CN1717628A - Curable composition, cured object, color filter, and liquid-crystal display - Google Patents

Abstract

A curable composition which not only has high sensitivity but is excellent in adhesion to substrates and thermal stability of the adhesion, especially a curable composition suitable for use as a solder resist or in direct drawing with a laser light. Also provided are: a curable composition which has high curability and excellent mechanical properties and is for use in producing a color filter, black matrix, overcoat, rib, and spacer for use in a liquid-crystal panel for, e.g., a liquid-crystal display; and a cured object obtained from the composition. The curable composition contains a compound represented by the following general formula (I) [wherein R<1> represents optionally substituted alkylene or optionally substituted arylene; n is an integer of 0 to 10; the four benzene rings may be further substituted; R<2> represents carbonyloxy containing optionally substituted, C5 or higher, ethylenically unsaturated group; and R<3> and R<4> each independently represents any desired substituent].

Description

Curable compositions, cured article, color filter and liquid crystal display device

Invention field

The present invention relates to light or heat solidifiable composition, and relate more specifically to curable compositions, it is used in, for example form solder resist (solder resist) film in printed wiring board, liquid crystal display device, plasma display apparatus, large scale integrated circuit, thin type transistor, semiconductor packages, color filter and the organic electroluminescence device or cover ray (cover ray) film, and, be applicable to particularly and pass through laser direct imaging as the insulating cover that is used for various electronic units.

In addition, the present invention relates to curable compositions, it is used for color filter, black matrix (blackmatrixes), finishing coat, rib (ribs) and pad, be used for for example liquid crystal panel of LCD, by cured article and the color filter and liquid crystal display device that uses said composition to form with this color filter.

Background technology

Up to now; when by being welded in the printed wiring board when electronic unit connected up; as diaphragm, be used to prevent solder deposition to the surface arrangement solder resist except the part to be welded of circuit conductor, and prevent that circuit directly is exposed in the air in unnecessary portions.When forming solder resist, adopt photoetching process (lithogrphy) usually, for example by using photosensitive imaging material (being also referred to as image forming material (A)).

Image forming material (A) refers to dry film erosion resistant (resist material), the surface that this material passes through to form the photosensitive composition layer on interim support membrane and covers the photosensitive composition layer with coverlay.

Carry out photoetching process by following process.At first, by the coverlay on the peeling imaged material (A), and it is stacked on the substrate to be made and preparation photosensitive imaging material (hereinafter being called image forming material (B)).Also can follow drying and also randomly cover the surface of photosensitive composition layer, and prepare image forming material (B) by on substrate to be made, directly applying the coating fluid of photosensitive composition with protective seam with formation photosensitive composition layer.

Then, the photosensitive composition layer of the image forming material on the substrate to be made (B) has formed circuit pattern by the exposure of mask imaging type at mask.Then, peel off interim support membrane or protective seam and, form resist image thus corresponding to circuit pattern by utilizing exposure area and unexposed area that the difference between the solubleness of liquid developer is developed.Then, forming the circuit pattern that is depicted on the mask on the substrate, for example, using scolder to substrate to be made and handle by using this resist image as resist.

In recent years, the laser direct imaging method has caused concern, this is because not only aspect throughput rate but also obtaining improvement aspect resolution capability or the positional precision, correspondingly also studied as possible and in photoetching process, utilized laser, this laser imaging method is by using laser not use mask as exposure source, directly forms image from the numerical information of for example computing machine etc.

Simultaneously, as the known various light sources from the ultraviolet to the region of ultra-red of lasing light emitter, and consider power, stability, photoperceptivity and cost, as the small source of the laser that can be used for image exposure (slightsource), as seen emission is to region of ultra-red those, and for example argon laser He-Ne Lasers, YAG laser and semiconductor laser have occupied advantage.For example using, wavelength has dropped into actual use at argon laser and the wavelength of 488nm in the photoetching process of the FD-YAG of 532nm laser.In addition, along with the marked improvement of laser technology in recent years, also can utilize can be at the semiconductor laser of blue-purple regional stability vibration.

Yet, existing photosensitive composition is in the direct imaging method of using laser, particularly when indigo plant-purple semiconductor laser, always do not have enough light sensitivity, therefore at present because this ability is lower with comparing in other visibility region, the light sensitivity of the photosensitive composition of its solution and development also not being reached can be in the level of direct imaging method and practical application in photoetching process.Thus, the material that in can the solder resist of laser explosure, uses of strong request.

On the other hand, as the solder resist that is used for printed wiring board, because high precision and high density, and consider environmental issue, used liquid resist printing ink, as liquid resist printing ink, known up to now photocurable resist ink composite, it contains for example α of epoxy resin, reaction product, photopolymerizable monomer and the Photoepolymerizationinitiater initiater of β-unsaturated monocarboxylic addition compound product and dicarboxylic acid anhydride.

In addition, be used for anti-plating agent (plating resist) in order to improve, the permanance of the light sensitivity of the photocurable photosensitive composition in anti-etchant or the anti-solder flux and development and the image that forms by said composition, known that (Epocryl is by polybasic carboxylic acid or its acid anhydrides being added the α of epoxy resin for the photosensitive composition of the modified epoxy acrylic ester resin that combines alkali-soluble, form in β-unsaturated monocarboxylic adduct), and by using high-pressure sodium lamp or visible laser or infrared laser exposure photoresist image forming material, and develop and form the method for image, the photoresist image forming material obtains by following steps: said composition is stacked on the substrate as the dry film erosion resistant, or on substrate, apply and the coating fluid of dry said composition (for example, referring to patent documentation 1, patent documentation 2 and patent documentation 3).

In addition, in order to improve scolder heating patience, also know the solder resist composition that uses the modified epoxy acrylic ester resin, this resin is by making the reaction of two (hydroxyphenyl) fluorenes type epoxy resin and (methyl) acrylic acid and further with itself and polybasic carboxylic acid or its anhydride reaction acquisition (for example, referring to patent documentation 4).

Yet, consider that light sensitivity and they and base plate bonding to be made are poor, particularly ought be at high temperature as the poor cohesive of solder resist etc., above-mentioned photocurable composition still leaves some room for improvement.

On the other hand, in fields such as LCD, the resin combination that comprises photopolymerizable monomer and Photoepolymerizationinitiater initiater is in being used to form color filter, black matrix, finishing coat, rib and the pad that liquid crystal panel uses.Consider development, pattern precision and cohesive, advised that various compositions are as resin combination.As one of them, in order to form and improve the productive rate that forms technology at short notice, disclosed the technology that contains the unsaturated group resin of using, by epoxy resin and the reaction product that contains unsaturated group carboxylic acid or its acid anhydrides are further obtained this resin (patent documentation 5) with polybasic carboxylic acid or acid anhydride resin reaction.On the other hand, the resin combination that requires sometimes to be used for liquid crystal panel has high curing performance and excellent mechanical property.

For example, keep constant distance in order to make between the substrate in the liquid crystal panel, (" pad " used herein refers to so-called column pad, light pad (photospacer) etc. to have used pad, they are formed by resin combination), and require this pad to have the physical property that before and after press fit (press fitting), causes than small deformation and also can keep the pad function, because in the manufacture process of liquid crystal panel, pad has passed through the step of press fit color filter and substrate under high temperature and high pressure.That is to say,,, be necessary after external pressure is removed, to recover its original-shape even when pad is out of shape by external pressure as the mechanical property of the resin combination that is used for pad in actual applications.Because their above-mentioned gratifying mechanical properties, the resin combination (patent documentation 6) of content of the polyfunctional acrylic ester monomer of appointment has been proposed.

Yet, require this pad to have the pattern precision and cohesive has above-mentioned mechanical property simultaneously.On the other hand,, only contain the unsaturated group resin, can not form and have the resin combination that is suitable for the mechanical property of making pad by what use above-mentioned routine in order to improve pattern precision and adhesion.In addition, for above-mentioned required mechanical property, when the pad that need in the press fit step, demonstrate big total deformation, when being cushion film, only use containing the unsaturated group resin and can forming cushion film of above-mentioned routine, but it is insufficient that they demonstrate the recovery of original-shape after external pressure is removed, thereby be unsuitable for actual use.

[patent documentation 1]

JP-A No.5-204150

[patent documentation 2]

JP-A No.2000-147767

[patent documentation 3]

JP-A No.2001-228611

[patent documentation 4]

JP-A No.4-355450

[patent documentation 5]

JP-A No.2001-174621

[patent documentation 6]

JP-A No.2002-174812

Summary of the invention

Consider that above-mentioned prior art finished the present invention, and the invention is intended to provide have ISO and with the base plate bonding to be made and the curable compositions of excellent heat resistance, particularly be suitable for the curable compositions make solder resist and be applicable to the direct imaging of using laser.

The present invention also provides the curable compositions that can overcome above-mentioned shortcoming, is used for forming image at color filter, and is used at liquid crystal panel, for example the black matrix that uses in the LCD, finishing coat, rib and pad.

The present inventor has carried out research very in earnest to the problems referred to above, and find that purpose of the present invention can obtain by the unsaturated group compound (the carbonyl oxygen base that contains the ethylenic unsaturated group that particularly comprises 5 or more a plurality of carbon atoms) that contains in conjunction with appointment in curable compositions, to finish the present invention.That is to say that main idea of the present invention is as described below.

1. a curable compositions comprises the compound that following formula (I) is represented

[in the formula (I), R ¹Expression can have substituent alkylidene maybe can have substituent arlydene, and n is 0 to 10 integer, and four phenyl ring can further have substituting group; R ²Represent the carbonyl oxygen base that contains the ethylenic unsaturated group of 5 or a plurality of carbon atoms, it can have substituting group; And R ³And R ⁴The substituting group that expression is independently of one another chosen wantonly].

2. curable compositions that can form cured article, described cured article is in the loading-unloading test of being undertaken by the microhardness test instrument, in total deformation is 1.35 μ m or bigger and/or loading bottom offset when being 0.25 μ m, load N is 0.50gf or littler, and its elastic restoration ratio (elasticrecovery) be 50% or bigger and/or recovery rate be 80% or bigger.

3. curable compositions that can form cured article, the bottom transverse sectional area of this cured article (bottom cross sectional area) is 25 μ m ²Littler and elastic restoration ratio be 50% or bigger and/or recovery rate be 85% or more.

4. cured article, it is by using above-mentioned 1 or 2 curable compositions to form.

5. the color filter that has above-mentioned 4 cured article.

6. the liquid crystal display device that has above-mentioned 4 cured article.

The present invention can provide have ISO and with the curable compositions of base plate bonding and excellent heat resistance, a kind of particularly being suitable for made solder resist or is applicable to the curable compositions that carries out direct imaging by laser.

In addition, the present invention can provide the curable compositions of the mechanical property with high curing performance and excellence, is used for using in color filter, black matrix, finishing coat, rib and the pad of liquid crystal panel (for example, LCD).

The accompanying drawing summary

Fig. 1 is a top view, has schematically explained the outline position of shim pattern.

Fig. 2 has schematically explained the longitudinal sectional view of shim pattern.

Fig. 3 has schematically explained load-displacement curve that the load/unload test produces.

In Fig. 1 to 3, mark 1 has shown shim pattern, mark 2 has shown the center line of shim pattern, mark 3 has shown outline position, mark 4 has shown the longitudinal sectional view of shim pattern, mark 5 shown apart from the height of the extreme higher position of substrate surface, and mark 6 has shown the diameter AA ' of circumference in the section above 90% and the mark 7 of the extreme higher position of substrate surface shown.

Embodiment

To specifically describe the present invention.Following description is at an example of preferred implementation of the present invention, and only otherwise exceed main idea of the present invention, the present invention is not limited to this description.

[1] curable compositions

Curable compositions of the present invention contains the compound of (A-1) formula (I) expression and/or the compound (hereinafter being commonly referred to as composition (A) sometimes) that (A-2) has triphenol methane structure.In addition, it preferably contains (B) Photoepolymerizationinitiater initiater and/or thermal polymerization and (C) ethylenically unsaturated compounds.

In addition, using curable compositions of the present invention to be used under the situation of solder resist, finishing coat, rib or pad, can be further combined with (D) epoxy compound, (E) epoxy hardener, (F) amino-compound and (H) inorganic filler.In addition, when using curable compositions of the present invention, preferably further contain (L) colorant and (M) spreading agent and/or dispersing aid as color filter or black matrix.

When the direct imaging method of using curable compositions of the present invention to be used for to be undertaken by laser, it further preferably contains (J) photosensitizing dye (sensitizer dye).

In addition, may further include other inscape (G) polymerization accelerant, (I) surfactant, (K) other alkali soluble resin (alkali soluble resin) and (N) other adjuvant.

Selectively, curable compositions of the present invention has following feature: can form cured article, this product total deformation be 1.35 μ m or bigger and/or when the load bottom offset is 0.25 μ m load N be that 0.50gf or littler and elastic restoration ratio are 50% or bigger and/or recovery rate 80% or bigger.

Selectively, curable compositions of the present invention can form a kind of cured article, and its bottom transverse sectional area is 25 μ m ²Littler and elastic restoration ratio be 50% or bigger and/or recovery rate be 85% or bigger, below will illustrate.

The following describes the various inscapes of curable compositions of the present invention.

[1-1] be the compound of formula (I) expression (A-1)

Curable compositions of the present invention is characterised in that it contains the compound (A-1) of following formula (I) expression:

[in the formula (I), R ¹Expression can have substituent alkylidene maybe can have substituent arlydene; R ²Represent the carbonyl oxygen base that contains the ethylenic unsaturated group of 5 or a plurality of carbon atoms, it can have substituting group; And R ³And R ⁴The substituting group that expression is independently of one another chosen wantonly; N is 0 to 10 integer, and four phenyl ring can further have substituting group].

R ¹The alkylidene of expression preferably has 1 to 5 carbon atom, more preferably methylene, ethylidene, propylidene or butylidene.Arlydene preferably has 6 to 10 carbon atoms, more preferably phenylenes.Wherein, in the present invention, be preferably alkylidene.Substituting group on above-mentioned alkylidene or the arlydene can comprise, for example, and the alkyl of 1 to 15 carbon atom.In addition, n is 0 to 10 integer, is preferably 0 to 5, more preferably 0 to 3.Surpass under the situation of this scope at n, when curable compositions was shaped to cured article, film thickness reduced and the thermotolerance reduction when causing image developing.

R ¹" can have " substituting group and for example comprise, the alkyl of hydrogen atom, halogen atom, hydroxyl, 1 to 10 carbon atom, the alkenyl of 2 to 10 carbon atoms, phenyl, carboxyl, alkylthio group (sulfanyl group), phosphino-, amino and nitro.

Can have substituent R ²The carbonyl oxygen base that contains the ethylenic unsaturated group in the carbon number purpose upper limit without limits, as long as it is 5 or bigger, and be preferably 50 and more preferably 30.When using curable compositions of the present invention to be used for solder resist, the carbon number purpose upper limit more preferably 20, and be preferably 10 especially.

In addition, R ²The carbonyl oxygen base that contains the ethylenic unsaturated group group of following formula (II) expression more preferably:

[in formula (II), R ⁷, R ⁸And R ⁹Represent hydrogen atom or methyl independently of one another, Y ¹* represents the bonding position with the compound of formula (I) expression in divalent group that expression is optional and the formula].

Y ¹Preferred expression divalent group comprises can having substituent alkylidene and/or can have substituent arlydene and carbonyl oxygen base.

Its further preferred expression divalent group comprises the alkylidene that can have substituent 1 to 10 carbon atom and/or can have the arlydene and the carbonyl oxygen base of substituent 1 to 10 carbon atom.

R ³Preferred expression hydrogen atom, by the substituting group of following formula (IIIa) expression with by the substituting group of following formula (IIIb) expression:

[in the formula (IIIa), R ⁵¹Expression can have substituent alkyl, can have substituent alkenyl, can have substituent naphthenic base, can have substituent cycloalkenyl group and maybe can have substituent aryl].

Be used for R ⁵¹Alkyl preferably have 1 to 20 carbon atom, alkenyl preferably has 2 to 20 carbon atoms, naphthenic base preferably has 3 to 20 carbon atoms, cycloalkenyl group preferably has 3 to 20 carbon atoms and aryl preferably has 6 to 20 carbon atoms.

R ⁵¹" can have " substituting group and for example can comprise, the alkyl of hydrogen atom, halogen atom, hydroxyl, 1 to 10 carbon atom, alkenyl, phenyl, carboxyl, carbonyl, alkylthio group, phosphino-, amino and the nitro of 2 to 10 carbon atoms.Wherein, preferably have carboxyl:

[in the formula (IIIb), R ⁵²Expression can have substituent alkyl, can have substituent alkenyl, can have substituent naphthenic base, can have substituent cycloalkenyl group maybe can have substituent aryl].

Be used for R ⁵²Alkyl preferably have 1 to 20 carbon atom, alkenyl preferably has 2 to 20 carbon atoms, naphthenic base preferably has 3 to 20 carbon atoms, cycloalkenyl group preferably has 3 to 20 carbon atoms, or aryl preferably has 6 to 20 carbon atoms.

R ⁵²The substituting group that " can have " for example can comprise, the alkyl of hydrogen atom, halogen atom, hydroxyl, 1 to 10 carbon atom, alkenyl, phenyl, carboxyl, carbonyl, alkylthio group, phosphino-, amino or the nitro of 2 to 10 carbon atoms.

To R ⁴The substituting group of expression is not particularly limited, and for example can comprise, by the substituting group of following formula (IV) expression:

[in formula (IV), R ¹, R ², R ³With n have with formula (I) in identical meaning and * represent bonding position with the compound of formula (1) expression].

Substituting group in the formula (I) on the phenyl ring for example can comprise; the alkoxy carbonyl or the halogen atom of the aryl of the acyl group of the alkoxy of the alkyl of 1 to 15 carbon atom, 1 to 15 carbon atom, 2 to 15 carbon atoms, 6 to 14 carbon atoms, carboxyl, hydroxyl, 2 to 16 carbon atoms, and alkyl, phenyl or the halogen atom of further preferred 2 to 5 carbon atoms.

Consider its preparation method, compound by formula (I) expression is not particularly limited, as long as it has described structure and for example can comprise, the compound that two (hydroxyphenyl) fluorenes type epoxy compounds of representing by following formula (V) obtain, more specifically, can comprise the compound that obtains by following steps: from compound by formula (V) expression, to forming 5 or the carbonyl oxygen base that contains the ethylenic unsaturated group of more a plurality of carbon atoms on it, further be selected from polybasic carboxylic acid and acid anhydride thereof or contain one or more compounds reactions in the compound of isocyanate groups:

[in the formula (V), R ¹, n and the substituting group that can on four phenyl ring, exist have respectively with formula (I) in identical implication, R ⁵Have and the middle R of formula (I) ¹Identical implication].

Two (hydroxyphenyl) fluorenes that form two (hydroxyphenyl) fluorenes type epoxy compounds of formula (V) for example can comprise, 9,9-pair (4 '-hydroxyphenyl) fluorenes, 9,9-pair (4 '-hydroxyl-3 '-tolyl) fluorenes, 9,9-pair (4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) fluorenes, 9,9-pair (4 '-hydroxyl-3 '-methoxyphenyl) fluorenes, 9,9-pair (4 '-hydroxyl-3 '-fluorophenyl) fluorenes, 9,9-pair (4 '-hydroxyl-3 '-chlorphenyl) fluorenes, 9,9-pair (4 '-hydroxyl-3 ', 5 '-dichlorophenyl) fluorenes, 9,9-pair (4 '-hydroxyl-3 '-bromophenyl) fluorenes and 9,9-pair (4 '-hydroxyl-3 ', 5 '-dibromo phenyl) fluorenes.Two (hydroxyphenyl) fluorenes type epoxy compound can use separately, or in them two or more are used in combination.

In addition, the carbon number purpose upper limit of the carbonyl oxygen base that contains the ethylenic unsaturated group that forms two (hydroxy phenyl) fluorenes type epoxy compounds of formula (V) expression is not particularly limited, and it is preferably 50, and more preferably 20.When using curable compositions of the present invention to be used for solder resist, this carbon number purpose upper limit more preferably 20, and be preferably 15 especially.At carbon atom number during less than above-mentioned scope, when curable compositions is shaped to cured article, flexible deficiency and deterioration with the cohesive of substrate.On the other hand, when carbon atom number is excessive, reduced thermotolerance.

The carbonyl oxygen base that contains the ethylenic unsaturated group is preferably the group of being represented by following formula (II):

[in the formula (II), R ⁷, R ⁸And R ⁹Represent hydrogen atom or methyl independently of one another; Y ¹The divalent group that expression is optional; * represents the bonding of two (hydroxyphenyl) fluorenes type epoxy compounds in the formula, and this compound has the methylene by the open loop acquisition of epoxide group].

Form formula (II) expression the carbonyl oxygen base that contains the ethylenic unsaturated group method without limits, so long as forms acquisition from compound by formula (V) expression.The formation method can for example comprise particularly, make the carboxylic acid that contains the ethylenic unsaturated group and formula (V) expression the compound reaction method and at first reaction do not comprise the carboxylic acid of ethylenic unsaturated group, the method that forms by subsequent reaction then.

The carboxylic acid that contains the ethylenic unsaturated group comprises, for example, (methyl) acrylic acid [" (methyl) acryloyl group " expression in the present invention " acryloyl group " and/or " methacryl "] and lactone (lacton) or polylactone, by reacting the half ester of (methyl) acrylate derivative acquisition that has one or more hydroxyls in saturated or unsaturated dicarboxylic acid anhydride and the molecule, this dicarboxylic anhydride is succinic anhydride for example, adipic anhydride, maleic anhydride, fumaric acid anhydride, itaconic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, (endo) methylene tetrabydrophthalic anhydride in the methyl, or phthalic anhydride, with (methyl) acrylate derivative that in a molecule, has one or more hydroxyls, (methyl) acrylic acid hydroxyethyl ester for example, (methyl) acrylic acid hydroxy-propyl ester, (methyl) acrylic acid hydroxybutyl ester, polyethyleneglycol (methyl) acrylate, two (methyl) acrylic acid glyceride, trimethylolpropane two (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate or dipentaerythritol five (methyl) acrylate; With by reacting above-mentioned saturated or unsaturated dicarboxylic acid anhydride and containing the half ester that the diglycidyl compound of unsaturated group obtains, for example phenylglycidyl ether, glycidyl (methyl) acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl ester, 8,9-epoxy [dicyclo [4.3.0] ninth of the ten Heavenly Stems-3-yl] (methyl) acrylate, 8,9-epoxy [dicyclo [4.3.0] ninth of the ten Heavenly Stems-3-yl] oxygen methyl (methyl) acrylate.Wherein, preferred in the present invention by reacting the half ester that succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride etc. and (methyl) acrylic acid hydroxyethyl ester, (methyl) acrylic acid hydroxy-propyl ester, (methyl) acrylic acid hydroxybutyl ester, pentaerythrite three (methyl) acrylate, dipentaerythritol ester five (methyl) acrylic acid etc. obtain.They can use separately, or two or more are used in combination.

In addition, the carboxylic acid that does not contain the ethylenic unsaturated group comprises the hydroxyl carboxylic acid, for example lactic acid and dihydroxy propylene and acid anhydride thereof; Saturated or unsaturated dicarboxylic, for example succinic acid, maleic acid, tetrahydrophthalic acid, phthalic acid, tartrate and acid anhydride thereof.Then, reaction forms has the compound that heap hydroxyl or carboxyl have reactive functional group, forms 5 or the carbonyl oxygen base that contains the ethylenic unsaturated group of more a plurality of carbon atoms.Have compound that heap hydroxyl or carboxyl have reactive functional group preferably include have epoxy radicals, the compound of carboxyl or isocyanate groups, they comprise carboxylic acid that contains the ethylenic unsaturated group and the compound that contains the ethylenic unsaturated group particularly, the glycidyl compound that for example contains unsaturated group, and to them without any restriction.

In addition, after the carbonyl oxygen base that contains the ethylenic unsaturated group of formation 5 or more a plurality of carbon atoms, the polybasic carboxylic acid or its acid anhydrides that further react two (hydroxyl) phenyl fluorenes epoxy compounds that form formula (V) expression for example comprise, saturated or unsaturated dicarboxylic, succinic acid for example, maleic acid, itaconic acid, tetrahydrophthalic acid, the methyl tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthaacid acid, methylene tetrahydrophthalic acid and phthalic acid and acid anhydrides thereof in the methyl, trimellitic acid and hydride thereof and can substituted aliphatic series or aromatic acid, for example pyromellitic acid, the benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid and diphenyl ether tetrabasic carboxylic acid, BTCA and acid anhydrides thereof.

Wherein, be preferably tetrahydrophthalic acid, dicarboxylic acid, for example phthalic acid and acid anhydrides thereof, trimellitic acid and acid anhydrides thereof, tetrabasic carboxylic acid is pyromellitic acid, biphenyltetracarboxyacid acid, BTCA and acid anhydrides thereof for example, this is that ternary or low-grade carboxylic acid be trimellitic acid and acid anhydrides thereof for example because they as the character excellence that the non-image part of curable compositions when alkali develops removed by dissolving, are preferably dicarboxylic acid for example tetrahydrophthalic acid and phthalic acid and acid anhydrides thereof especially.

In addition, compound with isocyanate groups comprises organic single-isocyanate, butane isocyanates for example, 3-chlorobenzene isocyanates, cyclohexane isocyanates and 3-isopropenyl-α, the α-Er Jiajibianji isocyanates, aromatic isocyanate is for example to phenylene vulcabond, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, naphthalene-1,5 ,-diisocyanate and tolidine diisocyanate, aliphatic vulcabond is hexamethylene diisocyanate for example, 2,4,4-trimethyl hexamethylene diisocyanate and dimer acid diisocyanate, cycloaliphatic diisocyanates, for example isophorone (isopholone) two isocyanic acids 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and ω, ω '-diisocyanate dimethyl cyclohexane; The aliphatic vulcabond that comprises aromatic ring, for example Xylene Diisocyanate, α, α, α ', α '-tetramethylxylene diisocyanate, triisocyanate be lysine ester triisocyanate, 1 for example, 6,11-undecane triisocyanate, 1,8-diisocyanate-4 isocyanates methyloctane, 1,3,6-hexa-methylene triisocyanate, norbornane triisocyanate, three (isocyanate benzene methylmethane), three (isocyanate phenyl) thiophosphate, and trimer and water addition compound product and polyvalent alcohol addition compound product thereof.

The preferably dipolymer of organic diisocyanate and trimer, the more preferably trimer of the trimethylolpropane addition product of toluene diisocyanate, toluene diisocyanate and Trimerization of Isophorone Diisocyanate thing.They can use separately or in them two or more are used in combination.

For the compound by formula (I) expression of the present invention, acid number is preferably 30 to 150mgKOH/g, and more preferably 40 to 100mgKOH/g.In addition, by gel permeation chromatography, the weight-average molecular weight that is transformed by polystyrene is preferably 1,000 to 100,000 and more preferably 1,500 to 10,000.

In addition, concrete synthetic method for the compound by formula (I) expression of the present invention, its for example known method preparation by describing so far, for example, method in patent documentation 4, especially by the following method: at for example MEK, suspend in the organic solvent of ethyl cellosolve acetate or butyl cellosolve acetate or two (hydroxyphenyl) fluorenes epoxy compounds of dissolving, add the carboxylic acid that contains the ethylenic unsaturated group, its addition is generally 0.8 to 1.5 chemical equivalent amount, be preferably 0.9 to 1.1 chemical equivalent amount, epoxide group based on a chemical equivalent amount of epoxy compound, in the presence of following material: tertiary amine is triethylamine for example, benzyl methyl amine and tribenzyl amine or quaternary ammonium salt, tetramethyl ammonium chloride for example, the methyl chloride triethyl ammonium, etamon chloride, tetrabutylammonium chloride and 3-ethyl benzyl ammonium chloride, phosphorus compound, for example triphenylphosphine or catalyzer, antimonous hydride for example, for example, the triphenyl antimonous hydride, at for example quinhydrones, under the common existence of the thermal polymerization of hydroquinone monomethyl ether and methylnaphthohydroquinone, be generally 60 to 150 ℃, carry out addition reaction when being preferably 80 to 120 ℃, then add polybasic carboxylic acid or its acid anhydrides, its addition is generally 0.05 to 1.0 chemical equivalent amount, hydroxyl based on the reaction of a chemical equivalent amount forms continues reaction under these conditions.

[1-2] (A-2) has a resin of triphenol methane structure

Except composition (A-1), curable compositions of the present invention can also contain the resin (A-2) with triphenol methane structure and the composition (A-1) that replacement is described in [1-1], as long as satisfy the physical property condition that the back is described in [1-15] and/or [1-16].

Resin with triphenol methane structure of the present invention is not particularly limited, as long as it has triphenol methane structure in resin structure, and can preferably include by reaction polybasic carboxylic acid or its acid anhydride and the epoxy resin with triphenol methane structure and (methyl) acrylic acid and its acid anhydride or contain the resin that the reaction product of the carboxylic acid of ethylenic unsaturated group obtains.

Epoxy resin with triphenol methane structure for example can comprise, [EPPN-501H], [EPPN-501HY] and [EPPN-502H] that Nippon Kayaku Co. makes.

In addition, the resin with triphenol methane structure for example can comprise, [TCR1025], [TCR1064] and [TCR1286] that Nippon Kayaku Co. makes.

Be illustrated in the composition (A-1) of neccessary composition of conduct curable compositions of the present invention of per unit weight and/or the number of the two keys in the composition (A-2) by two key equivalents, wherein two key equivalent=(weight of compound (g))/(molal quantity of two keys in the compound).The value of two key equivalents increases along with the double key number of unit weight and reduces.Double key number order in whole compositions (A) is preferably 550 or littler, and more preferably 400 or littler, most preferably be 350 or littler, it is used for recovery rate or the elastic restoration ratio that pad improves curable compositions of the present invention with box lunch.

The double key number order of the whole curable compositions of the present invention of per unit weight is preferably 220 or littler, and more preferably 160 or littler, most preferably be 150 or littler.

Can estimate the value of two key equivalents by following formula from the use amount of compound with the two keys of alkene, perhaps (for example at complication system, resist) under the situation, through type (two key equivalent)=(two key equivalents of resist solution) * (solids content in the resist) estimated the value of two key equivalents, and wherein each value on formula the right can obtain by known method.

[1-3] be Photoepolymerizationinitiater initiater and/or thermal polymerization (B)

Curable compositions of the present invention can also contain Photoepolymerizationinitiater initiater and/or thermal polymerization.Photoepolymerizationinitiater initiater as composition (B) is a kind of reactive compound, this compound produces active substance when curable compositions carries out the actinic ray irradiation, free radical for example, acid or alkali, and polymerization is by the compound of formula (I) expression and the ethylenically unsaturated compounds as composition (C) of the optional use that describes below, this Photoepolymerizationinitiater initiater for example comprises, acetophenones, Benzophenones, Hydroxybenzenes, the thioxanthene ketone, the anthraquinone class, the ketal class, six aryl bisglyoxaline classes, dicyclopentadienyltitanium class (titanocenes), the halogenated hydrocarbons derivant, organic borate (ester), salt, sulphones, carbamic acid derivative, sulfonamides (sulfoneaminds) and triaryl methyl alcohol class.

Respectively, acetophenones for example can comprise, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1-hydroxycyclohexylphenylketone, 1-hydroxyl-1-(right-dodecylphenyl) ketone, 1-hydroxyl-1-Methylethyl-(right-isopropyl phenyl) ketone, 1-trichloromethyl-(tert-butyl-phenyl) ketone, alpha-hydroxy-2-tolyl acetone and alpha-aminoacetophenone; Benzophenones for example can comprise, benzophenone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone 2-carbonyl benzophenone, 2-chloro benzophenone, 4-bromine benzophenone and rice Chi (Michler ') ketone; Hydroxybenzenes for example can comprise, 2-hydroxyl-4-n-octyloxy benzophenone, 2-hydroxyl-4-benzyl benzophenone, 2-(2-hydroxy-5-methyl phenyl) benzotriazole and 4-two-tert-butyl-phenyl-3,5-two-tertiary butyl-4-hydroxy benzoic ether; The thioxanthene ketone for example can comprise, thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones and 2-clopenthixal ketone; The anthraquinone class for example can comprise, 2-methylanthraquinone; For example can comprise benzyl dimethyl ketal with the ketal class.

In addition, six aryl bisglyoxaline classes for example can comprise 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-four (neighbour, right-dichlorophenyl) bisglyoxaline, 2,2 '-two (neighbours, right-dichlorophenyl)-(4,4 '-5,5 '-four (neighbour, right-dichlorophenyl) bisglyoxaline, 2,2 '-two (neighbour-dichlorophenyl)-4,4 ', 5,5 '-four (right-fluorophenyl) bisglyoxaline, 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-four (neighbour, right-dibromo phenyl) bisglyoxaline, 2,2 '-two (neighbour-bromophenyl)-4,4 '-5,5 '-four (neighbour, right-dichlorophenyl) bisglyoxaline, 2,2 '-two (neighbour-chloro)-4,4 ', 5,5 '-four (right-chloronaphthyl, methylnaphthyl) bisglyoxaline.Wherein, be preferably the hexaphenyl united imidazole, and more preferably wherein be bonded to 2 of bisglyoxaline ring, 2 '-phenyl ring of position replaced by halogen atom at the ortho position ripple those, especially preferably wherein be bonded to 4,4 of bisglyoxaline ring ', 5,5 '-phenyl ring of position is unsubstituted, perhaps those that are replaced by halogen atom or alkoxy carbonyl.

The dicyclopentadienyltitanium class for example can comprise, titanocene dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl two (2, the 4-difluorophenyl) titanium, two (2, the 6-difluorophenyl) titaniums of dicyclopentadienyl, dicyclopentadienyl two (2,4, the 6-trifluorophenyl) titanium, dicyclopentadienyl two (2,3,5,6-tetrafluoro phenyl) titanium, dicyclopentadienyl two (2,3,4,5, the 6-pentafluorophenyl group) titanium, two (methyl cyclopentadienyl) two (2, the 6-difluorophenyl) titanium, two (methyl cyclopentadienyl) two (2,3,4,5, the 6-pentafluorophenyl group) two [2,6-two fluoro-3-(1-pyrrole radicals) phenyl] titaniums of titanium and dicyclopentadienyl.Wherein, be preferably titanium compound with bicyclopentadiene based structures and biphenyl structural, more preferably wherein cyclohexyl biphenyl replaced by halogen atom at the ortho position those.

In addition, the halogenated hydrocarbons derivant for example can comprise, the s-triazine of halomethylation (s-triazine) derivant, and they comprise 2,4,6-three (monochloro methyl)-s-triazine, 2,4,6-three (dichloromethyl)-s-triazine, 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-just-propyl group-4, two (the trichloromethyl)-s-triazine of 6-, 2-(α, α, β-three chloroethyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(3, the 4-epoxy-phenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-chlorphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-[1-is right-methoxyphenyl) and-2, the 4-butadienyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-styryl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-methoxyl--hydroxystyrene based)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-the isopropoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-tolyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-the methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-the ethoxy naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(right-the ethoxy carbonyl naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-phenyl sulfenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-benzyl sulfenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2,4,6-three (two bromomethyls)-s-triazine, 2,4,6-three (trisbromomethyl)-s-triazine, 2-methyl-4, two (trisbromomethyl)-s-triazine of 6-and 2-methoxyl-4, two (the trisbromomethyl)-s-triazine of 6-wherein are preferably two (trihalomethyl)-s-triazine.

In addition, organic borate in them (ester) for example can comprise, organic boron ammonium complex compound, organic boron phosphine complex compound, organic boron sulfonium complex compound, organic boron oxygen sulfonium complex compound, organic boron iodo-complexes and organic boron transition metal coordination complexes, and its organic boron anion for example can comprise, alkyl-triphenyl borine negative ion is normal-butyl-triphenyl borine negative ion for example, normal-butyl-three (2,4, the 6-trimethylphenyl) boron anion, normal-butyl-three (right-methoxyphenyl) boron anion, normal-butyl-three (right-fluorophenyl) boron anion, normal-butyl-three (-fluorophenyl) boron anion, normal-butyl-three (3-fluoro-4-tolyl) boron anion, normal-butyl-three (2, the 6-difluorophenyl) boron anion, normal-butyl-three (2,4, the 6-trifluorophenyl) boron anion, normal-butyl-three (2,3,4,5, the 6-pentafluorophenyl group) boron anion, normal-butyl-three (right-chlorphenyl) boron anion and normal-butyl-three (2,6-two fluoro-3-pyrrole radicals phenyl)-boron anion; And kation for example can comprise that compound is ammonium cation, phosphonium cation, sulfonium cation and iodine kation for example, for example is preferably ammonium cation, is preferably tetra-allkylammonium especially.

Salt for example can comprise that ammonium salt is tetramethylammonium bromide, tetraethylammonium bromide etc. for example; Salt compounded of iodine, for example diphenyl iodine hexafluoro arsenate, diphenyl iodine tetrafluoroborate, diphenyl iodine right-toluene sulfonate, diphenyl iodine camsilate, dicyclohexyl iodine hexafluoro arsenate, dicyclohexyl iodine tetrafluoroborate, dicyclohexyl iodine be right-toluene sulfonate and dicyclohexyl iodine camsilate; Sulfonium salt, for example triphenylsulfonium hexafluoro arsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium right-toluene sulfonate, triphenylsulfonium camsilate, thricyclohexyl sulfonium, hexafluoro arsenate, thricyclohexyl sulfonium tetrafluoroborate, thricyclohexyl sulfonium be right-toluene sulfonate, thricyclohexyl sulfonium camsilate etc.

In addition, sulphones for example can comprise, for example two (phenyl sulfonyl) methane of two (sulfonyl) methane compounds, two (right-the hydroxyphenyl sulfonyl) methane, two (right-the methoxyphenyl sulfonyl) methane, two (Alpha-Naphthyl sulfonyl) methane, two (betanaphthyl sulfonyl) methane, two (cyclohexyl sulfonyl) methane, two (tert-butyl group sulfonyl) methane and phenyl sulfonyl (cyclohexyl sulfonyl) methane etc.; Carbonyl (sulfonyl) methane compounds, for example phenylcarbonyl group (phenyl sulfonyl) methane, naphthyl carbonyl (phenyl sulfonyl) methane, phenylcarbonyl group (naphthyl sulfonyl) methane, cyclohexyl-carbonyl (phenyl sulfonyl) methane, tert-butyl group carbonyl (phenyl sulfonyl) methane, phenylcarbonyl group (cyclohexyl sulfonyl) methane, phenylcarbonyl group (tert-butyl group carbonyl) methane etc.; Carbonyl (sulfonyl) diazomethane compound, for example two (phenyl sulfonyl) diazomethanes; two (right-the hydroxyphenyl sulfonyl) diazomethane; two (right-the methoxyphenyl sulfonyl) diazomethane; two (Alpha-Naphthyl sulfonyl) diazomethane; two (betanaphthyl sulfonyl) diazomethane; two (cyclohexyl sulfonyl) diazomethane; two (tert-butyl group sulfonyl) diazomethane; phenyl sulfonyl (cyclohexyl sulfonyl) diazomethane; two (sulfonyl) diazomethane compound; phenylcarbonyl group (phenyl sulfonyl) diazomethane; naphthyl carbonyl (phenyl sulfonyl) diazomethane; phenylcarbonyl group (naphthyl sulfonyl) diazomethane; cyclohexyl-carbonyl (phenyl sulfonyl) diazomethane; tert-butyl group carbonyl (phenyl sulfonyl) diazomethane; phenylcarbonyl group (cyclohexyl sulfonyl) diazomethane; phenylcarbonyl group (tert-butyl group carbonyl) diazomethane etc.

In addition, respectively, carbamic acid derivative for example can comprise, benzoyl cyclohexyl carbamate, 2-nitrobenzyl cyclohexyl carbamate, 3,5-dimethoxy-benzyl cyclohexyl carbamate, 3-nitrobenzophenone cyclohexyl carbamate etc., its sulfonamide, for example, just-cyclohexyl-4-aminomethyl phenyl sulfonamide, just-cyclohexyl-2-naphthyl sulfonamide; And triaryl methyl alcohol for example can comprise triphenylcarbinol, three (4-chlorphenyl) methyl alcohol etc.

The thermal polymerization that constitutes the composition (B) of curable compositions of the present invention is a kind of reactive compound, when the heating curable compositions, this active ingredient deposits yields active substance, free radical for example, and composition (C) ethylenically unsaturated compounds of the compound of gathering (I) expression and the optional use that describes below, and they for example can comprise, organic peroxide and azo-compound.

Organic peroxide compounds for example can comprise, ketone peroxide, for example methyl-ethyl-ketone peroxide, methyl-isobutyl ketone peroxide, acetyl acetone peroxide, cyclohexanone superoxide, methyl cyclohexanone peroxide, 3,3,5-trimethyl hexanone peroxide etc.; Diacyl peroxide, isobutyl peroxide, 3 for example, 5,5-trimethyl acetyl base superoxide, benzoyl peroxide base, neighbour-methyl benzoyl superoxide ,-chlorobenzene formacyl superoxide, 2,4-dichloro-benzoyl base superoxide ,-toluyl superoxide etc.; Hydroperoxides, for example tert butyl hydroperoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxides, right-the terpane hydroperoxides, 2,5-dimethylhexane-2,5-dihydro-peroxidase, 1,1,3,3-tetramethyl butyl hydroperoxides, 2,4,4-tri-methyl-amyl-2-hydroperoxides; Dialkyl peroxide, for example two-tert-butyl peroxide, tert-butyl group cumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) benzene, 2-two (tert-butyl hydroperoxide isopropyl), 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexin etc.; Ketal peroxide, for example 1, two (tert-butyl hydroperoxide) cyclohexanes of 1-, 1, two (tert-butyl hydroperoxide)-3,3 of 1-, 5-trimethyl-cyclohexane, 2, two (tert-butyl hydroperoxide) butane of 2-and normal-butyl 4, two (tert-butyl hydroperoxide) valerates of 4-; Alkyl super-acid ester, for example tert-butyl hydroperoxide acetic acid esters, tert-butyl hydroperoxide caprylate, t-butylperoxy pivarate, tert-butyl hydroperoxide neodecanoic acid ester, tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester, tert-butyl hydroperoxide laurate, two-tert-butyl hydroperoxide triethyl adipate, tert butyl peroxy benzoate, α-cumyl new decanoate ester peroxide, 2,4-4-triethyl amyl peroxy phenoxyacetic acid ester etc.; With peroxycarbonates two-2-ethylhexyl peroxidating heavy carbonic ester for example; two-2-ethoxyethyl group peroxidating heavy carbonic ester; diisopropyl peroxidating heavy carbonic ester; dimethoxy isopropyl peroxidating heavy carbonic ester; two-3-methoxyl butyl peroxy heavy carbonic ester; two (3-methyl-3-methoxyl butyl) peroxidating heavy carbonic ester; tert-butyl hydroperoxide isopropyl carbamate; the tert-butyl hydroperoxide alkyl carbonate; two (4-tert-butylcyclohexyl) peroxidating heavy carbonic esters and acetyl group cyclohexyl sulfonyl peroxidating heavy carbonic ester etc.

Azo-compound for example can comprise, 1,1 '-azo bis cyclohexane-1-nitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-two (the 4-methoxyls-2 of azo, the 4-methyl pentane nitrile), 2,2 '-azo two (methyl-isobutyl thing), α, α-azo two (isobutyronotrile), 4,4 '-azo two (4-cyanopentanoic acid) etc.

Among the present invention, between Photoepolymerizationinitiater initiater and/or thermal polymerization as mentioned component (B), be preferably the alpha-aminoacetophenone derivant, for example acetophenone is used for Photoepolymerizationinitiater initiater, and those of preferred especially following formula (VII) expression.

[in formula (VII), R ³⁵Expression can have substituent alkyl, can have substituent allyl maybe can have substituent phenyl, R ³⁶Expression can have substituent alkyl or have substituent allyl, R ³⁷And R ³⁸Expression independently of one another can have substituent alkyl, have substituent allyl and maybe can have substituent phenyl, R ³⁷And R ³⁸Can be bonded to each other, or R ³⁷Or R ³⁸And R ³⁵Or R ³⁶Can be bonded to each other respectively, form ring texture, and phenyl ring can have substituting group].

As being used for formula (VII) R ³⁵, R ³⁶, R ³⁷And R ³⁸Alkyl, preferably have the alkyl of 1 to 15 carbon atom, especially preferably have the alkyl of 1 to 10 carbon atom.In addition, the substituting group in alkyl, allyl and the phenyl comprises alkyl, alkoxy, hydroxy alkyl, hydroxy alkoxy base, acetoxyl group alkoxy, alkoxy alkoxy, alkyl-carbonyl alkyl, alkyl sulfide, haloalkyl, phenyl, halogen atom etc.In addition, by the R that is bonded to each other ³⁴And R ³⁵Or by the R that is bonded to each other ³⁷Or R ³⁸And R ³⁵Or R ³⁶The ring texture that forms comprises pyrrolidine, piperazine, piperidines, morpholine, oxazolidine, pyrazine etc.

In addition, the substituting group on the phenyl ring comprises alkyl, hydroxyl, alkoxy, allyloxy, phenoxy group, benzoyl, siloxy (silyoxy group), mercapto, alkylthio group, allyl sulfenyl, naphthenic base sulfenyl, benzyl sulfenyl, phenyl sulfenyl, alkyl sulphonyl, phenyl sulfonyl, alkyl sulphinyl, alkyl amino, allyl amino, acetophenone diazanyl, piperidyl, piperadinyl group, morpholinyl, halogen atom etc.; Phenyl ring can have fused rings, and this fused rings comprises Fluorenone, Dibenzosuberone, indoline, quinazoline (quinoquisaline), carbazole, azophenlyene (phenadine), 9-acridone, benzodioxan (benzodioxole), coumarone, xanthene, xanthone, phenoxazine (phenoxadine), benzodiazole (benzochiazole), phenothiazine etc.

When specifically dividing according to the basic framework of compound and enumerating the carbon atom of each number, above-mentioned alpha-aminoacetophenone derivant by formula (VII) expression comprises following compound.Wherein particularly preferably be a kind of compound: R wherein ³⁵And R ³⁶Represent methyl, ethyl or benzyl independently of one another, R ³⁷And R ³⁸Represent methyl separately or form the morpholinyl of ring texture by being bonded to each other, and phenyl ring do not have substituting group or have methyl sulfenyl, dimethylamino or morpholinyl as substituting group, preferred especially phenyl ring only has morpholinyl in contraposition.

Propane-1-ketone (propane-1-on) is divided those of the basic framework with 3 carbon atoms; and comprise for example 1-phenyl-2-dimethylamino-2-methyl-3-(4-aminomethyl phenyl) propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(4-methoxyphenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(3; the 4-Dimethoxyphenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(4-methyl mercapto phenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(4-fluorophenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(2-chlorphenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(4-chlorphenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(4-bromophenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-methyl-3-(4-benzoyl phenyl)-propane-1-ketone; 1-phenyl-2-dimethylamino-2-benzyl-propane-1-ketone; 1; 3-diphenyl-2-dimethylamino-2-benzyl-propane-1-ketone; 1-(4-fluorophenyl)-2-dimethylamino-2-benzyl-propane-1-ketone; 1-(4-fluorophenyl)-2-dimethylamino-2-benzyl-3-phenyl-propane-1-ketone; 1-(4-benzoyl phenyl)-2-dimethylamino-2-benzyl-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-methyl-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(4-tolyl)-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(4-methoxyphenyl)-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(3; the 4-Dimethoxyphenyl)-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(4-fluorophenyl)-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(2-chlorphenyl)-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(4-chlorphenyl)-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(4-bromophenyl)-propane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-3-(4-benzoyl phenyl)-propane-1-ketone; 1, two (4-methyl mercapto the phenyl)-2-dimethylamino-2-methyl-propane-1-ketone of 3-; 1-(4-butylthio phenyl)-2-dimethylamino-2-benzyl-3-phenyl-propane-1-ketone; 1-(4-hexamethylene sulfenyl phenyl)-2-dimethylamino-2-benzyl-3-phenyl-propane-1-ketone; 1-(4-benzylthio phenyl)-2-dimethylamino-2-benzyl-propane-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-benzyl-propane-1-ketone; 1-(4-dimethylamino-phenyl)-2-dimethylamino-2-benzyl-3-phenyl-propane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(2-chlorine pentenyl)-propane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-propane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-3-phenyl-propane-1-ketone; 1-(just-methyl indoline-5-yl)-2-dimethylamino-2-benzyl-propane-1-ketone and 1-(normal-butyl phenoxazine-2-yl)-2-morpholinyl-2-benzyl-propane-1-ketone.

Butane-1-ketone (butane-1-on) is divided into those of basic framework with 4 carbon atoms; for example can comprise; 1-phenyl-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-aminomethyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-methoxyphenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(3; 5-dimethyl-4-methoxyphenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(3; the 4-Dimethoxyphenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(3; 4; the 5-trimethoxyphenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-hydroxyphenyl)-2-dimethylamino-2-benzyl-butene-1-ketone; 1-(4-(2-hydroxyl-oxethyl) phenyl]-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-allyloxy phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-ethoxycarbonyl methoxy phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-[4-(1; 1; 2-trimethyl propyl-dimethyl siloxy) phenyl]-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-fluorophenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-chlorphenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(2; the 4-dichlorophenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(3; the 4-dichlorophenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(3; the 5-dichlorophenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-bromophenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-sulfydryl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-methyl mercapto phenyl)-2-dibutylamino-2-benzyl-butane-1-ketone; 1-(4-methyl mercapto phenyl)-2-two (2-methoxy ethyl) amino-2-benzyl-butane-1-ketone; 1-[4-(2-methoxyl ethylmercapto group) phenyl]-2-dimethylamino-2-benzyl-butane-1-ketone; 1-[4-(2-hydroxyl ethylmercapto group) phenyl] 2-dimethylamino-2-benzyl-butane-1-ketone; 1-(the hot sulfenyl phenyl of 4-)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-methyl sulphonyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-[4-(4-tosyl) phenyl]-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-benzenesulfonyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-methylsulfinyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-aminophenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-methylamino phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-(4-methyl-benzyl)-butane-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-(4-isopropyl benzyl)-butane-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-(4-dodexyl benzyl)-butane-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-(1-chlorine hexenyl methyl)-butane-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-(2-piperazine alkene-10-yl)-butane-1-ketone; 1-(4-dimethylamino-2-tolyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-dimethylamino-3-ethylphenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-diethylamino phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-isopropyl aminophenyl)-2-dimethylamino-2-butyl-butane-1-ketone; 1-[4-(2-methoxy ethyl amino) phenyl] 2-dimethylamino-2-benzyl-butane-1-ketone; 1-[4-(3-methoxy-propyl amino) phenyl] 2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-acetyl-amino phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-[4-(just-and the acetyl group methylamino) phenyl]-2-dimethylamino-2-benzyl-butane-1-ketone; 1-[4-(just-and acetyl group-3-methoxy-propyl amino) phenyl]-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-piperidino phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(3; the 4-dimethyl benzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-Ethylbenzyl) butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-isopropyl benzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-butyl benzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-isobutyl benzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-dodecylbenzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-hydroxymethylbenzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-acetoxyl group Ethylbenzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-methoxy-benzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-butoxy benzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-[4-(2-hydroxyl-oxethyl) benzyl]-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-[4-(2-methoxy ethoxy) benzyl]-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-[4-(2-(2-methoxy ethoxy) ethoxy) benzyl]-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-[4-(2-(2-methoxy ethoxy) ethoxy carbonyl) benzyl]-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-[4-(2-(2-(2-methoxy ethoxy) ethoxy carbonyl) ethyl) benzyl]-butane-1-ketone; 1-(4-morpholinyl phenyl) 2-dimethylamino-2-[4-(2-bromoethyl) benzyl]-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-[4-(2-diethylamino ethyl) benzyl]-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone-trifluoro-acetate; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone-DBS; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone-right-toluene sulfonate; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone-camsilate; 1-(4-morpholinyl phenyl)-2-diethylamino-2-benzyl-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-two (2-methoxy ethyl) amino-2-benzyl-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-butyl methyl amino-2-benzyl-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-butyl methyl amino-2-(4-isopropyl benzyl)-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-dibutylamino-2-benzyl-butane-1-ketone; 1-(4-morpholinyl phenyl)-2-benzyl methylamino-2-benzyl-butane-1-ketone; 1-(3-chloro-4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-[4-(2; 6-thebaine-4-yl) phenyl]-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(1; 4-dimethyl-1; 2; 3; 4-tetrahydroquinoxaline-6-yl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(normal-butyl carbazole-3-yl)-2-dimethylamino-2-benzyl-butane-ketone; 1-(1; 3-Ben Bing Er oxazole-5-yl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(2; 3-Dihydrobenzofuranes-5-base-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(xanthene-2-yl)-2-dimethylamino-2-benzyl-butane-1-ketone; 1-(2; 3-dihydro-2; 3-dimethyl-benzothiazole-5-yl)-2-dimethylamino-2-benzyl-butane-1-ketone; 2-(2-dimethylamino-2-benzyl-bytyry)-Fluorenone; 2-(2-dimethylamino-2-benzyl-bytyry)-Dibenzosuberone; with 3,6-two (2-dimethylamino-2-benzyl-bytyry)-9-butyl-carbazole.

Pentane-1-ketone is divided into those of basic framework with 5 carbon atoms, for example can comprise, 1-(4-morpholinyl phenyl)-2-dimethylamino-2-allyl-pentane-1-ketone, 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-pentane-1-ketone, 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(2-isopropyl benzyl)-pentane-1-ketone and 1-(4-morpholinyl phenyl)-2-butyl methyl amino-2-(4-isobutyl benzyl)-pentane-1-ketone, and 1-(4-morpholinyl phenyl)-2-butyl methyl amino-2-(4-butoxy benzyl)-pentane-1-ketone.

In addition; amylene-1-ketone for example can comprise; 1-phenyl-2-dimethylamino-2-methyl-4-amylene-1-ketone; 1-phenyl-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-phenyl-2-dimethylamino-2-benzyl-4-amylene-1-ketone; 1-phenyl-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-phenyl-2-morpholinyl-2-benzyl-4-amylene-1-ketone; 1; 2-diphenyl-2-morpholinyl-4-amylene-1-ketone; 1-(4-tolyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-dodecylphenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(4-methoxyphenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-(4-methoxyphenyl)-2-dibutylamino-2-methyl-4-amylene-1-ketone; 1-(4-methoxyphenyl)-2-piperidino-2-ethyl-4-amylene-1-ketone; 1-(4-methoxyphenyl)-2-oxazole alkyl-2-methyl-4-amylene-1-ketone; 1-(4-methoxyphenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(4-methoxyphenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(3; the 4-Dimethoxyphenyl)-2-morpholinyl-2-phenyl-4-amylene-1-ketone; 1-[4-(2-methoxy ethoxy) phenyl]-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-[4-(2-methoxy ethoxy) phenyl]-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-morpholinyl-2-methyl-4-amylene-ketone; 1-(4-isopropyl phenyl)-2-dimethylamino-2-benzyl-4-amylene-1-ketone; 1-(4-butoxy phenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-[4-(2-allyloxy ethoxy) phenyl]-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-[4-(2-allyloxy ethoxy) phenyl]-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(4-trimethylsiloxy phenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-dimethylamino-2-methyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-dimethylamino-2-benzyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-morpholinyl-2-ethyl-4-methyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-morpholinyl-2-ethyl-5-methyl-4-amylene-1-ketone; 1-(4-fluorophenyl)-2-morpholinyl-2-benzyl-4-amylene-1-ketone; 1-(3; the 4-dichlorophenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-(3; 5-two chloro-4-methoxyphenyls)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-bromophenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-bromophenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(4-the bromophenyl)-2-morpholinyl-2-tert-butyl group-4-amylene-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-methyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-phenyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-dimethylamino-2-benzyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-piperidino-2-ethyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-ethyl-4-methyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-phenyl-4-amylene-1-ketone; 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-benzyl-4-amylene-1-ketone; 1-(4-ethylmercapto group phenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(the different rosickyite base of 4-phenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-allyl sulfenyl phenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-[4-(2-hydroxyl ethylmercapto group) phenyl]-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-[4-(2-hydroxyl ethylmercapto group) phenyl]-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-[4-(2-hydroxyl ethylmercapto group) phenyl]-2-morpholinyl-2-propyl group-4-amylene-1-ketone; 1-[4-(2-hydroxyl ethylmercapto group) phenyl]-2-morpholinyl-2-tert-butyl group-4-amylene-1-ketone; 1-[4-(2-methoxycarbonyl ethylmercapto group) phenyl]-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-methyl sulphonyl phenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-(4-butyl sulfinyl phenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-[4-(4-toluene sulfenyl) phenyl]-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-[4-(4-tolylsulfonyl-base) phenyl]-2-morpholinyl-2-ethyl-4-methyl-4-amylene-1-ketone; 1-(4-chlorobenzene sulfenyl phenyl)-2-dimethylamino-2-benzyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-methyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-dimethylamino-2-benzyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-tolyl amino-2-ethyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-(pyrrolidine-1-yl)-2-methyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-morpholinyl-2-methyl-4-methyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-morpholinyl-2-ethyl-4-methyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-morpholinyl-2-benzyl-4-amylene-1-ketone; 1-(4-dimethylaminophenyl)-2-(2; 6-thebaine-4-yl)-2-ethyl-4-amylene-1-ketone; 1-(4-diethylamino phenyl)-2-dimethylamino-2-benzyl-4-amylene-1-ketone; two (2-methoxy ethyl) aminophenyls of 1-[4-] 2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-butyl aminophenyl)-2-dibutylamino-2-methyl-4-amylene-1-ketone; 1-(4-butyl aminophenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-dibutylamino phenyl)-2-morpholinyl-2-methyl-4-amylene-ketone; 1-(4-diallyl aminophenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-[4-(pyrrolidine-1-yl) phenyl]-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-piperidino phenyl)-2-piperidino-2-methyl-4-amylene-1-ketone; 1-[4-(piperazine-1-yl) phenyl]-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-[4-(4-methyl piperazine-1-yl) phenyl]-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-[4-(N methyl piperazine-1-yl) phenyl]-2-(N methyl piperazine-1-yl)-2-methyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-methyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-isopropyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-diethylamino-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-two (2-methoxy ethyl) amino-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-butyl methyl amino-2-methyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-allyl methyl amino-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-diallyl amino-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-benzyl methylamino-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-(piperazine-1-yl)-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone-DBS; 1-(4-morpholinyl phenyl)-2-morpholinyl-2-ethyl-4-methyl-4-amylene-1-ketone; 1-(4-morpholinyl phenyl)-2-morpholinyl-2-benzyl-4-amylene-1-ketone; 1-[4-(2; 6-thebaine-4-yl) phenyl]-2-morpholine-2-methyl-4-amylene-1-ketone; 1-[4-(2; 6-thebaine-4-yl) phenyl]-2-(2; 6-thebaine-4-yl)-2-ethyl-4-amylene-1-ketone; 1-(normal-butyl indoline-5-yl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(1; 4-di butyl-1; 2; 3; 4-tetrahydroquinoxaline-6-yl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(normal-butyl carbazole-3-yl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(5; 10-dibutyl-5; 10-dihydrophenazine-6-yl)-2-dimethylamino-2-methyl-4-amylene-1-ketone; 1-(1; 3-Ben Bing Er oxazole-5-yl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(coumarone-3-yl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(coumarone-6-yl)-2-morpholinyl-2-ethyl-4-amylene-1-ketone; 1-(2; the 3-dihydroxenzofran-5-yl)-2-morpholinyl-2-methyl-4-amylene-1-ketone; 1-(just-methyl phenothiazine-2-yl)-2-dimethylamino-2-allyl-4-amylene-1-ketone; 3; 6-two (2-morpholinyl-2-methyl-4-pentenoyl (pentenoyl))-carbazole; 2-(2-dimethylamino-2-allyl-4-pentenoyl)-9-acridone; 2-(2-morpholinyl-2-methyl-4-pentenoyl)-xanthone; 2-(4-morpholinyl benzoyl)-2-ethyl-just-methyl isophthalic acid; 2; 3, the 6-tetrahydropyridine.

Hexane-1-ketone is divided into those of basic framework with 6 carbon atoms, for example can comprise, 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-allyl-hexane-1-ketone, 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-hexane-1-ketone, 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-4,5,5-trimethyl-hexane-1-ketone, 1-(4-morpholinyl phenyl)-2-butyl methyl amino-2-(4-butyl benzyl)-hexane-1-ketone, 1-(4-morpholinyl phenyl)-2-dioctyl amino-2-(4-methyl-benzyl)-hexane-1-ketone.

In addition, hexene-1-ketone for example can comprise, 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-ethyl-4-methyl-4-hexene-1-ketone, 1-(4-dimethylaminophenyl)-2-dimethylamino-2,4,5-trimethyl-4-hexene-1-ketone, 1-(4-dimethylaminophenyl)-2-morpholinyl-2-ethyl-4-hexene-1-ketone, 1-(4-morpholinyl phenyl) 2-morpholinyl-2-ethyl-4-hexene-1-ketone etc.

Heptane-1-ketone is divided into those of basic framework with 7 carbon atoms, for example can comprise 1-(4-dimethylaminophenyl)-2-dimethylamino-2-[4-(2-methoxyl) benzyl]-heptane-1-ketone and 1-(4-morpholinyl phenyl-2-dimethylamino-2-benzyl-heptane-1-ketone.

In addition; heptan-1; the 6-diene for example can comprise; 4-benzoyl-4-dimethylamino-heptan-1; the 6-diene; 4-(4-methoxybenzoyl base)-4-dimethylamino-heptan-1; the 6-diene; 4-(4-methoxybenzoyl base)-4-morpholinyl-heptan-1; the 6-diene; 4-(3; 4-dimethoxy benzoyl)-4-dimethylamino-heptan-1; the 6-diene; 4-(4-phenoxy group benzoyl)-4-dimethylamino-heptan-1; the 6-diene; 4-(4-fluorobenzene formoxyl)-4-dimethylamino-heptan-1; the 6-diene; 4-(4-fluorobenzene formoxyl)-4-morpholinyl-heptan-1; the 6-diene; 4-(4-methylthio phenyl formoxyl)-4-dimethylamino-heptan-1; the 6-diene; 4-(4-methylthio phenyl formoxyl)-4-morpholinyl-heptan-1; the 6-diene; 4-(4-dimethylamino benzoyl)-4-dimethylamino-heptan-1; the 6-diene; 4-(4-dimethylamino benzoyl)-4-morpholinyl-heptan-1; the 6-diene; 4-(4-morpholinyl benzoyl)-4-dimethylamino-heptan-1; 6-diene and 4-(4-morpholinyl benzoyl)-4-morpholinyl-heptan-1, the 6-diene.

Octane-1-ketone is divided into those of basic framework with 8 carbon atoms, for example can comprise 1-(4-morpholinyl phenyl)-2-dimethylamino-2-benzyl-octane-1-ketone and 1-(4-morpholinyl phenyl)-2-dimethylamino-2-(4-dodecylbenzyl)-octane-1-ketone.

When curable compositions of the present invention contains the compound of formula (I) expression and Photoepolymerizationinitiater initiater and/or thermal polymerization as composition (B), the content of each composition preferably makes: composition (A) is 20 to 95 weight %, and 30 to 90 weight % more preferably, based on the total amount of curable compositions.

In addition, composition (B) is preferably 0.1 to 40 weight %, and 0.2 to 20 weight % more preferably.When excessive or not enough and composition (B) was not enough at composition (A), the curing performance of curable compositions tended to deficiency; And on the other hand, when composition (B) is excessive, when developing, be easy to take place background contamination.

[1-3] be ethylenically unsaturated compounds (C)

Curable compositions of the present invention can also contain ethylenically unsaturated compounds (C).Preferably mix ethylenically unsaturated compounds as composition (C), with the further curing performance that improves curable compositions of the present invention.Ethylenically unsaturated compounds is the compound that contains at least one free redical polymerization ethylenic unsaturated link in molecule, when curable compositions is subjected to photoactinic irradiation or heating, this key carries out addition polymerization containing under the effect as the polymerization initiating system of composition (B) of Photoepolymerizationinitiater initiater and/or thermal polymerization, and the condition that depends on is carried out crosslinked or solidify.

Ethylenically unsaturated compounds as composition (C) can be for having the compound of an ethylenic unsaturated link in molecule, unsaturated carboxylic acid, for example (methyl) acrylic acid, crotonic acid, iso-crotonic acid, maleic acid, itaconic acid or citraconic acid and Arrcostab thereof particularly; (methyl) vinyl cyanide, (methyl) acrylamide or styrene, and be preferably the compound that in molecule, has two or more ethylenic unsaturated links, it can amplify polymerism, bridging property and the difference of liquid developer dissolubility between exposed portion and unexposed portion, and special preferred acrylate compound, wherein unsaturated link is derived from (methyl) acryloxy.The compound that has two or more ethylenic unsaturated links in the molecule can comprise the ester of unsaturated carboxylic acid and polyol (hereinafter being also referred to as ester (methyl) acrylate) usually, contain carbamate (methyl) acrylate of phosphate, hydroxyl (methyl) acrylate compounds and polyisocyanate compounds of (methyl) acryloxy and epoxy (methyl) acrylate of (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides.

The ester of unsaturated carboxylic acid and polyol for example can comprise, the above-mentioned unsaturated carboxylic acid and the reaction product of following compound: ethylene glycol, polyglycol (adduct number is 2 to 14), propylene glycol, polypropylene glycol (adduct number is 2 to 14), trimethylene, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerine, pentaerythrite, dipentaerythritol and oxirane adduction product thereof, epoxypropane adduction product; With aliphatic series polyol for example diethanolamine and triethanolamine, ethylene glycol bisthioglycolate (methyl) acrylate particularly, diglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (methyl) acrylate of trimethylolpropane oxirane addition, glycerine two (methyl) acrylate, glycerine three (methyl) acrylate, three (methyl) acrylate of glycerine epoxypropane addition, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc. are with similar crotonates, the iso-crotonic acid ester, maleate, itaconate, citraconate etc.

In addition, the ester of unsaturated carboxylic acid and polyol for example can comprise, above-mentioned unsaturated carboxylic acid and aromatics polyol be the reaction product of quinhydrones, resorcinol, pyrogallol, Bisphenol F, bisphenol-A etc. or its oxirane adduction product for example, particularly for example, bisphenol-A two (methyl) acrylate, bisphenol-A two [oxyethylene group (methyl) acrylate], bisphenol-A two [glycidol ether (methyl) acrylate] etc., or above-mentioned unsaturated carboxylic acid and heterocycle polyol three (2-hydroxyethyl) isocyanuric acid ester etc. for example; Particularly for example, two (methyl) acrylate of three (2-hydroxyethyl) isocyanuric acid ester, the reaction product of three (methyl) acrylate etc., or the reaction product of unsaturated carboxylic acid, polybasic carboxylic acid and polyol, particularly for example, the condensation product of (methyl) acrylic acid, phthalic acid and ethylene glycol, the condensation product of (methyl) acrylic acid, maleic acid and diglycol, the condensation product of the condensation product of (methyl) acrylic acid, terephthalic acid (TPA) and pentaerythrite and (methyl) acrylic acid, hexane diacid, butylene glycol and glycerine.

In addition, the phosphate that contains (methyl) acryloxy is had no particular limits, as long as they are the phosphate compounds that contain (methyl) acryloxy, and in the middle of they all, preferably by the compound of following formula (VIIIa), (VIIIb), (VIIIc) expression.

[formula (VIIIa), (VIIIb) and (VIIIc) in, R ¹⁰Expression hydrogen atom or methyl, p and p ' represent that separately 1 to 25 integer and q are 1,2 or 3].

P and p ' are preferably 1 to 10 separately, and be preferably 1 to 4 especially, their object lesson for example comprises, (methyl) acryloxy ethyl phosphonic acid ester, two [(methyl) acryloxy ethyl] phosphate and (methyl) acryloyl-oxy ethyl glycol phosphate, and they can use separately or use as potpourri separately.

In addition, carbamate (methyl) acrylate for example comprises, hydroxyl (methyl) acrylate compounds is the reaction product of hydroxymethyl (methyl) acrylate, hydroxyethyl (methyl) acrylate and tetra methylol ethane three (methyl) acrylate and following material for example, polyisocyanate compounds is aliphatic polymeric isocyanate for example, for example, hexamethylene diisocyanate, 1,8-diisocyanate-4 isocyanates methyloctane etc.; Cycloaliphatic polyisocyanates, for example, cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isophorone diisocyanate, norbornane diisocyanate, etc.; Aromatic polyisocyanate, for example, 4,4 '-methyl diphenylene diisocyanate and three (isocyanate phenyl) thiophosphate and heterocycle polyisocyanate, for example, isocyanuric acid ester.

Wherein, preferably in a molecule, have 4 or more a plurality of amino-formate bond [NH-CO-O-] and have 4 or the compound of more a plurality of (methyl) acryloxy as carbamate (methyl) acrylate.Can obtain this compound by the reaction of for example compound (i-1), compound (i-2) or compound (i-3), compound (i-1) is by having the compound of 4 or more a plurality of hydroxyls in a molecule, for example pentaerythrite or polyglycereol and diisocyanate cpd, for example the reaction of hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate or toluene diisocyanate obtains; Compound (i-2) is by having the compound of two or more hydroxyls in a molecule, for example ethylene glycol and in a molecule, have the compound of three or more isocyanate groups, for example buret type: " DURANATE 24A-100 ", " DURANATE 22A-75PX ", " DURANATE21S-75E " or " DURANATE 18H-70B " or add-on type: " DURANATE P-301-75E ", " DURANATEE-402-90T " or " DURANATE E-405-80T "; Compound (i-3) has four or more a plurality of in a molecule, and preferred 6 or more a plurality of isocyanate groups, its polymerization or copolymerization by isocyanates ethyl (methyl) acrylate etc. obtains; Particularly, by reaction for example, " DURANATE ME 200 " and compound that Asahi Kasei Kogyo Co. makes (ii) obtain, and this compound (ii) has one or more hydroxyl and 2 or more a plurality of, preferred 3 or more a plurality of (methyl) acryloxy in a molecule.

The molecular weight of compound (i) is preferably 500 to 200,000, and is preferably 1,000 to 150,000 especially.In addition, the molecular weight of carbamate (methyl) acrylate is preferably 600 to 150,000.And, preferably have 6 or more a plurality of, preferred especially 8 or more a plurality of amino-formate bond, and preferably exist 6 or more a plurality of, be preferably 8 or more a plurality of (methyl) acryloxy.

Can prepare above-mentioned carbamate (methyl) acrylate by for example following method: at organic solvent, in toluene or ethyl acetate, with the isocyanates of front and the hydroxyl reaction compound (i) and the compound mol ratio (ii) of back is 1/10 to 10/1, and the optional catalyzer that uses, for example normal-butyl tin dilaurate reacted about 5 minutes to 3 hours at 10 to 150 ℃.

In the present invention, in above-mentioned carbamate (methyl) acrylate, especially preferably by the compound of following formula (IX) expression.

[in the formula (IX), Ra has the repetitive structure and the group of representing to be connected with Rb with 4 to 20 oxygen bases of alkylidene oxide group or oxidation arlydene group, Rb and Rc represent to have the alkylene of 1 to 10 carbon atom independently of one another, Rd represents to have organic residue of 1 to 10 (methyl) acryloxy, Ra, Rb, Rc and Rd can have substituting group separately, x is 4 to 20 integer, and y is that 0 to 15 integer and z are 1 to 15 integer].

The repetitive structure of the alkylidene oxide of Ra comprises in the formula (XI), for example, is derived from those of propylidene triol (propylene triol), glycerine and pentaerythrite, and the repetitive structure of oxidation arlydene for example comprises, 1,2,3,-thrihydroxy-benzene (pyrrogalol) and 1,3,5-benzene triol.The carbon atom number of the alkylidene of Rb and Rc be preferably independently 1 to 5 and Rd in (methyl) acryloxy number be preferably 1 to 7.In addition, respectively preferably, x is 4 to 15, y be 1 to 10 and z be 1 to 10.

In addition, be expressed from the next (in the formula, k is 2 to 10 integer) and Rb and Rc of preferred especially respectively Ra represents that independently of one another dimethylene, monomethyl dimethylene or trimethylene and Rd are expressed from the next.

-O-CH ₂-CH-(CH ₂-O-O) ₂

(wherein Q represents

)

In addition, epoxy (methyl) acrylate comprises, for example, (methyl) acrylic acid or above-mentioned hydroxyl (methyl) acrylate compounds and the reaction product of following material: polyepoxides, for example, aliphatic polyoxy compounds for example (is gathered) the ethylene glycol polyglycidyl ether, (gathering) propylene glycol polyglycidyl ether, (gathering) tetramethylene glycol poly epihydric alcohol base (grlcidyl) ether, (gathering) pentamethylene glycol poly epihydric alcohol base ether, (gathering) dimethyltrimethylene glycol poly epihydric alcohol base ether, (gathering) hexamethylene glycol poly epihydric alcohol base ether, (gathering) hexamethylene glycol poly epihydric alcohol base ether, (gathering) trimethylolpropane glycol poly epihydric alcohol base ether, (gathering) glycerine poly epihydric alcohol base (glycieyl) ether, (gathering) sorbierite polyglycidyl ether, Deng; The aromatics polyepoxides for example linear phenolic resin polyepoxides, bromination linear phenolic resin polyepoxides, (adjacent-,-, right-) cresols linear phenolic resin polyepoxides, polymer with bis phenol A epoxy compound, Bisphenol F polyepoxides and heterocycle polyepoxides for example anhydro sorbitol polyglycidyl ether, triglycidyl group isocyanuric acid ester, triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester.

In addition, except above-mentioned other ethylenically unsaturated compounds those comprises, as, (methyl) acrylamide, ethylenebis (methyl) acrylamide for example, allyl ester is diallyl phthalate for example, contain for example O-phthalic vinyl acetate of vinyl compound, contain the thioether bond compound, this compound is by vulcanizing with phosphoric sulfide, in the ether-containing key ethylenically unsaturated compounds, ehter bond is changed into thioether bond and the crosslinking rate improvement, with improved intensity and stable on heating compound as cured product, this improvement by reaction with is connected silicasol and extremely carries out to ethylenically unsaturated compounds by silane coupling agent, for example by connecting multifunctional (methyl) acrylate compounds, (for example, be described in JP No.3164407 and JP-ANo.9-100111) and the silicasol of 5 to 30nm granularities is [for example, the organic silicon sol that isopropyl alcohol disperses (" IPA-ST " that Nissan Chemical Co. makes), the organic silicon sol that MEK disperses (" MEK-ST " that NissanChemical Co. makes), the organic silicon sol that methyl isobutyl ketone disperses (" MIBK-ST " that NissanChemical Co. makes) etc.], use the silane coupling agent that contains isocyanate group or sulfydryl.

Above-mentioned ethylenically unsaturated compounds can use separately, or in them two or more are used in combination.In the present invention, above-mentioned ethylenically unsaturated compounds is preferably ester (methyl) acrylate, the phosphate that contains (methyl) acryloxy or carbamate (methyl) acrylate as composition (C), and preferred especially ester (methyl) acrylate.In ester (methyl) acrylate, preferably include polyoxyalkylene and those esters (methyl) acrylate that contains two or more (methyl) acryloxies, for example polyglycol of polyethylene oxide addition, polypropylene glycol or bisphenol-A especially.

In curable compositions of the present invention, ethylenically unsaturated compounds is preferably 1 to 70 weight % as the content of composition (C), and 5 to 60 weight % more preferably are based on the total amount of curable compositions.At composition (C) during less than above-mentioned amount, tend to deficiency as the curing performance of curable compositions, on the other hand, when it surpassed this scope, it is not enough that viscosity becomes.

[1-4] be epoxy compound (D)

Curable compositions of the present invention can also comprise epoxy compound (I).For cured product improve thermotolerance or chemical-resistant, when using curable compositions of the present invention, can be used as the hybrid epoxidized compound of composition (D) as solder resist, finishing coat, rib or pad.Epoxy compound comprises having low-molecular-weight those compounds to high molecular, for example by reaction polyol and chloropropylene oxide constitute poly epihydric alcohol ether compound that so-called epoxy resin repetitive obtains, diglycidyl (glydicyl) ester compounds that obtains by reaction poly carboxylic acid and chloropropylene oxide and poly epihydric alcohol base amine (polygrycilyamine) compound that obtains by reaction polyamine compounds and chloropropylene oxide.

The poly epihydric alcohol ether compound for example comprises, bisphenol A diglycidyl ether epoxy, linear phenolic resin epoxy and the cresols linear phenolic resin epoxy of polyethyleneglycol diglycidylether epoxy compound, two (4-hydroxyphenyl) diglycidyl ether epoxy, two (3,5-dimethyl-4-hydroxyphenyl) diglycidyl ether epoxy, Bisphenol F diglycidyl ether epoxy, bisphenol A diglycidyl ether epoxy, tetramethyl bisphenol A diglycidyl ether epoxy, oxirane addition.This poly epihydric alcohol ether compound can answer acid anhydrides or dibasic acid compound to import carboxyl to residual hydroxyl by sending out.

Poly epihydric alcohol base ester compounds for example comprises, hexahydrophthalic acid diglycidyl ester epoxy, phthalic acid diglycidyl ester epoxy, and the poly epihydric alcohol based compound for example comprises, two (4-aminophenyl) methane diglycidyl amine epoxy, isocyanuric acid triglycidyl group amine epoxy.

In curable compositions of the present invention, the content of the epoxy compound of composition (D) is preferably 1 to 70 weight %, and 5 to 50 weight % more preferably are based on the total amount of curable compositions.At composition (D) during less than above-mentioned amount, tend to deficiency as the curing performance of curable compositions, on the other hand, when it surpassed this scope, this tended to cause for example problem of the failure of the darkening in non-image areas (blackingfailure).

[1-5] be epoxy hardener (E)

Curable compositions of the present invention can also comprise epoxy hardener (E).Preferably, use epoxy hardener together as composition (E) when improving the curing performance as curable compositions and when containing epoxy compound as composition (D).Epoxy hardener for example comprises as composition (E), polybasic acid anhydride is as succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, 3-methyl tetrahydrophthalic anhydride, 4-methyl tetrahydrophthalic anhydride, 3-ethyl tetrabydrophthalic anhydride, 4-ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethyl hexahydrophthalic anhydride, 4-ethyl hexahydrophthalic anhydride, trimellitic anhydride and biphenyl tetracarboxylic acid acid anhydride; Organic phosphine, for example tributylphosphine, triphenylphosphine and three-2-cyano ethyl phosphine; Imidazoles is imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-(2-cyano ethyl)-2-phenylimidazole and 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole for example; Amines is dicyan diimide (dicyane diamide), benzyl methyl amine, 4-methyl-benzyl-N for example, N-dimethyl amine, 4-methoxy-benzyl-N, N-dimethyl amine and 4-dimethylamino benzyl-N, N-dimethyl amine; Amino-s-triazine, for example 2,4,6-triamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2,4-diamido-6-methacryloxyethyl-s-triazine and 2,4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid addition product; Quaternary ammonium salt, for example zephiran chloride ammonium methyl and chlorination phenyl tributyl ammonium; Phosphonium salt is bromination three-normal-butyl-2 for example, 5-Er Qiang Ben Ji Phosphonium and chlorination Shi six alkyl San Ding Ji Phosphonium.Wherein, preferably have-those of NH-group preferred amines compound and amino-s-triazine, preferred especially dicyan diamides and 2,4,6-triamido-s-triazine.

Epoxy hardener is preferably 1 weight % or littler as the content of composition (E) in curable compositions of the present invention, and more preferably 0.7 weight % or littler based on the total amount of curable compositions, considers the ageing stability of curable compositions.

[1-6] be amino-compound (F)

Curable compositions of the present invention can further include amino-compound (F).Preferably contain amino-compound as composition (F) to improve thermotolerance or chemical resistance.Amino-compound as composition (F) comprises following compound, and it has methylol and at least two functional groups of alkoxy methyl conduct of the pure modification of wherein using 1-8 carbon atom.They comprise, for example, the benzoguanamine resin that melamine resin, polycondensation benzoguanamine and the formaldehyde that forms by polycondensation melamine and formaldehyde forms, the glycoluril resin that forms by polycondensation glycoluril and formaldehyde, the carbamide resin that forms by polycondensation urea and formaldehyde, the resin by two or more and formaldehyde formation in copolycondensation melamine, benzoguanamine, glycoluril and the urea, and those pass through resins of methylols formation of condensed alcohols modified resin.Wherein, preferred in the present invention melamine resin and modified resin thereof, more preferably the modification ratio of methylol is 70% or bigger modified resin, preferred especially modification ratio is 80% or bigger.

As for the object lesson as the amino-compound of composition (F), melamine resin and modified resin thereof comprise (" THYMEL " (registered trademark) 300,301,303,350,736,738,370,771,325,327,703,701,266,267,285,232,235,238,1141,272,254,202,1156 of Mitsui Thytec Co. and 1158 and " NIKALACK " (registered trademark) E-2151, MW-100LM, the MX-750LM of Sanwa Chemical Co.; Benzoguanamine and modified resin thereof comprise " THYMEL " (registered trademark) 1123,1125 and 1128; Glycoluril resin and modified resin thereof comprise " THYMEL " (registered trademark) 1170,1171,1174 and 1172 and " NIKALACK " (registered trademark) MX-270; Carbamide resin and modified resin thereof comprise " NIKALACK " (registered trademark) of " UFR " (registered trademark) 65,300 and MitsuiThytec Co.

Amino-compound is preferably 20 weight % or littler as the content of composition (F) in the curable compositions of the present invention, and 10 weight % or littler more preferably are based on the total amount of curable compositions.

[1-7] be polymerization accelerant (G)

Curable compositions of the present invention may further include polymerization accelerant (G).Can contain polymerization accelerant (G) and cause performance with the polymerization that improves curable compositions.For polymerization accelerant as composition (G), preferred amino acid ester or dipole ion compound, and amino-acid ester or dipole ion compound preferably include following formula (Xa) or (Xb) those of expression.

[at (Xa) with (Xb), R ³⁹And R ⁴⁰Expression independently of one another can have substituent alkyl, can have substituent aryl, can have substituent heterocyclic group or hydrogen atom, R ⁴¹And R ⁴²Expression independently of one another can have substituent alkyl or hydrogen atom, R ⁴³Expression can have substituent alkyl, can have substituent alkenyl maybe can have substituent aryl, R ⁴⁴Expression can have substituent alkyl, can have substituent aryl maybe can have substituent heterocyclic group and s and represent 0 to 10 integer],

In formula (Xa) with (Xb), R ³⁹, R ⁴⁰, R ⁴¹, R ⁴², R ⁴³And R ⁴⁴Alkyl preferably have 1 to 8,1 to 4 carbon atom more preferably.In addition, R ⁴³Alkenyl for example can comprise vinyl, allyl, isopropenyl etc.; R ³⁹, R ⁴⁰, R ⁴¹And R ⁴⁴Aryl for example can comprise phenyl, naphthyl, R ³⁹, R ⁴⁰And R ⁴⁴Heterocyclic group for example can comprise furyl, furfuryl group (franyl group), pyrrole radicals and pyridine radicals etc.

The substituting group of alkyl and alkenyl for example can comprise, alkoxy, alkoxy carbonyl, alkene oxygen base, allyloxycarbonyl, phenyl, halogen atom etc.; The substituting group of aryl and heterocyclic radical for example can comprise; alkyl, alkoxy, alkenyl, alkene oxygen base, acyl group, acyloxy, alkoxy carbonyl, phenoxy group, alkyl sulfenyl, alkyl sulphonyl; their each had substituting group; for example alkoxy or phenyl and aldehyde radical, carboxyl, hydroxyl, sulfo group, nitro, cyano group, halogen atom.

In the present invention, above-mentioned formula (Xa) or (Xb) in the amino-acid ester or dipole ion compound of expression, preferred those amino-acid esters, R in its formula (Xa) ³⁹And R ⁴⁰One of expression hydrogen atom and another expression can have substituent phenyl, R ⁴¹And R ⁴²All represent hydrogen atom, R ⁴³Expression can have substituent alkyl and maybe can have substituent phenyl and s and represent 0,1 or 2, or amino acid dipole ion compound, R in the formula (Xb) ³⁹And R ⁴⁰All represent hydrogen atom, or one of them expression can have substituent alkyl, R ⁴¹And R ⁴²All represent hydrogen atom, R ⁴⁴Expression can have substituent alkyl maybe can have substituent phenyl, and s represents 0,1 or 2.Just particularly preferably be-ester of phenylglycine, wherein s represents 0, R ³⁹And R ⁴⁰Expression hydrogen atom and another other expression phenyl, and R ⁴¹And R ⁴²All represent hydrogen atom, and preferred especially just-benzyl ester of phenylglycine, R in the formula (Xa) ⁴³The expression benzyl, or just-the dipole ion compound of phenylglycine, s represents 0, R in the special preferred formula (Xb) ³⁹, R ⁴⁰, R ⁴¹And R ⁴²All represent hydrogen atom and R ⁴⁴The expression phenyl.

In the present invention, polymerization accelerant as composition (G), can further contain the polymerization accelerant except amino-acid ester or dipole ion compound, and this polymerization accelerant for example can comprise, the compound that contains sulfydryl, for example 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-sulfydryl-1,2,4-triazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene, ethylene glycol bisthioglycolate thiopropionate, trimethylolpropane tris thiopropionate, pentaerythrite tetrathio propionic ester etc.; Multi-functional thiol's compound, for example hexane two mercaptan, trimethylolpropane tris mercaptan gluconate, pentaerythrite four mercaptan propionic esters (proponate) etc.; Amino acid or derivatives thereof with aromatic ring comprises N, N-dialkyl amido benzoic ether, just-phenylglycine or its salt derivative, for example its ammonium salt and sodium salt etc.; Phenylalanine or its salt, for example ammonium salt or sodium salt or its ester.

In curable compositions of the present invention, the content of the polymerization accelerant of composition (G) is preferably 20 weight % or littler, and 10 weight % or littler more preferably are based on the total amount of curable compositions.

[1-8] (H) inorganic filler

Can contain as composition (H) and be used for the inorganic filler of curable compositions of the present invention, so that improve the intensity of cured article.The inorganic filler of composition (H) for example can comprise, talcum, silica, aluminium oxide, barium sulphate, magnesium oxide etc.

In curable compositions of the present invention, be preferably 70 weight % or littler a as the inorganic filler content of composition (H), and 50 weight % or littler more preferably, based on the total amount of curable compositions.

[1-9] be surfactant (I)

In addition, can contain as composition (I) and be used for the surfactant of curable compositions of the present invention, so that improve coating and the development of curable compositions as coating fluid.Object lesson can comprise nonionic, negative ion, kation, both sexes and fluorine surfactant.More specifically, the example of non-ionic surfactant can comprise polyoxyethylene alkyl ether, polyoxyethylene polyoxy propylidene alkyl ether, polyoxyethylene alkyl phenyl ether, polyxyethylated ester, polyoxyethylene fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid glyceride, pentaerythritol fatty ester, polyoxyethylene pentaerythritol fatty acid ester, fatty acid esters of sorbitan, polyoxyethylene sorbitan fatty acid ester and D-sorbite (sorbit) fatty acid ester and polyoxyethylene sorbitol fatty acid ester etc.; Anionic surfactant for example can comprise, alkyl sulfonate, alkyl benzene sulfonate, alkylnaphthalene sulfonate, polyoxyethylene alkyl ether sulfonate, alkyl sulfate, alkyl sulfate, higher alcohol sulfate, aliphatic alcohol sulfate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt, alkylphosphonic, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylphenyl ether sulfate salt; For example can comprise quaternary ammonium salt, imidazolidine derivatives and amine salt with cationic surfactant; For example can comprise betaine (betaine) compound, imidazoline salt, imidazoline, amino acid etc. with amphoteric surfactant.

In curable compositions of the present invention, be preferably 10 weight % or littler as the content of the surfactant of composition (I), and 5 weight % or littler more preferably, based on the total amount of curable compositions.

[1-10] be photosensitizing dye (J)

In addition, preferably contain the photosensitizing dye that is used for curable compositions of the present invention as composition (J), so that for example improve the photosensitivity of curable compositions.Photosensitizing dye is to be that indigo plant-purple zone of 350 to 430nm has the extinction dyestuff of absorption maximum at wavelength, and comprises dialkyl amido benzene compound, pyromethene compound and trihydroxy-pyrimidine derivant etc.; Preferred dialkyl amido benzene compound.

As preferred dialkyl amido benzene compound, preferred especially dialkyl amido benzophenone compound, have substituent dialkyl amido benzene compound that comprises the sulfonyl imino group and the dialkyl amido benzene compound that forms carbon styryl skeleton on as substituent dialkyl amido benzene compound, para-position carbon atom having heterocyclic radical on the para-position carbon atom of the amino on the phenyl ring at the amino on the phenyl ring.

As dialkyl amido benzo oxybenzene compound, those compounds of preferred following formula (XI) expression.

[in the formula (XI), R ¹¹, R ¹², R ¹⁵And R ¹⁶Expression independently of one another can have substituent alkyl, R ¹³, R ¹⁴, R ¹⁵And R ¹⁶Expression independently of one another can have substituent alkyl or hydrogen.With each to R ¹¹And R ¹², R ¹¹And R ¹³, R ¹²And R ¹⁴, R ¹⁵And R ¹⁶, R ¹⁵And r ¹⁷And R ¹⁶And R ¹⁸Form independently and contain azacyclo-].

In formula (XI), R ¹¹, R ¹², R ¹⁵And R ¹⁶The carbon atom number and the R of alkyl ¹³, R ¹⁴, R ¹⁷And R ¹⁸The carbon atom number of alkyl is preferably 1 to 6 when representing alkyl separately.In addition, when forming nitrogen heterocyclic ring, it is preferably 5-or 6-unit ring.Each is to R ¹¹And R ¹³, R ¹²And R ¹⁴, R ¹⁵And R ¹⁷Or R ¹⁶And R ¹⁸Be preferably formed 6-unit tetrahydroquinoline ring, and preferred especially R ¹¹, R ¹², R ¹³And R ¹⁴And/or R ¹⁵, R ¹⁶, R ¹⁷And R ¹⁸Form the durolidine ring.In addition, has alkyl more preferably at 2 as substituent tetrahydroquinoline ring or the durolidine ring that contains the tetrahydroquinoline ring.

The object lesson of the compound of formula (XI) expression comprises 4,4 '-two (dimethylamino) benzophenone, 4,4 '-compound of two (diethylamino) benzophenone and following structure.

In addition, have heterocyclic radical on the para-position carbon atom of the amino on phenyl ring and be preferably 5-or the 6-unit ring that comprises nitrogen-atoms, oxygen atom or sulphur atom as the heterocycle in the substituent dialkyl amido benzene compound, the 5-unit that especially preferably has fused benzene rings encircles, and keeps away those of that preferred following formula (XII) expression.

[in the formula (XII), R ¹⁹And R ²⁰Expression independently of one another can have substituent alkyl, R ²¹And R ²²Expression independently of one another can have substituent alkyl or hydrogen atom, and each is to R ¹⁹And R ²⁰, R ¹⁹And R ²¹, and R ²⁰And R ²²Can form the heterocycle that nitrogen forms independently, expression oxygen atom, sulphur atom, dialkyl methyl, imino group or alkyl imino, and can have substituting group with heterocyclic fused phenyl ring].

R ¹⁹And R ²⁰The carbon atom number and the R of alkyl ²¹And R ²²Carbon atom number during for alkyl is preferably 1 to 6 and when forming nitrogen heterocyclic ring, and it is preferably 5-or 6-unit ring, and each is to R ¹⁹And R ²¹, and R ²⁰And R ²²Be preferably formed the tetrahydroquinoline ring, and R ¹⁹, R ²⁰, R ²¹, R ²²Be preferably formed the durolidine ring especially.This external 2 on have alkyl as substituent tetrahydroquinoline ring or to contain the durolidine ring of tetrahydroquinoline ring preferred especially.In addition, when X is the dialkyl group ethylidene, the carbon atom number of alkyl be preferably 1 to 6 and during alkyl imino the carbon atom number of alkyl be preferably 1 to 6.

The object lesson of the compound of formula (XII) expression for example can comprise,

2-(right-dimethylaminophenyl) benzoxazole,

2-(right-diethylamino phenyl) benzoxazole,

2-(right-dimethylaminophenyl) benzo [4,5] benzoxazoles,

2-(right-dimethylaminophenyl) benzo [6,7] benzoxazoles,

2-(right-dimethylaminophenyl) benzothiazole,

2-(right-the diethylamino phenyl) benzothiazole,

2-(right-dimethylaminophenyl) benzimidazole,

2-(right-the diethylamino phenyl) benzimidazole,

2-(right-dimethylaminophenyl)-3,3-dimethyl-3H-indoles,

2-(right-the diethylamino phenyl)-3, the compound of 3-dimethyl-3H-indoles and following structure.

In addition, except the compound of formula (XII) expression, having heterocyclic radical on the para-position carbon atom of the amino on the phenyl ring for example can comprise as substituent dialkyl amido benzene compound, 2-(right-dimethylaminophenyl) pyridine, 2-(right-the diethylamino phenyl) pyridine, 2-(right-dimethylaminophenyl) quinoline, 2-(right-the diethylamino phenyl) quinoline (uinoline), 2-(right-dimethylaminophenyl) pyrimidine (pirimidine), 2-(right-the diethylamino phenyl) pyrimidine, 2, two (right-the diethylamino phenyl)-1 of 5-, 3,4-oxadiazole and 2, two (right-the diethylamino phenyl)-1 of 5-, 3, the 4-thiadiazoles.

In addition, on the para-position carbon atom of the amino on the phenyl ring, have the sulfonyl imino group and preferably include those of following formula (XIII) expression as substituent dialkyl amido benzene compound:

[in formula (XIII), R ²³And R ²⁴Expression independently of one another can have substituent alkyl, R ²⁵And R ²⁶Expression independently of one another can have substituent alkyl or hydrogen atom, and each is to R ²³And R ²⁶, R ²³And R ²⁵, and R ²⁴And R ²⁶Can form the nitrogen heterocyclic ring group independently, and R ²⁷Expression univalent perssad or hydrogen atom, and R ²⁸Expression univalent perssad].

In formula (XIII), R ²³And R ²⁴The carbon atom number and the R of alkyl ²⁵And R ²⁶Carbon atom number when being alkyl is preferably 1 to 6 and when forming the nitrogen heterocyclic ring group, and it is preferably 5-or 6-unit ring, and R ²⁵And R ²⁶Be preferably hydrogen atom.In addition, R ²⁷And R ²⁸Univalent perssad for example comprise alkyl, naphthenic base, alkenyl, cycloalkenyl group, alkoxy, alkene oxygen base, acyl group, acyloxy, aryl, aryloxy group, aralkyl, aromatic yl alkenyl, hydroxyl, formoxyl, carboxyl, carboxylic acid ester groups, carbamyl, amino, acylamino-, carbamate groups, sulfoamido (sulfine amide group), sulfonate groups, sulphonic acid ester, sulfamoyl, alkyl sulfenyl, imino group, cyano group and heterocyclic group.

Wherein, R ²⁷Be preferably hydrogen atom or R ²⁸Be preferably aryl.

In addition, the cinnamic dialkyl amido benzene compound of formation carbon preferably includes those of following formula (XIV) expression:

[in formula (XIV), R ²⁹, R ³⁰And R ³³Expression independently of one another can have substituent alkyl, R ³¹And R ³²Expression independently of one another can have substituent alkyl or hydrogen atom, and each is to R ²⁹And R ³⁰, R ²⁹And R ³¹, R ³⁰And R ³²Can form nitrogen heterocyclic ring and R independently ³⁴Expression can have substituent alkyl, can have substituent aryl or hydrogen atom].

In formula (XIV), R ²⁹, R ³⁰And R ³⁸The carbon atom number and the R of alkyl ³¹, R ³², and R ³⁵Carbon atom number during for alkyl is preferably 1 to 6, or when forming nitrogen heterocyclic ring, it is preferably 5-or 6-unit ring, R ³¹And R ³²Be preferably hydrogen atom.In addition, R ³⁴Be preferably phenyl.

In the present invention, particularly preferred above-mentioned photosensitizing dye as composition (J) is the dialkyl amido benzophenone compound of formula (XI) expression, has the dialkyl amido benzene compound of the formation carbon styryl skeleton of the substituting group dialkyl amido benzene compound that comprises the sulfonyl imino group or formula (XIV) expression in the contraposition of the amino of phenyl ring.

In curable compositions of the present invention, photosensitizing dye is preferably 0.01 to 20 weight % as the content of composition (J), and 0.1 to 10 weight % more preferably, based on the total amount of curable compositions.During less than above-mentioned amount, the light-cured performance of curable compositions tends to deficiency at composition (J), on the other hand, when surpassing this scope, is easy to take place background contamination in the developing process.

In addition, curable compositions of the present invention preferably has the maximum peak of spectral sensitivity in 350 to 430nm wavelength region may, more preferably the maximum peak that has spectral sensitivity in 390 to 430nm wavelength region may.When it has the maximum peak of spectral sensitivity in the wavelength region may less than above-mentioned scope, tend to deterioration for wavelength in the light sensitivity of 350 to 430 laser, on the other hand, when it is surpassing when having maximum peak in the wavelength region may of above-mentioned scope, the safety light character (safe light property) of photocurable composition under amber light is easy to deterioration.

On the other hand, when it is surpassing when having the peak in the wavelength region may of above-mentioned scope, the safety light character under amber light is easy to deterioration.Can control the wavelength region may of the maximum peak of spectral sensitivity by each component that suitable selection constitutes curable compositions, and particularly can be based on controlling as the Photoepolymerizationinitiater initiater of composition (B) and/or thermal polymerization with as the kind and the content of the photosensitizing dye of composition (J).

In the present invention, the maximum peak of spectral sensitivity refers to the maximum peak in the spectral sensitivity curve that obtains, its preparation method for example, (TsugioYamaoka writes at above-mentioned " Photopolymer Technology " particularly, 1988 deliver from Nikkan Kogyo Shinbunsha, p 262), by using from light source, the light photocurable image forming material sample that on the surface of substrate, forms with the curable compositions layer of the rayed of the spectrumization of xenon lamp or tungsten lamp and exposing for example, using the spectral sensitivity surveying instrument to regulate simultaneously makes exposure wavelength change along the ordinate logarithm along horizontal ordinate linear change and exposure intensity, then according to the image applications development treatment of light sensitivity to obtaining for each exposure wavelength, can form the exposure energy of image based on the high computational of image, and in wavelength on the horizontal ordinate and the mapping of the exposure energy logarithm on the ordinate.

In addition, when using indigo plant-purple semiconductor laser as the exposure light source of curable compositions of the present invention, the minimum exposure amount (S410) that preferably can form image under the 410nm wavelength is 50mJ/cm ²Or littler, 30mJ/cm more preferably ²Or littler, and preferred especially 20mJ/cm ²Or it is littler.When minimum exposure amount [S410] surpassed above-mentioned scope, the time shutter increased the validity of tending to deterioration reality, and this depends on the exposure intensity of LASER Light Source.The lower limit of preferred minimum exposure amount [S410] is littler, and it typically is 1mJ/cm ²Or it is bigger.

[S410]/S450] ratio be preferably 0.1 or littler, and more preferably 0.05 or littler, wherein [S450] is for forming the minimum exposure amount [S450 (mJ/cm of image at the 450nm wavelength ²)].When ratio [S410]/[S450] surpassed above-mentioned scope, it tended to be difficult to mention in the same breath with the light sensitivity of indigo plant-purple laser and the safety light character under amber light.

Preferred proportion [S450 to 650/S450] (can form minimum exposure amount [S450 to the 650 (mJ/cm of image under each wavelength in wavelength is 450nm or bigger and 650nm or littler scope ²)] and the ratio [S450 (mJ/cm between the minimum exposure amount that can form image under the 450nm wavelength ²)]) greater than 1.Little in ratio [S450 to 650/S450], when above-mentioned amount, it tends to be difficult to mention in the same breath with the light sensitivity of indigo plant-purple laser and the safety light character under amber light.

Can form minimum exposure amount [S450 to the 650 (mJ/cm that the minimum exposure amount [S410] of image, minimum exposure amount [S450] that the 450nm wavelength can form image and 450nm or bigger and 650nm or each littler wavelength can form image at the 410nm wavelength ²)] be defined as forming the exposure energy of image, high computational from the image that by the maximum peak that uses above-mentioned spectral sensitivity surveying instrument measure spectrum light sensitivity, obtains, and this means that for example the kind of developer, development temperature, development time lamp can form the maximum exposure amount of image under best development conditions by changing development conditions.At this moment, the best development conditions of use normally 25 ℃ temperature, pH be in 11 to 14 the akaline liquid developer dipping 0.5 to 3min.

[1-11] be other alkali soluble resin (K)

Can contain as composition (K) and be used for the bonding agent of the alkali soluble resin of curable compositions of the present invention as curable compositions.Alkali soluble resin for example can comprise, following all-or multipolymer: (methyl) acrylic acid, methyl) acrylate, (methyl) vinyl cyanide, (methyl) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride or maleimide, sour modified epoxy acrylic ester, polyamide, polyester, polyethers, polyurethane, polyvinyl butyral, polyvinyl butyl alcohol, polyvinyl pyrrolidone, acetylcellulose.

Wherein, consider alkali-developable, preferably contain the vinylite or the sour modified epoxy acrylic ester of carboxyl.

The resinoid example of vinyl that contains carboxyl can comprise the multipolymer of unsaturated carboxylic acid and vinyl compound; unsaturated carboxylic acid is (methyl) acrylic acid for example; crotonic acid; iso-crotonic acid; maleic acid; maleic anhydride; itaconic acid; citraconic acid etc.; vinyl compound is styrene for example; α-Jia Jibenyixi; hydroxy styrenes; (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) propyl acrylate; (methyl) butyl acrylate; (methyl) acrylic acid pentyl ester; (methyl) Hexyl 2-propenoate; (methyl) dodecylacrylate; (methyl) 2-EHA; (methyl) acrylic acid two ring pentyl esters; (methyl) acrylic acid diamantane ester; (methyl) acrylic acid isobornyl (isobonyl) ester; (methyl) acrylic acid hydroxyl methyl esters; (methyl) hydroxy-ethyl acrylate; (methyl) glycidyl acrylate; (methyl) acrylic acid benzyl ester; (methyl) acrylic acid N; N-dimethyl aminoethyl ester; acryloyl morpholine just-(methyl); (methyl) vinyl cyanide; (methyl) acrylamide; N-methylol (methyl) acrylamide; N; A-dimethyl (methyl) acrylamide; N, N-dimethyl aminoethyl (methyl) acrylamide; vinyl acetate etc.

Wherein, optimization styrene-(methyl) acrylate-(methyl) acrylic copolymer, further preferably include 3 to 30mol% styrene, 10 to 70%mol (methyl) acrylate and 10 to 60mo] the acrylic acid multipolymer of % (methyl), preferably include 5 to 25mol% styrene, 20 to 60mol% (methyl) acrylate and the acrylic acid multipolymer of 15 to 55mol% (methyl) especially.The acid number that preferably contains the vinylite of carboxyl is 30 to 250mgKOH/g, is 1,000 to 300,000 with the weight-average molecular weight of polystyrene conversion.

In addition, as the vinylite that contains carboxyl, preferably on side chain, have those of ethylenic unsaturated link, and for example comprise particularly, contain for example allyl glycidyl ether of epoxy radicals unsaturated compound by reaction carbonyl bearing polymer and aliphatic series, (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid α-ethyl glycidyl esters, the glycidyl crotonates, glycidyl iso-crotonic acid ester, crotonyl (chrotonyl) glycidol ether, monoalkyl list glycidyl itaconate, monoalkyl list glycidyl fumarate, monoalkyl list glycidyl maleate etc., or with alicyclic for example (methyl) acrylic acid 3 of epoxy radicals unsaturated compound that contains, 4-epoxycyclohexyl methyl ester, (methyl) acrylic acid 2,3-epoxide ring amyl group methyl ester, (methyl) acrylic acid 7, the reaction product of the acquisition of 8-epoxy [three ring [5.2.1.0]-2-decyls] oxygen methyl ester, its amount is approximately 5 to 90mol%, is preferably the carboxyl of 30 to 70mol% carbonyl bearing polymer; With the reaction product that obtains by the following compound compound of copolymerization: this has the compound of two or more unsaturated groups, for example (methyl) acrylic acid allyl ester, (methyl) acrylic acid 3-allyloxy-2-hydroxy-propyl ester, (methyl) acrylic acid cinnamyl ester, (methyl) acrylic acid crotyl ester, (methyl) acrylic acid methacrylic ester, N, N-diallyl (methyl) acrylamide etc.; Compound with two or more unsaturated groups, for example (methyl) acrylic acid vinyl esters, (methyl) acrylic acid 1-chlorovinyl ester, (methyl) acrylic acid 2-phenyl vinyl ester, (methyl) acrylic acid 1-propenyl ester, crotonic acid vinyl esters, vinyl (methyl) acrylamide etc.; And unsaturated carboxylic acid, for example (methyl) acrylic acid or esters of unsaturated carboxylic acids; The ratio that the front has a compound of unsaturated group is 10 to 90mol%, is preferably 0 to 80mol%, based on whole resin.

In addition, its can also comprise contain the epoxy-based polymerization thing and have can with the reaction product of the ethylenically unsaturated compounds of functional group's (for example carboxyl or hydroxyl) of epoxy reaction.

In addition, sour modified epoxy acrylic ester is to obtain compound with polybasic carboxylic acid or its acid anhydride (c) reaction again by compound that contains epoxy radicals and the reaction product that contains unsaturated group carboxylic acid or its acid anhydrides.In addition, they can further add to compound on a part of carboxyl in the compound for wherein containing epoxy compounds.Can prepare by known method.

Containing epoxy compounds for example can comprise, the epoxy compound of in JP-A No.2001-174621, describing [in a molecule, having the compound (a) of two or more epoxy radicals etc., in instructions] and comprise the bisphenol-A epoxy compound particularly, the Bisphenol F epoxy compound, the bisphenol S epoxy compound, the biphenyl glycidyl ether, the linear phenolic resin epoxy compound, cresols linear phenolic resin epoxy compound, the triglycidyl group isocyanuric acid ester, the cyclic aliphatic epoxy compound, epoxy compound (this addition structure is the addition structure that has the cyclic hydrocarbon compound and the phenol of two or more unsaturated groups in a molecule) with addition structure, the epoxy compound of copolymerization etc.

In curable compositions of the present invention, alkali soluble resin is preferably 70 weight % or littler as the content of composition (K), and 40 weight % or littler more preferably are based on the total amount of curable compositions.

[1-12] be colorant (L)

Using curable compositions of the present invention to be used under the situation of color filter or black matrix, the preferred use in conjunction with colorant simultaneously.Colorant points to those of look curable compositions of the present invention herein.Though dyestuff and pigment can be used for colorant, consider thermotolerance and photostability preferred pigments.As pigment, can use versicolor pigment, for example blue pigment, green pigment, red, yellow pigment, purple dye, orange pigment, brown pigment and mineral black.

In addition, except organic pigment for example azo, phthalocyanine, quinacridone, benzimidazolone, isoindoline ketone, dioxazine (dioxadine), indanthrene and perylene pigment, also can use various inorganic pigments as its structure.The object lesson of available herein pigment illustrates by the face item number.Term, for example Colour Index (C.I.) such as " C.I. paratonere 2 " expression.

Red can comprise C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48: 1,48: 2,48: 3,48: 4,49,49: 1,49: 2,50: 1,52: 1,52: 2,53,53: 1,53: 2,53: 3,57,57: 1,57: 2,58: 4,60,63,63: 1,63: 2,64,64: 1,68,69,81,81: 1,81: 2,81: 3,81: 4,83,88,90: 1,101,101: 1,104,108,108: 1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273.274,275 and 276.Wherein preferred C.I. pigment red 48: 1,122,168,177,202,206,207,209,224,242 and 254, and more preferably C.I. paratonere 177,209,224,254.

Blue pigment can comprise C.I. pigment blue 1,1: 2,9,14,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17,19,25,27,28,29,33,35,36,56,56: 1,60,61,61: 1,62,63,66,67,68,71,72,73,74,75,76,78 and 79.Wherein preferred C.I. pigment blue 15,15: 1,15: 2,15: 3,15: 4,15: 6 and more preferably C.I. pigment blue 15: 6.

Green pigment can comprise C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54 and 55.Wherein preferred C.I. pigment Green 7 and 36.

Yellow pigment can comprise C.I. pigment yellow 1,1: 1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35: 1,36,36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127: 1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191: 1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207 and 208.

Wherein preferred C.I. pigment yellow 83,117,129,138,139,150,154,155,180 and 185 and more preferably C.I. pigment yellow 83,138,139,150 and 180.

Orange pigment can comprise C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78 and 79.Preferred pigment orange 38 and 71 C.1. wherein.

Purple dye can comprise C.I. pigment violet 1,1: 1,2,2: 2,3,3: 1,3: 3,5,5: 1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49 and 50.Wherein preferred C.I. pigment violet 19 and 23 and more preferably C.I. pigment Violet 23.

When forming black matrix, can use black colorant by the use curable compositions.Black colorant can be that single black colorant maybe can obtain by mixing red, green and blue.In addition, those pigment can be suitably from inorganic or inorganic pigment and dye selection.Under the situation of organic or inorganic pigment, be 1 μ m or littler preferably to be dispersed to particle mean size, and preferred 0.5 μ m or littler and use them.

The colorant that can be mixed with black colorant for example can comprise Victoria's ethereal blue (42595), auramine O (41000), Cathilon brilliant flavine (basic 13), Rhodamine6GCP (45160), Rhodamino B (45170), Safranine OK 70:100 (50240), Erioglaucine X (42080), No.120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Simular FirstYellow 8GF (21105), Benzidine Yellow 4P-564D (21095), Simular First Red4015 (12355), Lionol Red 7B 4401 (15850), Firstgen Blue TGR-L (74160), LionolBlue SM (26150), Lionol Blue ES (pigment blue 15: 6), Lionolgen Red GD (paratonere 168), Lionol Red 2YS (pigment red 3 6) etc.(numeral in the bracket refers to Colour Index (C.I.)).

Other pigment that can mix in addition, comprises (with C.I. number): C.I. yellow pigment 20,24,86,93,109,110,117,125,137,138,147,148,153,154,166, C.I. orange pigment 36,43,51,55,59,61, C.I. red 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228,240, C.I. purple dye 19,23,29,30,37,40,50, C.I. blue pigment 15,15: 1,15: 4,22,60,64, C.I. green pigment 7, C.I. brown pigment 23,25 and 26 etc.

The black colorant that can use separately for example comprises, carbon black, acetylene black, dim, boneblack, graphite, iron oxide black, nigrosine, and cyanine is black, and titanium is black etc.

Wherein, consider light shield rate (light shielding rate) and the preferred carbon black of image property.The example of carbon black can comprise following carbon black.The MA7 that Mitsubishi Chemical Corp. makes, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL 31B; The Printex 3 that Degussa Co. makes, P rintex3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, PrintexG, Printex P, Printex U, Printex V, Printex G, SpecialBlack 550, Special Black350, Special Blak 250, Special Black 100, Special Black 6, Special Black5, Specia l Black 4, Color Black FW 1, Color Black FW2, Color BlackFW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170; The Monarch 120 that Cabot Co. makes, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, black PEARLS480, PEARLS 130, VULCAN XC 72R, ELFTEX-8; The RAVEN 11 that Columbian Carbon JapanLtd makes, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN3500, RAVEN 5000, RAVEN 5250, RAVEN 5750 and RAVEN 7000.

As the example of other mineral black, can use that titanium is black, the organic pigment of nigrosine, black iron oxide pigment and three kinds of blend of colors of red, green and blue is as mineral black.

In addition, barium sulphate, lead sulfate, titania, lead and yellow-collation, iron oxide red, chromium oxide etc. can be used as pigment.

Can be used in combination multiple pigment.For example, green pigment and yellow pigment can be used in combination, blue pigment and purple dye can be used in combination as being used to regulate the pigment of colourity.

The particle mean size of pigment is preferably 0.5 μ m or littler usually, more preferably 0.25 μ m or littler.In addition, can for example can comprise azo dyes, anthraquinone dye, phthalocyanine dye, quinoneimine dye, quinoline dye, nitro dye, carbonyl dyestuff and methine dyes as the dyestuff of colorant.

Azo dyes for example can comprise, C.I. acid is yellow 11, C.I. bitter orange 7, C.I. acid are red 37, C.I. acid is red 180, C.I. acid is blue 29, C.I. is directly red 28, C.I. is directly red 83, C.I. is directly yellow 12, C.I. direct orange 26, C.I. are directly red 28, C.I. is directly red 59, the C.I. reaction is yellow 2, C.I. reacts that red 17, C.I. reacts that red 120, C.I. reaction is black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. mordant rouge 7, C.I. mordant yellow 5, C.I. and mordant dyeing black 7.

Anthraquinone dye for example can comprise, C.I.Bat indigo plant 4, C.I. acid are blue 40, C.I. acid is red 25, the C.I. reaction is blue 19, the C.I. reaction is blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60 etc.

Except above-mentioned, phthalocyanine dye for example comprises, C.I.Pad indigo plant 5 etc.Quinoneimine dye for example comprises, C.I. alkali blue 3, C.I. alkali blue 9 etc.Quinoline dye for example comprises that C.I.Sobent Huang 33, C.I. acid Huang 3, C.I. dispersion yellow 64, nitro dye for example comprise, the yellow I of C.I. acid, C.I. bitter orange 3, C.I. Disperse Yellow 42 etc.

In the curable compositions, colorant can be selected from the scope of 1 to 70 weight % usually as the ratio of composition (L) in the total solids content, based on the total solids content of curable compositions.In above-mentioned scope, 10 to 70 weight % more preferably, and preferred especially 20 to 60 weight % all.When colorant contain quantity not sufficient the time, thickness and color depth are too big, have obtained unwanted effect, for example, have obtained the effect that do not need at preparation liquid crystal cells time control opening.On the contrary, when the ratio of colorant is excessive, can not obtains sufficient image sometimes and form character.The total solids content of curable compositions of the present invention is generally 10 weight % or bigger and 80 weight % or littler.

In addition, also can add pigment derivative etc., to improve dispersiveness and to improve dispersing of pigments stability.Pigment derivative can comprise azo, phthalocyanine, quinacridone, Benzimidazolinone, quinophthalone (quinophthalone), isoindoline ketone, dioxazine, dioxazine, anthraquinone, indanthrene, perylene, perylene ketone (perynone), diketopyrrolo-pyrrole He diox type derivant, wherein preferred quinophthalone type derivant.The substituting group of pigment derivative comprises sulphonate-base, sulfoamido and quaternary salt thereof, phthalic amide methyl, dialkylaminoalkyl group, hydroxyl, carboxyl and amide group, directly connect or be connected to the pigment skeleton by alkyl, aryl or heterocyclic radical, preferred sulfonic group.On a pigment skeleton, can replace a plurality of substituting groups.The instantiation of pigment derivative for example comprises that the sulfonic acid of the sulfonic acid of the sulfonic acid of phthalocyanine, the sulfonic acid of quinophthalone, anthraquinone, the sulfonic acid of quinacridone, diketopyrrolo-pyrrole is with the sulfonic acid of diox.

The addition of pigment derivative is generally 0.1 to 30 weight %, is preferably 0.1 to 20 weight % or littler, more preferably 0.1 to 10 weight %, more preferably 0.1 to 5 weight % or littler.

[1-13] be spreading agent and/or dispersing aid (M)

When using curable compositions of the present invention to be used for color filter or black matrix, when particularly using above-mentioned pigment to be used for coloring agent component (L), preferred combination uses spreading agent and/or dispersing aid as composition (M), so that improve dispersiveness and improve dispersing of pigments stability.Wherein, using polymeric dispersant is preferred as pigment dispersing agent, because it provides superior dispersion stability in time.Polymeric dispersant for example comprises, carbamate spreading agent, polyethyleneimine spreading agent, polyoxyethylene alkyl ether spreading agent, polyoxyethylene glycol diester spreading agent, anhydro sorbitol aliphatic (acid) ester spreading agent and aliphatic modified poly ester spreading agent.The instantiation of spreading agent for example comprises, trade name EFKA (FKA ChemicalBV (EFKA) manufacturing), Disperbik (Big Chemir Co. manufacturing), Disparon (Hashimoto Kasei manufacturing), SOLSPERSE (Zeneka Co. manufacturing), KP (Shinetsu Chemical Industry Co.) and Polyflow (Kyoeisha Chemical Co. manufacturing).Spreading agent can use separately or as two or more uses in them.In the solids content of photosensitive colored composition, the content of pigment dispersing agent is generally 50 weight % or littler, is preferably 30 weight % or littler.

In addition, dispersing aid can for example at random be selected from, the compound of formula (I) expression, ethylenically unsaturated compounds, epoxy compound (D) and other aqueous slkali resin (K) of composition (C), and can be used for dispersion treatment.

[1-14] be other adjuvant (N)

Curable compositions of the present invention can further contain various adjuvants, for example, 2 weight % or littler thermal polymerization inhibitor be quinhydrones for example, right-methoxyphenyl ketone (phenone), or 2,6-two-tert-butyl group-p-Cresol (cresole), 20 weight % or littler colorant, comprise organic or inorganic dyestuff or pigment, 40 weight % or littler plastifier be dioctyl phthalate for example, phthalic acid two (dodecyl) ester, tri cresyl phosphate, 10 weight % or littler photonasty improver be tertiary amine or mercaptan for example, 305 weight or littler pigment precursors, with 10 weight % or littler silane coupling agent, all based on curable compositions.

Displacement, elastic restoration ratio and recovery rate under [1-15] total deformation, the load

Curable compositions of the present invention has the performance of the cured article that can form, in the load/unload test of using the microhardness test instrument, this cured article be characterized as total deformation be 1.35 μ m or bigger and/or when the load bottom offset is 0.25 μ m load N be 0.50gf or littler, elastic restoration ratio be 50% or bigger and/or recovery rate be 80% or bigger.

For example, in the step of preparation panel, the pad that is used for the liquid crystal display device (hereinafter being called " panel " sometimes) of Large-size LCD Screen TV tends to be subjected to load and is subjected to big pad total deformation.Particularly, in the giant-screen panel, various piece is easy to produce inhomogeneous load.Curable compositions of the present invention can also be used for following situation, wherein cured article (pad) elastic restoration ratio and/or recovery rate height.

The following load/unload test of using the microhardness test instrument.

Using the microhardness test instrument, is 80 ± 10 μ m to the last cross-sectional area of shim pattern ²A pattern measure, this shim pattern is the method described by following [2-2] or makes by known method.

The last cross-sectional area of shim pattern refers to following area.At first, (Keyence Corp. is VK-9500) to the profile of shim pattern making by the longitudinal profile of center line to use super dense color (superdeepdepth color) 3D shape measure microscope (shape measuring microscope).Fig. 1 has shown the position that profile is made.Then, measure the length that is parallel to the straight line A A ' of substrate surface in shim pattern apart from 90% place of substrate surface extreme higher position Q.Referring to the profile synoptic diagram among Fig. 2.Have AA ' and be defined as the area of shim pattern as the area of the circle of diameter.

The microhardness test instrument (Shimazu Dynamicsuper-micro-hardness testerDUH-W201S) that use is made by Shimazu Seisakusho Co..

When the measurement temperature is 23 ℃, add press by the plane of using 50 μ m diameters, with constant speed (0.22gf/sec) load application on pad, when load reaches 5g, it was kept 5 seconds continuously, the speed unloading to communicate is tested then.According to load-displacement curve (Fig.3 has shown synoptic diagram) that this test is determined, measure maximum displacement H[max], final mean annual increment movement H[Last] and load under displacement be the load N (gf) of 0.25 μ m.Maximum displacement H[max] be defined as total deformation.

Total deformation is preferably 1.4 μ m or bigger, 1.5 μ m or bigger more preferably, and be preferably 5 μ m or littler, more preferably 3 μ m or littler.

Displacement under load is that the load N of 0.25 μ m is preferably 0.45gf or littler, and is preferably 0.1gf or bigger.

When excessive and/or load N was not enough when total deformation, elastic restoration ratio and/or recovery rate reduced.On the other hand, when total deformation deficiency and/or load N were excessive, cured article can not be dealt with the inhomogeneous of load in the manufacture process.

In addition, based on data difference calculating elastic recovery rate and the recovery rate measured in the load/unload test of being undertaken by above-mentioned microhardness test instrument.

Recovery rate (%)=H[last]/(pattern height before the test) * 100

Elastic restoration ratio (%)=(H[max]-H[last])/H[max] * 100

Recovery rate is preferably 85% or bigger, and more preferably 90% or bigger.

Elastic restoration ratio is preferably 60% or bigger, and more preferably 80% or bigger.

When recovery rate and/or elastic restoration ratio deficiency, cured article can not be dealt with the benefit uniform load in the panel manufacture process.

The composition of curable compositions of the present invention is not particularly limited, as long as it has above-mentioned feature, but can obtain this purpose by compound of being represented by formula (I) in conjunction with (A-1) and/or the compound that (A-2) has triphenol methane structure especially.

[1-16] bottom transverse sectional area and elastic restoration ratio and recovery rate

In addition, curable compositions of the present invention has following feature: can form a kind of cured article, the bottom transverse sectional area of this product is 24.5 μ m ²Littler and elastic restoration ratio be 50% or bigger and/or recovery rate be 85% or bigger.

For example, have little floorage as the pad of the screen panel of portable phone for example, so that deterioration image not, because pixel is little.On the other hand because this product for example portable phone be easy in use be subjected to impact load, it is subjected to load.Curable compositions of the present invention can also be used for following situation, wherein the elastic restoration ratio of curable product (pad) and/or recovery rate height.

The bottom transverse sectional area refers to the cured article of curable compositions formation of the present invention and the contact area of substrate, and measures this area by optical microscope observation shim pattern.The bottom transverse sectional area is preferably 20 μ m ²Or littler, and 15 μ m more preferably ²Or it is littler and be preferably 1 μ m ²Or bigger, 5 μ m more preferably ²Or it is bigger.

When the bottom transverse sectional area was excessive, it was unsuitable for the panel with little pixel of portable phone etc.On the other hand, when the bottom transverse sectional area too hour, can not obtain enough elastic restoration ratios and/or recovery rate.

The data of measuring in the load/unload test of carrying out based on above-mentioned microhardness test instrument are calculating elastic recovery rate and recovery rate in the same manner.

Recovery rate is preferably 90% or bigger.

Elastic restoration ratio is preferably 60% or bigger, and more preferably 80% or bigger.

When recovery rate and/or elastic restoration ratio deficiency, cured article can not be dealt with the load in the panel manufacture process.

In curable compositions of the present invention, composition is not particularly limited, as long as it has above-mentioned feature, still, can obtain this purpose by the compound of formula (I) expression and/or the compound that (A-2) has a triphenol methane structure by having (A-1) especially.

[2] method of use curable compositions

Curable compositions of the present invention can be used for various uses, for example, form the cured article of solder resist film or covering ray film, this film is used for transistor, semiconductor packages, color filter, organic electroluminescence device of printed wiring board, liquid crystal display device, plasma display, large scale integrated circuit, reduction thickness etc., with in forming the cured article of pixel, use, this pixel is the pixel of color filter, black matrix, finishing coat, rib and pad that is used for the liquid crystal panel of LCD etc.To using curable compositions to describe as solder resist or as the situation of pad especially.

[2-1] is as solder resist

Usually, provide with the film shape dissolving or or when being dispersed in curable compositions in the solvent, form pattern by the following method: for example be coated in and wait to be equipped with on the substrate of solder resist, dry this solvent, then it is provided with the film shape, and the formation pattern is randomly undertaken by the photoetching method that for example exposes-develop.Selectively, the curable compositions that is pre-formed to the dry film erosion resistant is provided on the substrate by conventional method, randomly forms pattern by the photoetching method that exposes-develop.By as required, the film of acquisition like this or the curable compositions layer of pattern form are applied the heat curing processing, on substrate, form solder mask layer.

[2-1-1] substrate

By using because the pattern that the curable compositions layer that exposure such as laser and developing forms thereon obtains, by applying the pattern formation substrate that welding manufacturing is used in its lip-deep circuit and electrode.Substrate can be sheet metal, itself is by copper, aluminium, gold, silver, chromium, zinc, tin, lead or nickel are made, but the preferred usually laminate that uses metal liner, this laminate closes by heating and shell of compression usually and states for example indium oxide of metal forming or metal oxide, the tin oxide that tin oxide or indium mix, or by sputter or vapour deposition or plated metal, on the surface of insulation support body, form the conductive layer of about 1 to 100 μ m thickness and obtain, this supporter comprises resin, for example thermoset resin, for example epoxy resin, polyimide resin, bimaleimide resin, unsaturated polyester resin, phenolics or melamine resin; Thermoplastic resin, for example saturated polyester resin, polycarbonate resin, polysulfone resin, acryloyl class (acryl) resin, polyamide, polystyrene resin, Corvic, polyolefin resin or fluororesin, paper, glass and inorganic material be aluminium oxide, silica, barium sulphate or lime carbonate for example, or compound substance, for example based on the glass cloth of epoxy resin, based on the glass nonwoven fabrics of epoxy resin, based on the paper of epoxy resin or based on the paper of phenolics, thickness is about 0.02 to 10mm.

[2-1-2] is fed to the method for substrate

When being fed on the substrate with dissolving or the state in the solvent of being dispersed in, for example can use known method, rotary coating, the excellent coating that winds the line, spraying, dip-coating, air knife blade coating, roller coat, scraper plate coating, silk screen coating, curtain are coated with.At this moment, consider the manufacturing capacity that welding subsequently that image forms and describes below is made, be preferably 5 μ m or bigger as the coating weight of build, more preferably 10 μ m or bigger, and it is preferably 200 μ m or littler to consider light sensitivity, more preferably 100 μ m or littler.

Adopt baking temperature for example, about 30 to 150 ℃, be preferably about 40 to 110 ℃, baking temperature for example about 30 to 150 ℃, and for example be preferably about 40 to 110 ℃ and drying time, about 5 seconds to 60 minutes, is preferably about 10 seconds to 30 minutes.

When the coating fluid by direct coating and dry curable compositions prepares curable image forming material; also can on the curable compositions layer that forms on the substrate above-mentioned to be made, form diaphragm by the solution by coating and dry following material; calcium substance is polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyethylene oxide, methylcellulose, carboxymethyl cellulose or hydroxy-methyl cellulose, so that prevent the polymerization depression effect to curable compositions that caused by oxygen.

In addition, when substrate was supplied as the dry film erosion resistant, it can be undertaken by known method.Particularly, with various components dissolved or be dispersed in the appropriate solvent to form coating fluid, with its coating and dry on interim film, randomly the surface of the curable compositions layer that so forms covers with covering ray film, to form so-called dry film erosion resistant.When dry film photoresist is coated with the covering ray film on the one side of curable compositions layer, peel off the covering ray film, and with this material layer by the pressure method for example, heat lamination is pressed onto substrate to be made, layer also so is fed on the substrate.

Interim film as when using dry film material against corrosion for example uses hitherto known film, polyethylene terephthalate film, polyimide film, polyamidoimide film, polypropylene screen and polystyrene film.When film has the preparation necessary solvent resistance of dry film erosion resistant or thermotolerance, can be by on interim support membrane, directly being coated with the solution of curable compositions, and be dried and prepare the dry film erosion resistant.Selectively, even when film has low solvent resistance or thermotolerance, can be for example, but by at first having the film of release property, but for example form the curable compositions layer on poly tetrafluoroethylene or the release film, lamination has low solvent resistance or stable on heating interim support membrane then, and the film that will have release property is then peeled off, thus preparation dry film erosion resistant.

The solvent that is used for coating fluid is not particularly limited, as long as it has the sufficient dissolubility of used composition and good film coating character is provided, this solvent for example can comprise, cellosolve solvent, for example methyl cellosolve, the molten fibre of ethyl, methylcellosolve acetate and ethyl cellosolve acetate; The propandiols solvent, for example propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters and dipropylene glycol dimethyl ether, esters solvent, for example butyl acetate, pentyl acetate, ethyl butyrate, butyl butyrate, diethy-aceto oxalate, pulvate ethyl ester, butyric acid ethyl-2-hydroxy ester, ethyl acetoacetate (ethyl acetatoacetate), methyl lactate, ethyl lactate and propionic acid methyl 3-methoxyl ester; Alcohols solvent is enanthol, hexanol, diacetone alcohol and fulfuric alcohol for example; Ketone solvent is cyclohexanone and methyl amyl ketone for example; High capital punishment solvent is dimethyl formamide, dimethyl acetamide, pyroracemamide and just-methyl pyrrolidone and mixed solvent thereof for example, and by in them, adding the solvent that aromatic hydrocarbon forms.The ratio of the solvent that uses is generally about 1 to 20 times (weight), based on the total amount of each composition of curable compositions.

[2-1-3] exposure method

By rayed or heating, by by using laser, expose under the scanning curable compositions layer, on substrate to be made, having the curable image forming material exposure of curable compositions layer as exposure light source.In this technology, when material has protective seam, can or peel off when having protective seam behind the protective seam its exposure.In addition, when forming the curable compositions layer, can when having interim support membrane or after it is peeled off, expose with the dry film erosion resistant.

Exposure source can comprise carbon arc lamp, mercury lamp, xenon lamp, metal halide lamp, fluorescent light, tungsten lamp, Halogen lamp LED, and LASER Light Source, for example HeNe laser, argon laser, YAG laser, HeCd laser, semiconductor laser and ruby laser.Particularly, preferably be created in the light source of laser in indigo plant-purple zone of 350 to 430 wavelength region may, further the preferred center wavelength is the light source of about 405nm.Particularly can mention InGaN semiconductor laser in the 405nm vibration.

In addition, the scanning exposure method that is undertaken by LASER Light Source is not particularly limited, and for example can comprises, flat scanning exposure system, outside surface drum-type (outer surface drum) scan exposure system and inside surface drum-type exposure system.Carry out scan exposure under following scan exposure condition: the best output intensity of laser is preferably 1 to 100mW, and more preferably 3 to 70mW, oscillation wavelength is preferably 390 to 430nm, and more preferably 400 to 420nm, beam spot diameter is preferably 2 to 30 μ m, 4 to 20 μ m more preferably, sweep velocity is preferably 50 to 500m/sec, and more preferably 100 to 400m/sec, scanning density is preferably 2,000dpi or bigger, more preferably 4,000dpi or bigger.

Can pass through in the presence of thermal polymerization, and not use above-mentioned photocuring, heat curable compositions of the present invention, on substrate, form cured resin.The heating condition that adopts is that temperature is generally 80 to 250 ℃, is preferably 100 to 200 ℃, is generally 10 heat time heating time to 120min, and is preferably 20 to 60min.

[2-1-4] developing method

In addition, carry out development treatment after exposure by using water developer, this developer preferably contains alkaline components and optional surfactant.Alkaline components for example can comprise, inorganic alkaline salt, for example sodium silicate, potassium silicate, lithium metasilicate, ammonium silicate, metasilicic acid (metasilicate) sodium, inferior potassium silicate, NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, sodium phosphite (sodiumsecondary phosphate), sodium hypophosphite (sodium tertiary phosphate), ammonium phosphite, ammonium hypophosphite, sodium borate, potassium borate and ammonium borate; And organic amine compound for example, monomethyl amine, dimethylamine, triethylamine, single ethylamine, diethylamine, triethylamine, single isopropylamine, diisopropylamine, monobutyl amine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and isopropanolamine, and its concentration with about 0.1 to 5 weight % is used.

In addition, surfactant comprises and above-mentionedly communicating for curable compositions is described, and wherein, preferred nonionic, negative ion or amphoteric surfactant, and wherein preferred especially amphoteric surfactant, wherein preferred betaine type compound.

The working concentration of surfactant is preferably 0.0001 to 20 weight %, and more preferably 0.0005 to 10 weight % is preferably 0.001 to 5 weight % especially.

In addition, liquid developer can for example randomly be combined with organic solvent, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, propylene glycol and diacetone alcohol.The pH of liquid developer is preferably 9 to 14 in addition, and more preferably 11 to 14.

Usually develop by known developing method, this method for example is being preferably about 10 to 50 ℃, under more preferably about 20 to 40 ℃ temperature, image forming material is immersed liquid developer or liquid developer is sprayed onto image forming material, and the time is about 5sec to 10min.In addition, after development, preferably, heat-treat under about 140 to 160 ℃ temperature so that improve the thermotolerance and the chemical-resistant of the resist of the image that cured article forms after development for example.

[2-2] is as pad

Usually, by method such as coating, dissolve or be dispersed in curable compositions in the solvent at the supply substrate of waiting to be equipped with pad with the shape of film or pattern, when dry solvent is supplied with the film shape then, method by for example photoetching forms pattern, exposes as required-develop.Handle by extra exposure or heat curing as required then and on substrate, form pad.

[2-2-1] is fed to the method on the substrate

Curable compositions of the present invention is fed on the substrate with the state that dissolves or be dispersed in the solvent usually.As Supply Method, can supply composition with known method, for example, spin coater method (spinnermethod), the excellent method that winds the line, flow coat method, punch die rubbing method (die coat method), rolling method or spraying process.Wherein, the amount of the coating fluid that make to use from comprehensive viewpoint reduces greatly, preferred die coat method, and the effect of the mist of the deposition when it not have spin-coating method for example, and suppress the generation of interference.Based on using the coating weight difference, under the pad situation, for example, this amount is generally 0.5 to 10 μ m, is preferably 1 to 8 μ m, and is preferably 1 to 7 μ m especially as dried thickness.In addition, the height of importantly dried thickness or the final pad that forms is uniform in the Zone Full of substrate.When scattering is big, liquid crystal panel has been produced uneven effect.In addition, also can be with the pattern form supply, for example, by ink-jet method or print process.

[2-2-2] drying means

Dry after curable compositions is to the substrate preferably undertaken by the drying means that uses hot plate, IR baking oven or convection oven.In addition, can be in conjunction with the drying under reduced pressure method temperature that do not raise, in the decompression chamber.Can be at common 40 to 130 ℃ and time 15sec to 5min, and to be preferably temperature be that 50 to 110 ℃ and time are in the scope of 30sec to 3min, according to for example, the type of solvent composition and the function of used exsiccator are suitably selected drying condition.According to the function selecting drying time of the used exsiccator of type of solvent composition.

[2-2-3] exposure method

By covering negative film mask pattern on the coated film of curable compositions, and the light source from ultraviolet light to visible luminosity, expose through mask pattern.Selectively, can adopt the scan exposure system that is undertaken by laser.At this moment, can be in oxygen-free atmosphere or randomly on photopolymerization layer, form barrier to oxygen, expose as after the polyvinyl alcohol layer, reduce the light sensitivity of photopolymerization layer so that prevent oxygen.The light source that is used to expose does not have special restriction, and this light source for example comprises, lamp source, for example xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc and fluorescent light; And lasing light emitter, for example argon laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, indigo plant-purple semiconductor laser and near infrared semiconductor laser.When the rayed of the wavelength that passes through regulation, can also use optical filter.

[2-2-4] developing method

After carrying out above-mentioned exposure, can on substrate, form pattern by aqueous solution with an organic solvent, described solution alkali compounds and optional surfactant.Aqueous solution can be further combined with inorganic solvent, damping fluid, complexing agent, dyestuff or pigment are arranged.

Alkali compounds comprises inorganic alkaline compound for example NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, biphosphate potassium ester and ammonium hydroxide; With organic basic compound for example, single-, two-or three-monoethanolamine, single-, two-or three-carbinolamine, single-, two-or three-ethamine; Single-or two-isopropylamine, just-butylamine, single adjacent-, two-or three-isopropanolamine, ethylenimine, bifurcation third pyridine (ethylene diimine), tetramethyl ammonium hydroxide (TMAH) and choline (holing).Alkali compounds can be two or more the potpourri in them.

Surfactant for example can comprise, non-ionic surfactant, for example polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyxyethylated ester, alkyl sorbitol dehydration ester and monoglyceride Arrcostab; Anionic surfactant, for example alkyl benzene sulfonate, alkylnaphthalene sulfonate, alkylthio group hydrochlorate, alkyl sulfonate, sulfo group (sulfo) succinate, and amphoteric surfactant, for example alkyl lactone and amino acid.

Organic solvent for example comprises, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, the molten acyl agent of phenyl, propylene glycol and diacetone alcohol.Organic solvent can use separately or be used in combination with aqueous solution.

Exposure that [2-2-5] is extra and heat curing are handled

Can carry out extra exposure or can after development, randomly carry out the heat curing processing by the method identical with above-mentioned exposure method to substrate.Especially preferably applying heat curing handles.The condition that heat curing is handled is at 100 to 280 ℃, preferred 150 to 250 ℃ temperature range and selecting in 5 to 60 minutes set times.

Embodiment

Below with reference to the instantiation that is used for solder resist and pad curable compositions of the present invention is described, unless but exceed essence of the present invention, the invention is not restricted to following examples.

[1] is used for the curable compositions of solder resist

Embodiment 1 to 3, Comparative Examples 1 to 2

By the compound of formula (I) expression and other compound as composition (A-1) to (A-6), Photoepolymerizationinitiater initiater as composition (B-1 to B-4), ethylenically unsaturated compounds as composition (C-1), epoxy compound as composition (D1), epoxy hardener as composition (E1), inorganic filler joins in the 100 weight portion propylene glycol methyl ether acetates with blending ratio shown in the table 1 as following compositions (X1) as composition (J1 to J3) and other composition separately as composition (H1 to H2), photosensitizing dye, and at room temperature stirs with the preparation coating fluid.

Individually, behind the laminated substrate of polish copper lining, wash with water and with blow air to regulate the surface drying, then it is preheated to 60 ℃ in baking oven, then the coating fluid of above-mentioned acquisition is coated on the Copper Foil of the laminate in the brass to build 25 μ m, and it is following dry 30 minutes at 80 ℃ in heat-wind circulate drying stove (hot blowcirculation drying furnace), with preparation photocuring image forming material, described laminated substrate forms by the surface that " the scotch bright SF " Copper Foil (1.5mm is thick, 250mm * 200mm size) that 35 μ m are thick that uses Sumitomo 3M Co. to make is adhered to polyimide resin.

(A1) compound that obtains by following preparation embodiment

In the 500ml four-necked bottle, add 9 of 231g, 9-pair (4 '-hydroxyphenyl) fluorenes diepoxide (epoxide equivalent: 231), the 2-acryloxy ethyl succinate (acid number: 260 of 216g, " HOA-MS " that Kyoei Chemical Co. makes), 0.45g 3-ethyl benzyl ammonium chloride and right-metoxyphenol of 0.1g, and dissolving with the speed blow air of 25ml/min in the heating under 90 to 100 ℃, in addition, under the state of solution muddiness, be heated to 120 ℃ gradually, with dissolving fully, then transparent under agitation the heating with solution thickness reached 0.8KOHmg/g until acid number in 8 hours, to obtain the water white transparency reaction product.Follow after the cellosolve acetic acid esters that adds 20g dissolves to the reaction product of the 447g that so obtains and with it, add 1 of 38g, 2,3, the biphenyl carboxylic acids dianhydride of 6-tetrabydrophthalic anhydride, 73.5g and the tetraethylammonium bromide of 1g, and heating and reaction 2 hours in the time of 110 to 115 ℃ gradually, to obtain compound (A1).The weight-average molecular weight of the compound that obtains be 3,500 and two key equivalents be 560.

(A2) compound that obtains by following preparation embodiment

In the presence of 2.5 weight portion triethylamines and 0.25 weight portion quinhydrones; 200 weight portion anhydrous succinic acids and the commercially available pentaerythritol triacrylate of 596 weight portions were reacted 5 hours at 100 ℃; to obtain the polyfunctional acrylic ester potpourri; its acid number is 94, comprises the polyfunctional acrylic ester that has a carboxylic acid group and two or more acryloyl groups in a molecule of 67mol% and the tetramethylol methane tetraacrylate of 33mol%.According to the same way as of the preparation embodiment that is used for (A1), obtain compound (A2), difference points out to be to use the functionalized acrylic acid g ester admixture of 597g to replace the 2-acryloxy ethyl succinate of 216g.The weight-average molecular weight of the compound that obtains be 3,000 and two key equivalents be 210.

(A3) compound that obtains by following preparation embodiment

Obtain compound (A3) in the identical mode of preparation embodiment that is used for (A1), difference is to use the benzophenone tetracarboxylic dianhydride of 80.5g to replace being used for the biphenyl tetracarboxylic dianhydride of the preparation embodiment 73.5g of (A1).The weight-average molecular weight of the compound that obtains be 3,500 and two key equivalents be 189.

(A4) compound that obtains by following preparation embodiment

Obtain compound (A4) in the identical mode of preparation embodiment that is used for (A1), difference is to use 9 of 231g, 9 ,-two (4 '-hydroxyl-3 '-tolyl) the fluorenes diepoxide replace being used for (A1) embodiment 231g 9,9-two (4 '-hydroxyphenyl) fluorenes.The weight-average molecular weight of the compound that obtains be 3,000 and two key equivalents be 187.

The compound that (A5: be used for Comparative Examples) obtains by following preparation embodiment

Obtain compound (A5) in the identical mode of preparation embodiment that is used for (A1), difference is to use the acrylic acid of 72g to replace being used for the 2-acryloxy ethyl succinate of 216g of the preparation embodiment of (A1).The weight-average molecular weight of the compound that obtains be 3,200 and two key equivalents be 416.

(A6: be used for Comparative Examples)

Compound (A1) (acid number 100mg KOH/g, weight-average molecular weight 5,000, two key equivalent 398 are by " PR-300J " of Showa Kobunshi Co. manufacturing) with following structural repeat unit

(B1) 1-(4-methyl mercapto phenyl)-2-morpholinyl-2-methyl-propane-1-ketone;

(B2) 2, the 4-diethyl thioxanthone;

(B3) the positive caprylyl benzophenone of 2-hydroxyl-4-;

(B4) 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline;

(C1) dipentaerythritol acrylate;

(D1) neighbour-cresols linear phenolic resin type epoxy resin (epoxide number 216, Japan Epoxy ResinCo. " Epicoat 180S70 "); (E1) dicyano diamines;

(H1) barium sulphate; (H2) talcum; (J1) following photosensitizing dye; (J2) following photosensitizing dye;

(J3) following photosensitizing dye

(X1) phthalocyanine green

[1-1] is to the light sensitivity of high-pressure sodium lamp exposure

The light curable image forming material of above-mentioned acquisition is measured the exposure light sensitivity by following method, the results are shown in table 1.

When the development in the time of 80 seconds during at 30 ℃ of the photocurable composition layer of the image forming material that obtains with 1kW ultra high pressure mercury light irradiation and the 1 weight % aqueous solution of using sodium carbonate, minimum exposure amount (mJ/cm that can the copy step image ²) be defined as light sensitivity.

[1-2] is to the cohesive of substrate

In addition, by following method, to the photocuring image forming material that obtains, the evaluate cure layer is treated the cohesive and the thermotolerance thereof of the substrate of manufacturing, the results are shown in table 1.

At ultrahigh pressure mercury lamp by use 1kW, shine the photocurable composition layer of the image forming material that is obtained with above-mentioned definite minimum exposure amount, behind the layer that forms all surfaces curing, cured layer 60min at 150 ℃ of thermal treatment gained, cut this cured layer according to JIS D0202 by cutting machine then, to form 100 cross-cut things (cross-cuts), each spacing 1mm, glass paper tape (Nichiban Co. manufacturing) is adhered on the cured layer, and the cross-cut thing number of the cured layer that measurement is peeled off when peeling off this paper tape is also used following standard evaluation.

A: in 100 cured layer cross-cut things, the number of the cross-cut thing of peeling off is 0,

B: in 100 cured layer cross-cut things, the number of the cross-cut thing of peeling off is 1 or bigger and less than 5,

C: in 100 cured layer cross-cut things, the number of the cross-cut thing of peeling off is 5 or bigger and less than 10,

D: in 100 cured layer cross-cut things, the number of the cross-cut thing of peeling off is 10 or bigger.

The thermotolerance that [1-3] is bonding

Cutting so that after forming 100 cross-cut things with above-mentioned same way as by cutting machine, solder flux (Tamura Kaken Co. manufacturing) is applied on the surface, repeat following process 6 times then: its scolder that immerses 290 ℃ is bathed 30sec, reduce temperature then to room temperature.Then the glass paper tape is adhered on the cured layer, and the number of the cross-cut thing that cured layer is peeled off when peeling off paper tape according to above-mentioned identical mode measurement, and based on identical standard evaluation.

[1-4] is to the light sensitivity of laser explosure

Embodiment 4 (the curable compositions that is used for solder resist: laser explosure)

For the photocuring image forming material for preparing in embodiment 1 to 3 identical mode, by following method, use laser as the light sensitivity of exposure light source measurement for laser explosure, in addition, estimate cohesive and thermotolerance thereof in the same manner described above to substrate, difference is to replace exposure light source with laser, the results are shown in table 1.The photocurable composition layer of gained image forming material is fixed on the cylinder of 7cm diameter made of aluminum, and by using centre wavelength as 405nm's, with laser power be the LASER Light Source (Nichia Chemical Industry Co. make " NLHV500C ") of 5mW, carry out scan exposure, change simultaneously revolution from 10 to 100rpm, in imaging surface brightness is that 2mW and beam spot diameter are under the 20 μ m, change bundle scanning distance and sweep velocity simultaneously, the 1wt% aqueous sodium carbonate that is blown into 30 ℃ then is as liquid developer, with at 0.15MPa, and spray development (spray developed), development time is 1.5 times of minimum development time, with developed image.For the image that obtains, be defined as light sensitivity to indigo plant-purple laser for duplicating the needed exposure of 20 μ m live widths.

[2] be used for the curable compositions of solder resist: dry film photoresist

Embodiment 5 to 7

By on the interim supporter of polyethylene terephthalate film (19 μ m are thick), amount with 25 μ m builds, by using the coating machine coating composition, drying is 5 minutes in 90 ℃ of baking ovens, and on the photocurable composition layer that so obtains lamination as tectal polyethylene film (25 μ m are thick), and with its placement 1 day, preparation dry film erosion resistant.Then, the dry film erosion resistant that obtains be laminated to embodiment 1 to 3 on the Copper Foil of laminate in the identical brass that uses, peel off polyethylene film simultaneously, on release surface, by using handheld cylinder laminator (hand type roll laminator), in bowl temperature is that 100 ℃ and drum pressure are that 0.3MPa and laminate speed are under the 1.5m/min, preparation light curable image forming material, and the photocurable composition layer is formed on the laminated substrate in the brass in this material.

For the photocurable composition layer of the photocuring image forming material that obtains, measure light sensitivity to laser explosure, in addition,, estimate cohesive and thermotolerance thereof, and the result sees table 1 to substrate according to mode identical among the embodiment 4.

Table 1

		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Comparative Examples 2	Comparative Examples 2
											Curable compositions (wt%)	(A) compound (A2) that contains unsaturated (A1) group of ethylenic and carboxyl is (A4) (A5) (A6) (A3)	100	100	100	100	100	100	100	100	100
(B) (B2) (B3) (B4) for polymerization initiator (B1)	12 0.5	12 0.5	12 0.5	12 0.5 5 4	12 0.5 5 4	12 0.5 5 4	12 0.5 5 4	12 0.5	12 0.5
										(C) ethylenically unsaturated compounds (C1)		50	50	50	50	50	50	50	50	50
(D) epoxy compound (D1)	20	20	20	20	20	20	20	20	20
										(E) epoxy hardener (E1)							0.5
(H) inorganic filler (H1) (H2)	30 15	30 15	30 15	30 15	30 15	30 15	30 15	30 15	30 15
										(J) photosensitizing dye (J1) (J2) (J3)					0.6	0.6	0.6	0.6
(X) other (X1)	0.75	0.75	0.75	0.75	0.75	0.75	0.75	0.75	0.75
										Composition character		Exposure high-pressure sodium lamp susceptibility laser	300	150	300	15	15	17	13	500	600
Substrate before thermotolerance test cohesive after thermotolerance is tested	A A	A A	A A	A A	A A	A A	A A	C B	B D

[3] be used for the curable compositions of pad

Embodiment 8 to 14, Comparative Examples 3 to 4

The compound of formula (I) expression and other compound as composition (A2), (A5) and following (A8) to (A12), polymerization initiator be used for composition (B1), ethylenically unsaturated compounds be used for composition (C1) and (C2), amino-compound is used for composition (F1), surfactant is used for composition (I1) and adjuvant is used for composition (N1) separately with blending ratio shown in the table 2, join in the propylene glycol methyl ether acetate of 100 weight portions, and at room temperature stir with the preparation coating fluid.For the coating fluid that obtains, estimate under the stable storing by following method, the results are shown in the table 2.

[3-1] storage stability

Sealing coating fluid and store under 7 days the situation at 35 ℃ in sample bottle changes and the variation of minimum development time according to following canonical measure and the viscosity estimated before and after storing.

Zero: viscosity changes in ± 3% and minimum development time changes in ± 3%

△: viscosity changes above ± 3%, but minimum development time changes in ± 3%

X: viscosity changes in ± 3%, but minimum development time changes above ± 3%

(A8) compound that obtains by following preparation embodiment

Same way as with the preparation embodiment that is used for (A2) obtains compound (A8), and difference is to use 1,2,3 of 137g, and the 6-tetrabydrophthalic anhydride replaces 1,2,3 of 38g, the biphenyl tetracarboxylic dianhydride of 6-tetrabydrophthalic anhydride and 73.5g.The acid number of the compound that obtains is 56, weight-average molecular weight be 2620 and two key equivalents be 216.

(A9) compound that obtains by following preparation embodiment

100 part 9,231), (used (acid number: 90.5)), 0.19 part of right-metoxyphenol, 7.4 parts of triphenylphosphines and 368 parts of propylene glycol methyl ether acetates join in the reaction vessel among the preparation embodiment as (A2), and are reduced to 5mg-KOH/g or littler 90 ℃ of stirrings until acid number for 273.2 parts of reaction mixtures of anhydrous succinic acid and pentaerythritol acrylate the 2-glycidyl etherificate product of 9-two (4 '-hydroxyphenyl) fluorenes (epoxide equivalent amount:.Acid number reaches desired value, and (acid number: 1.0) the needed time is 10 hours.Then, 6 parts of propylene glycol methyl ether acetates are joined in 80 parts of reaction solutions that obtain by reaction, and add 1.9 parts of hexamethylene diisocyanates and 0.01 part of dibutyltin dilaurate, 90 ℃ of reactions 3 hours, in addition, adds 3.8 parts of trimellitic anhydrides and reacted 2 hours at 90 ℃, to obtain the solution of compound (A9), the acid number of this compound is 52, and weight-average molecular weight is that 3100 (by gpc measurements, with the polystyrene conversion) and two key equivalent are 199.

(A10) have triphenol methane structure resin (diethylene glycol monoethyl ether acetate solution, its acid number be 101 and two key equivalents be 315, the TCR1286 that Nippon Kayaku Co. makes)

(A11) compound that obtains by following preparation embodiment (acrylic resin of describing in the synthetic embodiment 3 of JP-A No.11-133600 carries out check test)

Adding 7 weight portions 2,2 in the flask that is equipped with cooling tube and stirrer '-azo two (2, the 4-methyl pentane nitrile) and 200 weight portion diethylene glycol dimethyl ether.Then, after adding 10 parts by weight of styrene, 20 weight portion methacrylic acids, 45 weight portion glycidyl methacrylates and 25 weight portion methacrylic acids, two ring pentyl esters, and behind nitrogen purging, slowly begin to stir.Solution temperature is elevated to 70 ℃, and this temperature was kept 5 hours, to obtain to contain the polymer solution (A11) of this multipolymer.The solid concentration of resulting polymers solution be 33% and the weight-average molecular weight of polymkeric substance be 18,000.

(A12) compound that obtains by following preparation embodiment

Prepare compound (A12) according to the same way as of making embodiment (A2), difference is 1 of 38g, 2,3,1,2 of tetracarboxylic acid two dehydrates (New Japan Chemical, RIKACID BP-100) of the phenyl tetracarboxylic acid acid anhydride usefulness 57.5g of 6-tetrabydrophthalic anhydride and 73.5g and 43.8g, 3, the 6-tetrabydrophthalic anhydride replaces.The acid number of compound (A12) is 55, weight-average molecular weight be 4450 and two key equivalents be 208.

(C2) phosphate that contains (methyl) acryloxy of formula (VIIIc) expression (the KAYARAD PM21 that Nippon Kayaku Co. makes)

(F1) melamine resin and modified resin thereof (NIKARACE-2151 that Sanwa Chemical Co. makes)

(I1) fluorine surfactant (the MEGAFAX F475 that Dai-Nippon Ink Chemical Industry Co. makes)

(N1) silane coupling agent (SH6040 that Toray Dow Corning Co. makes)

Then, using spin coater, be formed with on the surface on the ITO film of glass substrate of ITO film behind this coating fluid of coating, 80 ℃ of dryings are 3 minutes on hot plate, to form coated film.By using mask pattern, working strength is 32mW/cm ²The coated film exposure of 365nm ultraviolet light to obtaining, make that exposure is 60mJ/cm ², described mask has the circular open that 9 diameters are respectively 5 to 20 μ m, and 5mm ²Or bigger opening, exposing clearance is 150 μ m.In air, carry out ultraviolet irradiation.Then, 23 ℃ with 0.1% potassium hydroxide aqueous solution spray development after, development time was 2 times of minimum development time, with purified water washing 1 minute.The minimum exposure time refers to the wherein consoluet time of unexposed area under above-mentioned development conditions.Removed that inessential part is heated with the substrate that forms shim pattern and in 230 ℃ of baking ovens dry 30 minutes, obtaining to have a plurality of shim pattern of different floorages, at 5mm ²Or the membrane portions that forms in the bigger opening, each pattern has the height of about 4 μ m.To the shim pattern of acquisition like this, estimate cohesive and compression performance by the method that shows below, the results are shown in the table 2.

[3-2] cohesive

Embodiment 8 to 11 and Comparative Examples 3 and 4 are estimated cohesive.

Shim pattern for the different floorages that obtain from the patterned mask of different mask open diameters, pattern height is that 3 μ m or bigger minimum pattern size (wherein form 8 or more a plurality of pattern (promptly in having 9 shim pattern of same size separately, (depleted) pattern that in 9 patterns to be formed, damages be 1 or still less)) be defined as cohesive, and its floorage sees Table 2.

[3-3] compression performance: the load/unload test that the microhardness test instrument carries out

For top shim pattern, (KeyenceCorp. VK-9500) makes the longitudinal profile profile that passes through center line to use super dense color 3D shape measure microscope.Below, measure the length (shown in Fig. 2 signal) that is parallel to the straight line AA ' of substrate surface in shim pattern apart from 90% place of substrate surface extreme higher position Q.AA ' is defined as the sectional area of shim pattern as the area of a circle of diameter.

In the shim pattern of above-mentioned acquisition, for having last area 80 ± 10 μ m ²Pattern, by the load/unload test evaluation compression performance that uses the dynamic ultra micro hardness tester of Shimazu DUH-W201S to carry out.Test under following test condition: measure 23 ℃ of temperature, the use diameter is that the plane of 50 μ m adds press, and (0.22gf/sec) is applied to pad with load with constant speed, keeps 5 seconds after load reaches 5gf, and reduces load continuously with identical speed.According to loading-displacement curve (curve shown in Fig. 3 signal) from determining this test, determine maximum displacement H[max], final mean annual increment movement H[last], recovery rate (%)=H[last]/(test before pattern height) * 100 and elastic restoration ratio (%)=(H[max]-H[last])/(H[max] * 100, load N (gf) when being 0.25 μ m with displacement under the load, and be displayed in Table 2.

[3-4] estimates gasket performance (panel evaluation (Panel Evaluation))

Prepare liquid crystal cells by following process, and estimate gasket performance.

Preparation electrode base board A and electrode base board B.The former is 2.5cm ²Alkali-free glass substrate (Asahi glass AN-100), it is coated with the ITO layer on the whole surface of a side; The latter is identical 2.5cm ²Glass substrate is coated with 1cm at the center of another side ²The ITO layer is connected to the wide interconnect electrode to 2mm.

By spin coating, with curable compositions (in each embodiment, preparing) coating electrode base board A, on hot plate, heated 3 minutes down in 80 ℃, be to expose under the 150 μ m at exposing clearance, (area is 1cm to cover its center with exposure mask simultaneously ²), this mask has grid with fixed intervals, and (900 circular patterns of 30/cm * 30/cm) arrange, each pattern has 80 μ m ²Basal plane long-pending (basal area).Irradiation energy is 60mJ/cm ²Develop with potassium hydroxide aqueous solution then, with the pure water washing, and in the hot air circulate baking oven 230 ℃ the time dry 30 minutes.Regulate the coating condition in a certain way, make that heat treated pad height is 4 μ m.The electrode base board A that handles has the test pad pattern at the center.

Then, by spin coating, with alignment agent (agent for alignment layer) (NISSANCHEMICAL INDUS three ES, SUNEVER 7492) coating electrode base board A and electrode base board B, following dry 1 minute in 110 ℃ on hot plate, 200 ℃ of dryings are 1 hour in the hot air circulate baking oven, to form the thick coating of 70nm.By rubbing machine each electrode is carried out registration process then.

Use decollator then, along the surperficial periphery that is coated with alignment, with (the diameter: epoxy resin sealant coating electrode base board B 4 μ m) that contains the silica grain, arranging this electrode base board B makes it towards the electrode base board A surface with test pad pattern, outward flange is 3mm away from each other, 180 ℃ of heating of air oven 2 hours, simultaneously they are kept extruding each other.

With liquid crystal (Merck ﹠amp; Co.ZLI-4792) fill the gained dummy cell, and with the sealing of the UV curable encapsulant on the periphery, with the preparation test unit.

This liquid crystal cells is applied alternating voltage, and (5V, 60Hz), visual and microscopic examination is at electrode part office electro-optic response.According to this test unit of following standard evaluation.

Zero: visual and microscope is not all observed unevenness

△: unevenness has been arrived in microscopic examination, but visualization does not have

*: be visually observed unevenness

The result provides in table 2.

Table 2

			Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Comparative example 3	Comparative example 4
												Curable compositions (weight ratio)	Compound	(A2)	46.95
(A8)		46.95	46.95	46.95
										(A9)							46.95
(A10)						46.95
										(A12)									46.95
(A5)								46.95
										(A11)											46.95
(B) polymerization initiator	(B1)	3	3	3	3	3	3	3	3													3
										(C) ethylenically unsaturated compounds	(C1)		46.95	46.95	46.95	46.95	46.95	46.95	46.95	46.95	46.95
(C2)	3	3			3	3	3	3
											(I) surfactant		(I1)	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
(F) amino-compound	(F1)			3
											(N) adjuvant		(N1)				I					3
Composition character	Storage stability		△	○	○	△	○	○	△	△													X
											Two key equivalents of whole composition		139.0	140.1	141.9	139.1	136.6	155.1	138.5	164.3	205.4
	Cohesive	Floorage (μ m)	12.6	13.8	19.6	22.9				16.9												25.8
											Compression performance	Maximum displacement (total deformation) H[max](μm)	1.35	1.42	1.39	1.38	1.40	1.58	1.65	1.30	1.26
	Final mean annual increment movement H[last] (μ m)	0.55	0.57	0.54	0.55	0.59	0.74	0.80	0.75	0.67
												Recovery rate (%)	86％	87％	87％	86％	85％	81％	84％	81％	83％
	Elastic restoration ratio	59％	60％	61％	60％	58％	53％	57％	42％	47％

		Load N (gf) when displacement is 0.25 μ m	0.63	0.60	0.62	0.63	0.60	0.41	0.38	0.60	0.56
												Panel is estimated			○	○	○	○	○	○	○	X	△

Though describe the present invention in detail, clearly can carry out various improvement and variation for those skilled in the art, and not break away from the spirit and scope of the present invention to it with reference to the specific embodiment of the present invention.

The application is hereby incorporated by its full content based on the Japanese patent application (application number 2003-380666) of application on November 11st, 2002.

Industrial applicibility

Curable compositions of the present invention can be used to form the solder resist film or cover ray film, for example, solder resist film in transistor, semiconductor packages, colour filter and the organic electroluminescence device of printed wiring board, liquid crystal display device, plasma display, large scale integrated circuit, reduction thickness or covering ray film, with the insulating cover that is used for various electronic units, and it is specially adapted to use in the direct imaging of being undertaken by laser.

In addition, curable compositions of the present invention can be with acting in the liquid crystal panel, for example, and the curable compositions of the colour filter that uses in the liquid crystal display, black matrix, finishing coat, rib and pad.

Claims (17)

1. curable compositions, it comprises the compound of following formula (1) expression:

In the formula (I), R ¹Expression can have substituent alkylidene maybe can have substituent arlydene, R ²The carbonyl oxygen base that contains the ethylenic unsaturated group of expression 5 or more a plurality of carbon atoms, it can have substituting group, R ³And R ⁴The substituting group that expression is independently of one another chosen wantonly, n is 0 to 10 integer, and four phenyl ring can further have substituting group.

2. the curable compositions of claim 1, wherein R ²The carbonyl oxygen base that contains the ethylenic unsaturated group for 5 or more a plurality of carbon atoms of following formula (II) expression:

In the formula (II), R ⁷, R ⁸And R ⁹Represent hydrogen atom or methyl independently of one another, Y ¹In the divalent group and formula that expression is optional ^*The compound of expression (I) expression-CH ₂-and R ²Between bonding.

3. claim 1 or 2 curable compositions, wherein R3 is selected from the substituting group of hydrogen atom, formula (IIIa) expression and the substituting group of formula (IIIb) expression:

In the formula (IIIa), R ⁵¹Expression can have substituent alkyl, can have substituent alkenyl, can have substituent naphthenic base, can have substituent cycloalkenyl group maybe can have substituent aryl;

In the formula (IIIb), R ⁵²Expression can have substituent alkyl, can have substituent alkenyl, can have substituent naphthenic base, can have substituent cycloalkenyl group and can have substituent aryl.

4. each curable compositions, wherein R in the claim 1 to 3 ⁴Substituting group for formula (IV) expression:

In the formula (IV), R ¹, R ², R ³With n have with formula (I) in defined identical meanings and the formula ^*The compound of expression (I) expression-O-and R ⁴Bonding.

5. each curable compositions in the claim 1 to 4 is a compound available from two (hydroxyphenyl) fluorenes type epoxy compound by the compound of formula (I) expression wherein.

6. each curable compositions in the claim 1 to 5, wherein the compound by formula (I) expression is following compound, it is by from two (hydroxyphenyl) fluorenes type epoxy compound, to forming 5 or the carbonyl oxygen base that contains the ethylenic unsaturated group of more a plurality of carbon atoms on it, further be selected from polybasic carboxylic acid and acid anhydride thereof and have one or more compounds reactions in the compound of isocyanate groups and obtain.

7. each curable compositions in the claim 1 to 6, further contain following compositions (B):

(B) Photoepolymerizationinitiater initiater and/or thermal polymerization.

8. each curable compositions in the claim 1 to 7, further contain following compositions (C):

(C) ethylenically unsaturated compounds.

9. each curable compositions in the claim 1 to 8, it further contains following compositions (J):

(J) photosensitizing dye.

10. curable compositions that can form cured article, described product is in the loading-unloading test of being undertaken by the microhardness test instrument, total deformation is 1.35 μ m or when bigger and/or when the load bottom offset is 0.25 μ m, load N is 0.50gf or littler, and elastic restoration ratio be 50% or bigger and/or recovery rate be 80% or bigger.

11. the curable compositions that can form cured article, the bottom transverse sectional area of this cured article are 25 μ m ²Littler and elastic restoration ratio be 50% or bigger and/or recovery rate be 85% or bigger.

12. the curable compositions of claim 10 or 11 further contains the compound with triphenol methane structure.

13. each the curable compositions that can form cured article in the claim 1 to 9, wherein in the loading-unloading test of being undertaken by the microhardness test instrument, in total deformation is 1.35 μ m or bigger and/or when the load bottom offset is 0.25 μ m, and load N is 0.50gf or littler.

14. each curable compositions in the claim 1 to 10, its can shape following one-tenth cured article, the bottom transverse sectional area of this product is 25 μ m ²Littler and elastic restoration ratio be 50% or bigger and/or recovery rate be 85% or bigger.

15. a cured article, it is that each curable compositions forms in the claim 1 to 14 by using.

16. color filter, it has the cured article of claim 15.

17. liquid crystal display device, it has the cured article of claim 15.

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