CN102399372B - Method for forming curing laminated film of siloxane resin compound - Google Patents
Method for forming curing laminated film of siloxane resin compound Download PDFInfo
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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Abstract
The invention relates to a method for forming curing laminated films of a siloxane resin compound. By using the siloxane resin compound, the curing laminated films which have the characteristics of excellent transparency, high scratch hardness, high insulation, low dielectric constant, excellent smoothness, no film loss during a sintering process, no crack even in case of thick films, no film peeling on a substrate interface and excellent sealing performances. The method comprises the steps of coating the siloxane resin compound containing a silanol group or an alkoxy silyl group on a substrate, pre-baking the siloxane resin compound, flushing and sintering the compound after the compound is processed in an alkaline aqueous solution. Then Sintered curing laminated films of the siloxane resin compound having the silanol group or the alkoxy silyl group are formed.
Description
Technical field
The present invention relates to the method for the curing overlay film forming the silicone resin composition containing silanol group or alkoxysilyl, relate to a kind of method forming the curing overlay film of the silicone resin composition containing silanol group or alkoxysilyl in more detail, the transparency of this curing overlay film is excellent, even if there is high scratch hardness, high-insulativity, low-k and planarization excellence form thick film and also can not produce slight crack, and substrate interface there is no film peels off, excellent adhesion.
Background technology
Silicone resin is known to the material of high heat resistance, high rigidity, high-insulativity, high transparent, in various uses.That composition containing silicone resin solidifies (following as a kind of in these purposes; sometimes also referred to as " firing solidification ") overlay film; by weather resistance, low-dielectric and make insulativity excellent; there is high rigidity; utilize these character, use as the insulating film in semiconductor element and liquid crystal display device or leveling film, protective membrane and semiconductor-encapsulating material etc.In addition, owing to being high transparent, so not only use in this field of electronic materials, the surface protection film that also can be used as optics and car etc. uses.
Use the silicone resin composition using silicone resin as tackiness agent, when forming curing overlay film, known method has preparation to comprise the composition of multifunctional polysiloxane, coating said composition, heat dryings etc. make it solidify, thus forming overlay film (with reference to patent documentation 1), the composition of this multifunctional polysiloxane has alkoxyl group or hydroxyl.Now, as solidifying agent (also referred to as " catalyzer "), use acidic cpd or basic cpd, metal alkoxide, metal chelate compound etc., but in the viscosity of multifunctional polysiloxane during high or solid component concentration height, if add above-mentioned solidifying agent in multifunctional polysiloxane, then can produce thickening immediately or this problem of gelation.In addition, after interpolation, even without thickening immediately or gelation, also can produce thickening when preserving, if catalyzer is weakly acidic, also can produces and being difficult to solidify such problem.In addition, when using this material to form curing overlay film, film must at high temperature process, but also can produce film reduction now problem so greatly.
In order to address this is that, also proposed and use acidic cpd and the basic cpd different from the boiling point of this acidic cpd as solidifying agent (with reference to patent documentation 2).Even if said composition is in the multifunctional polysiloxane with multiple alkoxyl group and/or hydroxyl, add the solidifying agent containing acidic cpd and the basic cpd different from the boiling point of this acidic cpd, also can not solidify immediately, in addition, when acidic cpd is different with the boiling point of basic cpd, under utilizing the temperature between these boiling points, heating polysiloxane compound, acidic cpd or basic cpd play the effect as solidifying agent, it is the silicone composition of excellent storage stability, can condensation and realize the solidification of film at low temperatures, but owing to using solidifying agent, so have the problem easily producing fracture phenomenon and the problem that can not fully suppress ageing stability low.
In addition, silanol group curing silicone resin can cured coating film at low temperatures, has the character that hardness is high.And then in addition, silanol group curing silicone resin is high due to the transparency of overlay film, also there is the such character of high heat resistance, low-dielectric, insulativity and receive publicity.Particularly, in 4 connecting keys of Siliciumatom, the silicone resin that 4 connecting keys of the silsesquioxane that carbon atom is connected with 3 Sauerstoffatoms and Siliciumatom are all connected with Sauerstoffatom, because silicon and oxygen are formed firmly three-dimensional cross-linked, demonstrate above-mentioned character more significantly, expect as the coating agent on the plastic base of flexible display and thin film transistor (below so special, also referred to as TFT) on barrier films or smooth agent, if but more than 250 DEG C, form curing overlay film, then particularly the electrical property of TFT reduces, so solidification must be carried out at less than 250 DEG C.Up to the present, disclose the silica overlay film formation coating fluid by the hydrolysate containing organoalkoxysilane and organosilicone surfactants, heat-treat at the temperature of 250 ~ 500 DEG C, form the method (with reference to patent documentation 3) of silica overlay film, according to the method, although formed and can not damage planarization, the character of slight crack boundary, and the overlay film of excellent adhesion, but must be cured under the high temperature more than 250 DEG C, or must organosilicone surfactants be had, and when forming thick film, there is the problem can only selecting material that weight-average molecular weight (Mw) is large.On the other hand, if film, although then Mw is little also passable, sublimate when firing increases, and it is large that film reduces quantitative change, is cured and the Mw narrow scope that can not distil, also cannot be used for practicality.
It is thicker or be exposed to more (even if less than 250 DEG C) under high-temperature that the overlay film of three-dimensional silicone resin has the thickness of generation, and stress when film is returned to normal temperature increases more, more easily produces the trend of fracture phenomenon.Be difficult to make the curing overlay film of silicone resin produce fracture phenomenon, comprise in 4 connecting keys using Siliciumatom, 2 link carbon atoms, the silicone resin of 2 link Sauerstoffatoms, or in silicone resin, add organic resin (such as, acrylic resin) method, but these methods all have the tendency hindering above-mentioned overlay film character.In addition, if add in addition or add silicone resin in the polymer repeating unit of silicone resin, then due to mobility improve while sublimability also improve, so pollute baking oven when there is film forming, form fold according to flowing trace, or the such problem of film hardness step-down after solidification.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 2004-99879 publication
[patent documentation 2] Japanese Unexamined Patent Publication 2008-208200 publication
[patent documentation 3] Japan No. 4079383 Gazette of Patent for Invention
Summary of the invention
The object of the present invention is to provide the formation method of the cured film of the silicone resin composition not having above-mentioned existing issue, namely, when it forms silicone resin curing overlay film in semiconductor element or liquid crystal cell, fire at the temperature less than 250 DEG C or more than 250 DEG C, also the transparency can be formed excellent, there is high scratch hardness, high-insulativity, low-k, film is not had to reduce and planarization excellence, even if form thick film also do not produce slight crack, and do not have film to peel off at substrate interface, the overlay film of excellent adhesion.
The present inventor is through conscientious research, after finding that coating contains the silicone resin composition of silanol group or alkoxysilyl on base material, carry out prebake, by this prebake film with after alkaline aqueous solution process, fire solidification, even if thus fire at temperature below 250 DEG C or more than 250 DEG C, and with the thickness of film independently, the transparency can be formed excellent, there is high scratch hardness, high-insulativity, low-k, even if when being coated with thick film, also slight crack can not be produced, the cured film of excellent adhesion, based on this understanding, complete the present invention.
Namely, the present invention relates to a kind of curing overlay film formation method of silicone resin composition, the method is the silicone resin composition used containing silanol group or alkoxysilyl, at least pass through the polymerization of silanol group or alkoxysilyl, be cured, form the curing overlay film formation method of the silicone resin composition of overlay film, it is characterized in that: foregoing is applied on base material, after carrying out pre-bake treatment, after alkaline aqueous solution process, rinse, fire.
In addition, the invention is characterized in the above-mentioned methods, the process of the aforementioned base aqueous solution by being impregnated in alkaline aqueous solution, or covers submergence (パ De Le) or shower is carried out by revolving.
In addition, the invention is characterized in the above-mentioned methods, the aforementioned base aqueous solution is the tetramethyl ammonium hydroxide aqueous solution.
In addition, the invention is characterized in the above-mentioned methods, aforementioned firing is carried out at the temperature of 120 ~ 400 DEG C.
In the present invention, the resin containing silanol group or alkoxysilyl is used as silicone resin, in addition, after the silicone resin composition that coating contains silanol group or alkoxysilyl, carry out the prebake of film, this prebake film alkaline aqueous solution process, thus not by the impact of firing temperature afterwards, thickness, form the transparency excellent, there is high scratch hardness, high-insulativity, low-k, and do not have film to reduce, even if when being coated with thick film, also slight crack is not produced, the cured film of excellent adhesion.Therefore, the surface protection film etc. of insulating film in semiconductor element and liquid crystal display device or leveling film, protective membrane, optics and car etc. is preferred for being formed.
Embodiment
Below, the curing overlay film formation method containing the silicone resin composition of silanol group or alkoxysilyl of the present invention is illustrated in greater detail.
As mentioned above, the feature containing the formation method of the curing overlay film of the silicone resin composition of silanol group or alkoxysilyl of the present invention is that coating contains silanol group or alkoxysilyl silicone resin composition on substrate, after carrying out pre-bake treatment, after alkaline aqueous solution process, carry out the flushing of film, fire, the material used in the curing overlay film formation method of silicone resin composition of the present invention, method are described in detail as follows successively.
(i) silicone resin composition containing silanol group or alkoxysilyl
First, be the silicone resin composition containing silanol group or alkoxysilyl for the formation of curing overlay film of the present invention, the additive that said composition is used containing silanol group or alkoxysilyl silicone resin, (b) organic solvent, (c) as required by (a) is formed.
(a) silicone resin containing silanol group or alkoxysilyl
As the silicone resin containing silanol group or alkoxysilyl used in the present invention, can be arbitrarily known to silanol group and/or the alkoxysilyl silicone resin as reactive group at present, the structure of polysiloxane has no particular limits.If illustrate the representational silicone resin containing silanol group or alkoxysilyl that can use in the present invention, then such as can list more than one of the organoalkoxysilane shown in following general formula (1), in organic solvent, the silicone resin (polysiloxane) obtained is hydrolyzed.
(R
1)
nSi(OR
2)
4-n (1)
(in formula, R
1represent hydrogen atom, can have substituent carbonatoms be 1 ~ 6 alkyl, carbonatoms be 3 ~ 6 cycloalkyl, carbonatoms be that the carbon atom of the α position of less than 15 does not connect the aralkyl of hydrogen atom, carbonatoms be 6 ~ 15 aryl or carbonatoms be the thiazolinyl of 1 ~ 6, R
2expression can have the alkyl that substituent carbonatoms is 1 ~ 6, and n is the integer of 0 ~ 3).
In above-mentioned general formula, as R
1can have substituent carbonatoms be 1 ~ 6 alkyl can list such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, positive decyl, trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro propyl, 3-hydroxypropyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl) ethyl, 3-aminopropyl, 3-mercaptopropyi, 3-isocyanate group propyl group, 4-hydroxyl-5-(para hydroxybenzene acyloxy) amyl group etc.In addition, as the cycloalkyl that substituent carbonatoms is 3 ~ 6 can be had, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc. can be listed; The carbonatoms connected as the carbon atom discord hydrogen atom can with substituent α position is the aralkyl of less than 15, can list propyloxy phenyl base etc.; As substituent aryl can be had, phenyl, tolyl, p-hydroxybenzene, naphthyl etc. can be listed; As the thiazolinyl that substituent carbonatoms is 1 ~ 6 can be had, vinyl, allyl group, 3-acryloxypropyl, 3-methacryloxypropyl etc. can be listed.
On the other hand, as R
2can have the alkyl that substituent carbonatoms is 1 ~ 6, to illustrate and as R
1can have substituent alkyl and illustrative same group, preferably do not have substituent carbonatoms be 1 ~ 4 alkyl.
As the object lesson of the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in above-mentioned general formula (1), following compound can be illustrated.
(1) tetraalkoxysilane: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane etc.,
(2) monoalkyltrialkoxysi.ane: monomethyl Trimethoxy silane, monomethyl triethoxyl silane, single ethyl trimethoxy silane, single ethyl triethoxysilane, single propyl trimethoxy silicane, single propyl-triethoxysilicane etc.,
(3) single aryltrialkoxysilane: single phenyltrimethoxysila,e, single phenyl triethoxysilane, single naphthyl Trimethoxy silane etc.,
(4) trialkoxy silane: Trimethoxy silane, triethoxyl silane, tripropoxy silane, three butoxy silanes etc.,
(5) dialkyl dialkoxy silicane: dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyl dimethoxysilane, dipropyl diethoxy silane etc.,
(6) phenylbenzene dialkoxy silicane: dimethoxydiphenylsilane, diphenyl diethoxy silane etc.,
(7) alkyl phenyl dialkoxy silicane: aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, ethylphenyl dimethoxysilane, Ethylphenyldiethoxysandne, propyl group phenyidimethoxysilane, propyl group phenyl diethoxy silane etc.
(8) trialkyl alkoxy silane: trimethylmethoxysilane, three normal-butyl Ethoxysilanes etc.
Among them, preferred compound is tetramethoxy-silicane, tetraethoxysilane, monomethyl Trimethoxy silane, monomethyl triethoxyl silane, single naphthyl Trimethoxy silane, single phenyltrimethoxysila,e.
The silicone resin (polysiloxane) that the silicone resin preferred reactive group containing silanol group or alkoxysilyl used in the present invention is only made up of silanol group or is made up of silanol group or alkoxysilyl.Namely, in silicone resin, can containing unreacted alkoxysilyl during synthesis silicone resin.The silicone resin containing silanol group that this reactive group is only made up of silanol group or is made up of silanol group and alkoxysilyl can use the one of the organoalkoxysilane shown in aforementioned formula (1) or two or more manufacture.In addition, the silicone resin containing silanol group or alkoxysilyl used in the present invention as required, can use aforementioned R as organoalkoxysilane
1and R
2in one or more and R of the not organoalkoxysilane of the reactive group such as hydroxyl
1and/or R
2in there are the one or more kinds of mixtures of the organoalkoxysilane of the reactive groups such as hydroxyl, use the silicone resin they hydrolytic condensations obtained.In addition, in the present invention, as raw material organoalkoxysilane, n is the organoalkoxysilane of 0 or 1 in preferred above-mentioned general formula (1), and n now can be used as required to be further the organoalkoxysilane of 2 or 3.
Molecular weight preferable weight-average molecular weight (Mw) is 400 ~ 20,000, be more preferably 400 ~ 10,000.During Weight-average molecular quantity not sufficient 400, may volatilize together with solvent when prebake, if be greater than 20,000, then be difficult to solidification.
The hydrolysis-condensation reaction of organoalkoxysilane carries out usually in organic solvent.As the solvent composition of organoalkoxysilane solution, as long as can dissolve or disperse the organic solvent of the resin formed, just there is no particular limitation.As this solvent, can suitably use known organic solvent, the monohydroxy-alcohols such as such as methyl alcohol, ethanol, propyl alcohol, butanols, isopropylcarbinol, primary isoamyl alcohol can be listed; The polyvalent alcohols etc. such as ethylene glycol, Diethylene Glycol, propylene glycol, glycerol, TriMethylolPropane(TMP), hexanetriol; The monoether class of the polyvalent alcohols such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, 3-methyl-3-methoxybutanol and their acetate esters; The ester classes such as methyl acetate, ethyl acetate, butylacetate; The ketones such as acetone, methyl ethyl ketone, methyl isoamyl ketone; The polyvalent alcohol ethers etc. that the hydroxyl of the polyvalent alcohols such as ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate propyl ether, ethylene glycol bisthioglycolate butyl ether, propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether is all alkyl etherified.The solvent used in the reaction of organoalkoxysilane generally can also use as the solvent of the silicone resin composition be applied to afterwards on base material.
The preferred boiling point of organic solvent is the liquid of 100 ~ 300 DEG C, and preferably in molecule, has the liquid of at least one hydroxyl and/or ehter bond, or in molecule, have the acetic ester of at least one ehter bond.These organic solvents can be used alone, or also can be used in combination of two or more.In addition, when flat-panel monitor etc. forms the curing overlay film of silicone resin, owing to generally using the ether-ether class of the polyvalent alcohol such as ethers, propylene glycol monomethyl ether (PGMEA) of the polyvalent alcohols such as current propylene glycol monomethyl ether (PGME), so when using silicone resin composition in this field, preferably use ethers, the ether-ether class of the polyvalent alcohols such as PGME or PGMEA.In addition, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetic ester etc. also exemplify as preferred solvent.Organic solvent, relative to 1mol organoalkoxysilane, uses with the ratio of 10 ~ 30 moles of times amount usually.
The hydrolysis-condensation reaction of organoalkoxysilane, even without catalyzer, also can carry out to a certain extent, but in order to give coating, storage stability, preferably use catalyzer.Also can use existing known arbitrary catalyzer as catalyzer, but from the stability of resin, preferably use acid catalyst.As acid catalyst, any one of organic acid, mineral acid can be used.As organic acid, the organic carboxyl acids such as acetic acid, propionic acid, butyric acid can be listed.As mineral acid, the mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid can be listed.Acid catalyst adds after can adding water in the solution, or also can mix with water, adds as after aqueous acid.The addition of acid catalyst can suitably be selected.Hydrolysis reaction completes usually under 5 ~ 100 hours, also can heat being no more than at the temperature of 60 ~ 70 DEG C, and dripping the acid catalyst aqueous solution in containing the organic solvent of alkoxysilane compound containing trialkylsilyl group in molecular structure reacts, within the short reaction times, complete reaction.
Degree of hydrolysis in the presence of a catalyst, can regulate according to the addition of water.Be generally the total mole number of the alkoxyl group relative to the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in general formula (1), wish that water reacts with the ratio of 20 ~ 1000mol%, preferably 50 ~ 500mol%.If the addition of water is more less than above-mentioned scope, then degree of hydrolysis step-down, is difficult to form overlay film, so improper, on the other hand, if too much, then easily produces gelation, so improper.
In addition, representational containing silanol group or alkoxysilyl silicone resin as other, more than one that can list the halogenated silanes shown in following general formula (2) are hydrolyzed the silicone resin (polysiloxane) obtained in organic solvent.
(R
1)
n Si X
4-n (2)
(in formula, R
1represent hydrogen atom, can have substituent carbonatoms be 1 ~ 6 alkyl, carbonatoms be 3 ~ 6 cycloalkyl, carbonatoms be that the carbon atom of the α position of less than 15 does not connect the aralkyl of hydrogen atom, carbonatoms be 6 ~ 15 aryl or carbonatoms be the thiazolinyl of 1 ~ 6, X represents halogen atom, and n is the integer of 0 ~ 3).
In addition, as the R in general formula (2)
1, the R as above-mentioned general formula (1) can be listed
1the identical group of group represented is as preferred group.In addition, as X, chlorine atom, bromine atoms, atomic iodine can be listed.In addition, n also with above-mentioned general formula (1) similarly, preferably 0 ~ 1, so use together with the halogenated silane compounds that it can be 2 or 3 with n as required.By using this halogenated silane compounds, the method that can pass through and use the situation of this organoalkoxysilane shown in general formula (1) same, manufactures the silicone resin containing silanol group.Such as, for trihalosilane compound, a part of chloro silyl is hydrolyzed, condensation reaction, and form Si-O-Si key, remaining hydrolysis, chloro silyl becomes silanol group.The content of the silanol group in the silicone resin formed can be regulated by the kind, amount, reaction conditions etc. controlling the halogenated silane compounds used.When using halogenated silane compounds, the reactive group of the silicone resin containing silanol group obtained all forms silanol group.
(b) organic solvent
Contain in the silicone resin composition of silanol group or alkoxysilyl of the present invention, use the organic solvent for dissolving or disperse the silicone resin containing silanol group or alkoxysilyl.The solvent identical with the organic solvent used when carrying out the hydrolysis-condensation reaction of above-mentioned organoalkoxysilane can be used as organic solvent.As previously mentioned, as the organic solvent containing the silicone resin composition of silanol group or alkoxysilyl of the present invention, can hydrolysis-condensation reaction by organoalkoxysilane time solvent, the direct organic solvent as the silicone resin composition containing silanol group or alkoxysilyl utilizes, or other solvent can be added further wherein, or isolate solvent from the silicone resin be obtained by reacting, not solvent-laden silicone resin is dissolved in new solvent or dispersion etc., form composition and use.As previously mentioned, because the ethers such as ether-ether class, PGME such as PGMEA use for general flat-panel monitor, so when using silicone resin composition in this field, preferably use ethers or the solvent of ether ester type such as PGME or PGMEA.In addition, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetic ester etc. is also listed as preferred solvent.
(c) additive
As additive, such as tensio-active agent, thickening material etc. can be listed.Tensio-active agent is for improving the coating property of silicone resin composition, the wettability etc. to base material containing silanol group or alkoxysilyl.As tensio-active agent, known nonionic class tensio-active agent, anionic based surfactants, cationic based surfactants, amphoterics etc., negatively charged ion, cationic based surfactants, amphoterics are as catalyst action, promote silicone resin composition through time deterioration, so preferred nonionic class tensio-active agent.As nonionic class tensio-active agent, such as polyoxyethylene lauryl ether can be listed, polyoxyethylene oleyl ether, the Voranol EP 2001 classes such as PCE and polyoxyethylene fatty acid diester, polyoxy fatty acid monoester, polyoxyethylene polyoxypropylene block copolymer, alkynol, acetylene ethylene glycol, the poly-b-oxide of alkynol, the propargyl alcohol derivatives such as the poly-b-oxide of acetylene ethylene glycol, fluorochemical surfactant, such as Off ロ ラ mono-De (trade(brand)name, Sumitomo 3M (Co., Ltd.) manufactures), メ ガ Off ア Star Network (trade(brand)name, DIC (Co., Ltd.) manufactures), ス Le Off ロ Application (trade(brand)name, Asahi Glass (Co., Ltd.) manufactures), or organo-siloxane tensio-active agent, such as KF-53, KF-54 (Dou Shi SHIN-ETSU HANTOTAI chemical industry (Co., Ltd.) manufacture), SH7PA, SH21PA, SH28PA, SH30PA, ST94PA (Shi East レ ダ ウ コ mono-ニ Application グ (Co., Ltd.) manufactures) etc.As aforementioned alkynol, 3-methyl isophthalic acid-butine-3-alcohol, methylpentynol, 3,6-dimethyl-4-octynes-3 can be listed, 6-glycol, 2,4,7,9-tetramethyl--5-decine-4,7-glycol, 3,5-dimethyl-1-hexin-3-alcohol, 2,5-dimethyl-3-hexin-2,5-glycol, 2,5-dimethyl-2,5-hexane diol etc.
Containing the content of the silicone resin containing silanol group or alkoxysilyl in the silicone resin composition of silanol group or alkoxysilyl, relative to 100 parts by weight solvent, be preferably 1 ~ 40 weight part.If more than 40 weight parts, then resin through time degradation speed accelerate, not preferably.
In addition, the content of tensio-active agent is 50ppm ~ 100 in the composition, 000ppm, is preferably 100ppm ~ 50, the scope of 000ppm.If very few, be then difficult to obtain surfactivity, wettability is bad; If too much, then acutely bubble, coating machine produce foam accumulation etc., operational difficulty.
(ii) be coated with
Silicone resin composition containing silanol group or alkoxysilyl is applied on base material, forms the silicone resin overlay film containing silanol group or alkoxysilyl.As base material, there is no particular limitation, can list the various substrates such as silicon substrate, sheet glass, metal sheet, ceramic plate, particularly must insulating film liquid-crystal display TFT surface etc. be as substrate of the present invention preferred those.There is no particular limitation for coating process, can adopt the various methods such as such as spin-coating method, dip coating, spread coating, rolling method, spraying method, slot coated method.In addition, the concentration containing the silicone resin of silanol group or alkoxysilyl in coating solution is according to kind (such as, the R containing the silicone resin of silanol group or alkoxysilyl used
1the difference of kind, molecular weight etc.) and the change such as coating process, desired coating film thickness, there is no particular limitation, can select arbitrarily.
(iii) prebake
The silicone resin composition overlay film containing silanol group or alkoxysilyl formed on substrate so then carries out prebake, the organic solvent in removing composition.Prebake temperature is different according to the kind of the organic solvent used in composition, but if temperature is too low, then the residual component of organic solvent becomes many, may become the reason of infringement basal plate conveyer device etc.; On the other hand, if temperature is too high, then dry rapidly, produce vaporific mottled, or likely distil containing the silicone resin of silanol group or alkoxysilyl, so preferably 60 ~ 200 DEG C, more preferably 70 ~ 180 DEG C.Prebake such as uses the heating unit such as hot plate, baking oven to carry out, and the time of prebake is different according to the kind of organic solvent used and the temperature of prebake, preferably 30 seconds ~ 10 minutes, more preferably 1 ~ 5 minute.
(iv) alkaline aqueous solution process
After prebake, overlay film carries out alkaline aqueous solution process.To alkaline aqueous solution process, there is no particular limitation, can by dipping (immersions) in alkaline aqueous solution, revolve cover submergence, shower, slit, lid coating, spray method general like this carry out.When said composition contains tensio-active agent, preferably dipping (immersion) carries out.In addition, even if containing tensio-active agent, can carry out immersion process, also can be other method, such as, revolve and cover submergence coating.
As alkali, can be mineral alkali, also can be organic bases.As mineral alkali, alkali metal hydroxide, alkali metal silicate (hydrate), alkali metal phosphate (hydrate) etc. that sodium hydroxide, potassium hydroxide are such can be listed, the alkali metal hydroxides such as preferred sodium hydroxide and potassium hydroxide.
In addition, as organic bases, such as quaternary ammonium compound, alkamine (alkanol amine), ammoniacal liquor, alkylamine, heterocyclic amine etc. can be listed.As quaternary ammonium compound, tetramethyl ammonium hydroxide (tetramethyl-ammonium oxyhydroxide, below also referred to as " TMAH "), tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, hydroxide ethyl ammonium, hydroxide (2-hydroxyethyl) ammonium (choline), triethyl (2-hydroxyethyl) ammonium, hydroxide tripropyl (2-hydroxyethyl) ammonium, hydroxide (2-hydroxypropyl) ammonium can be listed as preferred material.Among them, particularly preferably TMAH and choline.
As alkamine (alkanol amine), such as 2-thanomin can be listed, 2-monoethanolamine etc. monoethanolamine, diethanolamine, trolamine, single Propanolamine, dipropanolamine, tripropanol amine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, monobutanolamine, two butanolamines, neopentyl alcohol amine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethyl propanol amine, N, N-diethylpropanolamine, N-(beta-aminoethyl) thanomin, N-Mono Methyl Ethanol Amine, N methyldiethanol amine, N-n-butylethanolamine, N-tertiary butyl thanomin, N-tertiarybutyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-di-n-butyl thanomin, N-ehtylethanolamine etc., wherein preferably use ethanolamines, particularly preferably monoethanolamine.
But, if from the approach obtained and organismal toxicity or be cured, such convenience that gasifies, preferably use the process of the TMAH aqueous solution.
In the present invention, the concentration of the alkaline aqueous solution used in alkaline aqueous solution process changes according to various factorss such as the kind of the silicone resin containing silanol group or silyl of the kind of the alkali used, concentration, process and thickness, and there is no particular limitation.During due to alkali concn height, the silicone resin containing silanol group or silyl may be dissolved, so preferably use the alkaline aqueous solution of undissolved concentration.In general, relative to the molecular weight of the silicone resin containing silanol group or silyl, if the ratio of silanol group increases, be then more easily dissolved in alkaline aqueous solution.In addition, according to the kind of alkali, dissolving power is also different.Generally, the alkali concn of alkaline aqueous solution ranges preferably from 0.1 ~ 10%, is more preferably 0.1 ~ 7.5%, and more preferably 0.1 ~ 5%.In addition, as previously mentioned, at the molecular weight relative to the silicone resin containing silanol group or silyl, during the ratio height of silanol group, because resin dissolves in alkaline aqueous solution, so according to the intensity of alkali, preferably reduce the concentration of alkaline aqueous solution.In addition, the film minimizing that alkaline aqueous solution process causes is preferably less than 10%, if more than 10%, then the meltage difference in overlay film becomes large, produces irregular, so improper.
Treatment time also has a greater change according to the kind of the silicone resin containing silanol group or silyl of the alkali concn of the kind of alkali used, alkaline aqueous solution, process and thickness etc., there is no particular limitation, the general treatment time being preferably 15 seconds ~ about 3 minutes.If the treatment time is short, then likely technique is uneven, if long, then efficiency is poor.In addition, process is carried out at normal temperatures.
In the present invention, pass through alkaline purification, as previously mentioned, transparency excellence can be independently formed with coating thickness, there is high scratch hardness, high-insulativity, low-k, and do not have film to reduce, even if do not have slight crack to produce in coating for during thick film yet, the cured film of excellent adhesion, this can infer that one of them reason is that alkoxysilyl residual in film becomes silanol group, and the compound of not fully polymerization is polymerized, molecular weight increases, the compound of small-molecular-weight disappears, the distillation amount of the compound in the film caused due to heating when firing solidification thus reduces, thus the film reduction of cured film reduces, but the present invention does not limit thus.
In addition, the inorganic alkaline aqueous solution also can use in hard coat film etc. is to electrical property and the no problem purposes of semiconductor property, but due in the aqueous solution containing the metal ion such as sodium, potassium, must consider to use in the purposes of electrical property, semiconductor property so be not adapted at the interlayer dielectric of TFT and leveling film etc.
v () rinses process
Rinse the alkaline aqueous solution that the overlay film face of process water flushing alkaline aqueous solution process remains to carry out.Therefore, as long as rinse the alkaline aqueous solution in overlay film face, can be arbitrary method.Such as, can adopt and overlay film is dipped in water, or water is flow through overlay film face, with flushing of water shower shape etc. as existing purging method known proper method.As long as flush time can remove the time of the alkaline aqueous solution on overlay film, just there is no particular limitation, such as, when dipping carries out, can carry out 30 seconds ~ about 5 minutes, when flowing water carries out, can carry out 15 seconds ~ about 3 minutes.In addition, as rinsing the water that uses in process if must in the purposes of electrical property or semiconductor property, preferred ion exchanged water or pure water.In addition, flooding in the flushing carried out, also can change washing, carrying out repeatedly immersion rinse.
(vi) (solidification) process is fired
Fire process preferably under the torpescence atmosphere such as nitrogen, helium, argon gas or in air, use the heating unit such as hot plate, baking oven, at the temperature of 120 ~ 400 DEG C, carry out 15 minutes ~ 3 hours, more preferably at 150 ~ 350 DEG C, carry out 30 minutes ~ 2 hours.Thickness when firing reduces the least possible for relatively good, and generally, the film thickness reduction rates before and after firing is less than 7.5%, is preferably less than 5%, is more preferably less than 3%.If fire film thickness reduction rates about 7.5%, then the irregular change of film is large, and when firing, the distillation from the compound of film is many, so have the problem of the compound polluted machine due to distillation.
Thickness after solidification is different according to purposes, and there is no particular limitation, can be less than 20 μm, is preferably less than 15 μm.And, in order to form this solidification thickness, determine to contain the concentration of silicone resin in the silicone resin composition of silanol group or alkoxysilyl and the glue spread of composition.If thickness is blocked up, then solidify in (slaking), also may generating layer be separated, so improper between the resin in film.
The silicone resin containing silanol group or alkoxysilyl of such formation is fired overlay film and is not almost fired the film minimizing caused, the transparency is excellent, there is high scratch hardness, high-insulativity, low-k, in addition planarization is excellent, slight crack is not had to produce even if form thick film yet, and substrate interface does not have film to peel off, excellent adhesion.
[embodiment]
Below, enumerate embodiment, comparative example, the present invention is further illustrated, but the present invention is not subject to any restriction of these embodiments, comparative example.
Production Example 1
By 47.6g (0.35mol) methyltrimethoxy silane, 29.7g (0.15mol) phenyltrimethoxysila,e, 4.83g (0.015mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride is dissolved in the 3-methyl-3-methoxybutanol of 200g, 34.2g distilled water is added while stirring at 45 DEG C, heated and stirred 1 hour, is hydrolyzed, condensation.Afterwards, wash more than 5 times with water, reclaim ethyl acetate oil reservoir.Then, this ethyl acetate oil reservoir is concentrated, is replaced into propylene glycol monomethyl ether, obtain 40% solution of methylphenylsilsesquioxane polycondensate.
The silicone resin obtained to be weight-average molecular weight (Mw) be 1,000 methylphenylsilsesquioxane (methyl: phenyl=7: 3 mol ratios).
The mensuration of weight-average molecular weight (Mw) uses following device, condition to carry out (such as, in the following examples, also measuring under identical condition).
Using appts, using method: the HPLC (GPC system) that Shimadzu Seisakusho Ltd. manufactures
The GPC post (G2000HXL 1, G4000HXL 1) that post: East ソ mono-(Co., Ltd.) manufactures
Use said apparatus, with the analysis condition of flow 0.7 ml/min, stripping solvents tetrahydrofurane, column temperature 40 DEG C, by being that the gel permeation chromatography (GPC) of standard measures with monodisperse polystyrene.
Production Example 2
Except in Production Example 1, temperature of reaction becomes beyond 60 DEG C from 45 DEG C, carry out the method same with Production Example 1, obtain the methylphenylsilsesquioxane (methyl: phenyl=7: 3 mol ratios) that weight-average molecular weight (Mw) is 2,000 thus.
Production Example 3
Except in Production Example 1, temperature of reaction becomes 60 DEG C from 45 DEG C, reaction times became beyond 6 hours from 1 hour, carry out the method same with Production Example 1, obtain the methylphenylsilsesquioxane (methyl: phenyl=7: 3 mol ratios) that weight-average molecular weight (Mw) is 4,000 thus.
Production Example 4
In 4 mouthfuls of flasks of the 300mL with agitator, reflux exchanger, dropping funnel and thermometer, add 14.8g water, the 35 quality % hydrochloric acid of 1.4g and 44.8g toluene, 11.1g (0.05mol) 3-acetyloxypropyl Trimethoxy silane and 40.8g (0.3mol) methyltrimethoxy silane, 29.7g (0.15mol) phenyltrimethoxysila,e are dissolved in 30g toluene, this mixed solution are added drop-wise at 15 ~ 25 DEG C in these 4 mouthfuls of flasks.After dropping terminates, at the same temperature, stir after 30 minutes, add water after leaving standstill, carry out separatory, reclaim oil reservoir.
Afterwards, wash 3 times with water, reclaim toluene oil reservoir.Then, add in eggplant type flask by this toluene oil reservoir, concentrate with vaporizer, with methanol dilution, be methyl alcohol by solvent exchange, adjustment entire amount is 250g.In this solution, add 50g water, at room temperature drop into 30.8g (0.22mol) salt of wormwood.Afterwards, stir 1 hour, stir after terminating, add ethyl acetate and water, carry out separatory, reclaim oil reservoir.
Afterwards, wash more than 5 times with water, reclaim ethyl acetate oil reservoir.Then, this ethyl acetate oil reservoir concentrated, is replaced into propylene glycol monomethyl ether, obtains 40% solution of 3-hydroxypropyl silsesquioxane polycondensate.
The 3-hydroxypropyl silsesquioxane polycondensate obtained to be weight-average molecular weight (Mw) be 3,000 methyl, 3-hydroxypropyl, phenyl silsesquioxane (methyl: 3-hydroxypropyl: phenyl=6: 1: 3 mol ratio).
Production Example 5
Add 600mi water in the reactor, divide while stirring at 30 DEG C and within 2 hours, drip the mixed solution of 283.5g (1mol) to methoxy-benzyl trichlorosilane and 300ml toluene, be hydrolyzed.Afterwards, operated by separatory, removing water layer, organic layer vaporizer distillates solvent.Under the decompression of this concentrated solution, heat 2 hours at 200 DEG C, carry out polyreaction.Add 200g acetonitrile in the polymkeric substance obtained, obtain the solution to methoxy-benzyl silsesquioxane.
In the solution obtained like this, below 60 DEG C, drip 240g trimethylsilyl iodide, react 10 hours at 60 DEG C.After reaction terminates, adding 200g water, be hydrolyzed, then, by pouring out, obtaining polymer layer.This polymer layer vacuum-drying, obtains 165g to hydroxybenzyl silsesquioxane.The molecular weight of this polymkeric substance uses GPC (gel permeation chromatography) to measure, the Mw=3 of polystyrene conversion, 000.
Production Example 6
In the reaction vessel with reflux exchanger, dropping funnel and agitator, add 400ml water, stir, add 400ml n-butyl acetate wherein.Reaction vessel outside is ice-cooled, and stirring velocity is to keep organic layer and the such low speed of water layer.Then, within 10 minutes, 52.2g (0.35mol) METHYL TRICHLORO SILANE, 31.7g (0.15mol) phenyl-trichloro-silicane is dripped from dropping funnel part.Now, the temperature of reaction mixture rises to 40 DEG C.Then, directly stir 30 minutes.After reaction terminates, organic layer washs washing water for neutral, and then, decompression distillates the solvent of organic layer, is diluted to 40%, obtains the methylphenylsilsesquioxane of target with PGMEA.When the molecular weight of this polymkeric substance is measured by GPC (gel permeation chromatography), with polystyrene conversion, Mw=2,000 (methyl: phenyl=7: 3 mol ratios).
Embodiment 1
In propylene glycol monomethyl ether (PGMEA), the weight-average molecular weight (Mw) adding 10g Production Example 1 manufacture is 1, methylphenylsilsesquioxane (methyl: phenyl=7: 3 mol ratios) solution, the 0.08g tensio-active agent KF-54 (manufacture of chemical industrial company of SHIN-ETSU HANTOTAI) (5%PGMEA solution) of 000 are 1, the amount of 000ppm, stirring and dissolving, manufactures 35% solution thus.Syringe type strainer that this solution is manufactured by ア De バ Application テ ツ ク East ocean (Co., Ltd.) (
, PTFE, filtering accuracy 0.20 μm) filter, prepare silicone composition.Said composition uses ミ カ サ spinner (manufacture of ミ カ サ Co., Ltd.), and the silicon wafer of 6 inches carries out spin coating with 600rpm/10sec, and at 110 DEG C, on hot plate, prebake is after 2 minutes, obtains 5 μm of thick silicone resin films.After this resin molding flooded for 30 seconds in 0.4 % by weight tetramethyl ammonium hydroxide (TMAH) aqueous solution, carry out flushing process by ion exchanged water, after blocking water completely, carry out in an oven firing process in 60 minutes at 250 DEG C.
Transmitance (400nm), pencil hardness, the film thickness reduction rates (hereinafter referred to as " firing film decrement ") fired that the film obtained is carried out, fire film and have crackless evaluation result to represent in Table 1.In addition, each evaluation is undertaken by following method.
(transmitance)
The MultiSpec-1500 that the ultraviolet-visible absorption spectroscopy of the cured film obtained uses (strain) Shimadzu Seisakusho Ltd. to manufacture measures, and tries to achieve the transmitance of wavelength 400nm.
(pencil hardness)
Measure according to JIS K5600-5-4.If pencil hardness is below HB, then may damage during substrate conveying etc., so pencil hardness desirably more than H, be preferably more than 3H.
(firing film thickness reduction rates)
Thickness before firing and the thickness after firing use ラ system ダ エ mono-ス VM-1200 (manufacture of large Japanese ス Network リ mono-Application) to carry out, use the sample determination parameter that absolute thickness is known in advance, use this parameter to carry out optical detecting, by following formula, calculate the film thickness reduction rates fired.
Fire film thickness reduction rates (%)=[thickness before (thickness after the thickness before firing-fire)/fire] × 100
(firing film has flawless)
Firing film, to have flawless be after being fired by film, leaves standstill diel, 4 inches of center wafer
circle in, be visually confirmed whether slight crack.
Embodiment 2
Except the molecular weight 2 using manufacture 2 to obtain, the methylphenylsilsesquioxane of 000 is as silicone resin, and use 2.38 % by weight tetramethyl ammonium hydroxide (TMAH) aqueous solution as beyond alkaline purification liquid, and embodiment 1 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 3
Except the molecular weight 3 using manufacture 4 to obtain, the methyl of 000,3-hydroxypropyl, phenyl silsesquioxane (methyl: 3-hydroxypropyl: phenyl=6: 1: 3 mol ratio) are as silicone resin, and use 2.38 % by weight tetramethyl ammonium hydroxide (TMAH) aqueous solution as beyond alkaline purification liquid, with embodiment 1 similarly, formed silicone resin fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 4
Except using 0.3 % by weight aqueous ethanolamine as except alkaline aqueous solution, and embodiment 1 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 5
Except not using tensio-active agent KF-54, and embodiment 1 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 6
Except the molecular weight 4 using manufacture 3 to obtain, the methylphenylsilsesquioxane of 000 is as silicone resin, use 5 % by weight tetramethyl ammonium hydroxide (TMAH) aqueous solution as alkaline aqueous solution, and make beyond firing temperature 300 DEG C, with embodiment 1 similarly, formed silicone resin fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 7
Except making firing temperature 180 DEG C, and embodiment 1 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 8
Except making firing temperature 300 DEG C, and embodiment 1 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 9
Except making thickness be except 7 μm, and embodiment 2 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Embodiment 10
The methylphenylsilsesquioxane of the molecular weight 2,000 obtained except using manufacture 6 is as beyond silicone resin, and embodiment 2 similarly, forms silicone resin and fires curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Comparative example 1
Except not carrying out except alkaline aqueous solution process, and embodiment 1 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Comparative example 2
Except not carrying out except alkaline aqueous solution process, and embodiment 2 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Comparative example 3
Except do not carry out alkaline aqueous solution process and use Production Example 5 to obtain the silicone resin of weight-average molecular weight 3,000 beyond, and embodiment 1 is similarly, forms silicone resin and fires curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Comparative example 4
Except not carrying out except alkaline aqueous solution process, and embodiment 6 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Comparative example 5
Carry out process except using 1N hydrochloride aqueous solution to replace except the process of tetramethyl ammonium hydroxide (TMAH) aqueous solution, and embodiment 1 similarly, forming silicone resin and firing curing overlay film.Carry out the evaluation of firing cured film that the gained identical with embodiment 1 obtains, obtain the result of table 1.
Comparative example 6
Except not carrying out except alkaline aqueous solution process, and embodiment 10 similarly, forms silicone resin and fire curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Comparative example 7
Carry out process except using ion exchanged water to replace except the process of tetramethyl ammonium hydroxide (TMAH) aqueous solution, and embodiment 1 similarly, forming silicone resin and firing curing overlay film.Carry out the evaluation that the gained identical with embodiment 1 fires cured film, obtain the result of table 1.
Table 1
Show from table 1, by carrying out alkaline aqueous solution process, the transparency can be formed excellent, there is high scratch hardness, high-insulativity, low-k and planarization excellent, even if form thick film also can not produce slight crack, and substrate interface does not have film to peel off, the curing overlay film containing the silicone resin composition of silanol group or alkoxysilyl of excellent adhesion.
Claims (5)
1. the curing overlay film formation method of a silicone resin composition, the method uses by (a) silicone resin containing silanol group or alkoxysilyl, (b) organic solvent, the composition that c additive that () uses as required is formed, at least pass through the polymerization of silanol group or alkoxysilyl, be cured, form the curing overlay film formation method of the silicone resin composition of overlay film, wherein the aforementioned additive used as required is selected from tensio-active agent and thickening material, it is characterized in that: foregoing is applied on base material, after carrying out pre-bake treatment, after alkaline aqueous solution process, rinse, fire.
2. the curing overlay film formation method of the silicone resin composition described in claim 1, is characterized in that: the process of the aforementioned base aqueous solution is by being impregnated in alkaline aqueous solution, or covers that submergence or shower carry out by revolving.
3. the curing overlay film formation method of the silicone resin composition described in claim 1 or 2, is characterized in that: the aforementioned base aqueous solution is organic alkaline aqueous solutions.
4. the curing overlay film formation method of the silicone resin composition described in claim 3, is characterized in that: the aforementioned base aqueous solution is the tetramethyl ammonium hydroxide aqueous solution.
5. the curing overlay film formation method of the silicone resin composition described in any one of Claims 1 to 4, is characterized in that: aforementioned firing is carried out at the temperature of 120 ~ 400 DEG C.
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