TW201623391A - Siloxane resin composition, transparent cured product using same, transparent pixel, microlens, and solid-state imaging element - Google Patents

Abstract

The siloxane resin composition according to the present invention contains metal-containing particles, a siloxane resin, and a solvent, the siloxane resin having at least an acidic group (A), and contains metal-containing particles, a siloxane resin, an alkali-soluble resin, and a solvent, the refractive index of a cured film thereof being at least 1.5, wherein the siloxane resin has a silanol group.

Description

a decane resin composition, a transparent cured product using the decane resin composition, a transparent pixel, a microlens, and a solid-state imaging device

The present invention relates to a siloxane oxide resin composition, a transparent cured product using the siloxane oxide resin composition, a transparent pixel, a microlens, and a solid-state image sensor.

Examples of the transparent member such as a solid-state image sensor include a microlens or a transparent pixel. Alternatively, an antireflection film coated with these, a transparent pixel located at a lower portion thereof, a transparent insulating film, a planarizing film, or the like can be given. For each component, characteristics corresponding to its function are required. For example, for the above microlenses and transparent pixels, a higher refractive index and a higher transmittance are required. Further, recently, in order to realize the miniaturization of increasingly developed components, it is required for each material to have a manufacturing suitability suitable for fine machining accuracy.

Specifically, a technique of introducing a high refractive index particle into a transparent resin has been studied. Patent Document 1 proposes a positive photosensitive resin composition containing particles such as titanium oxide in polyimine.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2005/088396

An object of the present invention is to provide a decane resin composition suitable as a material for a transparent member such as a lens and a transparent pixel. Moreover, the object of the present invention is to provide a composition of a nonanethane resin which is not limited to a positive type, and can be handled as a heat-curable resin or a negative-type photosensitive resin, and can also appropriately handle micro-machining of microlenses and transparent pixels. It is possible to optimize its manufacturing suitability and properties of the cured film as needed. Further, an object of the present invention is to provide a transparent cured product, a transparent pixel, a microlens, and a solid-state imaging device using the above-described decane resin composition.

The above problems are solved by the following means.

[1] A siloxane oxide resin composition comprising metal-containing particles, a siloxane oxide resin, and a solvent, wherein the siloxane oxide resin has at least an acidic group (A).

[2] The oxirane resin composition according to [1], which further contains an alkali-soluble resin.

[3] A siloxane oxide resin composition comprising metal-containing particles, a siloxane oxide resin, an alkali-soluble resin, and a solvent, wherein the cured film has a refractive index of 1.5 or more, wherein the siloxane oxide resin has a decyl alcohol group. A siloxane resin.

[4] The oxirane resin composition according to [1] or [2] wherein the acidic group (A) has a pKa of 5.5 or less.

[5] The oxirane resin composition according to any one of [1] to [4] further comprising at least one selected from the group consisting of a polymerization initiator and an ultraviolet absorber.

[6] The hafnium oxide resin composition according to [5], wherein the ultraviolet absorber is selected from the group consisting of a benzotriazole compound, a benzophenone compound, a triazine compound, a diene compound, and a benzodithiol. Compounds and avobenzone compounds.

[7] The oxirane resin composition according to [1], [2] or [4] wherein the acidic group (A) is at least selected from the group consisting of a carboxyl group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group. One.

The oxirane resin composition according to any one of the above [1], wherein the decane resin is a decane represented by the following formula (S). A hydrolysis condensate prepared by the compound. (R ^S1 ) _e Si(R ^S2 ) _f (OR ^S3 ) _g (S) R ^S1 is a group containing an acidic group (A). R ^S2 and R ^S3 each independently represent a hydrogen atom or a hydrocarbon group. e is an integer from 1 to 3. f is an integer from 0 to 2. g is an integer from 1 to 3. e+g+f is 4.

[9] The oxirane resin composition according to [2] or [3] wherein the alkali-soluble resin is an acrylic resin.

[10] The oxirane resin composition according to [2] or [3], wherein the alkali-soluble resin is a resin represented by the following formula (R1). [Chemical Formula 1] L ^X1 represents a single bond or a linking group. R ^X1 and R ^Y1 are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group or a cyano group. R ^A is an acidic group (A). R ^Y2 represents a substituent. Nx and ny are the molar fractions.

[11] The oxirane resin composition according to any one of [1] to [10] wherein the total acid value of the resin blended in the decane resin composition is 50 mgKOH/g or more.

The oxime resin composition according to any one of the above [1], wherein the content of the siloxane resin is 1 part by mass or more and 80% by mass based on 100 parts by mass of the metal-containing particles. The following.

[13] The oxirane resin composition according to any one of [1] to [12], wherein the solid content of the composition contains 40% by mass or more and 80% by mass or less of the metal-containing particles.

[14] The hafnium oxide resin composition according to any one of [1] to [13], which is selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si. The metal serves as an element constituting the above metal-containing particles.

[15] The oxirane resin composition according to any one of [1] to [14] wherein the siloxane oxide resin is obtained by performing a hydrolysis condensation reaction in the presence of the metal-containing particles.

[16] The hafnium oxide resin composition according to any one of [1] to [15] wherein the cured film has a refractive index of 1.6 or more and 2.0 or less.

[17] A transparent cured product obtained by curing the oxirane resin composition according to any one of [1] to [16].

[18] A transparent pixel comprising the transparent cured product according to [17].

[19] A microlens comprising the transparent cured product according to [17].

[20] A solid-state imaging device comprising the transparent pixel according to [18], the microlens of [19], or both.

In the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expressions are not included in the formula and the substituent group. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In addition, the term "radiation" in the present specification means, for example, a far-line ultraviolet ray represented by a bright line spectrum of a mercury lamp, an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like. Further, in the present invention, light means active light or radiation. The "exposure" in the present specification includes not only exposure by far-field ultraviolet rays, X-rays, EUV light, etc. represented by a bright line spectrum of a mercury lamp, an excimer laser, but also an ion beam, unless otherwise specified. The depiction of the particle beam is also included in the exposure.

In the present specification, "(meth) acrylate" means either or both of acrylate and methyl acrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "( The "methyl) acrylonitrile group means either or both of an acryloyl group and a methacryl group.

In addition, in this specification, "single quantity" and "monomer" have the same meaning. The monoliths in the present specification are distinguished from oligomers and polymers, and refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a single body or a polymer. The polymerizable functional group refers to a group that participates in the polymerization reaction.

The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).

In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, the term "process" includes not only an independent process, but even if it is not clearly distinguishable from other processes, as long as the desired effect of the process is achieved, it is included in the term.

The decane resin composition of the present invention is suitable as a material for a transparent member such as a lens or a transparent pixel. It is not limited to the positive photosensitive resin, and a heat curing resin or a negative photosensitive resin can be used, and fine processing of the microlens and the transparent pixel can be appropriately handled. Moreover, the manufacturing suitability (especially the resolution) at the time of pattern formation and the characteristics (light resistance, suppression of residue defects) of the cured film can be optimized as needed. Further, it is possible to provide a transparent cured product, a transparent pixel, a microlens, and a solid-state imaging element which are excellent in quality by using the above-described silicone resin composition.

The naphthenic resin composition of the present invention contains a metal-containing particle, a siloxane oxide resin (or a combination of a siloxane oxide resin and an alkali-soluble resin), and a solvent. Hereinafter, preferred embodiments thereof will be described in detail.

<Metal-containing particles>

The metal-containing particles broadly include particles containing a metal as a constituent element. Here, the term "metal" should be interpreted in the broadest sense, and metals such as boron, antimony, and arsenic are also included herein. When the metal-containing particles are composed of an oxygen atom, they may be specifically referred to as metal oxide particles.

In the present invention, the metal-containing particles preferably contain a metal selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si. Among them, oxide particles containing two or more kinds of composite metals therein are preferred. For example, a combination of Ti and Zr (including Si as needed), Ti and Sn (including Si as needed), and Ti and Zr and Sn (including Si if necessary) are preferable, and have Ti, Zr, Sn, and Si. The combination is further preferred.

Examples of the constituent material of the metal-containing particles include titanium oxide, zirconium oxide, cerium oxide, barium titanate, barium sulfate, cerium oxide, cerium oxide, cerium oxide, tungsten oxide, and cerium oxide. These constituent materials may contain two or more kinds, and at least titanium oxide and zirconium oxide are preferable, and titanium oxide, zirconium oxide, and tin oxide are further preferably contained, and titanium oxide, zirconium oxide, tin oxide, and antimony oxide are particularly preferable. .

When titanium oxide is contained as a constituent material, rutile-type titanium oxide is preferable. In addition, the rutile-type titanium oxide is preferably contained in an amount of 80% by mass or more based on the total amount of the titanium oxide, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit is 100% by mass.

From the viewpoint of obtaining a high refractive index, the refractive index of the metal-containing particles is preferably 1.75 to 2.90, more preferably 1.75 to 2.70, and particularly preferably 1.90 to 2.70.

The number average particle diameter of the metal-containing particles is preferably 500 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, still more preferably 50 nm or less, and particularly preferably 30 nm or less. As the lower limit 値, 1 nm or more is preferable, and 3 nm or more is more preferable. It is preferable to set the range of the above-mentioned number average particle diameter to improve the transparency of the cured film. Moreover, it is preferable to provide insulation and durability depending on the homogeneity and the like of the cured film. The metal-containing particles can be prepared by pulverizing or dispersing a powder of an appropriate particle using a disperser such as a bead mill.

～Measurement of refractive index of particles~

The refractive index of the metal-containing particles can be measured by the following method. The content of the metal-containing particles was prepared to be 0% by mass, 20% by mass, 30% by mass, 40% by mass, or 50% by mass, and a mixed solution sample obtained by mixing the metal-containing particles and the matrix resin was prepared. The solid content concentration of each mixed solution sample was set to 10%. Each mixed solution sample was applied onto a tantalum wafer by a spin coater so as to have a thickness of 0.3 to 1.0 μm, and then heated and dried by a hot plate at 200 ° C for 5 minutes to obtain a coating film. Then, for example, a refractive index at a wavelength of 633 nm (25 ° C) can be obtained by an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.), and a value of 100% by mass of the metal-containing particles can be obtained by extrapolation.

~ Determination of average particle size ~

The number average particle diameter of the metal-containing particles (indicating the average particle diameter in the primary particle diameter) can be determined from a photograph obtained by observing the particles by a transmission electron microscope. The projected area of the particles was determined, and the equivalent circle diameter was determined as the average particle diameter. Further, in order to determine the average particle diameter, the particle diameter was measured for 100 particles, and among the measured particle diameters, the average value of 80 after the maximum side 10 and the minimum side 10 were subtracted as the average particle diameter. In the present specification, the expression "average particle diameter" means a number average particle diameter unless otherwise specified.

Examples of commercially available metal-containing particles include T-BTO-020RF (barium titanate; manufactured by Toda Kogyo Corporation), UEP-100 (zirconia; manufactured by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.) or STR-100N. STR-100W, STR-100WLPT (titanium oxide; all manufactured by Sakai Chemical Industry Co., Ltd.).

The metal-containing particles can also be obtained as a dispersion dispersed in a liquid. Examples of the cerium oxide-titanium oxide particles include "Optolake" (registered trademark) TR-502, "Optolake" TR-503, "Optolake" TR-504, "Optolake" TR-513, and "Optolake" TR-520. "Optolake" TR-527, "Optolake" TR-528, "Optolake" TR-529, "Optolake" TR-544 or "Optolake" TR-550 (all manufactured by JGC Catalysts and Chemicals Ltd.). Examples of the zirconia particles include "Bairaru" registered trademark Zr-C20 (average particle diameter = 20 nm; manufactured by Taki CHEMICAL Co., Ltd.), ZSL-10A (average particle diameter = 60-100 nm; DAIICHI KIGENSO KAGAKU KOGYO CO ., manufactured by LTD., "Nanouse" (registered trademark) OZ-30M (average particle size = 7 nm; manufactured by Nissan CHEMICAL Industries, Limited), SZR-M (manufactured by Sakai CHEMICAL Industry Co., Ltd.) or HXU-120JC (SUMITOMO) Made by Osaka Cement Company, Limited).

The content ratio (elemental composition) of the metal element in the metal-containing particles contains Ti and Zr, and the ratio thereof is preferably from 1 to 40 in terms of Ti/Zr ratio, more preferably from 1 to 30, still more preferably from 3 to 20. 4 to 12 is better, and 4 to 9 is the best. When such a range of numbers is satisfied, it is preferable to maintain the high refractive index while improving the preservability of the composition.

When Ti and Si are contained, the ratio is preferably from 1 to 40 in terms of Ti/Si ratio, more preferably from 1 to 30, still more preferably from 1 to 10.

When Ti and Sn are contained, the ratio is preferably 1 to 30 in terms of Ti/Sn ratio, more preferably 1 to 20, and still more preferably 1 to 10.

- Determination of the content of metal elements ~

In addition, the content ratio of the metal element containing the metal particle was evaluated by the elemental composition (atomic %) determined by X-ray fluorescence analysis (primus type II X-ray fluorescence analyzer manufactured by Rigaku Co., Ltd.). Regarding the ratio of the plurality of elements, the composition of each element (atomic %) was determined and evaluated in terms of the ratio of the respective elemental compositions (atomic %). Further, when the element composition ratio is obtained as the ratio of the molar number, the same meaning is also obtained.

The surface treatment of the metal-containing particles may be in any state, and examples thereof include a state in which a surfactant is treated by a later-described surfactant, a state in which a treatment agent containing another metal is used, and the like. For example, a state in which a specific metal-containing particle is formed and a coating film containing another metal-containing substance or the like is formed on the surface thereof can be mentioned. Alternatively, another coating film containing a gold-containing substance or the like may be made thick as a core-shell type metal-containing particle. When the ratio of the core to the shell is 100 parts by mass, the ratio of the core is preferably 85 parts by mass or more, more preferably 87 parts by mass or more, and particularly preferably 90 parts by mass or more. The upper limit is actually 97 parts by mass or less. The combination of the material constituting the core and the shell is a core composed of particles containing Ti, Sn, or the like, and is formed of a coating film containing Zr, a coating film containing Si, or a coating film containing Zr and Si. An example.

The content of the metal-containing particles is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less.

The metal-containing particles may be used singly or in combination of two or more.

In the present specification, the solid content (solid content) is a component which does not disappear by volatilization or evaporation when dried at 170 ° C for 6 hours. It generally refers to components other than the solvent and dispersion medium.

The metal-containing particles used in the present invention can be produced by a conventional method. For example, as described in the following examples, a salt of a metal which is a constituent element is added to a medium which forms a sol, and a base or an acid is further added as needed, thereby obtaining a dispersion sol (filter cake). Further, when the medium is an acid or a base, it is not necessary to add these additional amounts. An example of solidifying and pulverizing by heating the sol is mentioned. At this time, by adding the salt of the metal element to be mixed to the above sol, particles of the composite metal can be obtained. Alternatively, the core particles are formed in advance at a time, and at the same time, a sol containing a desired metal salt is formed in the same manner as described above. The core-shell type particles can be obtained by heating the sol and pulverizing the solidified person.

The metal salt to be used as a raw material may, for example, be a salt of each of the metals exemplified above. Specific examples thereof include titanium tetrachloride, potassium stannate, zirconium oxychloride, aluminum oxychloride, and aluminum chloride.

Examples of the solvent for forming the sol include an aqueous alkaline solution such as ammonia water, potassium hydroxide or sodium hydroxide; an acidic aqueous solution such as hydrochloric acid, nitric acid or sulfuric acid. Alternatively, a sol-gel method or the like in which a metal alkoxide is dissolved using water or various organic media may be mentioned.

For example, the method described in paragraphs <0015> to <0043> of JP-A-2008-69193 can be referred to as a method for producing a metal-containing particle which can be used in the present invention. Further, the specific metal-containing particles can be referred to in the paragraphs <0015> to <0043> of JP-A-2008-69193, which is incorporated herein by reference.

<矽 oxyalkylene resin>

The rhodium oxide resin is contained under the following conditions (a) or (b).

(Condition (a))

In the condition (a), the oxirane resin is defined to have an acidic group (A). The person who satisfies this condition is referred to as a decane resin (I). The pKa of the acidic group (A) of the decane resin (I) is preferably 5.5 or less, more preferably 5 or less, and particularly preferably 4 or less. Although there is no special lower limit, it is actually -3 or more.

The pKa is one of the indexes for quantitatively indicating the acid strength, and has the same meaning as the acidity constant. Considering the dissociation reaction of hydrogen ions from the acid, the equilibrium constant Ka is expressed by its negative common logarithm pKa. The smaller the pKa, the stronger the acidity. In the present specification, the value calculated by ACD/Labs (manufactured by Advanced Chemistry Development Ltd.) or the like is used. The following examples show calculation examples of representative substituents.

Substituent pKa -COOH 4.14 -SO ₃ H -2.80 -PO ₄ H ₂ 2.12, (2 segments 7.06)

The acidic group (A) is preferably at least one selected from the group consisting of a carboxyl group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group, and a carboxyl group, a phosphonic acid group, and a sulfonic acid group are more preferred.

The oxime resin (I) is preferably a resin (hydrolysis condensate) obtained by subjecting a decane compound containing an alkoxy decane compound of the following formula (S) to a hydrolysis condensation reaction. The hydrolyzed condensate of the alkoxy decane compound of the following formula (S) and the decane compound of the alkoxy decane compound represented by any one of the following formulas (1) to (3) is more preferable. It is further preferred to include at least a hydrolysis condensate reactant of an alkoxydecane compound of the following formula (S) and a decane compound of an alkoxydecane compound represented by the following formula (1).

(R ^S1 ) _e Si(R ^S2 ) _f (OR ^S3 ) _g (S)

R ^S1 is a group containing an acidic group (A). As described above, the preferred one of the acidic group (A) is also the same as defined above. When the acidic group (A) is bonded to Si via a linking group, examples of the linking group thereof include a linking group L to be described later.

Among them, R ^S1 is preferably a group represented by the following formula (S1).

R ^A -Lt-Ls-(Lu) _ns -* (S1)

R ^A is an acidic group (A).

Lt has the same meaning as a hydrocarbon linking group defined by a single bond or a linking group L described later, and the preferred range thereof has the same meaning. Among them, Lt is an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, further preferably 1 to 3) or an arylene group having 6 to 22 carbon atoms (carbon number 6~) 10 is better) is preferred. Lt may further have a substituent T. Further, examples of the substituent include a hydroxyl group and an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3), and an aryl group (having preferably 6 to 10 carbon atoms).

Ls has the same meaning as the hetero-linking group defined by the linking group L described later, and the preferred range thereof has the same meaning. Among them, an Ls-based ether group (-O-) or an ammonium linking group (-NR ^N ₂ ⁺ -) is preferred.

Lu has the same meaning as the hydrocarbon linking group defined by the linking group L described later, and the preferred range thereof has the same meaning. Among them, Lu is an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, further preferably 1 to 3) or an arylene group having 6 to 22 carbon atoms (carbon number 6) ~10 is better) is preferred. Lu may further have a substituent T.

Ns is 0 or 1. When the Ls is an ether group, ns is preferably 0. When the Ls is an ammonium linkage, the ns system 1 is preferred.

Further, the acidic group (A) can form a salt. However, those which form esters or anhydrides are not included. The ammonium linking group can also form a salt. Alternatively, the acid group and charge at the end may be eliminated to form a betaine structure.

R ^S2 and R ^S3 are each a group having the same meaning as R ¹ described below. The preferred range also has the same meaning.

R ^S1 to R ^S3 may each independently have an arbitrary substituent T. Alternatively, the adjacent ones may be bonded to each other or even condensed to form a ring.

e is an integer from 1 to 3, preferably 1 or 2, and 1 is particularly preferred. f is an integer from 0 to 2, and 0 or 1 is preferred. g is an integer from 1 to 3, and 2 or 3 is preferred. e+g+f is 4.

Further, the compound of the formula (S1) may be used singly or in combination of two or more.

Specific examples of the decane compound satisfying the above formula (S) include AX-1 to AX-6 and the like which are shown in Examples to be described later.

The synthesis of the alkoxydecane compound having an acidic group (A) can be carried out according to a conventional method. As the specific compound, for example, the alkoxydecane compound disclosed in the paragraphs <0016> to <0026> of Japanese Patent Laid-Open Publication No. 2012-180334 can be referred to and incorporated herein by reference.

(Condition (b))

In the condition (b), the decane resin is a decyl alcohol-based decane resin (referred to as a decane resin (II)), and further includes an alkali-soluble resin. The item of the alkali-soluble resin will be described in detail later. The nonanelkene resin (II) having a stanol group is not particularly limited, and an acidic group (A) is not preferred, and those generally used as such a resin can be suitably used. For example, a resin obtained by suitably using an alkoxydecane compound or combining and undergoing a hydrolysis condensation reaction can be suitably used.

The oxime resin (II) is preferably a resin obtained by subjecting an alkoxy decane compound represented by any one of the following formulas (1) to (3) to a hydrolysis condensation reaction. Further, it is preferred that the compound represented by the formula (1) is subjected to a hydrolysis condensation reaction together with the compound represented by the formula (2). Alternatively, the compound of the formula (1) may be subjected to a hydrolysis condensation reaction together with the compound of the formula (3), or a compound of the formula (2) and a compound of the formula (3) or a compound of the formula (1) may be used. The compound of the formula (2) and the compound of the formula (3) are subjected to a hydrolysis condensation reaction. In addition, one type of each of the compounds may be used alone or two or more types may be used.

(R ¹ ) _a Si(OR ² ) _4-a (1)

R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 or more preferably 1 to 3), or an alkenyl group (having preferably 2 to 12 carbon atoms and more preferably 2 to 6 carbon atoms). An alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6) or an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 or more preferably 6 to 10). An aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 and most preferably 7 to 11) is preferred, and an alkyl group, an aryl group or an alkenyl group is more preferred.

a is 0, 1, or 2.

R ³ Si(R ⁴ ) _C (OR ⁵ ) _3-C (2)

R ³ is a group containing a functional group (except for the acidic group (A)). As the functional group, a group containing a hetero atom (S, O, N, P, Si, etc.) in the structure is preferred. Alternatively, a polymerizable group or a basic group is preferred. (Meth) propylene decyloxy, thiol group (Sulfanyl group), epoxy group, oxetane group, glycidyl group, glycidoxy group, hydroxyl group, phenolic hydroxyl group, amino group , isocyanate group, urea group or a group having such a substituent. When R ³ is bonded to Si via a linking group, examples of the linking group include a linking group L which will be described later, and a hydrocarbon linking group is preferred. Even based acidic group (A) (carboxyl group, a sulfonic acid group, a phosphoric acid group, phosphonic acid group), an ester or anhydride functional group contained in R ^3. The amino group can also form a salt. In addition, in the present specification, when it is referred to as "acrylic acid" or "acrylonitrile", it is broadly understood to include not only an acrylonitrile group but also a derivative structure thereof, and it is considered to include a specific substituent at the α-position of the acryl fluorenyl group. Structure. However, in the narrow sense, when the α-position is a hydrogen atom, it is sometimes called acrylic acid or acrylonitrile. Sometimes a person having a methyl group at the α position is referred to as methacrylic acid, and refers to any one of acrylic acid (the α position is a hydrogen atom) and methacrylic acid (the α position is a methyl group), and is called (meth)acrylic acid. Wait.

R ⁴ and R ⁵ are each independently a group having the same meaning as R ¹ .

c is an integer from 0 to 2, and 0 or 1 is preferred.

R ⁶ ₃ Si-X-(SiR ⁷ ₃ ) _d (3)

R ⁶ and R ⁷ are each independently a group having the same meaning as the above R ¹ or an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 or more preferably 1 to 3). Alkenyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), alkynyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) or aryloxy group (carbon) The number of atoms is preferably from 6 to 22, more preferably from 6 to 14, more preferably from 6 to 10, or from aralkyloxy groups (from 7 to 23, more preferably from 7 to 15 and from 7 to 11). Very good). One to four of the plurality of R ⁶ and R ⁷ may be a group of R ³ .

X is a linking group of two or more valences. When X is a divalent linking group, an example of a linking group L to be described later may be mentioned. Specific examples thereof include S, O, CO, NR ^N and a polysulfide group (S to 2 or 6). When X is a trivalent linking group, for example, an isocyanuric acid skeleton can be mentioned. d is an integer of 1-4, and 1 or 2 is preferable.

R ¹ to R ⁷ may each independently have an arbitrary substituent T. Further, in the range in which the effects of the present invention are exerted, it is bonded to the ruthenium atom together with the linking group L. Alternatively, the adjacent members may be bonded to each other or even condensed to form a ring.

An example of a decane compound represented by the formula (1):

Examples of the trifunctional decane compound include methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltriisopropoxydecane, and methyltri-n-butoxy group. Decane, methyl tri-tert-butoxy decane, methyl tri-sec-butoxybutane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, butyl trimethoxy decane, Amyl methoxy decane, cyclopentyl trimethoxy decane, hexyl trimethoxy decane, cyclohexyl trimethoxy decane, octadecyl trimethoxy decane, octadecyl triethoxy decane, phenyl trimethyl Oxydecane, phenyltriethoxydecane, phenyltriisopropoxy, 1-naphthyltrimethoxynonane, 2-naphthyltrimethoxynonane, heptadecafluorodecyltrimethoxydecane, seventeen Fluorinated triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, p-styryl trimethoxy decane, allyl trimethoxy decane, and the like.

Examples of the bifunctional decane compound include dimethyl dimethoxy decane, dimethyl diethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, and methyl benzene. Dimethoxy decane, methyl vinyl dimethoxy decane, methyl vinyl diethoxy decane, cyclohexyl methyl dimethoxy decane, and the like.

The tetrafunctional decane compound may, for example, be tetramethoxy decane or tetraethoxy decane.

An example of a decane compound represented by the formula (2):

Examples of the trifunctional decane compound include 3-glycidyl ether propyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, and γ-methyl allyoxypropyl three. Ethoxy decane, γ-propylene decyloxytrimethoxy decane, γ-propylene methoxy propyl triethoxy decane, glycidyl ether methyl trimethoxy decane, glycidyl ether methyl triethoxy decane , α-glycidyl ether ethyl trimethoxy decane, α-glycidyl ether ethyl triethoxy decane, β-glycidyl ether ethyl trimethoxy decane, β-glycidyl ether ethyl triethoxy decane , α-glycidyl ether propyl trimethoxy decane, α-glycidyl ether propyl triethoxy decane, β-glycidyl ether propyl trimethoxy decane, β-glycidyl ether propyl triethoxy decane , γ-glycidyl ether propyl trimethoxy decane, γ-glycidyl ether propyl triethoxy decane, γ-glycidyl ether propyl tripropoxy decane, γ-glycidyl ether propyl triisopropyloxide Base decane, γ-glycidyl ether propyl tri-n-butoxy decane, γ-glycidyl ether propyl tri-tert-butoxy decane Γ-glycidyl ether propyl tri-sec-butoxy oxane, γ-glycidyl ether propyl trimethoxy decane, α-glycidyl ether butyl trimethoxy decane, α-glycidyl ether tert-butyl trimethoxy decane , α-glycidyl ether tert-butyl triethoxy decane, α-glycidyl ether tert-butyl triethoxy decane, β-glycidyl ether butyl trimethoxy decane, β-glycidyl ether butyl triethyl Oxydecane, γ-glycidyl ether butyl trimethoxy decane, γ-glycidyl ether butyl triethoxy decane, δ-glycidyl ether butyl trimethoxy decane, δ-glycidyl ether butyl triethyl Oxydecane, (3,4-epoxycyclohexyl)methyltrimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxydecane, 2-(3,4-epoxycyclohexyl Ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltripropoxydecane, 2- (3,4-epoxycyclohexyl)ethyltri-tert-butoxydecane, 2-(3,4-epoxycyclohexyl)ethyltri-n-butoxydecane, 2-(3,4-epoxy ring Hexyl)ethyl tri-sec-butoxy Alkanes, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxydecane, 4-(3,4-epoxy Cyclohexyl)butyltrimethoxydecane, 4-(3,4-epoxycyclohexyl)butyltriethoxydecane, 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)- 3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, 3-trimethoxyformamidopropylsuccinic anhydride, 3-ureidopropyl Triethoxy decane and the like.

Examples of the bifunctional decane compound include γ-glycidyl ether propyl methyl dimethoxy decane, γ-propylene methoxy propyl methyl dimethoxy decane, and γ-propylene methoxy propyl group. Methyl diethoxy decane, γ-methyl propylene methoxy propyl methyl dimethoxy decane, γ-methyl propylene methoxy propyl methyl diethoxy decane, glycidyl ether methyl diol Methoxy decane, glycidyl ether methyl methyl diethoxy decane, α-glycidyl ether ethyl methyl dimethoxy decane, α-glycidyl ether ethyl methyl diethoxy decane, β- Glycidyl ether ethyl methyl dimethoxy decane, β-glycidyl ether ethyl methyl diethoxy decane, α-glycidyl ether propyl methyl dimethoxy decane, α-glycidyl ether propyl Methyl diethoxy decane, β-glycidyl ether propyl methyl dimethoxy decane, β-glycidyl ether propyl methyl diethoxy decane, γ-glycidyl ether propyl methyl dimethoxy Base decane, γ-glycidyl ether propyl methyl diethoxy decane, γ-glycidyl ether propyl methyl dipropoxy decane, β-glycidyl ether propyl methyl 2 Butoxy decane, γ-glycidyl ether propyl methyl dimethoxy ethoxy decane, γ-glycidyl ether propyl ethyl dimethoxy decane, γ-glycidyl ether propyl ethyl diethoxy Basear, γ-glycidyl ether propyl vinyl dimethoxy decane, γ-glycidyl ether propyl vinyl diethoxy decane, 3-methyl propylene methoxy propyl dimethoxy decane, and the like.

Examples of the decane compound represented by the formula (3) include 1,3-bis(3-aminopropyl)tetramethyldioxane and 1,3-bis(3-aminoethyl)tetramethyl. Dioxane, 1,3-bis(3-aminopropyl)tetraethyldioxane, and the like.

The decane resin can be obtained by a hydrolysis reaction and a condensation reaction using the above alkoxydecane compound. As the hydrolysis condensation reaction, a known method can be used, and a catalyst such as an acid or a base can be used as needed. The catalyst is not particularly limited as long as it is a pH change. Specific examples of the acid (organic acid or inorganic acid) include nitric acid, phosphoric acid, oxalic acid, acetic acid, formic acid, and hydrochloric acid. Examples of the base include ammonia, triethylamine, ethylenediamine, and the like. The amount to be used is not particularly limited as long as the decane resin satisfies a predetermined molecular weight.

In the reaction system of the hydrolysis condensation reaction, a solvent may be added as needed. The solvent is not particularly limited as long as it can carry out the hydrolysis condensation reaction, and examples of the solvent to be described later can be mentioned. Examples thereof include alcohol compounds such as water, methanol, ethanol, propanol, diacetone alcohol, and tetrahydrofurfuryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and dipropylene glycol An ether compound such as ether; an ester compound such as methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate; ketone such as acetone, methyl ethyl ketone or methyl isoamyl ketone; Compound.

The conditions (temperature, time, and amount of solvent) of the hydrolysis condensation reaction may be appropriately selected depending on the type of the material to be used.

The weight average molecular weight of the decane resin used in the present embodiment is preferably 2,000 or more, and particularly preferably 3,000 or more. As the upper limit, 500,000 or less is preferable, 450,000 or less is more preferable, and 250,000 or less is particularly preferable.

In the present invention, the molecular weight of the polymer, unless otherwise specified, means the weight average molecular weight, which is measured by gel permeation chromatography (GPC) in terms of standard polystyrene. The measuring device used a device manufactured by TOSOH CORPORATION. As conditions, the conditions based on the following condition 1 are set. However, depending on the kind of the polymer, a preferred carrier (dissolving agent) and a column suitable for the carrier can be further suitably selected.

(Condition 1)

Column: using TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, TOSOH TSKgel Super HZ2000 column carrier: tetrahydrofuran Determination temperature: 40 ° C Carrier flow rate: 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI ( Refractive index) detector

In the case of a decyl alkane resin, the decane resin was adjusted and measured by dimethylformamide at a sample concentration of 0.3% by mass. However, depending on the kind and molecular weight, the measurement can be carried out in accordance with the above condition 1.

Although there is a part which is repeated, as the preferred alkane resin (II), the following may be mentioned.

Examples of the alkoxydecane having four or more alkoxy groups include tetramethoxynonane, tetraethoxydecane, tetraethoxydecane, tetraphenoxydecane, and tetramethoxy. Oxane, tetraethoxydioxane, bis(triethoxypropyl)tetrasulfide, tris-(3-methoxyformamidopropyl)isocyanurate, tri-(3) - Triethoxymethane alkyl propyl) isocyanurate. From the viewpoint of improving the chemical resistance of the cured film, in order to react a higher-component hexadecane decane with a tetrafunctional decane having a smaller steric hindrance, a mixture of a tetrafunctional decane and a hexa-functional decane is more preferable. good.

A hydrolyzate condensation reaction of a decane resin with a bifunctional or trifunctional alkoxydecane compound is preferred. Examples of the alkoxydecane compound constituting the siloxane oxide resin include dimethoxy dimethyl decane, diethoxy dimethyl decane, dimethoxy diphenyl decane, and diethoxy diphenyl. Baseline, dihydroxydiphenylnonane, dimethoxy(methyl)(phenyl)decane, diethoxy(methyl)(phenyl)decane,dimethoxy(methyl)(phenethyl) ) decane, dicyclopentyldimethoxydecane or cyclohexyldimethoxy(methyl)decane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyl Triethoxydecane, 3-propenyloxypropyltrimethoxydecane or 3-propenyloxypropyltriethoxydecane, 3-trimethoxymethylidenepropyl succinic anhydride, 3-triethyl Oxymethane alkyl succinic anhydride, 3-trimethoxymethyl decyl ethyl succinic anhydride, 3-trimethoxymethyl decyl butyl succinic anhydride, 3-glycidoxy propyl trimethoxy decane, 3 - glycidyloxypropyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethyl Base decane, methyltrimethoxy decane, ethyltrimethoxy decane, phenyltrimethoxydecane, phenethyltrimethoxydecane, naphthyltrimethoxydecane, methyltriethoxydecane, ethyltri Ethoxy decane, phenyl triethoxy decane, phenethyl triethoxy decane, naphthyl triethoxy decane, tetramethoxy decane or tetraethoxy decane.

When the content of the decane resin is such that the alkali-soluble resin is contained (condition (b)), the content of the decane resin is preferably reduced. When the alkali-soluble resin is not contained, the content of the siloxane resin is preferably increased. In other words, when the alkali-soluble resin is contained, the content of the siloxane oxide is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.

In addition, when the alkali-soluble resin is not contained, the content of the decane resin is preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

With respect to 100 parts by mass of the metal-containing particles, 1 part by mass or more is preferable, 10 parts by mass or more is more preferable, and 15 parts by mass or more is particularly preferable. The upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.

When the decane resin (I) and the decane resin (II) are used at the same time, the ratio thereof is adjusted depending on the properties required for developability, etc., but when the siloxane oxide resin (II) is set to 100 parts by mass. The hafnium oxide resin (I) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more. The upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. By applying the developable oxime resin (I) within this range, good developability can be obtained even without depending on the alkali-soluble resin, and it is suitable for use in the condition (a). On the other hand, even if the condition (b) is satisfied, the combined siloxane resin (I) is not hindered from being applied. In other words, as a preferred embodiment, the following aspects are included in the condition (a) or (b) of the present invention.

(i) Although it contains a siloxane resin having an acidic group (A), it does not contain an alkali-soluble resin.

(ii) a rhodium oxide resin having an acidic group (A), and further comprising an alkali soluble resin

(iii) comprising a decyl alkane resin having no acidic group (A), and further comprising an alkali-soluble resin

Among the above, the aspect of (ii) or (iii) is particularly preferable.

The decane resin can satisfy both conditions (a) and (b).

Further, in the present specification, when it is referred to as a decane resin, it basically means a polymer obtained by a hydrolysis condensation reaction of an alkoxydecane compound, but also includes a polymer based on other reactions and a decane compound which becomes a raw material. The meaning of itself. However, in the present invention, a hydrolyzed condensation reaction product of a decane compound is a decane compound. Further, the hydrolysis condensation reaction of the decane compound can be carried out in the presence of metal-containing particles. At this time, a "particle-resin matrix" in which a decane compound and a metal-containing particle react on the surface thereof or a "core-shell structure" in which a core is a metal-containing particle and a shell is a decane compound can be formed.

<UV absorber>

In the present invention, an ultraviolet absorber is preferably used. The molar absorption coefficient (unit: 1 mol ^-1 cm ^-1 ) at a wavelength of 365 nm is preferably 5,000 or more, more preferably 6500 or more, still more preferably 8,000 or more, and particularly preferably 10,000 or more. On the other hand, the Mohr absorption coefficient at a wavelength of 400 nm is preferably 3,500 or less, more preferably 2,500 or less, and particularly preferably 1,500 or less. In addition, in this specification, the molar absorption coefficient is based on the following measurement conditions unless otherwise specified.

<Method for measuring Mohr absorption coefficient>

A 1.00 × 10 ^-3 mol/L chloroform solution was prepared, and the absorbance was measured in the following order, whereby the molar absorption coefficient of each ultraviolet absorber was calculated.

The chloroform solution adjusted to the above concentration was placed in a glass tank having a width of 1 cm in the internal space, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary 5000) [trade name] manufactured by Agilent Technologies, Inc. The measurement temperature was set to 25 °C. The absorbance A obtained here was substituted into the following formula to calculate the molar absorptivity (mol ^-1 · L · cm ^-1 ).

ε=A/cl

Further, in the above formula, ε represents a molar absorption coefficient (mol ^-1 ·L·cm ^-1 ), A represents absorbance, c represents a concentration (mol/L), and 1 represents an optical path length (cm). The concentration c is 1.00 × 10 ^-3 mol / L. The optical path length l corresponds to the width of the internal space of the above-mentioned glass groove, thereby becoming 1 cm.

The ultraviolet absorber can be widely used as long as it has the above optical characteristics, and specific examples thereof include a (benzo)triazole compound, a benzophenone compound, a diene compound, an avobenzone compound, and a (benzo) compound. A thiazole compound, a (benzo)dithiol compound, a coumarin compound or a triazine compound. The ( ) mark here indicates that it may or may not be a benzo substituent. Among them, a diene compound, an avobenzone compound, a benzodithiol compound or a triazine compound is preferable in view of high resolution and light resistance, and a diene compound, an avobenzone compound or benzo disulfide compound. The alcohol compound is more preferable, and the diene compound and the avobenzone compound are further preferable.

The ultraviolet absorber used in the present invention is preferably composed of a compound having any one of the following formulas (a) to (g), and is composed of a compound having a skeleton of the formulae (d) to (g). Preferably, it is further preferably composed of a compound having a skeleton of the formula (d) to (f), and is particularly preferably composed of a compound having a skeleton of the formula (d) or (f). As the skeleton, a compound having an arbitrary substituent within a predetermined range can be used. Examples of the optional substituent include an example of the substituent T described later. Among them, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 or more preferably 1 to 3), a hydroxyl group or an alkoxy group (having 1 carbon atom) ～24 is more preferred, 1 to 12 is more preferred, 1 to 6 is further preferred, 1-3 is particularly preferred, and fluorenyl group is preferred (carbon number 2 to 24 is preferred, and 2 to 12 is more preferred, 2 ～6 is further preferred, 2 to 3 is particularly preferred), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 or more preferably 6 to 10), and a heterocyclic group (carbon number) 1 to 12 is preferred, and 2 to 5 is more preferred). It is preferred that the heterocyclic group contains N, O or S, and those containing N are preferred. The heterocyclic group is preferably a 5 to 7 membered ring, and a 5 or 6 membered ring is more preferred. In particular, it is preferred that the benzene ring of the formulae (a) to (f) has one or more substituents. When there are a plurality of substituents on the benzene ring, a ring can be formed.

[Chemical Formula 2]

In the formula (f), R ^U1 and R ^U2 are each independently a substituent T, and a cyano group or a fluorenyl group (preferably having 1 to 24 carbon atoms and more preferably 4 to 18 carbon atoms) is preferred. R ^U1 and R ^U2 may be the same or different.

In the formula (g), R ^U3 and R ^U4 are each independently a substituent T, wherein the alkyl group (having preferably 1 to 24 carbon atoms, more preferably 1 to 12, still more preferably 1 to 6) Preferably, ～3 is particularly preferred, and an alkyl group having a cyano group or a carboxyl group is preferred. It is preferred that R ^U5 and R ^U6 have the same meanings as R ^U1 and R ^U2 , respectively.

R ^U1 and R ^U2 , R ^U3 and R ^U4 , R ^U5 and R ^U6 may be bonded or even condensed to form a ring.

Specific examples of the ultraviolet absorber include Uvinul A, Uvinul 3000, Uvinul 3008, Uvinul 3049, Uvinul 3050 (manufactured by BASF SE), Sumisorb 130, Sumisorb 140, Sumisorb 200, Sumisorb 250, and Sumisorb 320. Sumisorb 340, Sumisorb 350 (manufactured by SUMITOMO CHEMICALCOMPANY, LIMITED), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by EVERLIGHT CHEMICAL INDUSTRIAl CORPORATION), Tomisob800 (manufactured by API CORPORATION), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (Manufactured by SHIPRO KASEI KAISHA. LTD.), benzophenone compound such as Jisuraiza M (SANKYO KASEI SANGYOO Co., Ltd.);

Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by SUMITOMO CHEMICALCOMPANY, LIMITED), JF77, JF78, JF79, JF80, JF83 (manufactured by JOHOKU CHEMICALCO., LTD), TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 171, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130 (manufactured by BASF SE), TINUVIN 70, TINUVIN 71, TINUVIN 72, TINUVIN 73, TINUVIN 74, TINUVIN 75, TINUVIN 76, TINUVIN 234, TINUVIN 77, TINUVIN 78, TINUVIN 80 a benzotriazole compound such as TINUVIN 81 (manufactured by EVERLIGHT CHEMICAL INDUSTRIA CORPORATION), Tomisob 100, Tomisob 600 (manufactured by API CORPORATION), SEESORB 701, SEESORB 702, SEESORB 703, SEESORB 704, SEESORB 706, SEESORB 707, SEESORB 709 (manufactured by SHIPRO KASEI KAISHA. LTD.);

a benzoate compound such as Sumisorb 400 (manufactured by SUMITOMO CHEMICALCOMPANY, LIMITED) or phenyl salicylate;

Hydroxyphenyl triazine compounds such as TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477 DW, and TINUVIN 479 (manufactured by BASF SE).

As the diene compound, a compound of the paragraphs 0144 to 0164 of JP-A-2010-78729 can be used, and the contents can be referred to and incorporated in the specification of the present application.

Among the solid components of the decane resin composition, the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

The ultraviolet absorber may be used singly or in combination of two or more.

<Polymerization initiator>

The polymerization initiator of the present invention may contain a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. For example, an organohalogen compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide, an azo compound, a coumarin compound, an azide compound, a metallocene compound, and six Aryl biimidazole compound, organoboric acid compound, disulfonic acid compound, hydrazine compound, phosphonium salt compound, hydroxyacetophenone compound, aminoacetophenone compound, mercaptophosphine oxide compound, trihalomethyltriazine compound, benzyl group Dimethyl ketal compound, α-hydroxyketone compound, α-aminoketone compound, mercaptophosphine compound, phosphine oxide compound, metallocene compound, triaryl imidazole dimer, anthraquinone compound, benzothiazole compound, diphenyl A ketone compound, a cyclopentadiene-benzene-iron complex, a halogenated methyl oxadiazole compound, a 3-aryl substituted coumarin compound, an α-aminoalkyl phenyl ketone compound, and a benzoic acid ester compound.

As a specific example of the above, it is possible to refer to the following paragraphs of the paragraph [0135] of the Japanese Patent Laid-Open Publication No. 2010-106268 (the <0163> of the specification of the corresponding US Patent Application Publication No. 2011/0124824), which is incorporated herein by reference. In the manual.

Specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969, and a sulfhydrylphosphine oxide-based initiator described in Japanese Patent No. 4,258,899.

Examples of the hydroxyacetophenone-based initiator include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF SE).

Commercial products of the aminoacetophenone-based initiators include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF SE). Further, a compound described in JP-A-2009-191179, which incorporates a long-wavelength light source having an absorption wavelength of 365 nm or 405 nm, can also be used.

As a commercial item of a mercaptophosphine-based initiator, IRGACURE-819, DAROCUR 4265, and DAROCUR-TPO (trade names: all manufactured by BASF SE) can be used.

Examples of the azo compound include 2,2-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleic acid nitrile, and dimethyl-2,2'-azobis (2). -Methylpropionate) [V-601] (manufactured by Wako Pure Chemical Industries, Ltd.) or the like.

In the present invention, a ruthenium compound is preferably used. The ruthenium compound effectively functions as a polymerization initiator which initiates and promotes polymerization in the oxirane resin composition of the present invention. Further, the ruthenium compound has less coloration in post-heating and is also excellent in hardenability. In particular, in the present invention, the resolution of the pattern and the light resistance of the cured product can be optimized, which is preferable in this respect. Among them, commercially available products such as IRGACURE OXE01 (the following formula) and IRGACURE OXE02 (the following formula) (all manufactured by BASF SE) can be suitably used.

[Chemical Formula 3]

The hydrazine compound to be a polymerization initiator is preferably represented by the following formula (OX), and more preferably represented by the formula (OX-1).

[Chemical Formula 4]

・A ¹

The -AC or alkyl group of the A ¹ formula (OX-1) is preferred. The alkyl group has preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent T described later. Further, the substituent T can be substituted with a linking group L which will be described later.

・C

C represents Ar, -SAr or -COAr.

・R

R represents a monovalent substituent, and is preferably a monovalent non-metal atomic group. The monovalent non-metal atomic group may, for example, be an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 or more preferably 1 to 3) or an aryl group (having a carbon number of 6 to 14). Preferably, 6 to 10 is more preferred), sulfhydryl groups (2 to 12 carbon atoms are preferred, 2 to 6 are more preferred, 2 to 3 are particularly preferred), and aryl sulfonyl groups (7 to 15 carbon atoms are preferred). Preferably, 7 to 11 is more preferred), alkoxycarbonyl group (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred, 2 to 3 is particularly preferred), and aryloxycarbonyl group (carbon number is 7 to 7). 15 is more preferred, 7 to 11 is more preferred, a heterocyclic group (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), and an alkylthiocarbonyl group (2 to 12 carbon atoms is preferred). 2 to 6 is more preferable, 2 to 3 is particularly preferred, and an arylthiocarbonyl group (preferably having 7 to 15 carbon atoms, more preferably 7 to 11 carbon atoms). Further, these groups may have one or more substituents. Further, the aforementioned substituent may be further substituted with another substituent T. In the substituent T, a halogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 or more preferably 1 to 3) or an aryl group (having preferably 6 to 14 carbon atoms, 6) ～10 is more preferable), an arylthio group (preferably having 6 to 14 carbon atoms, more preferably 6 to 10), and an aryl fluorenyl group (having preferably 7 to 15 carbon atoms, more preferably 7 to 11) ) is preferred. In the linking group L, an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR ^N or a combination thereof is preferred.

・B

B represents a monovalent substituent, an alkyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms), or a heterocyclic group (carbon). The number of atoms is preferably from 2 to 18, and the number of carbon atoms is preferably from 2 to 12. These groups may be bonded via a linking group L. Further, these groups may have one or more substituents T. The substituent T may also be substituted via any linking group L. Among them, the linking group L is also an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR ^N or a combination thereof. Specific examples of B include the following. * indicates the bonding position, which can be bonded at different positions. Further, the groups may be further accompanied by a substituent T. Specific examples thereof include a benzamidine group, a phenylthio group, and a phenyloxy group.

[Chemical Formula 5]

・A

A is a single bond or a linking group. A preferred example of the linking group is the above-mentioned linking group L or an arylene group (preferably having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms) or a heterocyclic linking group (aromatic heterocyclic linking group). Preferably, it is preferably 2 to 18 carbon atoms and more preferably 2 to 12 carbon atoms.

・Ar

Ar is an aryl group or a heteroaryl group (aromatic heterocyclic group). As the aryl group, a carbon number of 6 to 14 is preferred, a carbon number of 6 to 10 is more preferred, and a phenyl group or a naphthyl group is preferred. As the heteroaryl group, a carbon number of 2 to 18 is preferred, and a carbon number of 2 to 12 is more preferable, and a carbazolyl group having a substituent such as an alkyl group at the N position is preferable.

As the oxime initiator, the formula (OX-1), (OX) after paragraph 0513 of the Japanese Patent Application Laid-Open No. 2012-208494 (the <0632> of the specification of the corresponding US Patent Application Publication No. 2012/235099) can be referred to. -2) or a description of the compound represented by (OX-3), which is incorporated in the specification of the present application.

The polymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a higher absorbance at 365 nm and 455 nm. From the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000.

The content of the polymerization initiator (the total content in the case of two or more kinds) is preferably 0.1% by mass or more and 10% by mass or less based on the total solid content of the composition, and more preferably 0.3% by mass or more and 8% by mass or less. More preferably, it is more than 5% by mass or less. Good hardenability and transparency are obtained in this range.

Further, the polymerization initiator may be used singly or in combination of two or more kinds.

<solvent>

The rhodium oxide resin composition of the present invention contains a solvent. With respect to the solvent, the solvent used in the hydrolysis condensation reaction of the above decane compound can be directly used as a solvent of the composition, or the following solvent can be used in addition to or instead of the solvent.

Examples of the solvent include water, an aliphatic compound, a halogenated hydrocarbon compound, an alcohol compound, an ether compound, an ester compound, a ketone compound, a nitrile compound, a guanamine compound, an anthraquinone compound, and an aromatic compound. These solvents can be used in combination. Each example is listed below.

·water

・Fatty compounds

Hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, cyclopentane, etc.

・Halogenated hydrocarbon compounds

Methyl chloride, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, o-dichlorobenzene, chloropropene, HCFC, methyl chloroacetate, Ethyl chloroacetate, chloroacetic acid trichloroacetic acid, malodorous methane, methyl iodide, tris(tetra)vinyl chloride, etc.

・Alcohol compound

Methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, diacetone alcohol, tetrahydrofurfuryl alcohol, etc.

・Ether compound (including hydroxyl group containing ether compound)

Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, B Glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol Monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.)

・Ester compound

Ethyl acetate, ethyl lactate, 2-(1-methoxy)propyl acetate, propylene glycol monomethyl ether acetate, etc.

Ketone compound

Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, cyclopentanone, etc.

・Nitrile compound

Acetonitrile

・醯amine compound

N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, ε-caprolactam, A Indoleamine, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, hexamethylphosphonium triamine, etc.

・Azo compound

Dimethyl hydrazine

・Aromatic compounds

Benzene, toluene, etc.

As the solvent, in order to uniformly dissolve the components of the composition, an alcohol compound, an ester compound, or an ether compound is preferred. For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diacetone alcohol, ethylene glycol monobutyl ether, 2-ethoxyethyl acetate, 1-methoxypropyl-2-acetate , 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutanol acetate, 3-methoxybutyl acetate, 1,3-butanediol diethyl Acid ester, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl lactate, butyl lactate, ethyl acetate or γ-butyrolactone.

When the amount of the solvent to be used is, for example, the solid content is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less.

The solvent may be used alone or in combination of two or more.

<Polymerizable compound>

The rhodium oxide resin composition of the present invention may contain a polymerizable compound. The polymerizable compound is preferably an addition polymerizable compound having at least one polymerizable group such as an ethylenically unsaturated double bond, an epoxy group or an oxetanyl group. It is more preferable that a compound selected from at least one polymerizable group is selected from a compound having two or more polymerizable groups. There is no special upper limit, but it is actually 12 or less. For example, it may be a chemical form having a monomer, a prepolymer (i.e., a dimer, a trimer, or the like, and an oligomer) or a mixture thereof, and a copolymer such as these. Examples of the monomer and the copolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines. . It is preferred to use an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a fluorenyl group or an unsaturated carboxylic acid oxime amine and a monofunctional or polyfunctional isocyanate or epoxy group is also suitably used. And a dehydration condensation reaction of an unsaturated carboxylic acid ester or an unsaturated carboxylic acid amide with a monofunctional or polyfunctional carboxylic acid. Further, an addition reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an oxime amine of an unsaturated carboxylic acid, and a monofunctional or polyfunctional alcohol, an amine or a thiol Further, an unsaturated carboxylic acid ester having a detachable substituent such as a halogen group or a toluene sulfonic acid oxy group or a carboxylic acid amide containing an unsaturated group, and a substitution with a monofunctional or polyfunctional alcohol, an amine or a thiol The reactants are also suitable. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, styrene, vinyl ether or the like can be used instead of the above unsaturated carboxylic acid. As the specific compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can be suitably used in the present invention.

The polymerizable compound is further preferably represented by the following formulas (MO-1) to (MO-6).

[Chemical Formula 6]

In the formula, n is 0 to 14, respectively, and m is 1 to 8, respectively. Within a molecule, a plurality of R, T, and Z may be the same or different from each other. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least one of R is a polymerizable group.

It is preferable that n is 0 to 5, and 1 to 3 is more preferable.

m is preferably from 1 to 5, more preferably from 1 to 3.

As a specific example of the polymerizable compound represented by the above formula (MO-1) to (MO-6), the compound described in Paragraph No. 0248 to No. 0251 of JP-A-2007-269779 can be suitably used in the present invention. In the embodiment.

Among them, as a polymerizable compound, dipentaerythritol triacrylate (available as KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (a commercially available product is KAYARAD D-320; Nippon Kayaku Co., Ltd. manufactured) dipentaerythritol penta (meth) acrylate (available as KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (as a product) Commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) and these (meth)acrylonitrile groups are modified by a structure of ethylene glycol, a propylene glycol residue or diglycerin EO (ethylene oxide) ( Methyl) acrylate (commercially available as M-460; manufactured by Toagosei Company, Limited) is preferred. These types of oligomers can also be used.

The polymerizable compound may have an acidic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Thereby, the ethylenic compound can have an unreacted carboxyl group as in the case of a mixture, and can also be used as it is. The acidic group can be introduced by reacting the hydroxyl group of the above-mentioned ethylenic compound with a non-aromatic carboxylic acid anhydride as needed. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexahydroortane. Phthalic anhydride, succinic anhydride, maleic anhydride.

The molecular weight of the polymerizable compound is preferably 300 or more and 1,500 or less, more preferably 400 or more and 700 or less.

The content of the polymerizable compound is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 3% by mass to 40% by mass, and preferably 5% by mass to 30% by mass based on the total solid content in the composition. The range of % is further preferred. If it is in this range, the refractive index and transparency are not excessively lowered, and the curability is good, which is preferable.

The polymerizable compound may be used alone or in combination of two or more.

<alkali soluble resin>

The naphthenic resin composition of the present invention may contain an alkali-soluble resin (an essential component in the condition (b)). As the alkali-soluble resin, it is possible to obtain an alkali-soluble resin having at least one alkali-soluble group from a linear organic polymer and a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) Choose the appropriate one.

From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable. From the viewpoint of developability control, an acrylic resin, an acrylamide resin, an acrylic acid/acrylamide copolymer resin is preferable, and an acrylic resin is particularly preferable. The group which promotes alkali solubility (hereinafter, also referred to as an acidic group) is exemplified by the above acidic group (A). It is preferably soluble in a solvent and can be developed by a weak aqueous alkali solution, and particularly preferably, (meth)acrylic acid is mentioned. These acidic groups may be used alone or in combination of two or more.

As the linear organic high molecular polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. An alkali-soluble phenolic resin such as a maleic acid copolymer, a partially esterified maleic acid copolymer or a phenolic resin, and an acid anhydride derivative having a carboxylic acid in a side chain, and an acid anhydride added to a polymer having a hydroxyl group By. In particular, a copolymer of (meth)acrylic acid and other monomeric materials capable of copolymerizing therewith is suitable as the alkali-soluble resin. Examples of the other monomer which can be copolymerized with (meth)acrylic acid include an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound and the like. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Butyl (meth) acrylate, isobutyl (meth) acrylate, (iso) pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (Meth) acrylate, cyclohexyl (meth) acrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, and tetrahydrofurfuryl methacrylate. A polystyrene macromonomer, a polymethyl methacrylate macromonomer, etc., and the N-substituted maleimide monomer described in Japanese Laid-Open Patent Publication No. Hei 10-300922, the N-phenyl group is exemplified. Maleic imine, N-cyclohexylmaleimide, and the like.

The alkali-soluble resin is preferably a polymer of the following formula.

[Chemical Formula 7]

L ^X1 represents a single bond or a linking group L which will be described later. Among them, a single bond is preferred.

R ^X1 and R ^Y1 are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (preferably having 1 to 6 carbon atoms, more preferably 1 to 3) or a cyano group, wherein R ^X1 and R ^Y1 are each independently It is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a cyano group, and a hydrogen atom or a methyl group is more preferable.

R ^A is an acidic group (A).

R ^Y2 represents a substituent T in which an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 or more preferably 1 to 3), and an aryl group (having preferably 6 to 22 carbon atoms). 6~14 is better, 6~10 is especially good), aralkyl (better 7~23 is preferred, 7~15 is better, 7~11 is especially good). The group may further have a substituent T, and examples of the further substituent include a hydroxyl group and a carboxyl group.

Nx, ny is the molar fraction, nx+ny can be less than 1 (meaning that there may be other repeating units), but 1 is preferred. The lower limit of nx is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 0.2 or more. As the upper limit, 0.7 or less is preferable, 0.6 or less is more preferable, and 0.5 or less is particularly preferable. As the lower limit of ny, 0.3 or more is preferable, 0.4 or more is more preferable, and 0.6 or more is particularly preferable. As the upper limit, 0.9 or less is preferable, and 0.8 or less is more preferable.

Specific examples of the alkali-soluble resin include exemplified compounds of the BX number described later.

As the alkali-soluble resin, a benzyl (meth) acrylate / (meth) acryl copolymer or a multicomponent copolymer composed of benzyl (meth) acrylate / (meth) acrylate / other monomer is particularly suitable. Further, a 2-hydroxypropyl (meth) acrylate/polystyrene macromonomer described in JP-A-7-140654, which is a copolymer of 2-hydroxyethyl methacrylate, may be mentioned. /benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer /benzyl methacrylate / methacrylic acid copolymer and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

The content of the alkali-soluble resin is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, even more preferably 20 to 35% by mass, based on the total solid content of the composition. In the condition (b) When the siloxane oxide resin (II) is combined, the lower limit of the alkali-soluble resin is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and 50 parts by mass or more, based on 100 parts by mass of the siloxane oxide resin (II). Very good. The upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less.

The alkali-soluble resin can be used alone or in combination of two or more.

<Low molecular organic acid>

The naphthenic resin composition of the present invention may contain a low molecular organic acid (low molecular organic acid). The low molecular organic acid system is a molecule having virtually no molecular weight distribution and having an acidic function as long as it is a single molecule. The organic functional group has a pKa of 5.5 or less, more preferably 5 or less, more preferably 4 or less, and the lower limit is not particularly limited, but is actually -3 or more. At least one of a carboxyl group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group is preferred. The acid value is preferably 50 mgKOH/g or more, more preferably 100 mgKOH/g or more, further preferably 150 mgKOH/g or more, and 200 mgKOH. More preferably, the upper limit is 700 mgKOH/g or less, and more preferably 500 mgKOH/g or less.

The amount of the low molecular organic acid to be added is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more, more preferably 0.3% by mass or more. 2% by mass or less is more preferably 1% by mass or less. Further, 1% by mass or more of the solid content is preferable, and 1.5% by mass or more is more preferable, and 2% by mass or more is more preferable. 10% by mass or less is preferable, 8% by mass or less is more preferable, and 7% by mass or less is further more preferable.

The ratio of the decane resin to the low molecular organic acid is preferably 3 to 50, more preferably 5 to 30, and further preferably 6 to 25. It is especially good. By setting it as this range, the film can be infiltrated into the developing solution favorably, and the resolution can be improved further.

<developability>

The decyl alkane resin satisfying the condition (a) or (b) of the present invention or a combination thereof (hereinafter referred to as "specific alkali-soluble resin group") is a tetramethyl group which is soluble in a concentration of 0.1% by mass or more at 23 ° C. Aqueous ammonium hydroxide (TMAH) aqueous solution is preferred. Further, a TMAH aqueous solution which is soluble in 1% by mass or more is more preferably, and a TMAH aqueous solution which is soluble in 2% by mass or more is further preferable.

The acid value of the specific alkali-soluble resin group is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and particularly preferably 70 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, and 150 mgKOH/g or less is preferably 150 mgKOH/g or less. More preferably, it is particularly preferably 120 mgKOH/g or less. By setting it as such a range, it is possible to exhibit desired optical characteristics and to effectively reduce the development residue of the unexposed portion. Further, in the condition (a), oxygen is contained. The range of the above acid value of the alkane resin (I) is preferred. In the condition (b), the alkali-soluble resin is preferably in the range of the acid value described above. By having the above-mentioned acid value, the oxirane resin (I) can achieve compatibility between optical properties and developability at a high level. Therefore it is especially good.

・Measurement of acid value

In the present specification, the acid value is calculated by titration in a 0.1 N KOH ethanol solution. The specific item is based on the method for measuring the acid value in JIS K 0070: 1992. Specifically, a certain amount of the resin is dissolved in 1-methoxy- Among the 2-propyl acetates, phenolphthalein was used as an indicator and titrated in a KOH/ethanol solution to carry out measurement.

<Polymerization inhibitor>

The polymerization inhibitor may be contained in the rhodium oxide resin composition of the present invention. Examples of the polymerization inhibitor include a phenolic hydroxyl group-containing compound, an N-oxide compound, a piperidine 1-oxyl radical compound, a pyrrolidine 1-oxyl radical compound, and an N-nitrosobenzamide. And transition metal compounds such as diazo compounds and cationic dyes, sulfur-containing ether-based compounds, nitro-containing compounds, FeCl ₃ , and CuCl ₂ . As a polymerization inhibitor, the description of paragraphs 0260 to 0280 of the Japanese Patent Laid-Open Publication No. 2010-106268 (the <0284> to <0296> of the specification of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to. These are incorporated in the specification of the present application.

The amount of the polymerization inhibitor to be added is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 8 parts by mass or less, and more preferably 0.05 parts by mass or more, based on 100 parts by mass of the polymerization initiator. The range below the mass fraction is optimal.

The polymerization inhibitor may be used singly or in combination of two or more.

<dispersant>

As the dispersing agent, a polymer compound represented by the formula (1) represented by the first aspect of the application of the Japanese Patent Application Laid-Open No. 2007-277514 (corresponding to the first application of US2010/0233595) is preferred. The description of Japanese Patent Publication No. 2007-277514 (corresponding to US 2010/0233595) is incorporated herein by reference.

The polymer compound represented by the above formula (1) is not particularly limited, and can be synthesized in accordance with the synthesis methods described in paragraphs 0114 to 0140 and paragraphs 0266 to 0348 of JP-A-2007-277514.

The content of the dispersant is preferably 10 to 1000 parts by mass, more preferably 30 to 1000 parts by mass, even more preferably 50 to 800 parts by mass, per 100 parts by mass of the metal-containing particles. Further, it is preferably 10 to 30% by mass based on the total solid content of the composition. These dispersing agents may be used singly or in combination of two or more.

<Surfactant>

The decane resin composition of the present invention may comprise a surfactant. Examples of the surfactant include an anthrone-based surfactant, an anthraquinone surfactant such as an organic polyoxyalkylene-based surfactant, a fluorine-based surfactant, a polyoxyethylene lauryl ether, and a polyoxyethylene oleyl ether. Non-ionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol laurate or polyethylene glycol distearate, and polyalkylene oxide interface An active agent, a poly(meth)acrylate surfactant, or a surfactant composed of an acrylic or methacrylic polymer. The surfactant which is a commercial item is, for example, "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (all manufactured by DIC Corporation Co., Ltd.) or NBX- 15 or FTX-218 (both manufactured by NEOS COMPANYLIMITED) and other fluorine-based surfactants, BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (all manufactured by BYK Additives & Instruments) Is a surfactant.

The amount of the surfactant to be added is preferably 1% by mass or more, more preferably 1.5% by mass or more, and particularly preferably 5% by mass or more, based on the solid content of the composition. The upper limit 値 is preferably 30% by mass or less, more preferably 15% by mass or less.

The surfactant may be used singly or in combination of two or more.

The rhodium oxide resin composition of the present invention may contain other additives such as a dissolution inhibitor, a stabilizer or an antifoaming agent as needed.

<developer>

As the developer, an alkaline solution is preferably used. For example, the concentration of the basic compound is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethylammonium hydroxide. Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7 - undecene and the like. Among them, in the present invention, an organic base is preferred. Further, when an alkaline aqueous solution is used as the developer, the cleaning treatment is usually carried out with water after development. Among the developing solutions, a fourth-order ammonium salt is preferred, and tetramethylammonium hydroxide (TMAH) or choline is more preferred.

The developer may be used singly or in combination of two or more.

In addition, the expression of the compound in the present specification (for example, when a compound is added at the end) is used in addition to the above-mentioned compound itself in the meaning of including a salt thereof and an ion thereof. In addition, it means a derivative in which a part is changed such that a substituent is introduced, within a range in which a desired effect can be exhibited.

In the present specification, a substituent which is not indicated to be substituted or unsubstituted (the same for the linking group) means that any substituent may be present on the group. This also has the same meaning for compounds that are not labeled as substituted or unsubstituted. As a preferable substituent, the following substituent T is mentioned.

The substituent T is exemplified by the following substituents.

The alkyl group (alkyl group having 1 to 20 carbon atoms is preferred, and examples thereof include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a pentyl group, a heptyl group, a 1-ethylpentyl group, and a benzyl group. , 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (alkenyl having 2 to 20 carbon atoms is preferred, for example, vinyl, allyl, oleyl, etc.), alkynyl (Alkynyl group having 2 to 20 carbon atoms is preferable, for example, an ethynyl group, a butadiynyl group or a phenylethynyl group), and a cycloalkyl group (a cycloalkyl group having 3 to 20 carbon atoms is preferable, for example, , cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., but when it is referred to as an alkyl group, it usually contains a meaning of a cycloalkyl group.), an aryl group (an aryl group having 6 to 26 carbon atoms is Preferred, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (heterocyclic group having 2 to 20 carbon atoms) Preferably, a heterocyclic group having at least one oxygen atom, a sulfur atom, a nitrogen atom or a 5- or 6-membered ring is preferred, for example, tetrahydropyran, tetrahydrofuran, 2-pyridyl, 4-pyridyl, 2 -imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidine A ketone group or the like), an alkoxy group (an alkoxy group having 1 to 20 carbon atoms is preferable, for example, a methoxy group, an ethoxy group, an isopropoxy group, a benzyloxy group or the like), an aryloxy group (a carbon atom) An aryloxy group of 6 to 26 is preferred, for example, a phenoxy group, a 1-naphthyloxy group, a 3-methylphenoxy group, a 4-methoxyphenoxy group, etc.), an alkoxycarbonyl group (a carbon atom) The alkoxycarbonyl group having 2 to 20 is preferably, for example, an ethoxycarbonyl group, a 2-ethylhexyloxycarbonyl group or the like, and an aryloxycarbonyl group (an aryloxycarbonyl group having 6 to 26 carbon atoms is preferred). For example, a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 3-methylphenoxycarbonyl group, a 4-methoxyphenoxycarbonyl group, or the like), an amino group (an amino group having 0 to 20 carbon atoms is preferred) , comprising an alkylamino group, an arylamino group, for example, ammonia, N,N-dimethylamino, N,N-diethylamino, N-ethylamino, anilino, etc.), an amine sulfonyl group (carbon atom) Aminosulfonyl group of 0 to 20 is preferred, for example, N,N-dimethylaminesulfonyl, N-phenylaminesulfonyl, etc., fluorenyl (fluorenyl group having 1 to 20 carbon atoms) Preferred, for example, ethyl thiol, propyl fluorenyl, butyl fluorenyl, etc., aryl fluorenyl (carbon number 7) Preferably, the aryl group of ～23 is, for example, benzamidine or the like), a decyloxy group (an oxiranyl group having 1 to 20 carbon atoms is preferable, for example, an ethoxy group, etc.), and an aryloxy group (for example). An aryloxy group having 7 to 23 carbon atoms is preferred, for example, a benzylideneoxy group or the like, and an aminomethyl group (an aminopyridyl group having 1 to 20 carbon atoms is preferred, for example, N, N). - dimethylaminomethyl hydrazino group, N-phenylamine carbhydryl group, etc.), fluorenylamino group (p-amino group having 1 to 20 carbon atoms is preferable, for example, acetylamino group, benzamidine amino group, etc.), and alkane a sulfur group (an alkylthio group having 1 to 20 carbon atoms is preferred, for example, a methylthio group, an ethylthio group, an isopropylthio group, a benzylthio group, etc.), and an arylthio group (having a carbon number of 6 to 26) An arylthio group is preferred, for example, a phenylthio group, a 1-naphthylthio group, a 3-methylphenylthio group, a 4-methoxyphenylthio group, etc.), an alkylsulfonyl group (having a carbon number of 1 to 20) The alkylsulfonyl group is preferably, for example, a methylsulfonyl group or an ethylsulfonyl group, or an arylsulfonyl group (an arylsulfonyl group having 6 to 22 carbon atoms is preferred, for example, a phenyl sulfonyl group, etc., an alkyl formamyl group (an alkyl formyl group having 1 to 20 carbon atoms) Preferably, for example, monomethylformamidinyl, dimethylformamidinyl, trimethylformamidinyl, triethylcarbinyl, etc.), arylmethanyl (aryl group having 6 to 42 carbon atoms) A decyl group is preferred, for example, a triphenylcarbenyl group, etc., a phosphinium group (a phosphonium group having 0 to 20 carbon atoms is preferred, for example, -OP(=O)(R ^P ) ₂ ), A phosphinium group (phosphono group having 0 to 20 carbon atoms is preferred, for example, -P(=O)(R ^P ) ₂ ), and a phosphinyl group (oxyphosphinyl group having 0 to 20 carbon atoms is preferred). , for example, -P(R ^P ) ₂ ), (meth)acrylylene, (meth)acryloxy, (meth)acrylimidoimino ((meth)acryloylamino), hydroxyl, sulfur An alcohol group, a carboxyl group, a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like).

Further, in each of the groups described in the substituents T, the substituent T may be further substituted.

Further, when the above substituent is an acidic group or a basic group, a salt thereof can be formed.

When the compound or the substituent, the linking group or the like contains an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group or the like, these may be cyclic or chain-like, and may be a straight chain. It may be branched and may be substituted or unsubstituted as described above.

Each of the substituents defined in the present specification may be substituted by the following linking group L within the range in which the effects of the present invention are exerted, or a linking group L may be interposed in the structure. For example, an alkyl group, an alkylene group, an alkenyl group, an alkenylene group or the like may further have a hetero-linking group interposed in the structure.

As the linking group L, a hydrocarbon linking group [alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, further preferably 1 to 3) or an alkenylene group having 2 to 10 carbon atoms (carbon) The number of atoms is preferably 2 to 6 and more preferably 2 to 4, and the alkynylene group having 2 to 10 carbon atoms (more preferably 2 to 6 carbon atoms, still more preferably 2 to 4), and 6 carbon atoms. An arylene group of ～22 (more preferably 6 to 10 carbon atoms) or a combination thereof; a hetero linkage group [carbonyl (-CO-), thiocarbonyl (-CS-), ether group (-O-) ), a thioether group (-S-), an imino group (-NR ^N -), an ammonium linking group (-NR ^N ₂ +-), a polysulfide group (the number of S is 1 to 8), an imine linking group (R ^N -N=C<, -N=C(R ^N )-), sulfonyl (-SO ₂ -), sulfinyl (-SO-), phosphate linkage (-OP(OH)( O)-O-), a phosphonic acid linkage (-P(OH)(O)-O-), or a combination thereof, or a combination of these is preferred. Further, when the ring is formed by condensation, the hydrocarbon linking group may be appropriately bonded to form a double bond or a triple bond. The ring formed is preferably a 5-membered ring or a 6-membered ring. As the 5-membered ring, a nitrogen-containing 5-membered ring is preferred. Examples of the compound constituting the ring include pyrrole, imidazole, pyrazole, oxazole, indole, benzimidazole, piperidine, and imidazolidine. , pyrazolidine, porphyrin, carbazole or derivatives thereof. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. Further, when an aryl group, a heterocyclic group or the like is contained, they may be a monocyclic ring or a condensed ring, and may be substituted or unsubstituted in the same manner.

R ^N is a hydrogen atom or a substituent. The alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 or more preferably 1 to 3) or an alkenyl group (having 2 to 24 carbon atoms) is preferred. Preferably, 2 to 12 are more preferred, 2 to 6 are further preferred, 2 to 3 are particularly preferred, and alkynyl groups are preferred (carbon number 2 to 24 is preferred, 2 to 12 is more preferred, and 2 to 6 is Further preferably, 2 to 3 are particularly preferred), an aralkyl group (preferably having 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, and 7 to 10 is particularly preferred) and an aryl group (carbon number 6 to 22). Preferably, 6 to 14 is more preferred, and 6 to 10 is particularly preferred.

R ^P is a hydrogen atom, a hydroxyl group or a substituent. The alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 or more preferably 1 to 3) or an alkenyl group (having 2 to 24 carbon atoms) is preferred. Preferably, 2 to 12 are more preferred, 2 to 6 are further preferred, 2 to 3 are particularly preferred, and alkynyl groups are preferred (carbon number 2 to 24 is preferred, 2 to 12 is more preferred, and 2 to 6 is Further preferably, 2 to 3 are particularly preferred), an aralkyl group (preferably having 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, and 7 to 10 is particularly preferred) and an aryl group (carbon number 6 to 22). Preferably, 6 to 14 is more preferable, 6 to 10 is particularly preferred, and an alkoxy group (having preferably 1 to 24 carbon atoms, more preferably 1 to 12, still more preferably 1 to 6; 3 is particularly preferred), alkenyloxy group (2 to 24 carbon atoms is preferred, 2 to 12 is more preferred, 2 to 6 is further preferred, 2 to 3 is particularly preferred), alkynyloxy group (carbon atom) The number is preferably from 2 to 24, more preferably from 2 to 12, further preferably from 2 to 6, more preferably from 2 to 3, and an aralkoxy group (from 7 to 22, preferably from 7 to 14). More preferably, 7 to 10 is particularly preferred, and an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 or more preferably 6 to 10) is preferred.

The number of atoms constituting the linking group L is preferably from 1 to 36, more preferably from 1 to 24, further preferably from 1 to 12, particularly preferably from 1 to 6. The number of linking atoms of the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms refers to the number of atoms that are connected to a path between predetermined structural portions and participate in the connection. For example, in the case of -CH ₂ -C(=O)-O-, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.

Specifically, the combination of the linking groups is exemplified below. Oxycarbonyl (-OCO-), carbonate (-OCOO-), decylamino (-CONH-), urethane (-NHCOO-), ureido (-NHCONH-), (poly)alkyleneoxy (-(Lr-O)x-), carbonyl (poly)oxyalkylene (-CO-(O-Lr)x-, carbonyl (poly)alkyleneoxy (-CO-(Lr-O)x) -), carbonyloxy (poly)alkyleneoxy (-COO-(Lr-O)x-), (poly)alkyleneimino (-(Lr-NR ^N )x), alkylene (poly Iminoalkylene (-Lr-(NR ^N -Lr)x-), carbonyl (poly)iminoalkylene (-CO-(NR ^N -Lr)x-), carbonyl (poly)alkylene Imino (-CO-(Lr-NR ^N )x-), (poly)ester (-(CO-O-Lr)x-, -(O-CO-Lr)x-, -(O-Lr- CO) x -, - (Lr -CO-O) x -, - (Lr-O-CO) x -), ( poly) acyl amino group ^{(- (CO-NR N -Lr} ) x -, - (NR N -CO-Lr)x-, -(NR ^N -Lr-CO)x-, -(Lr-CO-NR ^N )x-, -(Lr-NR ^N -CO)x-), etc. x is 1 or more The integer is preferably from 1 to 500, more preferably from 1 to 100.

Lr is preferably an alkylene group, an alkenylene group or an alkynylene group. The number of carbon atoms of Lr is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3. The plural Lr and R ^N , R ^P , x, etc. need not be the same. The orientation of the linking group is not limited to the above description, and it can be understood that the orientation of the predetermined chemical formula is appropriately combined.

<Formation of transparent cured product>

A method of forming a transparent cured product (film) using the decane resin composition of the present invention will be described by way of example. When the rhodium oxide resin composition is used as a coating liquid, it can be applied by a micro gravure coating method, a spin coating method, a dip coating method, a Curtain Flow Coating method, a roll coating method, a spray coating method or a slit coating method. A known method such as cloth method is applied to the base substrate. Thereafter, prebaking can be performed by a heating means such as a hot plate or an oven to form a film. Prebaking is preferably carried out at 50 to 150 ° C for 30 seconds to 30 minutes. The film thickness after prebaking is preferably 0.1 to 15 μm.

After the prebaking, for example, an exposure machine such as a stepper, a mirror projection machine (MPA) or a parallel photolithography machine (hereinafter, PLA) is used to irradiate 10 to 4000 J/m with or without a desired mask. Light of about ² (wavelength of 365 nm exposure). The exposure light source (active radiation) is not limited, and ultraviolet rays such as i-ray (wavelength 365 nm), g-ray (wavelength 436 nm), or h-ray (wavelength 405 nm), KrF (wavelength 248 nm) laser or ArF (wavelength 193 nm) laser can be used. Wait. Thereafter, the film may be subjected to post-exposure baking by heating at 150 to 450 ° C for 1 hour using a heating means such as a hot plate or an oven. In the present invention, it is preferred to use i-rays.

After the patterning exposure, the non-exposed portion is dissolved by development, whereby a negative pattern can be obtained. As the developing method, a method of immersing in a developing solution for 5 seconds to 10 minutes by a method such as spraying, dipping or stirring is preferred. The developer will be exemplified as the developer. After development, it is preferred to rinse the film with water. Then, drying and drying can be carried out at 50 to 150 °C. Thereafter, the film is thermally cured at 120 to 280 ° C for about 1 hour by a heating means such as a hot plate or an oven to obtain a cured product (film).

Transparent pixels or the like assembled to the solid-state image sensor can be formed on the substrate in this order.

The film thickness of the obtained cured product (film) is preferably 0.1 to 10 μm. The leakage current is 10 ^-6 A/cm ² or less, and the dielectric constant is 6.0 or more.

The cured film of the decane resin composition of the present invention has a refractive index of preferably 1.5 or more, more preferably 1.6 or more, further preferably 1.7 or more, and particularly preferably 1.8 or more. There is no special upper limit, but it is actually 2.0 or less. Regarding the refractive index, unless otherwise specified, it is based on the conditions measured in the examples described later.

The cured film of the siloxane oxide resin composition of the present invention preferably has high transparency. The transmittance of visible light is preferably 80% or more, more preferably 88% or more, and particularly preferably 90% or more. There is no special upper limit, but it is actually 99% or less. The transmittance of visible light is used as a condition based on the measurement in the examples described later unless otherwise specified.

The cured film obtained by hardening the siloxane oxide resin composition of the present invention can be suitably used as a microlens or a transparent pixel of a solid-state image sensor.

<Method of Forming Microlens Array>

An example of a step of forming a microlens array will be described as an aspect of a method of forming a microlens. If necessary, the surface of the element having irregularities is filled by a spin coating method of a transparent resin to planarize it. The lens material is uniformly coated on the flattened surface. The resist is uniformly applied on the lens material. Ultraviolet irradiation was performed using a stepping machine with a cross wire (Reticle) as a mask to expose the space between the lenses. The photosensitive portion is decomposed and removed with a developer to form a pattern. By heating, a hemispherical pattern is obtained. At this time, the resist melts and becomes a liquid phase, and after changing to a hemispherical state, it changes to a solid phase. Thereafter, the layer of lens material is etched by dry etching. Thereby, a lens array in which hemispherical lenses are arranged can be formed.

As another embodiment of the step of forming the lens array, a method of patterning the lens material by exposure using the above-described resist is omitted. In this embodiment, the patterned lens material is directly melted to obtain a hemispherical lens.

<Solid image sensor>

A solid-state image sensor according to a preferred embodiment of the present invention has a transparent pixel and/or a microlens composed of a cured product of the siloxane oxide resin composition of the present invention. A lens unit is provided on the semiconductor light receiving unit, and is assembled in such a manner that the lens array member is adjacent to the color filter. The light-receiving element receives light transmitted through the transparent resin film, the lens, and the color filter in order, and functions as an image sensor. Specifically, the transparent resin film functions as an antireflection film, and the condensing efficiency of the lens is improved, and the light that is efficiently collected by the lens is detected by the light receiving element via the color filter. These transitions play a role in detecting the entire component of the light corresponding to each RGB. Therefore, even when the light-receiving element and the lens are arranged at a high density, an extremely sharp image can be obtained. As the transparent pixel involved in the above-described lens and RGB pixel arrangement, the cured product of the siloxane oxide resin composition of the present invention can be suitably used.

An example of a solid-state imaging device to which a lens array is applied is described in Japanese Laid-Open Patent Publication No. 2007-119744. Specifically, a transfer electrode is provided between the CCD region or the photoelectric conversion portion formed on the surface of the semiconductor substrate, and a light shielding film is formed thereon via the interlayer film. An interlayer insulating film based on BPSG (Boro-Phospho-Silicate Glass), a passivation film, and a transparent planarizing film having a low refractive index based on an acrylic resin or the like are laminated on the light-shielding film, and RGB is formed thereon. Color filter. Further, a plurality of microlenses are formed by arranging the protective film so as to be positioned above the photoelectric conversion portion, that is, the photoelectric conversion portion.

[Examples]

The invention is further illustrated by the following examples, but the invention is not to be construed as limited. In addition, in the present embodiment, "parts" and "%" are quality references unless otherwise specified.

<Synthesis Example of Cerium Oxide Resin A-1 Containing Metal Oxide Fine Particles>

<Preparation of water-dispersed sol (AA-1) of nuclear particles>

7.6 kg of an aqueous titanium tetrachloride solution containing 7.8 mass% of titanium tetrachloride in terms of TiO ₂ and 3.0 kg of ammonia water containing 15% by mass of ammonia were mixed to prepare a white slurry liquid having a pH of 9.5. Next, the white slurry was filtered, and then washed with ion-exchanged water to obtain 6.2 kg of an aqueous titanic acid filter cake having a solid content of 10% by mass.

Next, 7.1 kg of hydrogen peroxide water containing 35% by mass of hydrogen peroxide and 20.0 kg of ion-exchanged water were added to the cake, and then stirred and heated at a temperature of 80 ° C for 1 hour, and then 28.9 kg of ion-exchanged water was added. Thus, 62.2 kg of an aqueous solution of titania acid containing 1% by mass of perovskinic acid based on TiO ₂ conversion was obtained. The aqueous solution of titania acid was transparent yellowish brown and had a pH of 8.5.

Then, 3.0 kg of a cation exchange resin was mixed with 62.2 kg of the above aqueous solution of titania, and 7.8 kg of an aqueous potassium stannate solution containing 1% by mass of potassium stannate in terms of SnO ₂ was slowly added thereto with stirring. Next, after separating the cation exchange resin into which potassium ions or the like were introduced, the mixed aqueous solution was heated in an autoclave at a temperature of 165 ° C for 18 hours.

Then, the obtained mixed aqueous solution was cooled to room temperature, and then concentrated by an ultrafiltration membrane apparatus (Asahi Kasei Corporation., ACV-3010) to obtain a water-dispersed sol of core particles having a solid content of 10% by mass ( AA-1) 7.0kg.

The water-dispersed sol (AA-1) containing the metal oxide fine particles thus obtained was a transparent milky white color. In addition, when the content of the metal component contained in the metal oxide fine particles is measured, TiO ₂ is 87.5 mass%, SnO ₂ is 10.6 mass%, and K ₂ O is 1.8 mass% in terms of oxides of each metal component. .

<Preparation of water-dispersed sol (AB-1) of surface-treated metal oxide fine particles>

7.0 kg of the water-dispersed sol (AA-1) of the core fine particles obtained above, and a pH of 7.0 adjusted with potassium hydroxide aqueous solution while slowly adding a 3.6% strength aqueous solution of zirconium octachloride octahydrate in terms of ZrO ₂ mass conversion 1.5 kg was stirred and mixed at 40 ° C for 1 hour to obtain an aqueous dispersion of metal oxide fine particles surface-treated with zirconium. In this case, the amount of zirconium is 5.0 mol% based on the oxide equivalent of the metal element contained in the core fine particles.

Next, 8.5 kg of an aqueous dispersion of metal oxide fine particles surface-treated with zirconium was placed in a spray drying apparatus (NIRO ATOMIZER manufactured by NIRO Co., Ltd.) to carry out spray drying. Thereby, 0.9 kg of a dry powder composed of surface-treated metal oxide fine particles having an average particle diameter of about 2 μm was obtained.

Next, 0.9 kg of the dry powder of the surface-treated metal oxide fine particles obtained above was baked in an air atmosphere at a temperature of 500 ° C for 2 hours to obtain a calcined powder of the surface-treated metal oxide fine particles 0.8 Kg. 0.2 kg of the calcined powder of the surface-treated metal oxide fine particles obtained above was dispersed in 0.2 kg of pure water, and 0.1 kg of a tartaric acid aqueous solution having a concentration of 28.6% and 0.06 kg of a KOH aqueous solution having a concentration of 50% by mass were added thereto and sufficiently filled. Stir. Next, alumina beads having a particle diameter of 0.1 mm (high-purity alumina beads manufactured by TAIMEI Chemicals Co., Ltd.) were added, and this was supplied to a wet pulverizer (intermittent table sand manufactured by KANSAI PAINT CO., LTD.). In the mill, the calcined powder of the surface-treated metal oxide fine particles (titanium dioxide-based composite oxide fine particles) was pulverized and dispersed for 180 minutes. After that, the alumina beads were separated and removed by a stainless steel filter having a pore size of 44 μm, and then 1.4 kg of pure water was further added and stirred to obtain an aqueous dispersion of surface-treated metal oxide fine particles having a solid content of 11% by mass of 1.7 kg. .

Next, after the aqueous dispersion was washed with ion-exchanged water using an ultrafiltration membrane, 0.09 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to carry out deionization treatment. Then, it was supplied to a centrifugal separator (CR-21G manufactured by Hitachi Koki Co., Ltd.), and treated at a rate of 12,000 rpm for 1 hour, and then ion-exchanged water was added to prepare a surface-treated metal oxide having a solid concentration of 10% by mass. The water-dispersed sol (AB-1) of the microparticles was 1.9 kg.

When the content of the metal component contained in the surface-treated metal oxide fine particles is measured, TiO ₂ is 82.6 mass%, SnO ₂ is 10.3 mass%, and ZrO ₂ is 4.9% by mass, based on the oxide of each metal component. K ₂ O was 2.2% by mass. The Ti/Zr ratio (element composition) at this time was 26.00. The Ti/Sn ratio (element composition) was 10/1. The metal oxide fine particles obtained had an average particle diameter of about 15 nm.

<Preparation of surface-treated metal oxide fine particles of methanol-dispersed sol (AC-1)>

After adding 9.6 g of a cation exchange resin to 0.6 kg of the aqueous dispersion (AB-1) of the surface-treated metal oxide fine particles prepared above, the resin was separated to prepare deionized surface-treated metal oxide fine particles. Aqueous dispersion. Next, the aqueous dispersion of the deionized surface-treated metal oxide fine particles was replaced with water by a superfiltration membrane apparatus (filter membrane manufactured by Asahi Kasei Corporation, SIP-1013), and concentrated. 0.3 kg of a methanol-dispersed sol (AC-1) of surface-treated metal oxide fine particles was obtained. As a result, the solid content concentration contained in the obtained methanol dispersion liquid was 30% by mass, and the moisture content was about 0.3% by mass.

<Preparation of oxirane-based resin composition (A-1)>

10.9 g (0.08 mol) of methyltrimethoxydecane, 63.5 g (0.32 mol) of phenyltrimethoxydecane, and methanol dispersion sol (AC-1) (solid content concentration: 30% by mass, methanol: 70% by mass) 440.0 g DADA 370.0g was placed in a reaction vessel, and 32.0 g of water and 1.0 g of phosphoric acid were added to the solution while stirring at a reaction temperature of not more than 40 ° C. After dripping, the distillation apparatus was attached to a flask, and the obtained was obtained. The solution was heated and stirred at a bath temperature of 105 ° C for 2.5 hours, and the methanol formed by the hydrolysis was distilled off and reacted. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C for 2 hours, and then cooled to room temperature. The decane-based resin composition (A-1) (solid content: 35.8 mass%, metal oxide fine particle concentration in the composition solid content: 64 mass%) was obtained.

(Preparation of hydrolysis condensate of decane compound (AX-1), etc.)

Regarding the preparation of the above siloxane-based resin composition (A-1), carboxymethoxymethyldimethoxydecane was used instead of phenyltrimethoxydecane, and methanol-dispersed sol (AC-1) and DAA were not used. A hydrolysis condensate (AX-1) of a decane compound was obtained in the same manner except for the other AX-numbered resins, and in the same manner, instead of phenyltrimethoxydecane, each alkoxy group was used. The decane compound was prepared by the decane compound, and the acid value of the hydrolysis condensate (AX-1) of the decane compound was 3.2.

(Example 1, Comparative Example 1)

The curable resin composition of the examples and the comparative examples was obtained by mixing the components or the solvent substitution so as to have the composition of the following Table 1 by using the azide-based resin composition (A-1) obtained in the above ( Samples 101 to 112, 201 to 207, c01, and c02). The evaluations shown below were carried out using the curable resin compositions of the obtained examples and the comparative examples.

Metal oxide particles 70 parts by mass of a decyl alkane resin (I) 15 parts by mass of a decyl alkane resin (II) 25 parts by mass of PEGMEA 135 parts by mass of DAA 266 parts by mass (*) KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 2 parts by mass (*) Photopolymerization initiator 1 part by mass (*) Ultraviolet absorber of the structure described in Table 1 2 parts by mass of polymerization inhibitor (p-methoxyphenol) 0.01 part by mass (*) Alkali-soluble resin 15 parts by mass

(*) Component PGIEA omitted in Table 1: propylene glycol monomethyl ether acetate DAA: diacetone alcohol KAYARAD DPHA Compound with unsaturated double bond OXE02: manufactured by BASF SE IRGACURE OXE02 (trade name) Alkali-soluble resin with the following BX Numbered compound

The cured films of the curable resin compositions of the examples and the comparative examples were measured for transmittance as follows.

The curable resin composition was applied to a high-refractive-index glass (SFLD-6 [trade name] manufactured by SUMITA OPTICAL GLASS, Inc.) by a spin coater (H-360S [trade name] MIKASA CO., LTD.). Coating. The high refractive index glass coated with the curable resin composition was prebaked at 100 ° C for 2 minutes using a hot plate to obtain a coating film. Next, the coated film was exposed at 1000 mJ/cm ² by an ultrahigh pressure mercury lamp "USH-500BY" manufactured by USHIO INC. The coating film was heated at 200 ° C for 5 minutes on a hot plate under an air atmosphere to obtain a cured film having a film thickness of 0.5 μm. The light transmittance of each of the cured films of the examples and the comparative examples was measured by using "MCPD-3000" manufactured by Otsuka Electronics Co., Ltd., from 400 nm to 700 nm. The light transmittance of the cured film of the examples was the lowest transmittance of 400 to 700 nm, exceeding 90%.

Further, at this time, the refractive index at a wavelength of 633 nm at room temperature of 25 ° C was measured with an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.) using the same cured film sample. As a result, the cured films of the examples all had a refractive index of about 1.8, and a desired high refractive index was achieved.

<Light resistance [1-1]>

With respect to the cured film used for the transmittance measurement, a light resistance test of 5 million lx was performed using a light resistance tester (Xenon Weather Meter manufactured by Suga Test Instruments Co., Ltd.). After the light resistance test, the light resistance was evaluated by the transmittance measurement of the cured film. The lithographic performance was evaluated according to the following criteria. Five tests were carried out on each sample, and the average value of the three results of the removal of the maximum value and the minimum value was used.

"5": the amount of change in transmittance is ±5% or less "4": the amount of change in transmittance exceeds ±5% and ±8% or less "3": the amount of change in transmittance exceeds ±8% and ±10% or less "2": the amount of transmission of the transmittance exceeds ±10% and ±20% or less "1": the amount of transmission is more than ±20%

<Resolution test [1-2]>

The curable resin composition obtained in the above was applied to the undercoat layer by a spin coating method using Act8 [trade name] manufactured by Tokyo Electron Limited, in a thickness of 0.8 μm after coating. The hardened composition layer was obtained by heating on a hot plate at 8 ° C for 2 minutes on a hot plate of 8 inches.

Next, the obtained hardenable composition layer was exposed to a 1.1 μm square Bayer pattern via a mask using an i-ray stepper exposure apparatus FPA-3000i5+ [trade name] (manufactured by Canon Inc.). 50 to 1700 mJ/cm ² ).

Next, the developability of the curable composition layer after the exposure was evaluated using a developing device (Act8 [trade name] manufactured by Tokyo Electron Limited). As a developing solution, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and spray development was carried out at 23 ° C for 60 seconds. Thereafter, rinsing was performed by a rotary spray method using pure water to obtain a pattern. The strain of the obtained pattern was evaluated by scanning electron micromirror (SEM) (S-4800H [trade name], manufactured by Hitachi High-Technologies) (magnification: 20000 times). The lithographic performance was evaluated in accordance with the following criteria. Three samples were tested for each sample, and the results were combined to determine.

"5": The pattern is obvious and there is no residue. "4": The pattern has a slightly conical shape but no residue. "3": The pattern has a tapered shape but less residue. "2": The pattern has a tapered shape and has a large amount of residue. "1": Cannot be a pattern.

<residue gel defect number [1-3]>

The number of gel-like defects having a size of 0.4 μm or more was measured for the cured film used for the transmittance measurement by the defect inspection device ComPlus (manufactured by Applied Materials, Inc.). The results are shown in the following table. Observe the field of view and select any area of 10 cm square. Five tests were performed on each sample, and the average of three results of removing the maximum value and the minimum value was used.

"5" found no defect "4" number of defects is one or more, less than two "3" defects are two or more, and less than three "2" defects are three or more and less than four "1" "The number of defects is 4 or more and less than 5

[Table 1] Coordination: mass part No. from c to the comparative example Si resin: decane resin UV absorber: UV absorber

[Chemical Formula 8]

[Chemical Formula 9]

UV absorber

TINUVIN PS: 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole

[Chemical Formula 10]

——————————————————————————————UV absorber system ε@365nm ε@400nm —————————— ———————————————————— PS benzotriazole 35821 1021 U-1 avobenzone 41752 612 U-2 diene 54636 487 U-3 diene 49091 3432 U-4 benzodisulfide 28132 1913 ———————————————————————————— PS: TINUVIN PS

From the above results, it is understood that the rhodium oxide resin composition of the present invention has good suppression of residue defects when used as a cured film by using a naphthene resin composition satisfying the condition (a) or (b). It also has excellent resolution and high performance in terms of light resistance. Further, it is understood that the effect is further remarkable by selecting and containing a suitable ultraviolet absorber.

(Example 2)

In the sample 101 of Table 1, the acidic group (A) introduced into the siloxane resin was changed to prepare a composition including each siloxane oxide resin. Further, these compositions were subjected to light resistance test, developability test, and residue. The number of gel defects was measured. As a result, it was confirmed that good results were obtained in any of the samples. However, when the pKa of the acidic group (A) was -3 to 4, particularly excellent developability and light resistance were exhibited. And the inhibition of the residue results.

(Example 3)

In the sample 101 of Table 1, when the water-dispersed sol (AB-1) was prepared, a predetermined metal salt was used instead of the zirconium oxychloride octachloride, and the metal was introduced into the metal fine particles to prepare a composition. The metals were Ta, W, Y, Ba, Hf, Nb, V, and Si, respectively, in place of Zr. The above-mentioned compositions were evaluated for the developability, light resistance, and suppression of the residue. In the sample, all showed good results.

(Example 4)

In the sample 101 of Table 1, a composition was prepared by using methyl ethyl ketone, diacetone alcohol, PGME, dipropylene glycol monomethyl ether, cyclohexanone, and cyclopentanone instead of the solvent (PEGMEA) of Table 1. These compositions were evaluated for the above-mentioned developability, light resistance, and suppression of residue. As a result, it was confirmed that good results were obtained in any of the samples.

(Example 5)

<Preparation of a methanol-dispersed sol (AC-2~AC-11) of surface-treated metal oxide fine particles with a ratio of TiO ₂ , ZrO ₂ and SnO ₂ changed>

When the methanol dispersion sol (AC-1) used in Example 1 was prepared, methanol was prepared so that the content ratio of TiO ₂ , ZrO ₂ and SnO ₂ was as shown in Table 2, and the amount of each sample was adjusted. The dispersion sol (AC-2 to AC-11) and the content ratio of the methanol dispersion sol (AC-1) are also included in Table 2.

[Table 2]

<Preparation of water-dispersed sol (E-1) of non-core-shell type particles>

7.60 kg of an aqueous solution of titanium tetrachloride containing 7.75 mass% of titanium tetrachloride in terms of TiO ₂ and 2.91 kg of aqueous ammonia containing 15% by mass of ammonia were mixed. While mixing these, 7.6 kg of a 1.23% strength aqueous solution of zirconium octahydrate hydrate in a mass ratio of ZrO _{2 was} dropped over 24 hours to prepare a white slurry liquid of pH 8.8. Then, the white slurry liquid was diluted to 5 times with ion-exchanged water, filtered, and further washed with ion-exchange water to obtain 5.2 kg of an aqueous titanium zirconate filter cake having a solid content of 10% by mass.

Next, 7.1 kg of hydrogen peroxide water containing 35% by mass of hydrogen peroxide and 20.0 kg of ion-exchanged water were added to the cake, and the mixture was stirred and heated at a temperature of 80 ° C for 1 hour to further add ion-exchanged water of 28.90 kg. Thus, 61.39 kg of a titanium peroxide zirconic acid aqueous solution containing 1% by mass of titanium peroxide zirconic acid in terms of TiO ₂ was obtained. The titanium peroxide zirconic acid aqueous solution was transparent yellowish brown and had a pH of 8.9.

Next, the mixed cation 60.78kg above titanium peroxide aqueous zirconate exchange resin (Mitsubishi Chemical Corporation manufactured) 4.00 kg, was slowly added potassium containing the terms of SnO ₂ tin basis 1% by mass of stannic acid thereto with stirring The potassium aqueous solution was 8.01 kg. Next, after separating the cation exchange resin into which potassium ions or the like were introduced, the mixed aqueous solution was heated in an autoclave at a temperature of 168 ° C for 20 hours.

Then, the obtained mixed aqueous solution was cooled to room temperature, and then concentrated by an ultrafiltration membrane apparatus to obtain 6.89 kg of an aqueous dispersion of fine particles having a solid content of 10% by mass.

The water-dispersed sol (E-1) containing the metal oxide fine particles thus obtained was a transparent milky white color. When the content of the metal component contained in the metal oxide fine particles is measured, TiO ₂ is 90.0% by mass, SnO ₂ is 4.2% by mass, K ₂ O is 0.5% by mass, and ZrO is calculated based on the oxide of each metal component. ₂ is 5.3% by mass.

<Preparation of Methanol Dispersion Sol (EM-1) of Non-core-Shell Metal Oxide Particles>

7.51 kg of the above water-dispersible sol (E-1) was spray-dried by a spray dryer. Thereby, 0.90 kg of a dry powder composed of metal oxide fine particles having an average particle diameter of about 2 μm was obtained.

Then, 0.90 kg of the dry powder was calcined in an air atmosphere at a temperature of 500 ° C for 2 hours to obtain 0.90 kg of a calcined powder of metal oxide fine particles. 0.20 kg of the calcined powder was dispersed in 0.18 kg of pure water, and 0.13 kg of a tartaric acid aqueous solution having a concentration of 28.6% and 0.06 kg of a KOH aqueous solution having a concentration of 50% by mass were added thereto, and the mixture was stirred sufficiently.

Next, alumina beads having a particle diameter of 0.1 mm (high-purity alumina beads manufactured by TAIMEI Chemicals Co., Ltd.) were added, and this was supplied to a wet pulverizer (intermittent table sand manufactured by KANSAI PAINT CO., LTD.). The mill was subjected to pulverization and dispersion treatment of the calcined powder for 180 minutes. After that, the alumina beads were separated and removed by a stainless steel filter having a pore size of 44 μm, and then 1.39 kg of pure water was further added thereto and stirred to obtain 1.70 kg of an aqueous dispersion of metal oxide fine particles having a solid content of 11.0% by mass.

Next, after washing with ion-exchanged water using an ultrafiltration membrane, 0.09 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization treatment, and then supplied to a centrifuge (CR manufactured by Hitachi Koki Co., Ltd.). -21G), and the treatment was carried out at a rate of 11,000 rpm for 1 hour, and ion-exchanged water was added to prepare 1.86 kg of a water-dispersed sol (EZ-1) of metal oxide fine particles having a solid concentration of 10% by mass.

Further, when the content of the metal component contained in the fine metal oxide particles in the measurement, in terms of oxides of each metal component basis, TiO ₂ was 88.9 mass%, SnO ₂ was 5.3 mass%, ZrO ₂ 5.3% by mass, and K ₂ O was 0.5% by mass (TiO ₂ was 79.87 g/mol, ZrO ₂ was 123.2 g/mol, and Ti/Zr (Morby ratio) in the above-mentioned compound was 26).

Next, after cooling, an ultrafiltration membrane device (filter membrane manufactured by Asahi Kasei Corporation., SIP-1013) was used, and a dispersion medium of the water-dispersed sol (EZ-1) was replaced with water to methanol to obtain methanol of metal oxide fine particles. The dispersed sol (EM-1) was 0.32 kg. The solid content concentration contained in the obtained methanol dispersion sol (EM-1) was about 30% by mass, and the moisture content was 0.28% by mass.

<Changing the production ratio of TiO _2, ZrO ₂ and SnO _2, and methanol-dispersed sol (EM-2 ~ 3) of>

In the preparation of the water-dispersible sol (E-1), a methanol-dispersed sol (EM-2~3) was prepared by adjusting the amount of each sample by adjusting the Ti/Zr ratio and the Ti/Sn ratio to the values shown in Table 3. The Ti/Zr ratio and the Ti/Sn ratio of the methanol-dispersed sol (AC-1) are also included in Table 3.

[table 3]

<Preparation of Methanol Dispersion Sol (EM-4 to 7) with Changed Average Particle Size>

In the preparation of the water-dispersible sol (E-1) applied to the production of the methanol-dispersed sol (EM-2), the heat treatment temperature and the treatment time of the metal oxide fine particles are adjusted, in addition to the methanol-dispersed sol (EM- 2) Preparation of the dispersion EM-4~7 of different average particle diameters were prepared in the same manner. The number average particle diameter (Mn) of the particles contained in each dispersion (sol) is shown in Table 3. In addition, the measurement method is as described above.

<Preparation of a methanol-dispersed sol (CSTM-1) of core-shell type inorganic oxide fine particles>

Preparation of citric acid

After 0.31 kg of a commercially available water glass (manufactured by AGC Si-Tech Co., Ltd.) was diluted with pure water, the alkali was removed by a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) to obtain 2.0 in terms of SiO ₂ conversion. The weight % of citric acid aqueous solution of citric acid was 3.00 kg. Further, the pH of the aqueous citric acid solution was 2.3.

12.3 kg of pure water was added to 1.80 kg of the methanol dispersion sol (EM-1) and stirred, and after heating to a temperature of 90 ° C, 2.39 kg of the above aqueous solution of citric acid was slowly added thereto. After the end of the addition, the mixture was aged under stirring for 10 hours while maintaining the temperature at 90 °C. At this time, the amount of the composite oxide coated with the metal oxide fine particles was 12 parts by weight based on 100 parts by weight of the metal oxide fine particles.

Next, this mixed liquid was placed in an autoclave (manufactured by Trirtsu Techno), and heat treatment was performed at a temperature of 165 ° C for 18 hours. Then, the mixed solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane (manufactured by Asahi Kasei Corporation., SIP-1013) to obtain a water-dispersed sol having a solid content of 10.0% by weight. Thereby, a water-dispersed sol (CST-1) of core-shell type metal oxide fine particles obtained by coating the surface of the surface-treated metal oxide fine particles with an oxide of cerium element was obtained.

When the content of the metal component contained in the core-shell type metal oxide fine particles obtained is measured, TiO ₂ is 86.3 mass%, SnO ₂ is 5.1 mass%, and ZrO ₂ is 5.1 based on the oxide of each metal component. The mass% and K ₂ O were 0.5% by mass (TiO ₂ was 79.87 g/mol, ZrO ₂ was 123.2 g/mol, and Ti/Zr (Morby ratio) in the above-mentioned compounding was 26).

Then, after cooling, the dispersion medium of the water-dispersed sol (CST-1) was replaced with water to methanol by an ultrafiltration membrane device (filter membrane manufactured by Asahi Kasei Corporation., SIP-1013) to obtain metal oxide fine particles. Methanol dispersion sol (CSTM-1). As a result, the solid content concentration contained in the obtained methanol dispersion sol (CSTM-1) was about 30% by mass, and the moisture content was 0.28% by mass.

<Preparation of a methanol-dispersed sol (CSTM-2~3) of core-shell type inorganic oxide fine particles with a ratio of TiO ₂ , ZrO ₂ and SnO ₂ changed>

In the preparation of the methanol dispersion sol (CSTM-1), the Ti/Zr ratio and the Ti/Sn ratio were used as the enthalpy shown in Table 3, and the amount of each sample was adjusted to prepare a methanol dispersion sol (CSTM-2~3). ).

<Preparation of oxirane resin composition (A-1-2~A-1-11, A-1-EM-1~A-1-EM-7, A-1-CSTM-1~3)

In the preparation of the decane-based resin composition (A-1), the methanol-dispersed sol (A-1) was changed to the methanol-dispersed sol of Table 4, and in addition, a decane-based resin was prepared in the same manner. Composition (A-1-2~A-1-11, A-1-EM-1~A-1-EM-7, A-1-CSTM-1~3).

[Table 4]

In each of the above samples, a curable resin composition having the composition shown in Table 5 was obtained in the same manner as in Example 1. The same items as those in Table 1 were observed for the curable resin compositions (light resistance [1-1] ], the resolution test [1-2] and the number of residue gel defects [1-3]). In addition, the light resistance (severe light resistance) under more severe conditions was evaluated. In the above-mentioned conditions of the light resistance test [1-1], the temperature around the subject (in-device temperature) was set to 63 ° C, and the humidity was set to 90% RH. The irradiation time of light was 50 hours. In addition, the evaluation criteria were based on the light resistance test. The evaluation results are summarized in Table 5.

[table 5]

The results in Table 5 show good resolution, light resistance, and transparency. Therefore, as long as the Ti/Zr system is 1 to 40, the shape is core-shell type (No. 301 to 310, 501 to 503). Non-core shell types (No. 401 ~ 407) have shown good results.

Preparation of a decane-based resin composition (A-2)

In the preparation of the decane-based resin composition (A-1), 1-naphthyltrimethoxydecane was used instead of phenyltrimethoxydecane, and in addition, oxiranes were prepared in the same manner and in portions. Resin composition (A-2).

Preparation of a decane-based resin composition (A-3)

In the preparation of the decane-based resin composition (A-1), 9-phenanthryltrimethoxydecane was used instead of phenyltrimethoxydecane, and in addition, oxirane was prepared in the same manner and in the same amount. Resin composition (A-3).

Preparation of a decane-based resin composition (A-4)

In the preparation of the decane-based resin composition (A-1), 1,4-bis(trimethoxyformamido)naphthyl is used instead of phenyltrimethoxydecane, except in the same manner. The oxirane-based resin composition (A-4) was prepared in portions.

Preparation of a decane-based resin composition (A-5)

In the preparation of the decane-based resin composition (A-1), 1-mercaptotrimethoxydecane was used instead of phenyltrimethoxydecane, and in addition, oxiranes were prepared in the same manner and in portions. Resin composition (A-5).

Further, an experiment (No. 701 to 703) in which a low molecular organic acid (D-1) shown below was added was carried out. Further, the low molecular organic acid (D-1) was a compound having a carboxylic acid, and the acid value was 340 mg KOH / g. Regarding the amount of addition, the total mass measurement of "Si resin (I) + Si resin (II) + low molecular organic acid" is set to be the total mass measurement of "Si resin (I) + Si resin (II)" of Example 1. The same, and in terms of mass ratio, "Si resin (I) + Si resin (II)" / "Low molecular organic acid" = 9 / 1. The evaluation results are summarized in Table 6. In terms of calculation The composition contains 0.8 to 1% by mass of a low molecular organic acid (D-1), and the solid content contains 3 to 4% by mass of a low molecular organic acid (D-1).

[Chemical Formula 11]

[Table 6]

In the example 1, a composition in which the polymerizable compound DAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) was changed to tricyclodecane dimethanol diacrylate was prepared, and the composition was subjected to the same evaluation, and the results were similarly shown. Good performance.

no

no

no

Claims (21)

A siloxane oxide resin composition comprising metal-containing particles, a decane resin, and a solvent, wherein the siloxane oxide resin has at least an acidic group (A). The oxirane resin composition according to claim 1, which further comprises an alkali-soluble resin. The oxirane resin composition according to the first or second aspect of the invention, wherein the acidic group (A) has a pKa of 5.5 or less. The oxirane resin composition according to the first or second aspect of the invention, wherein the acidic group (A) is at least one selected from the group consisting of a carboxyl group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group. The oxime resin composition according to the first or second aspect of the invention, wherein the oxime resin contains a hydrolyzed condensate prepared by a decane compound represented by the following formula (S): (R ^S1 _e Si(R ^S2 ) _f (OR ^S3 ) _g (S) R ^S1 is a group containing an acidic group (A), and R ^S2 and R ^S3 each independently represent a hydrogen atom or a hydrocarbon group, and e is an integer of 1 to 3 , f is an integer from 0 to 2, g is an integer from 1 to 3, and e+g+f is 4. A cerium oxide resin composition comprising metal-containing particles, a decyl alkane resin, an alkali-soluble resin, and a solvent, wherein the cured film has a refractive index of 1.5 or more, wherein the siloxane oxide has a decyl alcohol-based oxime Resin. The oxirane resin composition according to claim 1 or 6, further comprising at least one selected from the group consisting of a polymerization initiator and an ultraviolet absorber. The oxirane resin composition according to claim 7, wherein the ultraviolet absorbing agent is selected from the group consisting of a benzotriazole compound, a benzophenone compound, a triazine compound, a diene compound, and a benzodithiol. Compounds and avobenzone compounds. The oxirane resin composition according to Item 2 or Item 6, wherein the alkali-soluble resin is an acrylic resin. The oxirane resin composition according to the second or sixth aspect of the invention, wherein the alkali-soluble resin is a resin represented by the following formula (R1): [Chemical Formula 1] L ^X1 represents a single bond or a linking group, and R ^X1 and R ^Y1 are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group or a cyano group, R ^A is an acidic group (A), and R ^Y2 represents a substituent, nx, Ny is the mole rate. The oxirane resin composition according to the first or sixth aspect of the invention, wherein the resin having a rhodium oxide resin composition has a total acid value of 50 mgKOH/g or more. The oxirane resin composition according to the first or sixth aspect of the invention, wherein the content of the siloxane oxide resin is 1 part by mass or more and 80 parts by mass or less based on 100 parts by mass of the metal particle-containing particles. . The oxime resin composition according to the first or sixth aspect of the invention, wherein the content of the metal-containing particles is 40% by mass or more and 80% by mass in the solid content of the siloxane oxide resin composition. %the following. The oxirane resin composition according to the first or sixth aspect of the invention, which comprises a metal selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V and Si. The above element containing metal particles. The oxirane resin composition according to the first or sixth aspect of the invention, wherein the siloxane oxide resin is obtained by performing a hydrolysis condensation reaction in the presence of the metal-containing particles. The pyrithion resin composition according to the first or sixth aspect of the invention, wherein the cured film has a refractive index of 1.6 or more and 2.0 or less. A transparent cured product obtained by curing the siloxane oxide resin composition according to any one of the first to sixteenth aspects of the invention. A transparent pixel comprising the transparent cured product of claim 17 of the patent application. A microlens comprising the transparent cured product of claim 17 of the patent application. A solid-state imaging device comprising the transparent pixel described in claim 18 of the patent application. A solid-state imaging device comprising the microlens described in claim 19.