CN101153121B - 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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CN101153121B
CN101153121B CN2006101718077A CN200610171807A CN101153121B CN 101153121 B CN101153121 B CN 101153121B CN 2006101718077 A CN2006101718077 A CN 2006101718077A CN 200610171807 A CN200610171807 A CN 200610171807A CN 101153121 B CN101153121 B CN 101153121B
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acid
polymkeric substance
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ester
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CN101153121A (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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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, keep certain in order to make 2 intervals between transparency carrier; The glass sphere, baton round that use has a regulation particle diameter be the thing particle uniformly-spaced, 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 on substrate, to be coated with radiation sensitive resin composition; Mask through regulation carries out developing after the uviolizing, forms point-like or strip spacer, because the prescribed position that can only form beyond the zone at pixel forms spacer; Therefore, the problems referred to above have been solved basically.
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 hopes 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, and radiation sensitive resin composition (opening 2001-354822 communique and Te Kai 2001-343743 communique with reference to the spy) therefore is widely used.
In above-mentioned electronic unit; For example TFT type liquid crystal display device is through on above-mentioned interlayer dielectric, forming ELD; Form above that again that the operation of liquid crystal orientation film makes, so interlayer dielectric to 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, Development Trend such as high-speed responsiveization, slimming; The interlayer dielectric that this requirement is used for it forms highly sensitive with compsn, and the interlayer dielectric that requires to form has at aspects such as specific inductivity, transmittances and is higher than the performance that has film now.
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, the radiation sensitive resin composition that is widely used (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 form the various insulating films on the welding zone partly in order to remove as distribution; Protective membrane is used in coating planarization film and etching, makes public, develops with required mask, removes the erosion shield of welding zone part; Remove planarization film, various insulating film through 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 is high, transmittance is 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 stated; When forming interlayer dielectric, microlens by radiation sensitive resin composition, it is highly sensitive requiring compsn, also requires 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 that forms is high, solvent resistance is high, specific inductivity is low, transmittance is high.On this basis; When forming microlens; Except above-mentioned all performances, requirement has as lenticular good fusion shape (required radius-of-curvature), thermotolerance is high, solvent resistance is high, transmittance is high, but does not also satisfy the radiation sensitive resin composition of such requirement at present.
And the sublimate that produces when carrying out sintering being used to form interlayer dielectric, microlens may pollute production line, equipment, hopes 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; ChargeCoupled Device), CMOS (CMOS; Complementary Metal Oxide Semiconductor) etc. in the operation of light device; Because display element will carry out dip treating with solvent, acid, alkali etc., 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 to be formed at the adaptation of the layer on the protective membrane high.In addition, require protective membrane self to have following performance: level and smooth and intensity is high; Has heigh clarity; Thermotolerance and photostabilization are high, and that 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, even for the box gap that keeps liquid crystal layer, 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 existence 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, require protective membrane to have high difference of altitude planarization performance and heat-resisting withstand voltage properties with high precision.
In addition, also be employed in recent years on the protective membrane of colored filter and 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 through 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 on the TFT element, forms colored filter.And, under such technical background, the good protective membrane of performance (planarization performance) of hoping 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 is following problem: promptly in the sintering circuit that forms protective membrane by thermoset composition, produce sublimate, 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.
In the formation of colored filter with protective membrane; 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 compsn also excellent material.
Summary of the invention
The present invention is based on above-mentioned situation completion; 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 the interlayer dielectric that " Development margin (now looking like マ-ジ Application) " is big and hear resistance is high, permeability is high, dielectric constant is low; Said " Development margin " still can form the index of good pattern even be in developing procedure, to surpass optimum development time to continue to develop;
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 satisfying high transparent, high heat resistance and high surface hardness, the withstand load property 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 through a kind of; (A) curable resin composition of polymkeric substance is realized; Said; (A) polymkeric substance is through 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 RE-S061H1807720070108D000051
(in the formula (1), p is the integer more than 1 or 1, Z 1Be Wasserstoffatoms, 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, cyanic acid, 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 (ア Le ア 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 Wasserstoffatoms that is had one or more can be by halogen atom, cyanic acid, hydroxyl or carboxyl substituted;
During p=1, R 1Be Wasserstoffatoms, cyanic acid, 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 Wasserstoffatoms that is had one or more can be replaced by halogen atom, cyanic acid, hydroxyl, carboxyl or Oxyranyle, wherein, and Z 1And R 1Be not Wasserstoffatoms simultaneously;
P is 2 or 2 when above, R 1Be from carbonatoms is 1～20 alkane, to remove p valency group that p Wasserstoffatoms obtain, from carbonatoms is 6～20 aromatic hydrocarbons, remove p valency group that p Wasserstoffatoms obtain or from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, remove the p valency group that p Wasserstoffatoms obtains, one or more in the Wasserstoffatoms that these groups had can be replaced by halogen atom, cyanic acid, hydroxyl, carboxyl or Oxyranyle);
Figure RE-S061H1807720070108D000061
(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 Wasserstoffatoms obtain, from carbonatoms is 6～20 aromatic hydrocarbons, remove m valency group that m Wasserstoffatoms obtain, from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, remove the m valency group that m Wasserstoffatoms obtains; In the Wasserstoffatoms that these groups had one or more can be replaced R by halogen atom, cyanic acid, hydroxyl, carboxyl or Oxyranyle 2Be Wasserstoffatoms, cyanic acid, 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 Wasserstoffatoms that is had one or more can be replaced by halogen atom, cyanic acid, hydroxyl, carboxyl or Oxyranyle).
Above-mentioned compsn 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 through a kind of containing (A ') polymkeric substance with (E) cationically polymerizable compound; The curable resin composition that is used to form protective membrane is realized; Wherein, Said (A ') polymkeric substance is to carry out polymerization through 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 through 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 through 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 through 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 through 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 in the preferred molecule and has 2 or 2 above Oxyranyles or oxa-cyclobutyl in 2 or 2 above Oxyranyles or oxa-cyclobutyl and the polymkeric substance that is selected from least a structure in ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure (below be called " polymkeric substance (A ' 1) ") or the molecule and do not have any the multipolymer (below be called " polymkeric substance (A ' 2) ") in carboxyl, acid anhydride, ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure.
Above-mentioned ethylidene ether structure or ketal structure are meant that the acetal formation property group that is described below or ketal form the structure of property group and carbon atom bonding formation.Polymkeric substance has ethylidene ether structure or the ketal structure is meant that the acetal formation property group or the ketal formation property group that are described below directly or through keys such as carbonyls are combined in the polymkeric substance on the carbon atom in the polymkeric substance.
The functional group (below be called " acetal formation property 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 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) 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) 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) methoxyl group; (benzyl) (benzyloxy) methoxyl group; 2-tetrahydrofuran base oxygen base; 2-THP trtrahydropyranyl oxygen base etc.In these acetal formation property 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.
The functional group (below be called " ketal form property group ") that in addition, 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 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 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 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 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) and in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression, carries out the polymkeric substance that active free radical polymerization obtains; Wherein, said (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) "); Said (a2) is for containing the unsaturated compound (below be called " compound (a2) ") of Oxyranyle or oxa-cyclobutyl; Said (a3) for except that (a1) with the unsaturated compound (a2), is the unsaturated compound that do not have ethylidene ether structure, ketal structure or tert-butoxycarbonyl structure in the molecule (below be called " compound (a3) ").
For example; (A) polymkeric substance can prepare through 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 through 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, said compound (a4) is for having the unsaturated compound that is selected from least a structure in ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure (below be called " compound (a4) ") in the molecule.In addition, polymkeric substance (A ' 2) in the presence of the compound of polymerization starter and above-mentioned formula (1) or (2) expression, makes the polymerizability mixture that contains compound (a2) and compound (a3) carry out the polymkeric substance that active free radical polymerization obtains preferably in appropriate solvent.
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; Matyjaszewskiet 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 (special 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, thus the present invention accomplished, and said polymkeric substance is the polymkeric substance with ad hoc structure that obtains through 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, 2-furyl, 3-furyl, 2-tetrahydrofuran base, 3-tetrahydrofuran base, 1-pyrryl, 2-pyrryl, 3-pyrryl, 1-pyrrolidyl, 2-pyrrolidyl, 3-pyrrolidyl, pyrazol-1-yl, pyrazole-3-yl, 2-THP trtrahydropyranyl, 3-THP trtrahydropyranyl, 4-THP trtrahydropyranyl, 2-チ ア ニ Le base, 3-チ ア ニ Le base, 4-チ ア ニ Le base, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-piperidyl, 3-piperidyl, 4-piperidyl, 2-morpholinyl, morpholinyl, 2-imidazolyl, 4-imidazolyl, indoles-1-base etc.
As the Z in the above-mentioned formula (1) 1Preferred object lesson, for example can enumerate Wasserstoffatoms, cyanic acid, chlorine atom, carboxyl, dodecyl, octadecyl, oxyethyl group, butoxy carbonyl, phenyl, phenoxy, 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 1Corresponding group or same group or the atom of atom of difference.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 Wasserstoffatoms, cyanic acid, the tertiary butyl, benzyl, 2-(2-cyanic acid) 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 p valency group that p Wasserstoffatoms obtain, from carbonatoms is 6～20 aromatic hydrocarbons, removes p valency group that p Wasserstoffatoms obtain or from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, removes the p valency group that p Wasserstoffatoms obtains 1～20 the alkane; 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, THF, pyrroles, tetramethyleneimine, pyrazoles, tetrahydropyrans, チ ア 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 representes etc.
Figure RE-S061H1807720070108D000111
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 Wasserstoffatoms obtain, from carbonatoms is 6～20 aromatic hydrocarbons, removes m valency group that m Wasserstoffatoms obtain or from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, removes the m valency group that m Wasserstoffatoms obtains 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 corresponding same compound of compound of difference.
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 1Corresponding group or same group or the atom of atom of difference.
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 RE-S061H1807720070108D000131
Figure RE-S061H1807720070108D000141
Figure RE-S061H1807720070108D000151
Figure RE-S061H1807720070108D000161
These thiocarbonyl group sulphur compounds both can use separately, also can two or more be mixed and use.
To the not special restriction of the radical polymerization initiator that uses in the active free radical polymerization; 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 cpds such as (4-methoxyl group-2,4-methyl pentane nitriles); Lucidol, lauroyl peroxide, 1, organo-peroxides such as 1 '-two (t-butyl peroxy) hexanaphthene, the peroxo-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 can two or more be mixed and use.
For the solvent that uses in the active free radical polymerization, as long as the just not special restriction of living radical non-inactivation for example has: Ucar 35 one alkylether compounds such as Glycol Monomethyl ether, Ucar 35 monoethyl ether; (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, Ucar 35 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 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; ETHYLE ACETATE; N-propyl acetate; Isopropyl acetate; N-butyl acetate; Isobutyl acetate; The formic acid n-pentyl ester; Isoamyl Acetate FCC; N-butyl propionate; Ethyl n-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, YLENE;
N-Methyl pyrrolidone, N, amide compounds such as dinethylformamide, DMAC N,N etc.
In these solvents; The solvability, tunicle of considering each composition when processing curable resin composition form property etc., preferred Glycol Monomethyl ether, terepthaloyl moietie monomethyl ether acetic ester, Glycol Monomethyl ether acetic ester, Ucar 35 monoethyl ether acetic ester, dipropylene glycol methyl ether acetic ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, pimelinketone, 2-heptanone, 3-heptanone, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methyl 3-methoxyl group butyl propionic ester, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, Isoamyl Acetate FCC, n-butyl propionate, ethyl n-butyrate, isopropyl butyrate, the positive butyl ester of butyric acid, Pyruvic Acid Ethyl ester etc.
Above-mentioned solvent both can use separately, also can two or more 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) propenoate, 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) propenoate " is the notion that propenoate 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, methylacrylic 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) propenoate that two ends have the polymkeric substance of carboxyl and hydroxyl respectively has for example ω-carboxyl polycaprolactone one (methyl) propenoate 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 property, with respect to the solvability of alkaline aqueous solution and the angle consideration that obtains easily, especially preferably use vinylformic acid, methylacrylic acid, maleic anhydride.These materials both can use separately, also can make up use.
In addition, when active free radical polymerization, can, the carboxyl that utilizes proper protection base protection above-claimed cpd (a1) to have or anhydride group carry out deprotection after carrying out polymerization.
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, SY-Monomer G, α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid 3; 4-Oxyranyle butyl ester, methylacrylic acid 3; 4-Oxyranyle butyl ester, α-Yi Jibingxisuan 3; 4-Oxyranyle butyl ester, vinylformic acid 6; 7-Oxyranyle heptyl ester, methylacrylic acid 6; 7-Oxyranyle heptyl ester, α-Yi Jibingxisuan 6; 7-Oxyranyle heptyl ester, vinylformic acid Beta-methyl glycidyl ester, methylacrylic acid Beta-methyl glycidyl ester, propenoic acid beta-ethyl glycidyl ester, methylacrylic acid β-ethyl glycidyl ester, propenoic acid beta-n-propyl glycidyl ester, methylacrylic acid β-n-propyl glycidyl ester, vinylformic acid 3,4-Oxyranyle cyclohexyl, methylacrylic 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) that has an oxa-cyclobutyl has for example vinylformic acid 3-ethyl-3-oxa-ring butyl ester, methylacrylic acid 3-ethyl-3-oxa-ring butyl ester etc.
In these compounds (a2); Consider from the curing film strength aspect that copolyreaction property and raising obtain; Preferable methyl glycidyl acrylate, methylacrylic acid 6; 7-Oxyranyle heptyl ester, methylacrylic acid 3,4-Oxyranyle cyclohexyl, methylacrylic acid Beta-methyl glycidyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, methylacrylic 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, methylacrylic 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 TEB 3K, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methylacrylic acid, methacrylic tert-butyl acrylate, methylacrylic acid 2-ethylhexyl, isodecyl methacrylate, methylacrylic acid dodecyl ester, methylacrylic acid tridecyl ester, methylacrylic acid Octadecane base ester etc.;
Alkyl acrylate has for example methyl acrylate, isopropyl acrylate etc.;
The methylacrylic acid cycloalkyl ester has for example cyclohexyl methacrylate, methylacrylic acid 2-methyl cyclohexane ester, three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate, three the ring [5.2.1.0 2,6] decane-8-base oxygen base ethyl-methyl propenoate, methylacrylic acid isobornyl (イ ソ ボ ロ ニ Le) ester etc.;
Methacrylic ester with hydroxyl has for example methylacrylic acid hydroxyl methyl esters, 2-hydroxyethyl methacrylate, methylacrylic acid 3-hydroxy propyl ester, methylacrylic acid 4-hydroxyl butyl ester, Diethylene Glycol monomethyl propenoate, methylacrylic acid 2,3-dihydroxyl propyl ester, 2-methylacryoyloxyethyl glucosides (2-メ タ Network リ ロ キ シ エ チ Le グ リ コ サ イ De), methylacrylic acid 4-hydroxylphenyl ester, polyoxyethylene glycol monomethyl propenoate, W 166 monomethyl propenoate etc.;
The vinylformic acid cycloalkyl ester has for example cyclohexyl acrylate, vinylformic acid 2-methyl cyclohexyl ester, three ring [5.2.1.0 2,6] decane-8-base propenoate, 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 for example has N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimido-3-maleimide Aminobenzoate, N-succinimido-4-maleimide propalanine ester (マ レ イ ミ De Block チ レ-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, acrylic amide, USAF RH-1, vinyl-acetic ester, (methyl) tetrahydrofurfuryl acrylate etc.
Wherein, The preferred methacrylic ester that uses alkyl methacrylate, methylacrylic 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 property with respect to the deliquescent angle of alkaline aqueous solution 2,6] decane-8-ylmethyl propenoate, to methoxy styrene, vinylformic acid 2-methyl cyclohexane ester, 1,3-butadiene, polyoxyethylene glycol monomethyl propenoate, W 166 monomethyl propenoate, two ring [2.2.1] hept-2-ene"s, tetrahydrofurfuryl methacrylate.These compound things both can use separately, also can make up use.
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 that is selected from least a structure of knot in ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure (below be called " specific norbornylene compounds "), has (methyl) acryliccompound of at least a structure that is selected from ethylidene ether structure and the ketal structure (below be called " specific (methyl) acryliccompound "), (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 (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) acryliccompound 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) acryliccompound or (methyl) tert-butyl acrylate; Special preferable methyl vinylformic acid 1-ethoxy ethyl ester, methylacrylic acid 1-isobutoxy ethyl ester, methylacrylic acid 1-(cyclopentyloxy) ethyl ester, methylacrylic acid 1-(cyclohexyloxy) ethyl ester, methylacrylic 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 property are high, and 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 can two or more be mixed and use.
As stated, (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 %, and more preferably 10～40 weight % further are 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 compsn 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.Through 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 compsn 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 stated; (A) polymkeric substance that uses among the present invention or (A ') polymkeric substance obtain through 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 RE-S061H1807720070108D000231
(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).
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 of gel permeation chromatography (below be called " Mw ") and polystyrene conversion number-average molecular weight (below be called " Mn "), are preferably below 1.5 or 1.5.If Mw/Mn surpasses 1.7, the thermotolerance of the cured film that then obtains sometimes is not enough.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 compsn is not enough sometimes, and the thermotolerance of the cured film that perhaps obtains is not enough.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 or (A ') polymkeric substance preferably less than 5.0%, are more preferably less than 3.0%, especially preferably less than 2.0% with the levels of residual monomers of gel permeation chromatography.Through 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 compsn; Can other mixed with polymers of other synthetic be used, perhaps also can be when synthetic (A) polymkeric substance or (A ') polymkeric substance, through 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) compsn of radiation-sensitive polymerization starter (below be sometimes referred to as " first compsn "); Except (A) polymkeric substance, also contain (D) 1, the compsn of 2-quinone di-azido compound (1,2-キ ノ Application ジ ア ヅ De compound) (below be sometimes referred to as " second compsn "); Or except (A) polymkeric substance, also contain (E) cationically polymerizable compound compositions (below be sometimes referred to as " the 3rd compsn ").The 3rd compsn 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 compsn "); The binary liquid shape curable resin composition that perhaps contains first liquid and second liquid, said first liquid contain (A ') polymkeric substance and (E) cationically polymerizable compound, and said second liquid contains (F) solidifying agent (below be sometimes referred to as " the 5th compsn ").At this, as (A ') polymkeric substance, in the 4th compsn, be preferably above-mentioned (A ' 1) polymkeric substance or (A ' 2) polymkeric substance, in the 5th compsn, be preferably above-mentioned (A ' 2) polymkeric substance.The 4th compsn preferably also contains (F) solidifying agent or (G) acid-producing agent.
Describe successively in the face of first to the 5th compsn down.
< first compsn >
First compsn 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 compsn, can enumerate for example styrene/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/glycidyl methacrylate copolymer, styrene/methacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/SY-Monomer G/1,3-butadiene multipolymer, styrene/methacrylic acid/vinylformic acid/benzyl methacrylate/n-BMA/methylacrylic acid 3-ethyl-3-oxa-ring butyl ester multipolymer, styrene/methacrylic acid/benzyl methacrylate/tetrahydrofurfuryl methacrylate/methylacrylic acid methyl glycidyl ester copolymer etc.
In first compsn preferred preferred 2 officials of (B) polymerizable unsaturated compound that use can or 2 officials can above (methyl) propenoate.
As 2 officials ability (methyl) propenoate; 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 article of 2 functional (methyl) propenoate so for example have: ア ロ two Star Network ス M-210; ア ロ two Star Network ス M-240; ア ロ two Star 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-ト 260; PVC ス コ-ト 312; PVC ス コ-ト 335HP (above is Osaka organic chemistry industry (strain) system) etc.
3 officials can or 3 officials can for example have by above (methyl) propenoate: Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-propenoate, Dipentaerythritol five propenoate, Dipentaerythritol pentamethyl-propenoate, dipentaerythritol acrylate, Dipentaerythritol hexamethyl propenoate, three (2-acryloxy ethyl) SULPHOSUCCINIC ACID ESTER, three (2-methacryloxyethyl) SULPHOSUCCINIC ACID ESTER etc.; In addition, urethane acrylate (urethane acrylate) compounds that also has the compound that has 1 or 1 above hydroxyl and have 3～5 (methyl) acryloxies by the compound and the intramolecularly that have straight-chain alkyl-sub-and alicyclic structure and have 2 or 2 above NCOs to react to obtain etc.
3 officials can or 3 officials can be above the commercially available article of (methyl) propenoate for example have: ア ロ two Star Network ス M-309; ア ロ two Star Network ス-400; ア ロ two Star Network ス-402; ア ロ two Star Network ス-405; ア ロ two Star Network ス-450; ア ロ two Star Network ス-1310; ア ロ two Star Network ス-1600; ア ロ two Star Network ス-1960; ア ロ two Star Network ス-7100; ア ロ two Star Network ス-8030; ア ロ two Star Network ス-8060; ア ロ ニ Star Network ス-8100; ア ロ two Star Network ス-8530; ア ロ two Star Network ス-8560; ア ロ two Star Network ス-9050; ア ロ two Star 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-ト 295; PVC ス コ-ト 300; PVC ス コ-ト 360; PVC ス コ-ト GPT; PVC ス コ-ト 3PA; PVC ス コ-ト 400 (above is Osaka organic chemistry industry (strain) system); Two ユ-Off ロ Application テ イ ア 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 can two or more 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 compsn, further is 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 compsn.
(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, UVNUL MS-40,4,4 '-two dimethylaminos) UVNUL MS-40,4, benzophenones such as 4 '-two (diethylamino) UVNUL MS-40; Methyl phenyl ketone, to dimethylamino benzoylformaldoxime, 4-(α; α '-dimethoxy acetoxyl group) UVNUL MS-40,2,2 '-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 article of radiation-sensitive radical polymerization initiator for example have: 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 ヤ Le テ イ 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); SANDORAY1000 (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 can two or more 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 compsn, further is 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 compsn,, can also obtain few, the highly sensitive radiation-sensitive curable resin composition of inactivation that causes by airborne oxygen through the sensitizing agent that a kind or multiple radioactive rays are responsive and (C) radiation-sensitive polymerization starter and usefulness.
The responsive sensitizing agent of such radioactive rays for example has: N methyldiethanol amine, 4; 4 '-two (dimethylamino) UVNUL MS-40,4; 4 '-two (diethylamino) UVNUL MS-40, 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) UVNUL MS-40 or 2,4-diethyl thioxanthone.
The responsive sensitizing agent of these radioactive rays can use two or more simultaneously.
With respect to 100 weight parts (C) radiation-sensitive polymerization starter, the usage ratio of the sensitizing agent that above-mentioned radioactive rays are responsive is preferably 40 weight parts or below 40 weight parts, further is preferably 20 weight parts or below 20 weight parts.If the usage ratio of the sensitizing agent that radioactive rays are responsive 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 compsn 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, NCO, epoxy group(ing) isoreactivity functional group; Its object lesson has trimethoxysilyl phenylformic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-NCO propyl-triethoxysilicane, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan etc.
These adhesive aids can use separately, also can two or more 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, further is 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.
Any position at least of the preferred end of above-mentioned fluorine class tensio-active agent, 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, and 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 Ucar 35 two (1,1,2; 2,3,3-hexafluoro n-pentyl) ether, eight Ucar 35 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, fluoro-alkyl Supragil GN, fluoro-alkyl sodium phosphate, fluoro-alkyl carboxylic acid sodium, two glycerine four (fluoro-alkyl Soxylat A 25-7), fluoro-alkyl ammonium iodide, fluoro-alkyl trimethyl-glycine, other fluoro-alkyl Soxylat A 25-7, perfluoroalkyl poly hydroxyl ethanol (perfluoroalkylpolyoxyethanol), perfluoroalkyl alcoxylates (perfluoroalkylalkoxylate), carboxylic acid fluoroalkyl etc.
The commercially available article of fluorine class tensio-active agent for example have: BM-1000; BM-1100 (above is BM CHEMIE corporate system); メ ガ Off ア Star Network F142D; メ ガ Off ア Star Network F172; メ ガ Off ア Star Network F173; メ ガ Off ア Star Network F183; メ ガ Off ア Star Network F178; メ ガ Off ア Star Network F191; メ ガ Off ア Star Network F471; メ ガ Off ア Star Network F476 (above is big Japanese イ Application キ chemical industry (strain) system); Off ロ ラ-De FC-170C; Off ロ ラ-De-171; Off ロ ラ-De-430; Off ロ ラ-De-431 (above is Sumitomo ス リ-エ system (strain) system); サ-Off ロ Application S-112; サ-Off ロ Application S-113; サ-Off ロ Application S-131; サ-Off ロ Application S-141; サ-Off ロ Application S-145; サ-Off ロ Application S-382; サ-Off ロ Application SC-101; サ-Off ロ Application SC-102; サ-Off ロ Application SC-103; サ-Off ロ Application SC-104; サ-Off ロ Application SC-105; サ-Off ロ Application SC-106 (above is Asahi Glass (strain) system); エ Off ト Star プ EF301; エ Off ト Star プ EF303; エ Off ト Star プ EF352 (above is that new autumn fields changes into (strain) system); Off タ-ジ エ Application ト FT-100; Off タ-ジ エ Application ト FT-110; Off タ-ジ エ Application ト FT-140A; Off タ-ジ エ Application ト FT-150; Off タ-ジ エ Application ト FT-250; Off タ-ジ エ Application ト FT-251; Off タ-ヅ エ Application ト FT-300; Off タ-ジ エ Application ト FT-310; Off タ-ジ エ Application ト FT-400S; Off タ-ジ エ Application ト FTX-218; Off タ-ジ エ Application ト FTX-251 (above is (strain) ネ オ 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-レ シ リ コ-Application DC3PA, ト-レ シ リ コ-Application DC7PA, ト-レ シ リ コ-Application SH11PA, ト-レ シ リ コ-Application SH21PA, ト-レ シ リ コ-Application SH28PA, ト-レ シ リ コ-Application SH29PA, ト-レ シ リ コ-Application SH30PA, ト-レ シ リ コ-Application SH-190, ト-レ シ リ コ-Application SH-193, ト-レ シ リ コ-Application SZ-6032, ト-レ シ リ コ-Application SF-8428, ト-レ シ リ コ-Application DC-57, ト-レ シ リ コ-Application DC-190 (the above eastern レ ダ ウ コ of being-ニ Application グ シ リ コ-Application (strain) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above is the シ リ of GE Toshiba コ-Application (strain) system) etc.
In addition, as the tensio-active agent beyond above-mentioned, can enumerate: Voranol EP 2001s such as polyoxyethylene lauryl ether, T 46155 octadecyl ether, polyoxyethylene oleyl ether; T 46155 aryl ethers such as T 46155 n-octyl phenyl ether, T 46155 n-nonyl phenyl ether; Non-ionics such as T 46155 dialkyl such as T 46155 dilaurate, T 46155 SUNSOFT Q-182S, organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), (methyl) acrylic copolymer Port リ Off ロ-No.57, Port リ Off ロ-No.95 (above is common prosperity society chemistry (strain) system) etc.
These tensio-active agents can use separately, also can two or more 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, further is 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 can two or more 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, further is 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 article for example have: two カ ラ Star Network N-2702, two カ ラ Star Network MW-30M (more than be three with ケ ミ カ Le (strain) system) etc.
As above-mentioned compound with 2 or 2 above Oxyranyles; Can enumerate for example ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, triethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, dipropylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, Hydrogenated Bisphenol A 99 diglycidylether, bisphenol A diglycidyl ether etc.
Commercially available article with compound of 2 or 2 above Oxyranyles for example have: エ Port ラ イ ト 40E, エ Port ラ イ ト 100E, エ Port ラ イ ト 200E, エ Port ラ イ ト 70P, エ Port ラ イ ト 200P, エ Port ラ イ ト 400P, エ Port ラ イ ト 1500NP, エ Port ラ イ ト 80MF, エ Port ラ イ ト 100MF, エ Port ラ イ ト 1600, エ Port ラ イ ト 3002, エ Port ラ イ ト 4000 (above is common prosperity society chemistry (strain) system) etc.
These thermotolerance rising agents can use separately, also can two or more be mixed and use.
First compsn is through 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 compsn is preferably dissolved in the appropriate solvent and uses with solution state.For example; Can through 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 compsn used solvent, use uniform dissolution (A) polymkeric substance, (B) polymerizable unsaturated compound and (C) radiation-sensitive polymerization starter and each composition of 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 easy property of filming and consider preferred for example alcohol, glycol ether, terepthaloyl moietie 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, terepthaloyl moietie 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.Through 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-NMF, N; Dinethylformamide, N-methyl formyl are for aniline, N-methylacetamide, DMAC N,N, 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, DMAC N,N.
And with high boiling solvent during as the solvent of first compsn, 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 further are 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; The i.e. ratio of the total amount of (A) polymkeric substance, (B) polymerizable unsaturated compound and (C) 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 method for use of first composition solution.To narrate in the back this.
The composition solution of preparation can supply in use after using the aperture to be the filtrations such as millipore filter, membranous filter about 0.5 μ m like this.
< second compsn >
Second compsn 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 compsn, can enumerate for example methylacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/SY-Monomer G/tetrahydrofurfuryl methacrylate multipolymer, methylacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/SY-Monomer G/to vinyl benzyl glycidyl ether/tetrahydrofurfuryl methacrylate multipolymer, methylacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/SY-Monomer G/polyoxyethylene glycol monomethyl Yodo Sol GH 28, methylacrylic acid/vinylbenzene/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/SY-Monomer G/W 166 monomethyl Yodo Sol GH 28 etc.
(D) 1 that uses in second compsn; The 2-quinone di-azido compound is to produce 1 of carboxylic acid through radiation exposure; The 2-quinone di-azido compound can use phenoloid or alcohol property compound (below be called " parent nucleus ") and 1, the condenses of 2-naphthoquinones two nitrine sulfonic acid halides.
This parent nucleus for example has: trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy-UVNUL MS-40, (gathering 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-UVNUL MS-40 for example has: 2,4,6,3 ', 4 ', and 5 '-hexahydroxy-UVNUL MS-40,3,4,5,3 ', 4 ', 5 '-hexahydroxy-UVNUL MS-40 etc.;
(gathering 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, 1,1 of 2-; 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)-and 4-(4-hydroxy phenyl)-7-hydroxychroman, 2-[two { (5-sec.-propyl-4-hydroxy-2-methyl) phenyl } methyl], 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 CHLORIDEs 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 property 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 can two or more combination be used.
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 was lower than 5 weight parts, radiation exposure part was difficult to form pattern with illuminated portion not little as the poor solubility in the alkaline aqueous solution of developing solution sometimes sometimes, and 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 compsn 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, epoxy resin, adhesive aid, tensio-active agent etc. as required.
Above-mentioned (B) polymerizable unsaturated compound is identical with above-mentioned preferred constituent as first compsn.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 compsn, more preferably 30 weight parts or below 30 weight parts.
Through 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 compsn 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), benzothiazolium salt, ammonium salt 、 phosphonium 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 benzothiazolium 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 benzothiazolium salts such as 5-chloro benzothiazole hexafluoro antimonate.
Wherein, Preferred sulfonium salt or the benzothiazolium 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 article of these materials for example have: サ Application エ イ De SI-L85, サ Application エ イ De SI L110, サ Application エ イ De SI-L145, サ Application エ イ De SI-L150, サ Application エ イ 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 compsn 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 epoxy resin needs only the not influence of intermiscibility to other composition or solvent; Just not special restriction, the resin that can preferably enumerate bisphenol A type epoxy resin, phenol novolac-type epoxy resin, cresols novolac-type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hetero ring type epoxy resin, SY-Monomer G (being total to) is polymerized etc.In these materials, further preferred bisphenol A type epoxy resin, cresols novolac-type epoxy resin, glycidyl ester type epoxy resin etc.
With respect to 100 weight parts (A) polymkeric substance, the usage ratio of the epoxy resin in second compsn is preferably 30 weight parts or below 30 weight parts.Through containing epoxy resin, can further improve thermotolerance, surface hardness of the cured film that obtains etc. with such ratio.If when this ratio, then formed filming of compsn 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 " epoxy resin ", but (A) polymkeric substance is different with above-mentioned epoxy resin aspect alkaline soluble.
The adhesive aid that can contain in second compsn is identical with adhesive aid and the tensio-active agent that the first above-mentioned compsn can contain with tensio-active agent.
Second compsn is through 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 compsn is preferably dissolved in the appropriate solvent and uses with solution state.For example, can through 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 compsn, 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 with the nonreactive solvent of each composition.The solvent phase that this solvent and above-mentioned can be used for prepare first compsn 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 other composition of adding arbitrarily can be 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 %, further be preferably 15～35 weight %.
Second composition solution can supply in use after using the aperture to be the filtrations such as millipore filter, membranous filter about 0.5 μ m.
< the 3rd compsn >
The 3rd compsn 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 compsn, can enumerate for example glycidyl acrylate/vinylformic acid/three ring [5.2.1.0 2,6] decane-8-base propenoate/styrol copolymer, SY-Monomer G/methylacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/methylacrylic acid/TEB 3K/styrol copolymer, SY-Monomer G/methylacrylic acid/cyclohexyl acrylate/to methoxy styrene multipolymer, glycidyl acrylate/vinylformic acid/N-phenylmaleimide/styrol copolymer, SY-Monomer G/methylacrylic acid/N-phenylmaleimide/styrol copolymer, SY-Monomer G/methylacrylic acid/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/methylacrylic acid/three ring [5.2.1.02; 6] decane-8-ylmethyl propenoate/1; 3-butadienecopolymer, methylacrylic acid 6,7-Oxyranyle heptyl ester/methylacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/methylacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/vinylbenzene/1; 3-butadienecopolymer, methylacrylic acid 6; 7-Oxyranyle heptyl ester/vinylformic acid/maleic anhydride/styrol copolymer, methylacrylic acid 6,7-Oxyranyle heptyl ester/vinylformic acid/maleic anhydride/methacrylic tert-butyl acrylate multipolymer etc.
Wherein, further preferable methyl glycidyl acrylate/methylacrylic acid/three encircle [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/methylacrylic acid/N-phenylmaleimide/styrol copolymer, SY-Monomer G/methylacrylic acid/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/methylacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/1,3-butadiene multipolymer or SY-Monomer G/methylacrylic acid/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/vinylbenzene/1,3-butadiene multipolymer.
(E) cationically polymerizable compound that uses in the 3rd compsn is except that (A) polymkeric substance or (A ') cationically polymerizable compound the polymkeric substance.
For such (E) cationically polymerizable compound; As long as can polymerization under acidic conditions; Just not special restriction; 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.
As the object lesson of such (E) cationically polymerizable compound, described compound can be listed below.
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, 3 of 7-; 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, 1 of 4-; Two ((3-ethyl-3-oxa-cyclobutyl) methoxymethyl) ethane, 1 of 2-; 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 ((3-ethyl-3-oxa-cyclobutyl) methoxyl group) butane, 1 of 4-, two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of reaction product, Bisphenol F of two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of reaction product, Hydrogenated Bisphenol A 99 of two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of reaction product, ditrimethylolpropane four ((3-ethyl-3-oxa-cyclobutyl) methyl) ether, dihydroxyphenyl propane of reaction product, Dipentaerythritol five ((3-ethyl-3-oxa-cyclobutyl) methyl) ether and the GBL of 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, Dipentaerythritol six ((3-ethyl-3-oxa-cyclobutyl) methyl) ether and GBL and reaction product, dihydroxyphenyl propane two ((3-ethyl-3-oxa-cyclobutyl) methyl) ether and the propylene oxide of oxyethane and two ((3-ethyl-3-oxa-cyclobutyl) methyl) ethers of reaction product, Hydrogenated Bisphenol A 99 of oxyethane and propylene oxide are with the reaction product of oxyethane etc.
Intramolecularly has more than 2 or 23, and the compound of 4-Oxyranyle cyclohexyl for example has: 3, and 4-Oxyranyle cyclohexyl methyl-3 '; 4 '-Oxyranyle cyclohexane carboxylate, 2-(3,4-Oxyranyle cyclohexyl-5,5-spiral shell-3; The 4-Oxyranyle) hexanaphthene--diox (メ タ-ジ オ 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), 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 99 diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, Hydrogenated Bisphenol A 99 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;
Through such aliphatic polyol of terepthaloyl moietie, Ucar 35, glycerine and the polyglycidyl ether a kind of or polyether glycol that two or more reactions of alkylene oxide obtains;
Phenol novolac-type epoxy resin, cresols novolac-type epoxy resin, gather phenol-type epoxy resin, the such epoxy resin 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 VT 18, Oxyranyle Semen Lini wet goods.
Have the commercially available article 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: エ Port ラ イ ト 100MF (common prosperity society chemistry (strain) system), エ ピ オ-Le TMP (Japanese grease (strain) system);
Bisphenol A type epoxy resin for example has: エ ピ コ-ト 828, エ ピ コ-ト 1001, エ ピ コ-ト 1002, エ ピ コ-ト 1003, エ ピ コ-ト 1004, エ ピ コ-ト 1007, エ ピ コ-ト 1009, エ ピ コ-ト 1010 (above is oiling シ エ Le エ Port キ シ (strain) system) etc.;
Bisphenol f type epoxy resin for example has: エ ピ コ-ト 807 (oiling シ エ Le エ Port ox シ (strain) system) etc.; Phenol novolac-type epoxy resin for example has: エ ピ コ-ト 152, エ ピ コ-ト 154, エ ピ コ-ト 157S65 (the above oiling シ エ Le エ Port キ シ (strain) of being system), DPPN201, DPPN202 (above is Japanese chemical drug (strain) system) etc.;
Cresols novolac-type epoxy resin for example has: DOCN102, DOCN103S, DOCN104S, 1020,1025,1027 (above is Japanese chemical drug (strain) system), エ ピ コ-ト 180S75 (oiling シ エ Le エ Port ox シ (strain) system) etc.;
Gathering phenol-type epoxy resin for example has: エ ピ コ-ト 1032H60, エ ピ コ-ト XY-4000 (above is oiling シ エ Le エ Port キ シ (strain) system) etc.;
Cyclic aliphatic epoxy resin for example has: CY-175; CY-177; CY-179; ア ラ Le ダ イ ト CY-182; ア ラ Le ダ イ ト CY192; ア ラ Le ダ イ ト CY184 (above is チ バ ス ペ シ ヤ Le テ イ-ケ ミ カ Le ズ (strain) system); DRL-4221; DRL-4206; DRL-4234; DRL-4299 (above is the U.C.C corporate system); シ ヨ-ダ イ Application 509 (clear and electrician's (strain) system); エ ピ Network ロ Application 200; エ ピ Network ロ Application 400 (above is big Japanese イ Application キ (strain) system); エ ピ コ-ト 871; エ ピ コ-ト 872 (above is oiling シ エ Le エ Port キ シ strain formula meeting corporate system); DD-5661; DD-5662 (above is セ ラ ニ-ズ コ-テ イ Application グ (strain) system) etc.
In these (E) cationically polymerizable compounds, preferred phenol novolac-type epoxy resin, gather phenol-type epoxy resin etc.
In the present invention, (E) the cationically polymerizable compound can use separately, also can two or more be mixed and use.
For the usage ratio of (E) cationically polymerizable compound in the 3rd compsn, with respect to 100 weight parts (A) polymkeric substance, (E) usage quantity of cationically polymerizable compound is preferably 3～100 weight parts, further is preferably 5～50 weight parts.
In the 3rd compsn, the usage quantity through 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 compsn particularly.
Except above-mentioned (A) polymkeric substance with (E) the cationically polymerizable compound, the 3rd compsn preferably also contains (F) solidifying agent or (G) acid-producing agent, can contain adhesive aid, tensio-active agent etc. as required.
(F) solidifying agent that the 3rd compsn 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) (below be called " 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.The aliphatic dicarboxylic acid anhydrides for example: itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, triphenyl carbamoyl anhydride (anhydrous Suites re Cal perfect ni Hikaru acid), maleic anhydride, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, chlorendic anhydride (anhydrous tension イ mini boots black acid) and the like;
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, UVNUL MS-40 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 can two or more 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) propenoate, N-phenylmaleimide, N-cyclohexyl maleimide etc.These other olefines unsaturated compounds both can use separately, also can two or more 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 Yodo Sol GH 28 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 %.Through 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.Through 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 can two or more be mixed and use.
For the usage ratio of (F) solidifying agent in the 3rd compsn, 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 further is preferably 10～60 weight parts.
In the 3rd compsn, the usage quantity through making (F) solidifying agent is in above-mentioned scope, can not influence the permanent stability of compsn and further improves the flatness of the cured film that obtains.
(G) acid-producing agent that the 3rd compsn can contain preferably passes through the irradiation radioactive rays and acidic compound or the acidic compound through 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 group iodized salt, triarylsulfonium salt, Er Fang Ji phosphonium salt etc.
Above-mentioned diaryl group iodized 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 group iodized salts, 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 Er Fang Ji phosphonium salt for example has: (1-6-η-cumene) (η-cyclopentadienyl moiety) iron hexafluoro phosphonate etc.
The commercially available article of radiation-sensitive acid-producing agent can be listed below respectively: diaryl group iodized salt for example has: UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above is ユ ニ オ Application カ-バ イ De corporate system), MPI-103, BBI-103 (the above body ど り of being chemistry (strain) system) etc.;
Triarylsulfonium salt for example has: ア デ カ オ プ ト マ-SP-150; ア デ カ オ プ ト マ-SP-151; ア デ カ オ プ ト マ-SP-170; ア デ カ オ プ ト マ-SP-171(is above to be rising sun electrochemical industry (strain) system); CI-2481; CI-2624; CI-2639; CI-2064(is above to be Japanese Cao Da (strain) system); DTS-102; DTS-103; NAT-103; NDS-103; TPS-103; MDS-103(is above to be body ど り chemistry (strain) system); CD-1010; CD-1011; CD-1012(is above to be サ-ト マ-corporate system) etc.;
Two fragrant basic phosphonium salts for example have: イ Le ガ キ ユ ア-261 (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) system), PCI-061T, PCI062T, PCI-020T, PCI-022T (above is Japanese chemical drug (strain) system) etc.
In these commercially available article, UVI-6970, UVI-6974, UVI-6990, ア デ カ オ プ ト マ-SP-170, ア デ カ オ プ ト マ-SP-171, CD-1012, MPI-103 etc. are preferred because the cured film that obtains has high surface hardness.
Above-mentioned radiation-sensitive acid-producing agent both can use separately, also can two or more be mixed and use.
The thermo-sensitivity acid-producing agent that the 3rd compsn can contain can be enumerated the compound of the thermo-sensitivity acid-producing agent identical type that can contain with above-mentioned second compsn.
Usage ratio for (G) acid-producing agent in the 3rd compsn; 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 further is preferably 0.1～10 weight part.
Adhesive aid that the 3rd compsn can contain and tensio-active agent, the adhesive aid that can contain with above-mentioned first compsn 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 compsn 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 of the cured film that then obtains sometimes is not enough.In addition, with respect to 100 weight parts (A) polymkeric substance, the amount of the tensio-active agent that the 3rd compsn 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 then to hold the liability film thickness sometimes.
The 3rd compsn is through above-mentioned (A) polymkeric substance other composition uniform mixing with (E) cationically polymerizable compound and interpolation is arbitrarily prepared.The 3rd compsn is preferably dissolved in the appropriate solvent and uses with solution state.For example, can through 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.
Be used to prepare solvent use ability uniform dissolution (A) polymkeric substance and (E) cationically polymerizable compound and each composition of other composition of cooperation arbitrarily of the 3rd compsn, and and the nonreactive solvent of each composition.The solvent phase that such solvent and above-mentioned can be used for preparing first compsn with.Components in proportions beyond desolventizing in the composition solution; The i.e. ratio of the total amount of (A) polymkeric substance and (E) 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 supply in use after using the aperture to be the filtrations such as millipore filter, membranous filter about 0.5 μ m.
< the 4th compsn >
The 4th compsn contains (A ') polymkeric substance and (E) cationically polymerizable compound.The 4th compsn is preferably (A) polymkeric substance in above-mentioned the 3rd compsn is replaced to the liquid type curable resin composition that (A ') polymkeric substance obtains.
(the A ') polymkeric substance that is used for the 4th compsn 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 compsn, can enumerate for example SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2., 6] decane-8-ylmethyl propenoate/styrol copolymer; SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer; SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer; SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer; SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer; SY-Monomer G/vinylformic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/methylacrylic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/vinylformic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/methylacrylic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/1,3-butadiene multipolymer, SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/1; 3-butadienecopolymer, SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/TEB 3K/styrol copolymer, SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/TEB 3K/styrol copolymer, SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/cyclohexyl acrylate/to methoxy styrene multipolymer, SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/cyclohexyl acrylate/to methoxy styrene multipolymer, glycidyl acrylate/methacrylic tert-butyl acrylate/N-phenylmaleimide/styrol copolymer, SY-Monomer G/methacrylic tert-butyl acrylate/N-cyclohexyl maleimide/styrol copolymer, methylacrylic acid 6; 7-Oxyranyle heptyl ester/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/methacrylic tert-butyl acrylate/copolymer-maleic anhydride, methylacrylic acid 6; 7-Oxyranyle heptyl ester/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/methacrylic tert-butyl acrylate/copolymer-maleic anhydride, methylacrylic acid 6,7-Oxyranyle heptyl ester/methacrylic tert-butyl acrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, methylacrylic acid 6,7-Oxyranyle heptyl ester/methacrylic tert-butyl acrylate/maleic anhydride/styrol copolymer, SY-Monomer G/vinylformic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/vinylbenzene/1,3-butadiene multipolymer, SY-Monomer G/methylacrylic acid 1-(cyclohexyloxy) ethyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/vinylbenzene/1,3-butadiene multipolymer etc.
In these materials, further preferred: SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer, methyl propenoic acid glycidyl ester at the tenth of the twelve Earthly Branches/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-phenylmaleimide/styrol copolymer, SY-Monomer G/vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/methylacrylic acid tetrahydrochysene-2H-pyrans-2-base ester/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/vinylformic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/methylacrylic acid 1-(cyclohexyloxy) ethyl ester/N-cyclohexyl maleimide/styrol copolymer, SY-Monomer G/2,3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/, 3-two (tetrahydropyrans-2-base oxygen base carbonyl)-5-norbornylene/N-cyclohexyl maleimide/styrol copolymer or SY-Monomer G/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 compsn, for example can enumerate: glycidyl acrylate/styrol copolymer, SY-Monomer G/styrol copolymer, glycidyl acrylate/three ring [5.2.1.0 2,6] decane-8-ylmethyl Yodo Sol GH 28, SY-Monomer G/three ring [5.2.1.0 2,6] decane-8-ylmethyl Yodo Sol GH 28, methylacrylic acid 6,7-Oxyranyle heptyl ester/styrol copolymer, SY-Monomer G/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer, SY-Monomer G/N-phenylmaleimide/styrol copolymer, SY-Monomer G/N-cyclohexyl maleimide/styrol copolymer, methylacrylic acid 6,7-Oxyranyle heptyl ester/three ring [5.2.1.0 2,6] decane-8-ylmethyl Yodo Sol GH 28, methylacrylic acid 6,7-Oxyranyle heptyl ester/N-cyclohexyl maleimide/styrol copolymer etc.
In these materials, further preferred: SY-Monomer G/styrol copolymer, SY-Monomer G/three ring [5.2.1.0 2,6] decane-8-ylmethyl Yodo Sol GH 28, SY-Monomer G/three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate/styrol copolymer or SY-Monomer G/N-cyclohexyl maleimide/styrol copolymer.
Relevant the 4th compsn (A ') polymkeric substance item in addition, can the situation of above-mentioned the 3rd compsn directly be used, or on the basis of carrying out the self-evident change of those skilled in the art, use.
< the 5th compsn >
The 5th compsn is the binary liquid shape curable resin composition that contains first liquid and second liquid, and said first liquid contains (A ') polymkeric substance and (E) cationically polymerizable compound, and said second liquid contains (F) solidifying agent.First liquid of the 5th compsn does not preferably contain (F) solidifying agent and (G) acid-producing agent.
Be preferably (A ' 2) polymkeric substance at (A ') of this use polymkeric substance.(A ' 2) polymer phase that (A ' 2) polymkeric substance that first liquid of the 5th compsn can contain and above-mentioned can be used for the 4th compsn with.In addition, first liquid of the 5th compsn (E) cationically polymerizable compound that can contain is identical with above-mentioned (E) cationically polymerizable compound that can be used for the 3rd compsn.
As for the usage ratio of (E) cationically polymerizable compound in first liquid of the 5th compsn, with respect to 100 weight parts (A ' 2) polymkeric substance, (E) usage quantity of cationically polymerizable compound is preferably 3～100 weight parts, further is preferably 5～50 weight parts.
Except above-mentioned (A ' 2) polymkeric substance with (E) the cationically polymerizable compound, first liquid of the 5th compsn 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 compsn can contain with tensio-active agent.
First liquid of the 5th compsn is preferably dissolved in the appropriate solvent and uses with solution state.
The solvent that is used to prepare first liquid of the 5th compsn uses can uniform dissolution (A) polymkeric substance and each composition of (E) cationically polymerizable compound and other composition of cooperating arbitrarily, and with the nonreactive solvent of each composition.The solvent phase that said solvent and above-mentioned can be used for first preparation of compositions with.Components in proportions beyond desolventizing in the composition solution; The i.e. ratio of the total amount of (A) polymkeric substance and (E) 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 compsn can supply in use after using the aperture to be the filtrations such as millipore filter, membranous filter about 0.5 μ m.
Second liquid of the 5th compsn preferably contains the solution of (F) solidifying agent.The kind of (F) solidifying agent that contains in second liquid of the 5th compsn is identical with (F) solidifying agent that above-mentioned the 3rd compsn can contain.
The solvent phase that the solvent and above-mentioned that can be used to prepare second liquid of the 5th compsn can be used for preparing first compsn with.
(F) concentration of solidifying agent in second liquid of the 5th compsn is preferably 1～80 weight %, more preferably 10～60 weight %.
Second liquid of the 5th compsn can use aperture 0.5 μ m for about filtrations such as millipore filter, membranous filter after supply in use.
" the formation method of cured film "
Below, the method for using above-mentioned first to the 5th compsn to form cured film is narrated.Above-mentioned first compsn is applicable to the spacer that forms liquid crystal display device, and second compsn is applicable to and forms interlayer dielectric or microlens that the 3rd to the 5th compsn is applicable to the formation protective membrane.
<using first compsn to form the method for spacer >
Use first compsn to form the method for the spacer of liquid crystal display device, carry out following operation (1)～(4) according to the order that is described below.
(1) operation of the tunicle of formation first compsn on substrate.
(2) at least a portion of above-mentioned tunicle is carried out the operation that radioactive rays make public.
(3) after will making public 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 compsn on substrate
At first, on substrate, form the tunicle of the compsn 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 White tin oxide (SnO 2) NESA film (registered trademark of U.S. PPG company), contain Indium sesquioxide-White tin oxide (In 2O 3-SnO 2) ITO film etc.
The method of tunicle that on substrate, forms the compsn of first composition solution 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.
To the not special restriction of the coating process of composition solution, 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 basement membrane, (below be called " photosensitive dry film ") of preferably containing in the flexible base film laminated that the photosensitive layer of photosensitive polymer combination of the present invention forms.
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 range upon range of photosensitive layer.The basement membrane of photosensitive dry film for example can use: the film of synthetic resins such as polyethylene terephthalate (PET), Vilaterm, Vestolen PP 7052, polycarbonate, SE.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 through heating under preferred 80～150 ℃ in about 1～10 minute.
In addition, photosensitive dry film can further range upon range ofly 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 compsn was used with solution morphology, its solid component concentration (from compsn, remove 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, to the not special restriction of the thickness of the tunicle that on substrate, forms, 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 make public
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 made public, can utilize the method for for example making public through photomask with predetermined pattern.
The radioactive rays that are used to make public 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 190～450nm scope.
Exposure is the radioactive rays wavelength that utilizes luxmeter (OAImodel 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 making public
Then, develop, remove part not, form the pattern of regulation through the tunicle after will making public.
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, Pottasium Hydroxide, yellow soda ash, water glass, (just) water glass (メ タ ケ イ acid Na ト リ ウ 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 through 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 that obtains (tunicle) 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; On hot-plate, being 5～30 minutes for example, is 30～180 minutes in baking oven, the spacer that can obtain stipulating thus.
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 compsn is, can Heating temperature be set at than low in the past 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.
<using second compsn to form interlayer dielectric or lenticular method >
Use second compsn to form interlayer dielectric or lenticular method, carry out following operation (1)～(4) according to the order that is described below.
(1) operation of the tunicle of formation second compsn on substrate.
(2) at least a portion of above-mentioned tunicle is carried out the operation that radioactive rays make public.
(3) after will making public 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 compsn on substrate
In operation (1), second composition solution is coated on substrate surface, then, preferably, form the tunicle of second compsn through 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 process, rolling method, method of spin coating (spin-coating method), slit die rubbing method (ス リ Star ト ダ イ rubbing method), rod are coated with appropriate method such as method, ink-jet application method, preferred especially spin-coating method or slit die rubbing 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, when forming microlens, be preferably for example 0.5～3 μ m.
(2) at least a portion of above-mentioned tunicle is carried out the operation that radioactive rays make public
In operation (2), preferably the tunicle that forms is shone radioactive rays through mask with predetermined pattern.Then, in subsequent processing (3),, carry out composition through carrying out the illuminated portion that development treatment is removed radioactive rays with developing solution.At this moment the radioactive rays that use 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 PRK 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 making public
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, Pottasium 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 compsn 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 compsn, can be for for example about 30～120 seconds.
In addition; If at present known interlayer dielectric or the lenticular compsn development time of being used to form surpasses optimum value and pattern will take place about 20～25 seconds peel off, therefore, must strict 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 stated; The tunicle that has formed pattern preferably cleans through for example flowing water and carries out rinsing processing; Preferably utilize comprehensive irradiation radioactive rays (post-exposure) such as high pressure mercury vapour lamp again; With remaining 1 in this tunicle, 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) thus.Through 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 on hot-plate, carrying out heat treated, can be set at for example 5～30 minutes, when in baking oven, carrying out heat treated, 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.
<using the 3rd or the 4th compsn to form the method for protective membrane >
Use the 3rd or the 4th compsn to form the method for protective membrane, carry out following operation (1) and (2) according to the order that is described below.
(1) operation of the tunicle of formation the 3rd or the 4th compsn on substrate.
(2) operation that above-mentioned tunicle is heated.
(1) operation of the tunicle of formation the 3rd or the 4th compsn on substrate
At first, the 3rd or the 4th composition solution is coated on the substrate, forms tunicle except that desolvating through 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 hydrogenate 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 through 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 compsn 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 that forms like this is preferably 0.1～8 μ m, and more preferably 0.1～6 μ m further is preferably 0.1～4 μ m.Wherein, when on the substrate with difference of altitude of colored filter, forming protective membrane, above-mentioned thickness is meant the thickness of starting at from the topmost of colored filter.
<using the 5th compsn to form the method for protective membrane >
Use the 5th compsn to form the method for protective membrane, carry out following operation (1)～(3) according to the order that is described below.
(1) with first liquid and the second liquid blended operation of the 5th compsn.
(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 compsn
At first, first liquid and second liquid preparation coating composition solution that mix the 5th compsn.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 compsn 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 compsn to form the method for protective membrane " respectively.
By after the embodiment that states can know; Aforesaid method forms in the heating process (sintering circuit) in the operation in cured film and does not in fact all produce sublimate; Can under the condition of cleaning, form cured film; In addition, particularly second compsn has the Development margin of height in developing procedure.In addition, the cured film that obtains is for the spacer that formed by first compsn time, and pattern form, compressive strength and rub resistance are good.When being the interlayer dielectric that is formed by second compsn, cured film thermotolerance and solvent resistance are high, specific inductivity is low, demonstrate high transmittance.When being the microlens that is formed by second compsn, cured film demonstrates good melt shape (required radius-of-curvature), and thermotolerance and solvent resistance be high, demonstrate high transmittance.Be when forming protective membrane by the 3rd to the 5th compsn, cured film thermotolerance and surface hardness be high, demonstrate high transmittance, and be simultaneously, that the ability of the difference of altitude planarization on the basal substrate is good.
" liquid crystal display device "
When the cured film that forms as stated is spacer or protective membrane, can it be applicable to liquid crystal display device.
The liquid crystal display device of explanation has the spacer or the protective membrane that form as stated below.
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 ヤ Star プ)) and makes the vertical or antiparallel of liquid crystal aligning direction in the alignment films separately, and the peripheral part of 2 substrates is fitted through 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, dioxane liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition; In these liquid crystal, also can add cholest-muriate (コ レ ス チ Le Network ロ ラ イ De) for example, cholesteryl nonanoate (cholesteryl liquid crystal such as コ レ ス テ リ Le ノ Na エ-ト), cholesteryl carbonate or wait with the chiral reagent of trade(brand)name " C-15 ", " CB-15 " sale such as (メ Le Network corporate systems) and to use.In addition, also can use oxygen base tolylene-in the last of the ten Heavenly stems strong dielectricity liquid crystal such as amino-2-methylbutyl laurate.
As the polarization plates that is used for the liquid crystal cell outside, can enumerate: will on one side Z 150PH 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, through the synthetic example of illustration, embodiment, the present invention is more specifically explained, but the present invention is not limited to following embodiment.
The gel permeation chromatography of synthetic polymkeric substance in the synthetic example of the following polymkeric substance of mensuration is obtained polystyrene conversion weight-average molecular weight (Mw) and number-average molecular weight (Mn) under following condition.
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 THF that contains 0.5 weight % phosphoric acid
(I) preparation of first compsn and evaluation
The synthetic example of polymkeric substance
Synthetic example 1
In flask, add 2 with prolong, whisking appliance; 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 vinylbenzene 20 weight parts, methylacrylic acid 17 weight parts, three ring [5.2.1.02; 6] decane-8-ylmethyl propenoate 18 weight parts and SY-Monomer G 45 weight parts, carry out nitrogen replacement after, Yi Bian slowly stir; 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 2,2 '-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 %.
Synthetic 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, and with the operation equally of synthetic example 1.The Mw of the polymkeric substance that each synthetic example obtains and the solid component concentration of Mw/Mn and each polymers soln are as shown in table 1.
Relatively more synthetic example 1
In the flask with prolong, whisking appliance, add 2,2 '-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, methylacrylic acid 17 weight parts, three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate 18 weight parts and SY-Monomer G 45 weight parts; After carrying out nitrogen replacement, Yi Bian slowly stir, Yi Bian reaction soln is warming up to 70 ℃; 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 MWD (Mw/Mn) is 2.4, and the solid component concentration of polymers soln is 29.5 weight %.
Table 1
Figure RE-S061H1807720070108D000561
Embodiment 1
The preparation of radiation sensitive resin composition
Will be as 2 of dipentaerythritol acrylate 100 weight parts of the solution that contains synthetic polymkeric substance (A-1) in the above-mentioned synthetic example of polymkeric substance (A-1) 100 weight parts (solids component) amount of being equivalent to of (A) composition, conduct (B) composition, conduct (C) composition; 2 '-two (2; The 4-dichlorophenyl)-4,4 ', 5; 5 '-tetraphenyl di-imidazoles, 8 weight parts, as γ-Huan Yangbingyangbingjisanjiayangjiguiwan 5 weight parts of adhesive aid, as the FTX-218 (trade(brand)name of tensio-active agent; (strain) ネ オ ス system) 0.5 weight part and mix as 4-methoxyphenol 0.5 weight part of preserving stabilizer adds the Glycol Monomethyl ether acetic ester and dissolves, and the solid component concentration that makes compsn is 30 weight %; Using the aperture then is the millipore filter filtration of 0.5 μ m, is mixed with composition solution.
Be described below and carry out the evaluation of formulated as stated composition solution.
The formation of spacer
On the alkali-free glass substrate with spin coater coating above-mentioned compsn 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 through 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 Pottasium 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 in above-mentioned " formation of spacer ", forming pattern, 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 compsn 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 compsn 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 compsn 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 compsn 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 as in above-mentioned " formation of spacer ", forms pattern; 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 compsn.
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.In this use JIS? K-5400 (1900) 8.5 8.5.2 adhesion trials with checkerboard method (AI Head rotation plate - plastic method) Evaluation of cured film formed adhesiveness.Residual checker number is 100 in 100 checkers.
The evaluation of sublimate
On the silicon substrate with spin coater coating above-mentioned compsn 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) makes public 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 (ペ ア シ リ コ Application ウ worker eight), 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 and embodiment 1 same operation compositions formulated are estimated.Evaluation result is as shown in table 3.
In addition, in table 2, represent that the abbreviation of each composition defines as follows respectively.When the kind of composition linked with "/" with amount, 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 that radioactive rays are responsive
H-1:4,4 '-two (dimethylamino) UVNUL MS-40
The H-2:2-mercaptobenzothiazole
H-3: tetramethylolmethane four (mercaptoacetate)
Figure RE-S061H1807720070108D000601
Figure RE-S061H1807720070108D000611
Figure RE-S061H1807720070108D000631
(II) preparation of second compsn and evaluation
The synthetic example of polymkeric substance
Synthetic example 21
In flask with prolong, whisking appliance; 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, methylacrylic acid 20 weight parts, three encircle [5.2.1.0 2,6] decane-8-ylmethyl propenoate 20 weight parts, SY-Monomer G 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 %.
Synthetic 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, and with the operation equally of synthetic example 21.The Mw of the polymkeric substance that each synthetic example obtains and the solid component concentration of Mw/Mn and each polymers soln are as shown in table 4.
Relatively more synthetic example 2
In flask, add 2, two (2, the 4-methyl pentane nitrile) 8 weight parts of 2 '-azo and vinylbenzene 20 weight parts, methylacrylic acid 20 weight parts, three ring [5.2.1.0 with prolong, whisking appliance 2,6] decane-8-ylmethyl propenoate 20 weight parts, SY-Monomer G 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
Figure RE-S061H1807720070108D000651
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 synthetic 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] 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; Adding Diethylene Glycol ethyl-methyl ether dissolves; Making its solid component concentration is 30 weight %, and the membranous 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 stated, be described below and estimate the various characteristics of interlayer dielectric.
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.Through 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 makes public, and using concentration is that the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight % developed 90 seconds down at 25 ℃ through the paddle method.Cleaned 1 minute with ultrapure water flowing water, carry out drying, on silicon substrate, form pattern.At this moment, investigate line with 3.0 μ m with (ペ-ス) intermittent pattern of (10 pairs 1) dissolves needed exposure to ラ イ Application ア Application De ス fully at interval.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 through 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 made public.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 makes public to filming of obtaining, and the accumulative total irradiation dose is 3,000J/m 2Silicon substrate in cleaning oven after 220 ℃ heating makes public 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 in the evaluation of solvent resistance, 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.
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-ニ Application グ 7059 " (コ-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-system ((strain) Hitachi system) ", filling does not have the コ-ニ Application グ 7059 of film in the control sides cup, under the wavelength of 400～800nm scope, measures the transmittance of the glass substrate with this cured film.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 the good SUS304 system substrate of polishing, 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 made public, 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, process the specific inductivity test sample.Use Yokogawa ヒ ユ-レ Star ト パ Star カ-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 and (D) composition; Further add siloxane type surfactants " SH-28PA " (trade(brand)name, eastern レ ダ ウ コ-ニ Application グ シ リ コ-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 defines 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
Figure RE-S061H1807720070108D000701
Figure RE-S061H1807720070108D000711
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 synthetic 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; Using the aperture is the membranous filter filtration of 0.2 μ m, is mixed with composition solution.
Lenticular performance evaluation
Use the radiation sensitive resin composition of preparation as stated, be described below and estimate lenticular various characteristics.
The evaluation of sensitivity
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.Through having the pattern mask of predetermined pattern; With two コ Application (strain) system NSR1755i7A reduced projection exposure machine (NA=0.50; λ=365nm) the variation time shutter of filming that obtains is made public, use concentration is that the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight % developed 1 minute down at 25 ℃ through the paddle method.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.Through 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 made public, and working concentration is the tetramethyl ammonium hydroxide aqueous solution of 0.4 weight %, uses the paddle method under 25 ℃, to develop as variable with development time.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
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.Filming of obtaining made public 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 in the evaluation of solvent resistance, 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.
Lenticular formation (evaluation of microlens shape)
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.Through 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 made public; 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, make public 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 the 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 the 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, all the other and embodiment 33 same operation preparation radiation sensitive resin compositions are estimated.Evaluation result is as shown in table 8.
Table 7
Figure RE-S061H1807720070108D000751
(III) preparation of the 5th compsn and evaluation
The synthetic example of polymkeric substance
Synthetic example 41
In flask, add 2 with prolong, whisking appliance; 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 SY-Monomer G 80 weight parts and vinylbenzene 20 weight parts, carry out nitrogen replacement after, Yi Bian slowly stir; 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 %.
Synthetic 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, in addition, and all the other and the operation equally of synthetic example 41.The Mw of the polymkeric substance that each synthetic example obtains and the solid component concentration of Mw/Mn and each polymers soln are as shown in table 9.
Relatively more synthetic example 3
In flask, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 7 weight parts and diethylene glycol methyl ethyl ether 200 weight parts with prolong, whisking appliance; Then add vinylbenzene 50 weight parts and SY-Monomer G 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 MWD (Mw/Mn) is 1.8.The solid component concentration of polymers soln is 30.0 weight %.
Table 9
Figure RE-S061H1807720070108D000771
Embodiment 41
The preparation of binary liquid shape curable resin composition
< preparation of first liquid >
Will be as the solution that contains the multipolymer (A-41) that obtains in above-mentioned synthetic routine 41 of the amount that is equivalent to 100 weight part multipolymer (A-41) solids components of (A ') composition, dihydroxyphenyl propane novolac epoxy resin " エ ピ コ-ト the 157S65 " (trade(brand)name of conduct (E) composition; Oiling シ エ Le エ 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 ウ コ-ニ Application グ シ リ コ-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 %; Using the aperture then is the millipore filter filtration of 0.5 μ m, is mixed with first liquid.
< preparation of 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.
< 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, on substrate, forming thickness 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-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
With the SiO that has formed protective membrane 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.
Heat-resisting dimensional stability (%)=(thickness after the heating)/(thickness before the heating) * 100
The evaluation of heat-resisting discolouration
With the SiO that has formed protective membrane 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 JIS K-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 イ Na ミ Star 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 Star 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 ℃, in the time of 140 ℃, is 25.
The evaluation of adaptation
To having formed the SiO of protective membrane 2After the dipping glass substrate carries out pressure kettle test (プ レ Star シ ヤ-Network Star カ-) (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-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), through 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-エ Le エ-テ Application コ-Le (strain) system); Mensuration has formed the concave-convex surface of the substrate of this colored filter, and 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 (adding up to n=10) that the mensuration of all directions is counted, and measures the MV of the difference of height (nm) of each the highest of measuring and bottommost, and 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, on colored filter, forming apart from the thickness above the 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 highest the MV with the difference of height (nm) of 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 compsn 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 same operation compositions formulated are estimated.Evaluation result is as shown in table 10.
In addition, in table 2, represent that the abbreviation of each composition defines as follows respectively.
(E) composition
E-1: dihydroxyphenyl propane line style phenol aldehyde type epoxy resin (trade(brand)name: エ ピ コ-ト 157S65, oiling シ エ Le エ Port キ シ (strain) system)
E-2: bisphenol A type epoxy resin (trade(brand)name: エ ピ コ-ト 828, oiling シ エ Le エ Port キ シ (strain) system)
Solvent
S-1: Glycol Monomethyl ether acetic ester
S-2: diethylene glycol dimethyl ether
Figure RE-S061H1807720070108D000811
(IV) preparation of the 3rd compsn and evaluation
Synthesizing of polymkeric substance
Synthetic example 51
In flask, add 2 with prolong, whisking appliance; 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 SY-Monomer G 50 weight parts, three and encircle [5.2.1.0 2,6] decane-8-ylmethyl propenoate 20 weight parts and methylacrylic 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 %.
Synthetic 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, in addition, and all the other and the operation equally of synthetic example 51.The Mw of the polymkeric substance that each synthetic example obtains and the solid component concentration of Mw/Mn and each polymers soln are as shown in table 11.
Relatively more synthetic example 4
In the flask with prolong, whisking appliance, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 6 weight parts and diethylene glycol methyl ethyl ether 200 weight parts then add SY-Monomer G 50 weight parts, three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate 20 weight parts and methylacrylic 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, MWD (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
Figure RE-S061H1807720070108D000831
Embodiment 51
The preparation of one liquid type curable resin composition
Will be as benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate 1 weight part of dihydroxyphenyl propane line style phenol aldehyde type epoxy resin (trade(brand)name: エ ピ コ-ト 157S65, oiling シ エ Le エ Port キ シ (strain) system) 10 weight parts of the solution that contains the polymkeric substance (A-51) that obtains in above-mentioned synthetic routine 51 of the amount that is equivalent to multipolymer (A-51) solids component 100 weight parts of (A ') composition, conduct (E) composition, conduct (G) acid-producing agent, as γ-Huan Yangbingyangbingjisanjiayangjiguiwan 15 weight parts of adhesive aid with as SH-28PA (eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system) the 0.1 weight part mixing of tensio-active agent; Further add the Glycol Monomethyl ether acetic ester; Making solid component concentration is 20%; Using the aperture then is the millipore filter filtration of 0.5 μ m, is 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, except that. this, all the other with the foregoing description 41 same operations estimate.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 same operation compositions formulated are estimated.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.
Figure RE-S061H1807720070108D000851
(V) contain the preparation and the evaluation of the compsn of (A ' 1) polymkeric substance
Synthetic example 61
In flask, add 2 with prolong and whisking appliance; 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 SY-Monomer G 40 weight parts, methylacrylic 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 MWD (Mw/Mn) is 1.60.
Embodiment 61
The preparation of the 4th compsn and evaluation
The preparation of one liquid type curable resin composition
Will be as dihydroxyphenyl propane line style phenol aldehyde type epoxy resin (trade(brand)name: エ ピ コ-ト 157S65, oiling シ エ Le エ Port キ シ (strain) system) 10 weight parts of the solution that contains the multipolymer (A-61) that obtains in above-mentioned synthetic routine 61 of the amount of the solids component that is equivalent to 100 weight part multipolymers (A-61) of (A ') composition, conduct (E) composition, as benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate 1 weight part of acid-producing agent, mix as γ-Huan Yangbingyangbingjisanjiayangjiguiwan 15 weight parts of adhesive aid with as SH-28PA (eastern レ ダ ウ コ-ニ Application グ シ リ コ-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 %; Using the aperture then is the millipore filter filtration of 0.5 μ m, is 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 are estimated with the foregoing description 41 same operations.The result is 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 (17)

1. curable resin composition is characterized in that it contains:
(A) polymkeric substance,
(B) polymerizable unsaturated compound and
(C) radiation-sensitive polymerization starter,
Said composition is used to form spacer;
Wherein, Said (A) polymkeric substance is in the presence of the compound of following formula (1) or following formula (2) expression, to be polymkeric substance 1.7 below through the ratio Mw/Mn that active free radical polymerization carries out polystyrene conversion weight-average molecular weight Mw that polymerization obtained, used gel permeation chromatography and number-average molecular weight Mn with the polymerizability mixture that contains following compound (a1), compound (a2) and compound (a3); Wherein, said compound (a1) is for being selected from least a in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides; Said compound (a2) is for being selected from least a in carbonate, vinylformic acid 3-ethyl-3-oxa-ring butyl ester and the methylacrylic acid 3-ethyl-3-oxa-ring butyl ester with Oxyranyle; Said compound (a3) is except that compound (a1) and the unsaturated compound the compound (a2); Be to be selected from least a in alkyl methacrylate, alkyl acrylate, methylacrylic 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 and the conjugated diolefine, formula (1) is:
Figure FSB00000776046100011
In the formula (1), p is the integer more than 1, Z 1Be Wasserstoffatoms, 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, cyanic acid, 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 Wasserstoffatoms that is had one or more can be by halogen atom, cyanic acid, hydroxyl or carboxyl substituted;
During p=1, R 1Be Wasserstoffatoms, cyanic acid, 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 Wasserstoffatoms that is had one or more can be replaced by halogen atom, cyanic acid, hydroxyl, carboxyl or Oxyranyle, wherein, and Z 1And R 1Be not Wasserstoffatoms simultaneously;
P is 2 when above, R 1Be from carbonatoms is 1～20 alkane, to remove p valency group that p Wasserstoffatoms obtain, from carbonatoms is 6～20 aromatic hydrocarbons, remove p valency group that p Wasserstoffatoms obtain or from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, remove the p valency group that p Wasserstoffatoms obtains, one or more in the Wasserstoffatoms that these groups had can be replaced by halogen atom, cyanic acid, hydroxyl, carboxyl or Oxyranyle;
Formula (2) is:
Figure FSB00000776046100021
In the formula (2), m is the integer more than 2, Z 2Be from carbonatoms is 1～20 alkane, to remove m valency group that m Wasserstoffatoms obtain, from carbonatoms is 6～20 aromatic hydrocarbons, remove m valency group that m Wasserstoffatoms obtain or from carbon atom and heteroatomic total atomicity are 3～20 1 divalent heterocyclic compound, remove the m valency group that m Wasserstoffatoms obtains; In the Wasserstoffatoms that these groups had one or more can be replaced R by halogen atom, cyanic acid, hydroxyl, carboxyl or Oxyranyle 2Be Wasserstoffatoms, cyanic acid, 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 Wasserstoffatoms that is had one or more can be replaced by halogen atom, cyanic acid, 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 FSB00000776046100031
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. a curable resin composition is characterized in that, it contains (A) polymkeric substance and (D) 1, and the 2-quinone di-azido compound is used to form interlayer dielectric or microlens;
Wherein, Said (A) polymkeric substance is in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression, to be polymkeric substance 1.7 below through the ratio Mw/Mn that active free radical polymerization carries out polystyrene conversion weight-average molecular weight Mw that polymerization obtained, used gel permeation chromatography and number-average molecular weight Mn with the polymerizability mixture that contains following compound (a1), compound (a2) and compound (a3); Wherein, said compound (a1) is for being selected from least a in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides; Said compound (a2) is for being selected from least a in carbonate, vinylformic acid 3-ethyl-3-oxa-ring butyl ester and the methylacrylic acid 3-ethyl-3-oxa-ring butyl ester with Oxyranyle; Said compound (a3) is for except that compound (a1) and the unsaturated compound the compound (a2), is to be selected from alkyl methacrylate, alkyl acrylate, methylacrylic acid cycloalkyl ester, the methacrylic ester with hydroxyl, vinylformic acid cycloalkyl ester, aryl methacrylate, vinylformic acid aryl ester, unsaturated dicarboxylic acid diester, two to encircle at least a in unsaturated compounds, maleimide compound, unsaturated aromatics and the conjugated diolefine.
4. a curable resin composition is characterized in that, it contains (A) polymkeric substance and (E) cationically polymerizable compound, is used to form protective membrane;
Wherein, Said (A) polymkeric substance is in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression, to be polymkeric substance 1.7 below through the ratio Mw/Mn that active free radical polymerization carries out polystyrene conversion weight-average molecular weight Mw that polymerization obtained, used gel permeation chromatography and number-average molecular weight Mn with the polymerizability mixture that contains following compound (a1), compound (a2) and compound (a3); Wherein, said compound (a1) is for being selected from least a in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides; Said compound (a2) is for being selected from least a in carbonate, vinylformic acid 3-ethyl-3-oxa-ring butyl ester and the methylacrylic acid 3-ethyl-3-oxa-ring butyl ester with Oxyranyle; Said compound (a3) is for except that compound (a1) and the unsaturated compound the compound (a2), is to be selected from alkyl methacrylate, alkyl acrylate, methylacrylic acid cycloalkyl ester, the methacrylic ester with hydroxyl, vinylformic acid cycloalkyl ester, aryl methacrylate, vinylformic acid aryl ester, unsaturated dicarboxylic acid diester, two to encircle at least a in unsaturated compounds, maleimide compound, unsaturated aromatics and the conjugated diolefine.
5. 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, Said (A ') polymkeric substance is in the presence of the compound of above-mentioned formula (1) or above-mentioned formula (2) expression, to be polymkeric substance 1.7 below through the ratio Mw/Mn that active free radical polymerization carries out that polymerization obtains, as to use gel permeation chromatography polystyrene conversion weight-average molecular weight Mw and number-average molecular weight Mn with the polymerizability mixture that contains following compound (a2), compound (a3) and compound (a4); Wherein, Said compound (a2) is for being selected from least a in carbonate, vinylformic acid 3-ethyl-3-oxa-ring butyl ester and the methylacrylic acid 3-ethyl-3-oxa-ring butyl ester with Oxyranyle; Compound (a3) is except that compound (a1) and the unsaturated compound the compound (a2); Be to be selected from least a in alkyl methacrylate, alkyl acrylate, methylacrylic acid cycloalkyl ester, methacrylic ester, vinylformic acid cycloalkyl ester, aryl methacrylate, vinylformic acid aryl ester, unsaturated dicarboxylic acid diester, two ring unsaturated compounds, maleimide compound, unsaturated aromatics and the conjugated diolefine with hydroxyl; Compound (a1) is for being selected from least a in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides, and compound (a4) has at least a in the norbornylene compounds that is selected from least a structure in ethylidene ether structure, ketal structure and the tert-butoxycarbonyl structure, (methyl) acryliccompound with at least a structure that is selected from ethylidene ether structure and the ketal structure and (methyl) tert-butyl acrylate for being selected from.
6. curable resin composition as claimed in claim 5, wherein, (A ') polymkeric substance has the structure that above-mentioned formula (i) or above-mentioned formula are (ii) represented.
7. like each described curable resin composition in the claim 4～6, it also contains (F) solidifying agent or (G) acid-producing agent.
8. a liquid type curable resin composition is characterized in that, it contains first liquid and second liquid, and said first liquid is each described curable resin composition in the claim 4～6, and said second liquid contains (F) solidifying agent.
9. the formation method of a spacer is characterized in that, it carries out following operation (1)～(4) according to the order that is described below:
(1) on substrate, form the tunicle of the described curable resin composition of claim 1 operation,
(2) at least a portion of above-mentioned tunicle carry out radioactive rays exposures operation,
(3) after will making public by the operation of film development and
(4) operation of the heating of the tunicle after will developing.
10. spacer, it is formed by the described method of claim 9.
11. a liquid crystal display device is characterized in that, it comprises the described spacer of claim 10.
12. an interlayer dielectric or lenticular formation method is characterized in that, it carries out following operation (1)～(4) according to the order that is described below:
(1) on substrate, form the tunicle of the described curable resin composition of claim 3 operation,
(2) at least a portion of above-mentioned tunicle carry out radioactive rays exposures operation,
(3) after will making public by the operation of film development and
(4) operation of the heating of the tunicle after will developing.
13. the interlayer dielectric or the microlens that form by the described method of claim 12.
14. the formation method of a protective membrane is characterized in that, it carries out following operation (1)～(2) according to the order that is described below:
(1) on substrate, forms the operation of the tunicle of each described curable resin composition in the claim 4～6; With
(2) operation that above-mentioned tunicle is heated.
15. the protective membrane that forms by the described method of claim 14.
16. the formation method of a protective membrane is characterized in that, it carries out following operation (1)～(3) according to the order that is described below:
(1) with first liquid of the described compsn of claim 8 and the second liquid blended operation,
(2) on substrate, form above-mentioned mixed solution tunicle operation and
(3) operation that above-mentioned tunicle is heated.
17. the protective membrane that forms by the described method of claim 16.
CN2006101718077A 2005-10-07 2006-09-30 Radiation-sensitive resin composition for spacer, spacer and method for forming the same Active CN101153121B (en)

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JP2005294721A JP4654867B2 (en) 2005-10-07 2005-10-07 Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof
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