enumerate the represented compound of following general formula (AC-1), utilize acid anhydrides to carry out to terminal hydroxyl the interior ester modified unsaturated monocarboxylic that sour modification forms and can enumerate the represented compound of following general formula (AC-2), the modification unsaturated monocarboxylic with ehter bond can be enumerated the represented compound of following general formula (AC-3).
[changing 20]
Figure BDA0000454732150000341
In general formula (AC-1)～general formula (AC-3), R aC1represent hydrogen atom or methyl, R aC2and R aC3the alkyl that represents independently respectively hydrogen atom, carbon number 1～4, m ac1～m ac3represent independently respectively 4～8 integer, n ac1～n ac3represent independently respectively 1～10 integer.Here, a plurality of R aC2and R aC3can be mutually the same also can be different.L aC1represent the divalence sturated aliphatic hydrocarbon base of carbon number 1～10, the divalence ester ring type saturated hydrocarbyl of the divalence unsaturated alkyl of carbon number 2～10, carbon number 3～6, divalence aromatic series base (preferably phenylene) or divalent heterocycle (preferably 5 yuan or 6 rings and become the divalent heterocycle that contains oxygen atom, sulphur atom, nitrogen-atoms in annular atoms).L aC1each group can there is substituting group.These substituting groups can be enumerated in general formula mentioned above (1)～general formula (3) at R 1～R 11organic group or substituting group in the group enumerated.
In addition, in general formula (AC-2), R aC2and R aC3preferred hydrogen atom, methyl or ethyl, in general formula (AC-2), R aC2and R aC3preferred hydrogen atom, methyl, ethyl, propyl group or butyl.
In-molecule, contain the compound of epoxy radicals and ethene unsaturated group-
There is no particular restriction in molecule, to contain the compound of epoxy radicals and ethene unsaturated group, can suitably select according to object, preferably sour modification mentioned above containing the polyurethane resin in the polyurethane resin of ethene unsaturated group, in molecule, contain the compound of epoxy radicals and ethene unsaturated group in (ii), preferable range is also identical.
Specifically, preferred described general formula (IV-1)～general formula (IV-16), most preferably (methyl) glycidyl acrylate, (methyl) acrylic acid-3,4-epoxycyclohexyl methyl esters.In these compounds, (methyl) glycidyl acrylate particularly preferably.
-contain acidic group and ethene unsaturated group (methyl) acrylic resin manufacture method-
As the manufacture method of (methyl) acrylic resin that contains acidic group and ethene unsaturated group, below manufacture method explanation one example to described modified copolymer.
First, manufacture described multipolymer.There is no particular restriction for the manufacture method of described multipolymer, can suitably select according to object, such as the manufacture method that can enumerate the well-known acrylic resins such as solution polymerization.
Then the compound that, contains epoxy radicals and ethene unsaturated group in addition molecule on a part of acidic group of described multipolymer is manufactured.
There is no particular restriction for described addition amount, can suitably select according to object.
In described addition, preferably use solvent and catalyzer.
There is no particular restriction for solvent, can be according to object and suitably select, and such as enumerating the solvent recorded in the paragraph [0020] of Japanese Patent Laid-Open 2009-086376 communique etc.
There is no particular restriction for catalyzer, can be according to object and suitably select, and such as enumerating the catalyzer recorded in paragraph [the 0021]～paragraph [0025] of Japanese Patent Laid-Open 2009-086376 communique etc.
(methyl) acrylic resin that contains acidic group and ethene unsaturated group for example can be enumerated the exemplary compounds of recording in Japanese Patent Laid-Open 2010-128275 communique, the compound using, and can utilize the manufacture method of recording in this patent gazette or take the manufacture method that the method is foundation and manufacture.
Stream.
The epoxy resin > > containing ethene unsaturated group of < < acid modification
In the application's case, so-called sour modification containing the epoxy resin of ethene unsaturated group, be by the resin of epoxy resin gained as described above, from chemical constitution, say, be mentioned above 2) polyether resin and 3) phenolic varnish type resin.For simplicity, these resins are called to epoxy resin.
As long as the epoxy resin containing ethene unsaturated group of acid modification contains acidic group and ethene unsaturated group, can be any epoxy resin.
The epoxy resin containing ethene unsaturated group of acid modification preferably has the resin of the represented part-structure of following general formula (EP).
[changing 21]
General formula (EP)
Figure BDA0000454732150000361
In general formula (EP), R a1and R a2any represent unsaturated aliphatic base, another represents carboxylic saturated or undersaturated aliphatic group or carboxylic aromatic group.R eP1～R eP3represent independently respectively hydrogen atom or substituting group.
The represented part-structure of described general formula (EP) be by (a) epoxy resin, (b) containing the monocarboxylic acid of unsaturated group and (c) reaction of multi-anhydride obtain.
That is, the unsaturated aliphatic group in general formula (EP) is the group deriving from containing the monocarboxylic acid of unsaturated group, is the group containing remove-COOH gained the monocarboxylic acid of unsaturated group from this.On the other hand, carboxylic saturated or undersaturated aliphatic group or carboxylic aromatic group are the group by multi-anhydride gained, for example, be the group in following cubic frame.
[changing 22]
Figure BDA0000454732150000362
Unsaturated aliphatic group in general formula (EP) preferably in the described general formula (1) of the polyurethane resin containing ethene unsaturated group of sour modification mentioned above-C (R 1)=C (R 2) (R 3).Here, R 1～R 3with the R in described general formula (1) 1～R 3for identical meanings, preferable range is also identical.
Above unsaturated aliphatic base can be enumerated: vinyl, Alpha-Methyl vinyl, Beta-methyl vinyl, β-furfuryl group vinyl, β-styryl vinyl, beta-phenyl vinyl, alpha-cyano-beta-phenyl vinyl, 1,3-pentadiene base.
In addition, if the monocarboxylic acid containing unsaturated group of (b) described in illustration, such as using: acrylic acid, acrylic acid dipolymer, methacrylic acid, β-furfuryl group acrylic acid, β-styrene acrylic, cinnamic acid, butenoic acid, alpha-cyano cinnamic acid and sorbic acid etc.Half ester compounds of the acrylate that in addition, also can be used as hydroxyl and the reaction product of dibasic acid anhydride containing saturated or unsaturated group, as the monoglycidyl ether containing unsaturated group or containing single ethylene oxidic ester of unsaturated group half ester compounds with the reaction product of dibasic acid anhydride containing saturated or unsaturated group.Here, so-called half ester compounds, for example, refer in 2 carboxyls an only compound forming through esterification.These (b) can be used separately containing the monocarboxylic acid of unsaturated group or and with two or more.
Half ester compounds can obtain in the following manner: make hydroxyl acrylate or containing the monoglycidyl ether of unsaturated group or containing single ethylene oxidic ester of unsaturated group, with contain dibasic acid anhydride saturated or unsaturated group and react with equimolar ratio.
The acrylate of hydroxyl for example can be used: hydroxy-ethyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylic acid hydroxy butyl ester, methacrylic acid hydroxy butyl ester, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethylacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, glycidyl acrylate and glycidyl methacrylate etc.
Containing the monoglycidyl ether of unsaturated group or containing single ethylene oxidic ester of unsaturated group, can use (methyl) glycidyl acrylate etc.
About carboxylic saturated or undersaturated aliphatic group or the carboxylic aromatic group in general formula (EP), carboxylic saturated or undersaturated aliphatic group can be enumerated: the group that carboxyl substituted forms on alkyl, thiazolinyl, naphthenic base, cycloalkenyl group, aryl, carboxylic aromatic series base can be enumerated the group that carboxyl substituted forms on phenyl.
If illustration multi-anhydride, contains the dibasic acid anhydride of saturated or unsaturated group such as using: succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride and itaconic anhydride etc.
R in general formula (EP) eP1～R eP3represent independently respectively hydrogen atom or substituting group, preferably hydrogen atom or alkyl, more preferably hydrogen atom or methyl, most preferably hydrogen atom.
The epoxy resin containing ethene unsaturated group of sour modification of the present invention is any represented epoxy resin of following general formula (P1)～general formula (P3) preferably.
[changing 23]
Figure BDA0000454732150000381
General formula (P1)～general formula (P3), R e1represent group or epoxy radicals that described general formula (EP) is represented.R e2and R e3represent independently respectively hydrogen atom or methyl, R e4～R e9represent independently respectively hydrogen atom, alkyl or aryl.N e1and n e2represent independently respectively more than 1 number, n e3represent more than 0 or 1 number.Wherein, R e1in molecule, be not all epoxy radicals.In addition, be present in intramolecular a plurality of R e1can be mutually the same also can be different, be present in intramolecular a plurality of R e2and R e3can be mutually the same also can be different.R e4～R e9in, be present in intramolecular each a plurality of R e4～R e9can distinguish mutually the same also can be different.
Acid modification containing the epoxy resin of ethene unsaturated group be the epoxy resin recorded in the epoxy resin recorded in paragraph [the 0107]～paragraph [0111] of Japanese Patent Laid-Open 2007-256943 communique, Japanese Patent Laid-Open 2006-11395 communique, particularly as the EPA-1～EPA-3 of illustration resin, can utilize the manufacture method of recording in these patent gazettes or take the manufacture method that this manufacture method is foundation and easily manufacture.
In addition, the commercially available product of the epoxy resin containing ethene unsaturated group of acid modification is for example ZAR-1626H(acid modified bisphenol A type epoxy acrylate), ZAR-2003H(acid modified bisphenol A type epoxy acrylate, quality mean molecular weight: 13000, acid number: 82mgKOH/g), ZFR-1158(acid modified bisphenol F type epoxy acrylate, quality mean molecular weight: 10000, acid number: 60mgKOH/g), ZFR-1492H(Bisphenol F type acid modification is containing the epoxy resin of ethene unsaturated group), ZCR-1534(biphenyl aralkyl-type acid modification is containing the epoxy resin of ethene unsaturated group), ZCR-1569H(has the phenolic varnish type acid modification of biphenyl backbone containing the epoxy resin of vinyl, quality mean molecular weight: 4, 500, acid number: 98mgKOH/g).Can enumerate: CCR-1219H(cresols phenolic varnish type epoxy acrylate), PCR-1050(acid modified phenol phenolic varnish type epoxy acrylate) [be above Japanese chemical drug incorporated company manufacture], (Chinese mugwort is than clone (EPICLON) HP-7200 to having the epoxy resin of tristane structure for EXP-2811(, Di Aisheng (DIC) incorporated company manufactures, trade name) carry out the sour modified epoxy acrylic ester containing tristane structure that modification forms), EXP-2810(acid modification cresols phenolic varnish type epoxy acrylate) [being above Di Aisheng (DIC) incorporated company manufactures], PR-300P-CP(cresols phenolic varnish type acid modification is containing the epoxy resin of ethene unsaturated group) [manufacture of Zhao He macromolecule incorporated company].
The vibrin > > containing ethene unsaturated group of < < acid modification
There is no particular restriction for the vibrin containing ethene unsaturated group of acid modification, can suitably select according to object, in the present invention, particularly preferably is the sour modified polyester resin that contains ethene unsaturated link on side chain.In the present invention, so-called side chain, illustrated with containing in the polyurethane resin of ethene unsaturated group of sour modification mentioned above.
The preferred carboxyl of acidic group, about ethene unsaturated group, can enumerate the group on its side chain with at least one functional group in the represented functional group of general formula (the 1)～general formula (3) containing the polyurethane resin of ethene unsaturated group of sour modification mentioned above.These ethene unsaturated groups are identical with the preferable range of the polyurethane resin containing ethene unsaturated group of sour modification mentioned above.
In order to import ethene unsaturated group on side chain, there is following methods: (iii) utilize the method that obtains described vibrin with the polyreaction in dicarboxylic compounds or diol compound with the compound of ethene unsaturated group; And (iv) make carboxylic polyester react with the compound that contains epoxy radicals and ethene unsaturated group in molecule and obtain the method for described vibrin.
The described method that imports ethene unsaturated group on side chain (iii) corresponding to following methods, be sour modification mentioned above the polyurethane resin containing ethene unsaturated group (i) utilize the method that obtains described polyurethane resin with the polyreaction in diisocyanate cpd or diol compound with the compound of ethene unsaturated group; The described method that imports ethene unsaturated group on side chain is (iv) corresponding to following methods: for the vibrin containing ethene unsaturated group containing the sour modification in the polyurethane resin of ethene unsaturated group of sour modification mentioned above, and polyurethane resin (ii) the making carboxylic polycarbamate react with the compound that contains epoxy radicals and ethene unsaturated group in molecule containing ethene unsaturated group of sour modification mentioned above and obtain the method for described polyurethane resin.
That is, can only by being replaced to dicarboxylic compounds, easily manufacture diisocyanate cpd.
In addition, sour modification containing the vibrin of ethene unsaturated group be by sour modification mentioned above containing the general formula in the polyurethane resin of ethene unsaturated group etc.-replace to-CO of term of NCO or " isocyanates " 2the term of H, " carboxyl ", the preferable range containing the vibrin of ethene unsaturated group of sour modification is identical with the polyurethane resin that contains ethene unsaturated group of sour modification mentioned above thus.
Wherein, the manufacture method of vibrin not only can be used dicarboxylic compounds, and can use acid anhydrides, ester, etheride, can utilize common esterification easily to manufacture.
Acid modification containing the vibrin of ethene unsaturated group, can enumerate the resin (1) of recording in vibrin, the particularly paragraph [0058] of recording in Japanese Patent Laid-Open 2007-128059 communique, can utilize the manufacture method of recording in this communique or take the manufacture method that this manufacture method is foundation and easily manufacture.
Polyamide or the polyimide resin > > containing ethene unsaturated group of < < acid modification
There is no particular restriction for the polyamide containing ethene unsaturated group of acid modification or polyimide resin, can suitably select according to object.The preferred carboxyl of acidic group, about ethene unsaturated group, can enumerate the group with at least one functional group in the represented functional group of general formula (the 1)～general formula (3) containing in the polyurethane resin of ethene unsaturated group of sour modification mentioned above.These ethene unsaturated groups are identical with the preferable range of the polyurethane resin containing ethene unsaturated group of sour modification mentioned above.
The polyamide containing ethene unsaturated group of acid modification for example can be enumerated the polyamide with the represented part-structure of following general formula (PI-1).
[changing 24]
General formula (PI-1)
Figure BDA0000454732150000401
In general formula (PI-1), L p11represent quadrivalent organic radical group, L p12represent divalent organic group, R p11and R p12in one represent hydroxyl, another represents the group containing ethene unsaturated group.
L p11carbon number preferably 6～32, L p12carbon number preferably 4～30.
The part-structure of the part-structure of general formula (PI-1) for tetrabasic carboxylic acid or derivatives thereof (acid anhydrides, ester or etheride) and diamines condensation are obtained.
L p11preferred following radicals.
[changing 25]
In described group, L p13represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-C (CF 3) 2-,-O-,-S-,-SO 2-or-C (=O)-.
L p12preferred following radicals.
[changing 26]
Figure BDA0000454732150000412
In described group, L p14represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-C (CF 3) 2-,-O-,-S-,-SO 2-,-C (=O)-,-CH=CH-or-NHC (=O)-.
R p13～R p15represent independently respectively hydrogen atom or substituting group, this substituting group represents halogen atom (for example fluorine atom, chlorine atom, bromine atoms), alkyl (for example methyl, trifluoromethyl, ethyl, tributyl), alkoxy (for example methoxyl, ethoxy).
Can the utilizing the manufacture method of recording in Japanese Patent Laid-Open 2009-230098 communique or take the manufacture method that this manufacture method is foundation containing the polyamide of ethene unsaturated group and easily manufacture of sour modification with the represented part-structure of described general formula (PI-1).
The polyimide resin containing ethene unsaturated group of acid modification further can be enumerated the polyimide resin with the represented part-structure of following general formula (PI-2).
[changing 27]
General formula (PI-2)
Figure BDA0000454732150000413
In general formula (PI-2), A p11and A p12represent independently respectively quadrivalent organic radical group, B p11represent contain-CO 2-CONH-R p13,-CONH-R p13,-NHCONH-R p13or-SCONH-R p13divalent organic group.Here, R p13represent ethene unsaturated group or-L p15-NHCO 2-R p14,-L p15-NHCO 2-CO-R p14,-L p15-NHCO-R p14,-L p15-NHCONH-R p14or-L p15-NHCO-S-R p14.Here, L p15represent saturated or undersaturated divalent organic group, preferably carbon number 1～20, can be substituted base and replace.R p14represent the group containing ethene unsaturated group, preferably-C (R 1)=C (R 2) (R 3).Here, R 1～R 3r with the general formula (1) of the polyurethane resin containing ethene unsaturated group of sour modification mentioned above 1～R 3for identical meanings, preferable range is also identical.
The concrete resin of the polyimide resin containing ethene unsaturated group of the sour modification that general formula (PI-2) is represented can be enumerated the compound of manufacturing in exemplary compounds, the particularly embodiment recording in Japanese Patent Laid-Open 2009-167414 communique.
In addition, the polyimide resin containing ethene unsaturated group of the represented sour modification of general formula (PI-2) can utilize the manufacture method of recording in Japanese Patent Laid-Open 2009-167414 communique or take the manufacture method that this manufacture method is foundation and easily manufacture.
Acid modification containing the non-polyurethane resin of ethene unsaturated group, preferably contain the epoxy resin containing ethene unsaturated group (the be mentioned above 2) polyether resin and 3 of (methyl) acrylic resin of acidic group and ethene unsaturated group, sour modification) phenolic varnish type resin).
Preferred molecular weight, acid number and the ethene unsaturated group equivalent of the non-polyurethane resin containing ethene unsaturated group of the sour modification of using in the present invention and the content in photosensitive polymer combination solid constituent are identical with preferred molecular weight, acid number and ethene unsaturated group equivalent and the content in photosensitive polymer combination solid constituent of the polyurethane resin containing ethene unsaturated group of sour modification.
In addition, in the situation that use the resin containing ethene unsaturated group of two or more sour modifications, preferably the total content of the resin containing ethene unsaturated group of sour modification is set in the scope of described preferred content.
< free radical polymerization monomer >
There is no particular restriction for free radical polymerization monomer, can suitably select according to object, preferably has the more than one functional group's containing ethene unsaturated group compound.
The described functional group containing ethene unsaturated group is such as enumerating: (methyl) acryloyl group, (methyl) acrylamido, ethenylphenyl, vinyl ester, vinyl ether, allyl ether, allyl ester group etc.
There is no particular restriction for the described compound with the more than one functional group containing ethene unsaturated group, can suitably select according to object, is preferably selected from least one in the monomer with (methyl) acrylic.
There is no particular restriction for the described monomer with (methyl) acrylic, can suitably select according to object, such as enumerating: monofunctional acrylate or simple function methacrylates such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) acrylic acid phenoxy ethyl, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexanediol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, isocyanuric acid three (acryloxy ethyl) ester, cyanuric acid three (acryloxy ethyl) ester, glycerine three (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, on the polyfunctional alcohols such as trimethylolpropane, glycerine, bis-phenol, carry out the compound that after the addition reaction of oxirane or epoxypropane, (methyl) acroleic acid esterification forms in addition, as the polyfunctional acrylic esters such as Epoxy Acrylates of epoxy resin and (methyl) acrylic acid reaction product or methacrylate etc.In these compounds, You Jia is trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate.
There is no particular restriction for the content of described free radical polymerization monomer in described photosensitive polymer combination solid constituent, can suitably select according to object, preferably 3 quality %～50 quality %, more preferably 5 quality %～40 quality %.If described content is less than 3 quality %, the sensitivity of exposing is deteriorated, if described content more than 50 quality %, the viscosity of photographic layer (stickability) became strong sometimes.
< thermal cross-linking agent >
There is no particular restriction for described thermal cross-linking agent, can suitably select according to object, in order to improve the film strength after the sclerosis of photographic layer, developability etc. is not being caused in dysgenic scope, for example can enumerate: epoxy compound (epoxy compound for example in a part with at least 2 oxirane bases), the oxetane compound in a part with at least 2 oxa-cyclobutyl, polyisocyanate compounds, make sealer (blocking agent) react compound (closure polyisocyanate compounds) of gained etc. with the isocyanate group of polyisocyanate or derivatives thereof.
There is no particular restriction for the content of described thermal cross-linking agent in described photosensitive polymer combination solid constituent, can suitably select according to object, preferably 1 quality %～50 quality %, more preferably 3 quality %～30 quality %.If described content is more than 1 quality %, the film strength of cured film improves, if described content is below 50 quality %, developability, exposure sensitivity become good.
Described epoxy compound is such as enumerating the epoxy compound recorded in paragraph [the 0071]～paragraph [0073] of Japanese Patent Laid-Open 2010-256399 communique etc.
Described oxetane compound is such as enumerating the oxetane compound recorded in the paragraph [0074] of Japanese Patent Laid-Open 2010-256399 communique etc.
Described polyisocyanate compounds is such as enumerating the polyisocyanate compounds recorded in the paragraph [0075] of Japanese Patent Laid-Open 2010-256399 communique etc.
Described closure polyisocyanate compounds is such as enumerating the closure polyisocyanate compounds recorded in the paragraph [0076] of Japanese Patent Laid-Open 2010-256399 communique etc.
Described melamine derivative is such as enumerating the melamine derivative recorded in the paragraph [0077] of Japanese Patent Laid-Open 2010-256399 communique etc.
< photopolymerization initiator >
As long as photopolymerization initiator has the ability of the polymerization that causes described free radical polymerization monomer, there is no particular restriction, can suitably select according to object, for example preferably ultraviolet range to luminous ray is had to photosensitive photopolymerization initiator, also can be the activating agent that generates living radical with there is certain effect through light activated sensitizer, also can be according to the kind of monomer and cause the initiator as cationic polymerization.
Photopolymerization initiator is such as enumerating: (two) acylphosphine oxide or its ester class, acetophenone based compound, benzophenone based compound, benzoin ether based compound, ketal derivatives compound, thioxanthone compound, 9 oxime derivate, organic peroxide, sulphur compound etc.In these compounds; from sensitivity, keeping quality and photographic layer and the printing distributing board of photographic layer, form the viewpoints such as adhesion with substrate, preferably 9 oxime derivate, (two) acylphosphine oxide or its ester class, acetophenone based compound, benzophenone based compound, benzoin ether based compound, ketal derivatives compound, thioxanthone compound.
Described (two) acylphosphine oxide, described acetophenone based compound, described benzophenone based compound, described benzoin ether based compound, described ketal derivatives compound, described thioxanthone compound are such as enumerating: (two) acylphosphine oxide of recording in the paragraph of Japanese Patent Laid-Open 2010-256399 communique [0042], acetophenone based compound, benzophenone based compound, benzoin ether based compound, ketal derivatives compound, thioxanthone compound etc.
Photopolymerization initiator can be used, or two or more may be used separately.
There is no particular restriction for the content of described photopolymerization initiator in described photosensitive polymer combination solid constituent, can suitably select according to object, preferably 0.1 quality %～30 quality %, more preferably 0.5 quality %～20 quality %, particularly preferably 0.5 quality %～15 quality %.
< inorganic filler >
The photosensitive polymer combination using in the present invention contains inorganic filler.Described inorganic filler can improve the skin hardness of permanent pattern, or linear expansion coefficient is suppressed lowly and improve pyroconductivity, or the specific inductive capacity of cured film self or dielectric loss angle tangent are suppressed to low, therefore can suitably select/use.
Inorganic filler is such as enumerating: porcelain earth, barium sulphate, barium titanate, silicon dioxide, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, mica etc.The commercially available product of described barium sulphate is manufactured such as enumerating B-30(Sakai chemical industrial company) etc.
In these inorganic fillers, compound (compound that contains silicon in constituting atom, for example silicon dioxide, talcum), barium sulphate, aluminium hydroxide that preferably silicon dioxide etc. contains silicon atom, more preferably contain the compound of silicon atom, particularly preferably silicon dioxide.
There is no particular restriction for the mean grain size of inorganic filler, can suitably select according to object, and suitable is below 5 μ m, preferably below 2 μ m, more preferably below 1 μ m.If described mean grain size is more than 5 μ m, sometimes because light scattering causes resolution deteriorated.
More than 20 volume % in nonvolatile component (solid constituent) cumulative volume that in the present invention, the content of inorganic filler is photosensitive polymer combination.Required effect can be effectively brought into play thus, and coefficient of thermal expansion can be reduced.The described content of inorganic filler is preferably more than 25 volume %, more preferably more than 30 volume %.The upper limit of inorganic filler is preferably below 60 volume %, more preferably below 50 volume %, and then preferably below 40 volume %, further preferably below 35 volume %, also can be set as below 32 volume %.If the content of inorganic filler is very few, the effect that reduces coefficient of thermal expansion is little, and the effect that improves resistance to impact becomes insufficient.On the other hand, if the too high levels of inorganic filler cannot obtain sufficient resolution.
The nonvolatile component of so-called photosensitive polymer combination, refers to nonvolatile composition, even and if be equivalent to be heated under the decompression of 20mmbar 150 ℃ also nonvolatile composition, be so-called solid constituent volume.In addition the organic solvent that, the boiling points such as cellosolve series solvent such as lower boiling organic solvent or propylene glycol methyl ether acetate, carbitol, butyl carbitol are relatively high is as volatile solvent and known.
< spreading agent >
In the photosensitive polymer combination using in the present invention, preferably contain spreading agent.
Wherein, the preferably dispersion for inorganic filler by spreading agent.Therefore, spreading agent preferably has with the group of the surface interaction of inorganic filler and does not have the macromolecule dispersing agent of ethene unsaturated group.Can enumerate basic group, acidic-group or adsorption group, particularly preferably basic group with the group of the surface interaction of inorganic filler.In addition, preferably, in the surface of inorganic filler, not at the Interpolymer Association of spreading agent, in order to suppress this association, preferably there is the group that becomes steric hindrance in these interactional groups under interactional state in molecule.In addition, quality mean molecular weight preferably 1,000～100,000.
In addition, in the situation that the functional group of spreading agent alkali-free and contain acid functional group, salt structure, sometimes cannot obtain the sufficient adsorbance to inorganic fillers such as silicon dioxide, in the situation that making film, sometimes cannot suppress silicon dioxide cohesion each other, so viscosity not reduce.
There is no particular restriction for basic group, such as enumerating one-level amino, secondary amino, tertiary amine base, nitrogen heterocycle etc., and preferred tertiary amine base, nitrogen heterocycle, particularly preferably tertiary amine base.
Basic group for example, adsorbs from the teeth outwards by the surface interaction of surface, particularly silicon dioxide particles with inorganic or organic filler or pigment, ionic interaction.
As long as nitrogen heterocycle is into and contains nitrogen-atoms in annular atoms and this nitrogen-atoms demonstrates alkaline group, can be any group.The heterocycle of nitrogen heterocycle is the heterocyclic radical of 5 yuan or 6 yuan preferably, can be aromatic rings, also can be unsaturated or saturated ring.In nitrogen heterocyclic ring, also can further contract and encircle aromatic rings, heterocycle or alicyclic ring, in nitrogen heterocyclic ring, can there is substituting group.This substituting group for example can be enumerated: alkyl, thiazolinyl, alkynyl, naphthenic base, aryl or heterocyclic radical, halogen atom, alkoxy, aryloxy group, alkylthio group, arylthio, amino, alkyl amino, arylamino, acyl amino, sulfoamido, alkyl sulphonyl or aryl sulfonyl, alkyl sulphinyl or aryl sulfonyl kia, alkoxy carbonyl, aryloxycarbonyl, acyl group, acyloxy, carbamyl, sulfamoyl, hydroxyl, sulfydryl, cyano group, nitro, carboxyl, sulfo group, urea groups, carbamate groups etc.
Nitrogen heterocyclic ring for example can be enumerated: Pyrrolizidine ring (pyrrolidine ring), pyrrolin ring, piperidine ring, piperazine ring, morpholine ring, imidazolidine ring, imidazoline ring, imidazole ring, pyrazoles pyridine ring, Pyrrolizidine ring, pyrazole ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indole ring, indazole ring, purine ring, quinoline ring, quinoxaline ring (quinoxaline ring), quinazoline ring, indole ring, quinuclidine (quinuclidine ring).
There is no particular restriction for acidic-group, and the group of the acid moieties of acidic-group for example can be enumerated: carboxyl, sulfo group, phosphono (phosphonyl) ,-COCH 2cO-R b,-CONHCO-R b,-COCH 2cN, phenol hydroxyl ,-R fcH 2oH ,-(R f) 2cHOH, alkylsulfonamido or aryl-sulfonyl amino etc.Here, R bthe alkyl that represents carbon number 1～10, R frepresent perfluoroalkyl.In addition, alkyl is the alkyl of saturated, unsaturated or ring-type, preferably the alkyl of ring-type.
In acidic-group, preferred carboxyl, sulfo group, phosphono, from the aspect of developability, particularly preferably carboxyl.
In addition, the acid moieties of acidic-group can have the group of described acid moieties in fatty group (alkyl, thiazolinyl, alkynyl, naphthenic base, cycloalkenyl group, cycloalkynyl radical etc.), aromatic series base, heterocyclic radical, and the group of described acid moieties also can directly become acidic-group.
More than the preferred 0.65mmol/g of amine value of the spreading agent that can preferably use in the present invention, more preferably more than 0.75mmol/g, and then preferably more than 0.9mmol/g.The upper limit of amine value is not particularly limited, preferably below 4mmol/g, and then preferably below 3mmol/g.
Here, about the mensuration of described amine value, for example can obtain in the following manner amine value: in beaker, take sample, add acetic acid, stir and sample is dissolved, mensuration temperature is adjusted to after 25 ℃, used 0.1N to cross chloric acid acetic acid as titration reagent, utilize titration apparatus to carry out titration.
Amine value is the value of the amount gained of chlorine excessively consuming while representing titration with respect to every 1g dispersant resin (solid constituent) with molal quantity.
More than the preferred 0.1mmol/g of acid number of the spreading agent that can preferably use in the present invention, more preferably more than 0.2mmol/g, and then preferably more than 0.3mmol/g.The upper limit of acid number is not particularly limited, preferably below 3.5mmol/g, more preferably below 2.5mmol/g.
Here, mensuration about described acid number for example can be obtained acid number in the following manner: in beaker, take sample, interpolation THF/ water=5/1(volume ratio) solution, stir and sample is dissolved, mensuration temperature is adjusted to after 25 ℃, use the NaOH aqueous solution of 0.1N as titration reagent, utilize titration apparatus to carry out titration.
Acid number is the value of the amount gained of the NaOH that consumed while representing titration with respect to every 1g dispersant resin (solid constituent) with molal quantity.
As described above, in the present invention preferred spreading agent preferably have basic group and high molecular steric hindrance base at least any.
Steric hindrance base can be enumerated: the alkyl of branch-like, bicyclic alkyl, aryl, heterocyclic radical (wherein aryl and heterocyclic radical preferably have 2 above substituting groups), number average molecular weight are 500～50,000 side chain polymer chain, preferably has the polymeric dispersant of grafted chain.
Wherein, if three-dimensional protecting group is low-molecular-weight but not high molecular; sometimes cannot obtain sufficient steric repulsion; sometimes when making film, cannot obtain the sufficient steric repulsion to inorganic fillers such as silicon dioxide; thereby in the situation that making film; sometimes cannot suppress inorganic filler cohesion each other, viscosity does not reduce.
-grafted chain-
Macromolecule dispersing agent preferably at least has grafted chain on any on side chain or at main chain end.
Grafted chain for example can be enumerated: polyester chain, polyalkyl acrylate chain, polyalkyl methacrylate chain, polyalkylene oxide chain (preferably polyethylene oxide chain, polypropyleneoxide chain), polycarbonate chain, polystyrene chain or the chain that these chains are combined and in part-structure, contain the grafted chain of these chains.In these grafted chains, from the aspect of resolution, preferably there is the grafted chain (polyester grafted chain) at polyester position.
About the chain length of described grafted chain, the degree of polymerization preferably 1～100, more preferably 1～80, particularly preferably 1～60.
Overall with respect to macromolecule dispersing agent resin, the content of described grafting is 10 quality %～60 quality % preferably, more preferably 20 quality %～50 quality %.
In the present invention, preferably amine value, acid number or amine value and acid number are the spreading agent of scope mentioned above, more preferably amine value and acid number are the spreading agent of scope mentioned above, and then preferably amine value and acid number are scope mentioned above and the spreading agent with grafted chain.
The commercially available product of described spreading agent for example can be enumerated: rope is exerted Paasche (Solsperse) 3000, rope is exerted Paasche (Solsperse) 17000, rope is exerted Paasche (Solsperse) 20000, rope is exerted Paasche (Solsperse) 24000GR, rope is exerted Paasche (Solsperse) 24000SC, rope is exerted Paasche (Solsperse) 26000, rope is exerted Paasche (Solsperse) 27000, rope is exerted Paasche (Solsperse) 28000, rope is exerted Paasche (Solsperse) 32000, rope is exerted Paasche (Solsperse) 33000, rope is exerted Paasche (Solsperse) 38500, rope is exerted Paasche (Solsperse) 39000, rope is exerted Paasche (Solsperse) 41000, rope is exerted Paasche (Solsperse) 55000, rope is exerted Paasche (Solsperse) 56000, rope is exerted Paasche (Solsperse) 71000, rope is exerted Paasche (Solsperse) 76500(and is the manufacture of Lu Borun (Lubrizol) company), Di Sipabike (Disperbyk)-161, Di Sipabike (Disperbyk)-167, Di Sipabike (Disperbyk)-182, Di Sipabike (Disperbyk)-2155, Di Sipabike (Disperbyk)-102, Di Sipabike (Disperbyk)-111, Di Sipabike (Disperbyk)-106, Di Sipabike (Disperbyk)-108, Di Sipabike (Disperbyk)-112, Di Sipabike (Disperbyk)-2000, Di Sipabike (Disperbyk)-2001, Di Sipabike (Disperbyk)-2008, Di Sipabike (Disperbyk)-2009, Di Sipabike (Disperbyk)-2015, Di Sipabike (Disperbyk)-2020, Di Sipabike (Disperbyk)-2022, Di Sipabike (Disperbyk)-2025, (being Bi Ke chemistry (BYK Chemie) company manufactures), EFKA (Efka)-4008, EFKA (Efka)-4009, EFKA (Efka)-4010, EFKA (Efka)-4015, EFKA (Efka)-4020, EFKA (Efka)-4046, EFKA (Efka)-4047, EFKA (Efka)-4400, EFKA (Efka)-4401, EFKA (Efka)-4002, EFKA (Efka)-4003, EFKA (Efka)-4480, EFKA (Efka)-4300, EFKA (Efka)-4310, EFKA (Efka)-4320, EFKA (Efka)-4330, EFKA (Efka)-4340, EFKA (Efka)-4061, EFKA (Efka)-5044, EFKA (Efka)-5244, EFKA (Efka)-5054, EFKA (Efka)-5055, EFKA (Efka)-5063, EFKA (Efka)-5065, EFKA (Efka)-5066, EFKA (Efka)-5070, EFKA (Efka)-5071, EFKA (Efka)-5207, EFKA (Efka)-6220, EFKA (Efka)-6225(is BASF (BASF) company and manufactures) etc.
In these spreading agents, preferably have basic group spreading agent, there is the spreading agent of steric hindrance base etc.
There is no particular restriction with respect to the content of inorganic filler for spreading agent, can suitably select according to object, with respect to the surface area 1m of inorganic filler 2, preferred 0.1mg～10mg, more preferably 1mg～3mg.
If described content is less than 0.1mg, the dispersiveness of inorganic filler becomes insufficient, if described content surpasses 10mg, the viscosity of film is deteriorated sometimes.On the other hand, if described content is within being better than the scope of described scope, have concurrently dispersed and viscosity aspect favourable.
< elastic body >
By add elastic body in photosensitive polymer combination of the present invention, can give thermotolerance, flexibility and obdurability to photosensitive polymer combination, thereby preferably.
There is no particular restriction for elastic body, can suitably select according to object, such as enumerating: styrene series elastomer, ethylene series elastic body, carbamate based elastomers, polyester based elastomers, polyamide-based elastic body, acrylic elastomer, silicone-based elastic body etc.These elastic bodys are consisted of hard section of (hard segment) composition and soft section of (soft segment) composition, and the former contributes to thermotolerance, intensity conventionally, and the latter contributes to flexibility, obdurability.In addition, there is no particular restriction for elastomeric character, can suitably select according to object, such as the aspects such as production efficiency from developing procedure, preferably has alkali-soluble or swelling.
There is no particular restriction for styrene series elastomer, can suitably select according to object, such as enumerating: styrene-butadiene-styrene block copolymer, SIS, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene segmented copolymer etc.
Except the styrene of the composition as formation styrene series elastomer, can use the styrene derivatives such as α-methyl styrene, 3-methyl styrene, 4-propylstyrene, 4-cyclohexyl benzene ethene.Specifically, commercially available product can be enumerated: spy is Pulan (Tufprene) not, Suo Lu Pulan (Solprene) T, Ah Sa Pulan (Asaprene) T, special Fluorene Tyke (Tuftec) (being that Asahi Chemical Industry's (thigh) manufactures above), the Longhua of elastic body AR(peace becomes (Aronkasei) to manufacture), Ke Laitong (Kraton) G, Ka Lifu lux (Califlex) (being Japanese shell (Shell Japan) manufacture above), JSR-TR, TSR-SIS, Di Nalong (Dynaron) (being Japanese synthetic rubber (thigh) manufacture above), electrification (Denka) STR(electrochemical industry (thigh) is manufactured), her Plutarch (Quintac) (Japanese auspicious father-in-law (Zeon) manufacture) of storehouse, TPE-SB series (Sumitomo Chemical (thigh) manufacture), La Balong (Rabalon) (Mitsubishi Chemical's (thigh) manufacture), Sai Pudun (Septon), sea Bradley (Hybrar) (being Kuraray (Kuraray) manufacture above), Su meter Fu Simon Rex (Sumiflex) (Sumitomo Berlet (Sumitomo Bakelite) (thigh) manufacture), LEO Si Tuoma (Leostomer), Ai Kedima (Actymer) (above is that reason is ground ethylene industry manufacture) etc.
There is no particular restriction for ethylene series elastic body, can suitably select according to object, such as the multipolymer that is the alpha-olefin of the carbon numbers 2～20 such as ethene, propylene, 1-butylene, 1-hexene, 4-methyl-amylene, such as enumerating ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) etc., can enumerate in addition: the non-conjugated diene of the carbon numbers such as bicyclopentadiene, Isosorbide-5-Nitrae-hexadiene, cyclo-octadiene, methene norbornene, ethylidene norbornene, butadiene, isoprene 2～20 and alpha olefin copolymer etc.In addition, can enumerate the carboxy-modified nitrile butadiene rubber (nitrile-butadiene rubber, NBR) that methacrylic acid and hycar copolymerization are formed.Specifically can enumerate: ethylene-α-olefincopolymerrubber, ethylene-alpha-olefin-nonconjugated diene copolymers rubber, propylene-alpha-olefin copolymers rubber, 1-butene-alpha-olefin copolymers rubber etc.
Specifically, commercially available product can be enumerated: meter La Si holds in the palm agate (Milastomer) (Mitsui Chemicals (thigh) manufacture), Exeter (EXACT) (Ai Kesen (Exxon) chemistry is manufactured), Ying Jiaji (ENGAGE) (DOW Chemical (The Dow Chemical) manufacture), hydrogenated styrene-butadiene rubber (Di Nabang (DYNABON) HSBR, Japan's synthetic rubber (thigh) is manufactured), hycar (NBR series, Japan's synthetic rubber (thigh) is manufactured), or modification hycar (the XER series that is carboxyl of two ends with crosslinking points, Japan's synthetic rubber (thigh) is manufactured) etc.
There is no particular restriction for urethane elastomers, can suitably select according to object, for example for comprise hard section with the structural unit of soft section, above-mentioned hard section comprises low molecular glycol and diisocyanate, above-mentioned soft section comprises macromolecule (long-chain) glycol and diisocyanate, macromolecule (long-chain) glycol can be enumerated: polypropylene glycol, polytetramethylene oxide, poly-(hexane diacid-1,4-fourth diester), poly-(ethene-hexane diacid-1,4-fourth diester), polycaprolactone, poly-(carbonic acid-1, the own diester of 6-), poly-(hexane diacid-1, own diester-Xin penta diester of 6-) etc.
The number average molecular weight of macromolecule (long-chain) glycol preferably 500～10,000, except ethylene glycol, can be used the short-chain diols such as propylene glycol, BDO, bisphenol-A, the number average molecular weight of short-chain diol preferably 48～500.The commercially available product of described urethane elastomers can be enumerated: spandex (PANDEX) T-2185, spandex (PANDEX) T-2983N(Di Aisheng (DIC) (thigh) manufacture), special blue (Siractran) E790 of uncommon clarke etc.
There is no particular restriction for polyester based elastomers, can suitably select according to object, for example, can enumerate and make dicarboxylic acid or derivatives thereof and diol compound or derivatives thereof carry out the polyester based elastomers of polycondensation gained.
Described dicarboxylic acid is such as enumerating: the aromatic dicarboxylic acid that the hydrogen atom of the aromatic proton of the aromatic dicarboxylic acids such as terephthalic acid (TPA), m-phthalic acid, naphthalene dicarboxylic acids and these dicarboxylic acid forms through replacements such as methyl, ethyl, phenyl, the aliphatic dicarboxylic acid of the carbon numbers 2～20 such as hexane diacid, decanedioic acid, dodecanedicarboxylic acid, and the ester ring type dicarboxylic acid such as cyclohexane dicarboxylic acid etc.These dicarboxylic acid can be used, or two or more may be used separately.
Described diol compound for example can be enumerated: ethylene glycol, 1,3-propane diol, BDO, 1,6-hexanediol, 1, dihydric phenol that the aliphatic diols such as 10-decanediol, Isosorbide-5-Nitrae-cyclohexanediol and ester ring type glycol, following structural formula are represented etc.
[changing 28]
Figure BDA0000454732150000511
In described formula, Y dOrepresent the alkylidene of carbon number 1～10, the cycloalkylidene of carbon number 4～8 ,-O-,-S-and-SO 2-any, or represent phenyl ring Direct Bonding (singly-bound) each other.R dO1and R dO2the alkyl that represents independently respectively halogen atom or carbon number 1～12. p do1and p do2represent independently respectively 0～4 integer, n do1represent 0 or 1.
The concrete example of polyester elastomer can be enumerated: bisphenol-A, two-(4-hydroxy phenyl) methane, two-(4-hydroxy-3-methyl phenyl) propane, resorcinol etc.These polyester elastomers can be used, or two or more may be used separately.
In addition, polyester elastomer also can be used aromatic polyester (for example polybutylene terephthalate) part is set as to hard segment components, aliphatic polyester (for example polytetramethylene glycol) part is set as to the segmented copolymer that soft segment components forms.
Segmented copolymer is looked hard section of different from kind, ratio and the molecular weight of soft section, can enumerate various ranks (grade).Concrete example can be enumerated: Hai Telaier (Hytrel) (Dong Li Du Pont (Du Pont-Toray) strand) manufactures), Pei Er Pulan (Pelprene) (Japan twist flax fibers and weave (thigh) manufacture), Ai Sipeier (Espel) (Hitachi changes into industry (thigh) manufacture) etc.
There is no particular restriction for polyamide-based elastic body, can suitably select according to object, for example roughly be divided into and firmly use mutually two kinds, polyamide, the soft polyether block amide type that uses mutually polyethers or polyester and polyether ester block amides type, polyamide can be used polyamide-6, polyamide-11, polyamide-12 etc., and polyethers can be used polyoxyethylene, polyoxypropylene, polytetramethylene glycol etc.Specifically, commercially available product can be enumerated: UBE polyamide elastomer (the emerging product of space portion (thigh) manufacture), for A meter De (Daiamide) (Daicel-Hess (Daicel-Huels) (thigh) manufacture), send Bath (PEBAX) (east beautiful (Toray) (thigh) manufacture), Gree dragon (Grilon) ELY(Japan's EMS chemistry (EMS-Chemie Japan) (thigh) manufacture), Nova Mead (Novamid) (Mitsubishi Chemical's (thigh) manufacture), Gree Simon Rex (Grilax) (Di Aisheng (DIC) (thigh) manufacture) etc.
There is no particular restriction for acrylic elastomer, can suitably select according to object, for example to using acrylate as major component, ethyl acrylate, butyl acrylate, acrylic acid methoxyl ethyl ester, acrylic acid ethoxy ethyl ester etc. can be enumerated, glycidyl methacrylate, allyl glycidyl ether etc. can be enumerated in addition as crosslinking points monomer.And then, also can make vinyl cyanide or ethene carry out copolymerization.Specifically can enumerate: vinyl cyanide-butyl acrylate copolymer, vinyl cyanide-butyl acrylate-ethyl acrylate copolymer, vinyl cyanide-butyl acrylate-glycidyl methacrylate copolymer etc.
There is no particular restriction for silicone-based elastic body, can suitably select according to object, and be for example to using organopolysiloxane as major component, can enumerate dimethyl silicone polymer system, PSI system, polydiphenylsiloxane etc.The concrete example of commercially available product can be enumerated: KE series (SHIN-ETSU HANTOTAI's chemical industry (thigh) manufacture), SE is serial, CY is serial, SH is serial (being eastern beautiful DOW CORNING silicone (Toray Dow-corning Silicone) (thigh) manufacture above) etc.
In addition, except described elastic body, can use rubber-modified epoxy resin.Rubber-modified epoxy resin is such as obtaining in the following manner: to utilize modified version butadiene-propylene nitrile rubber, end that two ends are carboxylic acid be amino modified silicone rubber etc., and part or all epoxy radicals of described bisphenol f type epoxy resin, bisphenol A type epoxy resin, salicylide type epoxy resin, phenol novolak type epoxy resin or cresols phenolic resin varnish type epoxy resin is carried out to modification.In these elastic bodys, aspect from shear bond, the modification hycar that preferably two ends are carboxyl, conduct have the Ai Sipeier (Espel) (Hitachi changes into industry (thigh) manufacture, Ai Sipeier (Espel) 1612, Ai Sipeier (Espel) 1620) of the polyester based elastomers of hydroxyl.
With respect to solid constituent 100 mass parts of described photosensitive polymer combination, described elastomeric content is 1 mass parts～50 mass parts preferably, more preferably 2 mass parts～20 mass parts, particularly preferably 3 mass parts～10 mass parts.
If described content is less than 2 mass parts, the tendency that has the elastic modulus of cured film in high-temperature area not reduce, if described content surpasses 50 mass parts, has the not tendency of stripping in developer solution of unexposed portion.
< ion capturing agent >
In the photosensitive polymer combination using in the present invention, contain the ion capturing agent (ion adsorbent) of mineral compound containing at least one of Zr, Bi or Sb.
As caught ion, negative ion and the free Na such as free Cl-or water-disintegrable Cl- +or the C in test u 2+centered by one-tenth.
The mineral compound that contains Zr (zirconium compounds) is such as enumerating basic zirconium phosphate, wolframic acid zirconium, molybdic acid zirconium, selenic acid zirconium, telluric acid zirconium etc.In these compounds, particularly preferably be and can optionally carry out Na +, K +etc. cationic ion-exchange and ion-exchange volume also excellent basic zirconium phosphate.
The mineral compound that contains Bi (bismuth compound) is such as enumerating bismuth oxide, bismuth titanates, bismuth nitrate, bismuth salicylate, waltherite etc.In these compounds, particularly preferably be the bismuth oxide that catches specifically Cl-.
The mineral compound that contains Sb (antimonial) preferential oxidation antimonial.Antimonial is such as enumerating antimony pentoxide, antimony oxide, phosphorus metaantimmonic acid, metaantimmonic acid zirconium, metaantimmonic acid titanium etc.In these compounds, from Na +aspect, antimony pentoxide particularly preferably.
In the present invention, the mineral compound of at least one that contains Zr, Bi or Sb is preferably selected from the mineral compound in basic zirconium phosphate, wolframic acid zirconium, molybdic acid zirconium, selenic acid zirconium, telluric acid zirconium, bismuth oxide, bismuth titanates, bismuth nitrate, bismuth salicylate, waltherite, antimony pentoxide, antimony oxide, phosphorus metaantimmonic acid, metaantimmonic acid zirconium and metaantimmonic acid titanium.
In described compound, from improving with interest by catching negative and positive two ions the aspect of insulating reliability preferably.Wherein, particularly preferably be combination and contain at least one inorganic chemical combination (zirconium compounds) that contains Zr metal and at least one mineral compound that contains Bi metal (bismuth compound).
The mass ratio (A:B) of described bismuth compound (A) and described zirconium compounds (B) is 1:0.1～1:10, more preferably 1:0.2～1:5 preferably.
The total content of described ion capturing agent in described photosensitive polymer combination solid constituent is 0.5 quality %～10 quality % preferably, more preferably 1 quality %～5 quality %.If described content is more than 10 quality %, the bad and resolution of hardening, adhesion reduce, if described content is that below 0.5 quality %, the effect that improves insulating reliability is little.
In addition,, in the present invention, also can use in the lump other ion capturing agents with described ion capturing agent.Other ion capturing agents can be enumerated following ion capturing agent.
Can enumerate: the hydrous oxide of the metals such as the inorganic ion exchanger (zwitterion agent for capturing is combined) of absorption negative and positive two ions, beryllia hydrate, gallium oxide hydrate, lanthana hydrate, iron oxide hydrate, hydrated alumina, titanium oxide hydrate, tin oxide hydrate, germanium oxide hydrate, thoria hydrate.
Anion catching agent can be enumerated talcite (talcite) class etc.Also include: synthesis of East Asia (shares) on sale of anion exchanger IXE-700 (magnesium, aluminum-based), IXE-700F (magnesium, aluminum-based), IXE-770 (magnesium, aluminum-based), IXE-770D (magnesium, aluminum-based), IXE-702 (aluminum-based), IXE-1000 (lead line) and the like.
Cation capture agent is such as enumerating: the hydrous oxide of the metals such as phosphate, manganese oxide hydrate, silicon oxide hydrate, niobium oxide hydrate, tantalum oxide hydrate, tantalum oxide hydrate, molybdena hydrate, tungstic oxide hydrate, ammonium phosphomolybdate, molybdic acid titanium, wolframic acid titanium, molybdic acid tin, wolframic acid tin, tripolyphosphate chromium etc.In addition, the cation exchange column IXE-200(tin that can enumerate by the list marketing of the synthetic incorporated company in East Asia is), IXE-400(titanium system) etc.
< coloring pigment >
Preferably in photosensitive polymer combination of the present invention, contain coloring pigment.
There is no particular restriction for coloring pigment, can suitably select according to object, for example, can enumerate: Victoria's pure blue B O(color index (Color Index, C.I.) 42595), auramine (C.I.41000), the black HB(C.I.26150 of liposoluble), special yellow (monolite yellow) the GT(C.I. pigment Yellow 12 of Monot's Lay), permanent yellow GR(C.I. pigment yellow 17), C.I. pigment yellow 55, permanent yellow HR(C.I. pigment yellow 83), forever consolidate carmine FBB(C.I. pigment red 146), Clariant type paratonere (Hosterberm red) ESB(C.I. pigment violet 1 9), forever consolidate ruby red (permanent rubine) FBH(C.I. paratonere 11) pinkish red B color lake (C.I. pigment red 81) monastral fast blue (Monastral Fast Blue) (C.I. pigment blue 15) of sun-proof, the special fast black B(C.I. of Monot's Lay pigment black 1), carbon, C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 168, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. pigment red 21 5, C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment blue 15: 1, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 64 etc.These pigment can be used, or two or more may be used separately.In addition, optionally can use the dyestuff of suitably selecting from well-known dyestuff.
The exposure sensitivity of the photographic layer when content of described coloring pigment in described photosensitive polymer combination solid constituent can be considered to form permanent pattern, resolution etc. decide, depending on the kind of described coloring pigment and difference, conventionally preferably 0.01 quality %～10 quality %, more preferably 0.05 quality %～5 quality %.
Other compositions of < >
There is no particular restriction for described other compositions, can suitably select according to object, such as enumerating thermmohardening promoter, thermal polymerization inhibitor, plasticiser, surface conditioning agent etc., and then can be used together substrate surface connected airtight to promoter and other auxiliary agent classes (such as electroconductive particle, filling agent, defoamer, fire retardant, levelling agent, peel off promoter, antioxidant, spices, surface tension adjusting agent, chain-transferring agent etc.).
By suitably containing these compositions, the character such as stability that can adjustment aim photosensitive polymer combination, photograph, film physical property.
Described thermal polymerization inhibitor is such as enumerating the thermal polymerization inhibitor recorded in paragraph [the 0101]～paragraph [0102] of Japanese Patent Laid-Open 2008-250074 communique etc.
Described thermmohardening promoter is such as enumerating the thermmohardening promoter recorded in the paragraph [0093] of Japanese Patent Laid-Open 2008-250074 communique etc.
Described plasticiser is such as enumerating the plasticiser recorded in paragraph [the 0103]～paragraph [0104] of Japanese Patent Laid-Open 2008-250074 communique etc.
Described surface conditioning agent can be enumerated the middle silane coupling agent of recording of paragraph [0017]～paragraph [0022] of Japanese Patent Laid-Open 2008-102486 communique etc.
Described connect airtight promoter such as can enumerate in paragraph [the 0107]～paragraph [0109] of Japanese Patent Laid-Open 2008-250074 communique, record connect airtight promoter etc.
There is no particular restriction for the use form of described photosensitive polymer combination, can be according to object and suitably select, can, with aqueous and use, also can use with the form of photosensitive film.
< photosensitive film >
The photographic layer that described photosensitive film at least has supporter and contain photosensitive polymer combination of the present invention on this supporter, and then optionally there is other layers.
-supporter-
There is no particular restriction for described supporter, can suitably select according to object, preferably can peel off the supporter that described photographic layer and optical transmission are good, more preferably the better supporter of flatness on surface.
There is no particular restriction for described supporter, can be according to object and suitably select, and such as enumerating the supporter recorded in paragraph [the 0115]～paragraph [0117] of Japanese Patent Laid-Open 2008-250074 communique etc.
-photographic layer-
Described photographic layer is as long as be the layer that comprises described photosensitive polymer combination of the present invention, and there is no particular restriction, can suitably select according to object.
In addition, there is no particular restriction for the lamination number of described photographic layer, can be according to object and suitably select, for example can be one deck, also can be two-layer more than.
The formation method of described photographic layer can be enumerated following methods etc.: make described photosensitive polymer combination of the present invention dissolving in water or solvent, emulsification or dispersion, prepare photosensitive polymer combination solution, this solution is directly coated on described supporter and is dried, thus the method for lamination photographic layer etc.
In described photosensitive polymer combination solution, there is no particular restriction for solvent used, can suitably select according to object.
There is no particular restriction for the method for described coating, can suitably select according to object, such as enumerating: use spin coater, slit spin coater, roll coater, mould painting machine, curtain application device (curtain coater) etc. are directly coated on the method on described supporter etc.
Described dry condition is also looked the kind, usage ratio of each composition, solvent etc. and different, conventionally at the temperature of 60 ℃～120 ℃ about dry 30 second～15 minute.
There is no particular restriction for the thickness of described photographic layer, can suitably select according to object, preferably 1 μ m～100 μ m, more preferably 2 μ m～50 μ m, particularly preferably 4 μ m～30 μ m.
-other layers-
There is no particular restriction for described other layers, can suitably select according to object, such as enumerating: the layer such as diaphragm, thermoplastic resin, barrier layer, peel ply, adhesive linkage, light absorbing zone, sealer.Described photosensitive film can have a kind of separately in these layers, also can have two or more.
-diaphragm-
Described photosensitive film also can form diaphragm on described photographic layer.
There is no particular restriction for described diaphragm, can be according to object and suitably select, and such as enumerating the diaphragm recorded in the paragraph [0118] of Japanese Patent Laid-Open 2008-250074 communique etc.
There is no particular restriction in the combination of described diaphragm and described supporter, can be according to object and suitably select, and such as enumerating the combination recorded in the paragraph [0118] of Japanese Patent Laid-Open 2008-250074 communique etc.
In addition, the coefficient of static friction of described supporter and described diaphragm preferably 0.3～1.4, more preferably 0.5～1.2.
If described coefficient of static friction is more than 0.3, can prevent from, because cross the sliding inclined to one side situation of volume that occurs when making web-like, if described coefficient of static friction is below 1.4, can being rolled into good web-like.
There is no particular restriction for the length of described photosensitive film, keeping method, can suitably select according to object such as the middle length of recording of the paragraph [0120] that can enumerate Japanese Patent Laid-Open 2008-250074 communique, keeping method etc.
Described diaphragm also can carry out surface treatment to adjust the cementability of described diaphragm and described photographic layer.About described surface treatment, such as form the undercoat that comprises the polymkeric substance such as polysiloxane, fluorinated polyolefin, polyvinyl fluoride, polyvinyl alcohol (PVA) on the surface of described diaphragm.About the formation of this undercoat, can form by the following method undercoat: after the coating fluid of described polymkeric substance being coated on the surface of described diaphragm, at 30 ℃～150 ℃ dry 1 minute～30 minutes.Particularly preferably 50 ℃～120 ℃ of described temperature when dry.
(photonasty laminate)
Photonasty laminate of the present invention is at least to have matrix and the photographic layer that is positioned on described matrix forms, and then other layers of lamination optionally.
Described photographic layer is the layer that contains described photosensitive polymer combination of the present invention.
Described photographic layer is for example that transfer printing forms from utilizing the described photosensitive film that described manufacture method makes, and has the formation identical with described photosensitive film.
< matrix >
Described matrix becomes the transfer printing body that will form the processed matrix of photographic layer or want at least photographic layer of transfer printing photosensitive film of the present invention, there is no particular restriction, can be according to object and suitably select, for example can to having the matrix of convex-concave surface, select arbitrarily from the high matrix of surface smoothness.Preferably tabular matrix, is used so-called substrate.Specifically can enumerate: the film of the substrate (printed base plate) of well-known printing distributing board manufacture use, glass plate (soda-lime glass plate etc.), synthetic resin, paper, sheet metal etc.
The manufacture method > of < photonasty laminate
There is no particular restriction for the manufacture method of described photonasty laminate, can suitably select according to object, for example can enumerate: Yi Bian heat and pressurize at least any, Yi Bian at least photographic layer of transfer printing photosensitive film of the present invention and carry out the method for lamination.
One example of the manufacture method of described photonasty laminate on the surface of described matrix while the method for at least any lamination photosensitive film of the present invention that heats and pressurize.In addition, in the situation that described photosensitive film has described diaphragm, preferably this diaphragm is peeled off, with the mode lamination of overlapping described photographic layer on described matrix.
There is no particular restriction for described heating-up temperature, can be according to object and suitably select, and for example preferably 15 ℃～180 ℃, more preferably 60 ℃～140 ℃.
There is no particular restriction for the pressure of described pressurization, can suitably select according to object, for example preferred 0.1MPa～1.0MPa, more preferably 0.2MPa～0.8MPa.
There is no particular restriction to carry out at least any device of described heating, can suitably select according to object, such as enumerating suitably: laminating machine (VP-II manufacturing such as great achievement laminating machine incorporated company, day are closed the VP130 that Morton (Nichigo-Morton) incorporated company manufactures) etc.
Photosensitive film of the present invention and described photonasty laminate can be used for forming the permanent pattern of the fine in field of electronic materials widely, especially can be used to form suitably the permanent pattern of printed base plate.
(permanent pattern forming method)
Permanent pattern forming method of the present invention at least comprises exposure process, and then optionally comprises other operations.
< exposure process >
Described exposure process is as long as be to the operation of utilizing the formed photographic layer of photosensitive polymer combination of the present invention to expose, there is no particular restriction, can suitably select according to object, for example, can enumerate the operation that the photographic layer of described photonasty laminate of the present invention is exposed.
The object of described exposure is as long as be described photographic layer, and there is no particular restriction, can suitably select according to object, while the laminate preferably at least any lamination photosensitive film that heats on base material and pressurize being formed exposes.
There is no particular restriction in described exposure, can suitably select according to object, such as enumerating digit explosure, analogue exposure etc.
Other operations of < >
There is no particular restriction for described other operations, can be according to object and suitably select, and such as the surface treatment procedure, developing procedure, cure process operation, post-exposure operation etc. that can enumerate base material.
-developing procedure-
The operation of described developing procedure for the unexposed portion of described photographic layer is removed.
There is no particular restriction for the method for removing of described exposed portion, can be according to object and suitably select, and such as enumerating the method etc. of removing unexposed portion with developer solution.
There is no particular restriction for described developer solution, can be according to object and suitably select, and such as enumerating the developer solution recorded in paragraph [the 0171]～paragraph [0173] of Japanese Patent Laid-Open 2008-250074 communique etc.
-cure process operation-
Described cure process operation, for after carrying out described developing procedure, is carried out the operation of cure process to the photographic layer of formed pattern.
There is no particular restriction for described cure process operation, can suitably select according to object, such as enumerating suitably blanket exposure processing, comprehensive heat treated etc.
Described blanket exposure process and the method for described comprehensive heat treated there is no particular restriction, can suitably select according to object, such as enumerating the method recorded in paragraph [the 0176]～paragraph [0177] of Japanese Patent Laid-Open 2008-250074 communique etc.
In the situation that the formation method of described permanent pattern is for forming at least any permanent pattern forming method of diaphragm, interlayer dielectric and solder resist pattern; can on printed base plate, by described permanent pattern forming method, form permanent pattern, and then weld as below.
That is, by described development, form the hardened layer as described permanent pattern, on the surface of described printed base plate, expose metal level.To the position of the metal level exposing on the surface of this printing distributing board carry out gold-plated after, weld.Then, on the position of having carried out welding, semiconductor or part etc. are installed.Now, the permanent pattern of described hardened layer performance, as the function of diaphragm or dielectric film (interlayer dielectric), solder resist, prevents from outside impact or adjacent electrode conducting each other.
(printed base plate)
Printed base plate of the present invention is at least have matrix and form by the formed permanent pattern of described permanent pattern forming method, and then has other formations of optionally and suitably selecting.
Other form, and there is no particular restriction, can suitably select according to object, such as enumerating increasing layer (build-up) substrate etc. that insulation course is further being set between base material and described permanent pattern.
Embodiment
Below, enumerate embodiment the present invention is more specifically illustrated, but the present invention is not subject to any restriction of these embodiment.
In addition, the acid number in synthesis example, quality mean molecular weight, ethene unsaturated group equivalent are to utilize following methods to measure.
< acid number >
Acid number is to measure according to JIS K0070.But, in the undissolved situation of sample, use dioxan or tetrahydrofuran etc. as solvent.
< quality mean molecular weight >
About quality mean molecular weight, use efficient GPC device (HLC-802A that Japan Cao Da Industries, Inc manufactures), using the THF solution of 0.5 quality % as sample solution, tubing string is to use a TSKgel HZM-M, and inject the sample of 200 μ L, utilize described THF solution carry out molten from, at 25 ℃, utilize RI-detector or UV detecting device (detection wavelength is 254nm) to carry out quality measurement mean molecular weight.
< ethene unsaturated group equivalent >
Ethene unsaturated group equivalent is to obtain by measuring bromine number according to JIS K2605.
(synthesis example 1)
The synthetic > of the polyurethane resin U1 that < contains acidic group and ethene unsaturated group
In the three mouthfuls of round-bottomed flasks of 500mL that possess condenser and stirring machine, by malic acid 1.9g(0.01 mole), 2, two (hydroxymethyl) propionic acid (DMPA) 8.4g(0.06 mole of 2-), glycerin monomethyl acrylic ester 12.7g(0.08 mole), polypropylene glycol (PPG1000) 10.6g(0.01 mole) and hexamethylene glycol 10.2g(0.07 mole) be dissolved in cyclohexanone 60g.Add therein 4,4'-methyl diphenylene diisocyanate (MDI) 48.1g(0.19 mole), hexamethylene diisocyanate (HMDI) 8.1g(0.05 mole), 2,6-bis--tributyl hydroxy-methylbenzene 0.1g and as the trade name of catalyzer: niostan (Neostan) U-600(day east changes into incorporated company and manufactures) 0.2g adds thermal agitation 5 hours at 75 ℃., with methyl alcohol 9.61mL dilute and stir 30 minute, obtaining the represented polyurethane resin U1 solution (solid constituent is 45 quality %) of following formula of 165g thereafter.
The solid constituent acid number of the polyurethane resin U1 of gained is 48mgKOH/g, and the quality mean molecular weight (polystyrene standard) that utilizes gel permeation chromatograph (GPC) to measure is 11,000.In addition, ethene unsaturated group equivalent is 1.3mmol/g.
[changing 29]
< polyurethane resin U1 >
Figure BDA0000454732150000611
(synthesis example 2)
The synthetic > of the elastomeric vibrin E-1 of <
Make dimethyl terephthalate (DMT) 699 mass parts, dimethyl isophthalate 524 mass parts, dimethyl adipate 226 mass parts, dimethyl sebacate 553 mass parts, 2, 2-dimethyl propylene glycol 417 mass parts, butylene glycol 324 mass parts, ethylene glycol 769 mass parts, Yi Lunuosi (Irganox) 1330(Japan vapour bar (Ciba Japan) incorporated company manufacture as antioxidant) 2 mass parts and butyl titanate 0.9 mass parts are mixed in reactor, under agitation from room temperature, reinstate and within 2 hours, be warmed up to till 260 ℃, then at 260 ℃, heat 1 hour and carry out ester exchange reaction.Then, by slowly decompression and intensification in reactor, with 30 minutes, at 245 ℃, with 0.5torr～2torr, carry out initial stage polycondensation reaction.And then, under 245 ℃, the state of 0.5torr～2torr, to carry out after 4 hours polyreactions, one side imports drying nitrogen and simultaneously with 30 minutes, gets back to normal pressure, with graininess, takes out polyester, acquisition vibrin E-1.Utilize propylene glycol methyl ether acetate that the vibrin E-1 of gained is diluted to dissolving to become the mode of the solid component concentration of 60 quality %, obtain vibrin E-1 solution.
The quality mean molecular weight (polystyrene standard) that utilizes gel permeation chromatograph to measure of the vibrin E-1 of gained is 3.4 ten thousand.
(synthesis example 3)
The synthetic > of < spreading agent D-1
In there-necked flask, add after cyclohexanone 36g, at 80 ℃, nitrogen, flow down with within 1.5 hours, dripping the huge monomer A S-633.6g, 2 that methacrylic acid 2-(dimethylamino) ethyl ester 21.6g, hexahydrophthalic acid list 2-(methacryloxy) ethyl ester 24.8g, East Asia synthetic (thigh) are manufactured, the solution that 2'-azo couple isobutyric acid dimethyl ester 1.28g, 3-mercaptopropionic acid 2-Octyl Nitrite 3.2g, cyclohexanone 78g mix.Reactant liquor was stirred after 3 hours, add cyclohexanone 200g, obtain dispersant solution D-1.
The solid component concentration of polymer dispersant D-1 in dispersant solution D-1 is 20 quality %.
(embodiment 1)
The manufacture > of < photosensitive film
It at the thickness as supporter, is polyethylene terephthalate film (east beautiful (Toray) company manufacture of 16 μ m, 16FB50), the photosensitive polymer combination solution that coating comprises following composition, and make it dry, on described supporter, form the photographic layer that thickness is 30 μ m.On described photographic layer lamination thickness be the polypropylene screen (the special paper company of prince manufactures, Alpha (Alpha) E-200) of 20 μ m as protective seam, manufacture photosensitive film.
-composition of photosensitive polymer combination solution-
Following each composition is mixed, prepare photosensitive composite solution.
The polyurethane resin U1 solution of synthesis example 1 (solid constituent is 45 quality %)
20.3 mass parts
Polymerizable compound: chemical company of DCP-A(common prosperity society manufactures) ... 5.3 mass parts
Thermal cross-linking agent: Albert (Epotohto) YDF-170(Dongdu changes into company and manufactures)
2.9 mass parts
Initiator: Yi Luka (Irgacure) 907(BASF (BASF) company manufactures)
0.6 mass parts
Sensitizer: DETX-S(Japan chemical drug company manufactures) ... 0.005 mass parts
Reaction promoter: EAB-F(hodogaya chemical company manufactures) ... 0.019 mass parts
Dispersible pigment dispersion (hereinafter referred to as " G-2 ") ... 30.1 mass parts
Coating additive: Mei Jiafa (Megafac) F-780F ... 0.2 mass parts
(Japanese ink chemical industrial company manufactures greatly: 30 quality % methyl ethyl ketone solution)
Elastic body: vibrin E-1(solid constituent is 60 quality %)
(vibrin of synthesis example 2) ... 2.7 mass parts
In addition, described dispersible pigment dispersion " G-2 " is that (Yadu agate (Admatechs) company manufactures by silicon dioxide, SO-C2) 32.0 mass parts, the spreading agent D-1 solution of synthesis example 3 (solid constituent is 20 quality %) 2.2 mass parts, the polyurethane resin U1 solution of synthesis example 1 (solid constituent is 45 quality %) 12.0 mass parts, phthalocyanine blue 0.21 mass parts, anthraquinone is yellow uitramarine (C.I.PY24) 0.06 mass parts, ion capturing agent IXE-6107(East Asia Synesis Company manufactures) 1.65 mass parts, after melamine (manufacture of He Guangchun medicine industrial group) 0.35 mass parts and cyclohexanone 77.4 mass parts are pre-mixed, utilize motor muller (Motor Mill) M-250(pure white lattice (Eiger) company to manufacture) use the zirconium oxide bead that diameter is 1.0mm within 3 hours, to prepare with the peripheral speed dispersion of 9m/s.
Here, ion capturing agent IXE-6107(East Asia Synesis Company manufactures) be the potpourri of bismuth oxide and basic zirconium phosphate.
-lamination on matrix-
Chemical grinding processing is implemented in the surface of copper foil laminates (without through hole, copper thickness is 12 μ m) and prepare matrix.On this copper foil laminates; the mode contacting with described copper foil laminates with the photographic layer of described photosensitive film; peel off the diaphragm of described photosensitive film on one side; (day closes Morton (Nichigo-Morton) incorporated company and manufactures to use vacuum laminator on one side; VP130) carry out lamination, preparation is by described copper foil laminates, described photographic layer and described polyethylene terephthalate film (supporter) the photonasty laminate that lamination forms successively.
Crimping condition is time of being set as vacuum draw to be that 40 seconds, crimping temperature are that 70 ℃, crimping pressure are that 0.2MPa, pressing time were 10 seconds.
-exposure process-
Photographic layer for the photonasty laminate of described preparation, from polyethylene terephthalate film (supporter) side, by thering is the glass shade of set pattern, utilize parallel exposing machine (extra-high-pressure mercury vapour lamp) to take energy as 60mJ/cm to obtain the mode of set pattern 2amount irradiate, make a part of region sclerosis of described photographic layer.
-developing procedure-
After at room temperature standing 10 minutes, from described photonasty laminate, strip polyethylene terephthalate film (supporter), use the aqueous sodium carbonate of 1 quality % as alkaline-based developer, at 30 ℃ with 0.18MPa(1.8kgf/cm 2) whole spray development 60 seconds of pressure to the photographic layer on copper foil laminates, unexposed region is dissolved and is removed.Then wash, make it dry, form permanent pattern.
-cure process operation-
To having formed whole of laminate of described permanent pattern, at 150 ℃, implement 1 hour heat treated, thereafter at 1J/cm 2condition under carry out post-exposure, make the surface sclerosis of permanent pattern, improve film strength, thereby make breadboard.
< evaluates >
As below, insulativity, development residue, resolution, thermotolerance and resistance to plating are evaluated.These results are gathered and are shown in following table 1.
< < insulativity > >
In described lamination on matrix, except copper foil laminates being changed into copper thick, be the comb shape substrate of 12 μ m, L/S=25 μ m/25 μ m, with lamination, exposure process, developing procedure, cure process operation of similarly carrying out on matrix mentioned above, make evaluation substrate.
In-service evaluation substrate is implemented the super hot and humid durability test (HAST) of accelerating under 130 ℃, 85%RH, 50V, the condition of 200 hours.
Utilize the optical microscope of 100 times to observe the generation degree of the migration (migration) of the solder resist of substrate for evaluation after this.
[metewand]
AA: without short circuit.And then cannot confirm the generation of migration, insulativity is excellent
A: without short circuit.But on copper, confirm slightly the generation of migration
B: have short circuit.On copper, confirm slightly the generation of migration
C: have short circuit.Also confirm the generation of migration
< < development residue > >
In the evaluation of described resolution, utilize sweep electron microscope (Scanning Electronic Microscopy, SEM) observe the residue of bottom of the circular hole of 80 μ m in formed circular hole pattern and 120 μ m, utilize optical microscope to observe the surface of the copper foil laminates with hardening resin pattern of gained like this, the circular hole bottom of pattern be there is no residue and there is no the curling of drafting department and the smallest circle sectional hole patterns width abnormal and that can form gap such as peel off and measure, by following benchmark, evaluate.
[metewand]
AA: be on the substrate of circular hole of 80 μ m at diameter and Nonvisualization residue, development residue removability is excellent
A: be on the substrate of circular hole of 120 μ m at diameter and Nonvisualization residue, development residue removability is good
B: be the residue that slightly develops on the substrate of circular hole of 120 μ m at diameter, development residue removability is slightly poor
C: be to have development residue on the substrate of circular hole of 120 μ m at diameter, development residue removability is poor
< < resolution > >
By described photonasty laminate under the condition of room temperature (23 ℃), 55%RH standing 10 minutes.The polyethylene terephthalate film (supporter) of the photonasty laminate of gained, use circular hole pattern, take and can form the mode that the diameter width of circular hole is the circular hole of 30 μ m～100 μ m, use patterning device with 60mJ/cm 2expose.
After at room temperature standing 10 minutes, from described photonasty laminate, strip polyethylene terephthalate film (supporter).
To the photographic layer on copper foil laminates whole, sprays the 1 quality % aqueous sodium carbonate of 30 ℃ as developer solution with the atomisation pressure of 0.15MPa, with 2 times of times of described the shortest development time, unhardened region is dissolved and removed.
Utilize optical microscope to observe the surface of the copper foil laminates with hardening resin pattern obtaining like this, to there is no residue, the undercutting (under cut) of drafting department and the minimum circular hole pattern width abnormal and that can form gap such as peeling off and measure, using it as resolution, by following benchmark, evaluate.Numerical value is less, and this resolution is better.
[metewand]
AA: can differentiate diameter is the circular hole below 50 μ m, excellent in resolution
A: can differentiate that diameter surpasses 50 μ m and be the circular hole below 70 μ m, resolution is good
B: can differentiate that diameter surpasses 70 μ m and be the circular hole below 100 μ m, resolution is slightly poor
C: cannot differentiate circular hole, differentiate rate variance
< < thermotolerance > >
By form the solder mask layer comprise each photosensitive composite the evaluation substrate that has been coated with rosin series scaling powder on substrate, in being redefined for the solder bath of 260 ℃, flooded for 30 seconds, utilize after modification alcohol cleaning scaling powder, by the range estimation of following benchmark to the expansion of solder mask layer, peel off and variable color is evaluated.
[metewand]
AA: completely unconfirmed to changing, thermotolerance is excellent especially
A: expand slightly as seen, peel off, variable color any, but excellent heat resistance
B: expand slightly as seen, peel off, but thermotolerance is good
C: part is expanded as seen, peeled off, poor heat resistance
D: the expansion of having filmed, peel off
The resistance to plating > of < < >
To as following like that and the permanent pattern of acquisition is evaluated resistance to plating.
Use to copper foil laminates (without through hole, copper thickness is 12 μ m) surface implemented chemical grinding processor as matrix, in addition, use not other to evaluate with and the photonasty laminate similarly newly made with the situation of the photonasty laminate of initial explanation mentioned above.
On the photographic layer surface of this photonasty laminate, through light shield, with the suitableeest exposure, form 30 μ m～1, the individual wired pattern of 000 μ m, after at room temperature standing 10 minutes, from described photonasty laminate, strip described supporter, for whole of the photographic layer on copper foil laminates, the 1 quality % aqueous sodium carbonate of 30 ℃ is carried out to spray development with the atomisation pressure of 0.15MPa, with the time of 2 times～3 times (or 40 seconds～60 seconds) of described the shortest development time, unhardened region is dissolved and removed.Utilize extra-high-pressure mercury vapour lamp with 200mJ/cm thereafter, 2carry out blanket exposure, and then at 150 ℃, carry out 1 hour heat treated (baking afterwards) and form permanent pattern.
[metewand]
A: completely unstripped
B: live width is less than in the image of 500 μ m and there is no and peel off
C: live width is to peel off in images more than 500 μ m
(embodiment 2, embodiment 3, comparative example 1～comparative example 3)
In embodiment 1, the content of the inorganic filler (silicon dioxide) in the kind of ion capturing agent and photosensitive polymer combination nonvolatile component is changed to the combination of following table 1, in addition, manufacture similarly to Example 1 photosensitive film, laminate and permanent pattern.In addition, the agent of Li Fill foot is to add in the total amount of the ion capturing agent mode identical with embodiment 1.
Similarly to Example 1 these article are evaluated.Its result is gathered to be shown in and state in table 1.
[table 1]
Figure BDA0000454732150000671
By described table 1, clearly learnt, by ion capturing agent, use bismuth, zirconium or antimonial, and to use the content of photoresist in forming be inorganic fillers more than 20 volume %, insulativity, resolution, thermotolerance and resistance to plating are excellent, and development residue is few.Learn in addition, if the content of the ion capturing agent as hydrotalcite or inorganic filler is few, cannot obtain required effect.
The present invention and its enforcement aspect are illustrated in the lump, but as long as the inventor is without specifying, should not limit the invention to any details of explanation, can think that the present invention should be in the situation that do not violate spirit and the scope of the invention shown in the claims of enclosing and explain widely.
The present invention advocates to propose in Japan based on August 19th, 2011 right of priority of the Jap.P. Patent 2011-179961 of patented claim, the content of these applications is usingd to the mode of reference and as the part of the record of this instructions, be incorporated in this instructions.

Claims (28)

1. a photosensitive polymer combination, contain at least respectively resin, inorganic filler, ion capturing agent, free radical polymerization monomer, photopolymerization initiator and thermal cross-linking agent containing ethene unsaturated group for a kind of sour modification, and described photosensitive polymer combination is characterised in that: the content of the described inorganic filler in the nonvolatile component cumulative volume of described photosensitive polymer combination is more than 20 volume %, and described ion capturing agent is at least one the mineral compound that contains Zr, Bi or Sb.
2. photosensitive polymer combination according to claim 1, is characterized in that: described ion capturing agent is the mineral compound being selected from basic zirconium phosphate, wolframic acid zirconium, molybdic acid zirconium, selenic acid zirconium, telluric acid zirconium, bismuth oxide, bismuth titanates, bismuth nitrate, bismuth salicylate, waltherite, antimony pentoxide, antimony oxide, phosphorus metaantimmonic acid, metaantimmonic acid zirconium and metaantimmonic acid titanium.
3. photosensitive polymer combination according to claim 1 and 2, is characterized in that: contain at least one mineral compound that contains Zr and at least one mineral compound containing Bi as described ion capturing agent.
4. according to the photosensitive polymer combination described in any one in claims 1 to 3, it is characterized in that: contain macromolecule dispersing agent, described macromolecule dispersing agent has with the group of the surface interaction of inorganic filler and do not have ethene unsaturated group.
5. photosensitive polymer combination according to claim 4, is characterized in that: described spreading agent is the spreading agent with basic group or acidic-group.
6. according to the photosensitive polymer combination described in claim 4 or 5, it is characterized in that: described spreading agent has one-level amino or secondary is amino.
7. according to the photosensitive polymer combination described in any one in claim 4 to 6, it is characterized in that: described spreading agent has grafted chain.
8. according to the photosensitive polymer combination described in any one in claim 4 to 7, it is characterized in that: the amine value of described spreading agent is more than 0.65mmol/g.
9. according to the photosensitive polymer combination described in any one in claim 4 to 8, it is characterized in that: the acid number of described spreading agent is more than 0.1mmol/g.
10. according to the photosensitive polymer combination described in any one in claim 1 to 9, it is characterized in that: described inorganic filler contains silicon in constituting atom.
11. according to the photosensitive polymer combination described in any one in claim 1 to 10, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin.
12. the photosensitive polymer combination according to described in any one in claim 1 to 11, is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has arbitrary structure of following general formula (1)～general formula (3),
[changing 1]
Figure FDA0000454732140000021
In general formula (1)～general formula (3), R 1～R 11represent independently respectively hydrogen atom or any monovalent organic radical group; X and Y represent independently respectively oxygen atom, sulphur atom or-N (R 12)-; Here, R 12represent hydrogen atom or any monovalent organic radical group; Z represents oxygen atom, sulphur atom ,-N (R 13)-maybe can have substituent phenylene; Here, R 13represent hydrogen atom or any monovalent organic radical group.
13. according to the photosensitive polymer combination described in any one in claim 1 to 12, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and aromatic series part shared ratio in described resin is more than 30 quality %.
14. according to the photosensitive polymer combination described in any one in claim 1 to 13, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has the represented part-structure of following general formula (UB),
[changing 2]
General formula (UB)
Figure FDA0000454732140000022
In general formula (UB), X l1represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-, R u1～R u8represent independently respectively hydrogen atom or substituting group.
15. according to the photosensitive polymer combination described in any one in claim 1 to 14, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and there is the represented part-structure of following general formula (UB), aromatic series part shared ratio in described resin of described general formula (UB) is more than 30 quality %
[changing 3]
General formula (UB)
Figure FDA0000454732140000031
In general formula (UB), X l1represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-, R u1～R u8represent independently respectively hydrogen atom or substituting group.
16. according to the photosensitive polymer combination described in claims 14 or 15, it is characterized in that: in described general formula (UB), and R u1～R u8be hydrogen atom.
17. according to the photosensitive polymer combination described in any one in claim 1 to 16, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has the represented part-structure of following general formula (UNCO),
[changing 4]
General formula (UNCO)
Figure FDA0000454732140000032
In general formula (UNCO), X l1represent singly-bound ,-CH 2-,-CH (CH 3)-,-C (CH 3) 2-,-SO 2-,-S-,-O-or-C (=O)-; R u1～R u8represent independently respectively hydrogen atom or substituting group.
18. photosensitive polymer combinations according to claim 17, is characterized in that: in described general formula (UNCO), and R u1～R u8be hydrogen atom, and X l1for-CH 2-.
19. according to the photosensitive polymer combination described in claim 17 or 18, it is characterized in that: the aromatic series part of described general formula (UNCO) is more than 30 quality % described sour modification containing shared ratio in the polyurethane resin of ethene unsaturated group.
20. according to the photosensitive polymer combination described in any one in claim 1 to 19, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has the represented part-structure of following general formula (UE1),
[changing 5]
General formula (UE1)
Figure FDA0000454732140000041
In general formula (UE1), L uErepresent bivalence linking base, do not contain in the key of main chain-NHC of described bivalence linking base (=O) O-or-OC (=O) NH-, and there is an ethene unsaturated group or containing the group of ethene unsaturated group as substituting group.
21. according to the photosensitive polymer combination described in any one in claim 1 to 20, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has the represented part-structure of following general formula (G1),
[changing 6]
General formula (G1)
Figure FDA0000454732140000042
In general formula (G1), R 1～R 3represent independently respectively hydrogen atom or any monovalent organic radical group; A represents the organic residue of divalence; X represent oxygen atom, sulphur atom or-N (R 12)-, R 12represent hydrogen atom or any monovalent organic radical group.
22. according to the photosensitive polymer combination described in any one in claim 1 to 21, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has the represented part-structure of following general formula (U1),
[changing 7]
General formula (U1)
Figure FDA0000454732140000051
In general formula (U1), L u1represent not contain the bivalence linking base of ethene unsaturated group and carboxyl.
23. according to the photosensitive polymer combination described in any one in claim 1 to 22, it is characterized in that: the resin containing ethene unsaturated group of described sour modification is polyurethane resin, and has carboxylic group in polymer ends.
24. according to the photosensitive polymer combination described in any one in claim 1 to 23, it is characterized in that: the ethene unsaturated group equivalent of the resin containing ethene unsaturated group of described sour modification is more than 1.00mmol/g.
25. 1 kinds of photosensitive films, is characterized in that: it is that the photographic layer having on supporter containing the photosensitive polymer combination described in any one in good grounds claim 1 to 24 forms.
26. 1 kinds of photonasty laminates, is characterized in that: it is that the photographic layer having on matrix containing the photosensitive polymer combination described in any one in good grounds claim 1 to 24 forms.
27. 1 kinds of permanent pattern forming methods, is characterized in that at least comprising: to utilizing, according to the formed photographic layer of the photosensitive polymer combination described in any one in claim 1 to 24, expose.
28. 1 kinds of printed base plates, is characterized in that: it is to utilize permanent pattern forming method according to claim 27 to form permanent pattern to form.
CN201280034051.5A 2011-08-19 2012-08-16 Photosensitive resin composition, and photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed substrate using same Pending CN103649831A (en)

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