DESCRIPTION
PHOTOSENSITIVE SILOXANE COMPOSITION, CURED FILM FORMED
[
.[ THEREFROM AND DEVICE HAVING THE CURED FILM
TECHNICAL FIELD [0001]
The present invention relates to a photosensitive siloxane composition for forming a planarization film for a thin film transistor (TFT) substrate of a liquid crystal display device, an organic EL display device or the like, an inter layer insulation film of a semiconductor device, or a core or clad material of a light waveguide, a cured film formed therefrom and a device having the cured Film.
BACKGROUND ART [0002]
In recent years, for example, in liquid crystal displays and organic EL displays, a method for enhancing the aperture
ratio of a display device is Icnown as a method for achieving
i further higher precision and higher resolution (refer to Patent
Document 1). This is a method in which a transparent
heat-resistant planarization film is prepared on a TFT device
i to transmit light with more efficiency by applying a
planarization material onto the TFT device formed on a substrate

and thermally curing the material. [0003]
The materials used as the planarization films for TFT substrates are required to become highly heat resistant and highly transparent after curing, and as the materials having these characteristics, polysiloxane and silicone polyimide precursor are known (refer to Patent Documents 2, 3, 4). [0004]
iJonerally, when an organic compound is used for the planarization films for TFT substrates, its cured film had a problem that an adequate adhesiveness to a substrate surface
or a device surface composed of metal or an inorganic substance
i
is not achieved in addition to the problems of heat resistance and transparency. Therefore, a composition made by adding a silane coupling agent to a phenolic resin and a quinone diazide compound for improving the adhesiveness (refer to Patent Document 5), and a composition made by adding a silane coupling agent to an acrylic resin and a quinone diazide compound (refer to Patent Document 6) are known. In either technology, the silane coupling agent is added in order to improve adhesiveness to a substrate. However, when the.silane coupling agent is added to polysiloxane for the same purpose, an adequate adhesiveness to a substrate surface or a device surface can be achieved without impairing high heat resistance and high transparency, but there

is a problem that strains or cracks are generated depending on kinds of solvents used in a resist-stripping treatment by an alkaline solvent, which is performed to process,an upper layer of a cured film after forming the cured film. [0005]
Further, it is known that the adhesiveness is improved by adding aromatic bisimide oligomer to polyimide (refer to Patent Document 7) . However, since aromatic bisimide oligomer has absorption in a visible light region, the addition of the aromatic bisimide oligomer to polysiloxane enables to provide adequate adhesiveness to the substrate surface or the device surface and inhibit the occurrence of cracks due to an alkaline solvent, but it causes a problem of transparency. [0006]
On the other hand, a silicone polyimide precursor has an excellent adhesiveness to the substrate surface or the device foil r^ice and crack resistance against the alkaline solvent because it has a structure of a silane coupling agent at the end and a cured film formed from the silicone polyimide precursor has an imido bond, but the silicone polyimide precursor has large shrinkage during curing in its conversion to imido by heat because it has an amic acid structure and therefore it does not have sufficient planarization characteristics. Patent Document 1: Japanese Patent Publication No. 2006-227649

{claim 1)
Patent Document 2: Japanese Patent Publication No. 2006-18249 (claim 1)
Patent Document 3: Japanese Patent Publication No. 8-259894 (claims 1, 2)
Patent Document 4: Japanese Patent Publication No. 9-291150 (claim 1)
Patent Document 5: Japanese Patent Publication No. 2003-43688 (P-8)
Patent Document 6: Japanese Patent Publication No. 2005-49691 (P-18)
Patent Document 7 : Japanese Patent PublicationNo. 10-1542 (claim 1)
DISCLOSURE OF THE INVENTION Problems to solved by the Invention [0007]
The present invention has been made in view of such a situation, and it is an object of the present invention to provide a photosensitive siloxane composition which makes it possible to provide a cured film having low shrinkage during curing and high transparency after thermal curing, suppressing the occurrence of cracks due to an alkaline solvent and exhibiting excellent adhesiveness to a substrate.

It-, is also an object of the present invention to provide device materials, such as a heat-resistant insulation film, a planarization film for a TFT substrate, an interlayer insulation film, a core or clad material, and the like, which have the above-mentioned characteristics.
Means for solving the Problems [0008]
That is, the present invention pertains to a photosensitive siloxane composition containing (a) polysiloxane, (b) a quinone diazide compound, (c) a solvent, and (d) one or more kinds of imidosilane compounds represented by the general formulas (1) to (3): [0009] [Formula 1]

R

O O

R

R *—Si-R"-N R^^ N~R-Si—R

(1)

R

O O

R

R^

y
R\ N~R"—Si R

(2)

R^

.1
k3 n2
Ra—N R-'—R" Si R'
O R1
[0010]
I
wherein R^s may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having
1 to 6 carbon atoms, a phenyl group, a phenoxy group or an organic
'i
group replaced with them, R^ and R^ represent eacli a divalent
i
';u -"l-'inlc group having 1 to 10 carbon atoms, R'' represents an organic group not containing a silicon atom and having 2 to 20 carbon atoms (provided that R^ represents an organic group other than aphenyl group in the general formula (1) and represents anorganic
group, not containing an unsaturated bond, other than an
j alicyclic group in the general formula (2)), and Ra represents
a hydrogen atom or an organic group not containing a silicon
atom and having 1 to 20 carbon atoms.
Effects of the Invention [0011]
The composition of the present invention nas niyn
i sensitivity and high resolution in forming patterns and makes
it possible to form a cured film having high transparency,
excellent solvent resistance and high adhesiveness to a

substrate.
BEST MODE FOR CARRYING OUT THE INVENTION [0012]
The present invention pertains to a photosensitive siloxane composition containing (a) polysiloxane, (b) a quinone diazide compound, (c) a solvent, and (d) one or more kinds of imidosilane compounds represented by the general formulas (1) to (3): [0013] [Formula 2]

R
R
O O
If J
R^—Si-R^-N^R^ N-R^~Si—R^
R
O O
R
r Y

(1)

,Z^^Kt r%2 i: r^1

R\ N-R^—Si R
R^

(2)

Y
O
Ra—N- -R R'

-Si

(3)

[0014]
wherein R^s may be the same or different and each represents
an alkyl group having 1 to 6 carbon atoms, an alkoxy group having

1 to 6 carbon atoms, a phenyl group, a phenoxy group or an organic group replaced with them, R^ and R'' represent each a divalent organic group having 1 to 10 carbon atoms, R"^ represents anorganic group not containing a silicon atom and having 2 to 20 carbon atoms (provided that R^ represents an organic group other than a phenyl group in the general formula (1) and represents an organic group, not containing an unsaturated bond, other than an alicyclic group in the general formula (2)), and Ra represents a hydrogen atom or an organic group not containing a silicon atom and having 1 to 20 carbon atoms.
A structure of (a) polysiloxane used in the present invention is not particularly limited, but preferable aspects of the polysiloxane include polysiloxane obtained by mixing and reacting one or more kinds of organosilanes represented by the general formula (4): [0015] [Formula 3]
(R^^-Sif OR^) (4)
^ 'm 4-m ^
[0016]
wherein R^s represent any of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms and an aryl group having 6 to 15 carbon atoms and plural R^ may be the same or different^ R5S represent any of hydrogen.

an alkyl group having 1 to 6 carbon atoms, an acyi group having It"' u'bon atoms and an aryl group having 6 to 15 carbon atoms and plural R^ may be the same or different, and m represents an integer of zero to 3.'
The alkyl group, the alkenyl group and the aryl group represented by R^ in the general formula (4) all may have a substituent or may be an unsubstituted group not having a substituent, and these can be selected according to a characteristic of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, an n-decyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 3-glycidoxypropylgroup, 2-{3,4-epoxycyclohexyl)ethyl group, a 3-aminopropyl group, a 3-mercaptopropyl group, and a 3~i3ocyanatepropyl group. Specific examples of the alkenyl group include a vinyl group, 3-acryloxypropyl group and 3-methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a p-hydroxyphenyl group, 1-.(p-hydroxyphenyl)ethyl group, a 2-(p-hydroxyphenyl)ethyl group,
4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl group and naphthyl group. [0017]

The alkyl group and the acyl group represented by R^ in the general formula (4) all may have a substituent or may be an unsubstituted group not having a substituent, and these can be selected according to a characteristic of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n~butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.
Tn the general formula (4), m represents an integer of 0 to 3. If m is 0, the formula represents a tetrafunctional silane, and if m is 1, the formula represents a trifunctional silane, and if m is 2, the formula represents a difunctional silane, and if m is 3, the formula represents a monofunctional silane, [0018]
Examples of the organosilanes represented by the general formula (4) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane and tetraphenoxysilane; trifunctional silanes such as methyItrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyl tri-n-buthoxy silane, ethyItrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl tri-n-buthoxy silane.

n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,
decyltrimethoxysilane, vinyltrimethoxysilane, i vinyl triethoxysi lane, 3-inethacryloxypropyltrimethoxysilane,
3-inethacryIoxypropyltriethoxysilane, '
i 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane,
phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane,
1-(p-hydroxyphenyl)ethyltrimethoxysilane,
2-(p-hydroxyphenyl)ethyltrimethoxysilane, '
4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysil
ane, trifluoromethyltrimethoxysilane,
trifluoromethyltriethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane,
3-glycidoxypropyltriinethoxysilane,
3-glycidoxypropyltriethoxysilane,
'J. i ^, A -ei^oxycyclohexyl) ethyltrimethoxysilane and
3-mercaptopropyltrimethoxysilane; difunctional silanes such as
dimethyldimethoxysilane, dimethyldiethoxysilane,
dimethyIdiacetoxysilane, di-n-butyldimethoxysilane and
i diphenyldimethoxysilane; and monofunctional silanes such as
trimethylmethoxysilane and tri-n-butylethoxysilane.

Among these organosilanes, a trifunctional silane is preferably used in view of the crack resistance and hardness of a cured film. Further, these organosilanes may be used singly or may be used in combination of two or more species. [0019]
As (a) polysiloxane of the present invention, polysiloxane formed by copolymer! zing silica particles may be used. Examples of a method of copolymerizing silica particles include a method in which polysiloxane synthesized from the above-mentioned
organosilane is reacted with silica particles, and a method in
I which the above-mentioned organosilane is reacted with silica
particles to obtain polysiloxane. The silica.particles are
incorporated into the polysiloxane and at least a part of the
polysiloxane is chemically coupled with the silica particles
(coupled with the silica particles by a covalent bond), and thereby, the fluidity of the polysiloxane is lowered, sagging in patters during thermal curing is inhibited, and the resolution of patterns after thermal curing is improved.
In the method in which polysiloxane is reacted with silica particles, the silica particles are contained in the composition as an independent component, but they are incorporated into the polysiloxane by heating during pre-baking or curing.
[0020]
A number average particle diameter of the silica particle

to be used is preferably 2 to 200 nm, and more preferably 5 to 70 nm. When the number average particle diameter is smaller I liMi. . hin, an improvement in the resolution of patterns is not sufficient, and when the particle diameter is larger than 200 nm, the resulting cured film scatters light and the transparency of the cured film is deteriorated. Herein, as for the number average particle diameter of the silica particle, in a specific surface area method, the silica particles are dried and fired, specific surface areas of the resulting particles are measured, and then particle diameters are derived from the specific surface areas assumed that the particles are spherical to determine an average particle diameter in terms of a number average value. Equipment used for measuring the average particle diameter is not particularly limited, and for example, ASAP 2020 (manufactured by Micromeritics Instrument Corp.) can be employed. [0021]
The silica particles are obtained by a method of hydrolyzing and polycondensating one or more kinds of alkoxy silanes in the presence of water, an organic solvent and a base (preferably ammonia) . The silica particles dispersed in the organic solvent is obtained by replacing water, which is a dispersion medium of the water-based silica particle, with the organic solvent. Examples of a method of replacing the dispersion medium include

a method in which an organic solvent is added to water-based silica particles and water is distilled off by way of distillation, and the like. There may be cases where a part of "the surface of the silica particle is esterified by addition of lower alcohol depending on the species of the solvent. The silica particle dispersed in the organic solvent is preferable from the viewpoint of compatibility with the polysiloxane or the quinone diazide compound. [0022]
Specific examples of the silica particlofj include IPA-ST niiiiui isopropanol as a dispersion medium and having a particle diameter of 12 nm, MIBK-ST using methyl isobutyl ketone as a dispersion medium and having a particle diameter of 12 nm, IPA-ST-L using isopropanol as a dispersion medium and having a particle diameter of 45 nm, IPA~ST-ZL using isopropanol as a dispersion medium and having a particle diameter of 100 nm, PGM-ST using propylene glycol monomethyl ether as a dispersion medium and having a particle diameter of 15 nm (these are trade names, manufactured by Nissan Chemical Industries, Ltd.), OSCAL 101 using gamma-butyrolactone as a dispersion medium and having a particle.diameter of 12 nm, OSCAL 105 using gamma-butyrolactone as a dispersion medium and having a particle diameter of 60 nm, OSCAL 106 using diacetone alcohol as a dispersion medium and having a particle diameter of 120 nm, CATALOID-S using water

as a dispersion medium and having a particle diameter of 5 to 80 nm (these are trade names, manufactured by Catalysts & Chemicals Ind. Co., Ltd.)/ Quartron PL-2L-PGME using propylene glycol monomethyl ether as a dispersion medium and having a particle diameter of 16 nm, Quartron PL-2L-BL using gamma-butyrolactone as a dispersion medium and having a particle diameter of 17 nm, Quartron PL-2L-DAA using diacetone alcohol as a dispersion medium and having a particle diameter of 17 nm, Quartron PL~2L and GP-2L using water as a dispersion medium and having a particle diameter of 18 to 20 nm (these are trade names, manufactured by FUSO CHEMICAL CO., LTD.), Silica (SiOz) SG-SO 100 having aparticle diameter of 100 nm (trade name, manufactured by KCM Corp.), and REOLOSIL having a particle diameter of 5 to 50 nm (trade name, manufactured by Tokuyama Corp.). Further, these silica particles may be may be used alone or in combination of two or more species. [0023]
It Is preferable the surface of the silica particle used have a reactive group since the coupling of the polysiloxane with the silica particles becomes easy and film strength is enhanced. Examples of the reactive group include hydroxyl groups such as silanol, alcohol and phenol, vinyl groups, acrylic groups, ethynyl groups, epoxy groups and amino groups. By reacting the silica particle with alkoxy silane having a reactive

group, the silica particle having a reactive group at the surface can be obtained. As a matter of course, the si'lica particle having a substituent not having the reactive group such as,a methyl group, a phenyl group or the like may be used as long as it does not impair the effect of the present invention. [0024]
In the case where the silica particle is used, a mixing ratio of the silica particle to the polysiloxane is not particularly limited, but it is preferably 1 to 50% in terms of the ratio of the number of Si atom-moles of the silica particle to the number of Si atom-moles of the whole polymer. When this ratio is more than 50%, the compatibility between the polysiloxane and the quinone diazide compound is deteriorated and the transparency of a cured film is deteriorated.
The ratio of the number of Si atom-moles of the silica particle to the number of Si atom-moles of the whole polymer can be determined by calculating a ratio of a value of integral of a peak of Si-C bond to a value of integral of a peak of Si-0 bond in IR. When this ratio cannot be determined because the overlap of the peaks is large, it can be determined by determining a structure of the monomer other than the particles by ^H-NMR, ^■^C-NMR, IR, TOF-MS or the like and analyzing I the proportion between a gas generated and ash remaining (assumed that all ash is SiOa) in an elemental analysis method.

[0025J
From the viewpoint of achieving compatibll.i ty between crack resistance and hardness of the film in polysiloxane, the content cif; the phenyl group in the polysiloxane is preferably 20 to 70 mol% with respect to the amount of Si atoms, and more preferably 35 to 55 inol%. When the content of the phenyl group is more than 70 mol%, the hardness of the film is lowered, and when the content of the phenyl group is less than 20 mol%, the crack resistance is deteriorated. The content of the phenyl group can be determined, for example, by measuring a Si-nuclear magnetic resonance spectrum of polysiloxane and calculating a ratio of the peak area of Si having a phenyl group bonded to the peak area of Si having no phenyl group bonded. [0026]
The weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but it is preferably 1000 to 100000 on the polystyrene equivalent basis measured by GPC (gel permeation chromatography), and more preferably 2000 to 50000. When the Mw is smaller than 1000, the coatability of the composition becomes poor, and when it is larger than 100000, the solubility of the composition in a developer during patterning is deteriorated. Polysiloxane which is soluble in an aqueous alkaline solution is preferably 2000 to 50000, and the weight

average molecular weight of the polysiloxane is preferably 5000 to 100000. When the Mw is smaller than 5000^ a temperature at which sagging in patterning due to heat occurs may be lowered. [0027]
The phrase ""at least apart of the polysiloxane is chemically coupled with the silica particles (coupled with the silica particles by a covalent bond)", described above, means that reaction occurs between silica components in the silica particles and a part of the polysiloxane of a matrix, and the silica particles are incorporated at a fixed density into the polysiloxane . This state can be verified by observing a boundary zone between the M I i (■ 'f particle and the polysiloxane with a transmission electron microscope (hereinafter, abbreviated as TEM). When the silica particles are chemically coupled with at least a part of the polysiloxane, a boundary line between the silica particle and the polysiloxane is not observed by a TEM observation.
A system, in which the silica particles are chemically coupled with at least a part of the polysiloxane, is more preferable than a system in which the same amount of silica particles are added to the polysiloxane in that this system not only prevents the precipitation of silica particles from a pre-baked film during development, but also lowers the fluidity of the polysiloxane, inhibits sagging in patters during thermal curing, and improves the resolution of patterns after thermal

curing. [0028]
Polysiloxane in the present invention is obtained by hydrolyzing and partially condensing the above-mentioned organosilane. A common method can be used for the hydrolysis and partial condensation. For example, a solvent, water, and a catalyst as required are added to a mixture, and the obtained mixture is heated and stirred. During stirring, as required, the hydrolysis by-product (alcohols such as methanol) and condensation by-product (water) may also be distilled off. [0029] .
AS for a production method of the polysiloxane in the case of coupling the polysiloxane with silica particles, the polysiloxane is obtained by a method in which a solvent and water, and a catalyst as required are added to the organosilane to hydrolyze the organosilane, and the silica particles and the hydrolyzed organosilane are partially condensed. The silica particles may coexist with the organosilane-from start, or the silica particles may be added after hydrolyzing find polymerizing v,he organosilane to form polysiloxane and the resulting mixture may be further heated, butamethod, in which the silica particles are added dropwise immediately after hydrolyzing the organosilane, is preferable from the viewpoint of compatibility. [0030]

The reaction solvent is not particularly limited but a solvent similar to (c) a solvent described later is commonly used. An additive amount of the solvent is preferably 10 to 1000% by weight with respect to 100% by weight of organosilane or 100% by weight of a total amount of organosilane and silica particles. An additive amount of water to be used for a hydrolysis reaction is preferably 0.5 to 2 moles with respect to 1 mole of a hydrolyzable group. [0031]
The catalyst added as required is not particularly limited but an acid catalyst and a basic catalyst are preferably used. Specific examples of the acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trif luoroacetic acid, formic acid, polyhydric carboxylic acid or anhydride thereof, and an ion-exchange resin. Specific examples of the basic catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxy silane having an amino group and an ion-exchange resin. An additive amount of the catalyst is preferably 0.01 to 10% by weight with respect to 100% by weight of organosilane. [0032]
In view of the coatability and the storage stability of

the composition, it is preferable that a polysiloxane solution obtained after hydrolysis and partial condensation do not contain alcohol of aby--product, water, and the catalyst. These alcohol, water and catalyst may be removed as required. A method for i:i_'iuuviiig these is not particularly limited. As the method for removing alcohol or water, a method, in which the polysiloxane solution is diluted with an adequate hydrophobic solvent and is washed with water several times and the resulting organic layer is concentrated using an evaporator, can' be preferably employed. Further, as themethod for removing catalyst, amethod of treating the catalyst with an ion-exchange resin in addition to the above washing with water, or a method of only treating with the ion-exchange resin can be employed. [0033]
The photosensitive siloxane composition of the present invention contains (b) a quinone diazide compound. The photosensitive siloxane composition containing the quinone diazide compound forms a positive type in which an exposed portion is removed by a developer. An additive amount.'of the quinone diazide compound to be used is not particularly limited but it
is preferably 3 to 30% by weight with respect to (a) polysiloxane.
i
The additive amount is more preferably A to 20% by weight. When the additive amount of the quinone diazide compound is less than 3% by weight, the photosensitive siloxane composition does not

have realistic photosensitivity because of too low dissolution contrast between an exposed area and an unexposed area. The additive amount of the quinone diazide compound is preferably 4%by weight or more inorder to attain a more excellent dissolution contrast. On the other hand, when the additive amount of the quinone diazide compound is more than 30% by weight, a transparent and colorless property of a cured film is deteriorated since a coated film is whitened because of deteriorated compatibility between the polysiloxane and the quinone diazide compound or coloring due to the decomposition of the quinone diazide compound occurring during thermal curing becomes remarkable. [0034]
I'tin quinone diazide compound to be used is not particularly limited, but it is preferably a compound having naphthoquinonediazidesulfonate-bonded to a compound having a phenolic hydroxyl group, and a compound, in which the ortho-position and the para-position of the phenolic hydroxyl group are, respectively independently, occupied by a hydrogen atom or a substituent group represented by the general formula (5), is used as the quinone diazide compound. [0035] [Formula 4]

R^
C-R« 1 (5) . R'
[0036]
In the above formula, R^ to R^ independently represent any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group and a substituted phenyl group. Further, R"^ and R^, R^ and R^, or R^ and R^ may form a ring.
In the substituent represented by the general formula (5) , R^ to R^ independently represent any of an alkyl group havxng 1 to 10 carbon atoms, a carboxyl group, a phenyl group and a substituted phenyl group. The alkyl group may have a substituent or may be an unsubstituted group not having a substituent, and these can be selected according to a characteristic of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, a trifluoromethyl group and a 2-carboxyethyl group. Further, examples of a substituent with which the phenyl group is replaced include a hydroxyl group. Further, R^ and K**, K' and R^, or R^ and R^ may form a ring, and specific examples of the ring include a cyclopentane ring, a cyclohexane ring, an adamantine ring, and a fluorene ring.

[0037]
When each group at the ortho position and the para position of the phenolic hydroxyl group is other than the above groups, for example, a methyl group, thermal curing causes oxidative decomposition, and a conjugated compound typified by a quinoid structure is formed to color the cured film, thus lowering the transparent and colorless property. These quinone diazide compounds can be synthesized by a publicly known esterif ication reaction of the compound having a phenolic hydroxyl group with naphthoquinonediazidesulfoni'c acid chloride.
Specific examples of the compound having a phenolic hydroxyl group include the following compounds (trade names, manufactured by Honshu Chemical Industry Co., Ltd.). [0038] [Formula 5]


OH HO
HO
t-Bu HO
// \N ^"^

Bisphenol A
t-Bu —^ CH3/=/
CH3 ^^ ^
t-Bu t-Bu
Bis26B-A

BisP-MIBK

■OH
'H HO
■OH HO
HO

CH3
/ V CH2
CH2 CH3
nisP-DEK

, , CH3 /=
GOGH BisP-PR

CH
// Wt^ //
GHz I
CH2 COOH BisP-LV

■OH HO
OH
HO-
^ //

GH
CH3
CH3 I
G
BisP-OT

r%
BisP-AP

BisOTBP-AP

HO

^>r-^
CH3 BisP-DE

, . CH3
OH TrisP-HAP

H
OH

HO-/ Vc-\ /)-0H
BisP-DP

TrisP-PA

[0039]



t-Bu

BisOTBP-Z

BisP-FL

OH HO

TekP-4HBP ^^ ^° TekP-4HBPA


HO'
TrisP-TC
[0040]
7\n the naphthoquinonediazidesulfonic acid, 4-naphthoquinonediazidesulfonic acid or
5-naphthoquinonediazidesulfonic acid can be employed- A 4-naphthoquinonediazidesulfonate compound is suitable for i-beam exposure since it has an absorption band of light in i-beam (wavelength 365 nm) region. Furthermore, a 5-naphthoquinonediazidesulfonic ester compound is suitable for

exposure in a wide range of wavelengths since it has an absorption band of light in a wide range of wavelength region. It is preferred to select the 4-naphthoquinonedia2idesulfonnate compound or the 5-naphthoquinonediazidesulfonnate compound, depending on the wavelength used for exposure. A mixture of the 4-naphthoquinonediazidesulfonate compound and the 5-naphthoquinonediazidesulfonate compound can also be used. [0041]
A molecular weight of the naphthoquinone diazide compound is preferably 300 to 1500, and more preferably 350 to 1200. When the molecular weight of the naphthoquinone diazide compound is larger than 1500, there is a possibility that a pattern cannot be formed by 4 to 10% by weight of an additive amount of the compound. On the other hand, when the molecular weight of the naphthoquinone diazide compound is smaller than 300, the transparent and colorless property of the cured film may be deteriorated. [0042]
The photosensitive siloxane composition of the present invention contains (c) a solvent. The solvent is not particularly limited but compounds having an alcoholic hydroxyl group and/or cyclic compounds having a carbonyl group are preferably used. When these solvents are used, polysiloxane and the quinone diazide compound are uniformly dissolved, and

even after the composition is applied to form a liilm, the film ..,,,, ,,,.-i,.ieve high transparency without being whitened.
[0b43]
The compounds having an alcoholic hydroxyl group are not particularly limited but they are preferably compounds having a boiling point of 110 to 250°C under an atmospheric pressure. When this boiling point is higher than 250°C, an amount of a solvent remaining in the film increases and film shrinkage in thermally curing the film increases, and good flatness is not achieved. On the other hand, when the boiling point is lower than 110°C, because drying in coating is too fast, coatability is deteriorated, for example, a film surface is roughened. [0044]
Specific examples of the compounds having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone {diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-l-butanol, and 3-methyl-3-methoxy-l-butanol. Among these compounds, compounds further having a carbonyl group are preferable and diacetone alcohol is particularly preferably used. These

compounds having an alcoholic hydroxyl group may be used alone or may be used in combination of two or more species.
[0045]
The cyclic compounds having a carbonyl group are not particularly limited, but these are preferably compounds having a boiling point of 150 to 250°C under an atmospheric pressure. When this boiling point is higher than 250°C, an amount of a solvent remaining in the film increases and film shrinkage in thermally curing the film increases, and good flatness is not achieved. On the other hand, when the boiling point is lower bliau 150°C, because drying in coating is too fast, coatability is deteriorated, for example, a film surface is roughened. [0046]
Specific examples of the cyclic compounds having a carbonyl qroup include gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, and cycloheptanone. Among these compounds, particularly, gamma-butyrolactone is preferably used. These cyclic compounds having a carbonyl group may be used alone or may be used in combination of two or more species. [0047]
The compounds having an alcoholic hydroxyl group and the cyclic compounds having a carbonyl group, described above, may

be used singly, or may be used as a mixture thereof. In the case where both the compounds are used as a mixture, a weight ratio between both the compounds is not particularly limited, but the ratio of the compound having an alcoholic hydroxyl group to the cyclic compound having a carbonyl group is preferably (99 to 50) / (1 to 50) , and more preferably (97 to 60) / (3 to 40) . When an amount of the compound having an alcoholic hydroxyl group is more than 99% by weight {an amount of the cyclic compound having a carbonyl group is less than 1% by weight), the compatibility between the polysiloxane and the quinone diazide compound is low and a cured film is whitened, resulting in the deterioration of transparency of the cured film. Further, when the amount of the compound having an alcoholic hydroxyl group is less than 50% by weight (the amount of a cyclic compound having a carbonyl group is more than 50% by weight), a condensation reaction of an unreacted silanol in the polysiloxane is apt to occur and storage stability becomes poor. [0048]
Tlie photosensitive siloxane composition of the present invention may contain other solvents as long as the solvent does not impair an effect of the present invention. Examples of other solvents include esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-l-butyl acetate.

3-methyl-3-methoxy-l~butyl acetate and the like; ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and the like; and ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether and the like.
An additive amount of the solvent is preferably within a range of 100 to 1000% by weight with respect to polysiloxane. [0049]
The photosensitive siloxane composition of the present invention contains one or more kinds of imidosilane compounds represented by the general formulas (1) to (3) . The compounds shown in the paragraph (d) contributes to an improvement in chemical resistance and an improvement in adhesiveness to a substrate of a film formed by thermally curing the composition [0050] [Formula 7]
R^ O O R1
-I il il I
■ 1 r Y
R^ O 6 R^
R^
RX >~R'-Si—R^ (2)

R

R^
Ra-N R'—R' Si R' (3)
T
[0051]
wherein R^s may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group or an organic group replaced with them, R^ and R^ represent each a divalent organic group having 1 to 10 carbon atoms, R-^ represents an organic group not containing a silicon atom and having 2 to 20 carbon atoms (provided that R"* represents an organic group other than a phenyl group in the general formula (1) and represents an organic group, not containing an unsaturated bond, other than an alicyclic group in the general formula (2)), and Ra represents a hydrogen atom or an organic group not containing R -si 1 iron atom and having 1 to 20 carbon atoms.
Among the imidosilane compounds of a paragraph (d) of the present invention, imidosilane compounds represented by the general formulas (1) and (2) can be readily prepared from the following isocyanate silane compound and acid dianhydride by a publicly known direct imidation process. [0052]
- NC0-R^-Si-{RM3, NC0-R^-Si-{R^)3

In the above general formulas, R^s may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group and an organic group replaced with them.
As the alkyl group, the alkyl groups having 1 to 6 carbon atoms are preferable, and specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among them, the methyl group and the ethyl group are preferable in that they can be readily prepared. Further, as the alkoxy group, the alkoxy group« liaving 1 to 6 (Ttrhon atoms are preferable, and specific examples of the alkoxy groups include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Among them, the methoxy group and the ethoxy group are preferable in that they can be readily prepared. Further, R^ may be an organic group replaced with an alkyl group, an alkoxy group, a phenyl group or a phenoxy group, and examples of groups include 1-methoxypropyl group. [0053]
R and R represent a divalent organic group having 1 to 10 carbon atoms . Specif ic examples of the divalent organic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, ann-pentylene group, anoxymethylene group, an oxyethylene group, an oxy-n-propylene group, an oxy-n-butylene group, and an oxy-n-pentylene group. Among

them,, the methylene group, the ethylene group, the n-propylene group, and the n-butylene group are preferable in that they can be readily prepared. [0054]
R^ represents a structural component of the acid dianhydride in the general formula (1) , and this aciddianhydride is anorganic group containing an aromatic ring or an aliphatic ring, and is preferably one of tetravalent to tetradecavalent organic groups having 5 to 20 carbon atoms among them. Specific examples of the acid dianhydrides include aromatic tetracarboxylic dianhydrides such as 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,l-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,l-bis{2,3-dicarboxyphenyl)ethane dianhydride, b l,M t i, 'l-dicarboxyphenyl) methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis{3,4-dicarboxyphenyl)sulfone dianhydride, bis{3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylie dianhydride.

9,9-bis(3,4~dicarboxyphenyl)fluorenic dianhydride,
9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl)fluorenic
dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride,
2,3,5,6-pyridinetetracarboxylic dianhydride,
3,4,9,10-perylenetetracarboxylic dianhydride,
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride,
3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride and the
like; hydrogenated pyrornellitic dianhydride,
butanetetracarboxylic dianhydride,
1,2,3,4-cyclopentanetracarboxylic dianhydride,
1,2,3, 4-cyclobutanetracarboxylic dianhydride, RIKACIDTDA-100
(trade name, manufactured by New Japan Chemical Co., Ltd.),
RIKACID BT-100 (trade name, manufactured by New Japan Chemical
Co. , Ltd.) , EPICLONB-4 400 {tradename, manufactured by Dainippon
Ink and Chemicals, Inc.), and aliphatic tetracarboxylic
dianhydrides having the following structures:
[0055]

[Formula 8]
O 0 o o o 0
°vO



K^°
IT
0 u
0 o 71 o (T
0 0
[0056]
When R^ is an aromatic group such as a tolyl group, a naphthyl group or the like, there is a possibility that the transparency

of a cured film obtained from a corresponding composition is deteriorated because the cured film contains a compound having a similar structure to the above-mentioned aromatic imido 'i| i'l' ''f'l" f>f a coloring source. Further, if the composition contains the above-mentioned aromatic group, the compatibility between R^ and the polysiloxane may be deteriorated. Furthermore, if the composition contains the above-mentioned aromatic group, this may cause phase separation and make the film cloudy when preparing the coated film to deteriorate the light transmittance of the cured film. Accordingly, when R^ is the aromatic group, an additive amount of R^ is limited, and therefore R^ is particularly preferably an aliphatic organic group. When R"^ is the aliphatic organic group, since the cured film does not have a structure of the coloring source, a transmittance is not reduced, and since the compatibility of R^ with the polysiloxane is high, the cured film can have a high light transmittance without causing the white turbidity in curing the film. Particularly preferable specific examples of the compounds represented by the general formula (1) are shownbelow. In the present invention, imidosilane compounds represented by the general formula (1) may be used and these imidosilane compounds may be used alone or may be used in combination of two or more species. [0057]

[Formula 9]

OCH3 N—C3H6—Si—OCH3 OCH3
OCH3
O
O
OCH3 H3CO—Si—C3H6—N
OCH3 o O
OCH3 CH3
H3CO—Si—CgHfi—N I ,N—C3H6—Si—OCH3
OCH3 CH3
O O
O O
I CH3
H^C—Si—CaHe—N N-C3H6—Si—CH3
O O
O O
CH3 H3C—Si—C3H6—N CH3
CH3 CH3
o o
N—C3H6—Si—CH3 CH3

OC2H5 N—C3H6-SI—OC2H5 OC2H5
O
OCH3 I N—CaHe—Si—OCH3
O OCH3
^ OCH3
N—C3H6—Si—OCH3
OCHa
OC2H5 N—CaHg-Si—OC2H5 OC2H5
OC2H5
N C3H6—Si—OC2H5
OC2H5
OC2H5
C2H5O—Si—CaHe—N
OC2H5 O
OCH3 I H3CO—Si—C3H6—N
OCH:, Q
O OCH3
H3CO—Si—C3H6—N
o 9*^3 o
OCH3 Q
OC2H5 C2H5O—Si—C3H6—N OC2H5
OC2H5
C2H5O St C3H6 N
OC2H5

C2H5O—Si—C2H4—N IT [iT^N—C2H,-Si-OC2H5
OC2H5 &^ ^O OC2HS
O
C2H3—Si-C3He-N TJ \T.N-C3He-Si-C2Hs
OC2H5 ^ S *^^2H5
[0058]
Further, R^ represents a structural component of the acid anhydride in the general formula (2), and this acid anhydride is any one of divalent to tetradecavalent organic groups containing an aliphatic ring other than maleic anhydride and an organic group having 4 to 20 carbon atoms. [0059]
Specific examples of the acid anhydrides include succinic anhydride, glutaric anhydride,
4-methylcyc_:lohtixanti-l, 2-dicarbGxylic anhydride, cis-4-cyclohexene-l,2-dicarboxylic anhydride, cis-1,2-cyclohexane dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (these are iii'*hufactured by TOKYO KASEI KOGYO CO., LTD.), 3,4,5,6-tetrahydrophthalic anhydride {manufactured by Wako Pure Chemical Industries, Ltd.), RIKACID HNA (trade name, manufactured by New Japan Chemical Co., Ltd.), and RIKACID

HNA-100 (trade name, manufactured by New Japan Chemical Co., Ltd. ) . Among them, particularly preferable acid anhydrides are succinic anhydride, glutaric anhydride, 4-methylcyclohexane-l,2-dicarboxylic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Among them, succinic anhydride, glutaric anhydride, and 5-norbornene-2,3-dicarboxylic anhydride are particularly preferable from the viewpoint of transparency and adhesiveness. With respect these, R'^ represents anorganicgroup, not containing an unsaturated bond, not containing a silicon atom and having 2 to 20 carbon atoms, other than an alicyclic group in the general formula (2). [0060]
Among the imidosilane compounds of a paragraph (d) of the present invention, imidosilane compounds represented by the general formula (3) can be readily obtained by a publicly known imidation process in which an imidosilane compound is synthesized from an amine compound and an acid anhydride-containing compound through amic acid. [0061]
The amine compound can be obtained from the following primary amine and the acid anhydride-containing compound can be obtained from the following acid anhydride-containing silane compound.

[00G2] [Formula 10]
o
H2N Ra o(^R^—R^—Si—(^R^
o
[0063]
In the above general formulas, R^s may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group and an organic group replaced with them.
As the alkyl group, the alkyl groups having 1 to 6 carbon atoms are preferable, and specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among them, the methyl group and the ethyl group are preferable in that they can be readily prepared. Further, as the alkoxy group, the alkoxy groups having 1 to 6 carbon atoms are preferable, and specific examples of the alkoxy groups include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Among them, the methoxy group and the ethoxy group are preferable in that they can be readily prepared. Further, R^ may be an organic group replaced with an alkyl group, an alkoxy group, a phenyl group or a phenoxy group, and examples of groups include a 1-methoxypropyl group-[0064]

R^ represents a divalent organic group having 1 to 10 carbon atoms. Specific examples of the divalent organic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an oxymethylene group, an oxyethylene group, an oxy-n-propylene group, an oxy-n-butylene group, and an oxy-n-pentylene group. Among them, the methylene group, the ethylene group, the n-propylene group, and the n~butylene group are preferable in that they can be readily prepared. [0065]
Ra represents a structural component of the above-mentioned primary amine and represents an organic group not containing r* hylr-igen atom and a silicon atom and having 1 to 20 carbon atoms . Specific examples of the organic groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a cyclohexyl group, a 2-hydroxyethyl group, a phenyl group, a methoxyphenyl group, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Among them, the methoxy group and the ethoxy group are preferable in that they can be readily prepared. Ra may be an organic group replaced with an alkyl group, an alkoxy group, a phenyl group or a phenoxy group, and examples of the groups include a 1-methoxypropyl group. Among them, a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, a

CLAIMS
1. A photosensitive siloxane composition containing (a) polysiloxane, (b) a quinone diazide compound, (c) a solvent, and (d) one or more kinds of imidosilane compounds represented by the general formulas (1) to (3): [Formula 1]

R
R
O O
1 ' 2 ^ 3^ 4 ■ 1
R^—Si-R1-N 11R12 N-R1-Si—R^
R
O O
R

(1)

R^

R'

N-R^—Si R'

(2)

R

O

R^

Ra—N ,R'
R" Si R' (3)
O R1
(wherein R1s may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group or an organic group replaced with them, R^ and R'' represent each a divalent organic group having 1 to 10 carbon atoms, R^ represents an organic group not containing a silicon atom and having 2 to 20 carbon
atoms (provided that R^ represents an organic group other than


group, not containing an unsaturated bond, other than an salicylic group in the general formula (2) ) , and Ra represents a hydrogen atom or an organic group not containing a silicon atom and having 1 to 20 carbon atoms).
2. The photosensitive siloxane composition according to
claim 1, wherein a total amount of (d) the compound represented
by the general formulas (1) to (3) is 0.1 to 10% by weight with
respect to polysiloxane.
3. The photosensitive siloxane composition according to
claim 1 or 2, wherein (a) the polysiloxane is a copolymer and
contains silica particles chemically coupled with at least a
part of the polysiloxane.
4. A cured film obtained by applying and patterning the
photosensitive siloxane composition according to any one of
claims 1 to 3, wherein said cured film has a light transmittance
per a film thickness of 3 fm at a wavelength of 400 nm is 95%
or more.