TW201307458A - Dispersion composition, curable composition, transparent film, microlens and solid-state image sensing device using the same, method for manufacturing transparent film, method for manufacturing microlens and method for manufacturing solid-state image sen - Google Patents

Abstract

A dispersion composition includes: colorless or transparent metal oxide particles (A) having a primary particle diameter of from 1 nm to 100 nm; a resin (B1) which has a repeating unit having a group X having a functional group with a pKa of 14 or less, and has an oligomer chain or polymer chain Y having the number of atoms of from 40 to 10, 000 in a side chain thereof, and which also contains a basic nitrogen atom; and a solvent (C).

Description

Dispersion composition, curable composition, transparent film, microlens, solid-state image sensing device using the same, method for producing transparent film, method for manufacturing microlens, and method for manufacturing solid-state image sensing device

The present invention relates to a dispersion composition, a curable composition using the same, a transparent film, a microlens and a solid-state image sensing device, a method for producing a transparent film, a method for producing a microlens, and a method for producing a solid-state image sensing device.

As microlenses or copper interconnects used in imaging optics, such as electronic photocopiers and solid-state image sensing devices, that use optical interconnects instead of color filters on a wafer, are required for forming transparent members. A composition having a high refractive index and capable of forming a micro-transparent film, a transparent interconnect, and the like.

In particular, with the miniaturization of solid-state image sensing devices, the microlenses used in solid-state image sensing devices need to be more miniaturized and require a high refractive index to achieve more efficient light focusing. For example, a photopolymerizable composition capable of forming a high refractive index pattern using titanium oxide particles coated with ceria is disclosed (see, for example, Japanese Patent Application Laid-Open No. 2009-179678). A composition for forming a solid-state image sensing device using a metal oxide having 20% or more of ruthenium atoms on a surface of a particle, and thereby obtaining a high refractive index and excellent pattern formation characteristics (see, for example, Japanese Patent Application Laid-Open) Description of Early Disclosure No. 2008-185683). In detail, recently, as the resolution becomes higher, the pixel size is correspondingly reduced, and thus it is necessary to collect light more efficiently. Therefore, a microlens having a higher refractive index is required. In order to create more devices in a manufacturing process, the size of the wafer used should be increased.

However, if the wafer size is increased, the film formed to obtain the microlens has the following problem: there may be a difference in performance in the plurality of solid-state image sensing device wafers obtained by wafer cutting, because the center of the wafer The difference in film thickness between the portion and the peripheral portion is increased.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dispersion composition having excellent dispersibility and dispersion stability and having high refractive index and light transmittance when formed into a curable composition. The curable composition can form a film having a small film thickness difference between the central portion and the peripheral portion even when the composition is coated on the large-sized wafer; and a hardenable composition using the foregoing dispersed composition; Transparent film; microlens and solid-state image sensing device; manufacturing method of transparent film; manufacturing method of microlens; and manufacturing method of solid-state image sensing device.

At the same time, although a resin for dispersing a black material which can form a light-shielding film for a solid-state image sensing device is known (the resin has a high molecular weight oligomer chain or polymer in its side chain) The chain also contains a nitrogen atom, see Japanese Patent Application Laid-Open No. 2010-6932, but there is no particular description of a dispersed composition having a high refractive index and light transmittance and capable of forming a film having a small film thickness difference. .

The specific way to solve the problem is as follows.

<1> A dispersion composition comprising: colorless or transparent metal oxide particles (A) having a primary particle diameter of from 1 nm to 100 nm; a resin (B1) having a repeating unit, the repeating unit containing a group Group X, the group X has a functional group having a pKa of 14 or less, and the side chain of the resin (B1) has an oligomer chain or a polymer chain Y having an atomic number of 40 to 10,000, and The resin also contains a basic nitrogen atom; and a solvent (C).

<2> The dispersion composition according to the above <1>, wherein the resin (B1) is a resin (B2) whose repeating unit contains a group X bonded to a functional group having a pKa of 14 or less A nitrogen atom, and the side chain of the resin (B2) has an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000.

The dispersion composition according to the above <1> or <2>, wherein the dispersion composition comprises: a colorless or transparent metal oxide particle (A) having a primary particle diameter of from 1 nm to 100 nm, a resin (B) having (i) at least one repeating unit containing a nitrogen atom, selected from the group consisting of a poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit and a polyvinylamine-based repeating unit, wherein the repeating unit contains a group X having a functional group having a pKa of 14 or less and the group X bond An oligomer chain or polymer chain Y which is bonded to the nitrogen atom, and (ii) has 40 to 10,000 atoms in its side chain, and a solvent (C).

The dispersion composition according to any one of <1> to <3> wherein the group X has a pKa of 14 or less, and the functional group is a carboxylic acid, a sulfonic acid or - COCH ₂ CO-.

<5> The dispersion composition according to the above <3>, wherein the resin (B) is a repeating unit represented by the following formula (I-1) and is represented by the formula (I-2) Resin representing the repeating unit:

In the above formula (I-1) and the formula (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group, and a each independently represents an integer of 1 to 5. , * represents a linking moiety between the repeating units, X represents a group having a functional group having a pKa of 14 or less, and Y represents an oligomer chain or a polymer chain having an atomic number of 40 to 10,000.

<6> The dispersion composition according to the above <3> or <4> wherein the resin (B) is a repeating unit represented by the following formula (II-1) and is represented by the formula (II-2) Resin representing the repeating unit:

In the above formula (II-1) and the formula (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and * represents the above. The linking moiety between the repeating units, X represents a group having a functional group having a pKa of 14 or less, and Y represents an oligomer chain or a polymer chain having an atomic number of 40 to 10,000.

The dispersion composition according to any one of <1> to <6> wherein the oligomer chain or polymer chain Y having an atomic number of 40 to 10,000 has the following formula (III-1) ) the structure of the representation:

In the above formula (III-1), Z is a polymer or oligomer having a polyester chain as a partial structure, and represents a shift from a polyester having a free carboxylic acid represented by the following general formula (IV) Residues other than carboxyl groups:

In the above formula (IV), Z is the same as Z in the above formula (III-1).

<8> A curable composition, comprising: the dispersion composition according to any one of <1> to <7> above, Wherein the dispersion composition further contains a polymerizable compound (D) and a polymerization initiator (E).

<9> The curable composition according to <8> above, further comprising: a binder polymer.

<10> The curable composition according to the above <8>, wherein the polymerization initiator (E) is a quinone polymerization initiator.

<11> The curable composition according to any one of <8> to <10> which is used for forming a microlens.

<12> A transparent film formed by using the curable composition according to any one of <8> to <11> above.

<13> A microlens formed by using a transparent film as described in <12> above.

<14> A solid-state image sensing device comprising: the microlens according to <13> above.

<15> A method for producing a transparent film, comprising: a process of applying a curable composition according to any one of the above <8> to <10> on a wafer, and heating the subsequent first heating of the composition And a subsequent second heating process for heating the composition at a temperature above the temperature of the first heating process.

<16> A method for producing a microlens, comprising: a process of post-baking a transparent film as described in <12> above to form the transparent film, and a process of dry etching the transparent film.

<17> A method of manufacturing a solid-state image sensing device, comprising: forming a red pixel, a blue pixel, and a green pixel on a substrate of a solid-state image sensing device having at least a photodiode, a light shielding film, and a device protective film The process of forming a resist pattern by performing a process of heating by performing a heating process according to any one of the above <8> to <10>, and performing the post-baking treatment to form the anti-resistance The etching pattern is formed into a process of a lens shape; and a process of performing dry etching.

In the dispersion composition of the present invention, as described in detail below, the metal oxide particles (A) interact with the nitrogen atom in the resin (B1) and the functional group of the group X having a pKa of 14 or less, and The resin (B1) has an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000, and thus, for example, an oligomer chain or a polymer chain Y can serve as a steric repellency group to exhibit excellent dispersibility, thereby The metal oxide particles are uniformly dispersed into high refractive index particles. Even when the dispersion composition is stored for a long period of time at room temperature and the like, the oligomer chain or the polymer chain Y can interact with the solvent, thereby suppressing precipitation of the metal oxide particles for a long period of time. Further, when a coating film is formed by dispersing a composition (more specifically, for example, a curable composition), the oligomer chain or polymer chain Y acts as a steric repellency group to prevent aggregation of metal oxide particles, thereby Even if the content of the metal oxide particles is increased, the dispersibility or dispersion stability is not easily attenuated as described above. That is, the dispersed composition of the present invention can be used for achieving excellent dispersibility and dispersion stability. And a film having a very high refractive index is obtained.

When the resin (B1) is used to constitute the dispersion composition and the dispersion composition is used to constitute the curable dispersion, the coating film obtained by the curable composition has excellent film thickness uniformity, and thus, even on a large-sized wafer When the composition is coated, a film having a small film thickness difference between the central portion and the peripheral portion of the wafer (for example, a film forming a microlens and the like) can be obtained. It is presumed that this is because, for example, in the coating film, the oligomer chain or the polymer chain Y of the resin (B1) of the present invention exhibits excellent interaction with each other.

According to the present invention, it is possible to provide a dispersion composition having excellent dispersibility and dispersion stability and having a high refractive index and light transmittance when formed into a curable composition, even when a composition is coated on a large-sized wafer. The curable composition can also form a film having a small film thickness difference between the central portion and the peripheral portion; and a curable composition using the same; a transparent film; a microlens solid-state image sensing device; and a transparent film manufacturing Method; method of manufacturing microlens; and method of manufacturing solid-state image sensing device.

The dispersed composition of the present invention will be described in detail below.

Meanwhile, when a group (atomic group) is recited in the present specification, any expression not described and substituted includes a group having a substituent (atomic group) and a group having no substituent (atomic group). For example, "alkyl" includes an unsubstituted alkyl group (unsubstituted alkyl group) and a substituted alkyl group (substituted alkyl group).

The following constituent elements may be described based on representative exemplary embodiments of the present invention, but the present invention is not limited to the exemplary embodiments. In this manual The range of values represented by the use of "to" indicates the range including the values described as the lower and upper limits before and after "to".

In the present specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) propylene group" means acryl fluorenyl and methacryl fluorenyl, and "methyl (acryloyl fluorenyl) ")" means propylene sulfhydryl and methacryl fluorenyl. In the present specification, "monomeric body" is the same as "monomer". In the present invention, the monomer is different from the oligomer and the polymer, and the monomer means a compound having a mass average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction.

In the present invention, "refractive index" means a refractive index for light having a wavelength of 500 nm unless otherwise specified.

<dispersed composition>

The dispersion composition of the present invention contains colorless or transparent metal oxide particles (A) having a primary particle diameter of from 1 nm to 100 nm; a resin (B1) having a repeating unit containing a functional group ( a group X having a pKa of 14 or less, and an oligomer chain or polymer having a number of atoms of 40 to 10,000 in the side chain of the resin (B1) (in a side chain of a resin or a repeating unit) Chain Y, and the resin also contains a basic nitrogen atom; and a solvent (C).

More preferably, the dispersion composition of the present invention contains colorless or transparent metal oxide particles (A) having a primary particle diameter of from 1 nm to 100 nm; and a resin (B) comprising (i) at least one of a repeating unit of a nitrogen atom, Selected from poly(lower alkyleneimine) repeating units, polyallylamine repeating units, polydiallylamine repeating units, meta-xylenediamine-epichlorohydrin polycondensate repeating units, and polyvinylamine a repeating unit wherein the repeating unit contains a group X having a functional group having a pKa of 14 or less, and the group X is bonded to a nitrogen atom, and (ii) the number of atoms in the side chain thereof is 40 to 10,000. Oligomer chain or polymer chain Y; and solvent (C).

Because of the configuration, it is possible to provide a dispersion composition having excellent dispersibility and dispersion stability and having a very high refractive index when formed into a hardening dispersion as described above, even on a large-sized wafer. In the composition, the curable dispersion can also form a film having a small film thickness difference between the central portion and the peripheral portion (a transparent film is representative).

<(A) Colorless or transparent metal oxide particles having a primary particle diameter of from 1 nm to 100 nm >

In the present invention, the colorless or transparent metal oxide particles (A) are colorless or transparent inorganic particles having a high refractive index, and examples thereof include titanium (Ti), zirconium (Zr), aluminum (Al), bismuth (Si). Oxide particles of zinc (Zn) or magnesium (Mg), preferably titanium dioxide (TiO ₂ ) particles, zirconium dioxide (ZrO ₂ ) particles or cerium oxide (SiO ₂ ) particles, and among them, titanium dioxide particles ( Hereinafter, in some cases, simply referred to as "titanium dioxide" is preferred.

In the present invention, the colorless or transparent titanium oxide particles may be represented by the chemical formula TiO ₂ and preferably have a purity of 70% or more, more preferably 80% or more, and even more preferably 85% or more. The content of lower order titanium oxide (n represents a value of 2 to 4), titanium oxynitride, and the like represented by the general formula Ti _n O _2n-1 is preferably 30% by mass or less, more preferably 30% by mass or less. It is 20% by mass or less and 20% by mass or even more preferably 15% by mass or less.

In the present invention, the metal oxide particles are not particularly limited as long as the particles have a primary particle diameter of from 1 nm to 100 nm, and may be appropriately selected, for example, from commercially available metal oxide particles.

The metal oxide particles have a primary particle diameter of from 1 nm to 100 nm, preferably from 1 nm to 80 nm, and particularly preferably from 1 nm to 50 nm. If the primary particle diameter of the metal oxide particles exceeds 100 nm, there are some cases where the refractive index and the transmittance may be lowered. When the diameter is less than 1 nm, there are some cases where the dispersibility may be lowered due to aggregation.

In the present invention, the average particle diameter can be used as an index of the primary particle diameter. In the present invention, the average particle diameter of the metal oxide particles refers to a rare form obtained by using a dynamic light scattering method to 80-fold dilution of a mixed solution or liquid dispersion containing metal oxide particles with propylene glycol monomethyl ether acetate. The value obtained by the solution performing the measurement.

This measurement was calculated by using a number average particle diameter obtained by performing measurement using MICROTRAC UPA-EX 150 (manufactured by NIKKISO Co., Ltd.).

In the present invention, the refractive index of the metal oxide particles is not particularly limited, but from the viewpoint of obtaining a high refractive index, it is preferably 1.75 to 2.70, and more preferably 1.90 to 2.70.

The specific surface area of the metal oxide particles is preferably from 10 square meters / gram to 400 square meters / gram, more preferably from 20 square meters / gram to 200 square meters / gram, and most preferably 30 square meters / Gram to 150 square meters / gram.

The shape of the metal oxide particles is not particularly limited. For example, the shape may be a rice-grain shape, a spherical shape, a cubic shape, a spindle shape, or an amorphous shape.

In the present invention, the metal oxide particles may be surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include a polyol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Among them, a decane coupling agent is preferred.

The surface treatment may be performed by a single surface treatment agent alone or in combination of two or more than two surface treatment agents.

The surface of the metal oxide particles is also preferably covered with an oxide such as alumina, yttria and zirconia. Thereby further improving the weather resistance.

As the metal oxide particles of the present invention, commercially available products can be preferably used.

Examples of commercially available products of titanium dioxide particles include TTO series (TTO-51 (A), TTO-51 (C) and the like), TTO-S and TTO-V series (TTO-S-1, TTO-S-2) , TTO-V-3 and the like) (manufactured by ISHIHARA SANGYO KAISHA, LTD.), MT series (MT-01, MT-05 and the like) (by TAYCA CORP.) )) and similar.

Examples of commercially available products of zirconium dioxide particles include UEP (manufactured by Daiichi Kigenso Kagaku Kogyo Ltd.), PCS (NIPPON DENKO CO., LTD.), JS-01, JS-03 and JS-04 (Japan Electric Works Co., Ltd. (NIPPON DENKO CO., LTD.)), UEP-100 (manufactured by Daiichi Kigenso Kagaku Kogyo Ltd.), and the like.

Examples of commercially available products of cerium oxide particles include OG502-31 (manufactured by Clariant Co.) and the like.

In the present invention, the metal oxide particles may be used singly or in combination of two or more thereof.

The content of the metal oxide particles in the dispersion composition (or the curable composition described below) of the present invention is preferably from 10% by mass to 90% by mass based on the total solid content of the dispersion composition, more preferably from the viewpoint of dispersion stability. It is 10% by mass to 50% by mass, even more preferably 12% by mass and 40% by mass and particularly preferably 15% by mass to 35% by mass (in the present specification, the mass ratio is equal to the weight ratio).

At the same time, particularly as a microlens having a high refractive index, the content is preferably from 50% by mass to 90% by mass, and more preferably from 52% by mass to 85% by mass, based on the total solid content of the dispersion composition.

<Resin (B1) having a repeating unit containing a group X having a functional group having a pKa of 14 or less, and the resin having an oligomer having an atomic number of 40 to 10,000 in a side chain thereof Chain or polymer chain Y, and the resin also contains a basic nitrogen atom >

Herein, the basic nitrogen atom is not particularly limited as long as the basic nitrogen atom exhibits basicity, but the resin (B1) preferably contains a structure having a nitrogen atom having a pKb of 14 or less, and more preferably has a structure. The structure in which pKb is a nitrogen atom of 10 or less.

In the present invention, the alkali strength pKb refers to pKb at a water temperature of 25 ° C, which is an index quantitatively indicating the strength of the base, and is the same as the basicity constant. The alkali strength pKb has the following relationship with the following acid strength pKa: pKb = 1 - pKa.

The group X having a functional group having a pKa of 14 or less is the same as the group X described below with respect to the resin (B).

The oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain of the resin (B1) and the oligomer chain or polymer having 40 to 10,000 atoms on the resin (B) described below The chain Y is the same.

Examples of the resin (B1) include a resin containing a repeating unit represented by the following formula: a repeating unit having a group X having a functional group having a pKa of 14 or less, and a repeating basic nitrogen atom represented by the following formula The unit and the repeating unit represented by the following formula having an oligomer chain of 40 to 10,000 or a polymer chain Y (corresponding from left to right in the structure of the following repeating unit).

In the above formula, x, y and z each represent a polymerized molar ratio of the repeating unit, and preferably x is from 5 to 50, y is from 5 to 60 and z is from 10 to 90. l represents the number of linkages of the polyester chain, which is an integer which can form an oligomer chain or a polymer chain having an atomic number of 40 to 10,000, and preferably 70 to 2,000.

The resin (B1) is preferably a resin (B2) having a repeating unit. The repeating unit contains a nitrogen atom bonded to a group X having a functional group having a pKa of 14 or less, and the resin (B2) has an oligomer chain having an atomic number of 40 to 10,000 in its side chain or Polymer chain Y.

The resin (B1) is particularly preferably a resin (B) (hereinafter referred to as "specific resin" as appropriate) having (i) at least one repeating unit containing a nitrogen atom selected from poly(low carbon alkylene imine) a repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a metaxylenediamine-epichlorohydrin polycondensate repeating unit, and a polyvinylamine repeating unit, wherein the repeating unit contains a pKa of 14 Or a group X having a functional group of less than 14 and the group X is bonded to a nitrogen atom, and (ii) an oligomer chain or polymer chain Y having 40 to 10,000 atoms in its side chain.

((i) at least one repeating unit containing a nitrogen atom selected from a poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, m-xylylenediamine- Epichlorohydrin polycondensate repeat unit and polyvinylamine repeat unit)

In the present invention, the specific resin has (i) at least one repeating unit containing a nitrogen atom, and is selected from a poly(lower alkyleneimine)-based repeating unit, a polyallylamine repeating unit, a polydiallylamine-based repeating unit, Meta-xylenediamine-epichlorohydrin polycondensate repeating unit and polyvinylamine repeating unit. Therefore, the adsorption force to the surface of the metal oxide particles (A) can be improved and the interaction between the metal oxide particles can also be lowered.

The poly(lower alkyleneimine) may be in the form of a chain or a network.

By repeating at least one repeating unit (i) containing a nitrogen atom (selected from a poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a poly The number average molecular weight of the main chain obtained by polymerization of a diallyl repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and a polyvinylamine repeating unit, that is, a side of the resin (B) The number average molecular weight of the portion other than the Y moiety of the chain or the polymer chain Y is preferably from 100 to 10,000, more preferably from 200 to 5,000, and most preferably from 300 to 2,000. The number average molecular weight of the main chain portion can be determined by the ratio of the end group of the main chain portion measured by nuclear magnetic resonance spectroscopy to the integral value of the hydrogen atom of the main chain portion, or by measuring the amino group-containing oligomer or polymerization as a raw material. Determination of the molecular weight of the substance.

The repeating unit (i) containing a nitrogen atom is particularly preferably a poly(lower alkyleneimine)-based repeating unit or a polyallylamine-based repeating unit. Meanwhile, in the present invention, the expression "low carbon" used in the poly(low carbon alkylene imine) means a carbon number of 1 to 5, and the low carbon alkylene imine means 1 to 5 An alkylimine of a carbon atom. When the structure is specified, the specific resin of the present invention preferably comprises a structure having a repeating unit represented by the formula (I-1) and a repeating unit represented by the formula (I-2) or having a formula (II- 1) The structure of the repeating unit represented by the formula (II-2).

(Repeating unit represented by the formula (I-1) and repeating unit represented by the formula (I-2))

The repeating unit represented by the formula (I-1) and the repeating unit represented by the formula (I-2) which are preferred constituent components of the specific resin of the present invention will be described in detail.

Formula (I-1) Formula (I-2)

In the general formula (I-1) and the general formula (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group. a each independently represents an integer from 1 to 5. * indicates the link portion between the repeating units.

X represents a group having a functional group having a pKa of 14 or less.

Y represents an oligomer chain or a polymer chain having an atomic number of 40 to 10,000.

The specific resin of the present invention preferably has a repeating unit represented by the formula (I-3) as a copolymerization component, in addition to the repeating unit represented by the formula (I-1) or the formula (I-2). When the resin is used as a dispersing agent for the metal oxide particles (A), the dispersion efficiency can be further improved by using these repeating units in combination.

In the formula (I-3), *, R ¹ , R ² and a are the same as those in the formula (I-1).

Y' represents an oligomer chain or a polymer chain having an anion group of 40 to 10,000 atoms.

By performing an addition polymerization reaction, an oligomer or a polymer having a group which forms a salt with an amine is reacted with a resin having a primary or secondary amine group in the main chain moiety to form a pass. A repeating unit represented by the formula (I-3). Here, as the anionic group, CO ₂ ^- or SO ₃ ^- is preferable, and CO ₂ ^- is preferred. The anionic group is preferably present at the end of the oligomer chain or polymer chain possessed by Y'.

In the general formula (I-1), the general formula (I-2) and the general formula (I-3), R ¹ and R ^{2 are} particularly preferably a hydrogen atom. A is preferably 2 from the viewpoint of raw material availability.

The specific resin of the present invention may contain a lower content containing a primary amine group or a tertiary amine group, in addition to the repeating unit represented by the general formula (I-1), the general formula (I-2) and the general formula (I-3). A carbon alkylene imine is used as a repeating unit. The lower alkylalkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms. The specific resin may or may not contain the low-carbon alkylene imine repeating unit, but when the specific resin contains a low-carbon alkylene imine repeating unit, it is contained in all repeating units contained in the specific resin. The amount of the low carbon alkylene imine repeating unit is preferably from 1 mol% to 60 mol%, and the amount thereof is preferably from 3 mol% to 40 mol%. At the same time, a group represented by X, Y or Y' may also be bonded to the nitrogen atom in the repeating unit of the low carbon alkylene imine. A resin having a repeating unit bonded to a group represented by X and a repeating unit bonded to Y in its main chain structure is also encompassed in the specific resin of the present invention.

The repeating unit represented by the general formula (I-1) is a repeating unit containing a nitrogen atom, and a group X having a functional group having a pKa of 14 or less is bonded to the nitrogen atom, and is storage stability and From the viewpoint of developability, the amount of the repeating unit containing a nitrogen atom is preferably from 1 mol% to 80 mol%, and the amount is preferably 3, based on all the repeating units contained in the resin of the present invention. Mole% to 50% by mole.

The repeating unit represented by the general formula (I-2) is a repeating unit having an oligomer chain or a polymer chain, and the number of atoms of the oligomer chain or the polymer chain is 40 to 10,000, from the viewpoint of storage stability The amount of the repeating unit contained in the repeating unit of the resin of the present invention is preferably from 10 mol% to 90 mol%, and the amount thereof is preferably from 30 mol% to 70 mol%.

In reviewing the content ratio of the two repeating units, the repeating unit (I-1): the repeating unit (I-2) has a molar ratio of 10: from the viewpoint of dispersion stability and balance of hydrophilicity and hydrophobicity: It is in the range of 1 to 1:100, and more preferably in the range of 1:1 to 1:10.

In the meantime, the repeating unit represented by the formula (I-3) which is used in combination as needed is a repeating unit in which a partial structure of an oligomer chain or a polymer chain having an atomic number of 40 to 10,000 is ion-bonded to The nitrogen atom of the main chain, and from the viewpoint of action, the amount of the repeating unit contained in all the repeating units of the resin of the present invention is preferably from 0.5 mol% to 20 mol%, and the amount thereof is preferably 1 mol. Ear to 10% by mole.

At the same time, the ionic bond of the polymer chain Y can be confirmed by infrared spectroscopy or alkali titration.

(repeating unit represented by the general formula (II-1) and repeating unit represented by the general formula (II-2))

The repeating unit represented by the formula (II-1) and the repeating unit represented by the formula (II-2) which are other preferred constituent components of the specific resin of the present invention will be described in detail.

In the general formula (II-1) and the general formula (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom and an alkyl group. *, X and Y are the same as *, X and Y in the formula (I-1) and the formula (I-2).

In the present invention, in addition to the repeating unit represented by the formula (II-1) and the repeating unit represented by the formula (II-2), the resin preferably further comprises a repeating unit represented by the formula (II-3) As a copolymerization component. When the resin is used as a dispersing agent for the metal oxide particles (A), the dispersion efficiency can be further improved by using these repeating units in combination.

In the formula (II-3), *, R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those in the formula (II-1). Y' is the same as Y' in the formula (I-3).

In the general formula (II-1), the general formula (II-2) and the general formula (II-3), R ³ , R ⁴ , R ⁵ and R ^{6 are} preferably a hydrogen atom from the viewpoint of availability of raw materials.

The formula (II-1) is a repeating unit containing a nitrogen atom in which a group X having a functional group having a pKa of 14 or less is bonded to the nitrogen atom, and from the viewpoint of storage stability and developability, The amount of the repeating unit containing a nitrogen atom is preferably from 1 mol% to 80 mol%, and the amount is preferably from 3 mol% to 50 mol, based on all the repeating units contained in the resin of the present invention. ear%.

The general formula (II-2) is a repeating unit having an oligomer chain of 40 to 10,000 or a polymer chain Y, and is contained in all repeating units of the resin of the present invention from the viewpoint of storage stability. The amount of the repeating unit is preferably from 10 mol% to 90 mol%, and the amount thereof is preferably from 30 mol% to 70 mol%.

In reviewing the content ratio of the two repeating units, the repeating unit (II-1): the molar unit of the repeating unit (II-2) is preferably at 10: from the viewpoint of dispersion stability and balance of hydrophilicity and hydrophobicity. It is in the range of 1 to 1:100, and more preferably in the range of 1:1 to 1:10.

The amount of the repeating unit represented by the formula (II-3) to be used in combination with all the repeating units of the resin of the present invention is preferably from 0.5 mol% to 20 mol%, and the amount is preferably the same. It is 1 mol% to 10 mol%.

In the specific resin of the present invention, the repeating unit represented by the formula (I-1) and the repeating unit represented by the formula (I-2) are preferably contained from the viewpoint of dispersibility.

<Group X containing a functional group having a pKa of 14 or less>

X has a functional group having a pKa of 14 or less at a water temperature of 25 °C. The "pKa" mentioned in this article is the Chemical Handbook (II) (Chemical Handbook). (II)) (Fourth Revision, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).

The structure and the like of the "functional group having a pKa of 14 or less" are not particularly limited as long as the physical properties satisfy the conditions, and examples thereof include a known functional group having a pKa within the above range, but a pKa of 12 A functional group of less than 12 is particularly preferred, and a group having a pKa of 11 or less is preferred. Specifically, examples thereof include a carboxylic acid (pKa of about 3 to 5), a sulfonic acid (pKa of about -3 to -2), a phosphonic acid (pKa of about -1 to 4), and -COCH ₂ CO. - (pKa is about 8 to 10), -COCH ₂ CN (pKa is about 8 to 11), -CONHCO-, phenolic hydroxyl group, -R _F CH ₂ OH or -(R _F ) ₂ CHOH (R _F represents perfluoro An alkyl group having a pKa of about 9 to 11), a sulfonamide (pKa of about 9 to 11), and the like, and particularly preferably a carboxylic acid (pKa of about 3 to 5) and a sulfonic acid (pKa of about - 3 to -2) and -COCH ₂ CO- (pKa is about 8 to 10).

The functional group of the group X has a pKa of 14 or less, thereby being able to interact with the metal oxide particles (A).

The group X containing a functional group having a pKa of 14 or less is preferably directly bonded to a nitrogen atom in a repeating unit containing a nitrogen atom, but the nitrogen atom of the repeating unit containing a nitrogen atom may be covalently bonded to the group X. The junctions are bonded by ionic bonding to form a salt.

In the present invention, the group X containing a functional group having a pKa of 14 or less particularly preferably has a structure represented by the formula (V-1), the formula (V-2) or the formula (V-3).

In the general formula (V-1) and the general formula (V-2), U represents a single bond or a divalent linking group.

d and e each independently represent 0 or 1.

In the formula (V-3), Q represents a mercapto group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include an alkylene group (more specifically, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CHMe-, -(CH ₂ ) ₅ -, - CH ₂ CH(nC ₁₀ H ₂₁ )- and similar groups), oxygen-containing alkylene groups (more specifically, such as -CH ₂ OCH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ - and the like) An aryl group (e.g., a phenyl group, a tolyl group, a phenyl group, a naphthyl group, a furanyl group, a pyrrolyl group, and the like), an alkoxy group (e.g., an ethoxy group, a propoxyl group) a phenoxy group and the like, and the like, but preferably an alkyl group having 1 to 30 carbon atoms or an extended aryl group having 6 to 20 carbon atoms, and preferably having 1 An alkyl group having up to 20 carbon atoms or an extended aryl group having 6 to 15 carbon atoms. From the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents a mercapto or alkoxycarbonyl group. As the thiol group of Q, a fluorenyl group having 1 to 30 carbon atoms (e.g., a decyl group, an ethyl fluorenyl group, a n-propyl fluorenyl group, a benzamidine group, and the like) is preferred, and the acetyl group is particularly Preferably. As the alkoxycarbonyl group of Q, an alkoxycarbonyl group having 2 to 30 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, and the like) It is better. As the Q, a mercapto group is particularly preferable, and an ethylidene group is preferable from the viewpoints of ease of production and availability of raw materials (precursor X' of X).

The group X in the present invention is preferably bonded to a nitrogen atom containing a repeating unit of a nitrogen atom. Therefore, the dispersibility and dispersion stability of the metal oxide particles (A) can be remarkably improved. The reason for this is not clear, but the applicant's knowledge is as follows. That is, the applicant believes that the nitrogen atom of the repeating unit containing a nitrogen atom exists in the structure of an amine group, an ammonium group or a guanamine group, and the group is acidic with respect to the surface of the metal oxide particle (A) to be adsorbed. Some have interactions, such as hydrogen bonding and ionic bonding. Further, X in the present invention functions as an acid group, thereby being mutually reactive with the basic portion of the metal oxide particles (A) (when the metal oxide particles are basic) or the metal atoms (Ti and the like of TiO ₂ ) effect. That is, the applicant believes that since the specific resin of the present invention can adsorb the basic portion and the acidic portion of the metal oxide particles (A) by the nitrogen atom and the group X, the adsorption ability can be improved, thereby significantly improving the dispersibility and storage stability. Sex.

Applicants believe that X in the present invention imparts solvent solubility and inhibits precipitation of the resin over time, thereby facilitating dispersion stability.

The group X contains a functional group having a pKa of 14 or less as its partial structure, thereby serving as an alkali-soluble group. Therefore, it is considered that when a resin is used in a curable composition or the like to impart energy to the coating film and partially cure the coating film, dissolve the unexposed portion to remove the portion and form a pattern, the uncured region is alkaline The developability in the developing solution is improved, and dispersibility, dispersion stability, and developability can be obtained.

The content of functional groups having a pKa of 14 or less in X is not particularly limited. It is preferably from 0.01 millimole to 5 millimoles, and most preferably from 0.05 millimoles to 1 millimole, based on 1 gram of the specific resin of the present invention. Within this range, the dispersibility and dispersion stability of the metal oxide particles (A) are improved, and when the resin is used in the curable composition, the developability of the uncured portion becomes excellent. From the viewpoint of acid value, when the specific resin of the present invention is used in a curable composition having pattern forming characteristics, in order to promote developability, the amount of the functional group is preferably such that the acid value of the specific resin is 5 mg KOH. / gram to 50 mg KOH / g.

(oligomer chain or polymer chain Y with an atomic number of 40 to 10,000)

Examples of Y include known polymer chains such as polyesters, polyamines, polyimines, and poly(meth)acrylates that can be bonded to the backbone portion of a particular resin. The linking moiety of Y to the specific resin is preferably the end of the oligomer chain or polymer chain Y.

Y is preferably bonded to at least one nitrogen atom of a repeating unit containing a nitrogen atom selected from a poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, and a polydiallylamine repeating unit. Unit, m-xylylenediamine-epichlorohydrin polycondensate repeating unit and polyvinylamine repeating unit. The bonding mode between Y and the main chain moiety is a covalent bond, an ionic bond or a combination of a covalent bond and an ionic bond, such as at least one repeating unit containing a nitrogen atom, which is selected Self-polymerizing (low-carbon alkylene imine) repeating unit, polyallylamine repeating unit, polydiallylamine repeating unit, meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and polyvinylamine repeating unit. The ratio of the bonding mode of Y to the main chain moiety is covalently bonded: ion bonding = 100:0 to 0:100, preferably 95:5 to 5:95 and optimal 90:10 to 10:90 Within the scope. When the ratio is outside the range, the dispersibility and dispersion stability are deteriorated and the solvent solubility is also lowered.

Y is preferably a nitrogen atom bonded or bonded in a carboxylate form to a repeating unit containing a nitrogen atom.

The atomic number of the oligomer chain or polymer chain Y is preferably from 50 to 5,000, and more preferably from 60 to 3,000, from the viewpoints of dispersibility, dispersion stability, and developability.

When the number of atoms of each oligomer chain or polymer chain Y is less than 40, the graft chain is short, whereby the steric repulsion effect may be lowered to deteriorate the dispersibility. At the same time, when the number of atoms of each oligomer chain or polymer chain Y is more than 10,000, the oligomer chain or the polymer chain Y is too long, whereby the adsorption force to the metal oxide particles may be lowered, thereby Reduce dispersion.

The number average molecular weight of Y can be measured from the polystyrene conversion value obtained by the GPC method. The number average molecular weight of Y is particularly preferably from 1,000 to 50,000, and most preferably from 1,000 to 30,000, from the viewpoints of dispersibility, dispersion stability, and developability.

In one resin molecule, preferably two or more than two and preferably five or more than five side chain structures represented by Y are bonded to the main chain bond.

In particular, Y preferably has a structure represented by the formula (III-1).

In the general formula (III-1), Z has a polyester chain as a partial structure. A polymer or oligomer, and represents a residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid represented by the following general formula (IV).

In the general formula (IV), Z is the same as Z in the general formula (III-1).

When the specific resin contains a repeating unit represented by the formula (I-3) or the formula (II-3), Y' is preferably represented by the formula (III-2).

In the formula (III-2), Z is the same as Z in the formula (III-1).

A polyester having a carboxyl group at one end (polyester represented by the general formula (IV)) can be condensed by a carboxylic acid with a lactone (IV-1), a condensed carboxylic acid containing a hydroxy group (IV-2), a diol Obtained by polycondensation (IV-3) with a divalent carboxylic acid (or cyclic anhydride) and the like.

The carboxylic acid used in the polycondensation reaction (IV-1) of a carboxylic acid and a lactone may be an aliphatic carboxylic acid (preferably a linear or branched carboxylic acid having 1 to 30 carbon atoms, such as formic acid, acetic acid, Propionic acid, butyric acid, valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, cyclohexanoic acid and the like), hydroxyl-containing carboxylic acid (more a carboxylic acid having a linear or branched chain hydroxyl group of 1 to 30 carbon atoms, such as glycolic acid, lactic acid, 3-hydroxyl Propionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, 2,2-bis(hydroxymethyl)butyl An acid and the like), but particularly preferably a linear aliphatic carboxylic acid having 6 to 20 carbon atoms or a hydroxy group-containing carboxylic acid having 1 to 20 carbon atoms. These carboxylic acids can be used in the form of a mixture. As the lactone, known lactones can be used, and examples thereof include β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-caprolactone, γ-caprolactone, and δ-valerolactone. , δ-caprolactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone and the like, and from the viewpoint of reactivity and usability Particularly preferred is ε-caprolactone.

These lactones can be used in combination with a plurality of lactones.

The feed molar ratio of the carboxylic acid to the lactone during the reaction depends on the molecular weight of the target polyester chain, whereby the ratio may not be determined to be a fixed value, but the carboxylic acid: lactone = 1:1 to 1:1,000 is preferred, and 1:3 to 1:500 is preferred.

The hydroxyl group-containing carboxylic acid in the hydroxyl group-containing carboxylic acid polycondensation (IV-2) is the same as the hydroxyl group-containing carboxylic acid in (IV-1), and the preferred range thereof is also the same.

The diol of the polycondensation reaction of the diol with the divalent carboxylic acid (or cyclic acid anhydride) (IV-3) may be a linear or branched aliphatic diol (preferably having 2 to 30 carbon atoms) Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 8-octanediol and the like), and particularly preferably an aliphatic diol having 2 to 20 carbon atoms.

Examples of the divalent carboxylic acid include a linear or branched divalent aliphatic carboxylic acid (preferably a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms, such as succinic acid, Maleic acid, adipic acid, sebacic acid, dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid and the like), and particularly preferably having 3 to 20 a divalent carboxylic acid of a carbon atom. Anhydride equivalent to these divalent carboxylic acids (e.g., anhydrous succinic acid, anhydrous glutaric acid, and the like) can also be used.

The divalent carboxylic acid and the glycol are preferably fed at a molar ratio of 1:1. Therefore, a carboxylic acid can be introduced to the terminal.

The polycondensation in the preparation of the polyester is preferably carried out by adding a catalyst. The catalyst preferably functions as a catalyst for Lewis acid, and examples thereof include Ti compounds (for example, Ti(OBu) ₄ , Ti(O-Pr) ₄ and the like), and Sn compounds (for example, tin octoate, oxidation Butyltin, dibutyltin laurate, monobutyltin hydroxybutyloxide, tin chloride and the like), protic acids (such as sulfuric acid, p-toluenesulfonic acid and the like), and the like. The amount of the catalyst is preferably from 0.01 mol% to 10 mol%, and most preferably from 0.1 mol% to 5 mol%, based on the moles of all monomers. The reaction temperature is preferably from 80 ° C to 250 ° C, and most preferably from 100 ° C to 180 ° C. The reaction time varies depending on the reaction conditions, but is usually from 1 hour to 24 hours.

The number average molecular weight of the polyester can be measured from the polystyrene conversion value obtained by the GPC method. The number average molecular weight of the polyester is from 1,000 to 1,000,000, preferably from 2,000 to 100,000, and most preferably from 3,000 to 50,000. The molecular weight within this range can achieve dispersibility and developability.

From the viewpoint of ease of production, the polyester moiety forming the polymer chain in Y is particularly preferably obtained by polycondensation of a carboxylic acid with a lactone (IV-1) and condensation of a hydroxy group containing a hydroxyl group (IV-2). And the polyester obtained.

Specific aspects of the specific resin of the present invention [(A-1) to (A-60)] are as follows Shown (shown by the specific structure of the repeating unit of the resin and combinations thereof), but the invention is not limited to the structure. In the following formula, k, l, m and n each represent a polymerized molar ratio of the repeating unit, k represents 1 to 80, 1 represents 10 to 90, m represents 0 to 80, n represents 0 to 70, and k + l +m+n=100. p and q represent the number of linkages of the polyester chains, and each independently represents 5 to 100,000. R' represents a hydrogen atom or an alkylcarbonyl group.

To synthesize the specific resin of the present invention, a specific resin can be prepared by the following method: (1) a method of reacting a resin having a primary or secondary amine group, a precursor X of X, and a precursor y of Y, (2) a method of polymerizing a monomer containing X with a macromonomer containing Y, or the like, and preferably preparing a specific resin by first synthesizing a resin having a primary or secondary amine group in the main chain, followed by a resin The precursor x and the pre-Y precursor y of X are reacted to introduce a reaction product into the nitrogen atom present in the main chain by a polymer reaction.

Examples of the resin having a primary or secondary amine group include an oligomer or polymer containing a primary or secondary amine group, which constitutes a nitrogen atom. The main chain portion is, for example, poly(lower alkyleneimine), polyallylamine, polydiallylamine, m-xylylenediamine-epichlorohydrin polycondensate, polyvinylamine and the like. Among them, an oligomer or polymer composed of poly(low carbon alkylene imine) or polyallylamine is preferred.

The precursor x of the group X having a functional group having a pKa of 14 or less represents a compound which can be reacted with a resin having a primary or secondary amine group to introduce X into the main chain.

Examples of x include a cyclic carboxylic anhydride (a cyclic carboxylic anhydride having 4 to 30 carbon atoms is preferred, and is, for example, succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, allyl butyl Anhydride, butyl succinic anhydride, n-octyl succinic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-docosyl succinic anhydride , (2-hexen-1-yl) succinic anhydride, (2-methylpropen-1-yl) succinic anhydride, (2-dodecen-1-yl) succinic anhydride, n-octenyl Succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, ethyl phthalic acid anhydride, diethyl tartaric anhydride, het acid anhydride, cyclohexane-1, 2 -Dicarboxylic anhydride, 3-methylcyclohexane-1,2-dicarboxylic anhydride or 4-methylcyclohexane-1,2-dicarboxylic anhydride, tetrafluoro succinic anhydride, 3-cyclohexene-1 , 2-Dicarboxylic anhydride or 4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, phthalic anhydride, tetrachloroortho Dicarboxylic anhydride, naphthalic anhydride, naphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, meso- Butane -1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanecarboxylic acid dianhydride and the like), a halogen atom-containing carboxylic acid (for example, chloroacetic acid, bromoacetic acid, iodoacetic acid, 4-chloro-n-butyric acid and the like), sultone (for example, propane sultone, 1,4-butane sultone and the like), dienone, cyclic sulfocarboxylic anhydride (for example 2- Sulfobenzoic anhydride and the like), a compound containing -COCH ₂ COCl- (for example, ethyl propylene dichloride and the like) or cyanoacetic acid chloride and the like, and particularly preferably from the viewpoint of productivity It is a cyclic carboxylic anhydride, a sultone and a dienone.

The oligomer chain of 40 to 10,000 or the precursor y of the polymer chain Y represents a compound which can be reacted with a resin having a primary or secondary amine group to introduce an oligomer chain or a polymer chain Y.

y is preferably an oligomer or polymer having an atomic number of 40 to 10,000 having a group which is covalently bonded or ionically bonded to a nitrogen atom of a specific resin at the terminal, and specifically, has a free carboxyl group at one end. The oligomer or polymer having an atomic number of 40 to 10,000 is preferred.

Examples of y include a polyester represented by the general formula (IV) having a free carboxylic acid, a polyamine having a free carboxylic acid at one end, a poly(meth)acrylic resin having a free carboxylic acid at one end, and the like, but In particular, a polyester represented by the formula (IV) containing a free carboxylic acid at one end is preferred.

y can be synthesized by a known method, for example, by polycondensation of the above carboxylic acid with a lactone (IV-1), condensation condensation of a hydroxyl group-containing carboxylic acid (IV-2) or a dihydric carboxylic acid (or a cyclic anhydride) Polycondensation (IV-3) to prepare a polyester comprising a free carboxylic acid at one end of the formula (IV). Polyamines containing a free carboxylic acid at one end can be prepared by self-condensation and the like by an amine group-containing carboxylic acid such as glycine, alanine, β-alanine, 2-aminobutyric acid, and the like. A poly(meth)acrylate containing a free carboxylic acid at one end can be subjected to radical polymerization by the presence of a (meth)acrylic monomer in the presence of a carboxyl group-containing chain transfer agent such as 3-mercaptopropionic acid and the like. preparation.

The specific resin of the present invention can be produced by (a) a method of simultaneously reacting a resin having a primary or secondary amine group with x and y, and (b) a resin having a primary or secondary amine group first. A method of reacting with x, followed by reaction with y, or (c) reacting a resin having a primary or secondary amine group with y first, followed by reaction with x. In particular, (c) a method of reacting a resin having a primary amine group or a secondary amine group with y first, followed by reacting with x is preferred.

The reaction temperature can be appropriately selected depending on the conditions, but is preferably from 20 ° C to 200 ° C, and most preferably from 40 ° C to 150 ° C. The reaction time is preferably from 1 hour to 48 hours, and more preferably from 1 hour to 24 hours, from the viewpoint of productivity.

The reaction can be carried out in the presence of a solvent. Examples of the solvent include water, an anthraquinone compound (for example, dimethyl hydrazine and the like), a ketone compound (for example, acetone, methyl ethyl ketone, cyclohexanone, and the like), and an ester compound (for example, ethyl acetate or butyl acetate). Ester, ethyl propionate, propylene glycol 1-monomethyl ether 2-acetate and the like), ether compounds (such as diethyl ether, dibutyl ether, tetrahydrofuran and the like), aliphatic hydrocarbon compounds (such as pentane, hexane) And analogs), aromatic hydrocarbon compounds (such as toluene, xylene, mesitylene and the like), nitrile compounds (such as acetonitrile, propionitrile and the like), guanamine compounds (such as N, N-dimethyl A) Hydrazine, N,N-dimethylacetamide, N-methylpyrrolidone and the like), carboxylic acid compounds (such as acetic acid, propionic acid and the like), alcohol compounds (such as methanol, ethanol, isopropyl) Alcohol, n-butanol, 3-methylbutanol, 1-methoxy-2-propanol and the like) and a halogen-based solvent (for example, chloroform, 1,2-dichloroethane and the like).

When a solvent is used, the solvent used is preferably 0.1 times by mass based on the substrate. (times by mass) to 100 mass times, and most preferably 0.5 mass times to 10 mass times.

The specific resin of the present invention can be purified by a reprecipitation method. When a specific resin obtained by removing a low molecular weight component by a reprecipitation method is used as a dispersing agent, the dispersing efficiency is improved.

For the reprecipitation method, a hydrocarbon solvent such as hexane and an alcohol solvent such as methanol are preferably used.

The weight average molecular weight of the specific resin of the present invention thus obtained is preferably 3,000 to 100,000, and more preferably 5,000 to 55,000, as measured by the GPC method. The molecular weight within the above range is advantageous in that high developability and high storage stability can be achieved. The presence of a nitrogen atom in (i) a repeating unit containing a nitrogen atom in the specific resin of the present invention can be confirmed by a method such as acid titration, and (ii) the presence of a functional group having a pKa of 14 or less and the functional group and The bonding of the nitrogen atom of the repeating unit can be confirmed by methods such as alkali titration, nuclear magnetic resonance spectroscopy, and infrared spectroscopy. It is confirmed by methods such as nuclear magnetic resonance spectroscopy and GPC methods that (ii) an oligomer chain having 40 to 10,000 atoms or a polymer chain Y is contained in the side chain.

Specific examples of the specific resin of the present invention and its molecular weight will be described below. R' represents an alkyl group.

In the dispersion composition of the present invention, the specific resin may be used singly or in combination of two or more thereof.

From the viewpoint of dispersibility and dispersion stability, the content of the specific resin is preferably in the range of 10% by mass to 50% by mass based on the total solid content of the dispersion composition (or the following curable composition) of the present invention. More preferably, it is in the range of 11% by mass to 40% by mass, and even more preferably in the range of 12% by mass to 30% by mass.

-Other dispersion resins -

For the purpose of controlling the dispersibility of the metal oxide particles and the like, the dispersion composition of the present invention may contain a dispersion resin other than the specific resin (hereinafter referred to as "other dispersion resin" in some cases).

Examples of other dispersing resins which can be used in the present invention include polymeric dispersing agents [e.g., polyamideamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyaminocarboxylic acids Ester, modified polyester, modified poly(meth) acrylate, (meth) acrylate copolymer, and naphthalene sulfonic acid-formalin condensate], polyoxyalkylene ethyl alkyl phosphate Polyoxyalkylene amine alkylamines, alkanolamines, pigment derivatives and the like.

Other dispersing resins may be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer depending on the structure thereof.

Other dispersing resins adhere to the surface of the metal oxide particles and are used to prevent re-aggregation. Accordingly, examples of preferred structures of the resin include terminal modified polymers, graft polymers, and block polymers each having an anchor portion anchored to the surface of the metal oxide particles. (anchor moiety).

At the same time, other dispersion resins have an effect of modifying the surface of the metal oxide particles to promote adsorption of the dispersion resin.

Specific examples of other dispersing resins include "Disperbyk-101 (polyamidoamine phosphate), dissip-107 (carboxylate), dissip-110 (copolymer containing acid groups) ), Dessig-130 (polyamide), Desbike-161, Desbike-162, Desbike-163, Desbike-164, Desbike-165, Desbike-166 and Dissic-170 (Polymerized Copolymer), "BYK-P104 and BYK-P105 (High Molecular Weight Unsaturated Polycarboxylic Acid)" (by BYK Chemicals) Manufactured by BYK Chemie GmbH, EFKA 4047, Efka 4050, Efka 4010, Efka 4165 (polyurethane), Efka 4330, Evka 4340 (block copolymer), Efka 4400, Efka 4402 (modified polyacrylate), Efka 5010 (polyester decylamine), Efka 5765 (high molecular weight polycarboxylate), Efka 6220 (fatty acid polyester), Efka 6745 (phthalocyanine derivative), Efka 6750 (azo pigment derivative) (which is manufactured by EFKA); "Ajinomoto (AJISPER) PB821, Ajinomoto PB822" (by Ajinomoto Fin Co., Ltd. (Ajinomoto Fin e-Techno Co., Inc.), "FLOWLEN TG-710 (urethane oligomer)", "Polyflow 50E", Pori Fula No. 300 (acrylic acid copolymer)" (manufactured by KYOEISHA CHEMICAL Co., Ltd.), "Disparlon" KS-860, Desparon 873SN, Dispa Long 874, Disparron No. 2150 (aliphatic polyvalent carboxyl Acid), Disparron No. 7004 (polyether ester), Disparron DA-703-50, Desparon DA-705, Desparon DA-725" (by Kusmoto) Chemicals Ltd.), DEMOL RN, Dyna N (naphthalenesulfonic acid-formalin polycondensate), "MS, C, SN-B (aromatic sulfonic acid-formalin polycondensate)" , "HOMOGENOL L-18 (Polymerized Polycarboxylic Acid)", "Aimujin (EMULGEN) 920, Ai Mujin 930, Ai Mujin 935, Ai Mujin 985 (Polyoxyethylidene) Phenylphenyl ether)", "ACETAMIN" 86 (stearylamine acetate) (manufactured by Kao Corporation), "Solsperse 5000" (phthalocyanine derivative), cable Spas 22000 (azo pigment derivative), Sospers 13240 (polyesteramine), Sospers 3000, Sospers 17000, Sospers 27000 (polymer with functional moiety at the end), Sospers 24000, Sospers 28000, Sospers 32000, Sospers 38500 (Grafted Polymer) (made by The Lubrizol Corporation), "Nikol ( NIKKOL) T106 (polyoxyethyl sorbitan monooleate) and MYS-IEX (polyoxygen ethene) Monostearate) "(produced by Nikko Chemicals Co., Ltd. (Nikko Chemicals Co., Ltd.) Ltd.) and the like.

These other dispersion resins may be used singly or in combination of two or more.

The dispersion composition of the present invention (or the curable composition described below) may or may not contain other dispersion resins, but when the composition contains other dispersion resins, the dispersion composition of the present invention (or a hardening composition described below) The total solid content is preferably from 1% by mass to 20% by mass of the other dispersed resin. Within the range of %, and more preferably in the range of 1% by mass to 10% by mass.

(C) solvent

The dispersion composition of the present invention contains a solvent, and the solvent can be configured by using a plurality of organic solvents.

Examples of the organic solvent usable herein include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene Alcohol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetonitrile acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethylene glycol Ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl hydrazine, γ - Butyrolactone, methyl lactate, ethyl lactate and the like.

These solvents may be used singly or in combination. The concentration of the solid content in the dispersion composition of the present invention is preferably from 2% by mass to 60% by mass.

The method of preparing the dispersion composition of the present invention is not particularly limited, and a usual method for preparing a dispersion composition can be applied. For example, the mixture can be prepared by mixing the metal oxide particles (A), the resin (B), and the solvent (C), and dispersing the mixture using a loop type dispersing device (bead mill) and the like.

<Sclerosing composition>

The dispersible composition of the present invention is preferably a curable composition, and the curable composition is configured to include the polymerizable composition of the dispersion composition of the present invention. Compound (D) and a polymerization initiator, and if necessary, other components.

The dispersion composition can be formed into a curable composition to have excellent dispersibility and dispersion stability, an extremely high refractive index, and has a central portion and a peripheral portion even when a hardenable composition is coated on a large-sized wafer. A film with a small film thickness (represented by a transparent film).

The present invention also relates to a transparent film formed by using the curable composition of the present invention.

The refractive index of the cured film (film formed of the curable composition and subsequently subjected to the hardening reaction) obtained from the curable composition is preferably from 1.72 to 2.60, and more preferably from 1.80 to 2.60.

The physical property of the cured film having a refractive index of 1.72 to 2.60 can be achieved by any means as long as the curable composition contains the dispersion composition of the present invention, the polymerizable compound (D), and the polymerization initiator (E), but the physical properties are preferably For example, by controlling the type and content of the polymerizable composition (D) or the binder polymer (F) which may be additionally added, or by including the metal oxide particles (A) in the curable composition and simultaneously controlling the metal oxide particles The type and content are achieved.

In detail, the above physical properties are preferably achieved by using the metal oxide particles as the above preferred examples.

Further, the composition of the present invention is preferably a transparent composition, and more specifically, when a cured film having a film thickness of 1.0 μm is formed from the composition, the composition is a composition in which 400 nm to 700 In the entire wavelength region of the nanometer, the light transmittance in the thickness direction of the cured film is 90% or more.

That is, the transparent film of the present invention means a film in which the light transmittance with respect to the film thickness direction is 90% or more at a film thickness of 1.0 μm in the entire wavelength region of 400 nm to 700 nm. .

The physical properties of the light transmittance may be achieved in any manner as long as the curable composition contains the dispersion composition of the present invention, the polymerizable compound (D), and the polymerization initiator (E), and it is preferred to control the polymerizable compound ( D) or the type and content of the binder polymer which can be additionally added. The physical properties of the light transmittance are preferably achieved by controlling the particle diameter of the metal oxide particles (A) or the type and amount of the resin (B).

For the curable composition of the present invention and the transparent film, a light transmittance of 90% or more in the entire wavelength region of 400 nm to 700 nm is an important factor for exhibiting desired characteristics, especially for exhibiting microlenses. An important factor in the characteristics.

In the entire wavelength region of from 400 nm to 700 nm, the light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100%.

In view of the above, the curable composition of the present invention contains substantially no colorant (the content of the colorant is preferably 0% by mass based on the total solid content of the composition).

(D) polymerizable compound

The polymerizable compound (D) of the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one and preferably two or more terminal ethylenically unsaturated bonds. The compounds are widely known in the art and these compounds are useful in the present invention Without any particular restrictions.

These compounds have the following chemical forms, such as monomers, prepolymers (i.e., dimers, trimers, and oligomers or mixtures thereof) and copolymers thereof. Examples of the monomer and its copolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, and the like), esters thereof and decylamines, and It is preferred to use an ester of an unsaturated carboxylic acid and an aliphatic polyol compound and a decylamine of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Suitable for the use of an addition reaction product of an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group and a fluorenyl group or a decylamine of an unsaturated carboxylic acid with a monofunctional or polyfunctional isocyanate or epoxide, an unsaturated carboxylic acid The dehydration condensation reaction product of an ester or unsaturated carboxylic acid decylamine with a monofunctional or polyfunctional carboxylic acid and the like. It is also suitable to use an addition reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group and an epoxy group or an oxime amine of an unsaturated carboxylic acid with a monofunctional or polyfunctional alcohol, an amine or a thiol; A substituted reaction product of an unsaturated carboxylic acid ester of a substituent such as a halogen group and a tosyloxy group or an unsaturated carboxylic acid amide and a monofunctional or polyfunctional alcohol, amine or thiol. As another example, a group of compounds obtained by substituting an unsaturated carboxylic acid with an unsaturated phosphonic acid, styrene, vinyl ether, and the like may also be used.

Specific examples of the monomer of the aliphatic polyol compound and the ester of the unsaturated carboxylic acid include an acrylate such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and butyl Diol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, trimethylolethane Triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol 4 Acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene oxyethyl)isocyanurate, polyester acrylate oligomer, triacetate modified with isocyanuric acid EO Esters and analogues.

Examples of methacrylates include butanediol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trishydroxyl Ethylene ethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethyl Acrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double [pair (3 -Methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis[p-(methacryloxyethoxy)phenyl]dimethylmethane and the like.

Examples of the itaconate include ethylene glycol pentoxide, propylene glycol isaconate, 1,3-butylene glycol isaconate, 1,4-butanediol diitaconate, and butyl Diol companate, pentaerythritol diitaconate, sorbitol tetraconate and the like.

Examples of the butenoate include ethylene glycol dimethyl acrylate, butane diol methacrylate, pentaerythritol dimethyl acrylate, sorbitol tetrabutyrate, and the like. Examples of methacrylates include ethylene glycol dimethacrylate, pentaerythritol Tetraol dimethacrylate, sorbitol tetramethacrylate and the like.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol di maleate, sorbitol tetramaleic acid Esters and analogues.

For example, the aliphatic alcohol ester described in Japanese Patent Laid-Open Publication No. S51-47334 and Japanese Patent Application Laid-Open No. S57-196231, Japanese Patent Application Laid-Open Publication No. S59-5240, No. S59- The esters having an aromatic skeleton described in No. 5241 and No. H2-226149 and the amine-containing esters and the analogs described in Japanese Patent Application Laid-Open No. H1-165613 are also applicable as examples of other esters. The above ester monomers can be used in the form of a mixture.

Specific examples of the monomer of the aliphatic polyvalent amine compound and the decylamine of the unsaturated carboxylic acid include methylene bis acrylamide, methylene bis methacrylamide, 1,6-hexamethylene bis propylene fluorene Amine, 1,6-hexamethylene bismethyl acrylamide, di-ethyltriamine triacrylamide, xylylene bis acrylamide, xylylene bis methacrylamide, and the like .

Examples of other preferred guanamine monomers include those having a cyclohexylene structure as described in Japanese Patent Laid-Open Publication No. S54-21726.

A urethane addition polymerizable compound prepared by an addition reaction of an isocyanate with a hydroxyl group is also suitable, and specific examples thereof include a vinylamine group having two or more polymerizable vinyl groups in the molecule. An acid ester compound having a hydroxyl group-containing vinyl monomer represented by the following formula (V) and having two or more than two isocyanate groups in the molecule, as described in Japanese Patent Laid-Open Publication No. S48-41708 Isocyanate compound plus Obtained.

In the formula (V), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.

H ₂ C=C(R ⁷ )COOCH ₂ CH(R ⁸ )OH (V)

The urethane urethane described in Japanese Patent Application Laid-Open No. S51-37193, Japanese Patent Publication No. H2-32293, and No. H2-16765, or Japanese Patent Publication No. S58-49860, S56 A urethane-based urethane compound as described in No. -17654, No. S62-39417 and No. S62-39418 is also suitable. The sclerosing composition having an excellent photo-sensing speed can have an amine structure or a sulfur group in the molecule described in Japanese Patent Application Laid-Open Publication No. S63-277653, No. S63-260909, and No. H1-105238. The structure of the polymerizable compound is obtained.

Other examples of the polymerizable compound include a polyfunctional acrylate or a methacrylate, such as those described in Japanese Patent Application Laid-Open No. S48-64183, and Japanese Patent Publication No. S49-43191 and No. S52-30490. An ester acrylate; and an epoxy acrylate obtained by reacting an epoxy resin with (meth)acrylic acid. Examples thereof include the specific unsaturated compound described in Japanese Patent Laid-Open Publication No. S46-43946, No. H1-40337, and No. H1-40336, and the ethylene described in Japanese Patent Application Laid-Open No. H2-25493. Phosphonic acid compounds and analogs. In some cases, a structure containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. S61-22048 is suitable. Can use Japan and then learn to Photohardenable monomer or oligomer described in Journal of the Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (1984).

For these polymerizable compounds, the details of the method of use (such as the structure of the compound, used alone or in combination, and the amount added) can be determined based on the final potency design of the curable compound. For example, the method is chosen for the following points of view.

From the standpoint of sensitivity, a structure in which each molecule has a high content of unsaturated groups is preferred, and in many cases, a difunctionality or a higher functionality is preferred. To enhance the strength of the cured film, trifunctional or higher functionality is desirable. A method of controlling sensitivity and strength by using a compound having different functionalities and/or different polymerizable groups (for example, acrylate, methacrylate, styrene compound, and vinyl ether compound) in combination can be effectively used.

The selection and use of the polymerizable compound are also compatible with the other components (for example, a polymerization initiator, metal oxide particles and the like) contained in the curable composition, and the dispersibility. Key factor. For example, compatibility can be improved by using a compound having a low purity or by using a combination of two or more than two other components. In some cases, a particular structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.

a compound having two or more than two epoxy or oxetane groups in the molecule -

As the polymer compound (D), there are two or more than two molecules Examples of the epoxy group-containing compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an aliphatic epoxy resin.

It is available in the form of a commercially available product. Thus, examples of the bisphenol A type epoxy resin are JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, and JER1010 (all manufactured by Japan Epoxy Resin) and Ipi EPICLON 60, Ipilon 1050, Ipilon 1051 and Ipilon 1055 (all manufactured by DIC Corporation); examples of bisphenol F-type epoxy resin are JER806, JER807 , JER4004, JER4005, JER4007, and JER4010 (both manufactured by Japan Epoxy Resin), Ipilon 830, and Ipilon 835 (both manufactured by DIC Corporation) LCE-21 and RE-602S (both manufactured by Nippon Kayaku Co., Ltd.); examples of phenol novolac type epoxy resins are JER152, JER154, JER157S70, and JER157S65 (from Japanese epoxy resin) Company (made by Japan Epoxy Resin) and Ipilon N-740, Ipilon N-770 and Ipilon N-775 (both manufactured by Dainippon Ink Chemical Industry Co., Ltd. (DIC Corporation)); cresol novolac An example of an epoxy resin is Ipilon N-660, Ipi N-665, Ipilon N-670, Ipilon N-673, Ipilon N-680, Ipilon N-690 and Ipilon N-695 (both from Dainippon Ink Chemical Industry Co., Ltd. (DIC) Corporation) and Ikon (EOCN)-1020 (manufactured by Nippon Kayaku Co., Ltd.); Examples of aliphatic epoxy resins are ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (both manufactured by ADEKA), Celloxide 2021P, race Jude 2081, Sai Bade 2083, Sai Bade 2085, EpPE 3150, EPOLEAD PB 3600 and PB 4700 (both manufactured by Daicel Corporation) and Dinaco ( Denacol) EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase Chemtex). In addition to the above, the Aidike resin EP-4000S, EP-4003S, EP-4010S, and EP-4011S (both manufactured by ADEKA), NC-2000, NC-3000, and NC-7300 are also exemplified. XD-1000, Ipeng (EPPN)-501 and Ipeng-502 (both manufactured by ADEKA) and JER1031S (manufactured by Japan Epoxy Resin).

Each of them may be used alone or two or more of them may be used in combination.

Specific examples of compounds having two or more than two oxetanyl groups in the molecule include Aron Oxetan OXT-121, OXT-221, OX-SQ, and Ponis (PNOX) (all manufactured by Toa Gosei Co., Ltd.).

The compound having an oxetane group is preferably used singly or in combination with a compound having an epoxy group.

The content of the (D) polymerizable compound is preferably in the range of from 1% by mass to 50% by mass, more preferably in the form of the total solid content of the hardenable composition. The amount is in the range of from 10% by mass to 40% by mass, and even more preferably in the range of from 5% by mass to 30% by mass.

The content is preferably in the range because the hardenability is excellent and the refractive index does not deteriorate.

(E) polymerization initiator

The polymerization initiator (E) which can be used in the present invention is a compound which initiates and promotes polymerization of (D) a polymerizable compound, and is used for an improved heating process (such as the process (IV) and process in the method of forming a microlens described below) The viewpoint of hardening during (b)) is preferably stable up to 45 ° C, but it is excellent to initiate polymerization during heating at a high temperature.

From the viewpoint of improving the hardening process by the irradiation process by irradiation of radiation (such as the process (II), process (b) and process (d) in the method of forming a microlens described below, it is preferable to be visible to the ultraviolet region. The beam of the zone is photosensitive. The polymerization initiator may be an activator which produces any action with a photoexcited sensitizer to generate a living radical and may be an initiator for initiating cationic polymerization depending on the monomer species.

The polymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of from about 300 nm to about 800 nm (more preferably from 330 nm to 500 nm).

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

Examples of the polymerization initiator (E) include an organic halide compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, and an azotization. a compound, a coumarin compound, an azide compound, a metallocene compound, a hexaarylbiimidazole compound, an organoboronic acid compound, a disulfonic acid compound, an oxime ester compound, a phosphonium salt compound, and a mercaptophosphine (oxide) compound.

Specific examples of the organic halide compound include "Bull Chem. Soc Japan", 42, 2924 (1969), Wakabayashi et al.; U.S. Patent No. 3,905,815; Japanese Patent Publication No. S46-4605 Japanese Patent Application Laid-Open No. S48-36281, No. S55-32070, No. S60-239736, No. S61-169835, No. S61-169837, No. S62-58241, No. S62-212401, Nos. S63-70243 and S63-298339; and "Journal of Heterocyclic Chemistry, 1 (No. 3), (1970)", a compound described in MP Hutt, In particular, it includes a trihalomethyl substituted oxazole compound and a s-triazine compound.

As the s-triazine compound, at least one mono-halogen, dihalogen or trihalogen-substituted methyl group is suitable for the s-triazine ring-coupled s-triazine derivative, and specific examples of the s-triazine compound include 2, 4, 6 -Tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2 -Methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β -trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxy Phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-2,4-butadienyl]- 4,6-bis(trichloromethyl)- Triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)- Homotriazine, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethane) -s-triazine, 2-(4-naphthyloxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl) -s-triazine, 2-phenylmethylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2, 4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis (three Bromomethyl)-s-triazine and analogs.

Examples of the oxadiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-tri Chloromethyl-5-(cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthoquinone-1-yl)-1,3,4-oxa Diazole, 2-trichloromethyl-5-(4-styryl)styryl-1,3,4-oxadiazole and the like.

Examples of the carbonyl compound include benzophenone; benzophenone derivatives such as Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl Benzophenone, 2-chlorobenzophenone and 4-bromobenzophenone, 2-carboxybenzophenone; acetophenone derivatives such as 2,2-dimethoxy-2-phenylbenzene Ethyl ketone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(different Propyl phenyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2-methyl-(4'-(methylthio)phenyl)-2-morpholinyl-1 -acetone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 1 1,1-trichloromethyl-(p-butylphenyl)one and 2-benzyl-2-dimethylamino-4-morpholinylbutanone; thioxanthone derivatives , such as thia Tons of ketone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone, 2 , 4-diisopropylthioxanthone; a benzoate derivative such as ethyl p-dimethylaminobenzoate or ethyl p-ethylaminobenzoate.

Examples of the ketal compound include benzylmethyl ketal, benzyl-β-methoxyethyl ethyl acetal, and the like.

Examples of the benzoin compound include meta-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-besylbenzoate, and the like.

Examples of the acridine compound include 9-phenyl acridine, 1,7-bis(9-acridinyl)heptane, and the like.

Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, etidylacetone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl Cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, tert-butyl hydroperoxide, isopropyl Benzene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydrogen Peroxide, tributyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-oxanoyl peroxide, succinate peroxide, benzammonium peroxide, 2,4-dichlorobenzhydryl peroxide, Diisopropyl oxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, Bis(3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate Ester, peroxyoctanoic acid Tributyl lauryl peroxy Tert-butyl acid, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(trihexylperoxy) Carbonyl)benzophenone, 3,3',4,4'-tetrakis(p-isopropylcumylperoxycarbonyl)benzophenone, carbonyl-bis(t-butylperoxydihydrogen) Diphthalate), carbonyl-bis(t-hexylperoxydihydrodiphthalate) and the like.

Examples of the azo compound include the azo compound described in Japanese Patent Application Laid-Open No. H8-108621.

Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl)amino)-3-phenylcoumarin, 3-chloro-5-diethylamino group -((H-triazin-2-yl)amino)-3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl)amino)- 3-phenylcoumarin and the like.

Examples of azide compounds include the organic azide compound, 2,6-bis(4-azidobenzylidene)-4-B, as described in U.S. Patent Nos. 2,848,328, 2,852,379, and 2,940,853. Cyclohexanone (BAC-E) and the like.

Examples of the metallocene compound include those described in Japanese Patent Application Laid-Open No. S59-152396, No. S61-151197, No. S63-41484, No. H2-249, No. H2-4705, and No. H5-83588. Various titanocene compounds, and specific examples thereof include dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, two Cyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, two Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Phenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl -Ti-bis-2,4,6-trifluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, Dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Japanese Patent Application Laid-Open No. H1-304453 and No. H1-152109 The iron-aromatic complex and the like.

As the biimidazole compound, for example, a hexaarylbiimidazole compound (an oxene dimer compound) and the like are preferable.

Examples of the hexaarylbiimidazole compound include the phenanthrene dimer described in Japanese Patent Laid-Open Publication Nos. S45-37377 and S44-86516, and Japanese Patent Publication No. H6-29285, and U.S. Patent No. 3,479,185. Various compounds and analogs described in Nos. 4,311,783 and 4,622,286, and specific examples thereof include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole , 2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-,p-dichlorophenyl)-4,4 ',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2, 2'-bis(o-o-o-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (ortho Trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole and the like.

Examples of the organic borate compound include Japanese Patent Application Laid-Open No. S62-143044, No. S62-150242, No. H9-188685, No. H9-188686, No. H9-188710, No. 2000-131837, and Japanese Patent No. 2002-107916, Japanese Patent No. 2764769, and Japanese Patent Application Laid-Open No. 2001-16539, and "Radio Tech'98. Proceeding", Chicago, 1998 "April 19-22," Kunz, the organic borate ester described by Martin; Japanese Patent Application Laid-Open No. H6-157623, H6-175564, and H6-175561 An organoboron oxime complex or an organoboron oxo complex as described in the Japanese Patent Application Laid-Open No. H6-175554 and No. H6-175553; The organic boron lanthanum complex described in the above-mentioned application No. H9-188710; Japanese Patent Application Laid-Open No. H6-348011, No. H7-128785, No. H7-140589, No. H7-306527, An organoboron transition metal complex complex and the like described in No. H7-292014.

Examples of the diterpene compound include the compounds and the analogs described in Japanese Patent Application Laid-Open No. S61-166544 and No. 2002-328465.

The antimony compound is preferably used as the (E) polymerization initiator used in the present invention from the viewpoints of hardenability, stability over time, and discoloration upon post-heating.

Examples of bismuth compounds include the British Chemical Society: JC Perkin II, (1979) 1653-1660, British Chemical Society: Berkin Journal 2 (JCS Perkin II), (1979) 156-162, Journal of Photopolymer Science and Technology, (1995) 202-232, and Japanese Patent Application Laid-Open No. 2000-66385; Japanese Patent Application The compounds and analogs described in Japanese Patent Application Laid-Open No. 2000-80068 and Japanese Patent Application No. 2004-534797.

For the sake of sensitivity and stability over time, the following general formula The compound represented by (a) is more preferably used as the hydrazine compound used in the present invention.

In the formula (a), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer from 0 to 5. When there are multiple Xs, each X may be the same or different from all other Xs.

Examples of the monovalent substituent represented by R in the formula (a) preferably include a monovalent non-metal atom group as shown below.

Examples of the monovalent non-metal atom group represented by R in the formula (a) include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and The alkylsulfinyl group having a substituent, the arylsulfinyl group which may have a substituent, the alkylsulfonyl group which may have a substituent, the arylsulfonyl group which may have a substituent, may have a substituent A mercapto group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a phosphinyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkylthiocarbonyl group which may have a substituent An arylthiocarbonyl group which may have a substituent, a dialkylaminocarbonyl group which may have a substituent, a dialkylaminothiocarbonyl group which may have a substituent, and the like.

As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferred, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and a dodecane group. Base, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, tri Fluoromethyl, 2-ethylhexyl, benzamidine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylthiobenzimidylmethyl, 4-phenyl Thiobenzoylmethyl, 4-dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl , 3-fluorobenzhydrylmethyl, 3-trifluoromethylbenzimidylmethyl, 3-nitrobenzimidylmethyl and the like.

As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, and 9 -phenanthryl, 1-indenyl, 5-naphthacenyl group, 1-indenyl, 2-azulenyl group, 9-fluorenyl, terphenyl group ), quarter phenyl group, o-tolyl, m-tolyl and p-tolyl, xylyl, o- cumyl, m-isopropylphenyl and p-cumyl, 2, 4, 6-trityl group, pentalenyl group, biphenylenyl group, ternaphthalenyl group, quarter naththalenyl group, parallel ring Heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl, acenaphthylenyl group, ethylene thiol group Aceanthrylenyl group), phenalenyl group, sulfhydryl group, fluorenyl group, bianthracenyl group, teranthracenyl group, quaternary Ter anthracenyl group), fluorenyl, phenanthryl, triphenylenyl group, sulfhydryl, chrysenyl group, naphthacenyl group, pleiadenyl group, 苉Base (picenyl Group), perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexabenzene Hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, sulfhydryl group (pyranthrenyl group), ovalenyl group, and the like.

As the alkenyl group which may have a substituent, an alkenyl group having 2 to 10 carbon atoms is preferred, and examples thereof include a vinyl group, an allyl group, a styryl group, and the like.

As the alkynyl group which may have a substituent, an alkynyl group having 2 to 10 carbon atoms is preferred, and examples thereof include an ethynyl group, a propynyl group, a propargyl group, and the like.

As the alkylsulfinyl group which may have a substituent, an alkylsulfinyl group having 1 to 20 carbon atoms is preferred, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and a C. Isosulfonyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl , fluorenyl sulfinyl, decylsulfenyl, octadecylsulfenyl, cyanomethylsulfinyl, methoxymethylsulfinyl and the like.

As the arylsulfinyl group which may have a substituent, an arylsulfinylene group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenylsulfinyl group and a 1-naphthylsulfinyl group. 2-naphthylsulfinyl, 2-chlorophenylsulfinium , 2-methylphenylsulfinyl, 2-methoxyphenylsulfinyl, 2-butoxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-tri Fluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfin Indenyl, 4-methoxyphenylsulfinyl, 4-methylthiophenylsulfinyl, 4-phenylthiophenylsulfinyl, 4-dimethylaminophenyl Sulfosyl groups and similar groups.

As the alkylsulfonyl group which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms is preferred, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group. , isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, twelve Alkylsulfonyl, octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonyl, perfluoroalkylsulfonyl and the like.

As the arylsulfonyl group which may have a substituent, an arylsulfonyl group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthalene group. Sulfosyl, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl, 2-butoxyphenylsulfonyl, 3-chlorobenzene Sulfosyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 4-fluorophenylsulfonyl, 4-cyano Phenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylthiophenylsulfonyl, 4-phenylthiophenylsulfonyl, 4-dimethylaminophenyl Sulfonyl and the like.

As the fluorenyl group which may have a substituent, a fluorenyl group having 2 to 20 carbon atoms is preferred, and examples thereof include an ethyl group, a propyl group, a butyl group, and a third group. Fluoromethylcarbonyl, pentamidine, benzhydryl, 1-naphthylmethyl, 2-naphthylmethyl, 4-methylthiobenzimidyl, 4-phenylthiobenzimidyl, 4-Dimethylaminobenzimidyl, 4-diethylaminobenzimidyl, 2-chlorobenzylidene, 2-methylbenzhydryl, 2-methoxybenzimidyl , 2-butoxybenzhydryl, 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4- Fluorobenzylidene, 4-cyanobenzylidene, 4-methoxybenzimidyl and the like.

As the alkoxycarbonyl group which may have a substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferred, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. , hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, trifluoromethoxycarbonyl and the like.

Examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylthiophenoxycarbonyl group, and a 4-phenylthiophenoxy group. Carbocarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxybenzene Oxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxycarbonyl 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl, 4-methoxyphenoxycarbonyl and the like.

As the phosphinoyl which may have a substituent, a phosphonium group having 2 to 50 total carbon atoms is preferred, and examples thereof include a dimethylphosphonium group, a diethylphosphonium group, a dipropyl group. Phosphonium, diphenylphosphonium, dimethoxyphosphonium, diethoxyphosphonium, benzoylphosphonium, bis (2,4,6-Trimethylphenyl)phosphonium and the like.

As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom is preferred. Examples thereof include a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thianthrenyl group, a furyl group, a piperidyl group, an isobenzofuranyl group, a benzopyrazine group. Chromenyl group, xanthene, phenothiphthyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridazinyl, Isoindolyl, 3H-indenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quinolizinyl, isoquinolinyl, quinolinyl, pyridazinyl, naphthyridinyl, quinoxaline , quinazolinyl, porphyrinyl, acridinyl, 4aH-carbazolyl, oxazolyl, β-carbolinyl, phenanthryl, acridinyl, acridinyl, morpholinyl, cyanozinyl , morphinazolyl, isothiazolyl, phenothiazine, isoxazolyl, furazinyl, phenoxazinyl, isobenzohydropyranyl, benzohydropyranyl, pyrrolidinyl, Pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, piperazinyl, porphyrin, isoindolyl, quinuclidinyl, morpholinyl, Thioxantholyl and the like.

Examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, a octylthiocarbonyl group, a sulfonylthiocarbonyl group, an octadecylthiocarbonyl group, and a third group. Fluoromethylthiocarbonyl and the like.

Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylthiophenylthiocarbonyl, 4-phenylthiophenylthiocarbonyl, 4- Dimethylaminophenylthiocarbonyl, 4-diethylaminobenzene Thiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthiocarbonyl, 2-butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3 -trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4-fluorophenylthiocarbonyl, 4-cyanophenylthiocarbonyl, 4-methoxy Phenylthiocarbonyl and the like.

Examples of the dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group, a dibutylaminocarbonyl group, and the like.

Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, a dibutylaminothiocarbonyl group, and the like.

Among them, from the viewpoint of enhancing sensitivity, R in the formula (a) is more preferably a sulfhydryl group, and specifically, an acetyl group, an ethyloyl group, a propyl group, a benzoyl group. Mercapto and tolyl groups are preferred.

Examples of the divalent organic group represented by A in the formula (a) include an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cyclohexylene group which may have a substituent, and a stretching group which may have a substituent Alkynyl.

Examples of the substituent which may be introduced into these groups include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group, and a third butoxy group; a group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; a decyloxy group such as an ethoxy group, a propyloxy group and a benzoyl group; Anthracene; anthracenyl, such as ethenyl, benzhydryl, isobutyl, acryl, methacryloyl and methoxalyl; alkylthio Such as methylthio and tert-butylthio; arylthio, such as phenylthio and p-tolylthio; alkylamino, such as methylamino and cyclohexylamine; dialkylamine a group such as a dimethylamino group, a diethylamino group, a morpholinyl group and a piperidinyl group; an arylamine group such as a phenylamino group and a p-tolylamino group; an alkyl group such as a methyl group, an ethyl group, a third butyl group and a dodecyl group; an aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumyl group, a naphthyl group, an anthranyl group, and a phenanthryl group; and other groups such as a hydroxyl group, a carboxyl group, and a Sulfhydryl, fluorenyl, sulfo, methanesulfonyl, p-toluenesulfonyl, amine, nitro, cyano, trifluoromethyl, trichloromethyl, trimethyldecyl, phosphinico Group), phosphono group, trimethylammonium group, dimethyl fluorenyl group and triphenylphenacylphosphoniumyl group.

Among them, in order to enhance sensitivity to suppress discoloration as the heating time elapses, A in the formula (a) is preferably an unsubstituted alkylene group, an alkyl group (for example, methyl group, ethyl group, third group). Butyl and dodecyl) substituted alkyl, alkyl (e.g., vinyl and allyl) substituted alkyl, and aryl (e.g., phenyl, p-tolyl, xylyl, iso) Alkyl groups substituted with propylphenyl, naphthyl, anthracenyl, phenanthryl and styryl).

The aryl group represented by Ar in the formula (a) is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.

Specific examples thereof include phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl, 9-phenanthryl, 1-indenyl, 5-fused tetraphenyl, 1-indenyl, 2- Mercapto, 9-fluorenyl, triphenyl, tetraphenyl, o-tolyl, m-tolyl and p-tolyl, xylyl, o- cumyl, m-isopropylphenyl and p-cumene base, 2,4,6-Trimethylphenyl, cyclopentadienyl, binaphthyl, tris-naphthyl, tetratetraphthyl, cycloheptatrienyl, phenylene, dicyclopentadienyl Base, fluorenyl, fluorenyl, vinyl fluorenyl, propylene naphthyl, anthracenyl, fluorenyl, hydrazino, hydrazinyl, hydrazino, fluorenyl, phenanthryl, stilbene Base, fluorenyl, fluorenyl, condensed tetraphenyl, heptaenyl, decyl, decyl, penthenyl, fused pentaphenyl, tetraphenyl, hexaphenyl, hexaphenyl, ru Base, fluorenyl, extended trinaphthyl, hexaphenyl, hexaphenyl, fluorenyl, fluorenyl and the like. Among them, a substituted or unsubstituted phenyl group is preferred from the viewpoint of enhancing sensitivity to suppress discoloration as the heating time elapses.

When the phenyl group has a substituent, examples of the substituent include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group, and a third butoxy group; An oxy group such as a phenoxy group and a p-tolyloxy group; an alkylthio group such as a methylthio group, an ethylthio group and a tert-butylthio group; an arylthio group such as a phenylthio group and a p-tolylthio group; an alkoxycarbonyl group; , such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; anthracenyloxy, such as ethoxylated, propyloxy and benzhydryloxy; fluorenyl, such as acetyl, benzhydryl , isobutyl fluorenyl, acryl fluorenyl, methacryl fluorenyl and methoxyoxazyl; alkylthio, such as methylthio and tert-butylthio; arylthio, such as phenylthio and A tolylthio group; an alkylamino group such as a methylamino group and a cyclohexylamino group; a dialkylamino group such as a dimethylamino group, a diethylamino group, a morpholinyl group and a piperidinyl group; an aryl group; Amino groups such as phenylamino and p-tolylamine; alkyl such as ethyl, tert-butyl and dodecyl; and hydroxy, carboxy, methionyl, fluorenyl, Group, acyl methanesulfonic, p-toluenesulfonic acyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, alkyl trimethyl silicon, A phosphinic acid group, a phosphonic acid group, a trimethylammonium group, a dimethyl fluorenyl group, a triphenyl benzamidine methyl fluorenyl group, and the like.

In the formula (a), the "SAr" structure formed of Ar and S adjacent to Ar is preferably any of the structures shown below from the viewpoint of sensitivity.

Examples of the monovalent substituent represented by X in the formula (a) include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and may have Alkoxy group of a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, may have a An arylthio group of a substituent, an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylsulfinyl group which may have a substituent, may have An arylsulfinylene group of a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an indenyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, Aminomercapto group which may have a substituent, an amine sulfonyl group which may have a substituent, an amine group which may have a substituent, a phosphinium group which may have a substituent, a heterocyclic group which may have a substituent, a halogen group, and Similar group.

As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferred, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and a dodecane group. Base, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, Benzamidine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylthiobenzimidylmethyl, 4-phenylthiobenzimidylmethyl, 4- Dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl, 3-Trifluoromethylbenzimidylmethyl, 3-nitrobenzimidylmethyl and the like.

As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, and 9 -phenanthryl, 1-indenyl, 5-thick tetraphenyl, 1-indenyl, 2-indenyl, 9-fluorenyl, triphenyl, biphenyl, o-tolyl, m-tolyl and Tolyl, xylyl, o-isopropylphenyl, m-isopropylphenyl and p-isopropylphenyl, 2,4,6-trimethylphenyl, cyclopentadienyl, binaphthyl, dinaphthyl , tetratetraphthyl, cycloheptatrienyl, phenylene, dicyclopentadiene Phenyl, fluorenyl, fluorenyl, vinyl fluorenyl, propylene naphthyl, anthracenyl, fluorenyl, hydrazino, hydrazinyl, hydrazino, fluorenyl, phenanthryl, hydrazine Phenyl, fluorenyl, fluorenyl, fused tetraphenyl, heptaenyl, fluorenyl, fluorenyl, bipentyl, fused pentaphenyl, tetraphenyl, hexaphenyl, hexaphenyl Rugi, fluorenyl, exemplified trinaphthyl, hexaphenyl, hexaphenyl, fluorenyl, fluorenyl and the like.

As the alkenyl group which may have a substituent, an alkenyl group having 2 to 10 carbon atoms is preferred, and examples thereof include a vinyl group, an allyl group, a styryl group, and the like.

As the alkynyl group which may have a substituent, an alkynyl group having 2 to 10 carbon atoms is preferred, and examples thereof include an ethynyl group, a propynyl group, a propargyl group, and the like.

As the alkoxy group which may have a substituent, an alkoxy group having 1 to 30 carbon atoms is preferred, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, Isobutoxy, second butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, Dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethoxy, aminocarbonylmethoxy, N,N-dibutylaminocarbonylmethoxy , N-methylaminocarbonylmethoxy, N-ethylaminocarbonylmethoxy, N-octylaminocarbonylmethoxy, N-methyl-N-benzylaminocarbonylcarbonyl Base, benzyloxy, cyanomethoxy and the like.

As the aryloxy group which may have a substituent, an aryloxy group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 2-chlorophenoxy group. Base, 2-methylphenoxy, 2-methoxyphenoxy, 2- Butoxyphenoxy, 3-chlorophenoxy, 3-trifluoromethylphenoxy, 3-cyanophenoxy, 3-nitrophenoxy, 4-fluorophenoxy, 4-cyano Phenoxy, 4-methoxyphenoxy, 4-dimethylaminophenoxy, 4-methylthiophenoxy, 4-phenylthiophenoxy and the like.

As the alkylthio group which may have a substituent, a thioalkylalkoxy group having 1 to 30 carbon atoms is preferred, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, and a butylthio group. , isobutylthio, second butylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, sulfonylthio , dodecylthio, octadecylthio, benzylthio and the like.

As the arylthio group which may have a substituent, an arylthio group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 2-chlorophenylthio group. , 2-methylphenylthio, 2-methoxyphenylthio, 2-butoxyphenylthio, 3-chlorophenylthio, 3-trifluoromethylphenylthio, 3-cyanobenzenesulfide , 3-nitrophenylthio, 4-fluorophenylthio, 4-cyanophenylthio, 4-methoxyphenylthio, 4-dimethylaminophenylthio, 4-methylsulfide A phenylthio group, a 4-phenylthiophenylthio group, and the like.

As the oxime group which may have a substituent, a decyloxy group having 2 to 20 carbon atoms is preferred, and examples thereof include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, a pentyloxy group, and a third group. Fluoromethylcarbonyloxy, benzylideneoxy, 1-naphthylcarbonyloxy, 2-naphthylcarbonyloxy and the like.

As the alkylsulfanyl group which may have a substituent, an alkylthio group having 1 to 20 carbon atoms is preferred, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, Isopropylthio, butylthio, Hexylthio, cyclohexylthio, octylthio, 2-ethylhexylthio, decylthio, decylthio, octadecylthio, cyanomethylthio, A Oxymethylthio groups and the like.

As the arylsulfanyl group which may have a substituent, an arylthio group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenylthio group, a 1-naphthylthio group, and a 2-naphthalene group. Thiothio, 2-chlorophenylthio, 2-methylphenylthio, 2-methoxyphenylthio, 2-butoxyphenylthio, 3-chlorophenylthio, 3 -trifluoromethylphenylthio, 3-cyanophenylthio, 3-nitrophenylthio, 4-fluorophenylthio, 4-cyanophenylthio, 4-methoxy Phenylthio, 4-methylthiophenylthio, 4-phenylthiophenylthio, 4-dimethylaminophenylthio and the like.

As the alkylsulfinyl group which may have a substituent, an alkylsulfinyl group having 1 to 20 carbon atoms is preferred, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and a C. Isosulfonyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl , fluorenyl sulfinyl, decylsulfenyl, octadecylsulfenyl, cyanomethylsulfinyl, methoxymethylsulfinyl and the like.

As the arylsulfinyl group which may have a substituent, an arylsulfinylene group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenylsulfinyl group and a 1-naphthylsulfinyl group. , 2-naphthylsulfinyl, 2-chlorophenylsulfinyl, 2-methylphenylsulfinyl, 2-methoxyphenylsulfinyl, 2-butoxyphenyl Sulfosyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxyphenylsulfinyl, 4-methylthiophenylsulfinyl, 4-phenyl Thiophenylsulfinyl, 4-dimethylaminophenylsulfinyl and the like.

As the alkylsulfonyl group which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms is preferred, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group. , isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, twelve Alkylsulfonyl, octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonyl and the like.

As the arylsulfonyl group which may have a substituent, an arylsulfonyl group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthalene group. Sulfosyl, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl, 2-butoxyphenylsulfonyl, 3-chlorobenzene Sulfosyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 4-fluorophenylsulfonyl, 4-cyano Phenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylthiophenylsulfonyl, 4-phenylthiophenylsulfonyl, 4-dimethylaminophenyl Sulfonyl and the like.

As the fluorenyl group which may have a substituent, a fluorenyl group having 2 to 20 carbon atoms is preferred, and examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoromethylcarbonyl group, a amyl group, and a benzamidine group. , 1-naphthylmethylhydrazine, 2-naphthylmethylhydrazine, 4-methylthiobenzimidyl, 4-phenylthiobenzimidyl, 4-dimethylaminobenzimidyl, 4-diethylaminobenzimidyl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzylidene, 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzene Formyl, 4-methoxybenzimidyl and the like.

As the alkoxycarbonyl group which may have a substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferred, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. , hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, trifluoromethoxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, 4 -methylthiophenoxycarbonyl, 4-phenylthiophenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxy Carbocarbonyl, 2-methylphenoxycarbonyl, 2-methoxyphenoxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl 3-cyanophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl, 4-methoxyphenoxycarbonyl and the like.

As the amine mercapto group which may have a substituent, an amine carbenyl group having 1 to 30 total carbon atoms is preferred, and examples thereof include N-methylamine methyl sulfonyl group, N-ethylamine methyl fluorenyl group, N-propylamine methyl sulfhydryl, N-butylamine methyl sulfhydryl, N-hexylamine methyl sulfhydryl, N-cyclohexylamine methyl sulfhydryl, N-octylamine methyl sulfhydryl, N-decylamine Mercapto, N-octadecylamine, mercapto, N-phenylamine, mercapto, N-2-methylphenylamine, N-2-chlorophenylamine, N-, N- 2-Isopropoxyphenylaminecarbamyl, N-2-(2-ethylhexyl)phenylaminecarbamyl, N-3-chlorophenylaminecarbamyl, N-3-nitrobenzene Base amide, N-3-cyanophenylamine, fluorenyl, N-4-methoxyphenylamine, fluorenyl, N-4-cyanophenylamine, fluorenyl, N-4- Methylthiophenylaminecarbamyl, N-4-phenylthiophenylamine Methyl, N-methyl-N-phenylamine, mercapto, N,N-dimethylamine, N,N-dibutylamine, N,N-diphenylamine Formyl and similar groups.

As the aminesulfonyl group which may have a substituent, an aminesulfonyl group having 0 to 30 total carbon atoms is preferred, and examples thereof include an aminesulfonyl group, an N-alkylaminesulfonyl group, and an N-aryl group. Aminesulfonyl, N,N-dialkylaminesulfonyl, N,N-diarylaminesulfonyl, N-alkyl-N-arylaminesulfonyl and the like. More specific examples thereof include N-methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonyl, N-butylamine sulfonyl, N-hexylamine sulfonyl, N - cyclohexylamine sulfonyl, N-octylamine sulfonyl, N-2-ethylhexylamine sulfonyl, N-decylamine sulfonyl, N-octadecylamine sulfonyl, N -Phenylamine sulfonyl, N-2-methylphenylamine sulfonyl, N-2-chlorophenylamine sulfonyl, N-2-methoxyphenylamine sulfonyl, N-2 -Isopropoxyphenylamine sulfonyl, N-3-chlorophenylamine sulfonyl, N-3-nitrophenylamine sulfonyl, N-3-cyanophenylamine sulfonyl, N-4-methoxyphenylamine sulfonyl, N-4-cyanophenylamine sulfonyl, N-4-dimethylaminophenylamine sulfonyl, N-4-methylsulfide Phenylaminosulfonyl, N-4-phenylthiophenylamine sulfonyl, N-methyl-N-phenylamine sulfonyl, N,N-dimethylamine sulfonyl, N , N-dibutylamine sulfonyl, N,N-diphenylamine sulfonyl and the like.

As the amine group which may have a substituent, an amine group having 0 to 50 total carbon atoms is preferred, and examples thereof include -NH ₂ , an N-alkylamino group, an N-arylamino group, and an N-fluorenyl group. Amine, N-sulfonylamino, N,N-dialkylamino, N,N-diarylamine, N-alkyl-N-arylamine, N,N-disulfonate Amino groups and the like. More specific examples thereof include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino, N-cyclohexylamino, N-octylamino, N-2-ethylhexylamino, N-decylamino, N-octadecylamino, N-phenyl Amino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropyl Oxyphenylamino, N-2-(2-ethylhexyl)phenylamino, N-3-chlorophenylamino, N-3-nitrophenylamino, N-3-cyano Phenylamino, N-3-trifluoromethylphenylamino, N-4-methoxyphenylamino, N-4-cyanophenylamino, N-4-trifluoromethylbenzene Amino group, N-4-methylthiophenylamino group, N-4-phenylthiophenylamino group, N-4-dimethylaminophenylamino group, N-methyl-N -phenylamino, N,N-dimethylamino, N,N-diethylamino, N,N-dibutylamino, N,N-diphenylamino, N,N- Diethyl decylamino, N,N-dibenzoylamino, N,N-(dibutylcarbonyl)amine, N,N-(dimethylsulfonyl)amine, N,N -(Diethylsulfonyl)amino, N,N-(dibutylsulfonate ) Amino, N, N- (diphenyl sulfonic acyl) amino, morpholinyl, 3,5-dimethyl-morpholinyl, carbazolyl group and the like.

As the phosphinium group which may have a substituent, a phosphonium group having 2 to 50 total carbon atoms is preferred, and examples thereof include a dimethylphosphonium group, a diethylphosphonium group, a dipropylphosphonium group. , diphenylphosphonium decyl, dimethoxyphosphonium decyl, diethoxyphosphonium decyl, diphenylmethylphosphonium decyl, bis(2,4,6-trimethylphenyl)phosphonium And similar groups.

As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom is preferred. Examples thereof include a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thiol group, a furyl group, a piperidyl group, an isobenzofuranyl group, a benzopyranyl group, an anthracene. Tonsyl, morphine, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, Pyrazinyl, pyrimidinyl, pyridazinyl, pyridazinyl, isodecyl, 3H-indenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quinazinyl, isoquinolinyl , quinolyl, pyridazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, porphyrinyl, acridinyl, 4aH-carbazolyl, oxazolyl, β-carboline, cyanodinyl , acridine, acridinyl, morpholinyl, cyanozinyl, morphazinyl, isothiazolyl, phenothiazine, isoxazolyl, furazinyl, phenoxazinyl, isobenzodihydro Piperidyl, benzohydropyranyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, piperazinyl, porphyrin , isoindolyl, quinuclidinyl, morpholinyl, thioxanthyl and the like.

Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, An alkylthio group which may have a substituent, an arylthio group which may have a substituent, an anthracene group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, may have a substitution Alkyl sulfinyl group, arylsulfinyl group which may have a substituent, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, fluorenyl group which may have a substituent An alkoxycarbonyl group which may have a substituent, an amine mercapto group which may have a substituent, an amine sulfonyl group which may have a substituent, an amine group which may have a substituent, and a heterocyclic group which may have a substituent may be subjected to the above Substituted for another substituent.

Examples of the substituent include a halogen group such as a fluorine atom or a chlorine atom. a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxy group; a carbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; a decyloxy group such as an ethoxy group, a propenyloxy group and a benzhydryloxy group; an anthracenyl group such as an ethyl fluorenyl group, a benzamidine group, an isobutyl group, a propylene group Anthracenyl, methacryl fluorenyl and methoxyoxazyl; alkylthio, such as methylthio and tert-butylthio; arylthio, such as phenylthio and p-tolylthio; Alkylamino groups such as methylamino and cyclohexylamino; dialkylamino groups such as dimethylamino, diethylamino, morpholinyl and piperidinyl; arylamine groups such as benzene Alkyl and p-tolylamine; alkyl, such as methyl, ethyl, tert-butyl and dodecyl; aryl, such as phenyl, p-tolyl, xylyl, cumyl, Naphthyl, anthryl and phenanthryl; and other groups such as hydroxy, carboxyl, methionyl, fluorenyl, sulfo, methylsulfonyl, p-toluenesulfonyl, amine, nitro, cyano, tri , Trichloromethyl, trimethyl silicon group, a phosphinic acid group, a phosphonic acid group, a trimethylammonium group, a sulfonium dimethyl benzoyl group and triphenylmethyl phosphonium methyl group.

Among them, X in the formula (a) is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or the like, from the viewpoint of improving solubility in a solvent and improving absorption efficiency in a long wavelength region. Alkenyl group having a substituent, alkynyl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthio group which may have a substituent, aryl sulfur which may have a substituent And an amine group which may have a substituent.

In the formula (a), n represents an integer of 0 to 5, and is preferably an integer of 0 to 2.

Specific examples of the hydrazine compound will be shown below, but the invention is not limited to the examples.

The ruthenium compound acts as a thermal polymerization initiator which decomposes by heating and initiates and promotes polymerization. In detail, the ruthenium compound represented by the formula (a) has a low degree of discoloration after heating and has excellent hardenability.

The ruthenium compound used in the present invention preferably has a maximum absorption wavelength in a wavelength region of from 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of from 360 nm to 480 nm, and an antimony compound is particularly preferred. It has high absorbance at 365 nm and 405 nm.

Among the antimony compounds, 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, from the viewpoint of sensitivity.

The molar absorption coefficient of a compound can be measured by using known methods, and in particular, the coefficient is preferably, for example, by ultraviolet and visible spectrophotometry. The meter (Carry-5 spectrophotometer, manufactured by Varian Inc.) was measured at a concentration of 0.01 g/liter using an ethyl acetate solvent.

As the hydrazine compound, commercially available products such as IRGACURE OXE01 and Yanjiao OXE02 (both manufactured by BASF Corporation) can be suitably used.

Examples of sulfonium salt compounds include SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and TSBal et al., Polymer, 21, 423 The diazonium salt described in (1980); the ammonium salt and the like described in U.S. Patent No. 4, 069, 055, the Japanese Patent Application Laid-Open No. H4-365049, and the U.S. Patent Nos. 4,069,055 and 4,069,056. The phosphonium salt and the like described in European Patent No. 104,143, Japanese Patent Application Laid-Open No. H2-150848, and No. H2-296514.

The onium salt which may be suitably used in the present invention is a diarylsulfonium salt, and from the viewpoint of stability, the onium salt preferably has two or more than two electron donating groups such as an alkyl group, an alkoxy group and an aryloxy group. Base) replaced.

Examples of hydrazine salts suitable for use in the present invention include European Patent Nos. 370,693, 390,214, 233, 567, 297, 443 and 297, 442, U.S. Patent Nos. 4,933,377, 4,760,013, 4,734,444 and 2,833,827. The onium salts described in German Patent Nos. 2,904,626, 3,604,580 and 3,604,581, and the sulfonium salt is preferably substituted with an electron withdrawing group from the viewpoint of stability and sensitivity. Pull electronics The Hammett value of the group is preferably greater than zero. Preferred examples of the electron withdrawing group include a halogen atom, a carboxylic acid group, and the like.

Other preferred examples of the onium salt include a phosphonium salt in which one of the substituents of the triarylsulfonium salt has a coumarin structure or an anthracene structure, whereby the phosphonium salt has an absorption at 300 nm or more. Other preferred examples of the onium salt include an onium salt in which the substituent of the triarylsulfonium salt has an allyloxy group or an arylthio group, whereby the onium salt has an absorption at 300 nm or more.

Examples of the onium salt include the following onium salts, such as JV Crivello et al., Macromolecules, 10 (6), 1307 (1977) and JV Crivino (JVCrivello), etc. Selenium salts described in J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), and CS Wen et al., Asian Radiation Strontium salt as described in Teh, Proc. Conf. Rad. Curing ASIA, page 478, Tokyo, October (1988).

Examples of the mercaptophosphine (oxide) compound include Yanjiagu 819, DAROCURE 4265, Daluo TPO, and the like, which are manufactured by BASF Corporation.

The (E) polymerization initiator used in the curable composition of the present invention is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl group, from the viewpoint of hardenability. a ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, a metallocene compound, a ruthenium compound, a triallyl imidazole dimer, Antimony compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyl oxadiazole compound and 3-aryl group Substituted coumarin compound.

a trihalomethyltriazine compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound, and an acetophenone compound are More preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound is preferred.

In particular, when the curable composition of the present invention is formed on a color filter of a solid-state image sensing device to form a microlens, in particular, the composition has a low degree of discoloration upon post-heating and also has excellent hardenability. Thus, it is preferred to use a ruthenium compound as the (E) polymerization initiator.

The content of the (E) polymerization initiator contained in the curable composition of the present invention is preferably from 0.1% by mass to 10% by mass, more preferably from 0.3% by mass to 8% by mass based on the total solid content of the curable composition. And even more preferably from 0.5% by mass to 5% by mass. Within these ranges, good hardenability can be obtained.

The hardenable composition of the present invention may further contain any of the components described in detail below, as necessary. Any component which the hardenable composition may contain is described below.

[sensitizer]

The curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generating efficiency of the (E) polymerization initiator and converting the sensitive wavelength to a longer wavelength.

The sensitizer which can be used in the present invention is preferably by electron transfer mechanism or energy The amount transfer mechanism sensitizes the (E) polymerization initiator.

Examples of the sensitizer include a sensitizer belonging to the following compounds and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.

That is, examples thereof include polynuclear aromatic groups (e.g., phenanthrene, anthracene, anthracene, anthracene, triphenylene and 9,10-dialkoxyfluorene), xanthene (e.g., luciferin, eosin) (eosin), erythrosine, rhodamine B, and rose bengal, thioxanthone (isopropyl thioxanthone, diethyl thioxanthone, and chlorothioxanthene) Ketones, cyanines (such as thiacarbocyanine and oxacarbocyanine), merocyanines (such as merocyanines and carbonaceous cyanines), phthalocyanines, thiazines (such as thionine) , Methylene Blue and Toluidine Blue, acridine (eg acridine orange, chloroflavin and acriflavine), terpenoids (eg hydrazine), aryl acid cyanines (eg aromatic Acid cyanine), acridine orange, coumarin (eg 7-diethylamino-4-methylcoumarin), keto coumarin, phenothiazine, phenazine, styrylbenzene, azo a compound, diphenylmethane, triphenylmethane, distyrylbenzene, oxazole, porphyrin, spiro compound, quinacridone, indigo, styryl, pyrylium compound, Pyrrole methylene group , pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, aromatic ketone compounds (such as acetophenone, benzophenone, thioxanthone and MICH A ketone and a heterocyclic compound such as N-aryl oxazolidinone.

More preferable examples of the sensitizer which can be used in the present invention include compounds represented by the following general formula (e-1) to (e-4).

In the formula (e-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents a basic nucleus which forms a dye together with A ¹ and a carbon atom adjacent to L ¹ . The non-metal atomic group, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metal atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acid core of the dye. W represents an oxygen atom or a sulfur atom.

In the formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group, and Ar ¹ and Ar ² are bonded to each other via a bond -L ² - therebetween. Here, -L ² - represents -O- or -S-. W is the same as described in the formula (e-1).

In the formula (e-3), A ² represents a sulfur atom or NR ⁵⁹ , and L ³ represents a non-metal atomic group which forms a basic core of a dye together with A ² and a carbon atom adjacent to L ³ , R ⁵³ and R ⁵⁴ And R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent non-metal atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In the formula (e-4), A ³ and A ⁴ each independently represent -S- or -NR ⁶² , and R ⁶² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, L ⁴ denotes a non-metal atomic group which forms a basic nucleus of a dye together with A ³ and a carbon atom adjacent to L ⁴ , and L ⁵ represents a non-metal nucleus forming a dye together with A ⁴ and a carbon atom adjacent to L ⁵ a metal atom group, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent non-metal atomic group, or R ⁶⁰ and R ⁶¹ may be bonded to each other to form an aliphatic or aromatic ring.

The content of the sensitizer in the curable composition is preferably from 0.1% by mass to 20% by mass, based on the solid content, from the viewpoint of the light absorbing efficiency of the deep portion and the decomposition efficiency of the initiator. Preferably, it is 0.5% by mass to 15% by mass.

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

In addition to the sensitizer, examples of preferred sensitizers which may be contained in the curable composition include at least one selected from the group consisting of a compound represented by the following formula (II) and a compound represented by the formula (III). By.

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

In the formula (II), R ¹¹ and R ¹² each independently represent a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. n represents an integer of 0 to 5, and n' represents an integer of 0 to 5, but there is no case where n and n' are both 0. When n is 2 or greater than 2, each of the plurality of R ¹¹ may be the same as or different from all of the other R ¹¹ . When n' is 2 or greater than 2, each of the plurality of R ¹² may be the same as or different from all of the other R ¹² . Meanwhile, the formula (II) is not limited to any one of its isomers which is produced by a double bond.

The molar absorption coefficient ε of the compound represented by the general formula (II) is preferably 500 mol ^-1 at a wavelength of 365 nm. liter. Centimeters ^-1 or greater than 500 moles ^-1 . liter. The centimeters ^-1 is preferably 3,000 m ^-1 at a wavelength of 365 nm. liter. Centimeters ^-1 or more than 3,000 moles ^-1 . liter. The centimeter is ^-1 and is preferably 20,000 m ^-1 at 365 nm wavelength. liter. Centimeters ^-1 or greater than 20,000 moles ^-1 . liter. Cm ^-1 . From the viewpoint of light absorption efficiency, the value of the molar absorption coefficient ε at each wavelength is preferably within the above range because the effect of enhancing sensitivity is high.

Preferred examples of the compound represented by the formula (II) are explained below, but the invention is not limited to the examples.

Meanwhile, in the present specification, unless an element or a substituent is additionally specified, the chemical formula may be described by a simplified structural formula, and the solid line represents a hydrocarbon group.

In the formula (III), A ⁵ represents an aromatic ring or a heterocyclic ring which may have a substituent, X ⁴ represents an oxygen atom, a sulfur atom or -N(R ²³ )-, and Y represents an oxygen atom, a sulfur atom or - N(R ²³ )-. R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent non-metal atomic group, and each of A ⁵ , R ²¹ , R ²² and R ²³ may be bonded to each other to form an aliphatic or aromatic ring.

In the formula (III), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent non-metal atomic group. When R ²¹ , R ²² and R ²³ each represent a monovalent non-metal atomic group, each of R ²¹ , R ²² and R ^{23 is} preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group or a halogen atom.

Among the compounds represented by the general formula (III), Y is preferably an oxygen atom or -N(R ²³ )- from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ²³ represents a hydrogen atom or a monovalent non-metal atomic group. Y is preferably -N(R ²³ )-.

Preferred specific examples of the compound represented by the general formula (III) will be shown below, but the invention is not limited to the examples. Isomers resulting from the attachment of a double bond between an acidic core and a basic nucleus are not specified, and the invention is not limited to any difference Structure.

[common sensitizer]

The curable composition of the present invention preferably further contains a co-sensitizer.

In the present invention, the co-sensitizer has a function of further enhancing (E) the sensitivity of the polymerization initiator or the sensitizer to actinic radiation, suppressing (D) polymerization inhibition of the polymerizable compound by oxygen, and the like. Features.

Examples of the co-sensitizer include amines, such as "Journal of Polymer Society" by MRSander et al., Vol. 10, p. 3173 (1972); Japan Patent Publication No. S44-20189; Japanese Patent Application Laid-Open No. S51-82102, No. S52-134692, No. S59-138205, No. S60-84305, No. S62-18537, and No. S64-33104 And the compounds described in Research Disclosure No. 33825. Specific examples thereof include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-nonyldimethylaniline, p-methylthiodimethylaniline, and the like.

Other examples of the co-sensitizer include a mercaptan and a sulfide, for example, Japanese Patent Application Laid-Open No. S53-702, Japanese Patent Publication No. S55-500806, and Japanese Patent Application Laid-Open No. H5-142772 The thiol compound described in the above, the disulfide compound described in Japanese Patent Application Laid-Open No. S56-75643, and the like. Specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, β-mercaptophthalene, and the like.

Other examples of the co-sensitizer include an amino acid compound (for example, N-phenylglycine and the like), an organometallic compound described in Japanese Patent Laid-Open Publication No. S48-42965 (for example, tributyltin acetate and the like). The hydrogen compound described in Japanese Patent Laid-Open Publication No. S55-34414, the sulfur compound (for example, trithiane and the like) and the like described in Japanese Patent Application Laid-Open No. H6-308727.

From the viewpoint of increasing the hardening rate by the balance of the polymerization growth rate and the chain transfer, the content of the co-sensitizer is preferably from 0.1% by mass to 30% by mass based on the total solid content of the hardening composition. Within the range, it is more preferably in the range of 1% by mass to 25% by mass, and even more preferably in the range of 1.5% by mass to 20% by mass.

[Polymerization inhibitor]

In the present invention, in order to prevent unnecessary polymerization of a compound having a polymerizable ethylenically unsaturated double bond during preparation or storage of the curable composition, it is preferred to add a polymerization inhibitor.

Examples of the polymerization inhibitor which can be used in the present invention 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-nitroso group. Phenylhydroxylamine, diazonium compound, cationic dye, sulfur group-containing compound, nitro group-containing compound, transition metal compound (such as FeCl ₃ or CuCl ₂ ).

The better aspect is as follows.

The phenolic hydroxyl group-containing compound is preferably a compound selected from the group consisting of hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, Phenylhydrazine, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), phenolic resin And cresol resin.

The N-oxide compound is preferably a compound selected from the group consisting of 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N- Oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide and isonicotinic acid N-oxide.

The piperidine-1-oxyl radical compound is preferably a compound selected from the group consisting of piperidin-1-oxyl free radicals, 2,2,6,6-tetramethylpiperidine-1- Oxyl radical, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine- 1-oxyl radical, 4-acetamide-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-m-butylenediamine-2,2,6, 6-Tetramethylpiperidin-1-oxide radical and 4-phosphoniumoxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical.

The pyrrolidine-1-oxyl radical compound is preferably a 3-carboxyproxyl radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl free base).

The N-nitrosophenylhydroxylamine is preferably a compound selected from the group consisting of N-nitrosophenylhydroxylamine sulfonium (I) salt and N-nitrosophenylhydroxylamine aluminum salt.

The diazonium compound is preferably hydrogen sulfide from 4-diazophenyldimethylamine A compound selected from the group consisting of a salt, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate.

Suitable polymerization inhibitors which can be used in the present invention are described below, but the invention is not limited to the materials. Meanwhile, the phenol polymerization inhibitor contains the following exemplified compound (P-1) to compound (P-24).

The amine polymerization inhibitor contains the following exemplified compound (N-1) to compound (N-7).

The sulfur polymerization inhibitor contains the following exemplified compound (S-1) to compound (S-5).

The phosphite polymerization inhibitor comprises the following exemplified compound (R-1) to compound (R-5).

The following compounds each may also be used as a suitable polymerization inhibitor.

Among the above exemplary compounds, preferred examples of the polymerization inhibitor include a phenolic hydroxyl group-containing compound such as hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and t-butyl group. Tea phenol, benzoquinone, 4,4-thiobis(3-methyl-6-tert-butylphenol) and 2,2'-methylene-bis(4-methyl-6-tert-butylphenol) a piperidine-1-oxyl radical compound such as 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-sided oxy-2,2,6,6-tetra Methylpiperidine-1-oxyl radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-acetamide-2,2,6,6 -tetramethylpiperidine-1-oxyl radical, 4-m-butylenediamine-2,2,6,6-tetramethylpiperidine-1-oxyl radical and 4-phosphine oxide a base-2,2,6,6-tetramethylpiperidine-1-oxyl radical; or an N-nitrosophenylhydroxylamine compound, Such as N-nitrosophenylhydroxylamine sulfonium (I) salt and N-nitrosophenylhydroxylamine aluminum salt, a more preferred example comprises a piperidine-1-oxy radical compound such as 2,2,6,6- Tetramethylpiperidin-1-oxide radical, 4-sided oxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-hydroxy-2,2,6, 6-Tetramethylpiperidine-1-oxyl radical, 4-acetamidamine-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-northene diazide Amine-2,2,6,6-tetramethylpiperidine-1-oxyl radical and 4-phosphoniumoxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical Or an N-nitrosophenylhydroxylamine compound such as N-nitrosophenylhydroxylamine sulfonium (I) salt and N-nitrosophenylhydroxylamine aluminum salt, and even more preferred examples thereof include N-nitroso Phenylhydroxylamine compounds such as N-nitrosophenylhydroxylamine ruthenium (I) salt and N-nitrosophenylhydroxylamine aluminum salt.

The amount of the polymerization inhibitor to be added is preferably from 0.01 part by mass to 10 parts by mass, more preferably from 0.01 part by mass to 8 parts by mass, and most preferably 0.05 part by mass, based on 100 parts by mass of the (E) polymerization initiator. Up to 5 parts by mass.

By setting the amount within the above range, the hardening reaction in the image-free region can be sufficiently suppressed and the hardening reaction in the image region can be promoted, whereby image formability and sensitivity are improved.

[Binder Polymer]

The curable composition of the present invention preferably further contains a binder polymer from the viewpoint of improving the properties of the coating film and the like.

As the binder polymer, a linear organic polymer is preferably used. As the linear organic polymer, any known polymer can be used arbitrarily. In order to enable water development or weak alkaline water development, a linear organic polymer which is soluble in water or weakly alkaline water or swellable in water or weakly alkaline water is preferably selected. Linear organic The polymer can be used not only as a film-forming agent but also as a water, weakly alkaline water or organic solvent developer depending on the use. For example, when a water-soluble organic polymer is used, water development can be performed. Examples of the linear organic polymer include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Application Laid-Open No. S59-44615, Japanese Patent Publication No. S54-34327, No. S58-12577 Polymers described in No. S54-25957, Japanese Patent Application Laid-Open No. S54-92723, No. S59-53836, and No. S59-71048, that is, by polymerization of monomers having a carboxyl group. Or a resin formed by copolymerization, a resin formed by hydrolyzing, semi-esterifying or semi-deaminating an acid anhydride unit formed by homopolymerizing or copolymerizing a monomer having an acid anhydride, by using an unsaturated monocarboxylic acid and an acid anhydride pair An epoxy acrylate and the like formed by upgrading an epoxy resin. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like, and monomers having an acid anhydride Examples include anhydrous maleic acid and similar monomers.

The binder polymer comprises an acidic cellulose derivative similar in the side chain having a carboxylic acid group. Polymers formed by addition of a cyclic acid anhydride to a polymer having a hydroxyl group and the like are also suitable.

In the present invention, when a copolymer is used as the binder polymer, a monomer other than the above monomers may be used as the copolymerized compound. Examples of the other monomer include the compounds described in the following (1) to (12).

(1) Acrylates and methacrylates having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-methacrylic acid 2- Hydroxyethyl ester, methyl propyl 2-hydroxypropyl enoate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate.

(2) alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, acrylic acid Benzyl methacrylate, 2-chloroethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexyl methacrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, acrylonitrile Propyl ester, 2-allyloxyethyl acrylate and propargyl acrylate.

(3) alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, methacrylic acid Hexyl ester, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, methyl methacrylate 3, 4-epoxycyclohexyl ester, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxy methacrylate Ester and propargyl methacrylate.

(4) acrylamide or methacrylamide, such as acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl Acrylamide, vinyl methacrylamide, N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide and allyl methyl Acrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(7) Styrene such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, p-ethoxylated styrene, and the like.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.

(11) unsaturated quinoid imines such as maleimide, N-propylene acrylamide, N-ethyl methacrylamide, N-propyl methacrylamide and N - (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid monomer in which a hetero atom is bonded to the α-position, and for example, a compound and the like described in Japanese Patent Application Laid-Open No. 2002-309057 and No. 2003-311569.

The binder polymer preferably further comprises a repeat formed by polymerizing a monomer component substantially comprising a compound represented by the following formula (ED) (hereinafter referred to as "ether dimer" in some cases). unit.

(In the formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent)

Therefore, the curable resin composition of the present invention can form a hard coat film having excellent heat resistance and excellent transparency. In the general formula (ED) representing an ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is not particularly limited, but examples thereof include a straight chain or a branched chain. Alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, third pentyl, stearyl, lauryl and 2-ethylhexyl; a group such as a phenyl group; a cycloaliphatic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl and 2-methyl-2- Adamantyl; alkyl substituted by alkoxy, such as 1-methoxyethyl, 1-ethoxyethyl and the like; alkyl substituted with aryl, such as benzyl; and similar groups group. Among them, in particular, from the viewpoint of heat resistance, it is not easy to desorb a primary or secondary carbon substituent by acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group.

Specific examples of ether dimers include dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2 - diethyl acrylate, 2,2'-[oxybis(methylene)]bis-2-propenyl bis(n-propyl), 2,2'-[oxybis(methylene)] bis- 2-Diisopropyl (isopropyl), 2,2'-[oxybis(methylene)]bis-2-n-butyl acrylate, 2,2'-[oxybis(methylene) )] bis(isobutyl acrylate), 2,2'-[oxybis(methylene)bis-2-propenoic acid di(tributyl butyl), 2,2'-[oxybis(methylene)]bis-2-propenoic acid di(tripentyl ester), 2,2'-[oxybis(methylene)]bis-2-propenoic acid di Stearyl ester), 2,2'-[oxybis(methylene)]bis-2-propenyl bis(lauryl), 2,2'-[oxybis(methylene)]bis-2- Di(2-ethylhexyl acrylate), 2,2'-[oxybis(methylene)]bis-2-propenoic acid bis(1-methoxyethyl), 2,2'-[oxy Bis(methylene)]bis(1-ethoxyethyl) bis-2-acrylate, diphenylmethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, 2, 2'-[oxybis(methylene)]bis-2-phenyl acrylate, 2,2'-[oxybis(methylene)]bis-2-cyclohexyl acrylate, 2,2 '-[oxybis(methylene)]bis-2-butylcyclohexyl acrylate, 2,2'-[oxybis(methylene)]bis-2-propenoic acid II ( Dicyclopentadienyl ester), 2,2'-[oxybis(methylene)]bis-2-propenyl bis(tricyclodecyl), 2,2'-[oxybis(methylene) Bis(isobornyl acrylate), 2,2'-[oxybis(methylene)]bis-2-adamantyl bis-2-adamenate, 2,2'-[oxybis(Asian) Methyl)] bis(2-methyl-2-adamantyl) bis-2-acrylate and the like. Among them, in particular, 2,2'-[oxybis(methylene)bis-2-acrylic acid dimethyl ester, 2,2'-[oxybis(methylene)]bis-2-propenoic acid diethyl ester , 2,2'-[oxybis(methylene)]bis-2-hexyl acrylate and 2,2'-[oxybis(methylene)]bis-2-propenoic acid diphenylmethyl ester It is better. These ether dimers may be used singly or in combination of two or more. The structure derived from the compound represented by the above formula (ED) can be copolymerized with other monomers.

Among them, a (meth)acrylic resin having an allyl group or a vinyl ester group and a carboxyl group in a side chain described in Japanese Laid-Open Patent Publication No. 2000-187322 and No. 2002-62698 has a double bond in a side chain. An alkali-soluble resin having a guanamine group in a side chain as described in Japanese Patent Application Laid-Open No. 2001-242612, because of film strength and sensitivity And the balance of developability is excellent and suitable.

Japanese Patent Publication No. H7-12004, No. H7-120041, No. H7-120042, No. H8-12424, and No. S63-287944, Japanese Patent Application Laid-Open No. S63-287947, No. S63-287947 An acid group-containing urethane-based adhesive polymer and the like described in No. H1-271741, or an acid group in a side chain described in Japanese Patent Application Laid-Open No. 2002-107918 The double bond urethane binder polymer has excellent strength and, therefore, is advantageous from the viewpoint of film strength.

The acetal-modified polyvinyl alcohol-based binder polymer having an acid group and the like described in the European Patent No. 993966, the European Patent No. 1204000, and the Japanese Patent Application Laid-Open No. 2001-318463 Good film strength is therefore suitable.

Polyvinylpyrrolidone, polyethylene oxide and the like are suitable as water-soluble linear organic polymers. Alcohol-soluble nylon, 2,2-bis(4-hydroxyphenyl)-propane and epichlorohydrin polyethers and the like are also suitable for enhancing the strength of the cured film.

The weight average molecular weight (polystyrene conversion value measured by the GPC method) of the binder polymer usable in the hardenable composition of the present invention is preferably 5,000 or more, and more preferably in the range of 10,000 to 300,000. And the number average molecular weight thereof is preferably 1,000 or more, and more preferably in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10.

The binder polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.

Adhesive polymers useful in the present invention can be synthesized by methods known in the art. Examples of the solvent used in the synthesis include tetrahydrofuran, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and acetic acid 2-methoxy group. Ethyl ester, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-di Methylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl hydrazine, water, and the like. These adhesives may be used singly or in combination of two or more.

Examples of the radical polymerization initiator which is used in the synthesis of the binder polymer which can be used in the curable composition of the present invention include compounds known in the related art, such as an azo initiator and a peroxide initiator.

In the curable composition of the present invention, the binder polymer may be used singly or in combination of two or more thereof.

The curable composition of the present invention may or may not contain a binder polymer, but when the composition contains a binder polymer, the binder polymer content is preferably 1 mass based on the total solid content of the curable composition. From 3% to 40% by mass, more preferably from 3% by mass to 30% by mass, and even more preferably from 4% by mass to 20% by mass.

[Surfactant]

From the viewpoint of improving the coatability of the curable composition of the present invention, various surfactants can be added thereto. Various surfactants can be used (such as fluorine-based surfactants, nonionic surfactants, cationic interfaces) A surfactant, an anionic surfactant, and a quinone surfactant are used as a surfactant.

In particular, when the curable composition of the present invention contains a fluorine-based surfactant and thus is made into a coating solution, the liquid characteristics (especially fluidity) can be further improved, thereby further improving the uniformity of the coating thickness or the liquid retention. Liquid saving.

That is, when a film is formed by using a coating solution, and a photosensitive transparent composition containing a fluorine-based surfactant is used in the coating solution, by reducing the interfacial tension between the surface to be coated and the coating solution. The wettability of the surface to be coated is improved to improve the applicability to the surface to be coated. Therefore, it is effective in that even when a film having a thickness of several micrometers is formed with a small amount of liquid, a uniform thickness film having a small thickness unevenness can be formed more suitably.

The content (%) of fluorine in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, and particularly preferably from 7% by mass to 25% by mass. From the viewpoint of the thickness uniformity of the coating film and the liquid retention property, the fluorine-based surfactant having a fluorine content (%) within the above range is effective, and exhibits good solubility in the curable composition.

Examples of fluorine-based surfactants include MEGAFAC F171, Meg Vanes F172, Meg Vanes F173, Meg Vans F176, Meg Vans F177, Meg Vans F141, Megfan F142, Meg Vans F143, Meg Vans F144, Meg Vans R30, Meg Vans F437, Meg Vans F475, Meg Vans F479, Meg Vans F482, Meg Vans F554 , Meg Vanes F780 and Meg Vans F781 (both by Dainippon Oil) Manufactured by DIC Corporation; Fluorad FC430, Flora FC431 and Flora FC171 (both manufactured by Sumitomo 3M Limited); Surflon S-382 Chevron SC-101, Chevron SC-103, Chevron SC-104, Chevron SC-105, Chevron SC-1068, Chevron SC-381, Chevron SC-383, Chevron SC393 and Chevron KH-40 (both manufactured by ASAHI GLASS CO.LTD), PF636, PF656, PF6320, PF6520, PF7002 (both manufactured by OMNOVA) And similar.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane and its ethoxylates, propoxylates (e.g., propoxylated glycerol, ethoxylated glycerin, and the like) , polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl ether, polyethyl b Diol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, Plonik L31, Plonik L61, Plonik L62, ProLogis Nick 10R5, Pluron 17R2, Pluronic 25R2 and Tetronic 304, Tetnik 701, Tetnik 704, Tetnik 901, Tetnik 904, Tetnik 150R1 (by BASF ( BASF Corporation), SOLSPERS 20000 (manufactured by The Lubrizol Corporation) and the like.

A specific example of the cationic surfactant includes a phthalocyanine derivative (product name: Efka-745, by Morishita & Co., Ltd.)); an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic copolymer Pori Ful No. 75, Pori Ful No. 90 and Puri Ful No. 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.); W001 (by Yusho Co., Ltd.) Manufactured) and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by YUSHO CO., LTD.) and the like.

Examples of quinone surfactants include "Toray silicone DC3PA", "Torayone SH7PA", "Torayone DC11PA", "Torayone SH21PA", "Torayone SH28PA" "Torayone SH29PA", "Torayone SH30PA" and "Torayone SH8400" (manufactured by Dow Corning Toray Co., Ltd.); "TSF-4440" "TSF-4300", "TSF-4445", "TSF-4460" and "TSF-4452" (manufactured by Momentive Performance Materials Inc.); "KP341", "KF6001" and " KF6002" (manufactured by Shin-Etsu Silicone Co., Ltd.); "Bick 307", "Bick 323" and BYK 330 (by BYK Chemie GmbH) )) and similar.

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

The sclerosing composition may or may not contain a surfactant, but when When the composition contains a surfactant, the amount of the surfactant to be added is preferably from 0.001% by mass to 2.0% by mass, and more preferably from 0.005% by mass to 1.0% by mass based on the total mass of the curable composition.

[Other additives]

In order to improve the physical properties of the cured film, known additives such as a plasticizer and a sensitizer may be added to the curable composition.

Examples of the plasticizer include dioctyl phthalate, di(dodecyl phthalate), triethylene glycol dicaprylate, dimethylglycol phthalate. , tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triethylene glyceryl and the like, and when a binder polymer is used, the total mass of the polymerizable compound and the binder polymer A plasticizer in an amount of 10% by mass or less may be added in an amount of 10% by mass or less.

[UV absorber]

The curable composition of the present invention may contain a UV absorber. As the UV absorber, a compound represented by the following formula (I) is particularly preferable, which is a conjugated diene compound.

In the formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² may each other The same or different, but never differently represents a hydrogen atom.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, a n-butyl group, a n-hexyl group, a cyclohexyl group, a n-decyl group, an n-dodecyl group, N-octadecyl, eicosyl, methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N,N-diethylaminopropyl, cyanide Ethyl ethyl, phenethyl, benzyl, p-tert-butylphenethyl, p-t-octylphenoxyethyl, 3-(2,4-di-t-pentylphenoxy)propyl , ethoxycarbonylmethyl, 2-(2-hydroxyethoxy)ethyl, 2-furylethyl and the like, and methyl, ethyl, propyl, n-butyl and n-hexyl are good.

The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a halogen atom, and an anthracene. Amino group, mercapto group, alkylthio group, arylthio group, hydroxyl group, cyano group, alkoxycarbonyl group, aryloxycarbonyl group, substituted amine carbenyl group, substituted amine sulfonyl group, nitro group, Substituted amine groups, alkylsulfonyl groups, arylsulfonyl groups and the like.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a monocyclic or condensed cyclic ring, and may be any of a substituted aryl group having a substituent and an unsubstituted aryl group. By. Examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, an acenabutenyl group, a fluorenyl group, and the like. Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a halogen atom, a mercaptoamine group, a mercapto group, an alkylthio group, an arylthio group. , hydroxy, cyano, alkoxycarbonyl, aryloxycarbonyl, substituted amine carbenyl, substituted sulfonyl, nitro, substituted amine, alkyl sulfonyl, aryl sulfonate Sulfhydryl and similar groups. Among them, a substituted or unsubstituted phenyl group, a 1-naphthyl group and a 2-naphthyl group are preferred.

R ¹ and R ² may form a cyclic amine group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amine group include piperidinyl, morpholinyl, pyrrolidinyl, hexahydroindenyl, piperazinyl and the like.

Wherein R ¹ and R ^{2 are} each preferably a lower alkyl group having 1 to 8 carbon atoms (e.g., methyl, ethyl, isopropyl, butyl, t-butyl, t-butyl, pentyl) , a third amyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a third octyl group, and the like), or a substituted or unsubstituted phenyl group (eg, tolyl, phenyl, anisyl) 2,4,6-trimethylphenyl, chlorophenyl, 2,4-di-t-pentylphenyl and the like). It is also preferred that R ¹ and R ² are bonded to each other to form a ring containing a nitrogen atom represented by N in the formula (e.g., a piperidine ring, a pyrrolidine ring, a morpholine ring, and the like).

In the formula (I), R ³ and R ⁴ each represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as "σ _p value") of 0.20 to 1.0. The electron withdrawing group is preferably an electron withdrawing group having a σ _p value of 0.30 to 0.8.

Hammett's rule is an empirical rule that LP Hammett proposed in 1935 to quantitatively discuss the effects of substituents on the reaction or equilibrium of benzene derivatives, and the validity of this rule is now widely accepted. The substituent constants determined by Hammett's rule contain σ _p values and σ _m values, and these values are disclosed in many general textbooks, the details of which are described in the following documents, such as JA Dean, "Lanshi"Lange's Handbook of Chemistry, 12th edition, 1979 (Mc Graw-Hill) or "Realms of Chemistry", 122, p. 96-v 103, 1979 (Nankodo Co. Ltd.) and Chemical Reviews, Vol. 91, pp. 165-195, 1991. In the present invention, the values described in these textbooks and known in the literature are not intended to be limited to a particular substituent, and even if the value is not known in the literature, as long as the value is in the measurement based on the Hammett's rule The stated ranges are also expressly included in the present invention.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 to 1.0 include a mercapto group, a decyloxy group, an amine carbaryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphonium group. , diarylphosphonium, diarylphosphino, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy, decylthio, Aminesulfonyl, thiocyanate, thiocarbonyl, alkyl substituted with at least two or more than two halogen atoms, alkoxy substituted with at least two or more than two halogen atoms, at least two or An aryloxy group substituted with more than two halogen atoms, an alkylamino group substituted with at least two or more than two halogen atoms, an alkylthio group substituted with at least two or more than two halogen atoms, and a σ _p value of 0.20 Or an aryl group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group or a selenocyanate group substituted by another electron withdrawing group of more than 0.20. Among these substituents, a group capable of having a more substituent may have a substituent such as the above substituent.

Wherein each of R ³ and R ^{4 is} preferably an indenyl group, an amine carbenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfonium oxide. And an amine sulfonyl group, and particularly preferably a mercapto group, an amine mercapto group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and Aminesulfonyl.

In the above group, in the present invention, R ^{3 is} preferably a group selected from the group consisting of a cyano group, -COOR ⁵ , -CONHR ⁵ , -COR ⁵ and -SO ₂ R ⁵ , and R ^{4 is} preferably selected from the group consisting of a group of cyano, -COOR ⁶ , -CONHR ⁶ , -COR ⁶ and -SO ₂ R ⁶ . R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ⁶ have the same meanings as those of R ¹ and R ² , respectively, and have the same preferred embodiments.

R ³ and R ⁴ may be bonded to each other to form a ring.

At least one of R ¹ , R ² , R ³ and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. Copolymers formed with other monomers can be used. In the case of a copolymer, examples of other monomers include acrylic acid, α-chloroacrylic acid, α-aracrylic acid (for example, an ester derived from acrylic acid (such as methacrylic acid), preferably a lower alkane. Esters and guanamines, such as acrylamide, methacrylamide, butyl butyl decylamine, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, acrylic acid N-butyl ester, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate and lauryl methacrylate, methylenebis acrylamide and the like), vinyl ester (such as vinyl acetate, propionic acid) Vinyl ester, vinyl laurate and the like), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (such as styrene and its derivatives, such as vinyl toluene, divinylbenzene, vinyl acetophenone, Sulfostyrene, styrene sulfinic acid and the like), itaconic acid, citraconic acid, crotonic acid, dichlorovinylidene, vinyl alkyl ether (eg vinyl ether and the like) , maleic acid ester, N-vinyl-2-pyrrole One, N- vinylpyridine, 2-vinylpyridine and 4-vinylpyridine, and the like.

Among them, acrylates, methacrylates, and aromatic vinyl compounds are particularly preferred.

Two or more than two other monomer compounds may be used in combination. For example, n-butyl acrylate and divinyl benzene, styrene and methyl methacrylate, methyl acrylate and methacrylic acid, and the like can be used in combination.

Preferred specific examples of the compound represented by the above formula (I) [exemplary compound (1) to compound (14)] will be explained below. However, the invention is not limited to the compounds.

The UV absorber represented by the general formula (I) can be obtained from the Japanese Patent Publication No. S44-29620, Japanese Patent Application Laid-Open No. S53-128333, No. S61-169831, No. S63-53543, No. S63-53544 and No. S63-56651, and the like, and the details of WO2009/123109 The method described is synthesized. In particular, the exemplary compound (1) can be synthesized by the method described in paragraph 0040 of the specification of WO 2009/123109.

The curable composition of the present invention may or may not contain a UV absorber, but when the composition contains a UV absorber, the content of the UV absorber is preferably from 0.1% by mass to 10% by mass based on the total solid content of the composition. More preferably, it is 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 3% by mass.

In the present invention, various UV absorbers may be used singly or in combination of two or more of them.

The curable composition of the present invention is preferably filtered by a filter to remove impurities or reduce defects. Filters and the like for filtering purposes in the related art can be used without any particular limitation. Examples thereof include filters formed of fluororesins such as polytetrafluoro ethylene (PTFE), polyamine resins (such as nylon-6 and nylon-6, 6), and polyolefin resins (including High density and ultra high molecular weight) (such as polyethylene and polypropylene (PP)). Among these materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is preferably from about 0.01 μm to 7.0 μm, preferably from about 0.01 μm to 2.5 μm, and more preferably from about 0.01 μm to 1.5 μm. By adjusting the diameter to this range, it is ensured that the removal of the dissolved pigment or the like prevents the preparation of uniform and smooth hardening in subsequent processes. Small impurities of the sexual composition.

When using a filter, other filters can be combined. At this time, the filtration of the first filter may be performed once or twice or more than twice. When other filters are combined to perform two or more filtrations, the pore size at the second filtration or after the second filtration is greater than the pore diameter at the first filtration. A first filter having a different pore size within the above range may be combined. As the aperture of this document, reference can be made to the nominal value of the filter manufacturer. As a commercially available filter, for example, Nihon Pall Corporation, Advantech Toyo Roshi Kaisha, Ltd., and Nihon Entegris, Inc. can be used. A filter selected from various filters provided by the original Nippon Microlith Co. Ltd., KITZ MICRO FILTER CORPORATION, and the like.

As the second filter, a filter formed of the same material as that of the above first filter and the like can be used. The second filter preferably has a pore size of from about 0.5 microns to 7.0 microns, preferably from about 2.5 microns to 7.0 microns and more preferably from about 4.5 microns to 6.0 microns. By setting the pore diameter within this range, impurities incorporated into the mixed liquid and hindering the preparation of a uniform and smooth hardenable composition in the subsequent process can be removed while retaining the component particles contained in the mixed liquid.

For example, filtration can be performed only on the liquid dispersion in the first filter, and a second filtration can be performed after mixing the other components.

[Method of Manufacturing Transparent Film]

The method for producing a transparent film of the present invention comprises a spray method, a roll coat method, a spin coating method, a bar coating method, and the like. A similar method of coating the above-described hardenable composition on a wafer; a subsequent first heating process; and a subsequent second heating process performed at a temperature higher than the heating temperature.

The conditions in the first heating process are the same as those described in the (I) process in the following manufacturing method of the microlens as the prebaking conditions.

The conditions in the second heating process are the same as those described in the (IV) process in the following microlens manufacturing method as post-baking conditions.

<microlens>

The curable composition of the present invention can form a transparent film having a high refractive index and a high transmittance, and thus can be extremely suitable for forming, for example, a microlens and a microlens array.

That is, the curable composition of the present invention is preferably used to form a microlens.

The present invention also relates to a microlens formed by using a transparent film formed by using the curable composition of the present invention.

[Method of forming microlens]

As a method of producing a microlens by using the curable composition of the present invention, a usual method can be applied without any particular limitation, and an example thereof includes a process further including post-baking the above transparent film to form a transparent film. And manufacturing methods including dry etching processes and the like.

The process of post-baking the transparent film to form the transparent film is the same as the process described in detail below in the process of (f).

The dry etching process is the same as the process described in detail below for the (g) process.

As a method for manufacturing a microlens by using the curable composition of the present invention In a preferred aspect of the method, examples thereof include a manufacturing method including at least the following (I) to (IV) processes.

(I) Process for forming a coating film of the curable composition of the present invention on a substrate

(II) a process for irradiating radiation on at least a portion of a coating film

(III) Process for developing the coating film after irradiation

(IV) Process for heating the coating film after development

These processes will be described below.

(I) Process

In this process, the curable composition is preferably applied as a liquid composition on the surface of the substrate, and prebaked to remove the solvent to form a coating film on the substrate.

Examples of the substrate include a glass substrate, a germanium wafer, a substrate on which various metal layers are formed, a substrate on which a color filter (a wafer for an image sensor) is applied, and the like.

The coating method is not particularly limited, and a suitable method such as a spray method, a roll coating method, a spin coating method, and a bar coating method may be employed.

The prebaking conditions may vary depending on the kind or amount of each component, but are usually from 60 ° C to 120 ° C for about 30 seconds to 15 minutes. The film thickness of the formed coating film is a value after prebaking, and is preferably from about 0.5 μm to 20 μm.

(II) Process

In this process, radiation is irradiated on at least a portion of the formed coating film.

When radiation is irradiated only on a certain portion of the coating film, the radiation is irradiated through a mask having a predetermined pattern.

As the radiation for irradiation, ultraviolet rays such as g rays and i rays; far ultraviolet rays such as KrF excimer laser and ArF excimer laser; X-rays such as synchrotron radiation; charged particle radiation such as electron radiation, but among them may be used. UV is best.

The exposure amount can be appropriately selected depending on the constitution of the curable composition and the like, but is preferably 50 mJ/cm 2 to 2,000 mJ/cm 2 .

(III) Process

In this process, the exposed coating film is developed from a developing solution, preferably an alkaline developing solution, and a pattern having a predetermined shape is formed by removing unirradiated portions of the radiation.

Examples of the alkaline developing solution include an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol. , di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5 4,0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene and the like. A water-soluble organic solvent such as methanol and ethanol, a surfactant or various organic solvents may be added to the alkaline developing solution and used.

As the developing method, a suitable method such as an adhesion method, a dipping method, a rocking immersion method, and a showering method can be employed. At the same time, developing in an alkaline developing solution Thereafter, the coating film is generally washed by, for example, running water.

The development time varies depending on the composition of the photosensitive resin composition and the composition of the developing solution, but is usually about 30 seconds to 120 seconds at room temperature.

(IV) Process

In this process, the coating film is hardened by heating (post-baking) the developed coating film using a heating device such as a hot plate and an oven.

In the post-baking, the heating temperature is usually from 120 ° C to 250 ° C, and preferably from 160 ° C to 230 ° C. The heating time may vary depending on the heating mode, but when heating is performed on the hot plate, the heating time is usually about 5 minutes to 30 minutes, and when heating is performed in the oven, the heating time is usually about 30 minutes to 90 minutes.

In the post-baking, a step-by-step baking method comprising performing two or more heat treatments may be employed.

As another preferred aspect of the method of producing a microlens by using the curable composition of the present invention, examples thereof include a formation method including at least the following processes (a) to (g).

(a) Process for forming a coating film on a substrate (such as a color filter) by using the curable composition of the present invention

(b) performing the process of at least one of heating the coating film to dry (or dry and harden) the coating film, or by means of a light source (g-ray, i-ray, and the like) having an appropriate wavelength Exposing the above coating film to harden the coating film, thereby obtaining a high refractive index film (transparent film)

(c) a process of forming a resist coating film on a high refractive index film after heating

(d) by using a light source of appropriate wavelength (g-ray, i-ray and a process similar to ray) for exposing a resist coating film

(e) a process for developing a resist coating film after exposure to form a resist pattern

(f) Process for forming a resist pattern into a lens type by means of post-heating

(g) a process of removing a resist pattern and a portion of a high refractive index film by dry etching to form a high refractive index film into a lens type

These processes will be described below.

- (a) Process -

In this process, the curable composition of the present invention is applied onto a substrate such as a color filter to form a coating film.

Examples of the coating method include the method in Process (I).

- (b) Process -

In this process, a preferred embodiment of the heated coating film may comprise a two-step heat treatment of prebaking and postbaking.

The prebaking conditions may vary depending on the kind or amount of each component, but are usually from 60 ° C to 120 ° C for about 30 seconds to 15 minutes. The film thickness of the formed coating film is a value after prebaking, and is preferably from about 0.5 μm to 20 μm. The prebaking process may be omitted in some cases.

Subsequently, the coating film is hardened by heating (post-baking) the coating film using a heating device such as a hot plate and an oven. The post-baking conditions are typically from about 120 to 300 ° C for about 30 seconds to 60 minutes. At the same time, hardening can be promoted by performing exposure before the post-baking process.

When the above coating film is hardened by exposure to a light source (g-ray, i-ray, and the like) having an appropriate wavelength, the same process as in the process (II) The type of radiation and the amount of exposure can be applied to radiation for irradiation.

- (c) Process -

In the process, a resist coating film is formed on the high refractive index film. As the resist, a general commercially available resist which can be patterned by ultraviolet exposure can be used. For the resist coating film, (a) prebaking in the process is performed.

- (d) Process -

In this process, the coating film is exposed to a pattern by using a mask. The radiation type and exposure amount which are the same as the process (II) can be applied to the radiation for irradiation.

- (e) Process -

In this process, the exposed resist coating film is developed by a developing solution (preferably an alkaline developing solution), and a pattern having a predetermined shape is formed by removing the unirradiated portion or the irradiated portion of the radiation.

An example of the alkaline developing solution contains the alkaline developing solution in the process (III).

Examples of the development method include the method described above in relation to Process (III).

The development time is the same as described in the above process (III).

- (f) Process -

In this process, post-heating (post-baking) is performed by a heating means such as a hot plate and an oven to form the resist into a lens type after patterning. The post-baking conditions are typically from about 120 to 300 ° C for about 30 seconds to 60 minutes. In order to form into a lens type, a step-by-step baking method including performing two or more heat treatments may also be employed.

- (g) process -

Dry etching can be performed by a known method (for example, Japanese Patent Application Laid-Open No. 2010-204154).

In this way, the desired microlens can be fabricated.

According to the method of the present invention for manufacturing a microlens, a high definition microlens and microlens array having excellent characteristics such as high refractive index and high transmittance can be simply formed with high product yield.

The microlens of the invention is formed by the curable composition of the invention and has excellent balance of characteristics, and can be extremely suitable for liquid crystal display devices of various OA equipment, liquid crystal televisions, portable telephones, projectors and the like; color filter on the wafer Imaging optics for light sheets, such as fax, electronic photocopiers, solid state image sensing devices, and the like; fiber optic connectors and the like.

<Solid Image Sensing Device>

The solid-state image sensing device of the present invention comprises a microlens formed by using the above-described curable composition of the present invention.

The solid-state image sensing device of the present invention comprises a microlens having a high refractive index and a high transmittance, and thereby reduces noise and exhibits excellent color reproducibility.

The solid-state image sensing device of the present invention is not particularly limited as long as the composition of the device includes a microlens formed by using the curable composition of the present invention and the configuration of the device can serve as a solid-state sensing device, and Examples include a light receiving device composed of a plurality of photodiodes, polysilicon, and the like constituting a light receiving region of a solid-state image sensing device (CCD image sensor, CMOS image sensor, and the like) Placed on the substrate; the microlens is composed of a color filter and the like.

The method of the present invention for manufacturing a solid-state image sensing device is not particularly limited, but as a preferred aspect, the method is included on a substrate having at least a photodiode, a light shielding film, and a protective film of the solid-state image sensing device. a process of forming a red pixel, a blue pixel, and a green pixel; a process of applying the hardenable composition and performing heating; a process of forming a resist pattern; forming a resist pattern formed by performing a post-baking process A process of a lens shape; and a process of performing dry etching.

Coating a hardenable composition and performing a heating process to form a coating film on the substrate in the (a) process and the (b) process of the above microlens manufacturing method, and heating the coating film to form a coating film The drying (or drying and hardening) process is performed in the same manner.

The process of forming the resist pattern is performed in the same manner as the (d) process and the (e) process in the above-described microlens manufacturing method.

The process of forming the resist pattern formed by performing the post-baking process into a lens shape is performed in the same manner as the (f) process in the above-described microlens manufacturing method.

The process of performing the dry etching is performed in the same manner as the (g) process in the above-described manufacturing method of the microlens.

Instance

The invention will be specifically described below with reference to examples, but the invention is not limited to the examples. At the same time, "parts" and "%" are by mass unless otherwise specified.

In the examples, the acid value and the amine value are determined by a potentio-metric method (solvent: tetrahydrofuran/water = 100/10 (volume ratio), The titration solution was measured by 0.01 equivalent of aqueous sodium hydroxide solution (acid value) and 0.01 equivalent of hydrochloric acid (amine value).

(Synthesis Example 1) Synthesis of Polyester (i-1)

6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed and heated at 160 ° C for 8 hours, followed by cooling to room temperature to obtain a polyester (i-1).

The process is shown below.

(Synthesis Example 2 to Synthesis Example 15)

(i-2) to (i-10) and in the same manner as in Synthesis Example 1, except that the carboxylic acid and the lactone in Synthesis Example 1 were changed as shown in Table 1 and the feed volume of the carboxylic acid was changed. (i-15) to (i-19) polyester. The number average molecular weight and the weight average molecular weight of these resins obtained in the synthesis examples were measured by the GPC method described above. The results are shown in Table 1 below. The number of atoms calculated from each polyester and the number of units of repeating units derived from the lactone calculated from the raw material feed ratio are shown in Table 1 below.

(Synthesis Example 16) Synthetic polyester (i-11)

Mix 100 grams of 12-hydroxystearic acid, 0.1 gram IV under a stream of nitrogen Titanium (IV) butoxide and 300 g of xylene were reacted with each other while water produced at an external temperature of 160 ° C was distilled off with a Dean-Stark tube. The heating was stopped when the number average molecular weight and the weight average molecular weight measured by GPC were 8,000 and 12,000, respectively, to obtain a polyester (i-11).

(Synthesis Example 17) Synthesis of Polyester (i-12)

The experiment was carried out in the same manner as in Synthesis Example 16, and heating was stopped when the number average molecular weight and the weight average molecular weight measured by GPC were 6,000 and 11,000, respectively, to obtain a polyester (i-12).

(Synthesis Example 18) Synthetic polyester (i-13)

307 g of adipic acid, 110 g of neopentyl glycol, 57 g of 1,4-butanediol and 26 g of ethylene glycol were reacted with each other under a nitrogen stream while distilling at 160 ° C with a Dean-Stark tube. Water produced at external temperatures. The reaction was stopped when the number average molecular weight and the weight average molecular weight measured by GPC were 8,000 and 13,000, respectively, to obtain a polyester (i-13).

(Synthesis Example 19) Synthesis of macromonomer (i-14)

50 grams (500 millimoles) of methyl methacrylate, 100 grams of propylene glycol monomethyl ether, and 2.5 grams (23.6 millimoles) of 2-mercaptopropionic acid were heated to 80 ° C under a stream of nitrogen. Subsequently, 0.1 g of V-601 (azobis(isobutyrate) dimethyl) (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and 0.1 was added thereto after 3 hours. Gram V-601 and heated for 4 hours. Thereafter, 3.35 g (23.6 mmol) of glycidyl methacrylate and 0.5 g of tetrabutylammonium bromide were added thereto and heated at 80 ° C for 5 hours. After cooling, use 200 ml of water It was reprecipitated with a mixed solvent of 800 ml of methanol, followed by drying to obtain 55 g of a macromonomer (i-14).

(Synthesis Example 20) [Synthetic Resin (J-1)]

10 g of polyethylenimine (SP-018, number average molecular weight 1,800, manufactured by Nippon SHOKUBAI CO., LTD.) and 100 g of polyester as Y precursor y were mixed (i -1) and heating at 120 ° C for 3 hours to obtain an intermediate (J-1B). Thereafter, the intermediate was cooled to 65 ° C and stirred for 2 hours while slowly adding 200 g of propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as PGMEA in some cases) containing 2.3 g of anhydrous succinic acid was slowly added thereto. (as X before the body x). Thereafter, PGMEA was added thereto to obtain a PGMEA solution of the resin (J-1) in an amount of 10% by mass. The resin (J-1) contains a group derived from a side chain of the polyester (i-1) and an anhydrous succinic acid-derived functional group (carboxyl group) having a pKa of 14 or less.

The synthesis process is shown below.

The acid value titration of the intermediate (J-1 B) was carried out, thereby confirming that the acid value was 6.4 mgKOH/g. The amine value titration and acid titration of the resin (J-1) were carried out, whereby the acid value was found to be 17.9 mg KOH/g and the amine value was 46.2 mgKOH/g. That is, the molar % corresponding to the repeating unit of the formula (J-1) can be calculated from the difference between the acid value of the resin (J-1) and the acid value of the intermediate (J-1B), (l ₁ + l ₂ ) (=mol % corresponding to the repeating unit of the formula (I-2)) can be calculated from the difference between the amine value of the resin (J-1) and the number of nitrogen atoms of the resin before the reaction, and (m ₁ +m ₂ ) (=% of the molar corresponding to the repeating unit of the formula (I-3)) can be calculated from the acid value of the intermediate (J-1B). The results show k/(l ₁ +l ₂ )/(m ₁ +m ₂ )/n=10/50/5/35.

That is, it is known that it is a resin containing 10 mol% of a repeating unit in which X is -COCH ₂ CO ₂ H in the repeating unit represented by the general formula (I-1), and contains 50 mol. The amount of % in the repeating unit represented by the formula (I-2) is a repeating unit of poly(ε-caprolactone). The weight average molecular weight measured by the GPC method was 15,000.

(Synthesis Example 21 to Synthesis Example 32 and Synthesis Example 47 to Synthesis Example 52)

[Synthesis Resin (J-2) to Resin (J-13) and Resin (J-28) to Resin (J-33)]

The synthesis was carried out in the same manner as in Synthesis Example 20 except that the amine group-containing resin, the X precursor x, and the polyesters obtained in Synthesis Example 1 to Synthesis Example 18 as described in Tables 2 to 4 were used. A PMEEA solution of the resin (J-2) to the resin (J-13) and the resin (J-28) to the resin (J-33) in an amount of 10% by mass. For resin (J-13), use water to make the opposite The solution was reprecipitated and dried to obtain a PGMEA solution of a resin (J-13) in an amount of 10% by mass, thereby using it.

The amine group-containing resin used in the synthesis is as follows.

SP-003 (polyethylenimine (manufactured by NIPPON SHOKUBAI CO., LTD.), number average molecular weight 300)

SP-006 (manufactured by NIPPON SHOKUBAI CO., LTD.), number average molecular weight 600)

SP-012 (manufactured by NIPPON SHOKUBAI CO., LTD.), number average molecular weight 1,200)

SP-018 (manufactured by NIPPON SHOKUBAI CO., LTD.), number average molecular weight 1,800)

SP-200 (manufactured by NIPPON SHOKUBAI CO., LTD.), number average molecular weight 10,000)

(Synthesis example 33)

[Synthetic Resin (J-14)]

In a reactor equipped with a Dean-Stark tube, an aqueous solution of 100 g of polyallylamine (PAA-08, weight average molecular weight 8,000, manufactured by NIPPON SHOKUBAI CO., LTD.) was used. And 500 g of toluene was refluxed until the moisture distillation at an external temperature of 130 ° C was stopped, and then the mixture was concentrated to remove toluene. Subsequently, 100 g of the polyester (i-1) was mixed, and the resulting mixture was heated at 120 ° C for 3 hours. Thereafter, the mixture was cooled to 65 ° C, and 200 g of PGMEA containing 9.0 g of anhydrous glutaric acid (X precursor x) was slowly added thereto and stirred for 2 hours. It Thereafter, PGMEA was added thereto to obtain a PGMEA solution of a resin (J-14) in an amount of 10% by mass.

(Synthesis Example 34 to Synthesis Example 45 and Synthesis Example 53 to Synthesis Example 56)

[Synthesis Resin (J-15) to Resin (J-26) and Resin (J-34) to Resin (J-37)]

The synthesis was carried out in the same manner as in Synthesis Example 33 except that the amine group-containing resin, the X precursor x, and the polyesters obtained in Synthesis Example 1 to Synthesis Example 18 as described in Tables 2 to 4 were used. A PMEEA solution of the resin (J-15) to the resin (J-26) and the resin (J-34) to the resin (J-37) in an amount of 10% by mass.

The amine group-containing resin used in the synthesis is as follows.

PAA-01 (polyallylamine (manufactured by Nitto Boseki Co., Ltd.), weight average molecular weight 1,000)

PAA-03 (polyallylamine (manufactured by Nitto Boseki Co., Ltd.), weight average molecular weight 3,000)

PAA-05 (polyallylamine (manufactured by Nitto Boseki Co., Ltd.), weight average molecular weight 5,000)

PAA-08 (polyallylamine (manufactured by Nitto Boseki Co., Ltd.), weight average molecular weight 8,000)

PAA-15 (polyallylamine (manufactured by Nitto Boseki Co., Ltd.), weight average molecular weight 15,000)

(Synthesis example 46)

[Synthetic Resin (J-27)]

0.50 g (3.5 mmol) monomer (B), 55 g (23 mmol) macromonomer (i-14), 1.50 g (9.6 mmol) methacrylic acid 2-(N, N -Dimethylaminoethyl) ester and 0.2 g (1.0 mmol) of dodecanethiol were dissolved in a mixed solvent of 200 g of dimethyl hydrazine and 100 g of N-methylpyrrolidone. After heating the mixture to 80 ° C, 0.1 g of V-601 was added and stirred for 3 hours. Thereafter, 0.1 g of V-601 was added thereto, stirred for 3 hours, and then allowed to cool. The resulting solution was added dropwise to 4,000 liters of water over 1 hour, and the precipitated resin was collected by filtration. After drying, the resin was dissolved in 1-methoxy-2-propanol to obtain a solution in an amount of 10% by mass.

The synthesis process is shown below.

(measuring acid value and amine value)

The acid value and the amine value of the obtained resin (J-1) to the resin (J-37) were measured by the above method. The results are entered together in Tables 2 to 4.

From these measurements, it can be determined from the acid value of the intermediate and the acid value of the target resin and the like that the side chain has a pKa of 14 or less. Functional group.

<Example 1>

[Preparation of titanium dioxide liquid dispersion (dispersion composition)]

By using ULTRA APEX MILL (manufactured by KOTOBUKI INDUSTRIES Co., Ltd.) as a loop type dispersing device (bead mill), the following composition was used in the following manner. The mixed liquid is subjected to dispersion treatment to obtain a titanium dioxide liquid dispersion as a dispersion composition.

-composition-

. Titanium dioxide (manufactured by ISHIHARA SANGYO KAISHA, LTD., TTO-51 (C)) (purity: 75% or more): 150 parts

. Specific resin J-1: 40.5 parts

. Propylene glycol monomethyl ether acetate: 462 parts

The dispersing device was operated under the following conditions.

. Bead diameter: φ0.05 mm

. Bead filling rate: 75% by volume

. Circumferential speed: 8 meters / sec

. Pump supply: 10 kg / hour

. Cooling water: tap water

. The internal volume of the bead mill annular passage: 0.15 liter

. Amount of mixed liquid used for dispersion treatment: 0.44 kg

After the dispersion was started, the average particle diameter was measured at intervals of 30 minutes (time of one pass).

The average particle size decreases with the dispersion time (operation number of passes), but the amount of change gradually decreases. The dispersion was terminated when the change in the primary particle diameter became 5 nm or less at a time when the dispersion time was increased by 30 minutes. At the same time, the primary particle diameter of the titanium dioxide particles in the liquid dispersion was 40 nm.

The viscosity at this time was measured to evaluate the dispersibility, and the viscosity change of the dispersion after one month was measured to evaluate the dispersion stability (storage temperature 25 ° C).

When the viscosity is 15 mPa. Seconds or less than 15 mPa. In seconds, the dispersion is excellent, and when the viscosity is greater than 15 mPa. In the second case, the dispersion is deteriorated.

The dispersion stability was evaluated according to the following evaluation criteria.

The viscosity change of the dispersion after 1 month is within ±10%: A

The viscosity change of the dispersion after 1 month is greater than ±10% and less than or equal to ±20%: B

The viscosity change of the dispersion after 1 month is greater than ±20%: C

Viscosity measurement was also performed on the dispersion composition corresponding to the compositions of Examples 2 to 37 and Comparative Example 1 and Comparative Example 2 described below (prepared based on the dispersion composition in Example 1) to evaluate dispersibility, and amount The viscosity change of the dispersion after one month was measured to evaluate the dispersion stability (storage temperature 25 ° C), wherein the content of titanium dioxide and the kind of the specific resin were changed as shown in Table 5 below, so that the dispersed composition corresponded to Examples 2 to 37 and compared. The compositions in Example 1 and Comparative Example 2 were as follows. The results are shown in Table 5.

Meanwhile, the primary particle diameter of titanium dioxide in the present example refers to a dilute solution amount obtained by diluting a mixed solution containing titanium oxide or a liquid dispersion by 80-folding with propylene glycol monomethyl ether acetate by using a dynamic light scattering method. Measure the value obtained.

This measurement was calculated by using a number average particle diameter obtained by performing measurement using a Maxim UPA-EX150 (manufactured by NIKKISO Co., Ltd.).

[Preparation of hardenable composition]

The titanium dioxide liquid dispersion (dispersion composition) obtained above was used and the components were mixed with each other to have the following composition, thereby obtaining a hardenable composition.

- the composition of the hardening composition -

(The following M-1; weight average molecular weight (Mw) and copolymerization ratio (mole ratio) are as follows)

(manufacturing transparent film)

The curable composition obtained above was coated on a 12-inch wafer by spin coating, and then heated at 100 ° C for 2 minutes on a hot plate to obtain a coating film having a film thickness of 1.05 μm. The coating film was heated on a hot plate at 200 ° C for 5 minutes to obtain a cured film (film thickness: 1.0 μm) as a transparent film.

[Measure the refractive index of transparent film]

For the substrate obtained above, the transparency was measured by using an ellipsometer (manufactured by J.A. Woollam JAPAN Co., Ltd.) The refractive index of the pattern versus light having a wavelength of 500 nm. The light transmittance of the transparent film in the entire wavelength region of 400 nm to 700 nm was measured by using the MCPD series (manufactured by Otsuka Electronics Co., Ltd.).

The results are each shown in Table 5 below.

[Measurement of film thickness difference between the center portion and the peripheral portion of the wafer]

For the wafer substrate on which the above-obtained transparent film was formed, Dekrak (manufactured by Veeco Instruments Inc.) was used to measure the thickness of the transparent film at the center portion of the wafer and the self-crystal The difference between the thickness of the transparent film which is recessed by 3 cm in the direction from the peripheral portion of the circle to the central portion of the wafer. Numerical results are shown in Table 5 below.

<Example 2 to Example 37 and Comparative Example 1 and Comparative Example 2>

Example 2 to Example 37 and Comparative Example 1 were prepared according to Example 1 except that the content of titanium dioxide (based on the total solid content of the hardenable composition) and the specific resin and polymerization initiator were changed as shown in Table 5 below. The hardenable composition of Example 2.

That is, in the example in which the specific resin was changed from J-1 used in Example 1, the titanium oxide liquid dispersion obtained by substituting J-1 using the specific resin shown in Table 5 was used for the preparation of Example 1. Titanium dioxide liquid dispersion.

Meanwhile, in Comparative Example 1 and Comparative Example 2, Sospers 5000 (manufactured by The Lubrizol Corporation) and Desbike 180 (by BYK Chemical Co., Ltd. (BYK) were respectively used. Manufactured by Chemie GmbH) as a resin different from the specific resin of the present invention.

In the example in which the polymerization initiator was changed from the compound K-1 used in Example 1, the polymerization initiator of the substitution compound K-1 shown in Table 5 was used for the preparation of the hardenable composition used in Example 1.

The change in the titanium dioxide content (concentration) (based on the total solid content of the hardenable composition) is performed in the following manner: in the total amount of titanium dioxide and the binder (based on the total solid content of the hardenable composition) is controlled in Example 1. At the same time, increase or decrease the content of titanium dioxide and increase or decrease the content of the binder polymer.

Each of the transparent films was produced in the same manner as in Example 1 using the obtained curable composition, and then evaluated in the same manner as in Example 1. The results are shown in Table 5.

As is apparent from Table 5, the dispersion compositions of Comparative Example 1 and Comparative Example 2 which did not use a specific resin had high viscosity, dispersibility was deteriorated, and dispersion stability was also deteriorated.

At the same time, it can be seen that the dispersion composition using the specific resin of the present invention in Examples 1 to 37 has a low viscosity, whereby the dispersibility is excellent and the dispersion stability is also excellent.

It can be seen that the hardenable composition of Comparative Example 1 and Comparative Example 2 which does not use a specific resin has a large film thickness difference between the central portion and the peripheral portion of the wafer.

At the same time, it can be seen that the hardenable composition using the specific resin of the present invention in Examples 1 to 37 is in the central portion and the peripheral portion of the wafer. There is a small difference in film thickness between.

It can be seen that the transparent film formed by using the curable composition of Comparative Example 1 and Comparative Example 2 which does not use a specific resin has low transmittance and refractive index.

At the same time, it can be seen that the transparent film formed by using the hardenable composition using the specific resin of the present invention in Examples 1 to 37 has high transmittance and refractive index.

Although the above example describes an example of forming a transparent film on a germanium wafer, in the case of manufacturing a solid-state image sensing device, only the germanium wafer can be turned into a solid-state image sensing device to form a photodiode thereon, A substrate of a light shielding film, a device protective film, and the like.

Forming a light-shielding film formed of tungsten on a germanium wafer having a photodiode, wherein only a light-receiving portion of the photodiode is opened, and a transfer electrode is formed thereon, and a device protective layer formed of tantalum nitride is formed In order to cover the entire surface of the formed light-shielding film and the photoreceptor light-receiving portion (the open portion in the light-shielding film).

Subsequently, red pixels each having a side length of 1.4 μm, blue pixels, and the like are formed on the formed protective layer of the device by the method described in Example 16 of the Official Gazette of Japanese Patent Application Laid-Open No. 2010-210702 A. Green pixels, followed by preparation of color filters.

The hardenable composition in the example controlled as described above was applied thereon to have a film thickness of 1.5 μm, heated at 100 ° C for 2 minutes by using a hot plate, and then by using a hot plate at 200 ° C The film was allowed to harden by heating for 5 minutes.

HPR-204ESZ-9-5 (mPa.s) was applied thereto (resist liquid, manufactured by FUJIFILM Electronic Materials Co., Ltd.), and then by using a hot plate, Heat at 90 ° C for 1 minute. The coating film was made of 100 mJ by an i-ray stepper (product name: FPA-3000i5+, manufactured by Canon Inc.) via a mask having a plurality of square patterns having a side length of 1.4 μm. / square centimeter exposure. Here, the mask is disposed such that the plurality of square patterns in the mask respectively have positions corresponding to the red, blue, and green pixels in the color filter.

The film was subjected to liquid-coat development using an alkaline developing solution HPRD-429E (manufactured by FUJIFILM Electronic Materials Co., Ltd.) at room temperature for 60 seconds, followed by spin-spraying with pure water. Rinse for 20 seconds. Thereafter, the film was further washed with pure water, and then the substrate was dried under high-speed rotation to form a resist pattern. The film was post-baked on a hot plate at 200 ° C for 300 seconds to shape the resist into a lens shape.

The substrate thus obtained was subjected to dry etching treatment by using a dry etching apparatus (U-621 manufactured by Hitachi High-Technologies Corporation) under the following conditions, and then the present invention having a high refractive index was processed. A transparent film is used as a microlens.

. RF power: 800 watts

. Antenna bias: 100 watts

. Wafer bias: 500 watts

. Pressure inside the chamber: 0.5 Pa

. Substrate temperature: 50 ° C

. Type and flow rate of mixed gas: CF ₄ /C ₄ F ₆ /O ₂ /Ar=175/25/50/200 ml/min

. Photoresist etching rate: 140 nm / min

Good images are obtained when images are taken using the obtained device.

Industrial utilization

According to the present invention, it is possible to provide a dispersion composition having excellent dispersibility and dispersion stability and having high refractive index and light transmittance when formed into a curable composition, even if the curable composition is in a large-sized wafer A film having a small film thickness difference between a central portion and a peripheral portion can also be formed when the composition is coated; and a curable composition; a transparent film; a microlens and a solid-state image sensing device using the same; and a method for producing a transparent film a method of manufacturing a microlens; and a method of manufacturing a solid-state image sensing device.

The present application is based on Japanese Patent Application No. JP 2011-111735, filed on May 18, 2011, and No. JP 2012-113719, filed on May 17, 2012, the entire contents of The detailed description is generally incorporated herein by reference.

Claims (17)

A dispersion composition comprising: a colorless or transparent metal oxide particle (A) having a primary particle diameter of from 1 nm to 100 nm; a resin (B1), wherein the repeating unit of the resin (B1) contains a group X, The group X has a functional group having a pKa of 14 or less, and the side chain of the resin (B1) has an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000, and the resin (B1) ) also contains a basic nitrogen atom; and a solvent (C). The dispersion composition according to claim 1, wherein the resin (B1) is a resin (B2), and the repeating unit of the resin (B2) is bonded to a functional group having a pKa of 14 or less The nitrogen atom of the group X, and the side chain of the resin (B2) has an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000. The dispersion composition according to claim 1, wherein the dispersion composition comprises: the colorless or transparent metal oxide particles (A) having a primary particle diameter of from 1 nm to 100 nm, and a resin ( B) having (i) at least one repeating unit containing a nitrogen atom selected from the group consisting of a poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, and a second a toluenediamine-epichlorohydrin polycondensate repeating unit and a polyvinylamine-based repeating unit, wherein the repeating unit contains a group X having a functional group having a pKa of 14 or less and the group X is bonded to The nitrogen atom, and (ii) the original in its side chain The oligomer chain of 40 to 10,000 or the polymer chain Y, and the solvent (C). The dispersion composition according to any one of claims 1 to 3, wherein the group X has a pKa of 14 or less, and the functional group is a carboxylic acid, a sulfonic acid or a -COCH. ₂ CO-. The dispersion composition according to claim 3, wherein the resin (B) is a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2) Resin: In the above formula (I-1) and the formula (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group, and a each independently represents an integer of 1 to 5. , * represents a linking moiety between the repeating units, X represents a group having a functional group having a pKa of 14 or less, and Y represents an oligomer chain or a polymer chain having an atomic number of 40 to 10,000. The dispersion composition according to claim 3, wherein the resin (B) is a repeating unit represented by the following formula (II-1) and a repeating unit represented by the formula (II-2) Resin: In the above formula (II-1) and the formula (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and * represents the above. The linking moiety between the repeating units, X represents a group having a functional group having a pKa of 14 or less, and Y represents an oligomer chain or a polymer chain having an atomic number of 40 to 10,000. The dispersion composition according to any one of claims 1 to 3, wherein the oligomer chain or polymer chain Y having an atomic number of 40 to 10,000 has the following formula (III-1) The structure of the representation: In the above formula (III-1), Z is a polymer or oligomer having a polyester chain as a partial structure, and represents a shift from a polyester having a free carboxylic acid represented by the following general formula (IV) Residues other than carboxyl groups: In the above formula (IV), Z is the same as Z in the above formula (III-1). A sturdy composition, comprising: the dispersion composition according to any one of claims 1 to 3, wherein the dispersion composition further contains a polymerizable compound (D) and a polymerization initiator ( E). Such as the sclerosing composition described in claim 8 of the patent scope, Includes: binder polymer. The sclerosing composition according to claim 8, wherein the polymerization initiator (E) is a quinone polymerization initiator. The sclerosing composition of claim 8, which is used to form a microlens. A transparent film formed by using the curable composition as described in claim 8 of the patent application. A microlens formed by using a transparent film as described in claim 12 of the patent application. A solid-state image sensing device comprising: the microlens according to claim 13 of the patent application. A method for producing a transparent film, comprising: coating a process of applying a curable composition as described in claim 8 on a wafer, heating a subsequent first heating process of the composition, and higher than the first The temperature of the temperature of the heating process heats the subsequent second heating process of the composition. A method for producing a microlens, comprising: a process of post-baking a transparent film according to claim 12 of the patent application to form the transparent film, and a process of dry etching the transparent film. A method for manufacturing a solid-state image sensing device, comprising: a solid state having at least a photodiode, a light shielding film, and a protective film of the device a process of forming a red pixel, a blue pixel, and a green pixel on a substrate of the image sensing device, coating a hardenable composition as described in claim 8 and performing a heating process to form a resist pattern process, The process of forming the formed resist pattern into a lens shape by performing a post-baking process, and performing a dry etching process.