JP2007293160A - Photosensitive cage-like silsesquioxane compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive cage-like silsesquioxane compound which exhibits photosensitivity with satisfactory contrast without using an acid of a photoacid generator or the like, and with which a film having high heat resistance is easily obtained by baking after film formation. <P>SOLUTION: The cage-like silsesquioxane compound has a quinonediazide structure, whereby the cage-like silsesquioxane compound exhibits photosensitivity with satisfactory contrast without using an acid of a photoacid generator or the like, and a film having high heat resistance is easily obtained by baking after film formation. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive cage silsesquioxane compound.

  Conventionally, compounds with a silsesquioxane structure have high heat resistance and low dielectric constant, which are characteristic of inorganic materials, so they can be used in applications such as flame retardant materials and insulating materials by dispersing them in resins. Has been. In particular, a compound in which an organic group is introduced into the silsesquioxane structure has various film materials such as moldability and organic solvent solubility, which are characteristics of organic materials, in addition to characteristics of inorganic materials. Useful as an electrical insulating material.

  Patent Document 1 describes that a compound obtained by polymerizing octakis (silsesquioxane) and a diyne compound exhibits high heat resistance. Although a cured product obtained by curing this polymer has high heat resistance, there is a problem that a photoresist is necessary for patterning because it has no photosensitivity.

  Patent Documents 2 and 3 describe compositions containing a cage silsesquioxane polymer whose solubility in an alkaline developer is increased by a photoacid generator. However, since these compounds use a photoacid generator to develop photosensitivity, it is difficult to manage amine fog and acid, and there is a problem that post-exposure baking is necessary. was there.

Patent Document 4 describes a polymer obtained by irradiating a cage silsesquioxane compound to which a photodimerizable functional group is bonded. This polymer does not use a photoacid generator for the development of photosensitivity, but the polymer and its precursor monomer do not have so much difference in solubility in solvents, so the photosensitivity contrast is insufficient. There was a problem of doing.
Japanese Patent No. 2884073 JP-A-2005-42085 JP 2004-264767 A JP 2003-268107 A

  The present invention has been made in view of such a point, and without using an acid such as a photoacid generator, it exhibits photosensitivity with sufficient contrast, and is easily heat resistant by baking after film formation. It is an object of the present invention to provide a photosensitive cage silsesquioxane compound capable of obtaining a high film.

  The cage silsesquioxane compound of the present invention has a quinonediazide structure.

  In the cage silsesquioxane compound of the present invention, the quinonediazide structure is preferably a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure.

  The photosensitive resin composition of the present invention is characterized by containing the above cage silsesquioxane compound.

  The cured product of the present invention is obtained by curing the photosensitive resin composition.

  The thick film dielectric of the present invention is constituted by the above cured product.

  Since the cage silsesquioxane compound of the present invention has a quinonediazide structure, it exhibits photosensitivity with sufficient contrast without using an acid such as a photoacid generator, and can be easily baked after film formation. In addition, a film having high heat resistance can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
The cage silsesquioxane compound in the present invention is a compound having a cage silsesquioxane structure and a quinonediazide structure. The compounds are classified as follows according to the number and manner in which one cage silsesquioxane structure is bonded to another cage silsesquioxane structure.
(A): The number of bonds is 0 (b): The number of bonds is 1 (c): The number of bonds is 2 or more, and the number of bonds to other cage silsesquioxanes is One or less cage silsesquioxane structures on average (d): The number of bonds is 2 or more, and the number of bonds to other cage silsesquioxanes is cage silsesquioxane More than one on average per structure

  Examples of those having 0 bonds include cage silsesquioxane compound monomers. Moreover, a cage-like silsesquioxane dimer is mentioned as a thing with one bond number. Furthermore, when the number of bonds is 2 or more and the average number of bonds to other cage silsesquioxanes is 1 or less per cage silsesquioxane structure, the cage silsesquioxane Examples thereof include a polymer having a monomer in which a vinyl group or the like is bonded to an oxane structure as a repeating unit, or a copolymer of the monomer and another monomer. 3D network type or dendrimer type as the number of bonds is 2 or more and the average number of bonds to other cage silsesquioxanes exceeds 1 per cage silsesquioxane structure. And a star polymer type.

The cage silsesquioxane structure in the present invention includes a cage silsesquioxane represented by the following general formula (1) and a partial cleavage structure of a cage silsesquioxane represented by the following general formula (2). Examples include the body.
(RSiO _3/2 ) _n (1)
(RSiO _3/2 ) _l (RXSiO _3/2 ) _k (2)
Here, n is an integer from 6 to 14, l is an integer from 2 to 12, and k is 2 or 3. For example, when n = 6, the structure is represented by the following general formula (3). When n = 8, the structure is represented by the following general formula (4). When n = 10, The structure is represented by the general formula (5). When n = 12, the structure is represented by the following general formula (6). When n = 14, the structure is represented by the following general formula (7). It becomes.

For example, when l = 4 and k = 3, the structure is represented by the following general formula (8). When l = 6 and k = 2, the following general formula (9) or (10) is satisfied. When l = 4 and k = 4, the structure is represented by the following general formula (11).

  R in the general formula (1) and the general formula (2) is a bond to a functional group having 1 to 30 carbon atoms, a hydrogen atom, a halogen atom, or another silsesquioxane structure. May be different.

  The functional group (R) having 1 to 30 carbon atoms may contain a halogen atom, a hetero atom and a metal atom. Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Moreover, oxygen, sulfur, nitrogen, and phosphorus are mentioned as a hetero atom here. Examples of the metal atom include silicon and titanium.

  In the present invention, the functional group (R) having 1 to 30 carbon atoms may be directly bonded to the silicon atom to which R is bonded, or may be bonded via a hetero atom.

X in the general formula (2) is an OR ₅ (R ₅ is a functional group having 1 to 30 carbon atoms and a quaternary ammonium radical) structure, a functional group having 1 to 30 carbon atoms or a group defined by halogen. And a plurality of Xs may be the same or different. A plurality of Xs in (RXSiO _3/2 ) _k may be connected to each other to form a connection structure.

  The functional group (R) having 1 to 30 carbon atoms in the present invention includes an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, a functional group containing a cyclic structure, an organosiloxane group, and a group obtained by combining them. Etc. In the present invention, the hydrocarbon group may have a functional group containing a hetero atom such as a halogen atom and / or a hydroxyl group and / or a metal atom such as a silanol group.

  Examples of the aliphatic saturated hydrocarbon group include primary hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group, secondary hydrocarbon groups such as isobutyl group and isopentyl group, and tertiary hydrocarbon groups such as t-butyl group.

  Examples of the aliphatic unsaturated hydrocarbon group include a hydrocarbon group containing a double bond such as a vinyl group and an allyl group, and a hydrocarbon group containing a triple bond such as an ethynyl group.

  Examples of the functional group containing a cyclic structure include a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, and a cyclooctyl group; a polycyclic functional group such as a norbornyl group and an adamantyl group; pyrrole, furan, A heterocyclic functional group having a thiophene, imidazole, oxazole, thiazole, tetrahydrofuran, dioxane structure; an aromatic hydrocarbon group containing a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring structure.

  In the present invention, the carbon number of R in the general formulas (1) and (2) is preferably 30 or less from the viewpoint of facilitating the functional group introduction reaction into the cage silsesquioxane. R preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

  Examples of the quinonediazide structure in the present invention include 1,2-benzoquinonediazide, 1,2-naphthoquinonediazide, 2,1-benzoquinonediazide, 2,1-naphthoquinonediazide structure, and the like. Among them, the 1,2-benzoquinonediazide and 1,2-naphthoquinonediazide structures are particularly preferable from the viewpoint of easy handling.

  The functional group having a quinonediazide structure may be bonded to a silsesquioxane structure, or may be bonded to a repeating unit having no silsesquioxane structure such as the above-mentioned other monomers. Among these, the case where it couple | bonds with the silsesquioxane structure from a viewpoint of reaction control is preferable. In the present invention, the quinonediazide is not simply mixed with the polymer, but the cage silsesquioxane compound has a quinonediazide structure, that is, the quinonediazide structure is introduced into the cage silsesquioxane structure. Characteristics satisfying photosensitivity and photosensitivity contrast can be obtained.

  The quinonediazide structure may be directly bonded to the silicon atom of the silsesquioxane structure, or may be bonded via any atom or functional group. For example, they may be bonded via an oxygen atom or an organic group. Among these, the case where it couple | bonds through an organic group from a viewpoint of melt | dissolution suppression before exposure is preferable.

  The organic group is not limited as long as it is a structure capable of binding a quinonediazide structure and a silsesquioxane structure. Examples of these structures include a structure containing a divalent alkyl group such as an alkylene group having 1 to 30 carbon atoms, a structure containing an aromatic group, and a structure containing a silicon atom such as siloxane and disiloxane. These structures may contain heteroatoms such as esters, sulfonic acid esters, amides and sulfonic acid amides as necessary. Here, examples of the hetero atom include oxygen, sulfur, nitrogen, and phosphorus.

  In the above, the quinonediazide structure and the binding mode of the structure with the cage silsesquioxane structure are exemplified. Among them, from the viewpoint of dissolution inhibition before exposure and reaction control, a quinonediazide structure is bonded to an aromatic group via a sulfonic acid ester, and a cage silsesquioxane structure is formed from the aromatic group via an alkylene group. A bonded structure is particularly preferred.

The structure of the bond to another silsesquioxane structure in the present invention is not limited as long as one cage silsesquioxane structure can be combined with another cage silsesquioxane structure. . As such a mode, a structure containing a divalent alkyl group such as an alkylene group having 1 to 30 carbon atoms, an oxyalkylene group, a structure containing an ester group having 1 to 30 carbon atoms, siloxane, disiloxane, etc. Examples include a structure containing a silicon atom, and heteroatoms such as an oxygen atom and a nitrogen atom. These may be one kind or two kinds or more. Among them, the structure represented by the following general formula (12) is particularly preferable from the viewpoint of the heat resistance of the compound.

R ₁ , R ₂ , R ₁ ′ and R ₂ ′ in the general formula (12) are at least one kind selected from a hydrogen atom, a halogen atom and a functional group having 1 to 30 carbon atoms, and may be the same. It may be different. R ₃ and R ₄ represent an alkylene group having 1 to 30 carbon atoms. a is a natural number of 1 or more and 10 or less, and b is 0 or 1. In addition, the case of 1 ≦ a ≦ 20 and b = 1 is preferable in view of good reactivity and good handling. R ₃ and _{R 4} are an ethylene group, a propylene group are preferable.

  The number (M) of the quinonediazide structure bonded to the cage silsesquioxane structure in the present invention is not limited as long as it is a number that can express photosensitivity. Among them, in consideration of dissolution inhibition and sensitivity before exposure, an average of 0.1 or more and less than 18 per cage silsesquioxane structure is preferable. From the viewpoint of photosensitive contrast, an average of 0.3 or more and less than 10 is preferable, and an average of 0.5 or more and less than 9 is particularly preferable.

  The number average molecular weight in the present invention is measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard.

  The number average molecular weight of the compound according to the present invention is 300 to 500,000 in consideration of the heat resistance of the cured product obtained from the compound and the viscosity and moldability of the photosensitive resin composition containing the compound. In the present invention, the molecular weight is preferably from 1,000 to 250,000, particularly preferably from 3,000 to 100,000.

  The number (M) of quinonediazide structures bonded to the cage silsesquioxane structure in the present invention can be calculated from a nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR).

Next, the manufacturing method of the compound used for this invention is demonstrated.
The compound of the present invention can be obtained by 1) directly reacting a cage silsesquioxane with a compound containing a quinonediazide structure and a functional group having at least one unsaturated bond in the molecule, or 2) a cage silsesquioxane. It can also be obtained by reacting oxane with a compound having at least one unsaturated bond in the molecule and then reacting with a compound having a quinonediazide structure. From the viewpoint of reaction control, 2) a method in which a cage silsesquioxane is reacted with a compound having at least one unsaturated bond in the molecule and then reacted with a compound having a quinonediazide structure.

  Although there is no restriction | limiting in particular as a synthesis method used by this invention, The hydrosilylation reaction using a catalyst used for normal silicon-carbon bond formation reaction is used suitably. In addition, as a method for producing the compound in the present invention, an arbitrary synthesis method is appropriately selected according to the structures of the compounds (a), (b), (c), and (d) described above. Among them, from the viewpoint of the ease of reaction, the ease of controlling the amount of the desired quinonediazide structure introduced, and the heat resistance of the resulting compound, the above-mentioned cage silsesquioxane and A method of reacting a compound having at least one unsaturated bond in the molecule with a compound having a quinonediazide structure is preferable.

  Examples of the reaction solvent used in the present invention include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane and ethylene glycol dimethyl ether; 2 or more carbon atoms such as acetone and methyl ethyl ketone. 6 or less ketone compounds; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; carbon numbers such as benzene, toluene, xylene, mesitylene and tetralin An aromatic hydrocarbon compound having 6 to 10 carbon atoms; an ester compound having 3 to 6 carbon atoms such as methyl acetate and ethyl acetate; a carboxylic acid having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid; Halogen-containing compounds having 1 to 10 carbon atoms such as roloform, methylene chloride and 1,2-dichloroethane; such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms; sulfur-containing compounds such as dimethyl sulfoxide and water. Moreover, it implements also in the absence of solvent. These can be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, etc., and may be one kind or a mixture of two or more kinds as necessary. Particularly preferred solvents include ether compounds having 2 to 6 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone.

The hydrosilylation reaction catalyst in the present invention is not particularly limited, but can be appropriately selected from known compounds such as a radical initiator and a transition metal catalyst. Specific examples of these compounds include radical initiators such as azobisisobutyronitrile, benzoyl peroxide, and di-t-butyl peroxide; active platinum, Pt (0) -1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane, chloroplatinic acid, Pt (COD) ₂ (wherein COD represents a 1,5-cyclooctadienyl group), H (C ₃ H ₆ ) PtCl _3, etc. Platinum catalyst; RhCl (PPh ₃ ) ₃ (wherein PPh ₃ represents a triphenylphosphine group), RhCl (CO) (PPh ₃ ) ₂ , RhCl (CO) (PEt ₃ ) ₂ (wherein PEt ₃ Represents a triethylphosphine group), HRh (CO) (PPh ₃ ) ₃ , [Rh (CO) ₂ Cl] ₂ , Rh (acac) (CO) ₂ (wherein acac represents an acetylacetonate group). ) Rhodium catalysts; [Ni (CO) (Cp )] 2 ( wherein, Cp represents a cyclopentadienyl group.), A nickel catalyst such as _{Ni (acac); H 3 Co} (PPh 3) 3, H 2 Co [Si (OEt) ₃ ] (PPh ₃ ) ₃ (where Et represents an ethyl group), cobalt catalysts such as cobalt carbon; RuCl ₃ , RuCl ₂ (PPh ₃ ) ₃ , RuHCl (PPh ₃ ) ₃ Ruthenium catalysts such as PdCl ₂ and palladium catalysts such as palladium carbon. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a platinum catalyst is particularly preferable from the viewpoint of high reactivity, and active platinum, Pt (0) divinyltetramethyldisiloxane, and chloroplatinic acid are particularly preferable.

  As the deprotection reaction reagent in the present invention, a known method can be appropriately selected depending on the selected protecting group. Examples of such a deprotection reagent include acids such as hydrochloric acid, formic acid, trifluoroacetic acid, and hydrobromic acid, and Lewis acids such as boron tribromide and trimethylsilane iodide.

  The catalyst used in the reaction with the compound having a quinonediazide structure in the present invention can be appropriately selected from known compounds such as tertiary amines. Such compounds include aliphatic tertiary amines such as trimethylamine and triethylamine, nitrogen-containing heterocyclic compounds such as pyridine and pyrimidine, and nitrogen-containing polycycles such as 1,4-diazabicyclo [2.2.2] octane. And formula compounds. Among these, triethylamine and pyridine are preferable from the viewpoint of easy handling.

  The reaction temperature in the present invention is preferably 15 ° C. or higher and 120 ° C. or lower in consideration of reaction initiation and catalyst activity. Preferably they are 20 degreeC or more and 100 degrees C or less, More preferably, they are 30 degreeC or more and 90 degrees C or less.

  The time required for the reaction varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

  After completion of the synthesis, the compound of the present invention can be recovered by distilling off the solvent in the reaction solution under reduced pressure.

  Examples of the method for purifying the compound of the present invention include a method in which an insoluble catalyst in the reaction solution is removed by vacuum filtration, pressure filtration or the like. In addition, a so-called reprecipitation purification method in which the reaction solution is precipitated by adding it to a poor solvent can be carried out. Furthermore, when a highly pure copolymer is required, an extraction method by a carbon dioxide supercritical method is also possible.

  By using the compound of the present invention, a photosensitive resin composition containing a solvent in which the compound can be uniformly dissolved and / or dispersed can be obtained.

  The density | concentration of the compound in the photosensitive resin composition containing the compound of this invention and a solvent will not be restrict | limited especially if a hardened | cured material is manufactured. Among them, the concentration of the compound is preferably 1% by weight or more from the viewpoint of producing a thick film cured product, and 90% by weight or less from the viewpoint of uniformity of the thick film cured product. From the viewpoint of the film thickness of the resulting cured product, it is more preferably 2% by weight or more and 80% by weight or less.

  The solvent which comprises the photosensitive resin composition in this invention will not be limited if it can melt | dissolve and / or disperse | distribute the compound of this invention uniformly. Examples of such solvents include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and propylene glycol monomethyl acetate; 2 or more carbon atoms such as acetone and methyl ethyl ketone. 6 or less ketone compounds; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; carbon numbers such as benzene, toluene, xylene, mesitylene and tetralin Aromatic hydrocarbon compound having 6 to 10 carbon atoms; ester compound having 3 to 6 carbon atoms such as methyl acetate and ethyl acetate; 1 carbon atom or more such as formic acid, acetic acid, propionic acid, butyric acid 6 or less carboxylic acids, chloroform, methylene chloride, chlorine-containing compounds having 1 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as 2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide; cyclic esters such as γ-butyrolactone, and water. From the viewpoint of the solubility of the compound, propylene glycol monomethyl acetate, N-methyl-2-pyrrolidone, γ-butyrolactone, and tetrahydrofuran are particularly preferable.

  Further, the photosensitive resin composition in the present invention may contain other components such as a surfactant as long as the composition is not adversely affected. The proportion of the other components is usually 10% or less when the proportion of the photosensitive resin composition of the present invention is 100%.

Next, it describes about the manufacturing method of the hardened | cured material obtained using the compound concerning this invention.
First, a photosensitive resin composition containing the compound of the present invention is coated on a substrate to form a photosensitive layer. The substrate is not limited as long as it is a substrate that is not damaged during the formation of the cured product. Examples of such a substrate include a silicon wafer, metal, glass, ceramic, and heat resistant resin. A silicon wafer and glass are preferably used because of good handling. Examples of the coating method include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating. After coating, if necessary, heat treatment called pre-baking may be performed by a hot plate or the like.

  Next, the photosensitive layer is patterned by light irradiation through a mask or the like. Examples of the light source for light irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a solid-state laser, a gas laser, a semiconductor laser, an excimer laser, a xenon lamp, and a metal halide lamp. Examples of the light irradiation method include a contact exposure method, a proximity exposure method, and a scanning exposure method.

  Next, the photosensitive layer irradiated with light is developed. As the developer, a tetramethylammonium hydroxide aqueous solution is preferably used. After development, washing and drying may be performed as necessary.

  Finally, the patterned film is cured by baking. The firing temperature is preferably 30 ° C. or more and 500 ° C. or less in consideration of sufficient curing, side reaction, decomposition, and the like. Preferably, it is 100 degreeC or more and 400 degrees C or less. When the silsesquioxane compound has a reactive group, it is preferably fired at a temperature higher than the temperature at which the reactive group reacts.

  The reaction atmosphere in the production method can be carried out in an air atmosphere or an inert gas atmosphere. From the viewpoint of thermal decomposition of the polymer, an inert gas atmosphere is preferred.

  The time required for producing the cured product varies depending on the reaction conditions, but is usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.

  The cured product produced using the compound according to the present invention has high heat resistance, which is a characteristic of inorganic compounds, and good film formability, which is a characteristic of organic compounds, and also has photosensitivity and low dielectric constant. Because of its features, dielectric films, semiconductor interlayer insulating films, interlayer insulating films for thin film transistors, circuit board photoresist films, heat resistant films for ceramic sensors, heat resistant paints, flame retardant and fire resistant paints, building materials coating agents, plasma It can be used for a dielectric film for a display panel.

Examples for clearly performing the effects of the present invention will be described below.
(reagent)
In Examples and Comparative Examples, PSS-octakis (dimethylsilyloxy) substitution (made by Aldrich), pt-butoxystyrene (made by Wako Pure Chemical Industries, Ltd.), Pt (0) -1,3 which are the reagents used. -Divinyl-1,1,3,3-tetramethyldisiloxane 3% xylene solution (manufactured by Aldrich), vinyl-terminated polydimethylsiloxane (DMS-V05) (manufactured by GELEST), toluene (manufactured by Wako Pure Chemical Industries, Ltd., For organic synthesis), hydrochloric acid, 4.0M 1,4-dioxane solution (manufactured by Aldrich), methanol (manufactured by Wako Pure Chemical Industries, special grade), tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free, special grade) Acetone (manufactured by Wako Pure Chemical Industries, for organic synthesis), triethylamine (manufactured by Wako Pure Chemical Industries, special grade), 1,2-naphthoquinone-2-diazide-5-sulfur Honyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade) were used for the reaction without carrying out any special purification.

(Purification of compounds)
The compound-containing reaction solution obtained by the reaction was poured into methanol, stirred for 10 minutes at room temperature, and after solids precipitated, purification was performed by removing the supernatant by decantation. When the solid did not precipitate, centrifugation was performed using a centrifuge (manufactured by Kubota Manufacturing Co., Ltd.) to precipitate the solid, and then the same operation was performed for purification.

(Number average molecular weight measurement)
In the present invention, the number average molecular weight was measured using gel permeation chromatography (GPC) under the following conditions.
Column: Shodex KF-804L (Showa Denko)
Mobile phase: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd., without stabilizer)
Flow rate: 0.6 mL / min Column temperature: 40 ° C
Pump: LC-10AT (manufactured by Shimadzu Corporation)
Detector: RID-6A (RI: differential refractometer, manufactured by Shimadzu Corporation)
SPD-10A (UV-VIS: UV-Visible Absorber, manufactured by Shimadzu Corporation)
A calibration curve for calculating the molecular weight was prepared using standard polystyrene (manufactured by Aldrich).

(NMR measurement)
For NMR measurement, JNM-GSX400 manufactured by JEOL was used. The solvent used for the measurement was deuterated chloroform (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.8% by weight), and deuterated chloroform 5.0 × 10 ⁻⁴ to 5.0 × 10 ⁻³ g of the copolymer. Measurements were taken at a concentration of liters. The measurement temperature was 30 ° C. The internal standard was 7.26 ppm, which is a non-deuterated peak of deuterated chloroform.

(Calculation of the number of bonds (M) of the quinonediazide structure bonded to the cage silsesquioxane structure)
The number of bonds of the quinonediazide structure bonded to the cage silsesquioxane structure in the present invention was determined by the NMR measurement described above. Under the measurement conditions described above, a peak derived from a phenol group was observed at δ6.6 to 7.1. Moreover, the peak of Si—CH ₂ CH ₂ —Si produced after the hydrosilylation reaction was observed at δ0.5. Then, from these integral ratios, the number of phenol groups bonded to the cage silsesquioxane structure is determined, and then reacted with 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. Since the peak of the naphthoquinone-2-diazido-5-sulfonyl group was observed at δ8.1, the number of 1,2-naphthoquinone-2-diazide-5-sulfonyl groups introduced into the phenol group was determined.

(Film thickness measurement)
The film thickness of the cured product obtained using the compound according to the present invention was measured with a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.). The measurement method was absolute reflectance, and the measurement mode was performed manually. Moreover, aluminum was used as a reference, and an Al adsorption holder was used as a standard reflector. In the algorithm, peak valley + least square method was used, the smoothing point was 7 points, the least square method calculation wavelength range was 240 to 800 nm, and the peak & valley method calculation wavelength range was 500 to 800 nm.

(Coating method)
The coating method of the photosensitive resin composition in the present invention was performed by a spin coating method using MIKASA COATER (manufactured by MIKASA, 1H-D7). The photosensitive resin composition was dropped onto alkali-free glass (Corning Corp., 1737 AMLCD), and coating was performed at 1000 rpm for 30 seconds.

(Curing product manufacturing method)
The manufacturing method of the hardened | cured material in this invention is by baking the alkali free glass which spin-coated this photosensitive resin composition by the above-mentioned method using a vertical baking furnace (the Koyo Lindberg company make, VF-1000). went. Firing was performed in a nitrogen atmosphere, and was performed at 150 ° C. for 60 minutes, followed by 350 ° C. for 60 minutes. In this way, a cured product was obtained.

(Heat resistance test)
The heat resistance test of the cured product in the present invention was performed by determining the weight loss rate after holding at 350 ° C. for 30 minutes using TGA2950 (TA Instruments).

(Photosensitivity test)
In the photosensitivity test of the photosensitive resin composition in the present invention, 2.38% tetramethylammonium hydroxide solution (25% tetramethylammonium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd., for precision analysis) is purified water (Kyoei). Using a product diluted with a pharmaceutical company). The film obtained by coating the photosensitive resin composition with alkali-free glass by the above-described method was immersed in a 2.38% tetramethylammonium hydroxide solution, and the time until the film started to dissolve was measured. Here, those that did not dissolve even after being immersed for 5 minutes were regarded as insoluble. The same measurement was performed after the film was exposed (low pressure mercury lamp, Philips TL / 10, 2000 mJ / cm ² ).

Example 1
In a three-necked flask equipped with a septum and a reflux under a nitrogen atmosphere, PSS-octakis (dimethylsilyloxy) substitution (4.913 mmol), pt-butoxystyrene (29.566 mmol), toluene (40 ml), Pt (0 ) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane 3% xylene solution (40 μl) was added and stirred at 60 ° C. for 2 hours. Subsequently, vinyl termination | terminus polydimethylsiloxane (DMS-V05) (19.79 mmol) was added, and it heated and stirred at 90 degreeC for 5 hours. After cooling to room temperature, the reaction solution was poured into methanol (400 ml), stirred at room temperature for 10 minutes, the supernatant was decanted, and dried in a vacuum drier to obtain a t-butyl protector.

  Next, the t-butyl protected product (5.03 g), hydrochloric acid, 4.0M 1,4-dioxane solution (50 mL) was placed in an eggplant-shaped flask, and heated and stirred at 80 ° C. for 4 hours. After cooling to room temperature, the reaction solution was concentrated and dried in a vacuum dryer to obtain a phenol group-introducing compound.

  Next, under a nitrogen atmosphere, the phenol group-introduced compound (2.71 g), 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (0.601 g, 2.237 mmol) and acetone (20 ml) were added, and at room temperature. After dissolution, a solution of triethylamine (0.489 g, 4.83 mmol) in acetone (3 ml) was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 1.5 hours, and then hydrochloric acid (0.101 g) was added. The precipitated white solid was filtered off, and the obtained filtrate was poured into a 0.5 wt% aqueous hydrochloric acid solution (100 ml). The precipitated solid was subjected to suction filtration and dried in a vacuum drier to obtain the target 1,2-naphthoquinone-2-diazide-5-sulfonyl group-containing compound (Example 1). For the obtained polymer (Example 1), the number of photosensitive groups bonded to the cage silsesquioxane structure (number of quinonediazide structures) (M), the number of bonds of residual phenol groups and the number average molecular weight were examined. It was. The results are shown in Table 1 below.

  Next, the obtained polymer (1.0 g) was dissolved in tetrahydrofuran (4.0 g) and stirred at room temperature to obtain a uniform photosensitive resin composition (Example 1). A photosensitivity test was performed on this photosensitive resin composition. The results are shown in Table 2 below.

  Next, the obtained photosensitive resin composition (2.0 g) was spin-coated on an alkali-free glass at 1000 rpm for 30 seconds, and then in a vertical baking furnace under a nitrogen atmosphere at 150 ° C. for 60 minutes, followed by 350 ° C. The target cured product (Example 1) was obtained by baking for 60 minutes. About the obtained hardened | cured material, the film thickness measurement was performed using the reflective spectral film thickness meter FE-3000. The results are shown in Table 3 below. Moreover, the obtained hardened | cured material was peeled off from the alkali free glass with the spatula, about the obtained solid, the weight before and behind hold | maintaining for 30 minutes at 350 degreeC was calculated | required using TGA2950, and the weight decreasing rate was calculated | required from those weights. . The results are shown in Table 3 below.

(Example 2)
Under a nitrogen atmosphere, a three-necked flask equipped with a septum and a reflux condenser was substituted with PSS-octakis (dimethylsilyloxy) (4.912 mmol), pt-butoxystyrene (39.374 mmol), toluene (40 ml), Pt (0 ) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane 3% xylene solution (40 μl) was added and stirred at 60 ° C. for 2 hours. Recovery and purification were performed under the same conditions as in Example 1 to obtain a t-butyl protected product.

  Next, the t-butyl protected product (3.12 g), hydrochloric acid, 4.0M 1,4-dioxane solution (50 mL) was placed in an eggplant-shaped flask, and heated and stirred at 80 ° C. for 4 hours. Recovery was performed under the same conditions as in Example 1 to obtain a phenol group-introducing compound.

  Next, under a nitrogen atmosphere, the phenol group-introduced compound (1.013 g), 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (1.074 g, 4.00 mmol) and acetone (20 ml) were added, and at room temperature. After dissolution, a solution of triethylamine (0.445 g, 4.40 mmol) in acetone (3 ml) was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 1.5 hours, and then hydrochloric acid (0.105 g) was added. The precipitated white solid was filtered off, and the obtained filtrate was poured into a 0.5 wt% aqueous hydrochloric acid solution (100 ml). The precipitated solid was subjected to suction filtration and dried in a vacuum drier to obtain the target 1,2-naphthoquinone-2-diazide-5-sulfonyl group-containing compound (Example 2). For the obtained polymer (Example 2), the number of photosensitive groups bonded to the cage silsesquioxane structure (number of quinonediazide structures) (M), the number of bonds of residual phenol groups and the number average molecular weight were examined. It was. The results are also shown in Table 1 below.

  Next, the obtained polymer (1.0 g) was dissolved in tetrahydrofuran (4.0 g) and stirred at room temperature to obtain a uniform photosensitive resin composition (Example 2). A photosensitivity test was performed on this photosensitive resin composition. The results are shown in Table 2 below.

  Next, the obtained photosensitive resin composition (2.0 g) was spin-coated on an alkali-free glass at 1000 rpm for 30 seconds, and then in a vertical baking furnace under a nitrogen atmosphere at 150 ° C. for 60 minutes, followed by 350 ° C. For 60 minutes to obtain the desired cured product (Example 2). About the obtained hardened | cured material, it carried out similarly to Example 1, and measured the film thickness and calculated | required the weight reduction rate. The results are also shown in Table 3 below.

(Comparative example)
In a three-necked flask equipped with a septum and a reflux under a nitrogen atmosphere, PSS-octakis (dimethylsilyloxy) substitution (4.913 mmol), pt-butoxystyrene (29.566 mmol), toluene (40 ml), Pt (0 ) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane 3% xylene solution (40 μl) was added and stirred at 60 ° C. for 2 hours. Subsequently, vinyl termination | terminus polydimethylsiloxane (DMS-V05) (19.79 mmol) was added, and it heated and stirred at 90 degreeC for 5 hours. Recovery was performed under the same conditions as in Example 1 to obtain a t-butyl protector.

  Next, the t-butyl protected product (5.03 g), hydrochloric acid, 4.0M 1,4-dioxane solution (50 mL) was placed in an eggplant-shaped flask, and heated and stirred at 80 ° C. for 4 hours. Recovery was performed under the same conditions as in Example 1 to obtain a phenol group-introduced compound (Comparative Example). The obtained polymer was examined for the number of photosensitive groups bonded to the cage silsesquioxane structure (number of quinonediazide structures) (M), the number of bonds of residual phenol groups, and the number average molecular weight. The results are also shown in Table 1 below.

  Subsequently, the obtained polymer (1.0 g) was dissolved in tetrahydrofuran (4.0 g) and stirred at room temperature to obtain a uniform resin composition (Comparative Example). The photosensitivity test was done about this resin composition. The results are shown in Table 2 below.

  Next, the obtained resin composition (2.0 g) was spin-coated on an alkali-free glass at 1000 rpm for 30 seconds, and then in a vertical firing furnace under a nitrogen atmosphere at 150 ° C. for 60 minutes, and subsequently at 350 ° C. for 60 minutes. By baking for a minute, the target hardened | cured material (comparative example) was obtained. About the obtained hardened | cured material, it carried out similarly to Example 1, and measured the film thickness and calculated | required the weight reduction rate. The results are also shown in Table 3 below.

  As can be seen from Table 2, the resin composition of the comparative example does not have photosensitivity because it does not dissolve in the 2.38% tetramethylammonium hydroxide solution before and after exposure. On the other hand, the photosensitive resin compositions of Examples 1 and 2 exhibited dissolution inhibition for 5 minutes or more before exposure, and also developed photosensitivity contrast because both dissolved within 60 seconds after exposure. Further, as can be seen from Table 3, the cured products of Examples 1 and 2 obtained a film having a desired film thickness, and the weight reduction rate after the heat resistance test was very good at less than 3%. From the above, it was found that the photosensitive resin composition containing the compound according to the present invention exhibits good photosensitivity. Moreover, it turned out that the hardened | cured material obtained using the compound based on this invention has favorable film forming property and favorable heat resistance.

  The present invention is not limited to the embodiment described above, and can be implemented with various modifications. It is not limited to this about the numerical value and component in the said embodiment, It is possible to change suitably and to implement. In addition, various modifications can be made without departing from the scope of the present invention.

  The compound according to the present invention is used as a compound excellent in moldability because it is soluble in a solvent and has sufficient fluidity when dissolved in a solvent. Moreover, since the photosensitive resin composition containing this compound has favorable photosensitivity, it is used as a photosensitive material. Further, a cured product obtained by curing the photosensitive resin composition is excellent in heat resistance, and thus is used in the dielectric material field. In addition, since the cured product obtained using the compound according to the present invention has both chemical resistance and low dielectric constant, it is a dielectric film, a semiconductor interlayer insulating film, a circuit board photoresist film, and a heat resistant film for ceramic sensors. Used in heat resistant paints, flame retardant and fire resistant paints, building materials coating agents, dielectric films for plasma display panels.

Claims (5)

  A cage silsesquioxane compound having a quinonediazide structure.   The cage silsesquioxane compound according to claim 1, wherein the quinonediazide structure is a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure.   A photosensitive resin composition comprising the cage silsesquioxane compound according to claim 1.   A cured product obtained by curing the photosensitive resin composition according to claim 3.   A thick film dielectric comprising the cured product according to claim 4.