TW201005443A - Photosensitive polyorganosiloxane composition - Google Patents

Abstract

Disclosed is a photosensitive polyorganosiloxane composition comprising component (a): 100 parts by mass of a polyorganosiloxane wherein the polyorganosiloxane has been obtained by mixing a silanol compound represented by general formula (1): R2Si(OH)2, an alkoxysilane compound represented by general formula (2): R'Si(OR'')3, and an alkoxysilane compound represented by general formula (3): R'''Si(OR'''')3 in a specific molar ratio range with a catalyst selected from the group consisting of metal alkoxides represented by general formula (4): M(OR''''')4, metal alkoxides represented by general formula (5): M'(OR'''''')3, and Ba(OH)2 and polymerizing the mixture without the addition of water, and component (b): 0.1 to 20 parts by mass of a photopolymerization initiator. The groups in the general formulae (1) to (5) are as defined in the claims.

Description

201005443 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a photosensitive organic polyoxo-oxygen composition, a semiconductor device using the same, and the like, which can be used for an electron. The formation of a surface protective film, an interlayer insulating film, an alpha ray shielding film, etc. in an insulating material of a component or a semiconductor device, and can be used for carrying an image sensor, or a micromachine (Micr〇MacMne) or a pico A semiconductor device of a Micro Actuator or the like. [Prior Art] In the use of insulating materials for electronic components, surface protective films for semiconductor devices, interlayer insulating films, and α-ray shielding films, polyimines having excellent heat resistance, electrical properties, and mechanical properties are widely used. (p〇lyimide) resin. The S-polymerized imine resin is generally characterized in that it is supplied in the form of a photosensitive polyimide intermediate precursor composition, which is applied to a substrate, and is soft-baked and soft-coated. A patterned mask is used to irradiate (exposure) the active light, develop it, and perform a heat hardening treatment, whereby a hardened relief pattern (Relief Pattern) containing a heat-resistant polyimide resin can be easily formed. (For example, refer to the patent literature!). In recent years, in the manufacturing steps of semiconductor devices, the materials are more and more demanding for materials which can be subjected to the above-described heat hardening treatment at a lower temperature, mainly depending on the material or structural design of the constituent elements. However, in the case of using the prior polyimine resin precursor composition, if the hardening treatment temperature is lowered, the thermal imidization cannot be completed, and the various hardened films are deteriorated, so that the hardening is caused. The lower limit of the processing temperature is up to about 3 〇〇t. However, the design concept of the recent semiconductor device attempts to increase the wiring profile of the desired portion to a large extent in order to follow the previous trend of high-density of the multilayer, while reducing the resistance, the resistance noise accompanying it, and the resistance heating 2 . In particular, if a "huge wiring" layer having a height of 1 Gm or more is covered with a prior polyimine precursor composition and thermally hardened, the volume shrinkage is about 4% due to the volatilization of the residual solvent component. This results in a large step difference on and around the "huge wiring", so the manufacturer has a higher requirement for materials that can cover it more evenly and flatly. Patent Document 2 listed below discloses a photosensitive Oxygen-based material which can be cured at a low temperature and has a small volume shrinkage during thermal curing. However, by the technique disclosed herein, it is difficult to achieve stable formation of only electronic parts or The properties of the surface protective medium, interlayer insulating film, and alpha ray shielding film of the semiconductor device, for example, coating properties to various substrates, adhesion to the underlying substrate, or mechanical properties at a practical level. Further, after the material disclosed in Patent Document 2 is applied onto a substrate, soft baking is carried out as in the prior polyimide polyimide precursor composition, and the coating film remains viscous and fluid. Therefore, it is undeniable that there will be a new process, a spoon, and a device contamination caused by contact between the coated substrate and the device in the transfer, or the substrate must be kept horizontal to prevent the coating. The film flows on the substrate and the like. On the other hand, a semiconductor device having an optical function or a mechanical function in or on an integrated circuit has been obtained.

Most of the system is manufactured by using a method known as I 139050.doc 201005443 to form a transistor (such as Transis (four)) on a crystalline substrate such as a semiconductor device to form a function corresponding to the purpose of the semiconductor device. An element (microstructure) is packaged as one. As an example of such a package technique, for example, in the following Patent Document 3, a semiconductor device and an example thereof are disclosed, and the semiconductor device has a microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, and a spacer for covering the package on the microstructure on the microstructure. Patent Document 3 The technique disclosed in the above can be preferably used in a wide range of various sensors such as a micro lens array, a chemical sensor, or a surface acoustic s (Aecmstic Wave) device. In the semiconductor device, in order to implement the invention described in Patent Document 3, a spacer for supporting the encapsulating material on the microstructure (which may also behave as a barrier) , the next door) plays an important role, as the characteristics required for the spacer, it is considered to have the following three aspects. The first spacer as the law should be formed only in the desired part, therefore, if it is itself a photosensitive member It is advantageous to form. The reason is that if the spacer itself is photosensitive, the usual lithography (Lith()gr) step and etching can be omitted because the spacer is only shackled in the desired portion. Further, in the (Etching) step, a member having a low heat resistance, for example, an adhesive such as an epoxy resin may be used around the spacer, and the heat resistance of the microstructure or the like located at the lower portion thereof may not be required. Therefore, secondly, it can be said that the degree of the process for forming the spacer is as low as possible. Third, because the spacer forms a closed space including the microstructure, 139050.doc 201005443 cited: Patent Document 3 The "cavity heart kiss" is formed, so it is unsatisfactory that the volatile components contained in the package remain after the end of the package. That is, the spacer is required to be a low volatile component. Although it is considered that the spacer is required to have the characteristics as described above, Patent Document 3 does not disclose a specific member for the spacer. Still found that it is excellent in low-temperature hardening property, that is, the current state is ~...one sigh, ^]匕" volume shrinkage is less, non-sticky and has a photosensitive property that can only replace the practical properties of the previous polyimine precursor Film forming material. [Patent Document 1] Japanese Patent No. 2826940 [Patent Document 2] European Patent No. 1196478 (Patent Document 3) Japanese Patent Laid-Open Publication No. Hei. No. Hei. The invention is intended to solve the problem of (4) in the pure light supply organic poly-stone oxygen burning group. 'The object' can be used for the formation of electronic components in recent years, the formation of surface protective films, interlayer insulating films, alpha ray shielding films, etc. in edge materials or semiconductor devices, and can be used to mount image sensors, or micromachines or The resin composition of a semiconductor device such as a microactuator is excellent in coating property and photosensitive property for various substrates, and can be subjected to low temperature hard enthalpy under 2 thieves and volatile at 150 C (all ^; f The amount of reduction rate) and the volume shrinkage ratio (residual film rate after curing) at the time of curing are small, and the coating composition and the soft baked film obtained by soft baking can be reduced (hereinafter, also referred to as " Soft bake film"). [Technical means to solve the problem] 139050.doc 201005443 This: The people of Ming and others worked hard to study and repeat the experiment, and the result unexpectedly was sent to the right using photopolymerizable carbon, carbon double bond and having 5 to 6 members containing nitrogen atoms. A soft-baked film of a photosensitive organic poly-baked composition using the same, which is a raw material for organic poly-dosing, which is a raw material for organic poly-money. The viscous property of the present invention is the following [1] to [19]: Π] A photosensitive filament 11 oxygen test composition comprising the following components (4) and (b): a) 1 part by mass of organic polyoxyl, wherein the organic polyoxo is obtained by the following formula: m: the following general formula (1): [Chemical 1] R*S 1 (OH), (1) In the formula, R is a valence group having at least one aromatic group and having a carbon number of from 6 to 18, and may be the same or different. } at least one kind of hospital alcohol compound represented by the following formula (2): [Chemical 2]

Rr S 1 (〇Rf,) , (2) wherein R1 is a photopolymerizable carbon-carbon double bond and has a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity). The organic group 'having a carbon number of 2 to u' and R'' is a methyl group or an ethyl group, and may be the same or different. } at least one alkoxydecane compound represented by the following formula (3): 139050.doc 201005443 [Chemical 3] R", SI <〇R,.,,), (3) { R is an organic group having a photopolymerizable carbon-carbon double bond group having 2 to 17 carbon atoms and R"" is a methyl group or an ethyl group, and may be the same or different. An alkoxydecane compound, which is selected from the group consisting of the following formula (4): [Chemical Formula 4] M (〇R,,...) < (4) {式中为石夕,锗,Titanium or erroneous and R , "" is the base of the carbon number 4 and can be the same or different. } The metal oxide represented by the following formula (5): [5] (5) (OR"" " {" in the form of 'M, for the 'trans, and vice,, ... is the carbon number!~ 4 of the hospital bases, all of which may be the same or different.} At least one of the group consisting of the metal lanthanum oxide and the Ba(〇H) 2 group is combined with the polymerization, and the polymerization is carried out without adding water. The molar ratio of the (four) alcohol compound represented by the formula (1) to the alkoxylate compound represented by the formula (10) and the alkoxylated compound represented by the formula (7) is 50: 3 (four): 7〇, and the molar ratio of the alkoxylated compound represented by the formula (7) to the amphoteric compound represented by the formula (3) is 70: 3〇~3〇: 7〇; (b) Photopolymerization initiator 〇.1 to 2 〇 parts by mass. m The photosensitive organic polyoxo-fire composition of the above π], wherein 139050.doc -8 - 201005443 is in the component (a), and further contains (c) a compound other than the component (a) having two or more photopolymerizable unsaturated bond groups. [3] A photosensitive organic polyoxyalkylene as described in [1] or [2] above. Composition, phase The component (a) further contains 5 Å to 2 parts by mass of (d) a secondary ruthenium network obtained by co-hydrolysis of an organodecane compound having 2 to 4 hydrolyzable groups. The photosensitive organic polyoxane composition according to any one of the above [1] to [3] wherein the catalyst is selected from the group consisting of the above-mentioned catalysts. At least one metal oxide oxide of the metal alkoxide represented by the formula (4) and the metal alkoxide represented by the formula (5). [5] as described above [1] The photosensitive organic polyoxoxane composition according to any one of the above-mentioned, wherein the catalyst is selected from the group consisting of a metal alkoxide represented by the formula and a metal alkoxide represented by the formula (5) And at least one catalyst selected from the group consisting of Ba(〇H)2 and a mixture of at least one catalyst selected from the group consisting of potassium hydroxide and sodium hydroxide. [6] As described above [ The photosensitive organic polyoxyalkylene composition according to any one of [1], wherein the (a) component further contains o.hM parts by mass (e) selected from CH30)3-SBu(CH2)3-〇-CO-C(CH3)=CH2, (CH30)3-Si-(CH2)3-0-CO-CH=CH2, and (CH30)3-Si- (CH2) 3-0-CH2-C2H30 {Note C2H30 is an epoxy group} of at least one or more of the organic ruthenium compounds. [7] The sensitization according to any one of the above [1] to [6] The organopolysiloxane composition [in the above-mentioned (4) component further contains (1) parts by mass of (1) a polyvalent thiol compound containing at least two or more thiol groups. [10] The photosensitive organic polyoxane composition of any one of the above [1] to [7], which further contains 〇.〇5~2〇 with respect to the component (4) (g) is given by the following general formula (6): [Chemical 6]

In the case where 'h is an integer of 1 or 2', when h is 1, 2 is a divalent aromatic group, and when h is 2, Xa is a tetravalent aromatic group, and Xc is a direct bond. a divalent organic group of a carbon atom of a halogen atom, (1 is an integer of 1 to 3, and Re and Rf are an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and 8 is 〇,

Rb is a hydrogen atom or! Valence hydrocarbon group. The carboxyl group-containing organic quinone compound represented. [9] The photosensitive organic polyoxymethane composition according to any one of the above [A] to [8], which further contains 0.01 to 10 parts by mass of (h) nonionic interfacial activity with respect to the component (a) Agent. [10] A method for forming an organopolysiloxane film, comprising the step of applying the photosensitive organic polyoxophobic composition according to any one of the above [1] to [9] to a substrate. . [11] An organic polyoxyalkylene cured film obtained by hardening an organic polyoxazine film obtained by the method of the above (10) by irradiation or heating with active light. 139050.doc 201005443 Π2] A method for forming an organopolyoxyalkylene hardened relief pattern, comprising: a step of forming an organic polyoxygen alkoxide film on a substrate by the method of [10] above; a spacer pattern a step of irradiating the film with active light and photohardening the exposed portion; a step of removing the uncured portion of the film using a developing solution; and a step of heating each substrate. [13] An organopolyoxane hardened relief pattern obtained by the method of [12] above. ❹ [14] A semi-guided vessel device which contains the organic polysulfide hardening medium of the above [11]. [15] A semiconductor device which contains an organic polyoxygenated embossed relief pattern as described above. [16] A semiconductor device having a microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, and a package for supporting the package on the microstructure The spacer material of the material, wherein the spacer material is an organopolyoxane-hardened relief pattern as described in [13] above. [17] The semiconductor device according to [16] above, wherein the integrated circuit includes a photodiode. [18] The semiconductor device according to [16] or [17] above, wherein the microstructure is a microlens. [19] A method of manufacturing a semiconductor device, which is used for manufacturing a semiconductor device according to any one of the above [6] to [18], which comprises: forming an organic polymer directly or via a thin film layer on the microstructure a step of argon oxide film, a step of irradiating the film with actinic light and subjecting the exposed portion to light 139050.doc 201005443, using a developing solution to remove the uncured portion of the film; and The step of heating the substrate. [Effects of the Invention] The photosensitive organic polyoxo composition of the present invention is excellent in coating property to various substrates, and has low viscosity in a soft baked film, volume shrinkage at 18 〇t curing, and 150 C under curing. The soaking weight reduction rate is small, and low temperature hardening can be performed below 25 〇t > c, and the photosensitivity is excellent. [Embodiment] Hereinafter, each component constituting the photosensitive organic polyoxo compound composition will be specifically described. (a) The organopolyoxane organopolyoxane is obtained by the following method, and will be at least one of the following Tables 7F of the following formula: - (6); Table # - at least! And an at least one alkoxylated compound represented by the following general formula (3) and a metal-fired oxide represented by the following general formula (4), which has the following formula ( 5) At least the cerium catalyst in the group consisting of the gold layer burned oxide ' and the Ba (〇H) 2 is mixed, and the polymerization is carried out without adding water. Here, "no water addition" means that the addition of the operation at the time of polymerization is not carried out, but the water or the polymerization environmental towel naturally contained in the raw material is not excluded. R*s I (OH), (1) 139050.doc iS ] -12- 201005443 {wherein R is a carbon number of at least i aromatic groups of 6 to i8, one valence group' may be the same It can also be different. [2] (2) where R is a photopolymerizable carbon-carbon double bond and has 5 to 6 members of nitrogen-containing material and a heterocyclic group (also (4) with (4) scented card carbon number is 2~ The organic base of u, R" is methyl or ethyl, which may be the same or different. Bu• [Chemical 9] R”. si (〇r”',> $ (3) {wherein 'R... An organic group having a photopolymerizable carbon-carbon double bond group having 2 to 17 carbon atoms, and R"" is a methyl group or an ethyl group, which may be the same or different. [10] In the formula, Μ is 矽, 锗, Titanium or tantalum, R,, m are alkyl groups of carbon number 4, and ® may be the same or different. '[11] M· (OR·..·.·), (δ) {式Wherein, Μ' is boron or aluminum, and Rmm is an alkyl group of carbon number 4, which may be the same or different. Among them, the above catalyst is preferably selected from the above formula (4) and the above formula (5). Any of a group of metal alkoxides in the group. Further, in the process of polymerizing the organopolyoxane without adding water, it is possible to mix at least one alkali in the group. 39〇5〇^ -13- 201005443 The metal is selected from the group consisting of hydroxides of potassium hydroxide and sodium hydroxide as its catalyst. R is at least 1 , Preferably selected from stone Xi general formula (1) an alcohol compound represented by the burning of the carbon atoms of the aromatic group is a group of 6~18, specifically the following structure: [Formula 12]

, CH 疒 CH = at least one of the groups represented by CHi. In the alkoxydecane compound represented by the formula (2), R is a photopolymerizable carbon-carbon double bond and has a 5- to 6-membered nitrogen atom-containing heterocyclic group (also including no aromaticity). The carbon number of the product is organic. Unlike the alkoxydecane compound represented by the formula (3), the compound represented by the formula (2) does not contain a group having a photopolymerizable carbon-carbon double bond. R" is methyl or ethyl group' which may be the same or different. As a specific example of R, it is preferred to be selected from the following structures: [Chemical 13] ^^0 ^^0 β-Η.ΟΗ,,Ο^·^ 139050.doc •14-201005443 At least 1 base. In the alkoxylated compound represented by the formula (3), R'" is an organic group having a carbon number of 2 to 17 containing a group having a photopolymerizable carbon-carbon double bond, R,,, , methyl or ethyl, both the same or different. As a specific example of RIM, it is preferred to be selected from the following structures: [Chem. 14]

°= C4I. At least one of the groups represented. The photosensitive organic polyoxyalkylene is obtained by at least one stanol compound represented by the formula (1) and at least one alkoxydecane compound represented by the formula (2). And at least one alkoxydecane compound represented by the formula (3), and a metal oxide oxide selected from the metal alkoxide represented by the formula (4) and represented by the formula (5) And at least one type of catalyst (hereinafter, simply referred to as "catalyst") among the groups of Ba(〇H) 2 is mixed, and polymerization is carried out without adding water. a metal alkoxide represented by the formula (4) and a metal alkoxide represented by the formula (5), a stanol compound (stanol group) and an alkoxy decane compound (a oxy-stone base) ) in the dealcoholization condensation reaction, which acts as a catalyst, and also acts as an alkoxy group-containing compound to participate in the dealcoholization condensation 139050.doc -15- 201005443 reaction, and forms a poly-mergated form ♦ Oxygen or P矽lysilse Squi〇xane structure. < 4 .

Into: the mixing ratio 'substantially 1: i (mole ratio) mixed with smelting alcoholic " with alkoxy decane compound, relative to 50 moles of decyl alcoholated input 'can be 30~70 m The alkoxydecane compound is mixed in proportion. In the case of a metal-fired oxide, it is preferred to adjust the overall mixing ratio in such a manner that the L moiety of the oxy-cobalt compound is substituted (the alkoxyalkylation amount is reduced at a fixed ratio). When the material is ~ _ octet and S, as the metal alkoxide, when using the tetravalent metal alkoxide of the formula (4), it is preferred to have the valence metal alkoxide and the appearance The oxetene compound was converted and replaced by a molar ratio of 1:2 (the amount of the tetravalent metal alkoxide mixed by 1 mol was reduced to 2 moles of the oxirane compound). Further, in the case of using a trivalent metal-sintered oxide represented by the general formula (5), it is preferred to carry out the trivalent metal oxide and the alkoxydecane compound at a molar ratio of 2:3, respectively. Convert and replace. Examples of preferred rare alkanol compounds include diphenylnonanediol, dioxime = benzyl diol, di-p-vinylidene diol, dichayl, mono-alcohol, etc., in consideration of price, Particularly preferred is the viewpoint of availability, copolymerization, and heat resistance, and is preferably diphenyl 7 calcined diol. 'A preferred compound as a compound having no photopolymerizable carbon-carbon double bond and having 5 to 6 members of a nitrogen-containing, hetero-nuclear group (including those having no aromaticity) Listed N.sup.3, oxyalkyl; ketone-1,2,4-tri-N-alkyloxyalkylimidazole, N-trialkoxydecylpyrrole, N-139050.d〇cm -16 - 201005443 Alkoxy fluorenyl alkyl pyridine, N-trialkoxy decyl pyrrolidine, pyridyl decyl trialkoxy decane, 2-piperidinylethyl trialkoxy decane, 3 morpholyl propyl tri Alkoxydecane, 3-piperidinylpropyltrialkoxyzepine, 3-piperidinylpropyltrialkoxydecane, 3-(4-mercaptopiperidylpropyl)trialkoxy• Decane, 3-(4-methylpiperidinylpropyl)trialkoxydecane, 4-(2-trialkoxydecylethyl)pyridine, N-(3-trialkoxydecylpropyl) 4·5_Dihydropyrazine, 2-(2-trialkoxydecylethyl)pyridine, ν-(3-trialkoxyindole-alkylpropyl)pyrrole (above, alkoxy) The part indicates methoxy or ethoxy) and the like. The present inventors have found that such an alkoxydecane compound which does not contain a photopolymerizable carbon-carbon double bond and has a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) As a raw material of the organic polydecane, the viscosity of the soft baked film using the photosensitive organic polyoxyalkylene composition thereof is dramatically eliminated. Among them, it is particularly preferable to use 3-morpholylpropyltrimethoxyxanthine, 3-pyroxypropyltrimethoxydecane, 3-piperidinylpropyltrimethoxy-decane, and (2- Trimethoxydecylethylethyl)pyridine, 4-(2-triethoxydecylethylethyl)pyridine. Further, as the alkoxy calcining compound containing a photopolymerizable carbon-carbon double bond group, vinyltrimethoxydecane, vinyltriethoxydecane, and 1-propenyltrimethoxy are preferable.矽, 丨-propenyl triethoxy decane, 2. propylene trimethoxy decane, 2- propylene triethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3 - A Acryloxypropyldiethoxylate; 3-propenyloxypropyltrimethoxydecane, 3-propyleneoxypropyltriethoxydecane, p-styryltrimethoxyphosphonium 139050 .doc •17· 201005443 alkane, p-styryltriethoxydecane, p-(1-propenylphenyl)trimethoxy decane, p-(1-propenylphenyl)triethoxydecane, p-( 2 acryloylphenyl)trimethoxy decane, p-(2-propenylphenyl)triethoxy decane, etc., in order to obtain excellent UV-i ray sensitization characteristics, 3_mercapto propylene oxime is more preferable. Propyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, Hongying Acyl oxy propyl triethoxysilane Silane, when considering the price or harmful, high flexibility and cross

It is particularly preferable that the 3-methacrylic acid-consuming propyl trimethoxide is burnt. As a metal wire compound represented by the formula (4) and a metal oxide oxide which is represented by the pass-through, a trimethoxy group, a triethoxy aluminum group, a tri-n-propoxy group, and a third are preferable. Isopropoxy-Ming, San-n-butoxyxan:, triisobutoxy-, three-butoxy-, and third-butoxy-based: dimethoxy boron, triethoxy boron, three positive Propoxy boron, triisopropyloxy:, tri-n-butoxy brom, triisobutoxy shed, three second butoxy...

f dibutoxy side, tetramethoxy money, tetraethoxy I, tetra-n-propoxy-oxygen, tetraisopropoxy-Xi Xing, tetra-n-butoxy, Si Yi Shi Xi Yuan, Si Di Dibutoxy alcohol, tetra-butoxy alcohol, tetramethoxy; ^ group: ethoxylated fluorene, tetra-n-propoxy fluorene, tetraisopropoxy fluorene, tetra-n-butyl, tetraisobutoxy fluorene , four second butoxy oxime, tetra-tert-butoxy, tetramethoxy titanium, tetraethoxy titanium, -milyl chinyl, tetra-n-butoxy propylene, titanium tetraisopropoxide ... butyl dioxy titanium, four second butoxy, wrong: oxygen, four? Oxygen, tetraethoxy fluorene, tetra-n-propoxy fluorene, propoxy pentoxide, tetra-n-butoxy zirconium, tetraisobutoxy volt, tetra 139,050.doc fs ] -18- 201005443 The second butoxy group is wrong. In order to achieve a rapid and uniform reaction, it is preferable to make it liquid in the reaction temperature region. Moreover, if the test r'2 is used as a high material or availability of a catalyst, it is difficult to (4) tetraisopropenyl titanium. . Medium: sterol compound and the above two kinds of alkoxylated compounds, touch, and field "'and heat" to polymerize to form organic polyoxo = the heating temperature or temperature increase rate at this time is controlled by organic The degree of polymerization of polyoxin is an important parameter. Although it depends on the degree of polymerization of the target 'but it is preferred to heat the above raw material mixture to the thief ~ (9).

When the amount of addition in the polymerization of the catalyst is less than 2 mol% relative to the phenolic compound, heating to the above preferred temperature range may cause the polymerization of the organic polyoxoxime to be insufficient. In this case, if an appropriate amount of potassium hydroxide or oxyhydrogen is added as an auxiliary catalyst, the catalyst can be compensated for, and the degree of polymerization of the produced organic polyoxygen can be appropriately controlled. In this case, after the completion of the reaction, potassium ions or sodium ions remain in the organic polydecane. However, these metal ions can be easily removed and purified by using an ion exchange resin or the like. Therefore, there is no particular problem in practical use, which is preferable. However, if the catalyst is not added during the polymerization and the glycol compound is polymerized with the alkoxy compound by the action of hydrogen hydroxide or sodium hydroxide, a polymer having a high degree of partial crystallinity is inevitably formed. The component is crystallized and precipitates to become cloudy or precipitated, resulting in system unevenness, which is not preferable. According to the meaning of avoiding the "crystallization", it is important to add the above catalyst at the time of polymerization. 139050.doc 201005443 For the above reasons, the lower limit of the amount of catalyst added is 〇_1 mol% or more with respect to the stanol compound, and more preferably 〇 5 mol% or more. The upper limit of the amount of catalyst added depends on the performance of the target organopolyoxane. In order to achieve excellent photosensitive characteristics, it is necessary to use the above-mentioned alkoxydecane compound containing a photopolymerizable carbon-carbon double bond, and the upper limit of the amount of polymerization of the metal alkoxide is calculated based on the minimum necessary amount with respect to the stanol compound. 30 Moer. /〇The following is better than 20% of the following. Further, the ratio of use of the two kinds of oxy-stone compounds is important for simultaneously satisfying the viscous-eliminating effect of the soft baked film and excellent sensitizing properties. As described in the foregoing, the stanol compound and the alkoxydecane compound are basically mixed at a ratio of 1:1 (mole ratio), wherein 'the photopolymerizable carbon-carbon double bond is not contained and has 5 to 6 members containing a nitrogen atom. Preferred examples of the alkoxy group of the ring group (including those having no aromaticity) and the alkoxylated compound containing a photopolymerizable carbon-carbon double bond group are preferred. Is set to 7〇: 3〇~3〇: , better is 60: 40~40: 60 range. When the alkoxydecane compound containing a photopolymerizable carbon-carbon double bond group has a molar ratio higher than 3 % by weight of the total alkoxydecane compound, the cost is excellent as expected. Meanwhile, the use ratio of the alkoxydecane compound having no photopolymerizable carbon-carbon double bond and having a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) is higher than the total When 30% of the alkylating compound is burned, the viscosity of the soft baked film of the photosensitive organic polyoxane composition can be lowered. (b) Photopolymerization initiator In order to impart photosensitivity, it is important to add a photopolymerization initiator to the photosensitive organic polyoxane combination 139050.doc -20·201005443. As the photopolymerization initiator, the following may be mentioned: (1) benzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-benzene a benzophenone derivative such as mercapto-4,-mercaptodiphenyl ketone, dibenzyl ketone or ketone; (2) 2,2'-diethoxyacetophenone, 2-carbyl group- 2-methylphenylpropanoid, 2,2-dimethoxyoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morphinylpropanone, 2-carbyl-1-{4-[4-(2-hydroxy-2-mercaptopropyl)-benzyl]-phenyl An acetophenone derivative such as 2-methylpropan-1-one or methyl phenylglyoxylate; (3) 9-oxopurine p-star, 2-mercapto-9-oxo-sulfonate p-star, 2-isopropyl-9-oxo-sulfonate p-star, diethyl- 9-oxo-sulfur p-P star, etc. 9-oxo-sulfur p-p-star derivative; (4) Stupid 醯, benzophene a benzoin derivative such as a methyl ketal or a benzophenone ββ-methoxyethyl acetal; (5) a benzoin such as benzoin, benzoin methyl ether, 2-hydroxyl-2-phenylphenylpropane- ketone Derivatives; (6) 1-phenyl-1,2-butanedione_2-(〇-methoxycarbonyl)anthracene, 丨_phenyl_ 1,2-propanedione-2-( 〇-methoxycarbonyl) oxime, phenyl phenyl group, propylene glycol ketone 2-(〇-ethoxycarbonyl) 肟, 1-phenyl-丨'2-propan-2-_2_(〇_benzoamidine肟, 1,3-diphenylpropanetrione_2_(〇_ethoxycarbonyl)anthracene, phenyl _3_ethoxypropanetrione-2-(indole-benzoinyl) , octyl ketone 'p-phenylene sulfonate phenyl 2-phenyl fluorenyl hydrazine -3·yl], 1-(〇_乙醯基肟) and other lanthanide compounds; (7) 2-hydroxy-2-indolyl i-phenylpropane, 1[4_(2_hydroxyethoxyl 139050. Doc -21 - 201005443 phenyl]-2-ylpropan-2-methylpropanin, 2_ylpyridinium (7) hydroxy-2-methylpropanyl)-]phenyl]phenyl} 2 methyl propyl ketone and other guanidine series compounds; (8) 2-benzyl-2-dimethylamino group small (4 morpholinophenyl butyl hydrazine _ 1 (legs deleted 69), 2 _ Α-aminoalkylphenone compound such as amidino-2_(4-methylphenyl)_1(4^4-yl-phenyl)butan-indole-ketone; (9) Double (2, 4) , 6-dimethylphenyl hydrazine) phenyl oxidized scale, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl phosphine oxide, 2, 4,6_ a phosphine oxide compound such as methylphenylhydrazine-diphenyl-phosphine oxide; (10) bis(η5_2,4-cyclopentadienyl small)_bis(26二气_3(1Ηpyrrole_ 1- a ferrotitanium compound such as phenyl)titanium; (11) a benzoic acid ester derivative such as p-(Ν, Ν-diamylaminobenzoate); (12) acridine such as 9-phenyl acridine derivative. When these photopolymerization initiators are used, they may be used singly or in combination of two or more. Among the above photopolymerization initiators, in particular, in terms of light sensitivity, 5' is more preferably an α-amino phenylbenzene (4) compound of (8). The amount of the component (a) is preferably 〇1 to 2 parts by mass, more preferably <10 psi. When the amount of addition is 〇1 parts by mass or more, it is possible to supply a light-exposed portion which is sufficiently photopolymerized only at the time of exposure, and it is possible to sufficiently perform the embossing. On the other hand, if the amount of addition is 20 mass or less, the exposure absorption near the surface of the coating film is not excessively large, and the exposure light reaches the vicinity of the substrate surface, and photopolymerization is uniformly performed in the film thickness direction, so that practical embossing can be obtained. pattern. 139050.doc 201005443 (C) A compound other than the component (4) having two or more photopolymerizable unsaturated bond groups may be added in order to improve film formation properties, photosensitivity, and mechanical properties after hardening (elongation after curing) A compound other than the component (a) of the photopolymerizable unsaturated bond group. As such a monomer, a polyfunctional (meth)acrylate compound which can be polymerized by the action of a photopolymerization initiator is preferred, and examples thereof include polyethylene glycol diacrylate [ethylene glycol unit number ❿ 2~20], polyethylene glycol dimethacrylate [the number of units of ethylene glycol, poly(1,2-propanediol) diacrylate (1) ^ propylene glycol unit number is 2~2 〇], poly (1, 2-propanediol)dimercapto acrylate (1)^propylene glycol unit number is 2~2〇], polytetramethylene glycol diacrylate [butylene glycol unit number is 2~10], polytetramethylene glycol dimercapto acrylate [ The number of units of butanediol is 2~1〇], 丨, 4_cyclohexane diacrylate, 1,4-cyclohexane dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylol Propane triacrylate, ethoxylated trimethylolpropane triacrylate [ethylene glycol unit number 2~2〇], trishydroxypyranyl propane trimethacrylate, tris (isocyanatoic acid 2-hydroxyethyl ester) Triacrylate, tris(2-hydroxyethyl isocyanurate) trimethacrylate, glyceryl diacrylate, dimethyl glyceride S, two (three methyl methacrylate) = acrylate, bis (trimethylolpropane) tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, methylene bis acrylamide, ethylene glycol Diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether _ acrylic acid adduct, bismuth A-glycidyl hydrazine-acrylic acid adduct, double-presence A diglycidyl ether-mercapto acrylic acid The product, ethoxylated double-aged a diacrylate (the number of ethylene glycol units is 2~30), ethoxylated bisphenol A dimethacrylate 139050.doc •23· 201005443 The early number is 4,]'N , bis(2-methylpropanoylethylenedioxy-methylpropane--, polybutylene glycol dimercapto acrylate [butanediol single-number 2, one or more compounds in the group. Ethoxylated bis-octane dimethyl acrylate vinegar [ethylene glycol unit number is 4~3 〇] 'The following formula can be cited: Nitrogen is [Chemical 15]

In the formula, q + r=? 4~30} is represented by BlemmerPDBE_2〇〇, 25〇, 45〇, 13〇〇 manufactured by 曰本油(股). The polybutanediol dimethacrylate [the number of units of butanediol is 2 to 1 Å], and the number of units of butanediol is preferably 5 to 1 Å, and the following formula is given: [Chemical 16] * ch4 In the formula, the Blemmer PDT-650 manufactured by Japanese Oils and Fats Co., Ltd. represented by S and 8} is taken as an example. Among these, particularly preferred are PDBE-450 or PDBE-1300, PDT-650. Further, when these are used, they may be used singly or in combination of two or more kinds of 139050.doc -24·201005443. The amount thereof to be added is preferably from 1 to 100 parts by mass, more preferably from 5 to 5 parts by mass, based on the above component (a). When the amount of addition is 1 part by mass or less, the stability of the resin liquid is high and the difference in quality is small, so that it is preferable. - (d) Oxide resin To further reduce the viscosity of the soft baked film and improve fluidity, a silicone resin can be added to the photosensitive organic polyoxane composition. Here, the "oxygen φ resin" is, for example, a hydrolyzable group having 2 to 4 alkoxyalkylene groups or gas alkyl groups as described in the "Nippon Oxygen Handbook" (1990). The organic decane compound is subjected to cohydrolysis polymerization to obtain a polymer having a three-dimensional network structure. Further, the above component (a) does not conform to (c) oxime resin. In order to achieve the object of the present invention, it is preferred to add a so-called linear (Straight) oxime resin such as an anthracene group, a phenyl group, a benzyl group, a phenethyl group or a phenylpropyl group. Examples of such an example include kr22〇l, • KR242A, KC89, 〇, KR500 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.), etc. 217 Flake (D〇w Corning) Toray), RP-based resin, SR_20, SR_21 (all manufactured by Xiaoxi Chemical Industry Co., Ltd.), KR213, KR921 8 (all manufactured by Shin-Etsu Chemical Co., Ltd.), 220 Flake, 223 Flake, 249 Flake (all Benzene-based oxime resin such as benzoquinone-based oxime resin, manufactured by Toray Dow Corning, SR_23 (manufactured by Xiaoxi Chemical Industry Co., Ltd.), phenylpropyl oxime resin such as Z-6018 (manufactured by Toray Dow Corning). In order to reduce the viscosity of the soft baked film and improve the fluidity, it is preferable to add a methoxy resin which has a higher density and a solid temperature in a common temperature region, in this sense: Among them, it is more preferable to select a phenyl group or a phenethyl propyl group. Specifically, among the above examples, 217 Flake, SR-2G, SR-21, SR-23, Z-6018, and the like are particularly preferable. These may be used singly or as appropriate. The amount of addition of the above-mentioned (O) resin is preferably 50 to 200 parts by mass based on the above component (4). Good in terms of stickiness or fluidity

It is 50 mass damage or more, and it is preferably 200 mass parts or less from the viewpoint of photosensitive characteristics such as t-ray sensitivity. (e) Organic stone compound

In order to improve the adhesion to various substrates, an organic ruthenium compound can be added to the photosensitive organic polyoxene group. (However, the following organic compound containing a carboxyl group is excluded.) The organic ruthenium compound may be exemplified below. (Herein, the description of the alkoxy group is a methoxy group or an ethoxy group.) Vinyl trialkoxy oxime 2-(3,4-epoxycyclohexyl)ethyl tris-oxygen oxime, 3_shrinkage Glycidoxypropyl trialkoxy decane, 3-glycidoxypropyl methyl dialkoxy decane, p-vinyl trialkoxy decane, 3-methyl propylene methoxy propyl trioxide Basestone, 3-methylpropenyloxypropylmethylditoxy oxime, 3-propene methoxypropyltrialkoxy decane, 3-propylene methoxypropylmethyl oxalate Base decane, N-2 (aminoethyl)-3-aminopropyltrialkoxide, N-2 (aminoethyl)_3-aminopropyl decyl dialkoxy decane, 3_ Aminopropyltrialkoxydecane, 3-trialkoxyalkyl-N-(i,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrialkoxy Decane, 3-ureidopropyl trioxy decane, 3-ureidopropylmethylditoxy decane, 3- 139050.doc m -26· 201005443 decyl propyl tris-oxydecane, 3- Mercaptopropylmethyldialkoxydecane, bis(trisoxyalkylidenepropyl)tetrasulfide, 3-isocyanate Xi cornerstone trialkoxysilane group burned. Particularly preferred is selected from (CH30)3-Si-(CH2)3-0-C0-C(CH3)=CH2, (CH30)3-Si-(CH2)3-〇-C〇-CH=CH2 And one or more compounds of the group consisting of (CH30)3-Si-(CH2)3-〇-CH2·C2H3〇 (the left is C2H3〇 is an epoxy group). Φ Wherein '(CH30)3-Si-(CH2)3-〇-CO-C(CH3)=CH2, that is, 3-methyl is preferable from the viewpoint of the effect of improving flexibility and adhesion. Acryloxypropyltrimethoxydecane (hereinafter sometimes referred to simply as MEMO). From the viewpoint of the stability of the composition, the amount of the adhesive to be added is preferably from 〇 to 2 parts by mass based on the component (a) of the present invention. More preferably, it is 0.1 to 15% by mass, and particularly preferably 3 to 1% by mass. (f) Multivalent thiol compound In order to improve the coating property (wettability) on various substrates, a polysulfide having two or more thiol groups may be added to the photosensitive organic polyoxane composition as needed. Alcohol compound. Examples of the polyvalent thiol compound include the following: (1) binary thiol compound 1,2-ethanedithiol, 1,2-propanedithiol, hydrazine, 3-propylenedithiol, , 4 · butyl dithiol, 2,3-butanedithiol, 1,5-pentanedithiol, deuterated hexanedithiol, hydrazine, 1 〇 癸 dithiol, 2,3-diyl -1,4-butanedithiol, 3,6-dioxa-, 8-octanedithiol, 3,7-dithia-1,9-nonanedithiol, hydrazine, 2-stall disulfide Alcohol, hydrazine, 3-phenyldithiol, 1,4-benzenedithiol, 2,3-diamino-M-benzenedithiol, free 5- to 139,050.doc -27- 201005443 methyl-neighbor Xylene dithiol, toluene-3,4-dithiol, 4,4,-biphenyldithiol, 1,5-naphthalenedithiol, 6·(dibutylamino)-1,3,5 - three tillage-2,4-dithiol, 2-amino-1,3,5-three tillage-4,6-dithiol, 6-anilino-l,3,5-three tillage-2, 4-disulfide S?·, 6-(4l-present amine basic isopropylamino)-l,3,5-dioxin I well-2,4-dithiol, 6-(3,,5'- Tributyl-4'-hydroxyanilino)-1,3,5-tris-2,4-dithiol, quinoxaline-2,3-dithiol, indole-2,6-dithiol 1,3,4-thiadiazole-2,5-dithiol, 1,4-bis(3-indenyl)醯oxy)butane (Karenz MT BD1) manufactured by Showa Denko (share); (2) ternary sulphur compound 1,3,5-benzenetrithiol, averaged-2,4,6-trisulfide Alcohol, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-trinol-2,4,6(111,311,511)-trione (manufactured by Showa Denko) Karenz MT NR1); (3) Tetravalent thiol compound pentaerythritol tetrakis(3-mercaptobutyrate) (Karenz MT PE1 manufactured by Showa Denko). When these times are used, they may be used singly or in combination of two or more. Among these polythiol compounds, a ternary thiol compound is particularly preferred, and among the ternary thiol compounds, particularly preferred is 弘三三·· 丁 butyloxyethyl)-1,3 , 5 - San Geng-2, 4, 6 (1 311, 511) - Sancha (Karenz MT NR1 manufactured by Showa Denko (share)). The amount of addition of the (f) polythiol compound is preferably 50 parts by mass, more preferably 1 to 3 parts by mass, based on the component (a). Opinion of the coating property (wettability) on various substrates 139,050.doc -28 - 201005443 It is preferable that it is 1 part by mass or more. From the viewpoint of heat resistance, it is preferably 50 parts by mass. . (g) a carboxyl group-containing organic ruthenium compound, and a coating property (wetability) on various substrates, may be added to the photosensitive organic polyoxo composition t as required by the following formula (6). Carboxy organic ruthenium compound: [Chem. 17]

• OH < (6) {wherein, h is an integer of K2, in the case of the case, it is considered to be an aromatic group, and when h is 2, it is considered to be a tetravalent aromatic group, which means that it contains a direct bond to the stone. The divalent organic group of the carbon atom of the atom, the integer of ...~3, to call Rf as the base of the carbon number 1~4, may be the same or different, #0, (4), and Rb is a hydrogen atom or a monovalent Smoke base. The organic 7 compound which is a cleavage group represented by the above formula (6) can be obtained by reacting a derivative of a second tremoric acid or a tetrabasic acid dianhydride with an amine group-containing organic hydrazine compound.祚 - - 络 , , , , , , , , , , , , , , , , , , 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一• Methyl cyclohexyl hydrazide dicarboxylic acid liver, cyclohexene-1,2-dicarboxylic anhydride, 5. Descending (tetra) _2,3-diphthalic anhydride, 1,2-naphthalic anhydride, i,8•naphthalene Phthalic anhydride, pyromellitic dianhydride, II I39050.doc •29· 201005443 The ketone tetradecanoic acid-hepatic, the two stupid stone wind tetracarboxylic acid di-hepatic, diphenylhexafluoropropylene tetracarboxylic acid one needle, two Benzene bond tetradecanoic acid di-hepatic, cyclopentalic acid tetracarboxylic acid two needles, privately burned tetradecanoic acid, one liver, and triphenyltetracarboxylic acid di-hepatic. When considering the improvement effect or the price of the coating property (wettability), it is particularly preferable to be adjacent to the benzoic acid needle and the benzophenone tetradecanoic acid. The amine group-containing organic hydrazine compound which reacts with the dicarboxylic anhydride or the tetracarboxylic dianhydride derivative may have various structures, and examples thereof include the following (hereinafter, the alkoxy group method refers to a decyloxy group). Or ethoxy). Mention may be made of 2-aminoethyltrialkoxydecane, 3-aminopropyltrialkoxydecane, 3-aminopropyl dialkoxymethyldecane, 2-aminoethylaminomethyl Di-oxyalkyl oxime, 2-aminoethylaminomethyldioxaxymethyl decane, 3-(2-aminoethylaminopropyl)trialkoxydecane, 3 (2-amine) Ethyl ethylaminopropyl) dialkoxymethyl decane, 3-allylaminopropyl trialkoxy decane, 2-(2-aminoethylthioethyl) trialkoxy decane, 2-(2-aminoethylthioethyl) dialkoxymethyl decane, 3-piperidinyl propyl trialkoxy decane, 3-piperidinyl propyl dialkoxymethyl decane, cyclohexane Aminopropyl trialkoxydecane, and the like. Particularly preferred is 3-aminopropyltriethoxydecane in consideration of the improvement effect or price of coatability (wettability). The amount of addition of the (g) carboxyl group-containing organic cerium compound is preferably 〇05 to 20 parts by mass, more preferably π parts by mass, based on the above component (a). From the viewpoint of the coating property (wettability) on various substrates, the amount of addition is preferably G.05 parts by mass or more, from the viewpoint of storage stability of the photosensitive organic poly-fired composition. It is preferably 2 parts by mass 2 139050.doc • 30· 201005443 This special use can be used alone or in combination of two or more. (h) Nonionic surfactant In order to improve the coatability (wettability) on various substrates, a nonionic surfactant may be added to the photosensitive organic polyoxane composition as needed. As the surfactant, it is preferred to add a nonionic surfactant as compared with the ionic surfactant from the viewpoint of preventing the wiring of the metal ground rice. 0 As a preferred nonionic surfactant, the following compounds can be mentioned: (1) spurred polyoxyethylene alkyl ether, polyoxyethylene alkyl stearyl ether, polyoxyethylene polycyclic phenyl ether, polyoxygen Propylene alkyl ether; (2) ester ether type polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene hardened castor oil fatty acid; (3) ester type climbing ethylene glycol fatty acid ester, polyoxyethylene trioxane a propane-based fatty acid ester; (4) a ruthenium-based surfactant, a dimercapto oxirane vinyloxy graft compound, a dimercapto methoxy propylene oxy-graft compound, (hydroxyvinyloxypropyl) A (5) Fluorine-based surfactant perfluoroalkyl carboxylic acid, perfluoroalkyl sulfonic acid, perfluoroalkyl-containing oligomer (Otsuka Ink Chemical Industry) (Dainippon Ink and Chemicals) (manufactured, trade name Megafac, part number R-08), with the following general formula (7): 139050.doc -31- 201005443 [Chem. 18]

In the formula, Rj is a trifluoromethyl group or a pentafluoro group. } The compound represented. & base, and k is 1 to 25, when it is used, it can be used alone or in combination of two or more kinds of φ ^ in the above-mentioned nonionic surfactant. In terms of the effect of the cloth, it is better (( 诂 诂 π, 弋 弋 系 surfactant, especially when using the compound of the formula (7) *, because it is harmful to the environment m structure (CnF2n+i, (4)~12), specifically, the following formula can be cited: [Chem. 19]

139050.doc -32 - 201005443 As for the addition amount of the nonionic surfactant, the above (4) component of the (10) mass damage is preferably set to 〇〇ι~ι〇, and the mass is preferably set to 0.1. ~ 5 parts by mass. From the viewpoint of improving the applicability to various substrates, the addition amount is preferably at least the mass portion, and the addition amount is better in terms of suppressing the development portion (4), the diagram (4), and the secret point in the lithography. The 丨〇 mass μ Γ (0 other additives in the photosensitive organic polyoxane composition, the solvent can be arbitrarily added to adjust the viscosity. As a preferred solvent, dimethyl dimethyl amide, Ν _ A W various ketones, Ν_ethyl_2·吼 slightly steel, tetraammine, hydrazine, hydrazine-monomethyl acetamide, dimethyl sulfoxide, hexamethylphosphonium, pyridine, cyclopentane Ketone, γ-butyrolactone, α-ethenyl butyrolactone, tetramethylurea, dimethyl-2-mi. Sit (4), Ν•cyclohexyl such as ketone, propylene glycol monomethyl hydrazine, propylene glycol A shouted acetic acid vinegar, methyl ethyl ketone, methyl isobutyl _, succinyl ketone, ethyl acetate vinegar, lactic acid ethyl vinegar, lactic acid butyl vinegar, etc., which may be used singly or in combination of one or more. A methyl TM W propylene glycol monomethyl = 酉 0 0 can be based on the coating film thickness, viscosity, and the material is added _ when added to the photosensitive organic polyoxylizing composition The component (4) is preferably used in an amount of from 5 to 120 parts by mass. A sensitizer for improving light sensitivity can be added to the photosensitive organic polyoxo composition as needed. Examples of the agent include, for example, Michelin®, 4,4′·bis(diethylamino)benzophenone, 2,5-bis...diethylaminophenyl 139050.doc-33-201005443 Ketone, 2,6-bis(4'-diethylaminosuccinic) cyclohexyl I, 2,6-bis(4,-monoindolyl)-methylcyclohexyl, 2,6-bis(4·-diethylaminosuccinylidene)-4-methylcyclohexanone, 4,4′-bis(diamine-amino)chaole _, 4,4, _bis (two Ethyl) chalcone, 2·(4,-dimethylaminobenzylidene) dihydrogen ketone, 2·(4 _-methylaminobenzylidene) indanone, 2-( For 4'-dimethylaminobiphenyl)benzothiazole, 1,3-bis(4-dimethylaminobenzylidene)acetone, L3-bisdiethylaminobenzylidene)acetone, 3,3 '-Carbonyl-bis(7-diethylaminocoumarin), 3-ethylidene-7-dimethylaminocoumarin, 3-ethoxycarbonyl_7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-diamine-based coumarin , 3_曱-oxycarbonyl _7-diethylamine coumarin, 3-ethoxycarbonyl _7-diethylamine coumarin, phenyl-indole-ethylethanolamine, N-phenyl Diethanolamine, n-p-phenylphenyldiethanolamine, hydrazine-phenylethanolamine, hydrazine, hydrazine-bis(2-hydroxyethyl)aniline, 4-morpholinyldimethylcarbazide, 4-methylaminobenzoic acid Isoamyl ester, isoamyl diethylaminobenzhydrate, stupid triazole, 2-mercaptobenzimidazole, 丨_phenyl_5_fluorenyl _ '2,3,4 tetradecyl, 1 ·cyclohexyl疏基_1,2,3,4_四〇,ι_(Third butyl)5-Siligeyl_ι,2,3,4-tetrasole, 2-mercaptobenzopyrene, 2-( P-dimethylamino stupid vinyl) benzo-quot; azole, 2-(p-dimethylaminostyryl)benzothilyl, 2-(p-diaminoaminostyryl)naphthalene 0,2 —ρ)thiazole, 2-(p-diamine-amino) styrene, and the like. Further, it may be used singly or in combination of two or more kinds at the time of use. The amount of addition of the above sensitizer is preferably 0.1 to part by mass, more preferably 1 to 5 parts by mass, based on the component (a). In order to improve the viscosity at the time of storage or the stability of light sensitivity, a polymerization inhibitor may be added to the photosensitive organic polyoxane composition as needed. As such a polymerization inhibitor of 139050.doc 201005443, for example, hydroquinone 'N_nitrosodiphenylamine, p-tert-butyl catechol, phenothimethamine, ice phenyl naphthylamine, B can be used. Diaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-dibutylbutyl-p-methylphenol, 5-nitrosohydroxyquinoline, 1 Nitroso-2-naphthol, 2-nitroso-naphthol, 2-nitroso-5-(N-ethyl-n-sulfonyl)propylphenol, N-nitroso-N- Phenylhydroxylamine ammonium salt, N_nitroso-N-phenylhydroxylamine ammonium salt, N_nitroso_N_(p-naphthyl)hydroxylamine ammonium salt, bis(4_0 hydroxy_3,5_di-t-butyl) Phenylmethane and the like. The amount of addition of the polymerization inhibitor is preferably 0.001 to $ parts by mass, more preferably 0.01 to 1 part by mass, based on the above component (a). In addition, as long as the physical properties of the photosensitive organic polyoxane composition are not inhibited, an ultraviolet absorber or a coating film smoothness imparting agent may be appropriately blended in the photosensitive organic polyoxane composition as needed. To represent the various additives. <Method of Forming Hardened Relief Pattern and Organic Polyoxyalkylene Membrane> Next, a preferred example of a method of forming a hardened relief pattern using the photosensitive organic polysiloxane composition of the present invention is shown below. First, the composition is applied to various substrates required for a ruthenium wafer, a ceramic substrate, an aluminum substrate, or the like. As the coating device or the coating method, a spin coater, a die coater, a spray coater, dipping, printing, blade coating, roll coating, or the like can be used. At 80~200. (: The coated substrate is soft baked for ~15 minutes to obtain a soft baked film of, for example, a film thickness of 10 to 1 μm, and a contact alignment machine (c〇ntact Aligner), mirror projection Exposure projection device such as Mirr〇r pr〇j.ecti〇n and stepper (such as beating), which illuminates the active light through the required mask. 139050.doc •35- 201005443 Available as active light X-ray, electron beam, ultraviolet ray, visible ray, etc. In the present invention, it is preferred to use a wavelength of 2 〇〇 to 5 〇〇 nm. The wavelength of the light source is in terms of resolution and operability of the pattern. Particularly preferred is uv-i ray (365 nm) as an exposure projection device, particularly preferably an alignment machine or a stepper. Thereafter, in order to improve the light sensitivity, etc., it may be carried out by any temperature and time as needed. The combination (preferably the temperature is 4〇ec~2〇〇£>c, the time is 1〇~360 seconds) of post-exposure baking (pEB,p(m Εχρ〇3ΐ^ 幻 or pre-development) Bake. Secondly, the development can be carried out by dipping, mixing and rotating spray methods. As a material, a good solvent of the photosensitive organic polyoxoxane composition of the present invention may be used singly or a good solvent may be appropriately mixed with a poor solvent, and as a good solvent, a methyl 2-carbon group can be used. , N· 醯 醯 _24 money _, N, Nm nitamine, N, N-dimethyl ketoamine, methyl T sulfoxide ' γ-butyrolactone, α 醯 醯 _ butyl vinegar , cyclopentane, cyclohexane, propylene glycol monomethyl, propylene glycol monomethyl acetate, methyl ethyl ketone, methyl ketone, jr-isobutyl ketone, methyl amyl ketone, etc. Using methanol, etc. Alcohol isopropanol, isobutanol and water are washed, and the developer is removed, whereby a coating film with a relief pattern can be obtained. As a Lin lotion, it can be used alone; , methanol, ethanol, isopropanol, isobutyl brewing $ j / alone using black «_, danbutanol, propylene glycol monomethyl or these are properly mixed

use. Use, in turn, can be combined in stages 139050.doc 36· 201005443 The embossed pattern thus obtained can be transformed at a hardening temperature of l5 〇 25 25 ° C which is much lower than that of the previous polyimide amide precursor composition. To harden the relief pattern. This heat curing can be carried out using a hot plate, an oxidizing oven (Inert oven), and a temperature-increasing oven capable of setting a temperature program. As the ambient gas during heat curing, air may be used, and an inert gas such as nitrogen or argon may be used as needed. The hardened relief pattern is used as a surface protective film or an interlayer insulating film selected from a semiconductor device formed of a germanium wafer or the like (a X-ray shielding film, and a microstructure such as a microlens array and a package material thereof) Any one of the groups consisting of the support (partition), and other steps using a well-known method of manufacturing a semi-conductor device. Thus, it is possible to manufacture a CMOS (C〇mplementaiy)

Metal Oxide Semiconductor (Complementary Metal Oxide Semiconductor) A variety of semiconductor devices for optical components such as image sensors. Further, an electronic component or a semiconductor device having a coating film containing a resin obtained by curing the photosensitive organic polysiloxane composition can be obtained. • a semiconductor device having a microstructure formed on a crystalline substrate on which an integrated circuit is formed, an encapsulation material for covering the microstructure, and a spacer material for supporting the encapsulation material on the microstructure Further, a semiconductor device can be produced by using the hardened relief pattern of the photosensitive organic polyoxylizing composition of the present invention as the spacer material. Here, as a specific example of the integrated circuit, an integrated circuit using a crystal substrate containing lithium or lithium silicate or crystal of yttrium, or an integrated circuit including a photodiode may be used. The term "microstructure" refers to micron-sized mechanical, optomechanical, and electromechanical components. Specifically, micro-transparent 139050.doc -37· 201005443 mirror. The encapsulating material is preferably transparent and may be formed of glass. The method for producing a semiconductor device includes the following steps: π, applying the photosensitive organic polyoxygen of the present invention directly or via a thin film layer on the microstructure formed on the crystal substrate on which the integrated circuit is formed a step of forming a coating film by burning the composition; a step of interposing a patterned mask having an opening portion only to form a portion of the spacer material, irradiating the coating film with active light and curing the exposed portion; and using a developing solution a step of removing the uncured portion of the coating film; and a step of heating the coating film of each of the substrates. Each step can be carried out by the above method. [Examples] The present invention will be specifically described by the following Synthesis Examples, Examples and Comparative Examples. [Synthesis Example 1] (Synthesis of Organic Polyoxane POS-ι) The three-port round bottom having a capacity of 5 〇〇 搅拌 安装 condens condens condens condens condens condens condens condens condens condens condens condens condens condens condens condens condens condens condens condens In the flask, 'diphenyl decanediol (hereinafter abbreviated as dPD) 86.52 g (04 mol), 3-methylpropenyloxypropyltrimethoxydecane (hereinafter referred to as ΜΕΜΟ) 52·45 g (0.211 mol) , 3-morpholinopropyltrimethoxydecane (hereinafter referred to as MOPS) 35.12 g (0.141 mol), titanium tetraisopropoxide (hereinafter, abbreviated as TIP) 6.82 g (0.024 mol) ' and stirring was started. This (MEMO: MOPS = 60: 40 mol% mixture ratio) was immersed in an oil bath (Oil Bath), the temperature was set to 120 ° C, and heating was started from room temperature. On the way, the methanol produced by the progress of the polymerization was refluxed by a water-cooled condenser, and allowed to react until the temperature of the reaction solution became constant, and then heating and stirring was continued for 30 139,050.doc -38 - 201005443 minutes. Then, install a hose connected to the cold trap (Cold Trap) and the vacuum system (Hose), heat it at 8 ° C using an oil bath, and stir vigorously so that the degree of vacuum is slowly increased without boiling the methanol. Thus, methanol was distilled off to obtain an organic polyoxane P〇S-1 (viscosity of 220 poise at 40 ° C). [Synthesis Example 2] (Synthesis of Organic Polyoxane POS-2) MO The MOPS of Synthesis Example 1 was changed to 2-(2-trimethoxydecylethyl)pyrole (hereinafter referred to as PES for short) 32.05 g ( Except for the above, the same operation as in Synthesis Example 1 was carried out, and an organic polyoxane p〇s 2 (viscosity at 191 Torr) was obtained. [Synthesis Example 3] (Synthesis of Organic Polyoxane POS-3) In a three-neck round bottom flask having a water-cooled condenser and a vacuum-sealed stirring blade of 500 ml, 'add 86 52 g (〇) 4 m〇l) of DPD, ❹58 36 g (0.235 mol) of MEMO, 39.16 g (0_157 mol) of MOPS, 1.14 g (〇.〇〇4 mol) of TIP, 3.79 g (0.02 mol) of hydroxide钡 monohydrate' and start stirring. It was immersed in an oil bath, and the heating temperature was set to 80 ° C, and heating was started from room temperature. On the way, the methanol produced by the progress of the polymerization was refluxed by a water-cooled cold condenser, and allowed to react until the temperature of the reaction solution became constant, and then heating and stirring were continued for another 30 minutes. Then 'install the hose connected to the cold trap and vacuum pump, use oil bath to heat at 80 C' and stir vigorously so that the degree of non-explosion of sterol is slow 139050.doc -39- 201005443 This steaming hall removes formazan, * obtains organic poly-stone oxysonic POS-3 (viscosity at 40 ° C is 181 poise). [Synthesis Example 4] (Synthesis of Organic Polyoxane POS-4) The synthesis example 1 was carried out except that the cesium hydroxide monohydrate of Synthesis Example 3 was changed to sodium hydroxide 〇g (0.02 mol). The same operation was carried out until the steaming chamber was removed before the methanol was removed. Thereafter, the reaction solution was cooled to room temperature, and passed through an Amberlyst filled with an ion exchange resin (organic), and a dry weight of 4 〇g was swollen and cleaned with decyl alcohol. The glass column is removed and sodium ions are removed. Transfer it to a round bottom flask equipped with a vacuum-sealed stirring wing and a hose connected to a cold trap and a vacuum pump, and immersed in an oil bath heated to 8 &>c for strong agitation' The degree of vacuum was gradually increased so that methanol did not boil, thereby distilling off methanol to obtain an organic polyoxane p〇s_4 (viscosity at 290 ° C of 298 poise). According to the results of ICP-MS ion analysis, the sodium ion concentration in POS-4 was less than 1. 〇 ppm. [Synthesis Example 5] (Synthesis of Organic Polyoxane POS-5) The MEMO of Synthesis Example 1 was changed to 54.19 g (0.218 mol), the MOPS was changed to 36.41 g (〇. 146 mol), and the TIP was changed to tetraisopropyl. In the same manner as in Synthesis Example 1, an organopolyoxane P〇S-6 (viscosity at 23 ° C) was obtained in the same manner as in Synthesis Example 1 except that the oxygen hammer and the isopropanol adduct were 9.30 g (〇.〇24 mol). It is 242 poise). [Synthesis Example 6] (Synthesis of Organic Polyoxane POS-6) 139050.doc -40- 201005443 The MEMO of Synthesis Example 1 was changed to 54.14 g (0.218 m〇i), the centistoke 1>8 was changed to 36.41 g. (有机. 146 mol), TIP was changed to aluminum triisopropoxide 49 〇笆 (〇·〇 24 m〇l), except that the organic polyoxane POS_6 was obtained in the same manner as in Synthesis Example i (23 The viscosity at °C is 198 poise). [Synthesis Example 7] . (Synthesis of Organic Polyoxane POS-7) 86.52 g (0.4 mol) was added to a three-neck round bottom flask equipped with a water-cooled condenser and a vacuum-sealed stirring blade having a capacity of ❹ 500. ) DpD, 59.60 g (〇.24 mol)^MEMO^ 39.90 g (〇.i6 m〇i)^M〇ps ^ 〇·8 g (0.02 mol) of sodium hydroxide, and start stirring. Immerse it in an oil bath, and set the heating temperature to 8 (TC, heating from room temperature. On the way, the methanol produced by the polymerization reaction is refluxed by a water-cooled condenser, and reacted until the reaction After the temperature of the solution reached a constant level, the mixture was further heated for 30 minutes. Then, the reaction solution was cooled to room temperature and passed through a pad filled with φ sub-exchange resin (organic (stock) Amberlyst I5, dry weight Remove the nano-ion from the glass column of 4〇g with sterol expansion* cleaning. Move it to a round bottom flask equipped with a vacuum-sealed stirring wing and a hose connected to the cold trap and vacuum pump. Internally, and immersed in an oil bath heated to 8 Torr <t, vigorously stirred, and slowly increase the degree of vacuum so that methanol does not bump, thereby distilling off sterol to obtain organic polyfluorene Oxytomane p〇s_ 7 (viscosity at 218 poise) is based on ICP-MS ion analysis. The sodium ion concentration in POS-7 is less than 1 ppm °. This is slowly removed during the distillation to remove methanol. Started to be cloudy, at room temperature -41 · 139050.doc 201005443 White turbidity also occurs during storage. [Synthesis Example 8] (Synthesis of organopolyoxane POS-8) The capacity of a water-cooled condenser and a vacuum-sealed stirring wing is 500 ml. In a round bottom flask, add 86.52 g (0.4 mol) of DPD, 87.42 g (0.352 mol) of MEMO, 6.82 g (0.024 mol) of TIP, and start stirring. Dip it in an oil bath and set the temperature to Heating at room temperature from 120 ° C. On the way, the sterol produced by the polymerization reaction was refluxed by a water-cooled condenser, and allowed to react until the temperature of the reaction solution became constant, and then heating and stirring were continued for another 30 minutes. Then, install a hose connected to the cold trap and the vacuum pump, heat it at 80 ° C using an oil bath, and perform strong agitation so that the degree of vacuum is slowly increased without slowing the methanol, thereby distilling off the methanol. The organic polyoxane POS-8 was obtained (viscosity at 290 ° C was 209 poise). [Synthesis Example 9] (Synthesis of organopolyoxane POS-9) The MEMO of Synthesis Example 1 was changed to 70.03 g (0.282). Mol), MOPS changed to 17.46 g (0.07 mol) (MEMO : MOPS = 80 : Except for the above, the same operation as in Synthesis Example 1 was carried out, and an organopolyoxane P〇S-9 (viscosity at 490 ° C) was obtained. [Synthesis Example 10] (Synthesis of Organic Polyoxane POS-10) The MEMO of Synthesis Example 1 was changed to 17.39 g (0.070 mol), and the MOPS was changed to 70.33 g (0-282 mol) (MEMO: MOPS=20: 80% by mole) 139050.doc -42- 201005443, except that the same operation as in Synthesis Example 1 was carried out to obtain an organopolyoxane P〇s-10 (viscosity at 40 ° C was 216 poise) ° [Synthesis Example 11] (Synthesis of organopolyoxane POS-11) The MEMO of Synthesis Example 1 was changed to 61.19 g (〇.246 mol), and the MOPS was changed to 26.34 g (0.106 mol) (MEMO : MOPS=70 : 30 Mo ear. /. Except for the above, the same operation as in Synthesis Example 1 was carried out to obtain a polyfluorene oxide P〇s-ll having a viscosity of 23 Torr at 40 ° C. [Synthesis Example 12] (Synthesis of Organic Polyoxane POS-12) The MEMO of Synthesis Example 1 was changed to 26.23 g (0.106 mol), and the MOPS was changed to 61.45 g (0.246 mol) (MEMO : MOPS = 30: 70) Except for the above, the same operation as in Synthesis Example 1 was carried out to obtain an organopolyoxane POS-12 (4 (viscosity at TC was 226 poise). [Example 1] Preparation of photosensitive organic polyoxane composition C-1) The organic polyoxane POS-1 obtained in the synthesis example of 100 parts by mass, 4 parts by mass of 2_block base 2_2 Methylamino-1-(4-morpholinylphenyl)-butanone-1, 4 parts by mass of 4,4.-bis(diethylamino)benzophenone, 3 parts by mass of B Oxidized bisphenol quinone dimethacrylate [3 酵 酵 单元 〇 〇 〇 〇 〇 〇 〇 PD PD PD PD 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本The mass fraction of Shixi Oxygen Resin (217 Flake manufactured by Toray Dow Corning Co., Ltd.), 40 parts by mass • methyl · 2 ♦ each burned, and this 〇 'use iron hole registrar 139050 with 0.2 micron. Doc -43- 201005443 Private system filter Filtering, to obtain a varnish of a photosensitive silicon oxide burning organopolysiloxane composition C -1. [Example 2] (Preparation of photosensitive organic polyoxane composition C-2) In the same manner as in Example 1, except that SR 50 manufactured by Xiaoxi Chemical Co., Ltd. of I50 parts by mass was used as the epoxy resin. A varnish-like photosensitive organic polyoxo-oxygen composition C_2 was obtained. [Example 3] (Preparation of photosensitive organic polyoxane composition C_3) The organopolyoxane POS-2 obtained in Synthesis Example 2 of 10 parts by mass, 4 parts by mass of 2 - benzyl was separately measured. 2,4'-bis(diethylamino)diphenyl hydrazine _, 3 篁 4 二甲 二甲 ( ( ( ( ( ( ( ( ( ( 、 、 、 、 、 、 、 、 A mass part of polybutylene glycol dimercapto acrylate (the number of units of butanediol is 8, PDT-650 manufactured by Nippon Oil Co., Ltd.), and 15 parts by mass of 3-methacryloxypropyltrimethoxy decane, 150 parts by mass of oxime resin (217 Flake manufactured by Toray Dow Corning), 40 parts by mass of N-methyl-2-pyrrolidone, and mixed, using a filter of Teflon (registered trademark) having a pore size of 0.2 μm Filtration was carried out to obtain a varnish-like photosensitive organic polyoxane composition c_3. [Example 4] (Preparation of photosensitive organic polyoxo-oxygen composition C_4) A varnish was obtained in the same manner as in Example 1 except that POS-3 of Synthesis Example 3 was used as the organic polyoxyalkylene oxide. Photosensitive organic polyoxymethane composition C-4. [Example 5] 139050.doc 44-201005443 (Preparation of photosensitive organic polyoxane composition c_5) POS-4 of Synthesis Example 4 was used as an organic polyoxan, except for "Example 1" In the same manner, a varnish-like photosensitive organic luminescent composition C-5 was obtained. % - [Example 6] - (Preparation of photosensitive organic polyoxane composition C-6) POS- of Synthesis Example 5 was used. (5) In the same manner as in Example 1, except for the above, in the same manner as in Example 1, the photosensitive organic polyoxynene composition C-6 of the enamel-like lacquer was obtained. (Preparation of photosensitive organic polyoxane composition C-7) A varnish was obtained in the same manner as in Example 1 except that POS-6 of Synthesis Example 6 was used as the organic polyoxyalkylene oxide. Photosensitive organic polyoxo-oxygen composition C-7 [Example 8] Φ (Preparation of photosensitive organic polyoxo-oxygen composition C-8) POS_9 of Synthesis Example 9 was used as an organic polyoxyalkylene oxide A varnish-like photosensitive organic polyoxygen-oxygen composition C·8 was obtained in the same manner as in Example 1 except for the above. [Example 9] (Photosensitive) Preparation of Organic Polyoxane Composition C-9) A varnish-like photosensitive organic polyfluorene was obtained in the same manner as in Example 1 except that POS-11 of Synthesis Example 11 was used as the organic polyoxoxane. Oxygen-fired composition C-9. 139050.doc •45·201005443 [Example ίο], (Preparation of photosensitive organic polyoxygenated composition c_丨〇) POS_12 of Synthesis Example 12 was used as the organic polyoxyalkylene oxide A varnish-like photosensitive organic polyoxoxane composition C-10 was obtained in the same manner as in Example 1. [Example 11] ' (Photosensitive organopolyoxane composition C-11 Preparation of the photosensitive varnish-oxygen-fired composition C-11 in the same manner as in Example 1 except that P〇S_1〇 of Synthesis Example 10 was used as the organic polyoxyalkylene. [Example 12] (Preparation of photosensitive organic polyoxo-oxygen composition c_12) 100 parts by mass of the organopolyoxane POS-1 obtained in Synthesis Example 1 and 4 parts by mass of 2- Benzyl-2-diamino-1 (4morpholinylphenyl)-butanone-1, 0.4 parts by mass of 4,4'-bis(diethylamino)diphenylhydrazine A ketone, a 4-inch mass-damaged N-methyl·2_吼 各 ketone, and mixed with a Teflon (registered trademark) filter having a pore size of micron to obtain a varnish-like sensitization The organopolyoxyalkylene composition c_12. [Comparative Example 1] (Preparation of photosensitive organic polyoxoxane composition C-13) POS-7 of Synthesis Example 7 was used as the organic polyoxoxime, and other things were metered and mixed in the same manner as in the practice of m. . Thereafter, it is intended to use a filter made of iron 说2 (micron micron) with a pore size of 〇2 μm, but the clogging caused by the white turbid component of the organic material oxygen pos_7 is considered to be the cause, 139050.doc IS 1 -46 - 201005443 It is impossible to filter, so the subsequent operations are abandoned. [Comparative Example 2] (Preparation of photosensitive organic polyoxo-oxygen composition c_丨4) The same procedure as in Example 1 was carried out except that POS-8 of Synthesis Example 8 was used as the organic polyoxymethane. In the manner, a varnish-like photosensitive organic polyoxylate composition C-14 was obtained. [Comparative Example 3] φ (Preparation of photosensitive organic polyoxane composition C-15) POS-8 of Synthesis Example 8 was used as the organic polyoxyalkylene, and no oxime resin was added, except for hydrazine, In the same manner as in Example ,, a varnish-like photosensitive organic polyoxane composition c_15 was obtained. [Comparative Example 4] (Preparation of photosensitive organic polyoxane composition c_丨6) Each of the organopolyoxane POS-8 obtained in Synthesis Example 8 was measured in an amount of 1 part by mass, and 4 parts by mass. 2_Bristyl 2_diaminomethyl-1(4morpholinylphenyl)_xanthone 1 〇4 parts by mass of 4,4'-bis(diethylamino)benzophenone, 4 A mass-damaged N-mercapto-2-pyrrolidone is mixed and filtered using a Teflon (registered trademark) filter having a pore size of 〇2 μm to obtain a varnish-like photosensitive organic polyoxane combination. Object c_丨6. [Evaluation of Viscosity] The varnish-like photosensitive organic polyoxyl oxide obtained in the examples and comparative examples of the present invention was applied using a spin coater (model name Clean Track Mark 8 manufactured by TOKYO ELECTRON). The alkane composition was coated on a 6-inch wafer and soft baked at 125t for 12 minutes to obtain a coating film having an initial film thickness of 139 139050.doc -47 - 201005443 μm. Touch the coating film with a fingertip.绰 benchmark, will not be disabled (four) touch the trace of (four) degrees. As a result of evaluating the slight contact trace, the grade "B" will touch the A. There is a stickiness in which the residual traces of the traces remain, and the stickiness of the equipotential is set to be equal to the second grade. A peer review. Show the results at the level of τ

[Photosensitivity evaluation J] By designing a lens array of a counterfeit CMOS image sensor to protect the structure of the spacer structure by a X-ray stepper (Nik2N model name NSR2〇〇5i8A) Evaluation of Patterns The coating film obtained in the same manner as described above was subjected to stepwise change exposure in the following manner, that is, the exposure 篁 was in the range of 1 〇〇 to 9 〇〇mj/cm 2 along the lateral direction. Exposure was performed with a variation of 100 mj/cm2, and exposure was performed in the range of 16 μm to 32 μm in the longitudinal direction with a variation of 2 μm in the longitudinal direction. After 30 minutes from the exposure, 'propane propylene glycol monomethyl ether acetate was used as the developing solution', and the rotation spray development was performed until the time when the unexposed portion was completely dissolved and disappeared, and the time obtained by multiplying by 1 to 4 was used, followed by using isopropanol. The spray was rinsed for 10 seconds to obtain a lattice-like relief pattern. The obtained relief pattern was visually observed under an optical microscope, and the presence or absence of residue in the developed portion was evaluated (level "A": no residue, grade "B": partial residue, grade "C": more residue), exposure The degree of swelling of the pattern under exposure of 200 mJ/cm2 (grade "A": no swelling and sharpness, grade "B": slightly swelled, grade "C": intense swelling), presence or absence of self-substrate 139050.doc - 48. 201005443 Float or peeling (Grade "A": no float or peeling, grade "B": slightly raised or peeled off, grade "C": full or apparently floating or peeling off). The results are shown in Table 1 below. [Table 1]

Soft Baked Film Sticky Sensitive Properties Residue Swelling Floating and Peeling Example 1 AAAA Example 2 AAAA Example 3 AAAA Example 4 AAAA Example 5 AAAA Example 6 AAAA Example 7 AAAA Example 8 BAAA Example 9 AAAA Implementation Example 10 AAAA Example 11 AABA Example 12 BABB Comparative Example 1 - One - Comparative Example 2 CAAA Comparative Example 3 DAAA Comparative Example 4 DABB

In Comparative Example 1, since the varnish-like composition could not be purified by filtration, evaluation could not be performed.

[Low-temperature hardening property; evaluation of tensile elongation of cured film] The respective compositions of the above examples and comparative examples were applied to a vacuum evaporation method on a 6-inch wafer using the same method as the above-mentioned photosensitive evaluation. On the aluminum substrate, soft baking (adjusting the initial film thickness after soft baking to a film thickness of 10 μm after hardening), using a vertical curing oven (Model No. VF manufactured by Koyo Thermo Systems) 2000B), a heat-hardening treatment was carried out for 2 hours in an air atmosphere at 180 ° C to prepare a resin film having a film thickness of 10 μm after hardening. The resin film was cut into a width of 3 mm using a Dicing Saw (139050.doc -49-201005443 model name DAD-2H/6T manufactured by Disco), and immersed in a 10% hydrochloric acid aqueous solution, self-twisted. The strip was peeled off and a strip film sample was prepared. The film sample was allowed to stand in an environment of 23 C and 55% RH for 24 hours, and then subjected to a tensile test using a Tensilon tensile tester according to ASTM D-882-88 to evaluate the elongation. The results are shown in Table 2 below. [Evaluation of the low-volatility '15 0 C-heating weight reduction rate> The above-mentioned strip-shaped film for the evaluation of the tensile elongation was used as a sample, and a thermogravimetric reduction measuring device (model name tga_5〇 manufactured by Shimadzu) was used. 1 5 (The weight reduction rate (unit %) at the time of TC soaking is measured and used as an index of degassing property. The measurement conditions are as follows: · The temperature rise rate is increased to 1 50 C, 15 〇 t: The heat treatment time was 22 hours in a nitrogen atmosphere. The results are shown in Table 2 below. [Evaluation of volume shrinkage at the time of heat hardening] Using a stylus profiler (model name P-15 manufactured by KLA-Tencor), When the sample for the evaluation of the tensile elongation was produced, the thickness of the coating film before and after the heat curing treatment (curing) at 180 C in a vertical curing oven was measured, and the rate of change (residual film ratio) was calculated. , unit %), as an indicator of volume shrinkage. The results are shown in Table 2 below. 139050.doc •50- 201005443 [Table 2] Low-temperature hardening characteristics; Elongation (%) Low volatility; 150〇C22 hrs Weight Reduction rate (%) volume shrinkage rate; solid Residual film rate after conversion (%) Example 1 22 0.4 96 Example 2 25 0.4 97 Example 3 26 0.5 95 Example 4 20 0.5 95 Example 5 23 0.4 97 Example 6 19 0.6 96 Example 7 20 0.5 94 Example 8 20 0.6 94 Example 9 23 0.5 95 Example 10 27 0.5 96 Example 11 25 0.5 95 Example 12 13 0.3 98 Comparative Example 1 — — — Comparative Example 2 22 0.5 94 Comparative Example 3 31 0.5 95 Comparative Example 4 10 0.3 98

The embodiment of the present invention greatly improves the viscosity of the soft baked film while exhibiting excellent photosensitive characteristics, low temperature hardening characteristics, minimal volume shrinkage upon heat hardening, and low volatility of the cured film. In Comparative Example 1, in the case of polymerization of an organopolysiloxane, only sodium hydroxide was used as a catalyst, but white turbidity was generated in the system during polymerization, and thus the varnish-like composition could not be filtered, so that it was not practical. Comparative Example 2 is a case where the structure of the organopolyoxane does not contain a photopolymerizable carbon-carbon double bond and is completely free of a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity). Compared to the embodiment of the present invention, it is difficult in terms of the stickiness of the soft baked film. Comparative Example 3 and Comparative Example 4 contained no photopolymerization in the structure of the organopolyoxane. 139050.doc -51 - 201005443 A homogeneous carbon-carbon double bond and completely free of a heterocyclic group of 5 to 6 members containing a nitrogen atom ( It is also a case where the epoxy resin which is not one of the main conditions of the present invention is added to the photosensitive organic polyoxane composition, and is of course worse than the embodiment of the present invention, and is compared. Example 2 is also inferior. [Example 13] (Preparation of photosensitive organic polyoxoxane composition c_17) In addition to the composition of Example 1, 25 parts by mass of 1,3,5-tris(3-fluorenyl) as a polythiol compound was separately measured. Butoxyethylethyl, 5_three tillers, 2,4,6(1H,3H,5H)-three-class (Karenz(10) NR1) manufactured by Showa Denko (share) and mixed, using a pore size of 〇.2 A micron-sized Teflon (registered trademark) was passed through a crucible to obtain a varnish-like photosensitive organic polyoxo-oxygen composition C-17. [Example 14] (Carboxyl group containing organic sulfonium compound S- 1 Preparation of solution) In a round bottom flask having a capacity of 1 L, 29.6 g (〇.2 mol) of phthalic anhydride and 195 g of N-methyl-2-pyrrolidone were added, and stirring was started. Cool to 〇 ° C ' and add 3-aminopropyltriethoxy decane to a solution of 44 2 g (〇. 2 mol) of N-methyl-2-pyrrolidone 100 g. Allow it to return to room temperature and stir. A solution of N-mercapto-2-pyrrolidone containing 20% by weight of a carboxyl group-containing organic compound S~1 was obtained in 4 hours'. The structure of S-1 is shown below.

139050.doc -52- 201005443 (Preparation of carboxyl group-containing organic deuterated S-2 solution) Add 32.2 g (〇.l mol) of 3,3',4,4 to a round bottom flask of 1 L. '-Dibenzophenone tetradecanoic acid dianhydride and 206 g of 2N-methyl-2-pyrrolidone, and stirring was started. The solution was cooled to dryness, and a solution of 44.2 g (0.2 mol) of N-mercaptopyrrolidone 1 〇〇 g was added as a 3-aminopropyldiethoxy decane. It was allowed to return to room temperature and stirred for 4 hours to obtain a N-methyl-2-n pirone solution containing 2% by weight of the ruthenium-containing organic compound S-2. The structure of S-2 is shown below. [化22]

(Preparation of photosensitive organic polyoxane composition C-18) In addition to the composition of Example 1, the above-mentioned adjusted carboxyl group-containing organic ruthenium compound was measured by mass fraction (s _ 丨 purely 2 parts by mass). 20% NMP solution, 5 parts by mass (S-2 purely 1 part by mass) of a 20% NMP solution of a carboxyl group-containing organic hydrazine compound solution S-2, and mixed, using a Teflon having a pore size of 0.2 μm Preparation of a filter made of a filter to obtain a varnish-like photosensitive organic polyoxyalkylene red compound C -1 8 〇 [Example 15] (Preparation of photosensitive organic polyoxane composition C_丨9) In addition to the composition of Example 1, 0.4 parts by mass is measured by the following formula: 139050.doc • 53· 201005443 [Chem. 23] m 0CH2—CF2CF3

-l« The nonionic surfactant (trade name P〇lyF〇x, part number PF_656) manufactured by OMNOVA Solutions, and mixed, using a Teflon (registered trademark) filter with a pore size of 0.2 μm Filtration was carried out to obtain a varnish-like organopolyoxane composition 19. (Evaluation of coating property (wetting property)) Using a spin coater (model name "Traditional name made by Tokyo Electronics Co., Ltd., Clean TracJc Mark 7" 'Polymerization of poly(glycidyl methacrylate) 〇0/〇methyl ethyl ketone The solution (manufactured by Wako Pure Chemical Industries, Ltd.) was coated on a 6-inch wafer and soft baked at i6〇t for 10 minutes to obtain a poly(methacrylic acid-reduced water) having a film thickness of 8 μm. 6 inch wafer of organic film of glyceride). Using a spin coater (East, y, model name C manufactured by Electronics) ean Track Mark 7) 'Only coated (spin coating) Examples 丨3 to 丨5 of the present invention, and Comparative Example 1 The photosensitive organic polyoxane composition obtained in the process, C-17, C-18, C-19, using cyclopentanone simultaneously, cutting from the edge of the wafer edge (edge rinsing) 3 mm width, at 125 < The mixture was soft baked for 12 minutes, and a coating film having an initial film thickness of 45 μm was obtained. The outer peripheral portion of the wafer on which the coating film was formed was observed, and the distance from the outermost periphery of the coating film to the wafer end was measured, and the coatability (wettability) was evaluated. (Level 139050.doc •54- 201005443 A": 3 mm from the wafer end, the coating film does not retreat. Grade rb": 3 mm or more and 5 mm or less from the wafer, slightly retracted. Rank rc": from the wafer End 5 mm or more 'backward'. The results are shown in Table 3 below. [Table 3] I-like (wetting property) evaluation Example 13 A Example 14 A Example 15 A Comparison: Example 1 B In the examples 13 to 15 of the present invention, the comparison with the present invention was carried out.

In comparison with Example 1, a photosensitive organic polyoxymethylene composition which is more excellent in coatability (wettability) on a substrate can be obtained. Incidentally, the evaluation of the tackiness, photosensitivity, low-temperature hardening property, low volatility, and volume shrinkage of the prebaked films of Examples 13 to 15 was the same as in Example 1. [Industrial Applicability] The photosensitive organic polyacetal composition of the present invention can be preferably used as a resin composition which can be used for an insulating material for an electronic component or a surface protective film for a semiconductor device. The formation of an interlayer insulating film, an alpha ray shielding film, and the like, and a semiconductor device or the like in which an image sensor, a micromachine or a microactuator is mounted, and the like can be formed. 139050.doc -55-

Claims (1)

201005443 'VII. Patent application scope: 1. A photosensitive organic polyoxymethane composition comprising the following components (a) and (b): (a) 1 part by mass of an organic polyoxane. Wherein, the organopolyoxyalkylene is obtained by the following formula: (将): [Chemical Formula 1] R, S 1 (OH) * (1) Reference (wherein R is at least 1) The aromatic group has a carbon number of 6 to 18, and may be the same or different. The at least one of the stanol compounds represented by the following formula (2): - [Chemical 2]. R* SI (OR*·) , (2) where R is a photopolymerizable carbon-carbon double bond and has a heterocyclic group of 5 to 6 members containing a nitrogen atom (including those having no aromaticity) The carbon number is 有机 有机 有机 有机 有机 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机: [Chemical 3] R-*S1(0H—)s (3) where R" is an organic group having a photopolymerizable carbon-carbon double bond group having a carbon number of 2 to 17 and R' "' is thiol or ethyl, and can be the same or not And at least one alkoxylated compound represented by the same formula, and selected from the group consisting of the following formula (4): 139050.doc 201005443 [Chemical 4] M (OR·····) < (4) 'M is any of yttrium, lanthanum, titanium or zirconium, and r,, ... is an alkyl group having 1 to 4 carbon atoms, and may be the same or different} metal alkoxide represented by the following formula (5): [5] M. (〇R", ",> 3 (δ) {wherein, Μ, is boron or aluminum 'and RΜ", is an alkyl group of carbon number 4, and The metal alkoxide and the at least one of the Ba(〇H)2 groups may be mixed and mixed without adding water; here, the general formula (1) The total molar ratio of the decyl alcohol compound represented by the alkoxydecane compound represented by the formula (2) and the alkoxydecane compound represented by the formula (3) is 5 (η 3 〇 5 〇: 7〇, and the molar ratio of the alkoxydecane compound represented by the formula (2) to the alkoxydecane compound represented by the formula is 7〇: 3〇~3〇: 7〇; (b) Photopolymerization initiator 〇.1~2〇 A photosensitive organic polyoxane composition according to claim 1, wherein the (a) component further contains 1 to 00 parts by mass of (c) having 2 or more photopolymerizable unsaturated bonds. A compound other than the component (a). The photosensitive organic polyoxane composition according to claim 1, wherein the component (a) further contains 5 to 200 parts by mass. A nonoxygen resin other than the component (a) which exhibits a three-dimensional network structure obtained by co-hydrolysis of an organic decane compound having 2 to 4 hydrolyzable groups. The photosensitive organic polyoxo composition according to any one of claims 1 to 3, wherein the catalyst is selected from the group consisting of metal alkoxides represented by the formula (4), And at least one metal alkoxide of the group consisting of metal alkoxides represented by the formula (5). 5. The photosensitive organic polyoxane composition according to any one of the preceding claims, wherein the catalyst is selected from the group consisting of metal alkoxides represented by the formula (4), And at least one catalyst selected from the group consisting of metal alkoxides and Ba(〇H) 2, and at least one catalyst selected from the group consisting of potassium hydroxide and sodium hydroxide mixture. 6. The photosensitive organic polyoxymethane composition according to any one of claims 1 to 3, wherein the component (a) further contains 0.1 to 20 parts by mass of (e) selected from (CH30)3-Si. .(CH2)3-0-C0-C(CH3)=CH2 ^(CH3O)3-Si-(CH2)3-0-CO-CH CH2, and (CH30)3-Si-(CH2)3-0 An organic ruthenium compound of at least one of the group consisting of -CH2-C2H30{left note C2H30 is an epoxy group}. 7. The photosensitive organic polyoxyalkylene composition according to any one of claims 1 to 3, further containing 1 to 50 parts by mass of (1) at least 2 or more thiol groups with respect to (a) component a polythiol compound. 8. The photosensitive organic polyoxymethane composition according to claim 1 or 2, wherein the component (a) further contains 〇.05 to 2 parts by mass (g) of the following formula (6): 6] 139050.doc (6) 201005443 {wherein h is an integer of 1 or 2, when h is 1, it is considered to be a divalent aromatic group, and when h is 2, 3 is a tetravalent aromatic The base, xc is a divalent organic group containing a carbon atom directly bonded to a ruthenium atom, an integer of dgi 〜3, and Re and Rf are alkyl groups of carbon number 4, which may be the same or different, and Lu or 2 Rb is An organic dream compound containing a mercapto group represented by a wind atom or a monovalent nicotine group. 9. The photosensitive organic polyoxymethane composition according to any one of items 1 to 3, wherein the (8) component further contains (8) a nonionic surfactant in an amount of GG1 to 1 Gf. 10. A method of forming a ruthenium polyoxyalkylene m, which comprises the step of applying a photosensitive organic polyoxymethane composition according to any one of claims 3 to 3 to a substrate. An organic polyoxyalkylene cured film obtained by hardening an organic polysiloxane film obtained by the method of claim 10 by irradiation or heating of active light. 12. A method of forming an organopolyoxyalkylene hardened relief pattern comprising: the step of forming an organopolyoxane film on a substrate by the method of claim 1; interposing a patterned mask pair a step of irradiating the active light and curing the exposed portion; a step of removing the uncured portion of the film using a developing solution; and a step of heating each of the substrates. 13. An organopolyoxane hardened relief pattern obtained by the method of claim 12. A semiconductor device comprising an organopolysiloxane hardened film as claimed in π. 139050.doc 201005443 15. A semiconductor device comprising the organic polyoxygenation hardened relief pattern of claim 13. 16. A semiconductor device having a microstructure formed on a crystalline substrate on which a wind-integrated circuit is formed, a sealing material for covering the microstructure, and a microstructure used in the microstructure The space for supporting the above-mentioned encapsulating material, #hopper, the spacer material is the organic polysulfide hardened relief pattern of claim 13. The semiconductor device of claim 16, wherein the integrated circuit comprises a photodiode. 18. The semiconductor device of claim 16, wherein the microstructure is a microlens. 19. A method of fabricating a semiconductor device for use in the manufacture of a semiconductor device according to claim 16, wherein the method comprises the steps of forming an organopolyoxane film directly or via a thin film layer on the microstructure; a step of irradiating the film with active light and photohardening the exposed portion; a step of removing the uncured portion of the film using a developing solution; and a step of heating each substrate. 139050.doc 201005443 、 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: R,S 1 (OH), (1) 139050.doc -2-