CN101153121A - Radiation-sensitive resin composition for spacer, spacer and method for forming the same - Google Patents

Radiation-sensitive resin composition for spacer, spacer and method for forming the same Download PDF

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CN101153121A
CN101153121A CNA2006101718077A CN200610171807A CN101153121A CN 101153121 A CN101153121 A CN 101153121A CN A2006101718077 A CNA2006101718077 A CN A2006101718077A CN 200610171807 A CN200610171807 A CN 200610171807A CN 101153121 A CN101153121 A CN 101153121A
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composition
polymkeric substance
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CN101153121B (en
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梶田彻
河本达庆
松本龙
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JSR Corp
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JSR Corp
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Abstract

The invention relates to a solidified resin composite, a method for forming a solidified membrane and a solidified membrane. The invention comprises a polymer which is polymerized through an actively free radical polymerization in the effect of a particular thiocarbonyl sulphur compound. The ratio (Mw/Mn) of the weight average molecular weight (Mw) of the polymer (expressed in terms of polystyrene) to the number average molecular weight (Mn) measured by gel permeation chromatography is1.7 or less than 1.7, the polystyrene also includes carboxyl, epoxy ethyl or oxygen heterocycle butyl.

Description

The formation method and the cured film of curable resin composition, cured film
Technical field
The present invention relates to a kind of curable resin composition that contains specific resin, use the formation method and the cured film of the cured film such as spacer (spacer), interlayer dielectric, microlens (microlens) or protective membrane of said composition.
Background technology
＜about the prior art of spacer 〉
All the time, in liquid crystal display device, in order to make 2 intervals between transparency carrier keep certain, use uniformly-spaced thing particle of glass sphere with regulation particle diameter, baton round, but the problem that these spacer particles exist is, because it is random distribution on transparency carriers such as glass substrate, therefore, when pixel forms the zone and has the spacer particle, can origination interval thing particle mirror phenomenon, or making the incident light scattering, the contrast gradient of liquid crystal display device reduces.
Therefore, in order to address these problems, adopt the method (for example opening the 2001-261761 communique) of utilizing photolithography to form spacer with reference to the spy.This method is to be coated with radiation sensitive resin composition on substrate, mask by regulation carries out developing after the uviolizing, forms point-like or strip spacer, because only the prescribed position beyond pixel forms the zone forms spacer, therefore, the problems referred to above have been solved substantially.
But the sublimate that existing radiation sensitive resin composition produces when carrying out sintering in order to form spacer may pollute production line or equipment, therefore wishes to have and can reduce the radiation sensitive resin composition that sublimate produces.
＜about interlayer dielectric and lenticular prior art 〉
In electronic units such as thin film transistor (below be designated as " TFT ") type liquid crystal display device, magnetic head element, integrated circuit component, solid-state imager, usually for the wiring closet insulation that makes the stratiform configuration and interlayer dielectric is set.Preferably to obtain the required process number of desired pattern form few and have the material of sufficient flatness owing to form the material of interlayer dielectric, therefore is extensive use of radiation sensitive resin composition (opening 2001-354822 communique and Te Kai 2001-343743 communique with reference to the spy).
In above-mentioned electronic unit, for example TFT type liquid crystal display device is through form ELD on above-mentioned interlayer dielectric, form thereon again that the operation of liquid crystal orientation film makes, therefore interlayer dielectric will be exposed under the hot conditions in the formation operation of ELD, perhaps place the stripping liquid of the photoresist material that is used to form electrode pattern, therefore, need sufficient patience be arranged to these conditions.And, in recent years the oriented big pictureization of TFT type liquid crystal display device, high brightnessization, height become more meticulous, the trend of development such as high-speed responsiveization, slimming, this requirement is used for its interlayer dielectric formation the highly sensitive of composition, and the interlayer dielectric that requires to form has the performance that is higher than existing film at aspects such as specific inductivity, transmittances.
On the other hand, use the microlens in the lens footpath that has about 3～100 μ m or the microlens array that so a plurality of microlenss are regularly arranged to carry the imaging optical system of colored filter or the optical material of the joints of optical fibre usually as crystalline substances such as facsimile recorder, electronic copier, solid-state imagers.
The formation method of microlens or microlens array is known to be had: after having formed the pattern-like film corresponding with desired lens shape, it is carried out heat treated make melt flow, directly be used as the method for lens; The lens pattern that melt flow is good makes mask, utilize dry etching with the lens shape transfer printing in suprabasil method etc.In the formation of said lens pattern, be extensive use of radiation sensitive resin composition (opening flat 6-18702 communique and the flat 6-136239 communique of Te Kai) with reference to the spy.
The element that will form aforesaid microlens or microlens array then offers following operation; promptly in order to remove as the various insulating films on the welding zone of distribution formation part; coating planarization film and etching protective membrane; expose, develop with required mask; remove the erosion shield of welding zone part; remove planarization film, various insulating film by etching then, expose the operation of welding zone part.Therefore, microlens or microlens array form in operation and the etching work procedure filming of planarization film and erosion shield, need solvent resistance, thermotolerance.
The radiation sensitive resin composition that uses in order to form such microlens except require be highly sensitive, the microlens that also require to form has required radius-of-curvature, and thermotolerance height, transmittance are high.
In addition, there are the problem of process management aspect in aforesaid interlayer dielectric, microlens: promptly in the developing procedure that forms these, even development time surpasses Best Times slightly, sometimes developing solution also can soak into between pattern and the substrate and peel off easily, therefore must strict control development time.
As mentioned above, when forming interlayer dielectric, microlens by radiation sensitive resin composition, it is highly sensitive requiring composition, also require in the developing procedure in forming operation, when even development time exceeds schedule time, peeling off of pattern can not taken place, demonstrate good adaptation yet, and by its layer insulation film heat resistance height, solvent resistance height that forms, specific inductivity is low, transmittance is high.On this basis, when forming microlens, except above-mentioned all performances, require to have as lenticular good fusion shape (required radius-of-curvature), thermotolerance height, solvent resistance height, transmittance height, but the present radiation sensitive resin composition that does not also satisfy such requirement.
And the sublimate that produces when carrying out sintering being used to form interlayer dielectric, microlens may pollute production line, equipment, wishes to have the radiation sensitive resin composition of the generation that can reduce sublimate.
＜about the prior art of protective membrane 〉
Making LCD (liquid crystal display device); CCD (charge coupled device; Charge Coupled Device); CMOS (CMOS (Complementary Metal Oxide Semiconductor); Complementary Metal Oxide Semiconductor) etc. in the operation of light device; because display element will be used solvent; acid; alkali etc. carry out dip treating; and element surface is local when utilizing sputter to form the distribution electrode layer can expose at high temperature; therefore; in order to prevent owing to such processing makes display element generation deterioration or sustains damage the common protective membrane that can tolerate such processing in the setting of the surface of display element.
Require such protective membrane with respect to substrate that will form this protective membrane or bottom and be formed on the protective membrane the layer the adaptation height.In addition, claimed film self has following performance: level and smooth and intensity is high; Has heigh clarity; That thermotolerance and photostabilization height, long-time use can not take place is painted, flavescence, whiting iso-metamorphism; Performances such as water tolerance, solvent resistance, acid resistance and alkali resistance are good.And, being used to form the material of protective membrane with above-mentioned various performances, the spy opens flat 5-78453 communique and discloses the thermoset composition that comprises the polymkeric substance with glycidyl.
When such protective membrane being used on the colored filter of LCD, CCD, cmos sensor, requirement can be with the difference of altitude planarization that is caused by the colored filter that is formed on the basal substrate.In addition; at color liquid crystal display device; for example (supertwist is to row for STN; Super Twisted Nematic) in the color liquid crystal display device of mode or TFT (ThinFilm Transister) mode; for the box gap that keeps liquid crystal layer even; be spherical spacer to be dispersed on the protective membrane fit with panel again; then sheet material is carried out thermo-compressed; thus liquid crystal cell is sealed; but at this moment the problem of Cun Zaiing is; under such heat and pressure, can see the protective membrane generation depressed phenomenon of the part that spacer exists, the entanglement of box gap.Particularly when making the color liquid crystal display device of STN mode, must strictly carry out the applying of colored filter and counter substrate with high precision, claimed film has high difference of altitude planarization performance and heat-resisting withstand voltage properties.
In addition, also adopt in recent years and on the protective membrane of colored filter, utilize sputter with distribution electrode (ITO:IndiumTin Oxide) film forming, with the mode with the ITO composition such as strong acid or highly basic.At this moment, protective membrane surface local when sputter can expose at high temperature, maybe will carry out plurality of reagents and handle.Thereby, require it can tolerate these and handle, also require to have the adaptation with the distribution electrode, so that ITO can not peel off from protective membrane when agent treated.
In the LCD panel, turn to purpose with high brightness, developed transparency electrode such as ITO and TFT element have been made lamination structure by the high interlayer dielectric of the transparency, the panel that port area is increased.In addition, colored filter and TFT element are to form with other substrate manufacture at present, but have also developed the technology that forms colored filter on the TFT element.And, under such technical background, the good protective membrane of performance (planarization performance) of wishing to develop the thermotolerance height and will be formed at the difference of altitude planarization of the colored filter on the basal substrate.
And; along with the maximization of display panel substrate in recent years; there are the following problems: promptly produce sublimate in the sintering circuit that is formed protective membrane by thermoset composition; be deposited in sintering oven inside; pollute baking oven; make sintering condition be difficult to control, or the sublimate of piling up is attached to polluting on the display panel substrate, causes problems such as demonstration is bad.
Use in the formation of protective membrane at colored filter; the curable resin composition that use has the advantage that can form the good protective membrane of surface hardness easily is suitable; do not satisfy beyond the transparency etc. requires as the general property of protective membrane but at present also have to form, can also adapt to aforesaid various new high request protective membrane and as the storage stability of composition also excellent material.
Summary of the invention
The present invention is based on that above-mentioned situation finishes, its first purpose is to provide a kind of curable resin composition, it is enough high, good with the adaptation on substrate or substrate or upper strata that it has high radiation-sensitive sensitivity, resolving power, and can be suppressed at and produce sublimate when film forms in the operation sintering.
Above-mentioned curable resin composition provides pattern form, compressive strength and rub resistance good spacer when being used to form spacer;
When being used to form interlayer dielectric, can form " Development margin (Now is as マ one ジ Application) " big and thermotolerance height, perviousness height, interlayer dielectric that specific inductivity is low, described " Development margin " still can form the index of good pattern even be to surpass optimum development time to continue to develop in developing procedure;
When being used to form microlens, can forming and have the height Development margin and have high transmission rate and the microlens of good fusion shape.
Second purpose of the present invention is to provide a kind of curable resin composition; it can form a kind of protective membrane; the adaptation on this protective membrane and substrate or substrate or upper strata is good and can be suppressed at and produce sublimate when film forms the sintering of operation; and satisfy high transparent, high heat resistance and high surface hardness; withstand load under heating condition is good simultaneously, and will be formed at the excellent property of the difference of altitude planarization of the colored filter on the basal substrate.
The 3rd purpose of the present invention is to provide a kind of method that is formed cured film by above-mentioned any curable resin composition.
The 4th purpose of the present invention is to provide a kind of cured film of utilizing aforesaid method to form.
According to the present invention, above-mentioned first purpose of the present invention contains by a kind of, (A) curable resin composition of polymkeric substance is realized, described, (A) polymkeric substance is by at following formula, (1) or following formula, (2) active free radical polymerization under compound shown in exists carries out polymerization, weight-average molecular weight with the polystyrene conversion of gel permeation chromatography, (Mw) and number-average molecular weight, (Mn) ratio, (Mw/Mn) be below 1.7 or 1.7, and have carboxyl and Oxyranyle, (oxiranyl) or the oxa-cyclobutyl, (oxetanyl) polymkeric substance
Figure A20061017180700101
(in the formula (1), p is the integer more than 1 or 1, Z 1Be hydrogen atom, carboxyl, group-R A, group-OR A, group-NR A 2, group-COOR A, group-C (=O) NR A 2, group-P (=O) R A 2, group-P (=O) (OR A) 2Or group-NR ANR A-C (=O) R A, R AIndependently for halogen atom, cyano group, hydroxyl, carbonatoms are that 1～20 alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl (ァ Le ァ Le キ Le base) or carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group, R ADuring for alkyl, thiazolinyl, aryl, aralkyl or heterocyclic group, R AIn the hydrogen atom that is had one or more can be by halogen atom, cyano group, hydroxyl or carboxyl substituted;
During p=1, R 1Be hydrogen atom, cyano group, group-R B, group-OR B, group-NR B 2, group-SR B, R BIndependently for carbonatoms is that 1～20 alkyl, carbonatoms are that 3～20 1 valency alicyclic alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl or carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group, R BIn the hydrogen atom that is had one or more can be replaced by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle, wherein, and Z 1And R 1Be not hydrogen atom simultaneously;
P is 2 or 2 when above, R 1Be to remove p valency group that p hydrogen atom obtain from carbonatoms is 1～20 alkane, removes p valency group that p hydrogen atom obtain or removes the p valency group that p hydrogen atom obtains from carbonatoms is 6～20 aromatic hydrocarbons from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, one or more in the hydrogen atom that these groups had can be replaced by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle);
Figure A20061017180700111
(in the formula (2), m is the integer more than 2 or 2, Z 2Be from carbonatoms is 1～20 alkane, to remove m valency group that m hydrogen atom obtain, from carbonatoms is 6～20 aromatic hydrocarbons, remove m valency group that m hydrogen atom obtain, from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, remove the m valency group that m hydrogen atom obtains, in the hydrogen atom that these groups had one or more can be replaced R by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle 2Be hydrogen atom, cyano group, group-R C, group-OR C, group-NR C 2, group-SR C, R CIndependently for carbonatoms is that 1～20 alkyl, carbonatoms are that 3～20 1 valency alicyclic alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl or carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group, R CIn the hydrogen atom that is had one or more can be replaced by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle).
Above-mentioned composition is preferred for the formation of formation, interlayer dielectric or the lenticular formation or the protective membrane of spacer.
Above-mentioned second purpose of the present invention is by (A ') polymkeric substance and (E) cationically polymerizable compound of a kind of containing; the curable resin composition that is used to form protective membrane is realized; wherein; described (A ') polymkeric substance is to carry out polymerization by the active free radical polymerization in the presence of compound shown in above-mentioned formula (1) or the above-mentioned formula (2); with the polystyrene conversion weight-average molecular weight (Mw) of gel permeation chromatography and the ratio (Mw/Mn) of number-average molecular weight (Mn) is below 1.7 or 1.7, and has the polymkeric substance of Oxyranyle or oxa-cyclobutyl.
Above-mentioned the 3rd purpose of the present invention realizes by spacer, interlayer dielectric or the microlens of above-mentioned any solidification compound of use or the formation method of protective membrane.
Above-mentioned the 4th purpose of the present invention realizes by spacer, interlayer dielectric or the microlens or the protective membrane that form according to aforesaid method.
Description of drawings
Fig. 1 is the synoptic diagram that the cross-sectional shape of spacer is shown for example.
Fig. 2 is the synoptic diagram of the lenticular cross-sectional shape of expression, (a) is semi-convex lens shape, (b) is trapezium-shaped roughly.
Embodiment
" curable resin composition "
Curable resin composition of the present invention contains above-mentioned (A) polymkeric substance or (A ') polymkeric substance.
(A) polymkeric substance is to carry out polymerization by the active free radical polymerization in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression, with the polystyrene conversion weight-average molecular weight (Mw) of gel permeation chromatography and the ratio (Mw/Mn) of number-average molecular weight (Mn) is below 1.7 or 1.7, and has the polymkeric substance of carboxyl and Oxyranyle or oxa-cyclobutyl.
On the other hand, (A ') polymkeric substance is to carry out polymerization by the active free radical polymerization in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression, with the polystyrene conversion weight-average molecular weight (Mw) of gel permeation chromatography and the ratio (Mw/Mn) of number-average molecular weight (Mn) is below 1.7 or 1.7, and the polymkeric substance with Oxyranyle or oxa-cyclobutyl has 2 or 2 above Oxyranyles or oxa-cyclobutyl and is selected from ethylidene ether structure in the preferred molecule, have 2 or 2 above Oxyranyles or oxa-cyclobutyl in polymkeric substance of at least a structure in ketal structure and the tert-butoxycarbonyl structure (hereinafter referred to as " polymkeric substance (A ' 1) ") or the molecule, and do not have carboxyl, the acid anhydride, ethylidene ether structure, the multipolymer of any in ketal structure and the tert-butoxycarbonyl structure (hereinafter referred to as " polymkeric substance (A ' 2) ").
Above-mentioned ethylidene ether structure or ketal structure are meant the structure that acetal formation group as described below or ketal formation property group and carbon atom bonding form.Polymkeric substance has ethylidene ether structure or ketal structure and is meant that acetal formation group as described below or ketal form the property group and directly or by bonds such as carbonyls be combined in polymkeric substance on the carbon atom in the polymkeric substance.
Functional group's (hereinafter referred to as " acetal formation group ") that can form ethylidene ether structure for example has: the 1-methoxy ethoxy, the 1-ethoxy ethoxy, 1-positive propoxy oxyethyl group, 1-isopropoxy oxyethyl group, 1-n-butoxy oxyethyl group, 1-isobutoxy oxyethyl group, 1-sec-butoxy oxyethyl group, 1-tert.-butoxy oxyethyl group, 1-cyclopentyloxy oxyethyl group, 1-cyclohexyloxy oxyethyl group, 1-norborneol oxygen base oxethyl, 1-borneol oxygen base oxethyl, 1-phenoxy group oxyethyl group, 1-(1-naphthyloxy) oxyethyl group, 1-benzyloxy oxyethyl group, 1-benzene ethoxy ethoxy, (cyclohexyl) (methoxyl group) methoxyl group, (cyclohexyl) (oxyethyl group) methoxyl group, (cyclohexyl) (positive propoxy) methoxyl group, (cyclohexyl) (isopropoxy) methoxyl group, (cyclohexyl) (cyclohexyloxy) methoxyl group, (cyclohexyl) (phenoxy group) methoxyl group, (cyclohexyl) (benzyloxy) methoxyl group, (phenyl) (methoxyl group) methoxyl group, (phenyl) (oxyethyl group) methoxyl group, (phenyl) (positive propoxy) methoxyl group, (phenyl) (isopropoxy) methoxyl group, (phenyl) (cyclohexyloxy) methoxyl group, (phenyl) (phenoxy group) methoxyl group, (phenyl) (benzyloxy) methoxyl group, (benzyl) (methoxyl group) methoxyl group, (benzyl) (oxyethyl group) methoxyl group, (benzyl) (positive propoxy) methoxyl group, (benzyl) (isopropoxy) methoxyl group, (benzyl) (cyclohexyloxy) methoxyl group, (benzyl) (phenoxy group) methoxyl group, (benzyl) (benzyloxy) methoxyl group, 2-tetrahydrofuran base oxygen base, 2-THP trtrahydropyranyl oxygen base etc.In these acetal formation groups, preferred 1-ethoxy ethoxy, 1-positive propoxy oxyethyl group, 1-cyclohexyloxy oxyethyl group, 2-tetrahydrofuran base oxygen base or 2-THP trtrahydropyranyl oxygen base.
In addition, functional group's (hereinafter referred to as " ketal form property group ") that can form the ketal structure for example has: 1-methyl isophthalic acid-methoxy ethoxy, 1-methyl isophthalic acid-ethoxy ethoxy, 1-methyl isophthalic acid-positive propoxy oxyethyl group, 1-methyl isophthalic acid-isopropoxy oxyethyl group, 1-methyl isophthalic acid-n-butoxy oxyethyl group, 1-methyl isophthalic acid-isobutoxy oxyethyl group, 1-methyl isophthalic acid-sec-butoxy oxyethyl group, 1-methyl isophthalic acid-tert.-butoxy oxyethyl group, 1-methyl isophthalic acid-cyclopentyloxy oxyethyl group, 1-methyl isophthalic acid-cyclohexyloxy oxyethyl group, 1-methyl isophthalic acid-norborneol oxygen base oxethyl, 1-methyl isophthalic acid-borneol oxygen base oxethyl, 1-methyl isophthalic acid-phenoxy group oxyethyl group, 1-methyl isophthalic acid-(1-naphthyloxy) oxyethyl group, 1-methyl isophthalic acid-benzyloxy oxyethyl group, 1-methyl isophthalic acid-benzene ethoxy ethoxy, 1-cyclohexyl-1-methoxy ethoxy, 1-cyclohexyl-1-ethoxy ethoxy, 1-cyclohexyl-1-positive propoxy oxyethyl group, 1-cyclohexyl-1-isopropoxy oxyethyl group, 1-cyclohexyl-1-cyclohexyloxy oxyethyl group, 1-cyclohexyl-1-phenoxy group oxyethyl group, 1-cyclohexyl-1-benzyloxy oxyethyl group, 1-phenyl-1-methoxy ethoxy, 1-phenyl-1-ethoxy ethoxy, 1-phenyl-1-positive propoxy oxyethyl group, 1-phenyl-1-isopropoxy oxyethyl group, 1-phenyl-1-cyclohexyloxy oxyethyl group, 1-phenyl-1-phenoxy group oxyethyl group, 1-phenyl-1-benzyloxy oxyethyl group, 1-benzyl-1-methoxy ethoxy, 1-benzyl-1-ethoxy ethoxy, 1-benzyl-1-positive propoxy oxyethyl group, 1-benzyl-1-isopropoxy oxyethyl group, 1-benzyl-1-cyclohexyloxy oxyethyl group, 1-benzyl-1-phenoxy group oxyethyl group, 1-benzyl-1-benzyloxy oxyethyl group, 1-methoxyl group cyclopentyloxy, 1-methoxyl group cyclohexyloxy, 2-(2-methyltetrahydrofuran base) oxygen base, 2-(2-methyl THP trtrahydropyranyl) oxygen base etc.In these ketals formation property functional group, preferred 1-methyl isophthalic acid-methoxy ethoxy or 1-methyl isophthalic acid-cyclohexyloxy oxyethyl group.
(A) polymkeric substance preferably contains (a1), (a2) and polymerizability mixture (a3) carry out the polymkeric substance that active free radical polymerization obtains in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression, wherein, described (a1) is for being selected from least a in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (following these are generically and collectively referred to as " compound (a1) "); Described (a2) is for containing the unsaturated compound (hereinafter referred to as " compound (a2) ") of Oxyranyle or oxa-cyclobutyl; Described (a3) is except that (a1) and the unsaturated compound (a2), is the unsaturated compound (hereinafter referred to as " compound (a3) ") that does not have ethylidene ether structure, ketal structure or tert-butoxycarbonyl structure in the molecule.
For example, (A) polymkeric substance can prepare by the following method: in appropriate solvent, in the presence of the compound of polymerization starter and above-mentioned formula (1) or (2) expression, make the polymerizability mixture that contains compound (a1), compound (a2) and compound (a3) carry out active free radical polymerization.(A) carboxyl that polymkeric substance had that obtains thus is from compound (a1), and Oxyranyle or oxa-cyclobutyl are from compound (a2).
Polymkeric substance (A ' 1) is preferably by in appropriate solvent, in the presence of the compound of polymerization starter and above-mentioned formula (1) or (2) expression, make the polymerizability mixture that contains compound (a2), compound (a3) and compound (a4) carry out the polymkeric substance that active free radical polymerization obtains, wherein, described compound (a4) has the unsaturated compound (hereinafter referred to as " compound (a4) ") that is selected from least a structure in ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure in the molecule.In addition, polymkeric substance (A ' 2) is preferably in appropriate solvent, in the presence of the compound of polymerization starter and above-mentioned formula (1) or (2) expression, make the polymerizability mixture that contains compound (a2) and compound (a3) carry out the polymkeric substance that active free radical polymerization obtains.
Above-claimed cpd (a1)～(a4) all preferably has free-radical polymerised compound.
Below, the active free radical polymerization that is used for making (A) polymkeric substance or (A ') polymkeric substance is described.
Radical polymerization initiator system about polymerizable unsaturated compound or its mixture are carried out radical polymerization has multiple motion, for example: M.K.Georges et al., Macromolecules, 1993, Vol.26 discloses so-called TEMPO system in p.2987; Matyjaszewski et al., Macromolecules, 1997, Vol.30 discloses the system of the combination that contains cupric bromide and brominated ester cpds in p.7348; Hamasaki, S.et al., Macromolecules, 2002, Vol.35 discloses the system of the combination that contains tetracol phenixin and ruthenium (II) complex compound in p.2934;
Specially permit to disclose in No. 3639859 (thing table 2000-515181 number), special table 2002-500251 number, special table 2004-518773 number, special table 2002-508409 number, special table 2002-512653 number, special table 2003-527458 number, special permission No. 3634843 (special table 2003-536105 communique) and the special table 2005-503452 number and contain the system of chain transfer constant greater than the combination of 0.1 thiocarbonyl group sulphur compound and radical initiator.
But, the inventor finds, the curable resin composition that contains certain polymkeric substance satisfies as the desired various characteristics of cured film, and the generation of sublimate in the time of can suppressing film and form sintering in the operation, thereby finished the present invention, described polymkeric substance is the polymkeric substance with ad hoc structure that obtains by the active free radical polymerization that uses specific thiocarbonyl group sulphur compound.
In the active free radical polymerization of the polymkeric substance that in synthetic the present invention, uses, use the compound of above-mentioned formula (1) or (2) expression.
In above-mentioned formula (1), p is the integer more than 1 or 1, is preferably 1～4 integer, more preferably 1 or 2.
As the Z in the above-mentioned formula (1) 1Halogen atom, for example can enumerate chlorine atom, bromine atoms, fluorine atom etc.; It as carbonatoms 1～20 alkyl, for example can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, 1,1-dimethyl propyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 1,1-dimethyl-3,3-dimethylbutyl, n-nonyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base etc.;
As carbonatoms is 2～20 thiazolinyl, for example can enumerate vinyl, allyl group, 1-propenyl, 2-propenyl, pseudoallyl, 1-butylene base, crotyl etc.;
As carbonatoms is 6～20 aryl, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 9-anthryl etc.;
As carbonatoms is 7～20 aralkyl, for example can enumerate benzyl, α-Jia Jibianji, α, α-Er Jiajibianji, styroyl etc.;
As carbon atom and heteroatomic total atomicity is 3～20 1 valency heterocyclic group, for example can enumerate Oxyranyle, aziridinyl, the 2-furyl, the 3-furyl, the 2-tetrahydrofuran base, the 3-tetrahydrofuran base, the 1-pyrryl, the 2-pyrryl, the 3-pyrryl, the 1-pyrrolidyl, the 2-pyrrolidyl, the 3-pyrrolidyl, pyrazol-1-yl, pyrazole-3-yl, the 2-THP trtrahydropyranyl, the 3-THP trtrahydropyranyl, the 4-THP trtrahydropyranyl, 2-チ ァ ニ Le base, 3-チ ァ ニ Le base, 4-チ ァ ニ Le base, the 2-pyridyl, the 3-pyridyl, the 4-pyridyl, the 2-piperidyl, the 3-piperidyl, the 4-piperidyl, the 2-morpholinyl, morpholinyl, the 2-imidazolyl, the 4-imidazolyl, indoles-1-base etc.
As the Z in the above-mentioned formula (1) 1Preferred object lesson, for example can enumerate hydrogen atom, cyano group, chlorine atom, carboxyl, dodecyl, octadecyl, oxyethyl group, butoxy carbonyl, phenyl, phenoxy group, dimethylamino, diethylamino, dimethylamino carbonyl, diethylamino carbonyl, 2-imidazolyl, 1-pyrazolyl, 1-indyl, group-P (=O) (OC 2H 5) 2, group-P (=O) (C 6H 5) 2, group-P (=O) (OC 6H 5) 2, group-N (C 2H 5) N (CH 3) C (=O) CH 2F, group-N (C 6H 5) 2, group-N (C 6H 5) CH 3Deng.
In above-mentioned formula (1), the R during as p=1 1Carbonatoms be that 1～20 alkyl, carbonatoms are that 3～20 1 valency alicyclic alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl or carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group and halogen atom, can enumerate and above-mentioned Z 1The group or the same group or the atom of atom of difference correspondence.In addition, be 3～20 1 valency alicyclic alkyl as carbonatoms, for example can enumerate cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl etc.
As the R during p=1 in the above-mentioned formula (1) 1Preferred object lesson, for example can enumerate hydrogen atom, cyano group, the tertiary butyl, benzyl, 2-(2-cyano group) propyl group, 2-cyano ethyl, 2-(2-hydroxyl) propyl group, 2-hydroxy phenyl, 2-(2-carboxyl) propyl group, 2-(2-ethoxy carbonyl) propyl group, 2-(2-Oxyranyle) propyl group etc.
P is 2 or 2 R when above in the above-mentioned formula (1) 1For from carbonatoms being removes the p valency group that p hydrogen atom obtains 1～20 the alkane, from being 6～20 aromatic hydrocarbons, carbonatoms removes the p valency group that p hydrogen atom obtains, or from being 3～20 1 divalent heterocyclic compound, carbon atom and heteroatomic total atomicity remove the p valency group that p hydrogen atom obtains, as above-mentioned carbonatoms is 1～20 alkane, for example can enumerate methane, ethane, propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, normal hexane, normal heptane, octane, positive nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, Octadecane, NSC 62789 etc.;
As carbonatoms is 6～20 aromatic hydrocarbons, for example can enumerate benzene, 1,4-dimethyl benzene, 1,1,2,3,4,5,6-hexamethyl-benzene, 1,4-diisopropyl benzene, naphthalene, anthracene etc.;
As carbon atom and heteroatomic total atomicity is 3～20 1 divalent heterocyclic compound, for example can enumerate oxyethane, ethylene imine, furans, tetrahydrofuran (THF), pyrroles, tetramethyleneimine, pyrazoles, tetrahydropyrans, チ ァ Application, pyridine, piperidines, morpholine etc.
In addition, as halogen atom, can enumerate and above-mentioned Z 1The same halogen atom of halogen atom.
As the R during p=2 in the above-mentioned formula (1) 1Preferred object lesson, for example can enumerate divalent group that following formula represents etc.
Figure A20061017180700161
In the above-mentioned formula (2), m is the integer more than 2 or 2, is preferably 2～4 integer, more preferably 2.
Z in the above-mentioned formula (2) 2For from carbonatoms being removes m valency group that m hydrogen atom obtain, removes m valency group that m hydrogen atom obtain or remove the m valency group that m hydrogen atom obtains from carbonatoms is 6～20 aromatic hydrocarbons from carbon atom and heteroatomic total atomicity is 3～20 1 divalent heterocyclic compound 1～20 the alkane, as above-mentioned carbonatoms is that 1～20 alkane, carbonatoms are that 6～20 aromatic hydrocarbons and carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, can enumerate with above-mentioned formula (1) in p be 2 or 2 R when above 1The same compound of compound of difference correspondence.
Z during p=2 in the above-mentioned formula (2) 2Preferred object lesson for example have: 1,4-phenylene etc.
As R in the above-mentioned formula (2) 2Carbonatoms be that 1～20 alkyl, carbonatoms are that 3～20 1 valency alicyclic alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl, carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group and halogen atom, can enumerate with above-mentioned formula (1) in R during p=1 1The group or the same group or the atom of atom of difference correspondence.
As R in the above-mentioned formula (2) 2Preferred object lesson, can enumerate and as the R during p=1 in the above-mentioned formula (1) 1The same group of above-mentioned group of preferred object lesson.
As the object lesson of compound shown in above-mentioned formula (1) or the above-mentioned formula (2), can enumerate the compound of following formula (T-1)～(T-21) expression etc.
Figure A20061017180700191
Figure A20061017180700201
Figure A20061017180700211
These thiocarbonyl group sulphur compounds both can use separately, also two or more can be mixed and use.
The radical polymerization initiator that uses in the active free radical polymerization is not particularly limited, can use usually as the radical polymerization initiator known substances, for example have: 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (4-methoxyl group-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, 1, organo-peroxides such as 1 '-two (t-butyl peroxy) hexanaphthene, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester; Hydrogen peroxide; Contain the redox class initiator of these superoxide and reductive agent etc.
These radical initiators both can use separately, also two or more can be mixed and use.
For the solvent that uses in the active free radical polymerization,, for example have: propylene glycol one alkylether compounds such as Glycol Monomethyl ether, propylene glycol monoethyl ether as long as the living radical non-inactivation just is not particularly limited; (gathering) aklylene glycol alkyl oxide acetate compounds such as Ethylene Glycol Methyl ether acetic acid ester, ethylene glycol monoethyl ether acetate, Diethylene Glycol methyl ether acetic ester, Diethylene Glycol ethyl ether acetic ester, methyl proxitol acetate, propylene glycol ethyl ether acetic ester, dipropylene glycol methyl ether acetic ester, dipropylene glycol ethyl ether acetic ester; (gathering) aklylene glycol dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol Anaesthetie Ether;
Other ether compound such as tetrahydrofuran (THF);
Ketone compounds such as methyl ethyl ketone, pimelinketone, 2-heptanone, 3-heptanone;
Keto-alcohol compounds such as Pyranton (being 4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one; Lactic acid alkyl ester such as methyl lactate, ethyl lactate compound;
2-hydroxy-2-methyl ethyl propionate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl-butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-3-methoxyl group butylacetic acid ester, 3-methyl-3-methoxyl group butyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, Isoamyl Acetate FCC, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl butyrate, the positive butyl ester of butyric acid, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the pyruvic acid n-propyl, methyl acetoacetate, methyl aceto acetate, other ester cpds such as 2-ketobutyric acid ethyl ester;
Aromatic hydroxy compound such as toluene, dimethylbenzene;
N-Methyl pyrrolidone, N, amide compounds such as dinethylformamide, N,N-dimethylacetamide etc.
In these solvents, consider the solvability of each composition when making curable resin composition, tunicle formation property etc., preferred Glycol Monomethyl ether, ethylene glycol monomethyl ether acetic ester, the Glycol Monomethyl ether acetic ester, propylene glycol monoethyl ether acetic ester, the dipropylene glycol methyl ether acetic ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, the dipropylene glycol dimethyl ether, pimelinketone, 2-heptanone, the 3-heptanone, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methyl-3-methoxyl group butyl propionic ester, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, Isoamyl Acetate FCC, n-butyl propionate, ethyl butyrate, isopropyl butyrate, the positive butyl ester of butyric acid, Pyruvic Acid Ethyl ester etc.
Above-mentioned solvent both can use separately, also two or more can be mixed and use.
In active free radical polymerization, with respect to whole unsaturated compound 100 weight parts, the usage quantity of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression is preferably 0.1～50 weight part, more preferably 0.2～16 weight part.With respect to whole unsaturated compound 100 weight parts, the usage quantity of radical polymerization initiator is preferably 0.1～50 weight part, more preferably 0.1～20 weight part.Polymerization temperature is preferably 0～150 ℃, and more preferably 50～120 ℃, polymerization time is preferably 10 minutes～and 20 hours, more preferably 30 minutes～6 hours.
The preferred compound (a1) that uses is to be selected to have at least a in free-radical polymerised unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides for synthetic (A) polymkeric substance.
Compound (a1) for example has: one (methyl) acrylate, the polynuclear compound with carboxyl and acid anhydrides thereof etc. that one [(methyl) acryloxyalkyl] ester of monocarboxylic acid, di-carboxylic acid, dicarboxylic acid anhydride, polycarboxylic acid, two ends have the polymkeric substance of carboxyl and hydroxyl respectively.In addition, in this manual, " (methyl) acrylate " is the notion that acrylate and methacrylic ester are combined." (methyl) acryloxy " waits other similar term also should do same understanding.
As their object lesson, can be listed below:
Monocarboxylic acid has for example vinylformic acid, methacrylic acid, Ba Dousuan etc.;
Di-carboxylic acid has for example toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid etc.;
Dicarboxylic acid anhydride for example has acid anhydrides of the above-claimed cpd of enumerating as above-mentioned di-carboxylic acid etc.;
One [(methyl) acryloxyalkyl] ester of polycarboxylic acid has for example succsinic acid one [2-(methyl) acryloxy ethyl] ester, phthalic acid one [2-(methyl) acryloxy ethyl] ester etc.;
One (methyl) acrylate that two ends have the polymkeric substance of carboxyl and hydroxyl respectively has for example ω-carboxyl polycaprolactone one (methyl) acrylate etc.;
Polynuclear compound and acid anhydrides thereof with carboxyl have for example 5-carboxyl two ring [2.2.1] hept-2-ene"s, 5,6-dicarboxyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl-6-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl two ring [2.2.1] hept-2-ene"s, 5, the acid anhydrides of 6-dicarboxyl two ring [2.2.1] hept-2-ene"s etc.;
In these materials, preferably use the acid anhydrides of monocarboxylic acid, di-carboxylic acid, from copolyreaction, with respect to the solvability of alkaline aqueous solution and the angle consideration that obtains easily, especially preferably use vinylformic acid, methacrylic acid, maleic anhydride.These materials both may be used alone, can also be used in combination.
In addition, when active free radical polymerization, can after carrying out polymerization, the carboxyl that utilizes suitable protecting group protection above-claimed cpd (a1) to have or anhydride group carry out deprotection.
For synthetic (A) polymkeric substance or (A ') polymkeric substance and the preferred compound (a2) that uses is to have free-radical polymerised and contain the unsaturated compound of Oxyranyle or oxa-cyclobutyl.
Compound (a2) with Oxyranyle has for example glycidyl acrylate, glycidyl methacrylate, the α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid 3,4-Oxyranyle butyl ester, methacrylic acid 3,4-Oxyranyle butyl ester, α-Yi Jibingxisuan 3,4-Oxyranyle butyl ester, vinylformic acid 6,7-Oxyranyle heptyl ester, methacrylic acid 6,7-Oxyranyle heptyl ester, α-Yi Jibingxisuan 6,7-Oxyranyle heptyl ester, vinylformic acid Beta-methyl glycidyl ester, methacrylic acid Beta-methyl glycidyl ester, propenoic acid beta-ethyl glycidyl ester, methacrylic acid β-ethyl glycidyl ester, propenoic acid beta-n-propyl glycidyl ester, methacrylic acid β-n-propyl glycidyl ester, vinylformic acid 3,4-Oxyranyle cyclohexyl, methacrylic acid 3,4-Oxyranyle cyclohexyl etc. has the carbonate of Oxyranyle;
Adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, vinyl benzyl glycidyl ether etc. had the ether compound of Oxyranyle etc.
In addition, the compound (a2) with oxa-cyclobutyl has for example vinylformic acid 3-ethyl-3-oxa-ring butyl ester, methacrylic acid 3-ethyl-3-oxa-ring butyl ester etc.
In these compounds (a2), consider from the curing film strength aspect that copolyreaction and raising obtain, preferable methyl glycidyl acrylate, methacrylic acid 6,7-Oxyranyle heptyl ester, methacrylic acid 3,4-Oxyranyle cyclohexyl, methacrylic acid Beta-methyl glycidyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, methacrylic acid 3-ethyl-3-oxa-ring butyl ester etc.
Above-claimed cpd (a2) both can use separately, also can be with two kinds or above mixing use.
For synthetic (A) polymkeric substance or (A ') polymkeric substance and the preferred compound (a3) that uses is the free-radical polymerised unsaturated compound that has except that (a1) and (a2), be the unsaturated compound that does not have ethylidene ether structure, ketal structure or tert-butoxycarbonyl structure in the molecule.
Compound (a3) has for example alkyl methacrylate, alkyl acrylate, methacrylic acid cycloalkyl ester, the methacrylic ester with hydroxyl, vinylformic acid cycloalkyl ester, aryl methacrylate, vinylformic acid aryl ester, unsaturated dicarboxylic acid diester, two ring unsaturated compounds, maleimide compound, unsaturated aromatics, conjugated diolefine etc.
As the object lesson of these compounds, alkyl methacrylate has for example methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, methacrylic tert-butyl acrylate, methacrylic acid 2-ethylhexyl, isodecyl methacrylate, methacrylic acid dodecyl ester, methacrylic acid tridecyl ester, methacrylic acid Octadecane base ester etc.;
Alkyl acrylate has for example methyl acrylate, isopropyl acrylate etc.;
The methacrylic acid cycloalkyl ester has for example cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate, three the ring [5.2.1.0 2,6] decane-8-base oxygen base ethyl-methyl acrylate, methacrylic acid isobornyl (ィ ソ ボ ロ ニ Le) ester etc.;
Methacrylic ester with hydroxyl has for example methacrylic acid hydroxyl methyl esters, 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, Diethylene Glycol monomethyl acrylate, methacrylic acid 2,3-dihydroxyl propyl ester, 2-methylacryoyloxyethyl glucosides (2-メ Network リ ロ キ シ ェ チ Le グ リ コ サ ィ De), methacrylic acid 4-hydroxylphenyl ester, polyoxyethylene glycol monomethyl acrylate, polypropylene glycol monomethyl acrylate etc.;
The vinylformic acid cycloalkyl ester has for example cyclohexyl acrylate, vinylformic acid 2-methyl cyclohexane ester, three ring [5.2.1.0 2,6] decane-8-base acrylate, three ring [5.2.1.0 2,6] decane-8-base oxygen base ethyl propylene acid esters, isobornyl acrylate etc.;
Aryl methacrylate for example has: phenyl methacrylate, benzyl methacrylate etc.;
The vinylformic acid aryl ester has for example phenyl acrylate, benzyl acrylate etc.;
The unsaturated dicarboxylic acid diester has for example ethyl maleate, DEF, diethyl itaconate etc.; Two ring unsaturated compounds have for example two ring [2.2.1] hept-2-ene"s, 5-methyl bicyclic [2.2.1] hept-2-ene", 5-ethyl two ring [2.2.1] hept-2-ene"s, 5-methoxyl group two ring [2.2.1] hept-2-ene"s, 5-oxyethyl group two ring [2.2.1] hept-2-ene"s, 5,6-dimethoxy two ring [2.2.1] hept-2-ene"s, 5,6-diethoxy two ring [2.2.1] hept-2-ene"s, 5-tert-butoxycarbonyl two ring [2.2.1] hept-2-ene"s, 5-cyclohexyloxy carbonyl two ring [2.2.1] hept-2-ene"s, 5-phenyloxycarbonyl two ring [2.2.1] hept-2-ene"s, 5,6-two (tert-butoxycarbonyl) two ring [2.2.1] hept-2-ene"s, 5,6-two (cyclohexyl oxygen base carbonyl) two ring [2.2.1] hept-2-ene"s, 5-(2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5,6-dihydroxyl two ring [2.2.1] hept-2-ene"s, 5,6-two (hydroxymethyl) two ring [2.2.1] hept-2-ene"s, 5,6-two (2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5-hydroxy-5-methyl base two ring [2.2.1] hept-2-ene"s, 5-hydroxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-hydroxymethyl-5-methyl bicyclic [2.2.1] hept-2-ene" etc.;
Maleimide compound has for example N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimido-3-maleimide Aminobenzoate, N-succinimido-4-maleimide aminobutyric acid ester (マ レ ィ ミ De Block チ レ one ト), N-succinimido-6-maleimide hexosamine ester, N-succinimido-3-maleimide alanine ester, N-(9-acridyl) maleimide etc.;
Unsaturated aromatics for example has vinylbenzene, alpha-methyl styrene, a vinyl toluene, p-methylstyrene, Vinyl toluene, to methoxy styrene etc.;
Conjugated diolefine has for example 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.;
Other unsaturated compound has for example vinyl cyanide, methacrylonitrile, vinylchlorid, vinylidene chloride, acrylamide, Methacrylamide, vinyl-acetic ester, (methyl) tetrahydrofurfuryl acrylate etc.
Wherein, the preferred methacrylic ester that uses alkyl methacrylate, methacrylic acid cycloalkyl ester, has hydroxyl, two ring unsaturated compounds, unsaturated aromatics, conjugated diolefine, wherein, consider special optimization styrene, methacrylic tert-butyl acrylate, three ring [5.2.1.0 from copolyreaction with respect to the deliquescent angle of alkaline aqueous solution 2,6] decane-8-ylmethyl acrylate, to methoxy styrene, vinylformic acid 2-methyl cyclohexane ester, 1,3-butadiene, polyoxyethylene glycol monomethyl acrylate, polypropylene glycol monomethyl acrylate, two ring [2.2.1] hept-2-ene"s, tetrahydrofurfuryl methacrylate.These compound things both may be used alone, can also be used in combination.
The preferred compound (a4) that uses is to have the unsaturated compound that is selected from least a structure in ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure in the molecule for synthetic (A ') polymkeric substance.
Compound (a4) has and for example has the norbornylene compounds (hereinafter referred to as " specific norbornylene compounds ") that is selected from least a structure of knot in ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure, (methyl) acrylic compound (hereinafter referred to as " specific (methyl) acrylic compound ") with at least a structure that is selected from ethylidene ether structure and the ketal structure, (methyl) tert-butyl acrylate etc.
The object lesson of above-mentioned specific norbornylene compounds for example has 2,3-two (1-methoxy ethoxy carbonyl)-5-norbornylene, 2,3-two (1-tert.-butoxy ethoxy carbonyl)-5-norbornylene, 2,3-two (1-benzyloxy ethoxy carbonyl)-5-norbornylene, 2,3-two (1-methyl isophthalic acid-methoxy ethoxy carbonyl)-5-norbornylene, 2,3-two (1-methyl isophthalic acid-isobutoxy ethoxy carbonyl)-5-norbornylene, 2,3-two ((cyclohexyl) (oxyethyl group) methoxycarbonyl)-5-norbornylene, 2,3-two ((benzyl) (oxyethyl group) methoxycarbonyl)-5-norbornylene, 2,3-two (tetrahydrofuran (THF)-2-base oxygen base carbonyl)-5-norbornylene, 2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene, 2,3-two (tert-butoxycarbonyl)-5-norbornylene etc.
The object lesson of above-mentioned specific (methyl) acrylic compound for example has (methyl) vinylformic acid 1-ethoxy ethyl ester, (methyl) vinylformic acid 1-positive propoxy ethyl ester, (methyl) vinylformic acid 1-n-butoxy ethyl ester, (methyl) vinylformic acid 1-isobutoxy ethyl ester, (methyl) vinylformic acid 1-(cyclopentyloxy) ethyl ester, (methyl) vinylformic acid 1-(cyclohexyloxy) ethyl ester, (methyl) vinylformic acid 1-(1,1-dimethyl oxyethyl group) ethyl ester, (methyl) vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester etc.
In these compounds (a4), preferably specific (methyl) acrylic compound or (methyl) tert-butyl acrylate, special preferable methyl vinylformic acid 1-ethoxy ethyl ester, methacrylic acid 1-isobutoxy ethyl ester, methacrylic acid 1-(cyclopentyloxy) ethyl ester, methacrylic acid 1-(cyclohexyloxy) ethyl ester, methacrylic acid 1-(1,1-dimethyl oxyethyl group) ethyl ester, (methyl) vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester or methacrylic tert-butyl acrylate.These preferred compound (a4) copolyreaction height, when obtaining the good curable resin composition of storage stability and planarization performance, thermotolerance, the surface hardness of the cured film that raising is obtained are effective.
Above-mentioned unsaturated compound (a4) both can use separately, also two or more can be mixed and use.
As mentioned above, (A) the polymkeric substance polymerizability mixture that preferably contains compound (a1), compound (a2) and compound (a3) carries out the polymkeric substance that active free radical polymerization obtains in the presence of the compound shown in above-mentioned formula (1) or (2).
On the other hand, the polymerizability mixture that preferably contains compound (a2), compound (a3) and compound (a4) as the polymkeric substance (A ' 1) of one of optimal way of (A ') polymkeric substance carries out the polymkeric substance that active free radical polymerization obtains in the presence of the compound shown in above-mentioned formula (1) or (2).In addition, the polymerizability mixture that preferably contains compound (a2) and compound (a3) as the polymkeric substance (A ' 2) of the another kind of optimal way of (A ') polymkeric substance carries out the polymkeric substance that active free radical polymerization obtains in the presence of the compound shown in above-mentioned formula (1) or (2).
In (A) polymkeric substance, with by compound (a1), (a2) and (a3) deutero-structural unit total amount be benchmark, content by compound (a1) deutero-structural unit is preferably 5～50 weight %, more preferably 10～40 weight %, more preferably 10～30 weight %.At this moment, if the content of this structural unit is lower than 5 weight %, curing film strength, thermotolerance, the chemical proofing that then obtains has the tendency of reduction, and on the other hand, if surpass 50 weight %, then the storage stability of curable resin composition reduces sometimes.
With by compound (a1), (a2) and (a3) deutero-structural unit total amount be benchmark, (A) polymkeric substance that uses among the present invention preferably contains by compound (a2) deutero-structural unit 10～70 weight %, especially preferably contains 20～60 weight %.When this structural unit was lower than 10 weight %, the thermotolerance of the cured film that obtains, surface hardness had the tendency of reduction, and on the other hand, when the amount of this structural unit surpassed 70 weight %, the storage stability of curable resin composition had the tendency of reduction.
Deutero-entire infrastructure unit is a benchmark to reach (a3) by compound (a1), (a2), (A) polymkeric substance that uses among the present invention preferably contains by compound (a3) deutero-structural unit 5～70 weight %, more preferably contain 10～60 weight %, further preferably contain 20～50 weight %.When this structural unit was lower than 5 weight %, the storage stability of curable resin composition had the tendency of reduction, on the other hand, when surpassing 70 weight %, in the developing procedure that forms cured film, was difficult to be dissolved in alkaline aqueous solution sometimes.
In (A ' 1) polymkeric substance, with respect to all repeating units, be preferably 10～70 weight % from the content of the repeating unit of compound (a2), be preferably 20～60 weight % especially.When the content from the repeating unit of compound (a2) was lower than 10 weight %, the thermotolerance of protective membrane, surface hardness had the tendency of reduction, and on the other hand, when surpassing 70 weight %, the storage stability of composition has the tendency of reduction.
Content from the repeating unit of compound (a4) in (A ' 1) polymkeric substance is preferably 5～60 weight %, is preferably 10～50 weight % especially.By being set in this scope, can realize the good thermotolerance and the surface hardness of protective membrane from the content of the repeating unit of compound (a4).
The amount that obtains for the total content that from 100 weight %, deducts from the repeating unit of compound (a2) and compound (a4) from the content of the repeating unit of compound (a3) in (A ' 1) polymkeric substance, with respect to whole repeating units, it is preferably 10～80 weight %, more preferably 20～60 weight %.
In (A ' 2) polymkeric substance, be preferably 1～90 weight % from the repeating unit of compound (a2) with respect to the content of all repeating units, be preferably 40～90 weight % especially.When the content from the repeating unit of compound (a2) was lower than 1 weight %, the thermotolerance of cured film, surface hardness had the tendency of reduction, and on the other hand, if surpass 90 weight %, then the storage stability of composition has the tendency of reduction.
The amount that obtains for the content that from 100 weight %, deducts from the repeating unit of compound (a2) from the content of the repeating unit of compound (a3) in (A ' 2) polymkeric substance.
As mentioned above, (A) polymkeric substance that uses among the present invention or (A ') polymkeric substance obtain by unsaturated compound is carried out active free radical polymerization, when active free radical polymerization, with the compound of above-mentioned formula (1) or above-mentioned formula (2) expression as molecular weight regulator.Therefore, (A) have in polymkeric substance, (A ') polymkeric substance the compound that comes from above-mentioned formula (1) expression following formula (i) expression group or come from the group that the following formula of the compound of above-mentioned formula (2) expression is (ii) represented.
Figure A20061017180700281
(in the formula (i), Z 1Identical with the definition in the above-mentioned formula (1), formula (ii) in, Z 2Identical with m) with the definition in above-mentioned (2).
Wherein, the group of above-mentioned formula (i) expression is preferably placed at the end of (A) polymkeric substance or (A ') polymkeric substance.
(A) polymkeric substance that uses among the present invention or (A ') polymkeric substance are below 1.7 or 1.7 with the ratio (Mw/Mn) of the polystyrene conversion weight-average molecular weight (hereinafter referred to as " Mw ") of gel permeation chromatography and polystyrene conversion number-average molecular weight (hereinafter referred to as " Mn "), are preferably below 1.5 or 1.5.If Mw/Mn surpasses 1.7, the thermotolerance deficiency of the cured film that then obtains sometimes.Mw is preferably 2 * 10 3～1 * 10 5, more preferably 5 * 10 3～5 * 10 4If Mw is lower than 2 * 10 3, then the coating of composition is not enough sometimes, the thermotolerance deficiency of the cured film that perhaps obtains.On the other hand, if Mw surpasses 1 * 10 5, then the planarization performance of sensitivity sometimes or the cured film that obtains is not enough.Mn is preferably 1.2 * 10 3～1 * 10 5, more preferably 2.9 * 10 3～5 * 10 4Be noted that and above-mentionedly should estimate with the tolerance range of 2 position effective digitals (radix point after 1) than Mw/Mn.
And (A) polymkeric substance that uses among the present invention (A ') polymkeric substance preferably less than 5.0%, is more preferably less than 3.0%, especially preferably less than 2.0% with the levels of residual monomers of gel permeation chromatography.By using the multipolymer of such residual monomer content, the curable resin composition that the sublimate in the time of can obtaining sintering reduces.
Curable resin composition of the present invention contains aforesaid (A) polymkeric substance or (A ') polymkeric substance.In the scope that does not influence effect of the present invention, curable resin composition of the present invention can replace the part of (A) polymkeric substance or (A ') polymkeric substance with other polymkeric substance.At this moment, when the preparation composition, other mixed with polymers of other synthetic can be used, perhaps also can be when synthetic (A) polymkeric substance or (A ') polymkeric substance, by compound and other molecular weight regulator with above-mentioned formula (1) or (2) expression, one or more and usefulness such as α-Jia Jibenyixierjuwu, uncle's dodecyl mercaptans for example, with other polymkeric substance with (A) polymkeric substance or (A ') polymkeric substance the synthetic and method of use.
The curable resin composition that contains (A) polymkeric substance is preferably: except polymkeric substance (A), also contain (B) polymerizable unsaturated compound and (C) composition of radiation-sensitive polymerization starter (below be sometimes referred to as " first composition "); Except (A) polymkeric substance, also contain (D) 1, the composition of 2-quinone di-azido compound (1,2-キ ノ Application ジ ァ ジ De compound) (below be sometimes referred to as " second composition "); Or except (A) polymkeric substance, also contain (E) cationically polymerizable compound compositions (below be sometimes referred to as " the 3rd composition ").The 3rd composition preferably also contains (F) solidifying agent or (G) acid-producing agent.
On the other hand, the curable resin composition that contains (A ') polymkeric substance is preferably: except (A ') polymkeric substance, also contain (E) cationically polymerizable compound compositions (below be sometimes referred to as " the 4th composition "), the binary liquid shape curable resin composition that perhaps contains first liquid and second liquid, described first liquid contains (A ') polymkeric substance and (E) cationically polymerizable compound, and described second liquid contains (F) solidifying agent (below be sometimes referred to as " the 5th composition ").At this, as (A ') polymkeric substance, in the 4th composition, be preferably above-mentioned (A ' 1) polymkeric substance or (A ' 2) polymkeric substance, in the 5th composition, be preferably above-mentioned (A ' 2) polymkeric substance.The 4th composition preferably also contains (F) solidifying agent or (G) acid-producing agent.
Below first to the 5th composition is described successively.
＜the first composition 〉
First composition is preferably and contains (A) polymkeric substance, (B) polymerizable unsaturated compound and (C) radiation sensitive resin composition of radiation-sensitive polymerization starter.
As the preferred object lesson of (A) polymkeric substance that is used for first composition, can enumerate for example styrene/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/glycidyl methacrylate copolymer, styrene/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/glycidyl methacrylate/1,3-butadiene multipolymer, styrene/methacrylic acid/vinylformic acid/benzyl methacrylate/n-BMA/methacrylic acid 3-ethyl-3-oxa-ring butyl ester multipolymer, styrene/methacrylic acid/benzyl methacrylate/tetrahydrofurfuryl methacrylate/methacrylic acid methyl glycidyl ester copolymer etc.
In first composition preferred preferred 2 officials of (B) polymerizable unsaturated compound that use can or 2 officials can above (methyl) acrylate.
As 2 officials energy (methyl) acrylate, can enumerate for example EDIA, glycolmethacrylate, 1,6-hexanediyl ester, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, TEG dimethacrylate, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, two phenoxyethyl alcohol fluorenes diacrylate, two phenoxyethyl alcohol fluorenes dimethacrylates etc.
The commercially available product of 2 functional (methyl) acrylate so for example has: ァ ロ ニ ッ Network ス M-210, ァ ロ ニ ッ Network ス M-240, ァ ロ ニ ッ Network ス M-6200 (above is that make in East Asia synthetic (strain)), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001 (above is Japanese chemical drug (strain) system), PVC ス コ one ト 260, PVC ス コ one ト 312, PVC ス コ one ト 335HP (above is Osaka organic chemistry industry (strain) system) etc.
3 officials can or 3 officials can for example have by above (methyl) acrylate: Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate, Dipentaerythritol five acrylate, Dipentaerythritol pentamethyl-acrylate, dipentaerythritol acrylate, Dipentaerythritol hexamethyl acrylate, three (2-acryloxy ethyl) phosphoric acid ester, three (2-methacryloxyethyl) phosphoric acid ester etc., in addition, urethane acrylate (urethane actylate) compounds that also has the compound that has 1 or 1 above hydroxyl and have 3～5 (methyl) acryloxies by compound that has straight-chain alkyl-sub-and alicyclic structure and have 2 or 2 above isocyanate group and intramolecularly to react to obtain etc.
3 officials can or 3 officials can be above the commercially available product of (methyl) acrylate for example have: ァ ロ ニ ッ Network ス M-309, ァ ロ ニ ッ Network ス-400, ァ ロ ニ ッ Network ス-402, ァ ロ ニ ッ Network ス-405, ァ ロ ニ ッ Network ス-450, ァ ロ ニ ッ Network ス-1310, ァ ロ ニ ッ Network ス-1600, ァ ロ ニ ッ Network ス-1960, ァ ロ ニ ッ Network ス-7100, ァ ロ ニ ッ Network ス-8030, ァ ロ ニ ッ Network ス-8060, ァ ロ ニ ッ Network ス-8100, ァ ロ ニ ッ Network ス-8530, ァ ロ ニ ッ Network ス-8560, ァ ロ ニ ッ Network ス-9050, ァ ロ ニ ッ Network ス TO-1450 (above is that make in East Asia synthetic (strain)), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARADDPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (above is Japanese chemical drug (strain) system), PVC ス コ one ト 295, PVC ス コ one ト 300, PVC ス コ one ト 360, PVC ス コ one ト GPT, PVC ス コ one ト 3PA, PVC ス コ one ト 400 (above is Osaka organic chemistry industry (strain) system), ニ ュ one Off ロ Application テ ィ ァ R-1150 (the first industrial pharmacy (strain) system) as the urethane acrylate compounds, KAYARAD DPHA-40H (Japanese chemical drug (strain) system) etc.
In the present invention, (B) polymerizable unsaturated compound both can use separately, also two or more can be mixed and use.
With respect to 100 weight parts (A) polymkeric substance, the usage quantity of (B) polymerizable unsaturated compound is preferably 10～150 weight parts in first composition, more preferably 20～120 weight parts.When the usage quantity of (B) polymerizable unsaturated compound was lower than 10 weight parts, the tangible one-tenth thickness tendency of difficulty of becoming of filming uniformly on the other hand, if surpass 150 weight parts, then had itself and the tendency of the adaptation reduction of substrate.
Preferred (C) radiation-sensitive polymerization starter that uses is induction radioactive rays and produce the composition that can cause (B) polymerizable unsaturated compound polymeric spike in first composition.
(C) radiation-sensitive polymerization starter like this can preferably use for example radiation-sensitive radical polymerization initiator.
As above-mentioned radiation-sensitive radical polymerization initiator, can enumerate for example α-diketone such as dimethyl diketone; Acyloins such as bitter almond oil camphor; Acyloin ethers such as benzoin methyl ether, bitter almond oil camphor ethyl ether, benzoin iso-propylether; Thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4, benzophenones such as 4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone; Methyl phenyl ketone, to dimethylamino benzoylformaldoxime, 4-(α, α '-dimethoxy acetoxyl group) benzophenone, 2,2 '-dimethoxy-2-phenyl methyl phenyl ketone, p-methoxy-acetophenone, 2-methyl-2-morpholino-1-(4-methylthio group phenyl (methylthiophenyl))-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-acetophenones such as 1-ketone; Anthraquinone, 1, quinones such as 4-naphthoquinones; Halogenide such as phenacyl chloride, trisbromomethyl phenyl sulfone, three (trichloromethyl)-s-triazines; 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4, acylphosphine oxides such as 4-tri-methyl-amyl phosphine oxide, two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide; Organo-peroxides such as two-tert-butyl peroxide etc.
The commercially available product of radiation-sensitive radical polymerization initiator for example has: IRGACURE-124, IRGACURE-149, IRGACURE-184, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907, IRGACURE-1000, IRGACURE-1700, IRGACURE-1800, IRGACURE-1850, IRGACURE-2959, Darocur-1116, Darocur-1173, Darocur-1664, Darocur-2959, Darocur-4034 (above is チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ corporate system), KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, KAYACURE-OA (above is Japanese chemical drug (strain) system), LUCIRIN TPO (BASF AG's system), VICURE-10, VICURE-55 (above is the STAUFFER corporate system), TRIGONALP1 (AKZO corporate system), SANDORAY 1000 (SANDOZ corporate system), DEAP (APJOHN corporate system), QUANTACURE-PDO, QUANTACURE-ITX, QUANTACURE-EPD (above is WARD BLEKINSOP corporate system) etc.
(C) radiation-sensitive polymerization starter like this can use separately, also two or more can be mixed and use.
With respect to 100 weight parts (A) polymkeric substance, the usage quantity of (C) radiation-sensitive polymerization starter is preferably 1～40 weight part in first composition, more preferably 3～35 weight parts.When the usage quantity of (C) radiation-sensitive polymerization starter was lower than 1 weight part, the thermotolerance of the cured film that obtains sometimes or surface hardness, chemical proofing reduced, and on the other hand, if surpass 40 weight parts, then the transparency has the tendency of reduction.
In first composition,, can also obtain few, the highly sensitive radiation-sensitive curable resin composition of inactivation that causes by airborne oxygen by with the sensitizing agent of a kind or multiple radioactive rays sensitivity and (C) radiation-sensitive polymerization starter and usefulness.
The sensitizing agent of such radioactive rays sensitivity for example has: N methyldiethanol amine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, ESCAROL 507 ethyl ester, ESCAROL 507 isopentyl ester, 2,4-diethyl thioxanthone, thioxanthone 4-sulfonic acid etc.In these sensitizing agents, preferred 4,4 '-two (diethylamino) benzophenone or 2,4-diethyl thioxanthone.
The sensitizing agent of these radioactive rays sensitivities can use two or more simultaneously.
With respect to 100 weight parts (C) radiation-sensitive polymerization starter, the usage ratio of the sensitizing agent of above-mentioned radioactive rays sensitivity is preferably 40 weight parts or below 40 weight parts, more preferably 20 weight parts or below 20 weight parts.If the usage ratio of the sensitizing agent of radioactive rays sensitivity surpasses 40 weight parts, it is residual then to take place easily sometimes to develop.
Except above-mentioned (A) polymkeric substance, (B) polymerizable unsaturated compound with (C) the radiation-sensitive polymerization starter, in the scope that does not influence effect of the present invention, first composition can contain any additive except that above-mentioned as required.Can cooperate for example any additive such as adhesive aid, tensio-active agent, preserving stabilizer, thermotolerance rising agent.
Above-mentioned adhesive aid is to can be used for improving the cured film that obtains and the close-burning composition of substrate.
Such adhesive aid preferably has the functional silanes coupling agent of carboxyl, methacryloyl, vinyl, isocyanate group, epoxy group(ing) isoreactivity functional group; its object lesson has trimethoxysilyl phenylformic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.
These adhesive aids can use separately, also two or more can be mixed and use.
With respect to 100 weight parts (A) polymkeric substance, the use level of adhesive aid is preferably 20 weight parts or below 20 weight parts, more preferably 15 weight parts or below 15 weight parts.If the use level of adhesive aid surpasses 20 weight parts, it is residual then to take place easily sometimes to develop.
Above-mentioned tensio-active agent is the composition that can be used for improving coating.
Such tensio-active agent preference such as fluorine class tensio-active agent, polysiloxane-based tensio-active agent etc.
Above-mentioned fluorine class tensio-active agent is preferably terminal, any position at least of main chain and side chain has the compound of fluoro-alkyl and/or fluoro alkylidene group, and its object lesson for example has: 1,1,2,2-tetrafluoro n-octyl (1,1,2,2-tetrafluoro n-propyl) ether, 1,1,2,2-tetrafluoro n-octyl (n-hexyl) ether, six ethylene glycol bisthioglycolates (1,1,2,2,3,3-hexafluoro n-pentyl) ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro normal-butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro n-pentyl) ether, eight propylene glycol two (1,1,2,2-tetrafluoro normal-butyl) ether, perfluor dodecyl sodium sulfonate, 1,1,2,2,3,3-hexafluoro n-decane, 1,1,2,2,8,8,9,9,10,10-ten fluorine n-dodecanes, the fluoro-alkyl benzene sulfonic acid sodium salt, the fluoro-alkyl sodium phosphate, the fluoro-alkyl carboxylic acid sodium, two glycerine four (fluoro-alkyl Soxylat A 25-7), the fluoro-alkyl ammonium iodide, the fluoro-alkyl trimethyl-glycine, other fluoro-alkyl oxygen Vinyl Ether, perfluoroalkyl poly hydroxyl ethanol (perfluoroalkylpolyoxyethanol), perfluoroalkyl alcoxylates (perfluoroalkylalkoxylate), carboxylic acid fluoroalkyl etc.
The commercially available product of fluorine class tensio-active agent for example has: BM-1000, BM-1100 (above is BM CHEMIE corporate system), メ ガ Off ァ ッ Network F142D, メ ガ Off ァ ッ Network F172, メ ガ Off ァ ッ Network F173, メ ガ Off ァ ッ Network F183, メ ガ Off ァ ッ Network F178, メ ガ Off ァ ッ Network F191, メ ガ Off ァ ッ Network F471, メ ガ Off ァ ッ Network F476 (above is big Japanese ィ Application キ chemical industry (strain) system), Off ロ ラ one De FC-170C, Off ロ ラ one De-171, Off ロ ラ one De-430, Off ロ ラ one De-431 (above is Sumitomo ス リ one ェ system (strain) system), サ one Off ロ Application S-112, サ one Off ロ Application S-113, サ one Off ロ Application S-131, サ one Off ロ Application S-141, サ one Off ロ Application S-145, サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-102, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC-106 (above is Asahi Glass (strain) system), ェ Off ト ッ プ EF301, ェ Off ト ッ プ EF303, ェ Off ト ッ プ EF352 (above is that new autumn fields changes into (strain) system), Off one ジ ェ Application ト FT-100, Off one ジ ェ Application ト FT-110, Off one ジ ェ Application ト FT-140A, Off one ジ ェ Application ト FT-150, Off one ジ ェ Application ト FT-250, Off one ジ ェ Application ト FT-251, Off one ジ ェ Application ト FT-300, Off one ジ ェ Application ト FT-310, Off one ジ ェ Application ト FT-400S, Off one ジ ェ Application ト FTX-218, Off one ジ ェ Application ト FTX-251 (above is (strain) ネ ォ ス system) etc.
Above-mentioned silicone tensio-active agent, can enumerate with the commercially available material of following trade(brand)name, for example have: ト one レ シ リ コ one Application DC3PA, ト one レ シ リ コ one Application DC7PA, ト one レ シ リ コ one Application SH11PA, ト one レ シ リ コ one Application SH21PA, ト one レ シ リ コ one Application SH28PA, ト one レ シ リ コ one Application SH29PA, ト one レ シ リ コ one Application SH30PA, ト one レ シ リ コ one Application SH-190, ト one レ シ リ コ one Application SH-193, ト one レ シ リ コ one Application SZ-6032, ト one レ シ リ コ one Application SF-8428, ト one レ シ リ コ one Application DC-57, ト one レ シ リ コ one Application DC-190 (above is eastern レ ダ ゥ コ one ニ Application グ シ リ コ one Application (strain) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above is GE Toshiba シ リ コ one Application (strain) system) etc.
In addition, as the tensio-active agent beyond above-mentioned, can enumerate: Voranol EP 2001s such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Nonionic surface active agent such as polyoxyethylene dialkyl such as polyoxyethylene dilaurate, polyoxyethylene SUNSOFT Q-182S, organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), (methyl) acrylic copolymer Port リ Off ロ one No.57, Port リ Off ロ one No.95 (above is common prosperity society chemistry (strain) system) etc.
These tensio-active agents can use separately, also two or more can be mixed and use.
With respect to 100 weight parts (A) polymkeric substance, the use level of tensio-active agent is preferably 1.0 weight parts or below 1.0 weight parts, more preferably 0.5 weight part or below 0.5 weight part.At this moment, if the use level of tensio-active agent surpasses 1.0 weight parts, it is irregular that film thickness then takes place sometimes easily.
As above-mentioned preserving stabilizer, can enumerate for example sulphur, quinones, hydroquinones, polyoxy compound, amine, nitro nitroso compound etc., more specifically can enumerate 4-methoxyphenol, N-nitroso-group-N-Phenylhydroxylamine aluminium etc.
These preserving stabilizers can use separately, also two or more can be mixed and use.
With respect to 100 weight parts (A) polymkeric substance, the use level of preserving stabilizer is preferably 3.0 weight parts or below 3.0 weight parts, more preferably 0.5 weight part or below 0.5 weight part.At this moment, if the use level of preserving stabilizer surpasses 3.0 weight parts, may make sensitivity reduce the pattern form deterioration.
As above-mentioned thermotolerance rising agent, for example can enumerate N-(alkoxy methyl) glycoluril compounds, N-(alkoxy methyl) melamine compound, have the compound of 2 or 2 above Oxyranyles etc.
As above-mentioned N-(alkoxy methyl) glycoluril compounds, can enumerate for example N, N, N ', N '-four (methoxymethyl) glycoluril, N, N, N ', N '-four (ethoxyl methyl) glycoluril, N, N, N ', N '-four (n-propoxymethyl) glycoluril, N, N, N ', N '-four (isopropoxy methyl) glycoluril, N, N, N ', N '-four (n-butoxy methyl) glycoluril, N, N, N ', N '-four (tert.-butoxy methyl) glycoluril etc.
In these N-(alkoxy methyl) glycoluril compounds, preferred N, N, N ', N '-four (methoxymethyl) glycoluril.
As above-mentioned N-(alkoxy methyl) melamine compound, can enumerate for example N, N, N ', N ' N "; N "-six (methoxymethyl) melamine, N, N, N ', N ', N "; N "-six (ethoxyl methyl) melamine, N, N, N ', N ', N "; N "-six (n-propoxymethyl) melamine, N, N, N ', N ', N "; N "-six (isopropoxy methyl) melamine, N, N, N ', N ', N "; N "-six (n-butoxy methyl) melamine, N, N, N ', N ' N " N "-six (tert.-butoxy methyl) melamine etc.
In these N-(alkoxy methyl) melamine compound, preferred N, N, N ', N ', N "; N "-six (methoxymethyl) melamine, its commercially available product for example has: ニ カ ラ ッ Network N-2702, ニ カ ラ ッ Network MW-30M (more than be three and ケ ミ カ Le (strain) system) etc.
As above-mentioned compound with 2 or 2 above Oxyranyles, can enumerate for example ethylene glycol diglycidylether, the Diethylene Glycol diglycidylether, the triethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, the dipropylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, the Hydrogenated Bisphenol A diglycidylether, bisphenol A diglycidyl ether etc.
Commercially available product with compound of 2 or 2 above Oxyranyles for example has: ェ Port ラ ィ ト 40E, ェ Port ラ ィ ト 100E, ェ Port ラ ィ ト 200E, ェ Port ラ ィ ト 70P, ェ Port ラ ィ ト 200P, ェ Port ラ ィ ト 400P, ェ Port ラ ィ ト 1500NP, ェ Port ラ ィ ト 80MF, ェ Port ラ ィ ト 100MF, ェ Port ラ ィ ト 1600, ェ Port ラ ィ ト 3002, ェ Port ラ ィ ト 4000 (above is common prosperity society chemistry (strain) system) etc.
These thermotolerance rising agents can use separately, also two or more can be mixed and use.
First composition is by above-mentioned (A) polymkeric substance, (B) polymerizable unsaturated compound and other composition uniform mixing of (C) radiation-sensitive polymerization starter and interpolation are arbitrarily prepared.First composition is preferably dissolved in the appropriate solvent and uses with solution state.For example, can by in appropriate solvent with above-mentioned (A) polymkeric substance, (B) polymerizable unsaturated compound and (C) radiation-sensitive polymerization starter and other composition of adding arbitrarily with the regulation mixed, the radiation sensitive resin composition of preparation solution state.
For preparation first composition used solvent, use uniform dissolution (A) polymkeric substance, (B) polymerizable unsaturated compound and (C) each composition of radiation-sensitive polymerization starter and other composition of cooperating arbitrarily, and with the nonreactive solvent of each composition.
As such solvent, can enumerate and the same solvent of crossing as operable solvent illustration in preparation above-mentioned (A) polymkeric substance of solvent.
In such solvent, from the solvability of each composition, with the reactive of each composition with form the aspects such as easiness of filming and consider preferred for example alcohol, glycol ether, ethylene glycol alkyl oxide acetic ester, ester and the Diethylene Glycol of using.Wherein, especially preferably use for example benzylalcohol, 2 phenylethyl alcohol, 3-phenyl-1-propyl alcohol, ethylene glycol monobutyl ether acetic acid ester, Diethylene Glycol monoethyl ether acetic ester, diethylene glycol diethyl ether, Diethylene Glycol ethyl-methyl ether, diethylene glycol dimethyl ether, Glycol Monomethyl ether, Glycol Monomethyl ether acetic ester, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.
And, also can and use high boiling solvent and above-mentioned solvent.By and with an amount of high boiling solvent, can expect to improve the effect of the inner evenness of thickness.As can and the high boiling solvent of usefulness, for example can enumerate: N-methylformamide, N, dinethylformamide, N-methyl formyl are for aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, benzyl ethyl ether, hexyl ether, acetonyl-acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, jasmal, ethyl benzoate, oxalic acid diethyl ester, ethyl maleate, gamma-butyrolactone, ethylene carbonate, Texacar PC, Rokafenol F 1 acetic ester etc.Wherein, preferred N-Methyl pyrrolidone, gamma-butyrolactone, N,N-dimethylacetamide.
And with high boiling solvent during as the solvent of first composition, with respect to the solvent total amount, its usage quantity is preferably 50 weight % or below the 50 weight %, 40 weight % or below the 40 weight % more preferably, more preferably 30 weight % or below the 30 weight %.If the usage quantity of high boiling solvent surpasses this usage quantity, the film uniformity of then filming sometimes, sensitivity and residual film ratio reduce.
When first preparation of compositions is become solution state, components in proportions in the solution beyond the solvent, i.e. (A) polymkeric substance, (B) polymerizable unsaturated compound and (C) ratio of the total amount of radiation-sensitive polymerization starter and other composition of adding arbitrarily, can set arbitrarily according to application target, required film thickness value etc., for example can be set at 5～80 weight %, preferred value is different because of the using method of first composition solution.To narrate in the back this.
Zhi Bei composition solution can be that millipore filter, membrane filter etc. about 0.5 μ m filter the back in use with the aperture like this.
＜the second composition 〉
Second composition is preferably and contains (A) polymkeric substance and (D) 1, the radiation sensitive resin composition of 2-quinone di-azido compound.
As the preferred object lesson of (A) polymkeric substance that is used for second composition, can enumerate for example methacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/glycidyl methacrylate/tetrahydrofurfuryl methacrylate multipolymer, methacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/glycidyl methacrylate/to vinyl benzyl glycidyl ether/tetrahydrofurfuryl methacrylate multipolymer, methacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/glycidyl methacrylate/polyoxyethylene glycol monomethyl acrylate copolymer, methacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/glycidyl methacrylate/polypropylene glycol monomethyl acrylate copolymer etc.
(D) 1 that uses in second composition, the 2-quinone di-azido compound is to produce 1 of carboxylic acid by radiation exposure, the 2-quinone di-azido compound can use phenoloid or alcohol compound (hereinafter referred to as " parent nucleus ") and 1, the condenses of 2-naphthoquinones two nitrine sulfonic acid halides.
This parent nucleus for example has: trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy-benzophenone, (poly-hydroxy phenyl) alkane, other parent nucleus.
As the object lesson of these materials, can be listed below respectively:
Trihydroxybenzophenone for example has: 2,3, and 4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone etc.;
Tetrahydroxybenzophenone for example has: 2,2 ', 4, and 4 '-tetrahydroxybenzophenone, 2,3,4,3 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone etc.;
Pentahydroxybenzophenone for example has: 2,3,4, and 2 ', 6 '-pentahydroxybenzophenone etc.;
The hexahydroxy-benzophenone for example has: 2,4,6,3 ', 4 ', and 5 '-hexahydroxy-benzophenone, 3,4,5,3 ', 4 ', 5 '-hexahydroxy-benzophenone etc.;
(poly-hydroxy phenyl) alkane for example has: two (2, the 4-dihydroxy phenyl) methane, two (p-hydroxybenzene) methane, three (p-hydroxybenzene) methane, 1,1,1-three (p-hydroxybenzene) ethane, two (2,3,4-trihydroxy-phenyl) methane, 2, two (2,3, the 4-trihydroxy-phenyl) propane of 2-, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl phenyl] ethylidene] bis-phenol, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, 3,3,3 ', 3 '-tetramethyl--1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol, 2,2,4-trimethylammonium 7,2 ', 4 '-trihydroxy-flavane etc.;
Other parent nucleus for example has: 2-methyl-2-(2, the 4-dihydroxy phenyl)-two { (5-sec.-propyl-4-hydroxy-2-methyl) phenyl } methyl of 4-(4-hydroxy phenyl)-7-hydroxychroman, 2-[], 1-[1-(3-{1-(4-hydroxy phenyl)-1-methylethyl }-4, the 6-dihydroxy phenyl)-the 1-methylethyl]-3-(1-(3-{1-(4-hydroxy phenyl)-1-methylethyl }-4, the 6-dihydroxy phenyl)-and the 1-methylethyl) benzene, 4, two { 1-(4-hydroxy phenyl)-1-methylethyl }-1 of 6-, 3-dihydroxy-benzene etc.
In addition, also can use ester bond to become 1 of amido linkage with the above-mentioned parent nucleus of enumerating, 2-naphthoquinones two nitrine sulfonamidess, for example, and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonamide etc.
In these parent nucleus, preferred 2,3,4,4 '-tetrahydroxybenzophenone or 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] bis-phenol.
1,2-naphthoquinones two nitrine sulfonic acid halides are preferred 1, and 2-naphthoquinones two nitrine SULPHURYL CHLORIDE can enumerate 1 as its object lesson, 2-naphthoquinones two nitrine-4-SULPHURYL CHLORIDE and 1, and 2-naphthoquinones two nitrine 5-SULPHURYL CHLORIDE wherein, preferably use 1,2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE.
In condensation reaction, with respect to the OH in phenoloid or alcohol compound base 1 equivalent, preferred use be equivalent to 30～85 moles of %, more preferably 50～70 moles of % 1,2-naphthoquinones two nitrine sulfonic acid halides.
Condensation reaction can utilize known method to implement.
(D) 1, the 2-quinone di-azido compound can use separately, also two or more can be used in combination.
With respect to 100 weight parts (A) polymkeric substance, (D) 1, the usage ratio of 2-quinone di-azido compound is preferably 5～100 weight parts, more preferably 10～50 weight parts.When this ratio is lower than 5 weight parts, sometimes radiation exposure part and not illuminated portion be difficult to form pattern sometimes little as the poor solubility in the alkaline aqueous solution of developing solution, the thermotolerance and the solvent resistance of the cured film that perhaps obtains sometimes are not enough.On the other hand, when this ratio surpassed 100 weight parts, the solubleness of radiation exposure part in above-mentioned alkaline aqueous solution was insufficient sometimes, is difficult to develop.
Second composition above-mentioned except containing (A) polymkeric substance and (D) 1 beyond the 2-quinone di-azido compound, can contain (B) polymerizable unsaturated compound, thermo-sensitivity acid-producing agent, Resins, epoxy, adhesive aid, tensio-active agent etc. as required.
Above-mentioned (B) polymerizable unsaturated compound is identical with above-mentioned preferred constituent as first composition.Wherein, with respect to 100 weight parts (A) polymkeric substance, the usage quantity of (B) polymerizable unsaturated compound is preferably 50 weight parts or below 50 weight parts in second composition, more preferably 30 weight parts or below 30 weight parts.
By contain (B) polymerizable unsaturated compound with such ratio, can improve thermotolerance, surface hardness of the cured film that obtains etc.If this usage quantity surpasses 50 weight parts, film then can take place in the operation of filming of formation composition on substrate sometimes chap.
Above-mentioned thermo-sensitivity acid-producing agent can be used for improving thermotolerance, the hardness of the cured film that obtains.As its object lesson, for example can enumerate:  salt such as sulfonium salt (wherein not comprising triarylsulfonium salt), benzothiazole  salt, ammonium salt,  salt.
As the object lesson of above-mentioned sulfonium salt, for example can enumerate: alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, substituted benzyl sulfonium salt etc.
The object lesson of these sulfonium salts can be listed below respectively:
The alkyl sulfonium salt for example has: 4-acetyl phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxycarbonyloxy base) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro arsenate, dimethyl-3-chloro-4-acetoxyl group phenyl sulfonium hexafluoro antimonate etc.;
The benzyl sulfonium salt for example has: benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, benzyl-4-anisole ylmethyl sulfonium hexafluoro antimonate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate etc.;
The dibenzyl sulfonium salt for example has: dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, dibenzyl-4-p-methoxy-phenyl sulfonium hexafluoro antimonate, dibenzyl-3-chloro-4-hydroxy phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro antimonate, benzyl-4-methoxy-benzyl-4-hydroxy phenyl sulfonium hexafluorophosphate etc.;
The substituted benzyl sulfonium salt for example has: p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, o-chlorobenzyl 3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate etc.
As the object lesson of above-mentioned benzothiazole  salt, can enumerate 3-benzyl benzothiazole  hexafluoro antimonate, 3-benzyl benzothiazole  hexafluorophosphate, 3-benzyl benzothiazole  a tetrafluoro borate, 3-(to methoxy-benzyl) benzothiazole  hexafluoro antimonate, 3-benzyl 2-methylthio group benzo thiazole  hexafluoro antimonate, 3-benzyl-benzyl benzothiazole  salt such as 5-chloro benzothiazole  hexafluoro antimonate.
Wherein, preferred sulfonium salt or the benzothiazole  salt of using especially preferably uses 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl sulfonium hexafluoro antimonate or 3-benzyl benzothiazole  hexafluoro antimonate.
The commercially available product of these materials for example has: サ Application ェ ィ De SI-L85, サ Application ェ ィ De SI-L110, サ Application ェ ィ De SI-L145, サ Application ェ ィ De SI-L150, サ Application ェ ィ De SI-L160 (more than be three new chemical industry (strain) systems) etc.
With respect to 100 weight parts (A) polymkeric substance, the usage ratio of the thermo-sensitivity acid-producing agent in second composition is preferably 20 weight parts or below 20 weight parts, more preferably 5 weight parts or below 5 weight parts.When this usage quantity surpasses 20 weight parts, in the formation operation of filming, have precipitate sometimes and separate out, bring obstacle for the formation of filming.
Above-mentioned Resins, epoxy needs only the not influence of intermiscibility to other composition or solvent, just be not particularly limited resin that preferably to enumerate bisphenol A type epoxy resin, phenol novolac-type Resins, epoxy, cresols novolac-type Resins, epoxy, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hetero ring type Resins, epoxy, glycidyl methacrylate (being total to) is polymerized etc.In these materials, further preferred bisphenol A type epoxy resin, cresols novolac-type Resins, epoxy, glycidyl ester type epoxy resin etc.
With respect to 100 weight parts (A) polymkeric substance, the usage ratio of the Resins, epoxy in second composition is preferably 30 weight parts or below 30 weight parts.By containing Resins, epoxy, can further improve thermotolerance, surface hardness of the cured film that obtains etc. with such ratio.If when this ratio, then formed filming of composition above 30 weight parts on substrate, the film uniformity of filming sometimes was not enough.
In addition, when (A) polymkeric substance had Oxyranyle, (A) polymkeric substance also can be called " Resins, epoxy ", but (A) polymkeric substance is different with above-mentioned Resins, epoxy aspect alkaline soluble.
The adhesive aid that can contain in second composition and tensio-active agent are identical with adhesive aid and tensio-active agent that above-mentioned first composition can contain.
Second composition is by with above-mentioned (A) polymkeric substance and (D) 1, and 2-quinone di-azido compound and other composition uniform mixing that adds arbitrarily prepare.Second composition is preferably dissolved in the appropriate solvent and uses with solution state.For example, can by in appropriate solvent with above-mentioned (A) polymkeric substance and (D) 1,2-quinone di-azido compound and other composition of adding arbitrarily be with the regulation mixed, the curable resin composition of preparation solution state.
Be used to prepare the solvent of second composition, using can uniform dissolution (A) polymkeric substance and (D) 1, each composition of 2-quinone di-azido compound and other composition of cooperating arbitrarily, and and the nonreactive solvent of each composition.The solvent phase that this solvent and above-mentioned can be used for prepare first composition with.Components in proportions in the composition solution beyond the solvent, i.e. (A) polymkeric substance and (D) 1, the ratio of the total amount of 2-quinone di-azido compound and any other composition that adds, can set arbitrarily according to application target, required film thickness value etc., for example, can be set at 5～50 weight %, be preferably 10～40 weight %, more preferably 15～35 weight %.
Second composition solution can be that millipore filter, membrane filter etc. about 0.5 μ m filter the back in use with the aperture.
＜the three composition 〉
The 3rd composition is preferably and contains (A) polymkeric substance and (E) liquid type of cationically polymerizable compound (a liquid type) curable resin composition.
As the preferred object lesson of (A) polymkeric substance that is used for the 3rd composition, can enumerate for example glycidyl acrylate/allyl phenol/three ring [5.2.1.0 2,6] decane-8-base acrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid/methyl methacrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid/cyclohexyl acrylate/to the methoxy styrene multipolymer, glycidyl acrylate/vinylformic acid/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/1,3-butadiene multipolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/vinylbenzene/1,3-butadienecopolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/vinylformic acid/maleic anhydride/styrol copolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/vinylformic acid/maleic anhydride/methacrylic tert-butyl acrylate multipolymer etc.
Wherein, further preferable methyl glycidyl acrylate/methacrylic phenol three encircles [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/1,3-butadiene multipolymer or glycidyl methacrylate/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/vinylbenzene/1,3-butadiene multipolymer.
(E) cationically polymerizable compound that uses in the 3rd composition is the cationically polymerizable compound except that (A) polymkeric substance or (A ') polymkeric substance.
For such (E) cationically polymerizable compound, as long as can polymerization under acidic conditions, just be not particularly limited, for example can enumerate: intramolecularly has and is selected from trimethylene oxide ring skeleton, 3 more than 2 or 2, and the compound of at least a group in 4-Oxyranyle cyclohexyl and the Oxyranyle etc. has the compound that can carry out the group of addition reaction with the Oxyranyle that preferably contains in (A) polymkeric substance or oxa-cyclobutyl.
Object lesson as such (E) cationically polymerizable compound can be listed below described compound.
The compound that intramolecularly has 2 or 2 above trimethylene oxide ring skeletons for example has: 3, two (3-oxa-the cyclobutyl)-5-oxa-nonanes of 7-, 3,3 '-(1,3-(2-methylene radical (メ チ レ ニ Le)) glyceryl two (oxygen methylene)) two (3-ethyl trimethylene oxide), 1, two ((3-ethyl-3-oxa-cyclobutyl) methoxymethyl) benzene of 4-, 1, two ((3-ethyl-3-oxa-cyclobutyl) methoxymethyl) ethane of 2-, 1, two ((3-ethyl-3-oxa-cyclobutyl) methoxymethyl) propane of 3-, ethylene glycol bis ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of dicyclopentenyl, two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of triethylene glycol, two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of TEG, two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of basic dimethylene in the three ring last of the ten Heavenly stems two, trimethylolpropane tris ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, 1, two ((the 3-ethyl 3-oxa-cyclobutyl) methoxyl group) butane of 4-, 1, two ((3-ethyl-3-oxa-cyclobutyl) methoxyl group) hexanes of 6-, tetramethylolmethane three ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, tetramethylolmethane four ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of polyoxyethylene glycol, Dipentaerythritol six ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, Dipentaerythritol five ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, Dipentaerythritol four ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, the reaction product of Dipentaerythritol six ((3-ethyl-3-oxa-cyclobutyl) methyl) ether and butyrolactone, the reaction product of Dipentaerythritol five ((3-ethyl-3-oxa-cyclobutyl) methyl) ether and butyrolactone, ditrimethylolpropane four ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, the reaction product of two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of dihydroxyphenyl propane and oxyethane, dihydroxyphenyl propane two (3-ethyl-3-oxa-cyclobutyl) methyl) reaction product of ether and propylene oxide, the reaction product of two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of Hydrogenated Bisphenol A and oxyethane, the reaction product of two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of Hydrogenated Bisphenol A and propylene oxide, the reaction product of two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of Bisphenol F and oxyethane etc.
Intramolecularly has more than 2 or 23, the compound of 4-Oxyranyle cyclohexyl for example has: 3,4-Oxyranyle cyclohexyl methyl-3 ', 4 '-Oxyranyle cyclohexane carboxylate, 2-(3,4-Oxyranyle cyclohexyl 5,5-spiral shell-3, the 4-Oxyranyle) hexanaphthene--two a  alkane (メ -ジ ォ キ サ Application), two (3,4-Oxyranyle cyclohexyl methyl) adipic acid ester, two (3,4-Oxyranyle 6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-Oxyranyle 6-methylcyclohexyl 3 ', 4 '-Oxyranyle 6 '-methylcyclohexanecarboxylic acid ester, methylene-bis (3,4-Oxyranyle hexanaphthene), the Dicyclopentadiene (DCPD) diepoxide, ethylene glycol bis (3,4-Oxyranyle cyclohexyl methyl) ether, ethylenebis (3,4-Oxyranyle cyclohexane carboxylate), in ester modified 3,4-Oxyranyle cyclohexyl methyl-3 ', 4 '-Oxyranyle cyclohexane carboxylate etc.
Have the compound of 2 or 2 above Oxyranyles as intramolecularly, can enumerate the diglycidylether of the such bisphenol cpd of bisphenol A diglycidyl ether for example, Bisphenol F diglycidylether, bisphenol-S diglycidyl ether, Hydrogenated Bisphenol A diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, Hydrogenated Bisphenol A D diglycidylether, brominated bisphenol A diglycidylether, brominated bisphenol F diglycidylether, brominated bisphenol S diglycidylether;
1,4-butanediol diglycidyl ether, 1, the polyglycidyl ether of the polyvalent alcohol that 6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether are such;
By such aliphatic polyol of ethylene glycol, propylene glycol, glycerine and the polyglycidyl ether a kind of or polyether glycol that two or more reactions of alkylene oxide obtains;
Phenol novolac-type Resins, epoxy, cresols novolac-type Resins, epoxy, poly-phenol-type epoxy resin, the such Resins, epoxy of cyclic aliphatic epoxy resin;
The 2-glycidyl ester of aliphatic long-chain diprotic acid;
The poly glycidyl ester of senior polyhydric aliphatic acid etc.; In addition, also have Oxyranyle soybean oil, Oxyranyle Semen Lini wet goods.
Have the commercially available product of the compound of 2 or 2 above Oxyranyles as intramolecularly, can be listed below respectively:
The polyglycidyl ether of polyvalent alcohol for example has: ェ Port ラ ィ ト 100MF (common prosperity society chemistry (strain) system), ェ ピ ォ one Le TMP (Japanese grease (strain) system);
Bisphenol A type epoxy resin for example has: ェ ピ コ one ト 828, ェ ピ コ one ト 1001, ェ ピ コ one ト 1002, ェ ピ コ one ト 1003, ェ ピ コ one ト 1004, ェ ピ コ one ト 1007, ェ ピ コ one ト 1009, ェ ピ コ one ト 1010 (above is oiling シ ェ Le ェ Port キ シ (strain) system) etc.;
Bisphenol f type epoxy resin for example has: ェ ピ コ one ト 807 (oiling シ ェ Le ェ Port キ シ (strain) system) etc.;
Phenol novolac-type Resins, epoxy for example has: ェ ピ コ one ト 152, ェ ピ コ one ト 154, ェ ピ コ one ト 157S65 (the above oiling シ ェ Le ェ Port キ シ (strain) of being system), DPPN201, DPPN202 (above is Japanese chemical drug (strain) system) etc.;
Cresols novolac-type Resins, epoxy for example has: DOCN102, DOCN103S, DOCN104S, 1020,1025,1027 (above is Japanese chemical drug (strain) system), ェ ピ コ one ト 180S75 (oiling シ ェ Le ェ Port キ シ (strain) system) etc.;
Poly-phenol-type epoxy resin for example has: ェ ピ コ one ト 1032H60, ェ ピ コ one ト XY-4000 (above is oiling シ ェ Le ェ Port キ シ (strain) system) etc.;
Cyclic aliphatic epoxy resin for example has: CY-175, CY-177, CY-179, ァ ラ Le ダ ィ ト CY-182, ラ Le ダ ィ ト CY192, ァ ラ Le ダ ィ ト CY184 (above is チ バ ス ペ シ ャ Le テ ィ one ケ ミ カ Le ズ (strain) system), DRL-4221, DRL-4206, DRL-4234, DRL-4299 (above is the U.C.C corporate system), シ ョ one ダ ィ Application 509 (clear and electrician's (strain) system), ェ ピ Network ロ Application 200, ェ ピ Network ロ Application 400 (above is big Japanese ィ Application キ (strain) system), ェ ピ コ one ト 871, ェ ピ コ one ト 872 (above is oiling シ ェ Le ェ Port キ シ strain formula meeting corporate system), DD-5661, DD-5662 (above is セ ラ ニ one ズ コ one テ ィ Application グ (strain) system) etc.
In these (E) cationically polymerizable compounds, preferred phenol novolac-type Resins, epoxy, poly-phenol-type epoxy resin etc.
In the present invention, (E) the cationically polymerizable compound can use separately, also two or more can be mixed and use.
For the usage ratio of (E) cationically polymerizable compound in the 3rd composition, with respect to 100 weight parts (A) polymkeric substance, (E) usage quantity of cationically polymerizable compound is preferably 3～100 weight parts, more preferably 5～50 weight parts.
In the 3rd composition, the usage quantity by making (E) cationically polymerizable compound can obtain having the cured film of enough surface hardnesses in above-mentioned scope.The prolonged preservation good stability of the 3rd composition particularly.
Except above-mentioned (A) polymkeric substance with (E) the cationically polymerizable compound, the 3rd composition preferably also contains (F) solidifying agent leather or (G) acid-producing agent, can contain adhesive aid, tensio-active agent etc. as required.
(F) solidifying agent that the 3rd composition can contain is the compound with functional group of one or more Oxyranyles that can preferably contain with (A) polymkeric substance or the reaction of oxa-cyclobutyl.
(F) solidifying agent so for example has: multipolymer of polycarboxylic acid, polybasic acid anhydride, unsaturated polybasic acid anhydride and other olefines unsaturated compound (wherein not comprising the multipolymer with 2 or 2 above Oxyranyles or oxa-cyclobutyl) (hereinafter referred to as " multipolymer that contains the acid anhydride ") etc.
As above-mentioned polycarboxylic acid, can enumerate for example aliphatics polycarboxylic acid, alicyclic polycarboxylic acid, aromatic series polycarboxylic acid etc.The aliphatics polycarboxylic acid for example has: succsinic acid, pentanedioic acid, hexanodioic acid, 1,2,3,4-ethylene-dimalonic acid, toxilic acid, methylene-succinic acid etc.;
Alicyclic polycarboxylic acid for example has: hexahydrobenzene dioctyl phthalate, 1,2-cyclohexane dicarboxylic acid, 1,2,4-hexanaphthene tricarboxylic acid, pentamethylene tetracarboxylic acid etc.;
The aromatic series polycarboxylic acid for example has: phthalic acid, m-phthalic acid, terephthalic acid, trihemellitic acid, pyromellitic acid, 1,2,5,8-naphthalenetetracarbacidic acidic etc.In these polycarboxylic acids, consider optimization aromatic polycarboxylic acid class from viewpoints such as thermotolerance reactive, the cured film that forms.
Above-mentioned polybasic acid anhydride for example has: aliphatic dicarboxylic acid acid anhydride, alicyclic polycarboxylic acid dicarboxylic anhydride, aromatic series polybasic acid anhydride, contain the acid anhydrides of ester group etc.Above-mentioned aliphatic dicarboxylic acid acid anhydride for example has: itaconic anhydride, succinyl oxide, citraconic anhydride, dodecenyl succinic anhydride, three carbaniloyl acid anhydrides (acid of No water ト リ カ Le バ ニ Le), maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexachloro endoethylene tetrahydrophthalic acid acid anhydride (acid of No water Ha ィ ミ ッ Network) etc.;
Alicyclic polycarboxylic acid dicarboxylic anhydride for example has: 1,2,3, and 4-ethylene-dimalonic acid dicarboxylic anhydride, pentamethylene tetracarboxylic acid dicarboxylic anhydride etc.;
The aromatic series polybasic acid anhydride for example has: Tetra hydro Phthalic anhydride, pyromellitic acid dianhydride, trimellitic acid 1,2-anhydride, benzophenone tetracarboxylic anhydride etc.;
The acid anhydrides that contains ester group for example has: ethylene glycol bisthioglycolate acid anhydrides trimellitate, glycerine three acid anhydrides trimellitates etc.
In these polybasic acid anhydrides, the optimization aromatic polybasic acid anhydride, particularly owing to can obtain the high cured film of thermotolerance, thereby preferred trimellitic acid 1,2-anhydride.
Unsaturated polybasic acid anhydride in the above-mentioned acid anhydride's of containing the multipolymer for example has: maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydronaphthalic anhydride etc.These unsaturated polybasic acid anhydrides can use separately, also two or more can be mixed and use.
Other olefines unsaturated compound for example has: vinylbenzene, p-methylstyrene, to methoxy styrene, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid 2-methyl cyclohexane ester, three ring [5.2.1.0 2,6] decane-8-base (methyl) acrylate, N-phenylmaleimide, N-cyclohexyl maleimide etc.These other olefines unsaturated compounds both can use separately, also two or more can be mixed and use.
As the preferred object lesson of the multipolymer that contains the acid anhydride, can enumerate for example maleic anhydride/styrol copolymer, citraconic anhydride/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate copolymer etc.
The copolymerization ratio that contains the unsaturated polybasic acid anhydride in acid anhydride's the multipolymer is preferably 1～80 weight %, more preferably 10～60 weight %.By using the multipolymer of such copolymerization ratio, can obtain the good cured film of planarization performance.
The Mw that contains acid anhydride's multipolymer is preferably 500～50, and 000, more preferably 500～10,000.By using the multipolymer of such molecular weight ranges, can obtain the good cured film of planarization performance.
Aforesaid (F) solidifying agent both can use separately, also two or more can be mixed and use.
Usage ratio for (F) solidifying agent in the 3rd composition, with respect to 100 weight parts (A) polymkeric substance, (F) usage quantity of solidifying agent is preferably 100 weight parts or below 100 weight parts, more preferably 1～80 weight part, more preferably 10～60 weight parts.
In the 3rd composition, the usage quantity by making (F) solidifying agent is in above-mentioned scope, can not influence the permanent stability of composition and further improves the flatness of the cured film that obtains.
(G) acid-producing agent that the 3rd composition can contain preferably passes through the irradiation radioactive rays and acidic compound or the acidic compound by heating.Wherein, the former is called " radiation-sensitive acid-producing agent ", and the latter is called " thermo-sensitivity acid-producing agent ".
As such radiation-sensitive acid-producing agent, can enumerate for example diaryl iodine  salt, triarylsulfonium salt, diaryl  salt etc.
Above-mentioned diaryl iodine  salt for example has: phenylbenzene iodine  a tetrafluoro borate, phenylbenzene iodine  hexafluoro phosphonate, phenylbenzene iodine  hexafluoro arsenate, phenylbenzene iodine  fluoroform sulphonate, phenylbenzene iodine  trifluoroacetate, phenylbenzene iodine  tosilate, 4-p-methoxy-phenyl phenyl-iodide  a tetrafluoro borate, 4-p-methoxy-phenyl phenyl-iodide  hexafluoro phosphonate, 4-p-methoxy-phenyl phenyl-iodide  hexafluoro arsenate, 4-p-methoxy-phenyl phenyl-iodide  fluoroform sulphonate, 4-p-methoxy-phenyl phenyl-iodide  trifluoroacetate, 4-p-methoxy-phenyl phenyl-iodide  tosilate, two (4-tert-butyl-phenyl) iodine  a tetrafluoro borate, two (4-tert-butyl-phenyl) iodine  hexafluoro arsenate, two (4-tert-butyl-phenyl) iodine  fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine  trifluoroacetate, two (4-tert-butyl-phenyl) iodine  tosilate etc.In these diaryl iodine  salt, preferred especially phenylbenzene iodine  hexafluoro phosphonate.
Above-mentioned triarylsulfonium salt for example has: the triphenylsulfonium a tetrafluoro borate, triphenylsulfonium hexafluoro phosphonate, the triphenylsulfonium hexafluoro arsenate, the triphenylsulfonium fluoroform sulphonate, the triphenylsulfonium trifluoroacetate, the triphenylsulfonium tosilate, 4-p-methoxy-phenyl phenylbenzene sulfonium a tetrafluoro borate, 4-p-methoxy-phenyl phenylbenzene sulfonium hexafluoro phosphonate, 4-p-methoxy-phenyl phenylbenzene sulfonium hexafluoro arsenate, 4-p-methoxy-phenyl phenylbenzene sulfonium fluoroform sulphonate, 4-p-methoxy-phenyl phenylbenzene sulfonium trifluoroacetate, 4-p-methoxy-phenyl phenylbenzene sulfonium tosilate, 4-thiophenyl phenyl phenylbenzene a tetrafluoro borate, 4-thiophenyl phenyl phenylbenzene hexafluoro phosphonate, 4-thiophenyl phenyl phenylbenzene hexafluoro arsenate, 4-thiophenyl phenyl phenylbenzene fluoroform sulphonate, 4-thiophenyl phenyl phenylbenzene trifluoroacetate, 4-thiophenyl phenyl phenylbenzene tosilate etc.In these triarylsulfonium salts, preferred especially triphenylsulfonium fluoroform sulphonate.
Above-mentioned diaryl  salt for example has: (1-6-η-cumene) (η-cyclopentadienyl) iron hexafluoro phosphonate etc.
The commercially available product of radiation-sensitive acid-producing agent can be listed below respectively: diaryl iodine  salt for example has: UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above is ュ ニ ォ Application カ one バ ィ De corporate system), MPI-103, BBI-103 (above is body ど り chemistry (strain) system) etc.;
Triarylsulfonium salt for example has: ァ デ カ ォ プ ト マ one SP-150, ァ デ カ ォ プ ト マ one SP-151, ァ デ カ ォ プ ト マ one SP-170, ァ デ カ ォ プ ト マ one SP-171 (above is rising sun electrochemical industry (strain) system), CI-2481, CI-2624, CI-2639, CI-2064 (above is this Cao of Ri Da (strain) system), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103 (above is body ど り chemistry (strain) system), CD-1010, CD-1011, CD-1012 (above is サ one ト マ one corporate system) etc.;
Diaryl  salt for example has: ィ Le ガ キ ュ ァ 1 (チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ (strain) system), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above is Japanese chemical drug (strain) system) etc.
In these commercially available products, UVI-6970, UVI-6974, UVI-6990, ァ デ カ ォ プ ト マ one SP-170, ァ デ カ ォ プ ト マ one SP-171, CD-1012, MPI-103 etc. are because the cured film that obtains has high surface hardness preferably.
Above-mentioned radiation-sensitive acid-producing agent both can use separately, also two or more can be mixed and use.
The thermo-sensitivity acid-producing agent that the 3rd composition can contain can be enumerated the compound of the thermo-sensitivity acid-producing agent identical type that can contain with above-mentioned second composition.
Usage ratio for (G) acid-producing agent in the 3rd composition, with respect to 100 weight parts (A) polymkeric substance, the usage quantity of acid-producing agent is preferably 20 weight parts or below 20 weight parts, more preferably 0.05～20 weight part, more preferably 0.1～10 weight part.
Adhesive aid that the 3rd composition can contain and tensio-active agent, the adhesive aid that can contain with above-mentioned first composition is identical with tensio-active agent.Wherein, with respect to 100 weight parts (A) polymkeric substance, the amount of the adhesive aid that the 3rd composition can contain is preferably 30 weight parts or below 30 weight parts, more preferably 25 weight parts or below 25 weight parts.If should value surpass 30 weight parts, the thermotolerance deficiency of the cured film that then obtains sometimes.In addition, with respect to 100 weight parts (A) polymkeric substance, the amount of the tensio-active agent that the 3rd composition can contain is preferably 5 weight parts or below 5 weight parts, more preferably 2 weight parts or below 2 weight parts.If should value surpass 5 weight parts, it is irregular that film thickness then takes place sometimes easily.
The 3rd composition is by above-mentioned (A) polymkeric substance other composition uniform mixing with (E) cationically polymerizable compound and interpolation is arbitrarily prepared.The 3rd composition is preferably dissolved in the appropriate solvent and uses with solution state.For example, can by in appropriate solvent with above-mentioned (A) polymkeric substance and (E) cationically polymerizable compound and other composition of adding arbitrarily with the regulation mixed, the radiation sensitive resin composition of preparation solution state.
The solvent that is used to prepare the 3rd composition uses can uniform dissolution (A) polymkeric substance and (E) each composition of cationically polymerizable compound and other composition of cooperating arbitrarily, and and the nonreactive solvent of each composition.Such solvent and the above-mentioned solvent phase that can be used for preparing first composition with.Components in proportions beyond desolventizing in the composition solution, i.e. (A) polymkeric substance and (E) ratio of the total amount of cationically polymerizable compound and other composition of adding arbitrarily, can be according to application target and required settings arbitrarily such as film thickness value, for example, can be set at 1～50 weight %, be preferably 5～40 weight %.
The 3rd composition solution can be that millipore filter, membrane filter etc. about 0.5 μ m filter the back in use with the aperture.
＜the four composition 〉
The 4th composition contains (A ') polymkeric substance and (E) cationically polymerizable compound.The 4th composition is preferably (A) polymkeric substance in above-mentioned the 3rd composition is replaced to the liquid type curable resin composition that (A ') polymkeric substance obtains.
(the A ') polymkeric substance that is used for the 4th composition is preferably above-mentioned (A ' 1) polymkeric substance or (A ' 2) polymkeric substance.
As the preferred object lesson of (A ' 1) polymkeric substance that can be used for the 4th composition, can enumerate for example glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/vinylformic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/vinylformic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/1,3-butadiene multipolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/1, the 3-butadienecopolymer, glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/methyl methacrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/methyl methacrylate/styrol copolymer, glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/cyclohexyl acrylate/to the methoxy styrene multipolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/cyclohexyl acrylate/to the methoxy styrene multipolymer, glycidyl acrylate/methacrylic tert-butyl acrylate/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/methacrylic tert-butyl acrylate/N-cyclohexyl maleimide/styrol copolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/methacrylic tert-butyl acrylate/copolymer-maleic anhydride, methacrylic acid 6,7-Oxyranyle heptyl ester/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/methacrylic tert-butyl acrylate/copolymer-maleic anhydride, methacrylic acid 6,7-Oxyranyle heptyl ester/methacrylic tert-butyl acrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/methacrylic tert-butyl acrylate/maleic anhydride styrol copolymer, glycidyl methacrylate/vinylformic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/vinylbenzene/1,3-butadiene multipolymer, glycidyl methacrylate/methacrylic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/vinylbenzene/1,3-butadiene multipolymer etc.
In these materials, further preferred: glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/vinylformic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/methacrylic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, glycidyl methacrylate/2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/N-cyclohexyl maleimide/styrol copolymer or glycidyl methacrylate/methacrylic tert-butyl acrylate/N-cyclohexyl maleimide/styrol copolymer.
As the preferred object lesson of (A ' 2) polymkeric substance that can be used for the 4th composition, for example can enumerate: glycidyl acrylate/styrol copolymer, glycidyl methacrylate/styrol copolymer, glycidyl acrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate copolymer, glycidyl methacrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate copolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/styrol copolymer, glycidyl methacrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer, glycidyl methacrylate/N-phenylmaleimide/styrol copolymer, glycidyl methacrylate/N-cyclohexyl maleimide/styrol copolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate copolymer, methacrylic acid 6,7-Oxyranyle heptyl ester/N-cyclohexyl maleimide/styrol copolymer etc.
In these materials, further preferred: glycidyl methacrylate/styrol copolymer, glycidyl methacrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate copolymer, glycidyl methacrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate/styrol copolymer or glycidyl methacrylate/N-cyclohexyl maleimide/styrol copolymer.
Relevant the 4th composition (A ') polymkeric substance item in addition, the situation of above-mentioned the 3rd composition directly can be used, or on the basis of carrying out the self-evident change of those skilled in the art, be used.
＜the five composition 〉
The 5th composition is the binary liquid shape curable resin composition that contains first liquid and second liquid, and described first liquid contains (A ') polymkeric substance and (E) cationically polymerizable compound, and described second liquid contains (F) solidifying agent.First liquid of the 5th composition does not preferably contain (F) solidifying agent and (G) acid-producing agent.
(A ') polymkeric substance is preferably (A ' 2) polymkeric substance as used herein.(A ' 2) polymkeric substance that first liquid of the 5th composition can contain and above-mentioned (A ' 2) polymer phase that can be used for the 4th composition with.In addition, first liquid of the 5th composition (E) cationically polymerizable compound that can contain is identical with above-mentioned (E) cationically polymerizable compound that can be used for the 3rd composition.
Usage ratio as for (E) cationically polymerizable compound in first liquid of the 5th composition, with respect to 100 weight parts (A ' 2) polymkeric substance, (E) usage quantity of cationically polymerizable compound is preferably 3～100 weight parts, more preferably 5～50 weight parts.
Except above-mentioned (A ' 2) polymkeric substance with (E) the cationically polymerizable compound, first liquid of the 5th composition can contain adhesive aid, tensio-active agent etc. as required.
Adhesive aid is identical with tensio-active agent with the adhesive aid that above-mentioned first composition can contain with tensio-active agent.
First liquid of the 5th composition is preferably dissolved in the appropriate solvent and uses with solution state.
The solvent that is used to prepare first liquid of the 5th composition uses can uniform dissolution (A) polymkeric substance and (E) each composition of cationically polymerizable compound and other composition of cooperating arbitrarily, and and the nonreactive solvent of each composition.Described solvent and the above-mentioned solvent phase that can be used for first preparation of compositions with.Components in proportions beyond desolventizing in the composition solution, i.e. (A) polymkeric substance and (E) ratio of the total amount of cationically polymerizable compound and other composition of adding arbitrarily, can be according to application target and required settings arbitrarily such as film thickness value, for example, can be set at 5～75 weight %, be preferably 10～50 weight %.
First liquid of the 5th composition can be that millipore filter, membrane filter etc. about 0.5 μ m filter the back in use with the aperture.
Second liquid of the 5th composition preferably contains the solution of (F) solidifying agent.The kind of (F) solidifying agent that contains in second liquid of the 5th composition is identical with (F) solidifying agent that above-mentioned the 3rd composition can contain.
Can be used to prepare the solvent of second liquid of the 5th composition and the above-mentioned solvent phase that can be used for preparing first composition with.
(F) concentration of solidifying agent in second liquid of the 5th composition is preferably 1～80 weight %, more preferably 10～60 weight %.
Second liquid of the 5th composition can filter the back in use at the millipore filter about with aperture 0.5 μ m being, membrane filter etc.
" the formation method of cured film "
Below, the method for using above-mentioned first to the 5th composition to form cured film is narrated.Above-mentioned first composition is applicable to the spacer that forms liquid crystal display device, and second composition is applicable to and forms interlayer dielectric or microlens that the 3rd to the 5th composition is applicable to the formation protective membrane.
＜use first composition to form the method for spacer 〉
Use first composition to form the method for the spacer of liquid crystal display device, carry out following operation (1)～(4) according to order as described below.
(1) operation of the tunicle of formation first composition on substrate.
(2) at least a portion of above-mentioned tunicle is carried out the operation that radioactive rays expose.
(3) after will exposing by the operation of film development.
(4) operation of the heating of the tunicle after will developing.
Below, each operation is described successively.
(1) operation of the tunicle of formation first composition on substrate
At first, on substrate, form the tunicle of the composition of first composition solution.
The preferred single face of substrate that present method is used has formed the transparency carrier of nesa coating.
The material that constitutes transparency carrier for example has: glass, resin etc.Above-mentioned glass for example has: soda-lime glass, non-alkali glass etc.; Resin for example has: polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide etc.
Above-mentioned nesa coating for example has: contain stannic oxide (SnO 2) NESA film (registered trademark of U.S. PPG company), contain Indium sesquioxide-stannic oxide (In 2O 3-SnO 2) ITO film etc.
The method of tunicle that forms the composition of first composition solution on substrate for example can be utilized: (i) coating method, (ii) dry film method.
When utilizing (i) coating method, be coated on first composition solution on the substrate after, heating (prebake conditions) coated face can form tunicle thus.
Coating process to composition solution is not particularly limited, and for example can adopt that spraying method, rolling method, method of spin coating (spin-coating method), slit die coating method, rod are coated with appropriate means such as method, ink-jet application method, preferred especially spin-coating method or slit die coating method.
The condition of prebake conditions is different because of the kind of each composition, cooperation ratio etc., but is preferably: about 70～120 ℃, 1～15 minute.
Adopt when (ii) the dry film method forms the tunicle of first composition solution on substrate, this dry film is at basement membrane, (hereinafter referred to as " photosensitive dry film ") that preferably the stacked photosensitive layer that contains photosensitive polymer combination of the present invention forms on flexible base film.
Above-mentioned photosensitive dry film can be formed by following: photosensitive polymer combination of the present invention preferably is coated on the basement membrane with the form of fluid composition, removes then and desolvate, thus stacked photosensitive layer.The basement membrane of photosensitive dry film for example can use: the film of synthetic resins such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride.The thickness of basement membrane suits in the scope of 15～125 μ m.The thickness of the photosensitive layer that obtains is preferably about 1～30 μ m.Removing of solvent can be carried out by heating under preferred 80～150 ℃ in about 1～10 minute.
In addition, photosensitive dry film can further stackedly on its photosensitive layer not preserved by overlay film when using yet.The release property that this must be had appropriateness by overlay film so that it does not peel off when using, and can be peeled off in use easily.Satisfy can being used in the surface coated of for example synthetic resin films such as PET film, polypropylene screen, polyethylene film, polychloroethylene film by overlay film or baking the film that the type siloxane releasing agent obtains of such condition.Just enough about 25 μ m usually by the thickness of overlay film.
When first composition was used with solution morphology, its solid component concentration (remove from composition after desolvating weight with respect to the ratio of total composition weight) was preferably 5～80 weight %.Further preferred solid component concentration is different because of the formation method of tunicle.Solid component concentration when adopting (i) coating method to form tunicle is preferably 15～30 weight %, adopts the solid component concentration when (ii) the dry film method forms tunicle to be preferably 50～70 weight %.
In addition, the thickness of the tunicle that forms on substrate is not particularly limited, but be preferably 0.5～10 μ m, more preferably about 1.0～7.0 μ m.
(2) at least a portion of above-mentioned tunicle is carried out the operation that radioactive rays expose
Then, at least a portion of the above-mentioned tunicle that forms is carried out the radioactive rays exposure.When the part of tunicle is exposed, can utilize the method for for example exposing by photomask with predetermined pattern.
The radioactive rays that are used to expose can use visible light, ultraviolet ray, far ultraviolet rays yue etc.The radioactive rays optimal wavelength especially preferably comprises the ultraviolet radioactive rays of 365nm at the radioactive rays of 1 90～450nm scope.
Exposure is the radioactive rays wavelength that utilizes luxmeter (QAImodel 356, OAI Optical Associates Inc. system) to measure exposure intensity value of obtaining when being 365nm, is preferably 100～10,000J/m 2, more preferably 1,500～3,000J/m 2
(3) operation of developing of the tunicle after will exposing
Then, develop, remove part not, form the pattern of regulation by the tunicle after will exposing.
The developing solution that is used to develop can use the aqueous solution of following basic cpd, for example: mineral alkalis such as sodium hydroxide, potassium hydroxide, yellow soda ash, water glass, (just) water glass (メ ケ ィ acid Na ト リ ゥ system), ammonia; Armeen such as ethamine, Tri N-Propyl Amine; Secondary aliphatic amine such as diethylamine, di-n-propylamine; Aliphatic tertiary amines such as Trimethylamine 99, methyl-diethyl-amine, dimethyl amine, triethylamine; Pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diazabicylo [5.4.0]-7-undecylene, 1,5-diazabicylo [4.3.0]-alicyclic tertiary amines such as 5-nonene; Aromatic nitrile bases such as pyridine, trimethylpyridine, lutidine, quinoline; Alkanolamines such as dimethylethanolamine, methyldiethanolamine, trolamine; Quaternary ammonium salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide etc.
Also can in the aqueous solution of above-mentioned basic cpd, add at least a use the in water-miscible organic solvents such as methyl alcohol, ethanol and the tensio-active agent in right amount.
Developing method can be any in the known developing methods such as paddle method (liquid is contained the り method), pickling process, spraying process, and development time is preferably about 10～180 seconds at normal temperatures.
After the development, after cleaning by the flowing water that for example carried out 30～90 seconds, make it air-dry, form required pattern with for example pressurized air or compressed nitrogen.
(4) operation of the heating of the tunicle after will developing
Then, the pattern (tunicle) that obtains is utilized for example suitable heating unit such as hot-plate, baking oven, in specified temperature, for example under 100～160 ℃, heating (back baking) specified time, being 5～30 minutes on hot-plate for example, is 30～180 minutes in baking oven, thus the spacer that can obtain stipulating.
In addition, if the existing radiation sensitive resin composition that is used to form spacer not about 180～200 ℃ or above temperature carry out heat treated, the spacer that then obtains can not be brought into play abundant performance, but the advantage of first composition is, Heating temperature can be set at than to live low low temperature, the result can not cause the xanthochromia or the distortion of resin substrate, the rub resistance in the time of can obtaining compressive strength, liquid crystal aligning, with the spacer of each excellent property such as adaptation of transparency carrier.
＜use second composition to form interlayer dielectric or lenticular method 〉
Use second composition to form interlayer dielectric or lenticular method, carry out following operation (1)～(4) according to order as described below.
(1) operation of the tunicle of formation second composition on substrate.
(2) at least a portion of above-mentioned tunicle is carried out the operation that radioactive rays expose.
(3) after will exposing by the operation of film development.
(4) operation of the heating of the tunicle after will developing.
(1) operation of the tunicle of formation second composition on substrate
In operation (1), second composition solution is coated on substrate surface, then, preferably, form the tunicle of second composition by carrying out prebake conditions except that desolvating.
The kind of operable substrate for example has: glass substrate, silicon wafer reach the substrate that is formed with various metals on these surface.
Coating process to composition solution is not particularly limited, for example can adopt: spraying method, rolling method, method of spin coating (spin-coating method), slit die coating method (ス リ ッ ト ダ ィ Tu cloth method), rod are coated with appropriate means such as method, ink-jet application method, preferred especially spin-coating method or slit die coating method.The condition of prebake conditions is different because of the kind of each composition, usage ratio etc.For example can be set at and carry out under 60～110 ℃ about 30 seconds～15 minutes.
The thickness of the tunicle that forms in the value after the prebake conditions, is preferably for example 3～6 μ m when forming interlayer dielectric, be preferably for example 0.5～3 μ m when forming microlens.
(2) at least a portion of above-mentioned tunicle is carried out the operation that radioactive rays expose
In operation (2), preferably the tunicle that forms is shone radioactive rays by mask with predetermined pattern.Then, in subsequent processing (3),, carry out composition by carrying out the illuminated portion that development treatment is removed radioactive rays with developing solution.At this moment the radioactive rays of Shi Yonging for example have: ultraviolet ray, far ultraviolet rays yue, X ray, charged particle ray etc.
Above-mentioned ultraviolet ray for example has: g ray (wavelength 436nm), i ray (wavelength 365nm) etc.Far ultraviolet rays yue for example has: KrF excimer laser etc.X ray for example has: synchrotron radioactive rays etc.The charged particle ray for example has: electron beam etc.
In these radioactive rays, preferred ultraviolet ray especially preferably comprises at least a radioactive rays in g ray and the i ray.
As for exposure, when forming interlayer dielectric, be preferably 50～1,500J/m 2, when forming microlens, be preferably 50～2,000J/m 2
(3) operation of developing of the tunicle after will exposing
The developing solution that is used for the development treatment of operation (3), can use the aqueous solution of following alkali (basic cpd), for example: sodium hydroxide, potassium hydroxide, yellow soda ash, water glass, (just) water glass, ammonia, ethamine, Tri N-Propyl Amine, diethylamine, DEAE diethylaminoethanol, di-n-propylamine, triethylamine, methyl-diethyl-amine, dimethylethanolamine, trolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrroles, piperidines, 1,8-diazabicylo [5.4.0]-7-undecylene, 1,5-diazabicylo [4.3.0]-5-nonene etc.Can add the aqueous solution that water-miscible organic solvent such as methyl alcohol, ethanol or tensio-active agent form or the various organic solvents that dissolve second composition as developing solution with an amount of in the aqueous solution of above-mentioned alkali.
Developing method can utilize paddle method, pickling process, shake appropriate means such as pickling process, spraying process.Development time is different because of the composition of composition, can be for for example about 30～120 seconds.
In addition, if at present known interlayer dielectric or the lenticular composition development time of being used to form surpasses optimum value and pattern will take place about 20～25 seconds peel off, therefore, must strictly control development time, and when using radiation sensitive resin composition of the present invention, even development time surpasses optimum development time more than 30 seconds or 30 seconds, also can form good pattern, have the advantage of supervision of construction aspect.
(4) operation of the heating of the tunicle after will developing
After having carried out operation (3) as mentioned above, the tunicle that has formed pattern preferably cleans by for example flowing water and carries out the rinsing processing, preferably utilize comprehensive irradiation radioactive rays (post-exposure) such as high pressure mercury vapour lamp again, thus with in this tunicle remaining 1, the 2-quinone di-azido compound carries out disaggregating treatment, then this tunicle is utilized heating units such as hot-plate, baking oven to carry out heat treated (back baking processing).By this processing, when cured film is interlayer dielectric, tunicle has been carried out solidification treatment, and when cured film was microlens, the tunicle of pattern-like formed melt and forms lens shape.
Exposure in the above-mentioned post-exposure operation is preferably 2,000～5,000J/m 2Heating temperature in the solidification treatment is for example 120～250 ℃.Heat-up time is different because of the kind of heating installation, when for example carrying out heat treated on hot-plate, can be set at for example 5～30 minutes, when carrying out heat treated in baking oven, can be set at for example 30～90 minutes.At this moment, also can adopt the segmentation of carrying out heating process more than 2 times or 2 times to bake method etc.
Thus, can form corresponding to target interlayer dielectric or lenticular pattern-like tunicle at substrate surface.
＜use the 3rd or the 4th composition to form the method for protective membrane 〉
Use the 3rd or the 4th composition to form the method for protective membrane, carry out following operation (1) and (2) according to order as described below.
(1) operation of the tunicle of formation the 3rd or the 4th composition on substrate.
(2) operation that above-mentioned tunicle is heated.
(1) operation of the tunicle of formation the 3rd or the 4th composition on substrate
At first, the 3rd or the 4th composition solution is coated on the substrate, forms tunicle except that desolvating by carrying out prebake conditions.
As at this operable substrate, can use the substrate that constitutes by for example glass, quartz, silicon, transparent resin etc.Above-mentioned transparent resin for example has: the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, cyclic olefin or its hydride etc.
Coating process for example can adopt: appropriate means such as spraying method, rolling method, method of spin coating, excellent coating method, ink-jet application method, can particularly suitable use the coating of spinner, ス ピ Application レ ス (registered trademark) spreader, slit die spreader.
The condition of above-mentioned prebake conditions is different because of the kind of each composition, cooperation ratio etc., is carrying out about 1～15 minute under 70～90 ℃ but for example be preferably.
(2) operation that above-mentioned tunicle is heated
Then, carry out heat treated, can form the protection of goal film by tunicle to above-mentioned formation.Treatment temp during heat treated is preferably about 150～250 ℃, and in addition, when using hot-plate as heating unit, the treatment time was preferably about 5～30 minutes, when using baking oven, was preferably about 30～90 minutes.
In addition, when the 3rd or the 4th composition contains the radiation-sensitive acid-producing agent, preferably after prebake conditions, carry out radiation exposure before the heating process and handle (exposure-processed).The radioactive rays that are used for this exposure-processed can adopt for example visible light, ultraviolet ray, far ultraviolet rays yue, electron rays, X ray etc., preferably comprise the ultraviolet ray that wavelength is the light of 190～450nm.Exposure is preferably 100～20,000J/m 2, more preferably 150～10,000J/m 2
The thickness of the protective membrane of Xing Chenging is preferably 0.1～8 μ m like this, more preferably 0.1～6 μ m, more preferably 0.1～4 μ m.Wherein, when forming protective membrane on the substrate with difference of altitude of colored filter, above-mentioned thickness is meant the thickness of starting at from the topmost of colored filter.
＜use the 5th composition to form the method for protective membrane 〉
Use the 5th composition to form the method for protective membrane, carry out following operation (1)～(3) according to order as described below.
(1) with first liquid and the second liquid blended operation of the 5th composition.
(2) operation of the tunicle of the above-mentioned mixed solution of formation on substrate.
(3) operation that above-mentioned tunicle is heated.
(1) with first liquid and the second liquid blended operation of the 5th composition
At first, first liquid and second liquid preparation coating composition solution that mix the 5th composition.As for the blending ratio of first liquid and second liquid, (A ') polymkeric substance 100 weight parts contained with respect to first liquid, the amount of (F) solidifying agent that second liquid contains is preferably 20～60 weight parts, more preferably 20～50 weight parts.
After mixing first liquid and second liquid and being mixed with composition solution, preferably in 24 hours, offer subsequent processing (2).
(2) operation of the tunicle of the above-mentioned mixed solution of formation on substrate
(3) operation that above-mentioned tunicle is heated
Above-mentioned operation (2) and operation (3) can be carried out with " (1) forms the operation of the tunicle of the 3rd or the 4th composition on substrate " and " (2) are with the operation of above-mentioned tunicle heating " the same mode in above-mentioned " using the 3rd or the 4th composition to form the method for protective membrane " respectively.
By embodiment described later as can be known, in fact all do not produce sublimate in the heating process (sintering circuit) of aforesaid method in cured film formation operation, can under the condition of cleaning, form cured film, in addition, particularly second composition has the Development margin of height in developing procedure.In addition, the cured film that obtains is for the spacer that formed by first composition time, and pattern form, compressive strength and rub resistance are good.When being the interlayer dielectric that is formed by second composition, cured film thermotolerance and solvent resistance height, specific inductivity be low, demonstrate high transmittance.When being the microlens that is formed by second composition, cured film demonstrates good melt shape (required radius-of-curvature), thermotolerance and solvent resistance height, demonstrates high transmittance.Be when forming protective membrane, cured film thermotolerance and surface hardness height, demonstrating high transmittance by the 3rd to the 5th composition, simultaneously, that the ability of the difference of altitude planarization on the basal substrate is good.
" liquid crystal display device "
When the cured film of Xing Chenging is spacer or protective membrane as mentioned above, it can be applicable to liquid crystal display device.
The liquid crystal display device that the following describes has the spacer or the protective membrane that form as mentioned above.
Method below such liquid crystal display device utilization is for example made.At first; make 2 substrates that are formed with protective membrane or liquid crystal orientation film; make 2 substrates opposed; the centre is provided with gap (box gap (セ Le ギ ャ ッ プ)) and makes the vertical or antiparallel of liquid crystal aligning direction in separately the alignment films; the peripheral part of 2 substrates is fitted by spacer; filling liquid crystal in the box gap that surface and spacer by substrate form, the sealing filling orifice constitutes liquid crystal cell.Then, at the outside surface of liquid crystal cell, promptly constitute the another side applying polarization plates of each substrate of liquid crystal cell, make the liquid crystal aligning direction of its polarization direction and the protective membrane that on the one side of this substrate, forms consistent or vertical, thereby obtain liquid crystal display device.
Above-mentioned liquid crystal can be enumerated nematic liquid crystal, smectic liquid crystal.Wherein, preferred nematic liquid crystal can use for example Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, biphenyl cyclohexanes liquid crystal, miazines liquid crystal, two  alkanes liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition, in these liquid crystal, also can add cholesteryl liquid crystal such as cholest-muriate (コ レ ス チ Le Network ロ ラ ィ De), cholesteryl nonanoate (コ レ ス テ リ Le ノ Na ェ one ト), cholesteryl carbonate for example or wait and use with the chiral reagent of trade(brand)name " C-15 ", " CB-15 " sale such as (メ Le Network corporate systems).In addition, also can use oxygen base benzylidene-in the last of the ten Heavenly stems strong dielectricity liquid crystal such as amino-2-methyl butyl laurate.
As the polarization plates that is used for the liquid crystal cell outside, can enumerate: will on one side polyvinyl alcohol be stretched and make its orientation, Yi Bian the polarization plates that its polarizing coating that is called the H film that absorbs iodine is clamped with the rhodia protective membrane; Or the polarization plates that itself constitutes by the H film etc.
Embodiment
Below, by illustration synthesis example, embodiment, the present invention is described more specifically, but the present invention is not limited to the following examples.
Measure the gel permeation chromatography of synthetic polymkeric substance in the synthesis example of following polymkeric substance under the following conditions, obtain polystyrene conversion weight-average molecular weight (Mw) and number-average molecular weight (Mn).
Device: GPC-101 (clear and electrician's (strain) system)
Post: with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (above is clear and electrician's (strain) system) series connection
Moving phase: the tetrahydrofuran (THF) that contains 0.5 weight % phosphoric acid
(I) preparation of first composition and evaluation
The synthesis example of polymkeric substance
Synthesis example 1
In flask, add 2 with prolong, agitator, 2 '-Diisopropyl azodicarboxylate, 2 weight parts, as compound 3 weight parts and diethylene glycol dimethyl ether 200 weight parts of the expression of the above-mentioned formula (T-1) of molecular weight regulator, then add vinylbenzene 20 weight parts, methacrylic acid 17 weight parts, three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate 18 weight parts and glycidyl methacrylate 45 weight parts, carry out nitrogen replacement after, Yi Bian slowly stir,, keep this temperature polymerization 6 hours Yi Bian reaction soln is warming up to 80 ℃.Then, reaction soln is warming up to 100 ℃, adds 2,2 '-Diisopropyl azodicarboxylate, 1 weight part is followed polymerization 1 hour again, obtains containing each solution of the polymkeric substance shown in the table 1 (A-1) thus.The Mw of the polymkeric substance that obtains (A-1) is 11,000, and Mw/Mn is 1.4.In addition, the solid component concentration that contains the solution of polymkeric substance (A-1) is 28.4 weight %.
Synthesis example 2～20
The material that the amount shown in the table 1 of pressing is used the kind shown in the table 1 substitutes as the compound shown in the above-mentioned formula (T-1) of molecular weight regulator, in addition, operates equally with synthesis example 1.The solid component concentration of the Mw of the polymkeric substance that each synthesis example obtains and Mw/Mn and each polymers soln is as shown in table 1.
Compare synthesis example 1
Add 2 in the flask with prolong, agitator, 2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts and diethylene glycol methyl ethyl ether 220 weight parts then add vinylbenzene 20 weight parts, methacrylic acid 17 weight parts, three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate 18 weight parts and glycidyl methacrylate 45 weight parts, after carrying out nitrogen replacement, slowly stir on one side, reaction soln is warming up to 70 ℃ on one side, under this temperature, keep carrying out polymerization in 4 hours, obtain containing the polymers soln of polymkeric substance (a-1) thus.The Mw of polymkeric substance (a-1) is 13,000, and molecular weight distribution (Mw/Mn) is 2.4, and the solid component concentration of polymers soln is 29.5 weight %.
Table 1
Synthesis example Molecular weight regulator Polymkeric substance
Kind Amount (weight part) Mw Mw/Mn Solid component concentration (weight %) The polymkeric substance title
1 T-1 3 11,000 1.4 28.4 A-1
2 T-2 3 11,000 1.4 28.4 A-2
3 T-3 3 11,000 1.4 28.4 A-3
4 T-4 3 11,000 1.4 28.4 A-4
5 T-5 3 11,000 1.4 28.4 A-5
6 T-6 3 11,000 1.4 28.4 A-6
7 T-7 3 11,000 1.4 28.4 A-7
8 T-8 3 11,000 1.4 28.4 A-8
9 T-9 3 11,000 1.4 28.4 A-9
10 T-10 3 11,000 1.4 28.4 A-10
11 T-11 6 11,000 1.4 28.4 A-11
12 T-12 6 11,000 1.4 28.4 A-12
13 T-13 3 11,000 1.4 28.4 A-13
14 T-14 6 11,000 1.4 28.4 A-14
15 T-15 5 11,000 1.4 28.4 A-15
16 T-16 4 11,000 1.4 28.4 A-16
17 T-17 4 11,000 1.4 28.4 A-17
18 T-18 6 11,000 1.4 28.4 A-18
19 T-19 4 11,000 1.4 28.4 A-19
20 T-20 5 11,000 1.4 28.4 A-20
Compare synthesis example 1 Do not have - 13,000 2.4 29.5 a-1
Embodiment 1
The preparation of radiation sensitive resin composition
Will be as the solution that contains synthetic polymkeric substance (A-1) in the above-mentioned synthesis example that is equivalent to polymkeric substance (A-1) 100 weight parts (solids component) amount of (A) composition, dipentaerythritol acrylate 100 weight parts as (B) composition, as 2 of (C) composition, 2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 8 weight parts, γ-Huan Yangbingyangbingjisanjiayangjiguiwan 5 weight parts as adhesive aid, FTX-218 (trade(brand)name as tensio-active agent, (strain) ネ ォ ス system) 0.5 weight part and mix as 4-methoxyphenol 0.5 weight part of preserving stabilizer, adding the Glycol Monomethyl ether acetic ester dissolves, the solid component concentration that makes composition is 30 weight %, be the millipore filter filtration of 0.5 μ m with the aperture then, be mixed with composition solution.
The evaluation of carrying out formulated as mentioned above composition solution as described below.
The formation of spacer
On the alkali-free glass substrate with spin coater coating above-mentioned composition solution after, prebake conditions is 3 minutes on 90 ℃ hot-plate, forming thickness is the tunicle of 6.0 μ m.
Then, be 250W/m by photomask to the intensity that the tunicle that obtains shines the 365nm place with the square residual pattern of 10 μ m 210 seconds of ultraviolet ray.Then, the 0.05 weight % aqueous solution that utilizes potassium hydroxide is after developing 60 seconds under 25 ℃, with pure water washing 1 minute.Further baking after carrying out 120 minutes under 150 ℃ in baking oven forms the spacer with predetermined pattern thus.
The evaluation of resolving power
When forming pattern in above-mentioned " formation of spacer ", the average evaluation that residual pattern can be differentiated is bad (*) for good (zero), the average evaluation that can't differentiate.The resolving power of above-mentioned formulated composition is good.
The evaluation of sensitivity
Calculate the residual film ratio (thickness/initial film thickness after the development * 100 (%)) after the pattern development that obtains in above-mentioned " formation of spacer ".With this value be average evaluation more than 90% or 90% for good (zero), to be lower than 90% average evaluation be bad (*).The sensitivity of above-mentioned formulated composition is good.
The evaluation of pattern form
With the cross-sectional shape of the pattern that obtains in the sem observation above-mentioned " formation of spacer ", estimate corresponding to any of A～D shown in Figure 1 according to it.At this moment, be during if resemble A or the B pattern edge along trapezoidal or vertical configuration, can think that the pattern form of spacer is good.Relative therewith, if as figure C, insufficient sensitivity, residual film ratio is low, sectional area ratio A or B is little, when the bottom surface of cross-sectional shape is the semi-convex lensing of planar, the pattern form of spacer is bad, in addition, if as figure D, cross-sectional shape is when falling the trapezoidal shape, because the possibility that pattern is peeled off when friction treatment thereafter is very big, therefore, the pattern form of spacer also is considered to bad.
The cross-sectional shape of the spacer that is formed by above-mentioned formulated composition is B, and cross-sectional shape is good.The evaluation of compressive strength
To the pattern that obtains in above-mentioned " formation of spacer ", under 23 ℃ mensuration temperature, use slight compression trier ((strain) Shimadzu Seisakusho Ltd. system, model " MCTM-200 "), measuring and utilizing diameter is the plane pressure head of 50 μ m, the deflection when applying the 10mN load.This value is 0.5 μ m or 0.5 μ m when following, can think that compressive strength is good.
The deflection of the spacer that is formed by above-mentioned formulated composition is 0.41 μ m, and compressive strength is good.
The evaluation of rub resistance
(JSR (strain) makes with printing press coating of liquid crystalline alignment agent with the liquid crystal orientation film coating on the substrate that forms pattern as in above-mentioned " formation of spacer ", trade(brand)name " AL3046 ") after, 180 ℃ of down heating 1 hour, form heating back thickness and be the filming of alignment agent of 0.05 μ m.Then, use rubbing machine this to be filmed under as 500rpm and platform translational speed and carry out friction treatment as the 1cm/ condition of second at the rotating speed of roller with the roller that is wound with polyamide fabric.At this moment, the investigation pattern has or not wearing and tearing or peels off.
For substrate, do not observe the wearing and tearing of pattern or peel off with the pattern that forms by above-mentioned formulated composition.
The evaluation of adaptation
Except the mask that does not use residual pattern, all the other are to operate the formation cured film with above-mentioned " formation of spacer " same mode.Utilize in the tack test of JIS K-5400 (1900) 8.5 8.52 checker band method (Acer Disk order テ one プ method at this), estimate the adaptation of the cured film that forms.Residual checker number is 100 in 100 checkers.
The evaluation of sublimate
On the silicon substrate with spin coater coating above-mentioned composition solution after, under 90 ℃ on hot-plate prebake conditions 2 minutes, forming thickness is filming of 3.0 μ m.Use Canon (strain) system exposure machine (model " PLA-501F ", extra-high-pressure mercury vapour lamp) exposes to filming of obtaining, and making the accumulative total irradiation dose is 3,000J/m 2, the substrate after the exposure was heated 1 hour down at 220 ℃ in cleaning oven (clean oven), obtain cured film.Above the cured film that obtains, reserve 1 centimetre interval, cooling is installed uses empty silicon wafer, in the heat treated of under 230 ℃, carrying out 1 hour on the hot-plate.Do not change cooling with empty silicon wafer (ベ ァ シ リ コ Application ゥ ェ Ha), handle continuously 20 carry out above-mentioned same operation and formed the silicon substrate of cured film in addition after, detecting by an unaided eye has or not the sublimate that is attached to the sky silicon wafer, results verification does not have sublimate.Embodiment 2～20 and comparative example 1
In " preparation of radiation sensitive resin composition " of the foregoing description 1, use (A), (B) of kind shown in the table 2 and amount and (C) composition respectively, in addition, all the other operate compositions formulated similarly to Example 1, estimate.Evaluation result is as shown in table 3.
In addition, in table 2, represent that the abbreviation of each composition is defined as follows respectively.When the kind of composition and amount linked with "/", expression used a plurality of kinds as its composition by the described amount of table respectively.In addition, the composition on this hurdle is not used in the expression of "-" in the table.
(B) composition
B-1: dipentaerythritol acrylate
(C) composition
C-1:2,2 '-two (2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl di-imidazoles (biimidazole)
C-2:2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl di-imidazoles
C-3:2-methyl [4-(methylthio group) phenyl]-2-morpholinyl-1-acetone
C-4:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1
The sensitizing agent of radioactive rays sensitivity
H-1:4,4 '-two (dimethylamino) benzophenone
The H-2:2-mercaptobenzothiazole
H-3: tetramethylolmethane four (mercaptoacetate)
Table 2
(A) composition (B) composition (C) composition The sensitizing agent of radioactive rays sensitivity
Kind Amount (weight part) Kind Amount (weight part) Kind Amount (weight part) Kind Amount (weight part)
Embodiment 1 A-1 100 B-1 100 C-1 8 - -
Embodiment 2 A-2 100 B-1 100 C-1/C-3 5/20 H-1/H-2/H-3 5/5/2.5
Embodiment 3 A-3 100 B-1 100 C-1/C-4 10/15 - -
Embodiment 4 A-4 100 B-1 100 C-1/C-3/C-4 5/10/10 - -
Embodiment 5 A-5 100 B-1 100 C-1 5 H-1/H-2/H-3 5/5/2.5
Embodiment 6 A-6 100 B-1 100 C-1/C-3 3/25 - -
Embodiment 7 A-7 100 B-1 100 C-1/C-4 5/20 H-1/H-2/H-3 5/5/2.5
Embodiment 8 A-8 100 B-1 100 C-1/C-3/C-4 5/10/10 H-1/H-2/H-3 5/5/2.5
Embodiment 9 A-9 100 B-1 100 C-1/C-2/C-3 4/1/20 H-1/H-2/H-3 6/6/3
Embodiment 10 A-10 100 B-1 100 C-1 7 H-1/H-2/H-3 6/6/3
Embodiment 11 A-11 100 B-1 100 C-1 8 - -
Embodiment 12 A-12 100 B-1 100 C-1/C-3 5/20 H-1/H-2/H-3 5/5/2.5
Embodiment 13 A-13 100 B-1 100 C-1 8 - -
Embodiment 14 A-14 100 B-1 100 C-1/C-3 5/20 H-1/H-2/H-3 5/5/2.5
Embodiment 15 A-15 100 B-1 100 C-1/C-3 5/20 H-1/H-2/H-3 5/5/2.5
Embodiment 16 A-16 100 B-1 100 C-1 8 - -
Embodiment 17 A-17 100 B-1 100 C-1/C-3 5/10 - -
Table 2 (continuing)
Embodiment (A) composition (B) composition (C) composition The sensitizing agent of radioactive rays sensitivity
Kind Amount (weight part) Kind Amount (weight part) Kind Amount (weight part) Kind Amount (weight part)
Embodiment 18 A-18 100 B-1 100 C-1/C-3 5/10 - -
Embodiment 19 A-19 100 B-1 100 C-1/C-3 5/10 - -
Embodiment 20 A-20 100 B-1 100 C-1 8 - -
Comparative example 1 a-1 100 B-1 100 C-1 8 - -
Table 3
Sensitivity Resolving power Cross-sectional shape Compression testing (μ m) What rub resistance was cut down, peeled off has or not The residual checker number of adaptation (individual/100) Sublimate
Embodiment 1 ○ ○ B 0.41 Do not have 100 Do not have
Embodiment 2 ○ ○ B 0.42 Do not have 100 Do not have
Embodiment 3 ○ ○ A 0.32 Do not have 100 Do not have
Embodiment 4 ○ ○ A 0.32 Do not have 100 Do not have
Embodiment 5 ○ ○ B 0.38 Do not have 100 Do not have
Embodiment 6 ○ ○ B 0.32 Do not have 100 Do not have
Embodiment 7 ○ ○ A 0.25 Do not have 100 Do not have
Embodiment 8 ○ ○ A 0.27 Do not have 100 Do not have
Embodiment 9 ○ ○ A 0.28 Do not have 100 Do not have
Embodiment 10 ○ ○ A 0.28 Do not have 100 Do not have
Embodiment 11 ○ ○ B 0.32 Do not have 100 Do not have
Embodiment 12 ○ ○ B 0.33 Do not have 100 Do not have
Embodiment 13 ○ ○ A 0.29 Do not have 100 Do not have
Embodiment 14 ○ ○ A 0.31 Do not have 100 Do not have
Embodiment 15 ○ ○ B 0.32 Do not have 100 Do not have
Embodiment 16 ○ ○ B 0.33 Do not have 100 Do not have
Embodiment 17 ○ ○ A 0.29 Do not have 100 Do not have
Embodiment 18 ○ ○ A 0.31 Do not have 100 Do not have
Table 3 (continuing)
Sensitivity Resolving power Cross-sectional shape Compression testing (μ m) What rub resistance was cut down, peeled off has or not The residual checker number of adaptation (individual/100) Sublimate
Embodiment 19 ○ ○ A 0.29 Do not have 100 Do not have
Embodiment 20 ○ ○ A 0.31 Do not have 100 Do not have
Comparative example 1 × ○ C 0.57 Have 80 Have
(II) preparation of second composition and evaluation
The synthesis example of polymkeric substance
Synthesis example 21
In flask with prolong, agitator, add 2,2 '-Diisopropyl azodicarboxylate, 2 weight parts, as compound 3 weight parts and diethylene glycol dimethyl ether 200 weight parts of the expression of the above-mentioned formula (T-1) of molecular weight regulator, then add vinylbenzene 20 weight parts, methacrylic acid 20 weight parts, three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate 20 weight parts, glycidyl methacrylate 40 weight parts, carry out nitrogen replacement after, Yi Bian slowly stir,, keep this temperature polymerization 6 hours Yi Bian reaction soln is warming up to 80 ℃.Then, reaction soln is warming up to 100 ℃, adds 2 again, 2 '-Diisopropyl azodicarboxylate, 1 weight part is followed polymerization 1 hour again, obtains containing the solution of polymkeric substance (A-21) thus.The Mw of the polymkeric substance that obtains (A-21) is 10,000, and Mw/Mn is 1.4.In addition, the solid component concentration that contains the solution of polymkeric substance (A-21) is 29.8 weight %.
Synthesis example 22～40
The material that the amount shown in the table 4 of pressing is used the kind shown in the table 4 substitutes the compound of above-mentioned formula (T-1) expression as molecular weight regulator, in addition, operates equally with synthesis example 21.The solid component concentration of the Mw of the polymkeric substance that each synthesis example obtains and Mw/Mn and each polymers soln is as shown in table 4.
Compare synthesis example 2
In flask, add 2, two (2, the 4-methyl pentane nitrile) 8 weight parts of 2 '-azo and vinylbenzene 20 weight parts, methacrylic acid 20 weight parts, three ring [5.2.1.0 with prolong, agitator 2,6] decane-8-ylmethyl acrylate 20 weight parts, glycidyl methacrylate 40 weight parts, carry out nitrogen replacement after, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept this temperature 5 hours, obtain containing the polymers soln of polymkeric substance (a-2).
The Mw of polymkeric substance (a-2) is 14,000, and Mw/Mn is 2.4.In addition, residual monomer is 5.8 weight %, is 29.5 weight % at the solid component concentration of this polymers soln that obtains.
Table 4
Synthesis example Molecular weight regulator Polymkeric substance
Kind Amount (weight part) Mw Mw/Mn Solid component concentration (weight %) The polymkeric substance title
21 T-1 3 10,000 1.4 29.8 A-21
22 T-2 3 10,000 1.4 29.8 A-22
23 T-3 3 10,000 1.4 29.8 A-23
24 T-4 3 10,000 1.4 29.8 A-24
25 T-5 3 10,000 1.4 29.8 A-25
26 T-6 3 10,000 1.4 29.8 A-26
27 T-7 3 10,000 1.4 29.8 A-27
28 T-8 3 10,000 1.4 29.8 A-28
29 T-9 3 10,000 1.4 29.8 A-29
30 T-10 3 10,000 1.4 29.8 A-30
31 T-11 6 10,000 1.4 29.8 A-31
32 T-12 6 10,000 1.4 29.8 A-32
33 T-13 3 10,000 1.4 29.8 A-33
34 T-14 6 10,000 1.4 29.8 A-34
35 T-15 5 10,000 1.4 29.8 A-35
36 T-16 4 10,000 1.4 29.8 A-36
37 T-17 4 10,000 1.4 29.8 A-37
38 T-18 6 10,000 1.4 29.8 A-38
39 T-19 4 10,000 1.4 29.8 A-39
40 T-20 5 10,000 1.4 29.8 A-40
Compare synthesis example 2 Do not have - 14,000 2.4 29.5 a-2
Embodiment 21
The preparation of radiation sensitive resin composition
Will be as the solution that contains synthetic polymkeric substance (A-21) in the above-mentioned synthesis example that is equivalent to polymkeric substance (A-1) 100 weight parts (solids component) amount of (A) composition with as 4 of (D) composition, 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] two phthaleins (1.0 moles) and 1, condenses (D-1) 30 weight parts of 2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE (2.0 moles) mix, adding Diethylene Glycol ethyl-methyl ether dissolves, making its solid component concentration is 30 weight %, membrane filter with aperture 0.2 μ m filters then, is mixed with composition solution.
The performance evaluation of interlayer dielectric
Use the radiation sensitive resin composition of preparation as mentioned above, the various characteristics of evaluation interlayer dielectric as described below.
The evaluation of sensitivity
On silicon substrate, be coated with the radiation sensitive resin composition of above-mentioned preparation with spin coater, under 90 ℃ on hot-plate prebake conditions 2 minutes, forming thickness is filming of 3.0 μ m.By having the pattern mask of predetermined pattern, with Canon (strain) system PLA-501F exposure machine (extra-high-pressure mercury vapour lamp), filming of obtaining changed after the time shutter exposes, with concentration be the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight % by the paddle method 25 ℃ of developments 90 seconds down.Cleaned 1 minute with ultrapure water flowing water, carry out drying, on silicon substrate, form pattern.At this moment, investigation is dissolved needed exposure fully with the line of 3.0 μ m and the intermittent pattern at interval (ラ ィ Application ァ Application De ス ペ one ス) (10 pairs 1).With this value is that sensitivity is estimated, and the result is 550J/m 2This value is 1,000J/m 2Or 1,000J/m 2When following, can think that sensitivity is good.
The evaluation of Development margin
On silicon substrate, be coated with the radiation sensitive resin composition of above-mentioned preparation with spin coater, under 90 ℃ on hot-plate prebake conditions 2 minutes, forming thickness is filming of 3.0 μ m.The line by having 3.0 μ m and the mask of the pattern of (10 pairs 1) at interval, use Canon (strain) system PLA-501F exposure machine (extra-high-pressure mercury vapour lamp), the exposure of the value of the sensitivity of mensuration in film above-mentioned to be equivalent to " evaluation of sensitivity " that obtain is exposed.Then, working concentration is the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight %, is that variable develops under 25 ℃ with the paddle method with the development time.Then, cleaned 1 minute, make its drying, on thin slice, form pattern with ultrapure water flowing water.At this moment, be that optimum development time is investigated so that the live width of line is the needed development time of 3 μ m, the result is 60 seconds.In addition, when surpassing this optimum development time and also continuing to develop, the time till peeling off with the line pattern to 3.0 μ m is that Development margin is measured, and the result is 30 seconds.This value is more than 30 seconds or 30 seconds the time, can think that Development margin is good.The evaluation of solvent resistance
On silicon substrate, be coated with the radiation sensitive resin composition of above-mentioned preparation with spin coater, under 90 ℃ on hot-plate prebake conditions 2 minutes, forming thickness is filming of 3.0 μ m.Exposure machine (model " PLA-501F ", (extra-high-pressure mercury vapour lamp)) with Canon (strain) system exposes to filming of obtaining, and the accumulative total irradiation dose is 3,000J/m 2Silicon substrate in cleaning oven after 220 ℃ heating exposes down 1 hour obtains cured film.The thickness of the cured film that mensuration obtains (T1), the result is 2.3 μ m.The silicon substrate that has formed this cured film was immersed in the methyl-sulphoxide that temperature is controlled at 70 ℃ after 20 minutes, measures the thickness (t1) of this cured film, calculate the Thickness Variation rate that causes because of dipping | t1-T1|/T1} * 100 (%), result are 0.1%.This value is 5% or 5% when following, can think that solvent resistance is good.
In addition, because the film that forms does not need composition, therefore, omit radiation exposure operation and developing procedure in the evaluation of solvent resistance, only film formation operation, back roasting procedure and heating process promptly supply in evaluation.
Stable on heating evaluation
Operate the formation cured film equally with the evaluation of above-mentioned solvent resistance, measure the thickness (T2) of the cured film that obtains, the result is 2.3 μ m.Then, the substrate with this cured film after 1 hour, is measured the thickness (t2) of this cured film at 240 ℃ of following rebake in cleaning oven, calculate the Thickness Variation rate that causes because of rebake | t2-T2|/T2} * 100 (%), result are 0%.This value is 5% or 5% when following, can think that thermotolerance is good.
The evaluation of the transparency
In above-mentioned stable on heating evaluation, use glass substrate " コ one ニ Application グ 7059 " (コ one ニ Application グ corporate system) to replace silicon substrate, in addition, operate equally, on glass substrate, form cured film.With spectrophotometer " 150-20 type ダ Block Le PVC one system ((strain) Hitachi system) ", filling does not have the コ one ニ Application グ 7059 of film in the control sides cup, measures the transmittance of the glass substrate with this cured film under the wavelength of 400～800nm scope.Investigate the value of minimum light transmission rate at this moment, the result is 92%.This value is 90% or 90% when above, can think that the transparency is good.
The evaluation of specific inductivity
On polished SUS304 system substrate, be coated with the radiation sensitive resin composition of above-mentioned preparation with spin coater, prebake conditions is 2 minutes on 90 ℃ hot-plate, and forming thickness is filming of 3.0 μ m.Exposure machine (extra-high-pressure mercury vapour lamp) with the model " PLA-501F " of Canon (strain) system), filming of obtaining exposed, making the accumulative total irradiation dose is 3,000J/m 2, in cleaning oven, heated this substrate 1 hour down at 220 ℃, obtain cured film thus.
On this cured film, utilize vapour deposition method to form the Pt/Pd electrode pattern, make the specific inductivity test sample.Use Yokogawa ヒ ュ one レ ッ ト パ ッ カ one De (strain) system HP16451B electrode and the accurate LCR tester of HP4284A, the specific inductivity of substrate when utilizing the CV method to measure frequency for 10kHz, specific inductivity is 3.3 as a result.This value is 3.6 or 3.6 when following, can think that specific inductivity is good.
In addition, in the evaluation of specific inductivity, because the film that forms does not need composition, therefore, omit radiation exposure operation and developing procedure, only film formation operation, back roasting procedure and heating process promptly supply in evaluation.
The evaluation of sublimate
Use the radiation sensitive resin composition and the embodiment 1 same operation of above-mentioned preparation to estimate, confirm not have sublimate.
Embodiment 22～32 and comparative example 2
For (A) composition among the embodiment 21 and (D) composition, use the kind shown in the table 5, amount respectively, in addition, all the other and embodiment 21 same operation preparation radiation sensitive resin compositions are estimated.Evaluation result is as shown in table 6.
In addition, in embodiment 32, preparation is during radiation sensitive resin composition, except (A) composition shown in the table 5 with (D) the composition, further add siloxane type surfactants " SH-28PA " (trade(brand)name, eastern レ ダ ゥ コ one ニ Application グ シ リ コ one Application (strain) system) 0.01 weight part.In addition, in embodiment 32, on substrate, form when filming, utilize the coating method that uses the slit die spreader to replace spin-coating method.
In the table 5, the abbreviation of composition is defined as follows respectively.
(D) composition
(D-1): 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condenses of 2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE (2.0 moles)
(D-2): 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condenses of 2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE (1.0 moles)
(D-3): 2,3,4,4 '-tetrahydroxybenzophenone (1.0 moles) and 1,2-naphthoquinones two nitrine-5-sulphonate (2.44 moles)
(D-4): 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condenses of 2-naphthoquinones two nitrine-4-SULPHURYL CHLORIDE (2.0 moles)
Table 5
(A) composition (D) composition
Kind Amount (weight part) Kind Amount (weight part)
Embodiment 21 A-21 100 D-1 30
Embodiment 22 A-22 100 D-1 30
Embodiment 23 A-23 100 D-1 30
Embodiment 24 A-24 100 D-1 30
Embodiment 25 A-25 100 D-2 25
Embodiment 26 A-26 100 D-3 25
Embodiment 27 A-27 100 D-4 25
Embodiment 28 A-28 100 D-1 30
Embodiment 29 A-29 100 D-1 30
Embodiment 30 A-30 100 D-1 30
Embodiment 31 A-31 100 D-1 30
Embodiment 32 A-32 100 D-1 30
Comparative example 2 a-2 100 D-1 30
Table 6
Sensitivity (J/m 2) Development margin Solvent resistance Thermotolerance The transparency (%) Specific inductivity Sublimate
Optimum development time (second) Development margin (second) Solidify back thickness (μ m) Thickness Variation rate (%) Solidify back thickness (μ m) Thickness Variation rate (%)
Embodiment 21 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 22 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 23 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 24 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 25 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 26 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 27 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 28 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 29 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 30 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 31 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Embodiment 32 550 60 30 2.3 0.1 2.3 0 92 3.3 Do not have
Comparative example 2 700 60 15 2.3 3.8 2.3 0 92 3.3 Have
Embodiment 33
The preparation of radiation sensitive resin composition
Will be as the solution that contains synthetic polymkeric substance (A-33) in the above-mentioned synthesis example of the amount that is equivalent to 100 parts by weight polymer (A-33) (solids component) of (A) composition with as 4 of (D) composition, 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, condenses (D-1) 30 weight parts of 2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE (2.0 moles) mix, be dissolved in Diethylene Glycol ethyl-methyl ether, making solid component concentration is 30 weight %, then, with the aperture is the membrane filter filtration of 0.2 μ m, is mixed with composition solution.
Lenticular performance evaluation
Use the radiation sensitive resin composition of preparation as mentioned above, the lenticular various characteristics of evaluation as described below.
The evaluation of sensitivity
Be coated with the radiation sensitive resin composition of above-mentioned preparation on silicon substrate with spin coater, prebake conditions is 2 minutes on 90 ℃ hot-plate, and forming thickness is filming of 3.0 μ m.By having the pattern mask of predetermined pattern, with ニ コ Application (strain) system NSR1755i7A reduced projection exposure machine (NA=0.50, λ=365nm) the variation time shutter of filming that obtains is exposed is that the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight % developed 1 minute down at 25 ℃ by the paddle method with concentration.Use water rinse, carry out drying, on silicon substrate, form pattern.At this moment, investigation makes the line of 0.8 μ m and the interval live width at interval (1 pair 1) reach the necessary exposure of 0.8 μ m, is sensitivity with this value, and the result is 750J/m 2
The evaluation of Development margin
On silicon substrate, be coated with the radiation sensitive resin composition of above-mentioned preparation with spin coater, prebake conditions is 2 minutes on 90 ℃ hot-plate, and forming thickness is filming of 3.0 μ m.By having the pattern mask of predetermined pattern, use ニ コ Application (strain) system NSR1755i7A reduced projection exposure machine (NA=0.50, λ=365nm), exposure to the value of the sensitivity of mensuration in film above-mentioned to be equivalent to " evaluation of sensitivity " that obtain is exposed, working concentration is the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight %, is that variable develop with the development time with the paddle method under 25 ℃.Use water rinse, carry out drying, on silicon substrate, form pattern.So that the interval live width of the line of 0.8 μ m and intermittent pattern (1 pair 1) is that the needed development time of 0.8 μ m is an optimum development time, it is 60 seconds as a result in investigation.When surpassing this optimum development time and also continuing to develop, the time of peeling off with the pattern of wide 0.8 μ m is that Development margin is measured, and the result is 30 seconds.This value is 30 seconds or when above, can think that Development margin is good.
The evaluation of solvent resistance
Be coated with the radiation sensitive resin composition of above-mentioned preparation on silicon substrate with spin coater, prebake conditions is 2 minutes on 90 ℃ hot-plate, and forming thickness is filming of 3.0 μ m.Filming of obtaining exposed for the exposure machine (extra-high-pressure mercury vapour lamp) of " PLA-501F " with the model of Canon (strain) system, making the accumulative total irradiation dose is 3,000J/m 2, in cleaning oven, heated this silicon substrate 1 hour down at 220 ℃, obtain cured film.Being determined at the thickness (T3) of this cured film that obtains, is 2.3 μ m.The silicon substrate that will have this cured film was immersed in the Virahol that temperature is controlled at 50 ℃ after 10 minutes, measured the thickness (t3) of this cured film, calculate the Thickness Variation rate that dipping causes | t3-T3|/T3} * 100 (%) is 0.1%.This value is 5% or 5% when following, can think that solvent resistance is good.
In addition, because the film that forms does not need composition, therefore, omit radiation exposure operation and developing procedure in the evaluation of solvent resistance, only film formation operation, back roasting procedure and heating process promptly supply in evaluation.
Lenticular formation (evaluation of microlens shape)
Be coated with the radiation sensitive resin composition of above-mentioned preparation on silicon substrate with spin coater, prebake conditions is 2 minutes on 90 ℃ hot-plate, and forming thickness is filming of 3.0 μ m.By having the pattern mask of 4.0 μ m points, 2.0 μ m intermittent patterns, use ニ コ Application (strain) system NSR1755i7A reduced projection exposure machine (NA=0.50, λ=365nm) exposure of the Sensitirity va1ue of mensuration in film above-mentioned to be equivalent to " evaluation of sensitivity " that obtain is exposed, utilizing concentration is the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight %, develops 1 minute down at 25 ℃ with the paddle method.Use water rinse, carry out drying, on silicon substrate, form pattern.Then, expose with the model of Canon (strain) the system exposure machine (extra-high-pressure mercury vapour lamp) for " PLA-501F ", making the accumulative total irradiation dose is 3,000J/m 2, then, utilize hot-plate to heat 10 minutes down at 160 ℃, heated 10 minutes down at 230 ℃ again, make the molten stream formation of pattern microlens.
Measure the size (diameter) of the lenticular bottom (face that connects substrate) that forms, the result is 4.2 μ m, and its cross-sectional shape is the semi-convex lens shape shown in Fig. 2 (a).When lenticular bottom size surpasses 4.0 μ m and is lower than 5.0 μ m, when lenticular cross-sectional shape is a semi-convex lens shape shown in Fig. 2 (a), can think that microlens shape is good.When lenticular base diameter is 5.0 μ m or 5.0 μ m when above, be contact condition between the adjacent lenses, not preferred.In addition, when lenticular cross-sectional shape was a roughly trapezium-shaped shown in Fig. 2 (b), shape was bad.
The evaluation of stable on heating evaluation, the transparency and the evaluation of sublimate
These estimate with the performance evaluation of above-mentioned interlayer dielectric in the same mode of various evaluations carry out.Thickness is that 2.3 μ m, Thickness Variation rate are 0% after the curing in the thermotolerance evaluation, and the minimum light transmission rate of the scope of 400～800nm was 92% during the transparency was estimated, and in sublimate is estimated, does not observe sublimate in cooling with empty silicon wafer surface.
Embodiment 34～40 and comparative example 3
(A) composition among the embodiment 33 uses the polymkeric substance shown in the table 7 respectively, and in addition, radiation sensitive resin compositions are prepared in all the other and embodiment 33 same operations, estimate.Evaluation result is as shown in table 8.
Table 7
(A) composition
Kind Amount (weight part)
Embodiment 33 A-33 100
Embodiment 34 A-34 100
Embodiment 35 A-35 100
Embodiment 36 A-36 100
Embodiment 37 A-37 100
Embodiment 38 A-38 100
Embodiment 39 A-39 100
Embodiment 40 A-40 100
Comparative example 3 a-2 100
Table 8
Sensitivity (J/m 2) Development margin Solvent resistance Thermotolerance The transparency (%) Microlens shape Sublimate
Optimum development time (second) Development margin (second) Solidify back thickness (μ m) Thickness Variation rate (%) Solidify back thickness (μ m) Thickness Variation rate (%) Bottom size (μ m) Cross-sectional shape
Embodiment 33 750 60 30 2.3 0.1 2.3 0 92 4.2 (a) Do not have
Embodiment 34 800 60 30 2.3 0.1 2.3 0 93 4.2 (a) Do not have
Embodiment 35 750 60 30 2.3 0.1 2.3 0 92 4.2 (a) Do not have
Embodiment 36 750 60 30 2.3 0.1 2.3 0 93 4.2 (a) Do not have
Embodiment 37 800 60 30 2.3 0.1 2.3 0 93 4.2 (a) Do not have
Embodiment 38 750 60 30 2.3 0.1 2.3 0 93 4.2 (a) Do not have
Embodiment 39 800 60 30 2.3 0.1 2.3 0 93 4.2 (a) Do not have
Embodiment 40 750 60 30 2.3 0.1 2.3 0 93 4.2 (a) Do not have
Comparative example 3 900 60 15 2.3 3.8 2.3 0 92 4.4 (a) Have
(III) preparation of the 5th composition and evaluation
The synthesis example of polymkeric substance
Synthesis example 41
In flask, add 2 with prolong, agitator, 2 '-Diisopropyl azodicarboxylate, 2 weight parts, as compound 3 weight parts and diethylene glycol dimethyl ether 200 weight parts of the above-mentioned formula (T-1) of molecular weight regulator expression, then add glycidyl methacrylate 80 weight parts and vinylbenzene 20 weight parts, after carrying out nitrogen replacement, slowly stir on one side, reaction soln is warming up to 80 ℃ on one side, keeps this temperature polymerization 6 hours.Then, reaction soln is warming up to 100 ℃, adds 2 again, 2 '-Diisopropyl azodicarboxylate, 1 weight part is followed polymerization 1 hour again, obtains containing the solution of polymkeric substance (A-41) thus.Measure the Mw and the Mw/Mn of polymkeric substance (A-41), be respectively 10,500 and 1.4.In addition, the solid component concentration that contains the solution of polymkeric substance (A-41) is 28.4 weight %.
Synthesis example 42～50
The material that the amount shown in the table 9 of pressing is used the kind shown in the table 9 replaces the compound as above-mentioned formula (T-1) expression of molecular weight regulator, and in addition, all the other and synthesis example 41 are operated equally.The solid component concentration of the Mw of the polymkeric substance that each synthesis example obtains and Mw/Mn and each polymers soln is as shown in table 9.
Compare synthesis example 3
In flask, add 2 with prolong, agitator, 2 '-azo two (2, the 4-methyl pentane nitrile) 7 weight parts and diethylene glycol methyl ethyl ether 200 weight parts, then add vinylbenzene 50 weight parts and glycidyl methacrylate 50 weight parts, after carrying out nitrogen replacement, Yi Bian slowly stir, Yi Bian reaction soln is warming up to 70 ℃, keep this temperature polymerization 5 hours, obtain containing the solution of multipolymer (a-3) thus.The polystyrene conversion weight-average molecular weight (Mw) of multipolymer (a-3) is 14,000, and molecular weight distribution (Mw/Mn) is 1.8.The solid component concentration of polymers soln is 30.0 weight %.
Table 9
Synthesis example Molecular weight regulator Polymkeric substance
Kind Amount (weight part) Mw Mw/Mn Solid component concentration (weight %) The polymkeric substance title
41 T-1 3 10.500 1.4 28.4 A-41
42 T-2 3 10.500 1.4 28.4 A-42
43 T-3 3 10.500 1.4 28.4 A-43
44 T-4 3 10.500 1.4 28.4 A-44
45 T-5 3 10.500 1.4 28.4 A-45
46 T-6 3 10.500 1.4 28.4 A-46
47 T-7 3 10.500 1.4 28.4 A-47
48 T-8 3 10.500 1.4 28.4 A-48
49 T-9 3 10.500 1.4 28.4 A-49
50 T-10 3 10.500 1.4 28.4 A-50
Compare synthesis example 3 Do not have - 14.000 1.8 30.0 a-3
Embodiment 41
The preparation of binary liquid shape curable resin composition
The preparation of＜the first liquid 〉
Will be as the solution that contains the multipolymer (A-41) that obtains in the above-mentioned synthesis example 41 of the amount that is equivalent to 100 weight part multipolymer (A-41) solids components of (A ') composition, dihydroxyphenyl propane novolac epoxy resin " ェ ピ コ one ト 157S65 " (trade(brand)name as (E) composition, oiling シ ェ Le ェ Port キ シ (strain) system) 10 weight parts, mix as γ-Huan Yangbingyangbingjisanjiayangjiguiwan 15 weight parts of adhesive aid with as SH-28PA (eastern レ ダ ゥ コ one ニ Application グ シ リ コ one Application (strain) system) 0.1 weight part of tensio-active agent, further add the Glycol Monomethyl ether acetic ester, making the solid component concentration in first liquid is 20 weight %, be the millipore filter filtration of 0.5 μ m with the aperture then, be mixed with first liquid.
The preparation of＜the second liquid 〉
To be dissolved in diethylene glycol methyl ethyl ether 65 weight parts as trimellitic acid 1,2-anhydride 35 weight parts of (F) composition, be mixed with second liquid.
The preparation of＜curable resin composition 〉
Above-mentioned first liquid and second liquid are mixed, be mixed with composition solution.Said composition solution is water white.
The evaluation of curable resin composition
To the composition solution that obtains, on substrate, form protective membrane and estimate according to following method.
The formation of-protective membrane-
At SiO 2After being coated with above-mentioned composition prepared solution with spin coater on the dipping glass substrate; under 80 ℃ on hot-plate prebake conditions 5 minutes; formation is filmed, further in baking oven 230 ℃ of following heat treated 60 minutes, forming thickness on substrate is the protective membrane of 2.0 μ m.
The evaluation of-protective membrane-
The evaluation of the transparency
To having formed the SiO of protective membrane 2The dipping glass substrate, with spectrophotometer 150-20 type ダ Block Le PVC one system (Hitachi (strain) system), filling does not have the SiO of protective membrane in the control sides cup 2Flooding glass substrate, be determined at the transmittance (%) of the wavelength region of 400～800nm, is that the transparency is estimated with its minimum value, and the result is 99%.This value is 95% or 95% when above, can think that the transparency of protective membrane is good.
The evaluation of heat-resisting dimensional stability
The SiO of protective membrane will have been formed 2The dipping glass substrate heated 1 hour in 250 ℃ baking oven, measured the thickness of heating front and back, was that heat-resisting dimensional stability is estimated with the value of being calculated by following formula, and the result is 99%.This value is 95% or 95% when above, can think that heat-resisting dimensional stability is good.
The evaluation of heat-resisting dimensional stability (%)=(thickness after the heating)/(thickness before the heating) * 100 heat-resisting discolourations
The SiO of protective membrane will have been formed 2The dipping glass substrate heated 1 hour in 250 ℃ baking oven, measured the wavelength region transmittance of heating front and back at 400～800nm, estimated as heat-resisting discolouration with the value of being calculated by following formula with each minimum value, and the result is 3%.This value is 5% or 5% when following, can think that heat-resisting discolouration is good.
Heat-resisting discolouration (%)=(minimum value of the transmittance (%) before the heating)-(minimum value of the transmittance after the heating (%))
The evaluation of surface hardness
To having formed the SiO of protective membrane 2The dipping glass substrate carries out the 8.4.1 pencil scraping experiment of JISK-5400-1990, estimates, and its hardness is 6H.This evaluation result is 4H or when also harder than it, can think that surface hardness is good.
The evaluation of dynamic small hardness (the small hardness of ダ ィ Na ミ ッ Network)
With the dynamic micro-hardness tester DUH-201 in Tianjin, island ((strain) Shimadzu Seisakusho Ltd. system) to having formed the SiO of protective membrane 2The dipping glass substrate carries out 115 ° of triangle pressure heads of corner angle (ヘ Le コ PVC ッ チ type) indentation test, under the condition of loading 0.1gf, speed 0.0145gf/ second, 5 seconds hold-times, making temperature be 23 ℃ and 140 ℃ and estimate, is 29 in the time of 23 ℃, is 25 in the time of 140 ℃.
The evaluation of adaptation
To having formed the SiO of protective membrane 2After the dipping glass substrate carries out pressure kettle test (プ レ ッ シ ャ one Network ッ カ one) (temperature is 120 ℃, and humidity is 100%, measures 24 hours), utilize the 8.5.3 tack checker band method of JISK-5400-1990, estimate and SiO 2The adaptation of dipping glass substrate, 100 in 100 of the checkers are whole residual as a result.
In addition, except using the Cr substrate to replace SiO 2Beyond the dipping glass substrate, other and above-mentioned " formation of protective membrane " same operation, the formation thickness is the protective membrane of 2.0 μ m, and with the adaptation of above-mentioned same evaluation and Cr substrate, 100 in 100 checkers are whole residual as a result.
The evaluation of-planarization performance-
At SiO 2Utilize spin coater coating pigment class colored photoresist material (カ ラ one レ ジ ス ト) (trade(brand)name " JCR RED 689 ", " JCR GREEN 706 " and " CR8200B " on the dipping glass substrate respectively; More than be JSR (strain) system), under 90 ℃ on hot-plate prebake conditions 150 seconds, formation is filmed.Then, use exposure machine Canon PLA501F (Canon (strain) system), by the pattern mask of regulation, carry out g/h/i ray (strength ratio of wavelength 436nm, 405nm and 365nm=2.7: 2.5: 4.8) exposure, it is 2 that its exposure is scaled the i ray, 000J/m 2, then, develop with 0.05% potassium hydroxide aqueous solution, cleaned 60 seconds with ultrapure water, again in baking oven 230 ℃ of following heat treated 30 minutes, form red, green and blue 3 vitta shape colored filters (the wide 100 μ m of bar) thus.
Then, use surfaceness meter α-step (ケ one ェ Le ェ one テ Application コ one Le (strain) system), mensuration has formed the concave-convex surface of the substrate of this colored filter, it measures long 2,000 μ m, measurement range 2,000 μ m is square, the mensuration direction is the bar line short-axis direction of red, green, blue direction and red, green, blue 2 directions of whole-colored line length direction of principal axis, it is n=5 (total n=10) that the mensuration of all directions is counted, measure the mean value of the difference of height (nm) of each the highest of measuring and bottommost, the result is 1.0 μ m.
In addition; in being formed with on the substrate of colored filter with spin coater coating above-mentioned " preparation of radiation sensitive resin composition " behind the composition prepared solution with above-mentioned same operation; prebake conditions formation in 5 minutes is filmed on hot-plate under 80 ℃; again in baking oven 230 ℃ of following heat treated 60 minutes, forming apart from the thickness above the colored filter on colored filter is the protective membrane of 2.0 μ m.
Then, to the substrate that has protective membrane on this colored filter and the concave-convex surface of above-mentioned same time-and-motion study protective membrane, promptly measure the mean value of the difference of height (nm) of the highest and bottommost, the result is 200nm.When this value is 300nm or 300nm when following, can think that its planarization performance is good.
The evaluation of-sublimate-
On the silicon substrate with spin coater coating above-mentioned composition solution after, under 90 ℃ on hot-plate prebake conditions 2 minutes, forming thickness is filming of 3.0 μ m.In cleaning oven, heated this silicon substrate 1 hour down, obtain cured film at 220 ℃.Above the cured film that obtains, reserve 1 centimetre interval, cooling is installed uses empty silicon wafer, in the heat treated of under 230 ℃, carrying out 1 hour on the hot-plate.Do not change the cooling use empty silicon wafer, handle 20 silicon substrates that form above-mentioned cured film in addition continuously after, detecting by an unaided eye has or not the sublimate that is attached to the sky silicon wafer, results verification does not have sublimate.
Embodiment 42～50 and comparative example 4
For (the A ') composition of " the binary liquid shape curable resin composition " of the foregoing description 41 and (E) composition, use kind shown in the table 10 and amount respectively, use the solvent shown in the table 10 as solvent, in addition, all the other and embodiment 41 be the operation compositions formulated equally, estimate.Evaluation result is as shown in table 10.
In addition, in table 2, represent that the abbreviation of each composition is defined as follows respectively.
(E) composition
E-1: dihydroxyphenyl propane line style phenol aldehyde type epoxy resin (trade(brand)name: ェ ピ コ one ト 157S65, oiling シ ェ Le ェ Port キ シ (strain) system)
E-2: bisphenol A type epoxy resin (trade(brand)name: ェ ピ コ one ト 828, oiling シ ェ Le ェ Port キ シ (strain) system)
Solvent
S-1: Glycol Monomethyl ether acetic ester
S-2: diethylene glycol dimethyl ether
Table 10
Embodiment Composition Evaluation result
Polymkeric substance (E) composition Solvent Outward appearance The transparency (%) Heat-resisting dimensional stability (%) Heat-resisting discolouration (%) Surface hardness Dynamic small hardness Adaptation Planarization performance (nm) Sublimate
Kind Amount (weight part) Kind Amount (weight part) SiO 2 Cr
23℃ 140℃
41 A-41 100 E-1 10 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
42 A-42 100 E-1 10 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
43 A-43 100 E-2 15 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
44 A-44 100 E-2 15 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
45 A-45 100 E-1 10 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
46 A-46 100 E-1 10 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
47 A-47 100 E-1 10 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
48 A-48 100 E-1 10 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
49 A-49 100 E-1 10 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
50 A-50 100 E-1 10 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
Comparative example 4 a-3 100 E-1 10 S-1 Water white transparency 97 98 3 5H 28 24 100 100 200 Have
(IV) preparation of the 3rd composition and evaluation
Synthesizing of polymkeric substance
Synthesis example 51
In flask, add 2 with prolong, agitator, 2 '-Diisopropyl azodicarboxylate, 2 weight parts, as compound 6 weight parts and diethylene glycol dimethyl ether 200 weight parts of the expression of the above-mentioned formula (T-11) of molecular weight regulator, then add glycidyl methacrylate 50 weight parts, three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate 20 weight parts and methacrylic acid 30 weight parts, carry out nitrogen replacement after, Yi Bian slowly stir,, keep this temperature polymerization 6 hours Yi Bian reaction soln is warming up to 70 ℃.Then, reaction soln is warming up to 100 ℃, adds 2 again, 2 '-Diisopropyl azodicarboxylate, 1 weight part is followed polymerization 1 hour again, obtains containing the solution of polymkeric substance (A-51) thus.Measure the Mw of polymkeric substance (A-51) and the value of Mw/Mn, the result is respectively 9,500 and 1.4.In addition, the solid component concentration that contains the solution of polymkeric substance (A-51) is 28.4 weight %.
Synthesis example 52～60
The material that the amount shown in the table 11 of pressing is used the kind shown in the table 11 replaces the compound as above-mentioned formula (T-11) expression of molecular weight regulator, and in addition, all the other and synthesis example 51 are operated equally.The solid component concentration of the Mw of the polymkeric substance that each synthesis example obtains and Mw/Mn and each polymers soln is as shown in table 11.
Compare synthesis example 4
Add 2 in the flask with prolong, agitator, 2 '-azo two (2, the 4-methyl pentane nitrile) 6 weight parts and diethylene glycol methyl ethyl ether 200 weight parts then add glycidyl methacrylate 50 weight parts, three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate 20 weight parts and methacrylic acid 30 weight parts, after carrying out nitrogen replacement, Yi Bian slowly stir, Yi Bian reaction soln is warming up to 70 ℃, keep this temperature polymerization 5 hours, obtain containing the polymers soln of polymkeric substance (a-4) thus.The polystyrene conversion weight-average molecular weight (Mw) of polymkeric substance (a-4) is 15,000, molecular weight distribution (Mw/Mn) is 2.4, and the solid component concentration that contains the solution of polymkeric substance (a-4) is 30.5 weight %.
Table 11
Synthesis example Molecular weight regulator Polymkeric substance
Kind Amount (weight part) Mw Mw/Mn Solid component concentration (weight %) The polymkeric substance title
51 T-11 6 9.500 1.4 28.4 A-51
52 T-12 6 9.500 1.4 28.4 A-52
53 T-13 3 9.500 1.4 28.4 A-53
54 T-14 6 9.500 1.4 28.4 A-54
55 T-15 5 9.500 1.4 28.4 A-55
56 T-16 4 9.500 1.4 28.4 A-56
57 T-17 4 9.500 1.4 28.4 A-57
58 T-18 6 9.500 1.4 28.4 A-58
59 T-19 4 9.500 1.4 28.4 A-59
60 T-20 5 9.500 1.4 28.4 A-60
Compare synthesis example 4 Do not have - 15.000 2.4 30.5 a-4
Embodiment 51
The preparation of one liquid type curable resin composition
Will be as the solution that contains the polymkeric substance (A-51) that obtains in the above-mentioned synthesis example 51 of the amount that is equivalent to multipolymer (A-51) solids component 100 weight parts of (A ') composition, dihydroxyphenyl propane line style phenol aldehyde type epoxy resin (trade(brand)name: ェ ピ コ one ト 157S65 as (E) composition, oiling シ ェ Le ェ Port キ シ (strain) system) 10 weight parts, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate 1 weight part as (G) acid-producing agent, mix as γ-Huan Yangbingyangbingjisanjiayangjiguiwan 15 weight parts of adhesive aid with as SH-28PA (eastern レ ダ ゥ コ one ニ Application グ シ リ コ one Application (strain) system) 0.1 weight part of tensio-active agent, further add the Glycol Monomethyl ether acetic ester, making solid component concentration is 20%, be the millipore filter filtration of 0.5 μ m with the aperture then, be mixed with composition solution.The outward appearance of said composition solution is water white.The evaluation of one liquid type curable resin composition
A liquid type curable resin composition that uses above-mentioned preparation is as composition solution, and in addition, all the other and the foregoing description 41 same operations are estimated.The result is as shown in table 12.
Embodiment 52～60 and comparative example 5
For (the A ') composition in " preparation of a liquid type curable resin composition " of the foregoing description 51, use kind and the amount shown in the table 12, use the solvent shown in the table 12 as solvent, in addition, all the other and embodiment 51 be the operation compositions formulated equally, estimate.Evaluation result is as shown in table 12.
In addition, the abbreviation on the solvent hurdle in the table 12 is identical with the definition in the table 10.
Table 12
Embodiment Composition Evaluation result
Polymkeric substance Solvent Outward appearance The transparency (%) Heat-resisting dimensional stability (%) Heat-resisting discolouration (%) Surface hardness Dynamic small hardness Adaptation Planarization performance (nm) Sublimate
Kind Amount (weight part) SiO 2 Cr
23℃ 140℃
51 A-51 100 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
52 A-52 100 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
53 A-53 100 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
54 A-54 100 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
55 A-55 100 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
56 A-56 100 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
57 A-57 100 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
58 A-58 100 S-1 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
59 A-59 100 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
60 A-60 100 S-2 Water white transparency 99 99 3 6H 29 25 100 100 200 Do not have
Comparative example 5 a-4 100 S-1 Water white transparency 97 98 3 4H 28 24 100 100 200 Have
(V) contain the preparation and the evaluation of the composition of (A ' 1) polymkeric substance
Synthesis example 61
In flask, add 2 with prolong and agitator, 2 '-Diisopropyl azodicarboxylate, 2 weight parts, as compound 3 weight parts and diethylene glycol dimethyl ether 200 weight parts of the above-mentioned formula (T-1) of molecular weight regulator expression, then add glycidyl methacrylate 40 weight parts, methacrylic acid 1-(cyclopentyloxy) ethyl ester 40 weight parts, vinylbenzene 10 weight parts and N-cyclohexyl maleimide 10 weight parts, after carrying out nitrogen replacement, slowly begin to stir.The temperature of solution is warming up to 70 ℃, keeps this temperature after 5 hours, add 2 again, 2 '-azo two (2, the 4-methyl pentane nitrile), 2 weight parts stirred 2 hours down at 70 ℃ again, obtained the solution of multipolymer (A-61).The Mw of the multipolymer that obtains (A-61) is 8,000, and molecular weight distribution (Mw/Mn) is 1.60.
Embodiment 61
The preparation of the 4th composition and evaluation
The preparation of one liquid type curable resin composition
Will be as the solution that contains the multipolymer (A-61) that obtains in the above-mentioned synthesis example 61 of the amount of the solids component that is equivalent to 100 weight part multipolymers (A-61) of (A ') composition, dihydroxyphenyl propane line style phenol aldehyde type epoxy resin (trade(brand)name: ェ ピ コ one ト 157S65 as (E) composition, oiling シ ェ Le ェ Port キ シ (strain) system) 10 weight parts, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate 1 weight part as acid-producing agent, mix as γ-Huan Yangbingyangbingjisanjiayangjiguiwan 15 weight parts of adhesive aid with as SH-28PA (eastern レ ダ ゥ コ one ニ Application グ シ リ コ one Application (strain) system) 0.1 weight part of tensio-active agent, further add the Glycol Monomethyl ether acetic ester, making solid component concentration is 20 weight %, be the millipore filter filtration of 0.5 μ m with the aperture then, be mixed with composition solution.The outward appearance of said composition solution is water white.
The evaluation of one liquid type curable resin composition
Use a liquid type curable resin composition of above-mentioned preparation, in addition, all the other and the foregoing description 41 same operations are estimated.The result is as described below.
The transparency: 99%
Heat-resisting dimensional stability: 99%
Heat-resisting discolouration: 3%
Surface hardness: 6H
Dynamic small hardness
23℃：29
140℃：25
Adaptation
SiO 2：100
Cr：100
Planarization performance: 200nm
Sublimate: do not have

Claims (18)

1. curable resin composition, it is characterized in that, it contains (A) polymkeric substance, described (A) polymkeric substance is by carry out polymerization by active free radical polymerization in the presence of the compound of following formula (1) or following formula (2) expression, with the polystyrene conversion weight-average molecular weight (Mw) of gel permeation chromatography and the ratio (Mw/Mn) of number-average molecular weight (Mn) is below 1.7 or 1.7, and have carboxyl and Oxyranyle or oxa-cyclobutyl, wherein, formula (1) is:
Figure A2006101718070002C1
In the formula (1), p is the integer more than 1 or 1, Z 1Be hydrogen atom, carboxyl, group-R A, group-OR A, group-NR A 2, group-COOR A, group-C (=O) NR A 2, group-P (=O) R A 2, group-P (=O) (OR A) 2Or group-NR ANR A-C (=O) R A, R AIndependently for halogen atom, cyano group, hydroxyl, carbonatoms are that 1～20 alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl or carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group, R ADuring for alkyl, thiazolinyl, aryl, aralkyl or heterocyclic group, R AIn the hydrogen atom that is had one or more can be by halogen atom, cyano group, hydroxyl or carboxyl substituted;
During p=1, R 1Be hydrogen atom, cyano group, group-R B, group-OR B, group-NR B 2, group-SR B, R BIndependently for carbonatoms is that 1～20 alkyl, carbonatoms are that 3～20 1 valency alicyclic alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl or carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group, R BIn the hydrogen atom that is had one or more can be replaced by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle, wherein, and Z 1And R 1Be not hydrogen atom simultaneously;
P is 2 or 2 when above, R 1Be to remove p valency group that p hydrogen atom obtain from carbonatoms is 1～20 alkane, removes p valency group that p hydrogen atom obtain or removes the p valency group that p hydrogen atom obtains from carbonatoms is 6～20 aromatic hydrocarbons from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, one or more in the hydrogen atom that these groups had can be replaced by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle;
Formula (2) is:
Figure A2006101718070003C1
In the formula (2), m is the integer more than 2 or 2, Z 2Be from carbonatoms is 1～20 alkane, to remove m valency group that m hydrogen atom obtain, from carbonatoms is 6～20 aromatic hydrocarbons, remove m valency group that m hydrogen atom obtain or from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, remove the m valency group that m hydrogen atom obtains, in the hydrogen atom that these groups had one or more can be replaced R by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle 2Be hydrogen atom, cyano group, group-R C, group-OR C, group-NR C 2, group SR C, R CIndependently for carbonatoms is that 1～20 alkyl, carbonatoms are that 3～20 1 valency alicyclic alkyl, carbonatoms are that 2～20 thiazolinyl, carbonatoms are that 6～20 aryl, carbonatoms are that 7～20 aralkyl or carbon atom and heteroatomic total atomicity are 3～20 1 valency heterocyclic group, R CIn the hydrogen atom that is had one or more can be replaced by halogen atom, cyano group, hydroxyl, carboxyl or Oxyranyle.
2. curable resin composition as claimed in claim 1, wherein, (A) polymkeric substance has the structure that following formula (i) or following formula are (ii) represented:
Figure A2006101718070003C2
In the formula (i), Z 1Identical with the definition in the above-mentioned formula (1), formula (ii) in, Z 2Identical with m with the definition in the above-mentioned formula (2).
3. curable resin composition as claimed in claim 1 is characterized in that, it also contains (B) polymerizable unsaturated compound and (C) radiation-sensitive polymerization starter, is used to form spacer.
4. curable resin composition as claimed in claim 1 is characterized in that it also contains (D) 1, and the 2-quinone di-azido compound is used to form interlayer dielectric or microlens.
5. curable resin composition as claimed in claim 1 is characterized in that, it also contains (E) cationically polymerizable compound, is used to form protective membrane.
6. curable resin composition; it is characterized in that; it contains (A ') polymkeric substance and (E) cationically polymerizable compound; be used to form protective membrane; wherein; described (A ') polymkeric substance is by carry out polymerization by active free radical polymerization in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression; with the polystyrene conversion weight-average molecular weight (Mw) of gel permeation chromatography and the ratio (Mw/Mn) of number-average molecular weight (Mn) is below 1.7 or 1.7, and has Oxyranyle or oxa-cyclobutyl.
7. curable resin composition as claimed in claim 6, wherein, (A ') polymkeric substance has the structure that above-mentioned formula (i) or above-mentioned formula are (ii) represented.
8. as each described curable resin composition in the claim 5～7, it also contains (F) solidifying agent or (G) acid-producing agent.
9. a liquid type curable resin composition is characterized in that, it contains first liquid and second liquid, and described first liquid is each described curable resin composition in the claim 5～7, and described second liquid contains (F) solidifying agent.
10. the formation method of a spacer is characterized in that, it carries out following operation (1)～(4) according to order as described below:
(1) on substrate, form the tunicle of the described curable resin composition of claim 3 operation,
(2) to the above-mentioned tunicle of at least a portion carry out radioactive rays exposures operation,
(3) after will exposing by the operation of film development,
(4) operation of the heating of the tunicle after will developing.
11. spacer, it is formed by the described method of claim 10.
12. a liquid crystal display device is characterized in that, it comprises the described spacer of claim 11.
13. an interlayer dielectric or lenticular formation method is characterized in that, it carries out following operation (1)～(4) according to order as described below:
(1) on substrate, form the tunicle of the described curable resin composition of claim 4 operation,
(2) at least a portion of above-mentioned tunicle carry out radioactive rays exposures operation,
(3) after will exposing by the operation of film development,
(4) operation of the heating of the tunicle after will developing.
14. the interlayer dielectric or the microlens that form by the described method of claim 13.
15. the formation method of a protective membrane is characterized in that, it carries out following operation (1)～(2) according to order as described below:
(1) on substrate, forms the operation of the tunicle of each described curable resin composition in the claim 5～7.
(2) operation that above-mentioned tunicle is heated.
16. the protective membrane that forms by the described method of claim 15.
17. the formation method of a protective membrane is characterized in that, it carries out following operation (1)～(3) according to order as described below:
(1) with first liquid of the described composition of claim 9 and the second liquid blended operation,
(2) on substrate, form the tunicle of above-mentioned mixed solution operation,
(3) operation that above-mentioned tunicle is heated.
18. the protective membrane that forms by the described method of claim 17.
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