JP2019203932A - Photosensitive resin composition, cured product, image display device and illumination - Google Patents

Abstract

To provide a photosensitive resin composition having a high refractive index and an excellent flattening ability.SOLUTION: The photosensitive resin composition of the present invention comprises (A) metal oxide particles, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable monomer, (E) a photopolymerization initiator and (F) a solvent, in which the (A) metal oxide particles comprise at least one type selected from a group consisting of zirconium dioxide particles, titanium dioxide particles and barium titanate particles; a content percentage of the (A) metal oxide particles is 50 mass% or more in the whole solid content; and the (F) solvent comprises a high boiling point solvent having a boiling point of 170°C or higher at 1013.25 hPa.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a cured product, an image display device, and illumination.

2. Description of the Related Art Conventionally, there has been reported a technique for increasing the light extraction efficiency from a light emitting element using a cured product having a high refractive index in an image display device or illumination including the light emitting element (see, for example, Patent Documents 1 and 2).
As a method for producing a fine cured product having a high refractive index, it is generally known to use a negative photosensitive resin composition containing specific metal oxide fine particles. For example, Patent Document 3 describes a method of forming a cured product having a refractive index of about 1.6 using specific metal oxide fine particles, a specific resin, and a specific polyfunctional monomer. .

On the other hand, when the cured product is used as a protective film, it may be required to have the ability to flatten the unevenness of the lower structure to be protected. For example, Patent Document 4 describes a technique for improving flatness by using a high boiling point solvent.
In recent years, development of a protective film having a high refractive index is desired from the viewpoint of production cost.

Japanese Patent Laid-Open No. 10-65220 JP 2006-12826 A JP 2014-160228 A JP 2017-186550 A

In recent years, there has been a demand for higher luminance of display devices, and it is necessary to increase the refractive index in order to further increase the light extraction efficiency from the light emitting element, and the content ratio of metal oxide particles must be increased. . As a result of studies by the present inventors, it has been found that when the content ratio of the metal oxide particles is increased, the flatness of the obtained cured film is deteriorated and it is difficult to use it as a protective film.
The photosensitive resin described in Patent Document 3 has a low refractive index and is insufficient to increase the light extraction efficiency, and the curable resin composition described in Patent Document 4 contains metal oxide particles. Since it does not contain, the refractive index is insufficient.

  Therefore, an object of the present invention is to provide a photosensitive resin composition having a high refractive index and excellent planarization ability.

  As a result of intensive studies by the present inventors, it is possible to solve the above problems by including a specific solvent even when the content ratio of the specific metal oxide fine particles is increased and the refractive index is increased. The headline and the present invention were completed. That is, the gist of the present invention is as follows.

[1] Photosensitivity containing (A) metal oxide particles, (B) dispersant, (C) alkali-soluble resin, (D) photopolymerizable monomer, (E) photopolymerization initiator, and (F) solvent. A resin composition comprising:
The (A) metal oxide particles contain at least one selected from the group consisting of zirconium dioxide particles, titanium dioxide particles, and barium titanate particles,
The content ratio of the (A) metal oxide particles is 50% by mass or more in the total solid content, and
The photosensitive resin composition, wherein the solvent (F) contains a high-boiling solvent having a boiling point of 170 ° C. or higher at 101.25 hPa.
[2] The photosensitive resin composition according to [1], wherein the high boiling point solvent contains at least one selected from the group consisting of alkylene glycol diacetate and dialkylene glycol dialkyl ether.
[3] The high-boiling solvent contains at least one selected from the group consisting of 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and diethylene glycol ethyl methyl ether. Photosensitive resin composition.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein a content ratio of the high boiling point solvent is 10% by mass or more in the solvent (F).

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the (C) alkali-soluble resin includes an acrylic copolymer resin having a partial structure represented by the following general formula (I): Stuff.

(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. * Represents a bond.)

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the (B) dispersant contains a polymer dispersant having a phosphate group.
[7] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [6].
[8] An image display device comprising the cured product according to [7].
[9] An illumination containing the cured product according to [7].

  According to the present invention, a photosensitive resin composition having a high refractive index and excellent planarization ability can be provided.

FIG. 1 is an explanatory diagram of a method for evaluating a flattening rate.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not specified to these, unless the summary is exceeded.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.
Further, “total solid content” means all components other than the solvent in the photosensitive resin composition. Furthermore, the numerical range represented using “to” in the present invention means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present invention, the term “(co) polymer” means that both a single polymer (homopolymer) and a copolymer (copolymer) are included, and “(acid) anhydride”, “ The term “(anhydrous)... Acid” means to include both an acid and its anhydride.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present specification, the percentage and part expressed by “mass” are synonymous with the percentage and part expressed by “weight”.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises (A) metal oxide particles, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable monomer, (E) a photopolymerization initiator, and (F ) It contains a solvent as an essential component and, if necessary, contains other compounding components.

[(A) Metal oxide particles]
The (A) metal oxide particles in the photosensitive resin composition of the present invention contain at least one selected from the group consisting of zirconium dioxide particles, titanium dioxide particles, and barium titanate particles. By containing these specific metal oxide particles, a protective film having a high refractive index can be obtained.

  In general, particles of a compound having a group 4 element of a long-period type periodic table, particularly oxide particles having a group 4 element of a long-period type periodic table have a high relative dielectric constant and are used for an organic insulating film having a high refractive index. Are suitable. Among these, zirconium dioxide particles, titanium dioxide particles, and barium titanate particles have a high refractive index. In order to set the refractive index of the obtained cured film to a desired value, the content ratio of these specific metal oxide particles may be increased.

  Among these, from the viewpoint of dispersibility, zirconium dioxide particles and titanium dioxide particles are preferable, and zirconium dioxide particles are more preferable.

Further, (A) the metal oxide particles may be a combination of other metal oxide particles in addition to the zirconium dioxide particles, titanium dioxide particles, and barium titanate particles.
Specifically, aluminum oxide, iron oxide, copper oxide, zinc oxide, yttrium oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, tantalum oxide, tungsten oxide, lead oxide, bismuth oxide, cerium oxide, antimony oxide, Examples thereof include germanium oxide. A composite oxide composed of two or more metal elements can also be used.

(A) Although the average particle diameter of the primary particle of a metal oxide particle is not specifically limited, Usually, it is 100 nm or less, Preferably it is 80 nm or less, More preferably, it is 70 nm or less, More preferably, it is 60 nm or less. Moreover, it is 1 nm or more normally. When the average particle diameter of the primary particles is not more than the above upper limit value, there is no surface roughness and the patterning characteristics tend to be good. Moreover, if it is more than the said lower limit, there exists a tendency for a dispersibility to become favorable.
(A) The average particle diameter of primary particles of metal oxide particles is directly measured from the electron micrograph using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). Measure by the method Specifically, the primary particle diameter of each particle is calculated as the equivalent circle diameter. The measurement is performed on all particles within the range by imaging a 100 to 500 nm square range. A different range is imaged several times, the particle diameter of a total of 200 to 1000 primary particles is measured, and the average particle diameter is obtained by taking the number average. The primary particle diameter can be measured, for example, on a metal oxide particle alone, a dispersion thereof, or a cured film of the photosensitive resin composition. When producing a measurement sample, (A) metal oxide particles must be uniformly present in the sample. In the case of a dispersion, the measurement is carried out after volatilizing the solvent using the dispersion immediately after dispersion. In the case of a cured film, a measurement is performed by preparing a cured film using a photosensitive resin composition in which particles are uniformly dispersed, cutting the film in the thickness direction, and observing the cross section.

  (A) Although the shape of a metal oxide particle is not specifically limited, For example, it is spherical shape, hollow shape, porous shape, rod shape, plate shape, fiber shape, or indefinite shape, Preferably it is spherical shape.

  In the photosensitive resin composition of the present invention, the content ratio of (A) metal oxide particles is 50% by mass or more in the total solid content. A cured film having a higher refractive index can be obtained by setting the lower limit value or more. On the other hand, since the content rate of other components, such as alkali-soluble resin and a photopolymerizable monomer, becomes relatively small, the flatness of the obtained cured film tends to deteriorate.

  (A) The content ratio of the metal oxide particles is usually 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, and further preferably 65% in the total solid content of the photosensitive resin composition. % By mass or more, particularly preferably 70% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, still more preferably 80% by mass or less, particularly preferably 75%. It is below mass%. When the amount is not less than the lower limit value, a film having a high refractive index tends to be obtained, and when the value is not more than the upper limit value, flatness tends to be improved.

  On the other hand, the content ratio of at least one selected from the group consisting of zirconium dioxide particles, titanium dioxide particles, and barium titanate particles is not particularly limited, but is 50% by mass or more in the total solid content of the photosensitive resin composition. Is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, particularly preferably 70% by mass or more, and more preferably 95% by mass or less, and 90% by mass. The following is more preferable, 85% by mass or less is further preferable, 80% by mass or less is further more preferable, and 75% by mass or less is particularly preferable. When the amount is not less than the lower limit value, a film having a high refractive index tends to be obtained, and when the value is not more than the upper limit value, flatness tends to be improved. In addition, when only 1 type chosen from the group which consists of a zirconium dioxide particle, a titanium dioxide particle, and a barium titanate particle | grain is included, the 1 type of content rate is meant, and when it contains 2 or more types, it contains 2 or more types. It means the total value of percentage.

  In addition, the content ratio of at least one selected from the group consisting of zirconium dioxide particles, titanium dioxide particles, and barium titanate particles in the metal oxide particles is usually 50% by mass or more, preferably 70% by mass. Above, more preferably 90% by mass or more, and usually 100% by mass or less. A film having a high refractive index tends to be obtained by setting the lower limit value or more. In addition, when only 1 type chosen from the group which consists of a zirconium dioxide particle, a titanium dioxide particle, and a barium titanate particle | grain is included, the 1 type of content rate is meant, and when it contains 2 or more types, it contains 2 or more types. It means the total value of percentage.

[(B) Dispersant]
The photosensitive resin composition of the present invention contains (B) a dispersant. (B) By containing a dispersing agent, (A) metal oxide particle can be stably disperse | distributed in the photosensitive resin composition.
(B) The dispersant is not particularly limited as long as (A) the metal oxide particles can be dispersed, but a polymer dispersant having a functional group is preferable, and further, a carboxyl group; phosphorus from the viewpoint of dispersion stability. Polymers having functional groups such as acid groups; sulfonic acid groups; or these bases; primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine A dispersant is preferred. Among these, a polymer dispersant having a basic functional group such as a primary, secondary, or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine, is particularly preferable.

  Examples of the polymer dispersant include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, and a polyoxyethylene alkyl ether type. Examples thereof include a dispersant, a polyoxyethylene diester dispersant, a phosphoric acid dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

  Specific examples of such a dispersant are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), DISPERBYK (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), and SOLPERSE (manufactured by Lubrizol). , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Co., Inc.) and the like. These polymer dispersants may be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the polymer dispersant is not particularly limited, but is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.

Among polymer dispersants, from the viewpoint of affinity with a developer, a polymer dispersant having a primary, secondary or tertiary amino group, a polymer dispersant having a quaternary ammonium base, and a high phosphate group. A molecular dispersant is preferable, and a polymer dispersant having a phosphate group is more preferable from the viewpoint of dispersibility.
In polymer dispersants having primary, secondary or tertiary amino groups, polymer dispersants having quaternary ammonium bases, and polymer dispersants having phosphate groups, ether bonds such as polyesteramine and polyetheramine can be used. What has is preferable.

  From the viewpoint of dispersibility, the amine value of the polymer dispersant having a primary, secondary or tertiary amino group, the polymer dispersant having a quaternary ammonium base, and the polymer dispersant having a phosphate group is 60 mgKOH / g. The following is preferable, 50 mgKOH / g or less is more preferable, and 40 mgKOH / g or less is more preferable. The amine value here represents an amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per gram of solid content of the dispersant.

  Among polymer dispersants having a phosphoric acid group, it is preferable to further have a polyether structure from the viewpoint of patterning characteristics. The polyether structure is a part having a function of further improving the affinity with the developer and improving the dispersibility, and by having the polyether structure, patterning at a higher resolution tends to be possible.

  The chemical structure of the polymer dispersant having a phosphoric acid group is not particularly limited, but has a chemical structure represented by the following general formula (X), for example, from the viewpoint of compatibility between patterning characteristics and dispersibility. Is preferred.

In the above formula (X), R ^A represents an alkyl group which may have a substituent, α represents a polyether structure, and β represents a direct bond or a polyester structure. N represents an integer of 1 to 3.

R ^A is an alkyl group which may have a substituent, but the carbon number of the alkyl group is not particularly limited, and is usually 1 or more, preferably 20 or less, more preferably 15 or less, and still more preferably Is 10 or less, more preferably 5 or less, and particularly preferably 3 or less. By being in the said range, there exists a tendency for affinity with a developing solution to improve and a patterning characteristic to become favorable.
Examples of the substituent that the alkyl group in R ^A may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, it is preferably unsubstituted.

  α represents a polyether structure, but from the viewpoint of affinity with a developer, a polyethylene glycol structure, a polypropyl ether structure, a polyisopropyl ether structure, and a polybutyl ether structure are preferable, a polyethylene glycol structure is more preferable, and the following formula (X- More preferably, the structure is represented by 1).

In the above formula (X-1), R ^B represents an alkylene group which may have a substituent. x represents an integer of 5 to 30.

In the above formula (X-1), R ^B represents an alkylene group which may have a substituent. The number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. By being in the said range, there exists a tendency for a patterning characteristic to become favorable.

Examples of the substituent that the alkylene group in R ^B may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, an unsubstituted group is preferable.

Moreover, in said formula (X-1), x represents the integer of 5-30. x is preferably 8 or more, more preferably 20 or less, and even more preferably 15 or less. There exists a tendency for affinity with a developing solution to become favorable by setting it as the said lower limit or more. Moreover, there exists a tendency for storage stability to become favorable by setting it as the said upper limit or less. Incidentally, R ^B together contained more in one molecule may be the same or different and for example, as a butylene group and a pentylene group, may contain an alkylene group having a carbon number differs.

  On the other hand, in the above formula (X), β represents a direct bond or a polyester structure, and a structure represented by the following formula (X-2) is more preferable.

In said formula (X-2), R < ^C > represents the alkylene group which may have a substituent, y represents the integer of 0-10.

R ^C is an alkylene group which may have a substituent, but the number of carbon atoms of the alkylene group is not particularly limited and is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less. When it is at least the lower limit, the storage stability tends to be good, and when it is at most the upper limit, the patterning characteristics tend to be good. Examples of the substituent that the alkylene group in R ^C may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, and from the viewpoint of ease of synthesis, an unsubstituted group is preferable.

y is an integer of 0 to 10, preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and preferably 7 or less, preferably 5 or less. More preferably. Storage stability tends to be good when the lower limit is exceeded. Moreover, there exists a tendency for a patterning characteristic to become favorable by setting it as the said upper limit or less. In addition, when y is an integer greater than or equal to 2, ^RC contained in two or more in one molecule may be the same or different, for example, carbon number is different like a butylene group and a pentylene group. An alkylene group may be contained.

  The weight average molecular weight (Mw) of the polymer dispersant having a phosphate group is not particularly limited, but is preferably 1,000 or more. Further, it is preferably 20,000 or less, more preferably 10,000 or less, and further preferably 5,000 or less. Dispersibility tends to be good when it is at least the lower limit, and patterning characteristics tend to be good when it is less than or equal to the upper limit.

  As the polymer dispersant having a phosphoric acid group, commercially available ones can be used. For example, DISPERBYK (registered trademark, the same applies hereinafter) -102, 110, 111, 140, 142, 145, 180, 2001 (Bic Chemie) DA-7301, DA-325, DA-375, DA-234, ED-152, ED-251 (manufactured by Enomoto Kasei), TEGO (registered trademark) Dispers s628, 655 (manufactured by Evonik), etc. Can be mentioned.

  (B) Although the content rate of a dispersing agent is not specifically limited, It is 1 mass% or more normally in the total solid of the photosensitive resin composition, Preferably it is 2 mass% or more, More preferably, it is 3 mass% or more, Preferably it is 10 mass% or less, More preferably, it is 7 mass% or less, More preferably, it is 5 mass% or less. By setting it as the said lower limit or more, there exists a tendency for the stability of the photosensitive resin composition to improve, and there exists a tendency for a patterning characteristic to improve by setting it as the said upper limit or less.

  (B) The content ratio of the polymer dispersant having a phosphate group in the dispersant is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, Usually, it is 100 mass% or less, Most preferably, it is 100 mass%. There exists a tendency for a patterning characteristic to improve by setting it as the said lower limit or more.

  Further, the content ratio of the (B) dispersant with respect to 100 parts by mass of the (A) metal oxide particles is not particularly limited, but is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 8 parts by mass or less. Moreover, 1 mass part or more is preferable and 3 mass parts or more is more preferable. By setting it to the above lower limit or higher, dispersibility tends to be good, and by setting it to the upper limit or lower, patterning characteristics tend to be good.

[(C) Alkali-soluble resin]
The photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it can be developed with a developer. Examples of the alkali-soluble resin include various resins containing a carboxyl group or a hydroxyl group, and those having a carboxyl group are preferable from the viewpoint of excellent developability.
Among the alkali-soluble resins, from the viewpoint of resolution, (C1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain (hereinafter sometimes abbreviated as “(C1) acrylic copolymer resin”) is preferable. .

((C1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain)
(C1) The acrylic copolymer resin has an ethylenically unsaturated group in the side chain. By having an ethylenically unsaturated group, the exposed portion tends to be photocured to become a stronger film, while the unexposed portion tends to have good developability.

(Partial structure represented by general formula (I))
(C1) The partial structure including a side chain having an ethylenically unsaturated group, which the acrylic copolymer resin has, is not particularly limited, but from the viewpoint of easiness of radical emission accompanying the flexibility of the film, for example, the following general formula It preferably has a partial structure represented by (I).

(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. * Represents a bond.)

  Among the partial structures represented by the formula (I), the partial structure represented by the following general formula (I ′) is preferable from the viewpoint of sensitivity and alkali developability.

(In Formula (I ′), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polybasic acid residue.)

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

  (C1) The content ratio of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol% or more. Is more preferably 40 mol% or more, more preferably 50 mol% or more, particularly preferably 60 mol% or more, most preferably 70 mol% or more, more preferably 99 mol% or less, and 95 mol%. The following is more preferable, 90 mol% or less is further preferable, and 80 mol% or less is particularly preferable. When the amount is not less than the lower limit, the remaining film ratio tends to be improved, and when the amount is not more than the upper limit, the developability tends to be good.

  (C1) The content ratio of the partial structure represented by the general formula (I ′) contained in the acrylic copolymer resin is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol. % Or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, particularly preferably 60 mol% or more, most preferably 70 mol% or more, and preferably 99 mol% or less, 95 The mol% or less is more preferable, the 90 mol% or less is further preferable, and the 80 mol% or less is particularly preferable. There exists a tendency which is easy to carry out alkali development by setting it as the said lower limit or more, and there exists a tendency for developing adhesiveness to be ensured by setting it as the said upper limit or less.

(Partial structure represented by general formula (II))
(C1) When the acrylic copolymer resin has a partial structure represented by the general formula (I), it may further include another partial structure. From the viewpoint of development adhesion, for example, it is also preferable to have a partial structure represented by the following general formula (II).

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, and R ⁴ has an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alkenyl group which may be substituted.

(R ⁴ )
In the formula (II), R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent.
Examples of the alkyl group for R ⁴ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, It is more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. By setting it as the said lower limit or more, film | membrane intensity | strength becomes high and there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
The substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like. From the viewpoint of heat resistance and film strength, a phenyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the aryl group for R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene. And groups such as a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, or a pyrazole ring. Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolino Rings include groups such as azulene ring. Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.
The substituents that the aryl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group, Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkenyl group for R ⁴ include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less. 14 or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  Examples of the substituent that the alkenyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Thus, R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoint of developability and film strength, an alkyl group or alkenyl is preferable, and an alkyl group is more preferable.

  (C1) When the acrylic copolymer resin has a partial structure represented by the general formula (II), the content ratio is not particularly limited, but is preferably 1 mol% or more, more preferably 80 mol% or less, and 70 The mol% or less is more preferable, and 60 mol% or less is more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

(Partial structure represented by general formula (III))
(C1) When the acrylic copolymer resin has a partial structure represented by the general formula (I), it is preferable to further have a partial structure represented by the following general formula (III) from the viewpoint of heat resistance and film strength. .

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group is represented. t represents an integer of 0 to 5.

(R ⁶ )
In the formula (III), R ⁶ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group. , A halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group.
Examples of the alkyl group for R ⁶ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and is preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of developability and film strength, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
The substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁶ include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less. 14 or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  Examples of the substituent that the alkenyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkynyl group for R ⁶ include linear, branched or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less. 14 or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  Examples of the substituent that the alkynyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group, Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the halogen atom in R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable from the viewpoint of ease of synthesis.

Examples of the alkoxy group for R ⁶ include linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  In addition, as the substituent that the alkoxy group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the alkyl sulfide group for R ⁶ include linear, branched or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  In addition, as the substituent that the alkyl group in the alkyl sulfide group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl Group, carboxyl group, acryloyl group, methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Thus, R ⁶ represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxyl group, a carboxyl group, a halogen, An atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkyl sulfide group that may have a substituent is represented, but among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred. preferable.

  In the formula (III), t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of synthesis.

  (C1) When the acrylic copolymer resin has a partial structure represented by the general formula (III), the content ratio is not particularly limited, but is preferably 1 mol% or more, and preferably 30 mol% or less, 20 The mol% or less is more preferable, and 10 mol% or less is more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

(Partial structure represented by general formula (IV))
(C1) When the acrylic copolymer resin has a partial structure represented by the general formula (I), it is also preferable to further have a partial structure represented by the following general formula (IV) from the viewpoint of developability.

In the above formula (IV), R ⁷ represents a hydrogen atom or a methyl group.

  (C1) When the acrylic copolymer resin has a partial structure represented by the general formula (IV), the content is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and 20 mol % Or more is more preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60% mol or less is more preferable. There exists a tendency for developability to improve by making it into the said lower limit or more, and there exists a tendency for image development adhesiveness to improve by making it into the said upper limit or less.

  On the other hand, the acid value of the (C1) acrylic copolymer resin is not particularly limited, but is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and even more preferably 60 mgKOH / g or more. Moreover, 150 mgKOH / g or less is preferable, 140 mgKOH / g or less is more preferable, 130 mgKOH / g or less is more preferable, 120 mgKOH / g or less is more preferable. There exists a tendency for developability to improve by making it into the said lower limit or more, and there exists a tendency for image development adhesiveness to improve by making it into the said upper limit or less.

  (C1) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 5000 or more, still more preferably 6000 or more, Moreover, it is 30000 or less normally, Preferably it is 20000 or less, More preferably, it is 15000 or less, More preferably, it is 10,000 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  Specific examples of the (C1) acrylic copolymer resin include copolymers described in JP-A No. 2001-089533 and JP-A No. 08-292574.

  In the photosensitive resin composition according to the present invention, (C2) other alkali-soluble resin is used as (C) alkali-soluble resin, in addition to (C1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain. Also good.

  (C2) The other alkali-soluble resin is preferably an alkali-soluble resin containing a carboxyl group or a hydroxyl group, such as an epoxy (meth) acrylate resin, an acrylic resin other than (C1), or a carboxyl group-containing epoxy. Resins, carboxyl group-containing urethane resins, novolac resins, polyvinylphenol resins and the like can be mentioned, among which epoxy (meth) acrylate resins and acrylic resins other than (C1) are preferred. These can be used individually by 1 type or in mixture of multiple types.

  (C) Although the content rate of alkali-soluble resin is not specifically limited, 5 mass% or more is preferable in the total solid of the photosensitive resin composition, 10 mass% or more is more preferable, 12 mass% or more is further more preferable, 15 It is particularly preferably at least 40% by mass, more preferably at most 40% by mass, more preferably at most 30% by mass, further preferably at most 25% by mass, particularly preferably at most 20% by mass. There exists a tendency for developability to become favorable by setting it as the said lower limit or more, and there exists a tendency for a residual film ratio to become favorable by setting it as the said upper limit or less.

  The content ratio of the (C1) acrylic copolymer resin is not particularly limited, but is preferably 10% by mass or more, more preferably 12% by mass or more, and further preferably 15% by mass or more in the total solid content of the photosensitive resin composition. 15 mass% or more is especially preferable, 40 mass% or less is preferable, 30 mass% or less is more preferable, 25 mass% or less is further more preferable, and 20 mass% or less is especially preferable. There exists a tendency for developability to become favorable by setting it as the said lower limit or more, and there exists a tendency for a residual film ratio to become favorable by setting it as the said upper limit or less.

  Further, the content ratio of the (C1) acrylic copolymer resin in the (C) alkali-soluble resin is not particularly limited, but is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, Usually, it is 100 mass% or less. There exists a tendency for a remaining-film rate to become favorable by setting it as the said lower limit or more.

[(D) Photopolymerizable monomer]
The photosensitive resin composition of the present invention contains (D) a photopolymerizable monomer. (D) It is thought that it becomes high sensitivity by including a photopolymerizable monomer.
As used herein, the photopolymerizable monomer means a compound having at least one ethylenically unsaturated bond in the molecule, but is polymerizable, crosslinkable, and accompanyingly dissolves the developer in the exposed and unexposed areas. From the standpoint that the difference in sex can be expanded, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group, More preferably, it is a (meth) acrylate compound.

In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and preferably 15 or less, more preferably 10 The number is more preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less. By setting it as the said lower limit or more, there exists a tendency for polymerizability to improve and to become high sensitivity, and there exists a tendency for developability to become more favorable by setting it as the said upper limit or less.
Specific examples of the photopolymerizable monomer include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic polyhydroxy compound, etc. And an ester obtained by an esterification reaction of an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
Esters obtained by esterification reaction of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily a single substance, but are representative. Specific examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, acrylic acid, adipic acid, Examples include butanediol and glycerin condensates.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (made by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (made by Kyoeisha Chemical Co., Ltd.), UV-1700B UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

Among these, it is preferable to use ester (meth) acrylates or urethane (meth) acrylates from the viewpoints of curability and developability. Of these, ester (meth) acrylates are preferred.
Specifically, it is preferable to use dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylol. More preferred is propane triacrylate, and even more preferred is trimethylolpropane triacrylate.
These may be used alone or in combination of two or more.

  In the present invention, the molecular weight of the photopolymerizable monomer (D) is not particularly limited, but from the viewpoint of curability and developability, it is preferably 100 or more, more preferably 150 or more, still more preferably 180 or more, and still more preferably. 200 or more, particularly preferably 250 or more, preferably 1000 or less, more preferably 700 or less, further preferably 400 or less, particularly preferably 300 or less. In addition, the number of carbon atoms of the photopolymerizable monomer (D) is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 12 or more, and still more preferably 15 or more, from the viewpoints of curability and developability. It is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.

  The content ratio of the photopolymerizable monomer (D) in the photosensitive resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10%, based on the total solid content. % By mass or more, more preferably 15% by mass or more, usually 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 20% by mass or less. By making it the above lower limit or more, the sensitivity at the time of exposure is good, and there is a tendency that a coating film is formed without causing film reduction at the time of development, and by making the above upper limit value or less, the developability tends to be good. is there.

  Further, the content ratio of (D) the photopolymerizable monomer with respect to 100 parts by mass of (C) alkali-soluble resin is not particularly limited, but is usually 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, The amount is preferably 70 parts by mass or more, and is usually 200 parts by mass or less, preferably 150 parts by mass or less, and more preferably 120 parts by mass or less. When it is at least the lower limit, the sensitivity tends to be good during exposure, and when it is at most the upper limit, the developability tends to be good.

[(E) Photopolymerization initiator]
The photosensitive resin composition of the present invention contains (E) a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated bond of the photopolymerizable monomer (D) with actinic rays, and a known photopolymerization initiator may be used. it can.

  The photopolymerization initiator generally used in this field can be used as the photopolymerization initiator (E) in the photosensitive resin composition of the present invention. Examples of such photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexagons described in JP-A-2000-56118. Arylbiimidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acids Salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester compounds described in JP 2000-80068 A, JP 2006-36750 A, etc. Is mentioned.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclo Tantadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is.

  As the photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate making properties. Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in the structure, so they are highly sensitive in a small amount and stable against thermal reactions. Thus, it is possible to obtain a highly sensitive photosensitive resin composition in a small amount.

  Examples of the oxime ester compound include compounds represented by the following general formula (IV).

In the above formula (IV), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents an arbitrary substituent containing an aromatic ring.
R ^22a represents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent.
n represents an integer of 0 or 1.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. It is. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl. Group or N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked. From the viewpoint of properties, an alkyl group, an alkoxy group, or a group in which these are connected is preferable, and a connected alkoxy group is more preferable.
Among these, from the viewpoint of sensitivity, R ^21a is preferably an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

R ^21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, or an optionally substituted diphenyl sulfide group. Among these, from the viewpoint of sensitivity, an optionally substituted carbazolyl group or an optionally substituted diphenyl sulfide group is preferable.

The number of carbon atoms of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent or sensitivity. 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the substituent may be unsubstituted. Is preferred.

The number of carbon atoms of the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent or sensitivity. 10 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted. .
Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and further preferably an acetyl group.

A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
A sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarins having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. Dyes, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A-47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Examined Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005. JP, 59-56403, JP 2-69, JP 57-168888, JP 5-107761. JP-5-210240 discloses, mention may be made of dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethyl) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

  Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine. A polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.

  Although the content rate of the (E) photoinitiator in the photosensitive resin composition of this invention is not specifically limited, Usually 0.01 mass% or more with respect to the total solid of the photosensitive resin composition, Preferably it is 0. 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, particularly preferably 3% by mass or more, and usually 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass. % Or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and particularly preferably 5% by mass or less. When the amount is not less than the lower limit, there is a tendency that a film is not formed during development, and a coating pattern is formed. When the amount is not more than the upper limit, a desired pattern shape tends to be easily formed.

  Further, the blending ratio of (E) photopolymerization initiator to (D) photopolymerizable monomer in the photosensitive resin composition is preferably 1 part by mass or more with respect to 100 parts by mass of (D) photopolymerizable monomer. 5 parts by mass or more is more preferable, 10 parts by mass or more is further preferable, 12 parts by mass or more is further preferable, 15 parts by mass or more is particularly preferable, 200 parts by mass or less is preferable, and 100 parts by mass or less is more preferable. 50 parts by mass or less is more preferable, and 30 parts by mass or less is particularly preferable. There exists a tendency for it to become suitable sensitivity by setting it as the said lower limit or more, and there exists a tendency for a desired pattern shape to become easy to form by setting it as the said upper limit or less.

[(F) Solvent]
The photosensitive resin composition of the present invention contains (F) a solvent. (F) The solvent is not particularly limited as long as it can dissolve and disperse each component and has good handleability.

The (F) solvent in the photosensitive resin composition of the present invention may be referred to as a high boiling point solvent (hereinafter referred to as “(F1) high boiling point solvent”) having a boiling point of 170 ° C. or higher at 1013.25 hPa. "Means the boiling point at 1013.25 hPa.).
In order to obtain a cured film having a high refractive index, it is necessary to increase the content ratio of (A) metal oxide particles in the photosensitive resin composition, and accordingly (C) an alkali-soluble resin or (D) Since the content ratio of the clear component such as the photopolymerizable monomer is lowered and the fluidity at the time of preliminary baking on the hot plate is lowered, the planarization performance tends to be lowered. (F1) By containing a high-boiling solvent, the solvent tends to remain in the coating film even after drying under reduced pressure, and the evaporation of the solvent during pre-baking is slow, so that the remaining solvent causes the flow during pre-baking on the hot plate. It is considered that the flatness is improved.

The (F1) high boiling point solvent that can be used in the present invention is described below. The values in parentheses are boiling point values.
Ethylene glycol monobutyl ether (171 ° C.), propylene glycol mono-n-butyl ether (170 ° C.), diethylene glycol monomethyl ether (194 ° C.), diethylene glycol monoethyl ether (196 ° C.), diethylene glycol mono-n-butyl ether (231 ° C.), methoxy Methylpentanol (174 ° C.), dipropylene glycol monomethyl ether (188 ° C.), dipropylene glycol monopropyl ether (210 ° C.), 3-methyl-3-methoxybutanol (174 ° C.), triethylene glycol monomethyl ether (248 ° C.) ), Glycol monoalkyl ethers such as triethylene glycol monoethyl ether (255 ° C.), tripropylene glycol monomethyl ether (243 ° C.) ;

  Glycol dialkyl ethers such as diethylene glycol ethyl methyl ether (176 ° C), diethylene glycol diethyl ether (189 ° C), diethylene glycol dibutyl ether (255 ° C), dipropylene glycol dimethyl ether (175 ° C), dipropylene glycol methylpropyl ether (203 ° C) ;

  Ethylene glycol mono-n-butyl ether acetate (192 ° C), methoxybutyl acetate (170 ° C), diethylene glycol monoethyl ether acetate (218 ° C), diethylene glycol mono-n-butyl ether acetate (247 ° C), dipropylene glycol monomethyl ether acetate ( Glycol alkyl ether acetates such as 213 ° C);

  Ethylene glycol diacetate (197 ° C.), propylene glycol diacetate (191 ° C.), 1,3-butylene glycol diacetate (232 ° C.), 1,4-butanediol diacetate (232 ° C.), 1,6-hexanol dia Glycol diacetates such as acetate (260 ° C.);

Alkyl acetates such as cyclohexanol acetate (173 ° C.);
Ethers such as amyl ether (188 ° C.);
Ketones such as methyl hexyl ketone (173 ° C.) and methyl nonyl ketone (232 ° C.);
Ethylene glycol (197 ° C), propylene glycol (188 ° C), butanediol (230 ° C), diethylene glycol (244 ° C), dipropylene glycol (231 ° C), triethylene glycol (244 ° C), glycerin (290 ° C), benzyl Mono- or polyhydric alcohols such as alcohol (205 ° C.);
Linear or cyclic esters such as ethyl caprylate (207 ° C.), ethyl benzoate (213 ° C.), γ-butyrolactone (204 ° C.);
It can be used in addition to this.

  Of these, (F1) the high boiling point solvent preferably contains at least one selected from the group consisting of alkylene glycol diacetate and dialkylene glycol dialkyl ether. This is because the structure of alkylene glycol diacetate and dialkylene glycol dialkyl ether increases the molecular skeleton, and the metal oxide particles and alkali-soluble resin in the coating prevent evaporation, resulting in a more reduced membrane during drying under reduced pressure. This is because it tends to remain inside.

  Among these, from the viewpoint of flatness, (F1) it is preferable to contain alkylene glycol diacetate as a high boiling point solvent, and propylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate. Are more preferable, and 1,4-butanediol diacetate and 1,3-butylene glycol diacetate are more preferable.

  On the other hand, from the viewpoint of solubility, (F1) a high-boiling solvent preferably contains dialkylene glycol dialkyl ether, more preferably diethylene glycol ethyl methyl ether or diethylene glycol diethyl ether, and even more preferably diethylene glycol ethyl methyl ether.

  Among these, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and diethylene glycol ethyl methyl ether are more preferable as the (F1) high boiling point solvent from the viewpoint of flatness and solubility.

  (F1) The high boiling point solvent is a solvent having a boiling point of 170 ° C. or higher, preferably has a boiling point of 172 ° C. or higher, more preferably 174 ° C. or higher, and further preferably 176 ° C. or higher. Moreover, 300 degrees C or less is preferable, 270 degrees C or less is more preferable, and 240 degrees C or less is further more preferable. When the value is not less than the lower limit value, the flatness tends to be high, and when the value is not more than the upper limit value, the remaining film ratio tends to be high.

  These (F1) high boiling point solvents can be used alone or in combination of two or more.

In the present invention, (F2) a solvent having a boiling point of less than 170 ° C. at 1013.25 hPa (hereinafter sometimes referred to as “(F2) low-boiling solvent”) is used as a solvent other than (F1) a high-boiling solvent. can do.
Specifically, ethylene glycol monomethyl ether (124 ° C.), ethylene glycol monoethyl ether (135 ° C.), ethylene glycol monopropyl ether (151 ° C., propylene glycol monomethyl ether (120 ° C.), propylene glycol monoethyl ether (133 ° C.) ), Glycol monoalkyl ethers such as propylene glycol monopropyl ether (149 ° C.), 3-methoxy-1-butanol (158 ° C.);

Glycol dialkyl ethers such as ethylene glycol dimethyl ether (84 ° C.), ethylene glycol diethyl ether (121 ° C.), diethylene glycol dimethyl ether (162 ° C.);
Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate (145 ° C.), ethylene glycol monoethyl ether acetate (156 ° C.), propylene glycol monomethyl ether acetate (146 ° C.), propylene glycol monoethyl ether acetate (160 ° C.);

Ethers such as diethyl ether (35 ° C.), dipropyl ether (91 ° C.), diisopropyl ether (69 ° C.), dibutyl ether (140 ° C.), ethyl isobutyl ether (81 ° C.);
Acetone (56 ° C), methyl ethyl ketone (80 ° C), methyl isopropyl ketone (94 ° C), methyl butyl ketone (116 ° C), methyl isobutyl ketone (116 ° C), methyl amyl ketone (151 ° C), methyl isoamyl ketone (144 ° C) ), Diisopropyl ketone (125 ° C.), diisobutyl ketone (116 ° C.), cyclohexanone (156 ° C.), methoxymethylpentanone (156 ° C.) and the like;

Monovalent or polyvalent such as methanol (65 ° C), ethanol (78 ° C), propanol (97 ° C), isopropanol (83 ° C), butanol (99 ° C), hexanol (157 ° C), cyclohexanol (162 ° C) Alcohols;
Ethyl acetate (77 ° C.), propyl acetate (102 ° C.), butyl acetate (126 ° C.), amyl acetate (149 ° C.), methyl isobutyrate (90 ° C.), ethyl propionate (99 ° C.), propyl propionate (123 ° C.), butyl butyrate (166 ° C.), isobutyl butyrate (147 ° C.), methyl isobutyrate (93 ° C.), methyl 3-ethoxypropionate (165 ° C.), ethyl 3-ethoxypropionate (166 ° C.), 3 -Chain or cyclic esters such as methyl methoxypropionate (143 ° C), ethyl 3-methoxypropionate (158 ° C);
It can be used in addition to this.

  The low boiling point solvent (F2) can dissolve or disperse each component in the photosensitive resin composition, and can maintain good storage stability of the composition. Use of the photosensitive resin composition of the present invention Although it is selected according to the method, it is preferable to select one having a boiling point of 60 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 120 ° C. or higher from the viewpoint of applicability. Specifically, propylene glycol monomethyl ether, 3-methoxy-1-butanol, and propylene glycol monomethyl ether acetate are preferable, and 3-methoxy-1-butanol and propylene glycol monomethyl ether acetate are more preferable.

  These (F2) low-boiling solvents can be used alone or in combination of two or more.

  In addition, in the solvent (F), from the viewpoint of applicability, (F1) at least one selected from the group consisting of 1,4-butanediol diacetate and 1,3-butylene glycol diacetate as the high boiling point solvent; It is preferable to contain at least one selected from the group consisting of 3-methoxy-1-butanol and propylene glycol monomethyl ether acetate as a low boiling point solvent.

The content ratio of the (F) solvent in the photosensitive resin composition is not particularly limited, but the content ratio of the total solid content in the photosensitive resin composition is usually 10% by mass or more, preferably 15% by mass or more, more preferably. Is preferably 20% by mass or more, usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less. There exists a tendency which can suppress generation | occurrence | production of a coating nonuniformity by setting it as the said lower limit or more, and there exists a tendency which can suppress generation | occurrence | production of a foreign material, a repellency, etc. by setting it as the said upper limit or less.
The content ratio of the (F1) high boiling point solvent in the (F) solvent is not particularly limited, but is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and usually 60% by mass or less, preferably It is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less. When the amount is not less than the lower limit value, the flatness tends to be high, and when the value is not more than the upper limit value, the remaining film ratio tends to be high and the dispersibility tends to be good.

  The content ratio of the (F2) low boiling point solvent in the (F) solvent is not particularly limited, but is usually 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and usually 90% by mass or less, preferably Is 85% by mass or less, more preferably 80% by mass or less. By setting it to the lower limit value or more, the remaining film ratio tends to increase, and by setting the upper limit value or less, the flatness tends to increase.

[Other ingredients of photosensitive resin composition]
In the photosensitive resin composition of the present invention, in addition to the above-described components, adhesion improvers such as silane coupling agents, surfactants (coatability improvers), colorants, photoacid generators, amino compounds, mercapto compounds In addition, additives such as a polymerization inhibitor and an ultraviolet absorber can be appropriately blended.

(1) Adhesion improver The photosensitive resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
As the type of silane coupling agent, various types such as epoxy, (meth) acrylic, amino and the like can be used alone or in combination of two or more.

Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Epoxyglycans such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, it is a silane coupling agent of epoxy silanes.
As the phosphoric acid group-containing compound, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.

In the general formulas (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2, or 3.
These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

(2) Surfactant The photosensitive resin composition of the present invention may contain a surfactant in order to improve coatability.

As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.
Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340. (Shin-Etsu Silicone), F-470, F-475, F-478, F-559 (DIC), SH7PA (Toray Dow Corning), DS-401 (Daikin), L-77 (Manufactured by Nihon Unicar), FC4430 (manufactured by 3M) and the like.
In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

(3) Colorant The colorant may be contained in the photosensitive resin composition of this invention. As the colorant, known colorants such as pigments and dyes can be used. For example, when using a pigment, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the photosensitive resin composition without agglomeration.
The content ratio of the colorant is usually 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably from the viewpoint of permeability, based on the total solid content of the photosensitive resin composition. 0% by mass.

(4) Photoacid generator The photosensitive resin composition of the present invention may contain a photoacid generator in order to improve sensitivity and curability.
Examples of such a photoacid generator include diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p Diaryliodonium such as -chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium , Bromide or borofluoride, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic sulfonate, tetrakis (pentafluorophenyl) borate salt, and diphenyl Sulfonium organoboron complexes such as enacilsulfonium (n-butyl) triphenylborate, 2-methyl-4,6-bistrichloromethyltriazine, 2- (4-methoxyphenyl) -4,6-bistrichloromethyl Triazine compounds such as triazine can be mentioned, but not limited thereto.

(5) Amino compound The photosensitive resin composition of the present invention may contain an amino compound in order to promote thermosetting.
Examples of the amino compound include an amino compound having at least two methylol groups as functional groups and alkoxymethyl groups obtained by subjecting the methylol group to alcohol condensation modification having 1 to 8 carbon atoms. Specifically, for example, a melamine resin obtained by polycondensation of melamine and formaldehyde; a benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; a glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; urea and formaldehyde Examples include polycondensed urea resins; resins obtained by copolycondensation of two or more of melamine, benzoguanamine, glycoluril, and urea with formaldehyde; modified resins obtained by alcohol condensation modification of methylol groups of the above-described resins. These may be used alone or in combination of two or more. Among the amino compounds, melamine resins and modified resins thereof are preferable, modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins having 80% or more are particularly preferable.

Specific examples of the amino compound include melamine resins and modified resins thereof, for example, “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327 manufactured by Cytec Corporation, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nikarak” (registered trademark) MW-390, MW-100LM manufactured by Sanwa Chemical Co., Ltd. MX-750LM, MW-30M, MX-45, MX-302 and the like. Examples of the benzoguanamine resin and modified resins thereof include “Cymel” (registered trademark) 1123, 1125, and 1128 manufactured by Cytec Corporation. Examples of the glycoluril resin and the modified resin thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172 manufactured by Cytec, and “Nicarak” (registered trademark) MX manufactured by Sanwa Chemical Co., Ltd. -270 and the like. Examples of the urea resin and its modified resin include “UFR” (registered trademark) 65 and 300 manufactured by Cytec, and “Nicarak” (registered trademark) MX-290 manufactured by Sanwa Chemical Co., Ltd. It is done.
In this case, the content ratio of the amino compound in the photosensitive resin composition is usually 40% by mass or less, preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. Moreover, it is 0.5 mass% or more normally, Preferably it is 1 mass% or more. There exists a tendency which can maintain storage stability by setting it as the said upper limit or less, and there exists a tendency which can ensure sufficient thermosetting by setting it as the said lower limit or more.

(6) Mercapto Compound As a polymerization accelerator, a mercapto compound may be contained for improving sensitivity and adhesion.
Examples of mercapto compounds include mercapto compounds having an aromatic ring, mercapto compounds having a heterocyclic ring, and aliphatic polyfunctional mercapto compounds.
Examples of the mercapto compound having an aromatic ring include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole and the like.
Examples of the mercapto compound having a heterocyclic ring include 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. It is done.
Aliphatic polyfunctional mercapto compounds include butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane Tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), butane Diol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mer Ptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), tri And methylolpropane tris (3-mercaptoisobutyrate).
These can be used alone or in combination of two or more.

(7) Polymerization inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of shape control.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, 2,6-di-tert-butyl-4-cresol is preferable from the viewpoint of shape control. From the viewpoint of safety to the human body, hydroquinone monomethyl ether and methylhydroquinone are preferred.
A polymerization inhibitor may contain 1 type (s) or 2 or more types. (C) When producing an alkali-soluble resin, a polymerization inhibitor may be contained in the resin, and it may be used as the polymerization inhibitor of the present invention, or in addition to the polymerization inhibitor in the resin. The same or different polymerization inhibitor may be added during the production of the photosensitive resin composition.

(8) Ultraviolet absorber The photosensitive resin composition of the present invention may contain an ultraviolet absorber. By containing the ultraviolet absorber, the resolution tends to be improved.
As the ultraviolet absorber, a benzotriazole compound and / or a triazine compound is preferable.
Examples of other UV absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and derivatives thereof, dinaphthalene compounds, and phenanthroline compounds.

(9) Thermal polymerization initiator The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there is a tendency that the degree of crosslinking of the film can be increased. Specific examples of such a thermal polymerization initiator include azo compounds, organic peroxides and hydrogen peroxide. These may be used alone or in combination of two or more.

  In addition, in the case where a thermal polymerization initiator is used in combination with the photopolymerization initiator in order to improve sensitivity and increase the crosslink density of the film, the total content of these is the content of the photopolymerization initiator in the photosensitive resin composition. The combined proportion of the photopolymerization initiator and the thermal polymerization initiator is preferably 5 to 5. From the viewpoint of sensitivity, the thermal polymerization initiator is 5 to 100 parts by mass of the photopolymerization initiator. It is preferable to set it as 300 mass parts.

<Method for producing photosensitive resin composition>
Next, a method for preparing the photosensitive resin composition of the present invention will be described.

<Method for producing metal oxide particle dispersion>
In order to prepare the photosensitive resin composition in the present invention, it is preferable to first produce a metal oxide particle dispersion. The metal oxide particle dispersion contains (A) metal oxide particles, (B) a dispersant, (F) a solvent, and optionally contains a dispersion resin. It can be obtained by mixing these materials and dispersing other components in the solvent (F).
The dispersing method is not particularly limited, and examples thereof include paint shakers, sand grinders, ball mills, roll mills, stone mills, jet mills, and homogenizers.

  The order of mixing the components is not particularly limited as long as the effects of the present invention are not impaired. (F) After the solvent is added, (A) the metal oxide particles, (B) the dispersant, and the dispersion resin may be added. Well, or vice versa. As the dispersion resin, those described as the above (C) alkali-soluble resin can be used. A part of the alkali-soluble resin (C) used when preparing the photosensitive resin composition can also be used as a dispersion resin, and is different from that used when preparing the photosensitive resin composition (C) alkali Soluble resins can also be used. When (A) metal oxide particles are dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.05 to 5 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C.

<Method for preparing photosensitive resin composition>
Next, a method for preparing the photosensitive resin composition of the present invention will be described.
First, the metal oxide particle dispersion described above is composed of (C) an alkali-soluble resin, (D) a photopolymerizable monomer, (E) a photopolymerization initiator, and (F) a solvent, which are optional components. A photosensitive resin composition is obtained by mixing with a certain surfactant and other components to obtain a uniform solution. Mixing is preferably performed at room temperature, and is usually performed under ultraviolet light blocking so that the polymerization reaction does not start. Moreover, in each process, such as mixing, since fine dust may mix, it is preferable to filter the obtained photosensitive resin composition with a filter or the like.

<Hardened product>
A cured product can be obtained by curing the photosensitive resin composition of the present invention. In particular, the photosensitive resin composition of the present invention can be suitably used as a material for forming a high refractive index cured film. Below, the formation method of the high refractive index cured film using the photosensitive resin composition of this invention is demonstrated.
[1-1] Coating process First, a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray is applied to the photosensitive resin composition of the present invention described above on a substrate on which a TFT array is formed. Use to apply. The coating film thickness of the photosensitive resin composition is usually 0.1 to 5 μm.

[1-2] Drying / pre-baking step A volatile component is removed (dried) from the coating film to form a dry coating film. For drying, vacuum drying, preliminary baking, a hot plate, an IR oven, a convection oven, or the like can be used. Preferred pre-baking conditions are a temperature of 40 to 150 ° C. and a drying time of 10 seconds to 60 minutes.

[1-3] Exposure / Development Step Next, a photomask is placed on the dry coating film of the photosensitive resin composition layer, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel. Note that post-exposure baking may be performed after exposure for the purpose of improving sensitivity before development. For baking in this case, a hot plate, an IR oven, a convection oven, or the like can be used. Post-exposure bake conditions are usually in the range of 40 to 150 ° C. and drying time of 10 seconds to 60 minutes.

  Examples of the light source used in the exposure process of the dried coating film include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and other light sources, argon ion lasers, and YAG lasers. And laser light sources such as excimer laser and nitrogen laser. When only light of a specific wavelength is used, an optical filter can be used.

The solvent used for the development treatment is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured portion, but as mentioned above, points such as environmental pollution, harm to the human body, fire risk, etc. Therefore, it is preferable to use an alkali developer instead of a solvent.
Examples of such alkali developer include inorganic alkali compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethylamine, An aqueous solution containing an organic alkali compound such as ethanolamine or tetramethylammonium hydroxide can be mentioned.

  The alkali developer may contain a surfactant, a water-soluble solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, and the like, if necessary. Examples of the surfactant used in the developer include an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And cationic surfactants.

The development processing method is not particularly limited, but it is usually carried out by immersion development, paddle development, spray development, brush development, ultrasonic development or the like at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C.
[1-4] Firing Step The photosensitive resin composition film on which an image has been formed by the exposure / development step then becomes a cured product (thermosetting film) through a firing (hard baking) step. Note that the entire surface exposure may be performed for the purpose of suppressing the generation of outgas during firing after development and before firing.

  When performing overall exposure before firing, ultraviolet light or visible light is used as the light source, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, etc. And a laser light source such as an argon ion laser, a YAG laser, an excimer laser, and a nitrogen laser.

  For the baking, a hot plate, an IR oven, a convection oven or the like can be used. The hard baking conditions are usually 80 to 250 ° C. and a drying time of 30 seconds to 90 minutes.

<Evaluation method of flattening rate>
Evaluation of the planarization rate of the photosensitive resin composition of the present invention can be performed, for example, as follows.
First, as a base substrate for flatness evaluation, as shown in FIG. 1 (1), a pattern having a thickness of 2.0 μm and a 25 μm square (hereinafter sometimes referred to as “cured product X”) is arranged at intervals of 25 μm. Prepare a glass substrate.
A photosensitive resin composition is applied onto a base substrate for flatness evaluation, dried, entirely exposed, developed and baked, and a cured product of the photosensitive resin composition as shown in FIG. In some cases, it is referred to as “product Y”).

When the cured product Y is laminated on the flatness evaluation substrate having the cured product X, the cured product Y on the cured product X becomes a convex portion, while the cured product Y on the glass substrate becomes a concave portion.
The flattening rate is, for example, the film thickness H1 of the cured product X (3 in FIG. 1 (2)) and the depth H2 of the recessed portion with respect to the film surface of the cured product Y (5 in FIG. 1 (2). The difference between the height of the cured product Y on X and the height of the cured product Y on the glass substrate) can be calculated as the flattening rate R1.
Flattening rate R1 (%) = (H1-H2) / H1 × 100

In addition, since the flatness may change depending on the film thickness of the cured product Y, the flatness is obtained by the following equation, taking into consideration the film thickness H3 (6 in FIG. 1 (2)) of the cured product Y on the cured product X. The conversion rate R2 can also be calculated.
Flattening rate R2 (%) = (H1 + H3-H2) / (H1 + H3) × 100

  The flattening rate indicates that the larger the numerical value, the less the unevenness. From the viewpoint of optical characteristics, the flattening rate R1 is desirably 80% or more. The planarization rate R2 is desirably 91% or more.

<Image display device and illumination>
The image display apparatus and illumination of the present invention include the above-described cured product, and preferably includes a high refractive index cured film as the cured product. There are no particular restrictions on the type and structure of the image display device and illumination as long as it includes a high refractive index cured film.
For example, it may be used for any of a protective film application, a flat film application, an insulating film application, and an antireflection film application, and can also be used for an image display device of any of a liquid crystal display device and an organic EL device, or illumination.

The image display device usually includes a TFT (Thin Film Transistor) active matrix substrate.
A TFT active matrix substrate is formed, for example, by forming a high refractive index cured film as an interlayer insulating film on a substrate on which a TFT element array is formed, forming an ITO film thereon, and then producing ITO wiring using a photolithography method It can produce by doing. Then, a TFT active matrix substrate is bonded to a counter substrate to form a liquid crystal cell, a liquid crystal is injected into the formed liquid crystal cell, and a counter electrode is connected to complete a liquid crystal display device.

A high refractive index cured film may be combined with a low refractive index film. First, a low refractive index material having a nano lattice structure is formed on a glass substrate, and the above-described high refractive index cured film is formed thereon as a planarizing film. By using the light extraction film thus formed together with a light emitting element such as an organic electroluminescent element, an image display device and illumination can be completed.
On the other hand, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-12826, an organic electroluminescent device can be completed by using a high refractive index cured film as a part of the light loss prevention layer.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist thereof.
The structural components of the photosensitive resin compositions used in the following examples and comparative examples are as follows.

<(A) Metal oxide particles>
(A1) Zirconium dioxide particles (UEP manufactured by Daiichi Rare Element Chemical Industries, Ltd.)
Primary particle size: 10-30 nm

<(B) Dispersant>
(B1) Phosphate group-containing polymer dispersant (DISPERBYK-111 manufactured by Big Chemie)

<(C) Alkali-soluble resin (c1)>
A copolymer resin containing dicyclopentanyl methacrylate / cyclohexyl methacrylate / methacrylic acid / methyl methacrylate (molar ratio 0.091 / 0.435 / 0.434 / 0.040) as a constituent monomer has a solid content acid value of 76 mgKOH. Glycidyl methacrylate was added so as to be / g to obtain an alkali-soluble resin (c1). The obtained resin had a weight-average molecular weight (Mw) in terms of polystyrene measured by GPC of 6,000 and a solid content acid value of 76 mgKOH / g.

<(C) Alkali-soluble resin (c2)>
A copolymer resin containing dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio 0.02 / 0.05 / 0.93) as a constituent monomer is subjected to an addition reaction of acrylic acid with an equal amount of glycidyl methacrylate, followed by anhydrous tetrahydro Phthalic acid was added at a molar ratio of 0.1 to 1 mol of the above copolymer resin to obtain an alkali-soluble resin (c2). The obtained resin had a weight-average molecular weight (Mw) in terms of polystyrene measured by GPC of 7,700, and a solid content acid value of 28.5 mgKOH / g.

<(D) Photopolymerizable monomer>
(D1): Trimethylolpropane triacrylate (Kyoeisha Chemical Co., Ltd. Light acrylate TMP-A)

<(E) Photopolymerization initiator>
(E1): Oxime ester polymerization initiator. A compound of the following structure:

<(F) Solvent (boiling point is a value at 1013.25 hPa)>
(F1):
Propylene glycol monomethyl ether acetate (PGMEA) Boiling point 146 ° C
(F2):
3-Methoxy-1-butanol (MB) Boiling point 161 ° C
(F3):
1,4-butanediol diacetate (1,4-BDDA) Boiling point 232 ° C.
(F4):
Diethylene glycol ethyl methyl ether (EDM) Boiling point 176 ° C
(F5):
Propylene glycol monoethyl ether (PGEE) Boiling point 132 ° C

<Additives>
Surfactant: (Megafac F-554 manufactured by DIC)
Adhesion improver: (Nippon Kayaku KAYAMER PM-21)

(Preparation of metal oxide particle dispersion 1)
Metal oxide particles, a dispersant, an alkali-soluble resin, and a solvent were prepared with the following composition, and a metal oxide particle dispersion 1 was prepared by the following method.
First, the solid content of the metal oxide particles, the dispersant, and the alkali-soluble resin was prepared as follows. In addition, the amount of the following solvent is a total amount including the amount of the solvent contained in the dispersant and the alkali-soluble resin.

-Zirconium dioxide particles (a1) 100.00 parts by mass-Dispersant (b1) 6.67 parts by mass / solid content-Alkali-soluble resin (c1) 6.67 parts by mass / solid content-Solvent (f1) 110. 81 parts by mass / solvent (f2) 27.70 parts by mass

The above was sufficiently stirred and mixed to obtain a mixed solution.
Next, 20 g of zirconia beads having a diameter of 0.3 mm and 10 g of the mixed solution were subjected to a dispersion treatment in a range of 25 to 45 ° C. for 6 hours using a paint shaker. After completion of the dispersion treatment, the beads and the dispersion were separated by a filter to prepare a metal oxide particle dispersion 1 having a total solid content of 45% by mass.

(Preparation of photosensitive resin compositions 1-4)
Using the metal oxide particle dispersion 1 prepared as described above, each component was added so that the ratio in the solid content was the ratio shown in Table 1, and the solvent composition was the ratio shown in Table 1 and all Various solvents were added such that the solid content was 35% by mass, and the mixture was stirred and dissolved to prepare photosensitive resin compositions 1 to 4.

(Preparation of flatness evaluation composition)
Each component shown below was mixed and stirred in a glass bottle at the following mixing ratio, and PGMEA was added so that the content ratio of the total solid content was 26% by mass to prepare a composition for evaluating flatness.

Alkali-soluble resin (c2): 47.5 parts by mass Photopolymerizable monomer (d2): Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.)
47.5 parts by mass Photopolymerization initiator (e2): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.) )
3.0 parts by mass Photopolymerization initiation assistant: 2-mercaptobenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
1.5 parts by mass Surfactant: Fluorosurfactant (BYK330 manufactured by BASF)
0.1 parts by mass Adhesion improver: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)
0.5 parts by weight

(Create a base substrate for flatness evaluation)
The flatness evaluation composition was applied onto a glass substrate with a spin coater so that the film thickness after firing was 2.0 μm. Next, after drying under reduced pressure for 60 seconds, it was dried by heating on a hot plate at 100 ° C. for 90 seconds. Thereafter, patterning exposure was performed using an exposure apparatus MA-1100 (manufactured by Dainippon Kaken Co., Ltd.) using a mask in which 25 μm square covering portions were arranged at intervals of 25 μm. At this time, the gap between the mask and the substrate was 5 μm, and the exposure amount was 20 mJ / cm ² (intensity at a wavelength of 365 nm).
Next, development processing was performed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide as a developing solution using a developing device of AD-1200 manufactured by Mikasa. In the development processing, the developer was sprayed for 50 seconds at a spray pressure of 0.5 MPa while rotating the substrate at 30 rpm. Thereafter, the substrate was washed with water for 30 seconds while rotating the substrate at 300 rpm. Next, baking was performed at 230 ° C. for 30 minutes to obtain a base substrate for flatness evaluation having a cured product of the composition for flatness evaluation (hereinafter sometimes abbreviated as “cured product X”). Then, the film thickness H1 (3 in FIG. 1 (1)) of the hardened | cured material X was measured by the non-contact surface and layer cross-sectional shape measurement system VertScan (R) 2.0 by Ryoka System.

(Flatness evaluation)
On the flatness evaluation base substrate obtained as described above, the photosensitive resin composition of Example 1 was applied by a spin coater so that the film thickness on the cured product X was 3.0 μm after firing. Next, after drying under reduced pressure for 60 seconds, it was pre-baked for 90 seconds on a hot plate at 85 ° C. Then, the whole surface exposure was performed with the exposure amount of 20 mJ / cm ² (intensity at a wavelength of 365 nm) without using a mask.
Next, using a developing device AD-1200 manufactured by Mikasa Co., Ltd., development treatment and water washing treatment were performed under the same conditions as the production of the flatness evaluation base substrate. Thereafter, baking was performed at 85 ° C. for 60 minutes. Thus, a flatness evaluation substrate having a cured product of the photosensitive resin composition (hereinafter sometimes abbreviated as “cured product Y”) was obtained. In the obtained flatness evaluation substrate, the cured product Y on the cured product X is a convex portion, while the cured product Y on the glass substrate is a concave portion. Thereafter, the depth H2 of the dent portion with respect to the film surface of the cured product Y (5 in FIG. 1 (2). Difference between the height of the cured product Y on the cured product X and the height of the cured product Y on the glass substrate. ) Was measured. From the values of the film thickness H1 and the depth H2, the flattening rate R1 (%) was calculated by the following formula.
Flattening rate R1 (%) = (H1-H2) / H1 × 100
The flattening rate is preferably 80% or more from the viewpoint of optical characteristics with little unevenness.
The flattening rate R1 (%) of Example 2 and Comparative Examples 1 and 2 was calculated by the same method. Table 1 shows the results of the depth H2 and the flattening rate R1.

(Creation of refractive index evaluation board)
The photosensitive resin composition of Example 1 was applied on a glass substrate with a spin coater so that the film thickness after firing was 3.0 μm. Next, after drying under reduced pressure for 60 seconds, it was pre-baked for 90 seconds on a hot plate at 85 ° C. Then, the whole surface exposure was performed with the exposure amount of 20 mJ / cm ² (intensity at a wavelength of 365 nm) without using a mask. Next, using a developing device AD-1200 manufactured by Mikasa Co., Ltd., using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide as a developer, development treatment and washing with water under the same conditions as in the production of the base substrate for flatness evaluation Processed. Thereafter, baking was performed at 85 ° C. for 60 minutes to obtain a refractive index evaluation substrate with a cured product of the photosensitive resin composition.
Next, using a reflection spectral film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd., the absolute reflectance of the cured product of the photosensitive resin composition is measured by a light interference method, and fitting is performed using Cauchy's dispersion formula. The refractive index was calculated. At this time, as a comparison, the refractive index of glass without a cured product of the photosensitive resin composition was used, and the refractive index of air was 1.0. In the same manner, the refractive indexes of Example 2 and Comparative Examples 1 and 2 were measured. The results are shown in Table 1.

  From Table 1, the photosensitive resin compositions of Examples 1 and 2 were both high in the flattening rate and good in spite of the high content of metal oxide particles in the total solid content and the high refractive index. It was. On the other hand, the photosensitive resin compositions of Comparative Examples 1 and 2 had low flatness. Thereby, even when the content rate of the metal oxide particle was high, it turned out that flatness becomes favorable by using a solvent with a high boiling point.

In order to increase the refractive index, it is necessary to increase the content ratio of the metal oxide particles, but the content ratio of clear components such as alkali-soluble resin and photopolymerizable monomer is decreased accordingly, Since the fluidity at the time of preliminary firing is lowered, the planarization performance tends to be lowered.
The photosensitive resin compositions of Examples 1 and 2 contain a high-boiling solvent having a boiling point of 170 ° C. or higher at 101.25 hPa, so that the solvent tends to remain in the coating film even after drying under reduced pressure. Since the evaporation of the solvent is slow, the fluidity at the time of pre-baking on the hot plate is increased, and it is estimated that the flatness is improved.
In contrast, the photosensitive resin compositions of Comparative Examples 1 and 2 do not contain a high-boiling solvent having a boiling point of 170 ° C. or higher at 1013.25 hPa. Since the fluidity of the resin composition is lost, it is estimated that the planarization performance is lowered.
From the comparison between Example 1 and Example 2, the flatness of Example 1 was better than that of Example 2. This is because 1,4-BDDA has a higher boiling point than EDM, and has a diacetate structure, resulting in a larger molecular skeleton and evaporation to metal oxide particles and alkali-soluble resins in the coating. This is presumed to be because it was more likely to remain in the film during drying under reduced pressure.

1 Glass substrate 2 Cured product X
3 Thickness H1 of cured product X
4 Cured material Y
5 Depth H2 of recessed portion in cured product Y
6 Film thickness H3 of cured product Y on cured product X

Claims (9)

Photosensitive resin composition containing (A) metal oxide particles, (B) dispersant, (C) alkali-soluble resin, (D) photopolymerizable monomer, (E) photopolymerization initiator, and (F) solvent. Because
The (A) metal oxide particles contain at least one selected from the group consisting of zirconium dioxide particles, titanium dioxide particles, and barium titanate particles,
The content ratio of the (A) metal oxide particles is 50% by mass or more in the total solid content, and
The photosensitive resin composition, wherein the solvent (F) contains a high-boiling solvent having a boiling point of 170 ° C. or higher at 101.25 hPa.   The photosensitive resin composition according to claim 1, wherein the high-boiling solvent contains at least one selected from the group consisting of alkylene glycol diacetate and dialkylene glycol dialkyl ether.   The photosensitivity according to claim 2, wherein the high-boiling solvent contains at least one selected from the group consisting of 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and diethylene glycol ethyl methyl ether. Resin composition.   The photosensitive resin composition of any one of Claims 1-3 whose content rate of the said high boiling point solvent is 10 mass% or more in the said (F) solvent. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (C) alkali-soluble resin includes an acrylic copolymer resin having a partial structure represented by the following general formula (I).

(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. * Represents a bond.)   The photosensitive resin composition of any one of Claims 1-5 in which the said (B) dispersing agent contains the polymer dispersing agent which has a phosphoric acid group.   Hardened | cured material which hardened the photosensitive resin composition of any one of Claims 1-6.   An image display device comprising the cured product according to claim 7.   The illumination containing the hardened | cured material of Claim 7.

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