WO2015076160A1 - Curable composition, method for producing cured film, cured film, and display device - Google Patents

Abstract

Provided are: a curable composition which can achieve high hardness even when heated at a low temperature; a method for producing a cured film using the curable composition; a cured film; and an organic EL display device and a liquid crystal display device each produced using a cured film. A curable composition comprising (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group, (J) a compound having a carboxyl group and having a weight average molecular weight of 1000 to 50,000 (wherein a compound corresponding to the component (I) is excluded), (C) an alkoxysilane compound, (D) an organic solvent and (E) inorganic particles having an average particle diameter of 1 to 200 nm and/or polymer particles having an average particle diameter of 1 to 200 nm. In the curable composition, the average porosity which is an arithmetic average value of area ratios determined with respect to 200 particles selected from the inorganic particles and the polymer particles is less than 10%, wherein each of the area ratios is the ratio of the area of a void part to the area of a particle cross section in a cross sectional image of each of the particles as observed on an electron microscope. When the curable composition is cured to produce a film, the total light transmittance of the film as measured in accordance with JIS-K-7136 is 90% or more.

Description

Curable composition, method for producing cured film, cured film, and display device

The present invention relates to a curable composition, a method for producing a cured film, a cured film, and an organic EL display device and a liquid crystal display device using the cured film.

Flat panel displays such as liquid crystal display devices and organic EL display devices are widely used. Recently, in the manufacturing process of these displays, it is necessary to lower the heating temperature of various cured films in the manufacturing process from the viewpoint of reducing damage to substrates and circuits and saving energy.
As such a curable composition, for example, Patent Document 1 discloses a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, an epoxy group-containing radically polymerizable compound, and a monoolefin unsaturated compound. A thermosetting resin composition is disclosed in which a polymer is dissolved in an organic solvent.

JP-A-6-157716

However, the curable composition described in Patent Document 1 requires a heating temperature of 200 ° C. or higher. When heated at a low temperature (for example, 180 ° C. or lower, further 150 ° C. or lower), sufficient hardness cannot be obtained.
An object of the present invention is to provide a curable composition capable of obtaining high hardness even when heated at a low temperature. Furthermore, it aims at providing the manufacturing method and cured film of a cured film using the said curable composition, and the organic electroluminescent display device and liquid crystal display device using the cured film.

As a result of investigations by the inventors of the present invention in such a situation, the above problem has been solved by the following means <1>, preferably <2> to <12>.
<1> (I) an acrylic resin having an epoxy group and / or a styrene resin having an epoxy group,
(J) a compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 (except for those corresponding to the component (I)),
(C) an alkoxysilane compound,
(D) an organic solvent, and (E) inorganic particles having an average particle diameter of 1 to 200 nm and / or polymer particles having an average particle diameter of 1 to 200 nm, and voids in a cross-sectional image of the particles of the inorganic particles and the polymer particles by an electron microscope Measured in accordance with JIS-K-7136 of a curable composition having an average porosity of less than 10%, which is the arithmetic average of 200 area ratios between the part and the particle cross-section, and in which the curable composition is cured A curable composition having a total light transmittance of 90% or more.
<2> The curable composition according to <1>, further comprising (F) a crosslinking agent.
<3> (F) The curable composition according to <2>, wherein the crosslinking agent comprises a blocked isocyanate compound.
<4> (F) The curable composition according to <2> or <3>, wherein the crosslinking agent contains a polyfunctional mercapto compound.
<5> The curable composition according to any one of <1> to <4>, wherein the solid content concentration of the curable composition is 20 to 40% by mass.
<6> (1) A step of applying the curable composition according to any one of <1> to <5> on a substrate,
(2) a step of removing the solvent from the applied curable composition;
(3) A method for producing a cured film, comprising a step of thermosetting.
The manufacturing method of the cured film as described in <6> whose thermosetting temperature in a <7> (3) process is 150 degrees C or less.
<8> The method for forming a cured film according to <6> or <7>, including a step of exposing the entire surface after the step of (2) removing the solvent and before the step of (3) thermosetting.
<9> A cured film obtained by curing the curable composition according to any one of <1> to <5>.
<10> The cured film according to <9>, which is a protective film.
<11> The cured film according to <9> or <10>, wherein the pencil hardness at a load of 750 g measured according to JIS 5600 is 2H or more.
<12> An organic EL display device or a liquid crystal display device having the cured film according to any one of <9> to <11>.

According to the present invention, it is possible to provide a curable composition that can obtain high hardness even when heated at a low temperature. Furthermore, it has become possible to provide a method for producing a cured film and a cured film using the curable composition, and an organic EL display device and a liquid crystal display device using the cured film.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 is a conceptual diagram illustrating a configuration of an example of a liquid crystal display device having a touch panel function.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
The solid content in the present invention refers to a solid content at 25 ° C.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene converted values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgelｇSuper AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

The composition of the present invention comprises (I) an acrylic resin having an epoxy group and / or a styrene resin having an epoxy group, (J) a compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 (provided that (I) (C) alkoxysilane compound, (D) organic solvent, and (E) inorganic particles having an average particle size of 1 to 200 nm and / or polymer particles having an average particle size of 1 to 200 nm, The curable composition having an average porosity of less than 10%, which is an arithmetic average of 200, of the area ratio between the void portion of the cross-sectional image of the inorganic particle and the polymer particle and the cross-section of the particle, and the cured The total light transmittance measured according to JIS-K-7136 of the film obtained by curing the adhesive composition is 90% or more.
By setting it as such a structure, the cured film which can be hardened | cured at low temperature and has high hardness is obtained. The curable composition of the present invention may further contain other components such as a crosslinking agent and a surfactant.

<(I) Acrylic resin having an epoxy group and / or a styrene resin having an epoxy group>
The curable composition of the present invention contains an acrylic resin having an epoxy group and / or a styrene resin having an epoxy group (hereinafter sometimes referred to as “an acrylic resin having an epoxy group”). The acrylic resin in the present invention means a polymer of acrylic ester and / or methacrylic ester, and other radical polymerizable monomers may also be copolymerized. The styrene resin having an epoxy group includes a repeating unit derived from styrene and may have other radical polymerizable monomers. Moreover, in this specification, about the resin containing both the repeating unit derived from (meth) acrylate and the repeating unit derived from styrene, a resin having a higher molar ratio of the repeating unit derived from (meth) acrylate is referred to as an acrylic resin. A resin having a higher molar ratio of repeating units derived from styrene is referred to as a styrene resin.
The repeating unit derived from (meth) acrylate in the acrylic resin having an epoxy group is preferably 70 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. The upper limit is not particularly defined and may be 100 mol%.
The repeating unit derived from styrene in the styrene-based resin having an epoxy group is preferably 70 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. The upper limit is not particularly defined and may be 100 mol%.

<< Repeating unit having an epoxy group >>
The acrylic resin having an epoxy group and / or the styrene resin having an epoxy group in the present invention includes a repeating unit having an epoxy group. The repeating unit having an epoxy group is preferably a repeating unit derived from (meth) acrylate having an epoxy group or a repeating unit derived from styrene having an epoxy group.
(I) In the acrylic resin having an epoxy group, the content of the repeating unit having an epoxy group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and particularly preferably 30 to 80 mol%.

As the acrylic resin having an epoxy group used in the present invention, one containing a repeating unit represented by any of the following formulas (3) to (5) is preferable. Further, it may contain repeating units derived from other radical polymerizable monomers.

(In the formulas (3) to (5), R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are Each represents a hydrogen atom or an alkyl group, and n is an integer of 1 to 10.)
R ¹ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Specific examples of the radical polymerizable monomer used to form the repeating unit containing an epoxy group include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-methacrylic acid 3,4- (Meth) acrylates such as epoxybutyl, 4,5-epoxypentyl acrylate, 4,5-epoxypentyl methacrylate, 6,7-epoxyheptyl acrylate, and 6,7-epoxyheptyl methacrylate; o-vinylbenzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, etc. Vinyl Vinyl glycidyl ethers such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether, p-vinylphenyl glycidyl ether; 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl Methacrylate is mentioned. Among these, glycidyl acrylate, glycidyl methacrylate, p-vinylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate are preferable, and glycidyl acrylate and glycidyl methacrylate are particularly preferable. These monomers can be used alone or in combination of two or more.

<< Other radical polymerizable monomers >>
The acrylic resin having an epoxy group in the present invention may have a repeating unit other than the repeating unit having an epoxy group. Other repeating units are not particularly limited as long as they can be copolymerized with the radical polymerizable monomer represented by any one of the above formulas (3) to (5). Specific examples include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, α-methyl-acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate. Acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, tert-butyl acrylate, methacryl Tert-butyl acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate , Repeating units of benzyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile and the like.
These monomers can be used alone or in combination of two or more.
When other repeating units are included, it is preferably 50 mol% or less, more preferably 30 mol% or less in (I) an acrylic resin having an epoxy group. The lower limit is preferably 5 mol% or more, and more preferably 10 mol% or more.

(I) The weight average molecular weight of the acrylic resin having an epoxy group and / or the styrene resin having an epoxy group is preferably 1,000 to 200,000, more preferably 2,000 to 50,000 in terms of polystyrene. Range.

In the effect composition of the present invention, the content of (I) the acrylic resin having an epoxy group and / or the styrene resin having an epoxy group is in the solid content of 100 parts by mass from the viewpoint of the cured film hardness. 20 to 80 parts by mass, preferably 25 to 70 parts by mass, and more preferably 29 to 60 parts by mass.
The curable composition of the present invention preferably contains (I) an acrylic resin having an epoxy group and / or a styrene resin having an epoxy group in an amount of 20 to 80% by mass, preferably 25 to 70% by mass. More preferably, it is more preferably 29 to 60% by mass.
(I) As for acrylic resin etc. which have an epoxy group, only 1 type may be used and 2 or more types can also be mixed and used. When blending two or more, the total amount is preferably in the above range. In the present invention, it is preferable to include at least an acrylic resin having an epoxy group.

<(J) Compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 (except for those corresponding to component (I))>
The curable composition of the present invention contains (J) a compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000. However, (J) a compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 is not a compound corresponding to the above (I) acrylic resin having an epoxy group.
As the compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000, a known compound can be used. Of these, acrylic resins are preferred.

The compound having a carboxyl group and having a weight average molecular weight of 1000 to 50,000 is preferably a resin having a repeating unit represented by any one of formulas (1) to (4) and a repeating unit having a carboxylic acid group. More preferably, it is an acrylic resin.

(In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each represent a hydrogen atom or a monovalent organic group, and W ¹ , W ² , W ³ and W ⁴ represents —O— or —NH—, respectively, R represents a hydrogen atom or a monovalent organic group, R ′ represents a branched or straight chain alkylene group, and Y ¹ , Y ² , Y ³ and Y ⁴ each represent a divalent linking group, Z ¹ , Z ² , Z ³ and Z ⁴ each represent a hydrogen atom or a monovalent organic group, and n, m, p and q are Each is independently an integer of 3 to 500, and j and k are each independently an integer of 2 to 8.)
X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.
W ¹ , W ² , W ³ and W ⁴ each represent —O— or —NH—, preferably —O—.

(J) The content of the repeating unit represented by any one of formulas (1) to (4) in the compound having a carboxyl group and a weight average molecular weight of 1,000 to 50,000 is preferably 10 to 90 mol%, ˜80 mol% is more preferred, 30˜80 mol% is still more preferred, and 30˜70 mol% is particularly preferred.
The repeating unit represented by any one of the formulas (1) to (4) may include only one type or two or more types. When two or more types are included, the total amount is within the above range.

As the repeating unit having a carboxylic acid group, acrylic acid and methacrylic acid are preferable. (J) In the compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000, the content of the repeating unit having a carboxylic acid group is preferably 10 to 90% by mole, more preferably 20 to 80% by mole of the total repeating unit. 30 to 80 mol% is more preferable, and 30 to 70 mol% is particularly preferable. The repeating unit having a carboxylic acid group may contain only one type or two or more types. When two or more types are included, the total amount is within the above range.

Furthermore, (J) the compound having a carboxyl group and having a weight average molecular weight of 1000 to 50,000 can also contain other known repeating units.
Other repeating units are not particularly limited as long as they can be copolymerized with any one of the formulas (1) to (4). Specific examples include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, α-methyl-acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate. , Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylic 2-hydroxyethyl acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, isoboacrylate Mention may be made of repeating units such as lunyl, isobornyl methacrylate, acrylonitrile and the like.

(J) In the compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000, the other repeating unit is preferably in the range of 0 to 50 mol%, more preferably in the range of 10 to 30 mol%. preferable. Other repeating units may include only one type or two or more types. When two or more types are included, the total amount is within the above range.

(J) As the compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000, a compound represented by the formula (5) can also be used.

(In Formula (5), R ³ represents a (m + n) -valent linking group, R ⁴ and R ⁵ each represent a single bond or a divalent linking group, and A ² represents a monovalent organic compound containing a carboxyl group. Each of n A ² and R ⁴ may be the same or different, m represents 0 to 8, n represents 2 to 9, and m + n represents 3 to 10; Yes, P ² represents a polymer skeleton, and m P ² and R ⁵ may be the same or different, respectively.

In the above formula (5), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. n R ^{4 s} may be the same or different. Further, m R ^{5 s} may be the same or different.
Examples of the divalent linking group in R ⁴ and R ⁵ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. And a group consisting of 0 to 20 sulfur atoms, may be unsubstituted or may further have a substituent.

Specific examples of the divalent linking group include the following structural units or groups formed by combining the above structural units.

R ⁴ and R ⁵ are each independently a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 Divalent linking groups consisting of up to 10 hydrogen atoms and 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms More preferred are divalent linking groups consisting of atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 From 0 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. Particularly preferred are divalent linking groups.

Among the above, when the divalent linking group has a substituent, examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxy group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like having 6 to 16 carbon atoms, methoxy group, ethoxy group, etc. To 6 alkoxy groups, halogen atoms such as chlorine and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, and t-butyl carbonate group And the like, and the like.

In the above formula (5), R ³ represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
The (m + n) -valent linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.

Specific examples of the (m + n) -valent linking group include the following structural units or groups formed by combining the above structural units (which may form a ring structure).

(M + n) -valent linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And preferred are groups consisting of 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to More preferred are groups consisting of up to 100 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 atoms. Particularly preferred are groups consisting of up to oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.

Among the above, when the (m + n) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbons having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, and cyclohexyloxycarbonyl group, cyano group, and t-butyl Examples thereof include carbonate groups such as carbonate groups.

Specific examples (specific examples (1) to (17)) of the (m + n) -valent linking group represented by R ³ are shown below. However, the present invention is not limited to these.

Among the above specific examples, the most preferable (m + n) -valent linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In the above formula (5), m represents 0-8. m is preferably 0.5 to 5, more preferably 0.5 to 4, and particularly preferably 0.5 to 3.
In the above formula (5), n represents 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

Further, P ² in the formula (5) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. M P ² present in the formula (5) may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified products or copolymers of [for example, polyether / polyurethane copolymers, copolymers of polyether / vinyl monomers, etc. (any of random copolymers, block copolymers, and graft copolymers). May be included). And at least one selected from the group consisting of vinyl monomers, polymers or copolymers, ester polymers, ether polymers, urethane polymers, and their modified products or copolymers. At least one selected is more preferable, a polymer or copolymer of a vinyl monomer is further preferable, and an acrylic resin (a polymer or copolymer of a (meth) acryl monomer) is particularly preferable.

In the present invention, the polymer skeleton in P ² preferably has at least one acid group.
Examples of the polymer having an acid group constituting the polymer skeleton include, for example, a polyamidoamine and salt thereof, a polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified polymer having acid groups. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like. Among these, a (meth) acrylic acid copolymer is preferable.

The means for introducing an acid group into the polymer skeleton is not particularly limited. For example, a means for introducing an acid group with a vinyl monomer, a means for introducing an acid group using a crosslinkable side chain, and the like are adopted. However, as will be described later, the mode in which the acid group is introduced by the constitution of the polymer skeleton including a structural unit derived from a vinyl monomer having an acid group makes it easy to control the amount of acid group introduced. From the viewpoint of synthesis cost.
Here, examples of the “acid group” include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
Hereinafter, preferable examples of these vinyl monomers will be described.

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-Methylhexyl acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) (meth) acrylate ) Ethyl, (meth) acrylic acid 3-phenoxy-2-hydroxypropyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, (meth) acrylic Vinyl acetate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meth) Benzyl acrylate, (meth) acrylic acid diethylene glycol monomethyl ether , (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene Glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acryl Trifluoroethyl acid, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) Acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid γ- butyrolactone-2-yl.

Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Le acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-butoxycarbonyl group (t-Boc), etc.), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

Also used are (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. it can.

In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or urea group can be appropriately synthesized by utilizing an addition reaction between an isocyanate group and a hydroxyl group or an amino group, for example. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group, or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer, primary or It can be appropriately synthesized by an addition reaction between a secondary amino group-containing monomer and monoisocyanate.

Next, a vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P ² will be described.
Examples of the vinyl monomer having an acid group include a vinyl monomer having a carboxy group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxy group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxypolycaprolactone mono (Meth) acrylate and the like can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

Furthermore, as the vinyl monomer having an acid group, a vinyl monomer containing a phenolic hydroxy group or a vinyl monomer containing a sulfonamide group can be used.
When the polymer skeleton P ² includes a monomer unit derived from a vinyl monomer containing an acid group, the content of the monomer unit derived from a vinyl monomer having an acid group in the polymer skeleton is expressed in terms of mass in the entire polymer skeleton. On the other hand, the content is preferably 3% by mass to 40% by mass, and more preferably in the range of 5% by mass to 20% by mass.

The content of acid groups in component J is appropriately determined depending on the acid value of component J. The acid value of Component J is preferably 20 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, and particularly preferably 50 to 210 mgKOH / g. When the acid value is 20 mgKOH / g or more, the alkali developability of the photosensitive resin composition is sufficiently obtained, and when the acid value is 300 mgKOH / g or less, the development stability and film reduction are excellent.

(J) Examples of commercially available compounds having a weight average molecular weight of 1000 to 50,000 having a carboxyl group include Joncryl 67 (manufactured by BASF).
(J) Examples of the compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 include the carboxylic acid-containing resins described in paragraphs 0019 to 0032 of JP2013-83698A, in addition to the above. The contents of which are incorporated herein by reference.

(J) The weight average molecular weight of the compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 is preferably 2000 to 20,000, more preferably 3,000 to 50,000.

The curable composition of the present invention may contain (J) a compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 in a proportion of 10 to 60 parts by mass with respect to 100 parts by mass of the solid content of the composition. The content is preferably 15 to 50 parts by mass, more preferably 20 to 45 parts by mass.
The curable composition of the present invention may contain only one type (J) a compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000, or two or more types. When two or more types are included, the total amount is preferably within the above range.

<(C) Alkoxysilane compound>
The curable composition of the present invention contains an alkoxysilane compound. When an alkoxysilane compound is used, the adhesion between the film formed from the curable composition of the present invention and the substrate can be improved. The alkoxysilane compound that can be used in the curable composition of the present invention includes a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, molybdenum, titanium, and aluminum, and an insulating film. It is preferable that it is a compound which improves the adhesiveness of. Specifically, a known silane coupling agent or the like is also effective. A silane coupling agent having an ethylenically unsaturated bond is preferred.
Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Of these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltriacoxysilane are more preferable. These can be used alone or in combination of two or more.
Examples of commercially available products include KBM-403 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

The content of the alkoxysilane compound in the curable composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 2 to 20 parts by mass, with respect to 100 parts by mass in total of the total solid content. Part is more preferred. Only one type of alkoxysilane compound may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

<(D) Solvent>
The curable composition of the present invention contains a solvent. It is preferable that the curable composition of this invention is prepared as a solution which melt | dissolved the component A which is an essential component, the component B, the component C, and the below-mentioned arbitrary component in the solvent.
As the solvent used in the curable composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether. , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, di Propylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones Etc. can be exemplified. As specific examples of these solvents, reference can be made to paragraph 0062 of JP-A-2009-098616. Specific examples include propylene glycol monomethyl ether acetate and methyl ethyl diglycol.
The boiling point of the solvent is preferably 100 ° C. to 300 ° C., more preferably 120 ° C. to 250 ° C. from the viewpoint of applicability.
The solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
The content of the solvent in the curable composition of the present invention is preferably 100 to 3,000 parts by mass per 100 parts by mass of the solid content from the viewpoint of adjusting the viscosity to be suitable for coating, and 200 to 2, The amount is more preferably 000 parts by mass, and still more preferably 250 to 1,000 parts by mass.
The solid content concentration of the curable composition is preferably 3 to 50% by mass, and more preferably 20 to 40% by mass.

The viscosity of the curable composition is preferably 1 to 200 mPa · s, more preferably 2 to 100 mPa · s, and most preferably 3 to 800 mPa · s. The viscosity is preferably measured at 25 ± 0.2 ° C. using, for example, a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed during measurement is preferably 100 rpm for less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 10 rpm for 30 mPa · s or more.

<(E) Inorganic particles having an average particle size of 1 to 200 nm and / or polymer particles having an average particle size of 1 to 200 nm>
The curable composition of the present invention contains inorganic particles having an average particle size of 1 to 200 nm and / or polymer particles having an average particle size of 1 to 200 nm. By containing such particles, the hardness of the cured film becomes more excellent.
From the viewpoint of the hardness of the cured film, the porosity of the particles is preferably less than 10%, more preferably less than 3%, and most preferably no void. The term “void” as used herein means a portion that becomes a hole inside the particle, which is seen when a cross section of the particle is observed. The void ratio of the particles is an arithmetic average of 200 of the area ratio between the void portion of the cross-sectional image of the particles by the electron microscope and the particle cross-section.

The particle diameter is from 1 to 200 nm, preferably from 5 to 100 nm, more preferably from 5 to 50 nm, from the viewpoint of the hardness and transparency of the cured film. The particle diameter is an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.

<< Inorganic particles >>
Examples of the inorganic particles include metal, metal oxide, and mica particles from the viewpoints of particle stability, cured film hardness, transparency, and refractive index controllability.
As the metal particles, any of transition metal elements and typical metal elements can be applied. For example, iron, cobalt, nickel, ruthenium, rhodium, palladium belonging to Group VIII of the periodic table, which are widely used for various purposes. Application of osmium, iridium, platinum, copper, silver, gold, etc. belonging to Group IB of the periodic table is preferred. Among these, gold, silver, platinum, palladium, copper, and nickel that are excellent in conductivity are preferable, and copper, silver, and nickel are more preferable. These are not limited to one type, but may be a combination of two or more types, or may be an alloy.

As metal oxide particles, Si, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn , Oxide particles containing atoms such as B, Al, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferable, silicon oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, Antimony / tin oxide is more preferable, and silicon oxide, titanium oxide, titanium composite oxide, and zirconium oxide are still more preferable.

Natural mica (hereinafter simply referred to as mica) is an important family of rock-forming minerals, and is a generic name for minerals that form a laminated structure and have cleavage properties (features that each layer is easily peeled off). Mica is an octahedron composed of two or three metal oxides / hydroxides between four tetrahedral structures formed by oxides of three atoms of silicon (Si) and one atom of aluminum (Al). It is a 2: 1 type clay mineral that forms a structure sandwiching the structure. Since 1/4 of the tetrahedron is substituted with Al, the layers of each layer of mica that is configured with the tetrahedron-octahedron-tetrahedron as one unit have a negative charge. It has a structure in which a valent cation (cation) is incorporated in the form of a 12-coordinate at the center of a 6-membered ring formed by 6 tetrahedra.
In addition, mica can be artificially synthesized. Synthetic mica containing OH, like the crystal structure of natural mica, needs to melt the raw material mixture under pressure. Fluorine mica, in which OH in natural mica crystals is replaced with fluorine, melts under normal pressure. Since they can be synthesized, most of the industrially synthesized mica is fluorine mica, and synthetic mica usually refers to such fluorine mica. For example, synthetic potassium phlogopite [theoretical formula: KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ] that is often blended in cosmetics among synthetic mica is natural phlogopite [theoretical formula: KMg ₃ (AlSi ₃ O ₁₀ ) (OH ) ₂ ] is a synthetic fluorophlogopite having a structure in which OH is replaced by F.
Examples of commercially available products include PMA-ST (manufactured by Nissan Chemical Co., Ltd.), MIBK-ST-L (manufactured by Nissan Chemical Co., Ltd.), TTO-51 (manufactured by Ishihara Sangyo Co., Ltd.), silver nanoparticles (manufactured by Adachi Shin Sangyo Co., Ltd.), etc. Is done.

<< Polymer inorganic particles >>
Examples of polymer particles include linear polymers such as polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polycarbonate, and polyamide; divinylbenzene, hexatriene, divinyl ether, divinylsulfone, diallylcarbyl Nord, alkylene diacrylate, oligo or polyalkylene glycol diacrylate, oligo or polyalkylene glycol dimethacrylate, alkylene triacrylate, alkylene tetraacrylate, alkylene trimethacrylate, alkylene tetramethacrylate, alkylene bisacrylamide, alkylene bismethacrylamide, both end acrylic Modified polybutadiene oligomer etc. Or a network polymer obtained by polymerization with other polymerizable monomers; thermosetting resins such as phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, γ- (meth) acryloxypropyltrimethoxysilane, Examples thereof include resins obtained by copolymerizing silane-containing monomers such as trimethoxysilylstyrene and vinyltrimethoxysilane alone or with other polymerizable monomers. From the viewpoint of film strength, polymer crosslinked particles are preferred.
Examples of commercially available products include Chemisnow MP-1451 (manufactured by Soken Chemical Co., Ltd.).

In the present invention, the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
From the viewpoint of hardness, the content of these particles is preferably 1 to 80 parts by mass, more preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass per 100 parts by mass of the solid content. Is more preferable.
These particles may include only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.

<(F) Crosslinking agent>
If necessary, a crosslinking agent can be added to the curable composition of the present invention.
As the crosslinking agent, a polymerizable monomer having an ethylenically unsaturated bond, a compound having two or more epoxy groups and / or oxetanyl groups in the molecule (except for those corresponding to the component (I)), Alkoxymethyl group or methylol group-containing crosslinking agent, blocked isocyanate compound, polyfunctional mercapto compound (preferably aliphatic polyfunctional mercapto compound), known epoxy curing agent (except for those corresponding to component (I)) Etc. By adding a crosslinking agent, the cured film can be made a strong film.

<< Polymerizable monomer having an ethylenically unsaturated bond >>
The curable composition of the present invention may contain a polymerizable monomer having an ethylenically unsaturated bond. As the polymerizable monomer having an ethylenically unsaturated bond, (meth) acrylate is preferable, polyfunctional (meth) acrylate is more preferable, and tri- to hexafunctional (meth) acrylate is more preferable.
Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like.

<< Compound having two or more epoxy groups and / or oxetanyl groups in the molecule (excluding those corresponding to component (I)) >>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

These are available as commercial products. For example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 And bisphenol F-type epoxy resins such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Co., Ltd.), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.) As the phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (or higher) The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (above, made by Nippon Kayaku Co., Ltd.), etc., and ADEKA RES as the aliphatic epoxy resin N EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Chemical) Kogyo Co., Ltd.). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) and the like. These can be used alone or in combination of two or more.

As specific examples of the compound having an oxetanyl group, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used. Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

<< Block isocyanate compound >>
The curable composition of the present invention may contain a blocked isocyanate compound. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. The upper limit is not particularly defined, but 6 or less is preferable.
The skeleton of the blocked isocyanate compound is not particularly limited, and any skeleton may be used as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetraisocyanate Methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, , 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane 1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane Isocyanates such as diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate Compounds and compounds having a prepolymer type skeleton derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the blocked isocyanate compound in the composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

The blocked isocyanate compound that can be used in the composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, Nippon Polyurethane Industry) Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals), Duranate 17B-60P, 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 ( Asahi Kasei Chemicals), Death Mod BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumijoule BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are preferable Can be used.

<< Polyfunctional mercapto compound >>
The curable composition of the present invention may contain a polyfunctional mercapto compound. The polyfunctional mercapto compound is not particularly limited as long as it is a compound having two or more mercapto groups, but is preferably a compound having 2 to 6 mercapto groups, more preferably a compound having 2 to 4 mercapto groups. As the polyfunctional mercapto compound, an aliphatic polyfunctional mercapto compound is preferable. A preferred example of the aliphatic polyfunctional mercapto compound is a compound comprising a combination of an aliphatic hydrocarbon group and —O—, —C (═O) —, wherein at least two hydrogen atoms of the aliphatic hydrocarbon group are present. Examples are compounds in which one is substituted with a mercapto group.

Examples of the aliphatic polyfunctional mercapto compound include pentaerythritol tetrakis (3-mercaptobutyrate) and 1,4-bis (3-mercaptobutyryloxy) butane. Examples of commercially available products include Karenz MT-PE-1, Karenz MT-BD-1, Lens MT-NR-1 (manufactured by Showa Denko).

<< Epoxy curing agent >>
Examples of the epoxy curing agent include amines such as aliphatic amines and aromatic amines, and acid anhydrides such as aliphatic acid anhydrides and aromatic acid anhydrides.

<< Other cross-linking agents >>
Other cross-linking agents such as alkoxymethyl group and methylol group-containing cross-linking agents can also be used, and specific examples include cross-linking agents described in paragraph numbers 0187 to 0199 of JP 2011-212494A. The contents of which are incorporated herein by reference.

From the viewpoint of obtaining excellent hardness of the cured film, the addition amount of the crosslinking agent is preferably 0 to 50 parts by weight, more preferably 1 to 30 parts by weight, more preferably 1.5 to 20 parts by mass is more preferable, and 2 to 10 parts by mass is particularly preferable.
The curable composition of the present invention may contain only one type of crosslinking agent or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<(G) Surfactant>
The curable composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. The surfactant is preferably a nonionic surfactant, and more preferably a fluorosurfactant.
As the surfactant that can be used in the present invention, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780 are commercially available. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), KP ( Shin-Etsu Chemical Co., Ltd., Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by JEMCO), MegaFac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass) PolyFox (OMNOVA) And other series).

In addition, the surfactant includes a structural unit A and a structural unit B represented by the following formula (W), and has a polystyrene-reduced weight average molecular weight (Mw) of 1 measured by gel permeation chromatography using tetrahydrofuran as a solvent. As a preferable example, a copolymer having a molecular weight of 1,000 or more and 10,000 or less can be given.

In the formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10. )

L is preferably a branched alkylene group represented by the following formula (W-2). R ⁵ in formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

When blended, the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass in the total solid content of the curable composition. More preferred is 01 to 2.0 parts by mass.
Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
If necessary, the curable composition of the present invention may contain other components such as a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid proliferating agent, and an antioxidant. As these components, for example, those described in JP2009-98616A, JP2009-244801A, and other known ones can be used. Further, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like may be added to the curable composition of the present invention.

In the present invention, a composition containing the following components (preferably a composition having a compounding amount other than the following components of 3% by mass or less of the composition) is exemplified as a specific embodiment.
<First Embodiment>
(I) an acrylic resin having an epoxy group and / or a styrene resin having an epoxy group,
(J) A compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 (excluding those corresponding to component (I))
(C) alkoxysilane compound (D) organic solvent (E) inorganic particles having an average particle diameter of 1 to 200 nm

<Second Embodiment>
(I) Acrylic resin having an epoxy group and / or a styrene resin having an epoxy group (J) A compound having a carboxyl group and having a weight average molecular weight of 1000 to 50,000 (except for those corresponding to the component (I))
(C) Alkoxysilane compound (D) Organic solvent (E) Inorganic particles with an average particle size of 1 to 200 nm (F) Compounds having two or more epoxy groups in the molecule (excluding those corresponding to component (I) )

<Third Embodiment>
(I) Acrylic resin having an epoxy group and / or a styrene resin having an epoxy group (J) A compound having a carboxyl group and having a weight average molecular weight of 1000 to 50,000 (except for those corresponding to the component (I))
(C) Alkoxysilane compound (D) Organic solvent (E) Inorganic particles having an average particle size of 1 to 200 nm (F) Blocked isocyanate compound

<Fourth Embodiment>
(I) Acrylic resin having an epoxy group and / or a styrene resin having an epoxy group (J) A compound having a carboxyl group and having a weight average molecular weight of 1000 to 50,000 (except for those corresponding to the component (I))
(C) alkoxysilane compound (D) organic solvent (E) inorganic particles having an average particle size of 1 to 200 nm (F) polyfunctional mercapto compound

<Fifth Embodiment>
(I) an acrylic resin having an epoxy group and / or a styrene resin having an epoxy group,
(J) A compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000 (excluding those corresponding to component (I))
(C) Alkoxysilane compound (D) Organic solvent (E) Inorganic particles with an average particle size of 1 to 200 nm (F) Compounds having two or more epoxy groups in the molecule (excluding those corresponding to component (I) )
(F) Block isocyanate compound

<Sixth Embodiment>
(I) A weight average molecular weight of 1000 having an acrylic resin (J) carboxyl group obtained by copolymerizing a compound represented by the following formula (3), (meth) acrylic acid, and other radical polymerizable monomers. ~ 50,000 compounds (except those corresponding to component (I))
(C) Alkoxysilane compound (D) Organic solvent (E) Inorganic particles with a particle size of 1 to 200 nm (F) Blocked isocyanate compound

(In the formula (3), R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and R ² , R ³ and R ⁴ each represents a hydrogen atom or an alkyl group. N represents 1 to 10 (It is an integer.)

<Seventh Embodiment>
In the first to sixth embodiments, (E) Inorganic particles having an average particle diameter of 1 to 200 nm are changed to polymer particles having an average particle diameter of 1 to 200 nm.

<Eighth Embodiment>
Embodiments in which a surfactant is further blended in the first to seventh embodiments.

<The manufacturing method of the cured film of this invention>
The method for producing a cured film of the present invention preferably includes the following steps (1) to (3).
(1) The process of apply | coating the curable composition of this invention on a board | substrate,
(2) a step of removing the solvent from the applied curable composition;
(3) Step of thermosetting

In the step of applying (1), the curable composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the curable composition to the substrate, the substrate can be cleaned such as alkali cleaning or plasma cleaning. Furthermore, the substrate surface can be treated with hexamethyldisilazane or the like after cleaning the substrate. By performing this treatment, the adhesiveness of the curable composition to the substrate tends to be improved.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like. These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.

Since the curable composition of the present invention has good adhesion to a metal film or metal oxide formed by sputtering, the substrate preferably contains a metal film formed by sputtering. The metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium, and oxides or alloys thereof, molybdenum, titanium, aluminum, copper And alloys thereof are more preferred. In addition, a metal and a metal oxide may be used individually by 1 type, or may use multiple types together.

The coating method on the substrate is not particularly limited, and for example, an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.

(2) In the step of removing the solvent, the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds.

Furthermore, in the present invention, after the step of (2) removing the solvent and before the step of (3) thermosetting, a step of exposing the entire surface from the viewpoint of improving the film hardness may be included. In this case, it is preferable to perform energy exposure of about 50 to 3000 mJ / cm ² with a mercury lamp or an LED lamp.
For pattern formation, pattern exposure and development steps can be performed after the solvent removal step (2). The pattern exposure method is preferably a method using a mask or a direct drawing method using a laser or the like.

(3) In the step of thermosetting, a cured film is formed by heating. As heating temperature, 180 degrees C or less is preferable, 150 degrees C or less is more preferable, and 130 degrees C or less is further more preferable. The lower limit is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and about 20 to 120 minutes in other cases. Within this range, the substrate and the device can be cured without damage.

<Curing film>
The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention. The cured film of the present invention can have a total light transmittance measured according to JIS-K-7136 of 90% or more, and more preferably 95% or more. The thickness of the cured film of the present invention can be appropriately determined according to the application, but can be, for example, 0.5 to 3 μm.
The cured film of the present invention can be suitably used as a protective film or an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the curable composition of the present invention, a cured film having sufficient hardness can be obtained even when cured at a low temperature. For example, a cured film having a pencil hardness of 2H or more at a load of 750 g measured according to JIS 5600 is obtained. Since the protective film using the curable composition of the present invention is excellent in cured film properties, it is useful for applications of organic EL display devices and liquid crystal display devices.

Since the curable composition of the present invention is excellent in curability and cured film properties, a resist pattern formed using the curable composition of the present invention as a partition as a structural member of a MEMS device, Used as part of it. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

Since the curable composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the flattening film (57) described in FIG. 2 of JP2011-107476A, JP2010-9793A. Partition wall (12) and planarization film (102) described in FIG. 4A of Japanese Patent Publication No. 2010, and bank layer (221) and third interlayer insulating film (216b) described in FIG. 10 of JP 2010-27591A. The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of Japanese Patent Laid-Open No. 2009-128577, and the planarization described in FIG. 3 of Japanese Patent Laid-Open No. 2010-182638. It can also be used to form the film (12), the pixel isolation insulating film (14), and the like. In addition, spacers for maintaining the thickness of the liquid crystal layer in the liquid crystal display device, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, or micro lenses for optical fiber connectors are also used. It can be used suitably.

<Organic EL display device>
The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the curable composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

<Liquid crystal display device>
The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a protective film, a planarizing film, and an interlayer insulating film formed using the curable composition of the present invention, and is known in various structures. A liquid crystal display device can be mentioned.
For example, specific examples of TFTs (Thin-Film Transistors) included in the liquid crystal display device of the present invention include amorphous silicon-TFTs, low-temperature polysilicon-TFTs, and oxide semiconductor TFTs. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, It can be used as an organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the curable composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, it is suitable for a protective film other than a flattening film and an interlayer insulating film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, etc. Can be used.

FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.

Examples of the touch panel type include a so-called in-cell type (for example, FIG. 6 in JP-A-2012-517051), a so-called on-cell type (for example, FIG. 14 in JP 2012-43394), an OGS type, a TOL type, and other configurations (for example, JP-A 2013-2013). 164871 of FIG. 6). For example, the cured film of the present invention is preferably applied to a protective film between the layers in FIG. 3, and is also preferably applied to an interlayer insulating film that separates the detection electrodes of the touch panel.
In FIG. 3, reference numeral 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes a counter substrate, and 130 denotes a sensor unit. The pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in order from the lower side of FIG. The counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG. The sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127. In FIG. 3, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes an insulating layer (114) (also referred to as an interlayer insulating film) and various protective films (not shown) in the pixel substrate portion, various protective films (not shown) in the pixel substrate portion, and various sensor portions. It can be used for a protective film (not shown).

Furthermore, a statically driven liquid crystal display device can display a pattern with high designability by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
The following abbreviations were used.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Acrylic resin having epoxy group and / or styrene resin having epoxy group>
I-1: Alfon UG-4000 (manufactured by Toagosei Co., Ltd.)
I-2: Compound 2 (Synthetic product, see below)

<Compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000>
J-1: Joncryl 67 (manufactured by BASF), Mw12500
J-2: Compound 3 (Synthetic product, see below)
J-3: Compound 4 (Synthetic product, see below)

<Alkoxysilane compound>
C-1: KBM-403 (manufactured by Shin-Etsu Chemical)
C-2: KBM-5103 (Shin-Etsu Chemical Co., Ltd.)

<Organic solvent>
D-1: Propylene glycol monomethyl ether acetate (manufactured by Daicel)
D-2: Methyl ethyl diglycol (manufactured by Daicel)

<Inorganic particles>
E-1: PMA-ST (manufactured by Nissan Chemical Industries, Ltd.), silica fine particles, average particle size of 10 to 15 nm
E-2: MIBK-ST-L (Nissan Chemical Co., Ltd.), silica fine particles, average particle diameter of 40 to 50 nm
E-3: TTO-51 (Ishihara Sangyo Co., Ltd.) titanium oxide, average particle size 20 nm
E-4: Silver nanoparticles (manufactured by Adachi Shin Sangyo Co., Ltd.), average particle size 200 nm
E-5: Chemisnow MP-1451 (manufactured by Soken Chemical Co., Ltd.) polymer crosslinked particles, average particle size 100 nm

<Crosslinking agent>
F-1: JER157S65 (manufactured by Mitsubishi Chemical Corporation), compound having two or more epoxy groups in the molecule F-2: Takenate B870N (manufactured by Mitsui Chemicals), blocked isocyanate compound F-3: Karenz MT-PE-1 (Manufactured by Showa Denko), mercapto compound with 4 functional groups

<Surfactant>
W-1: MegaFuck F554 (manufactured by DIC), fluorosurfactant

<Synthesis Example of Compound 2>
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 12 parts by mass of methacrylic acid (corresponding to 19.5 mol% in the polymer), 50 parts by mass of glycidyl methacrylate (corresponding to 49.4 mol%), 8 parts by mass of 3-ethyl (2-methacryloyloxymethyl) oxetane (6 0.0 mol%), 10 parts by mass of N-cyclohexylmaleimide (corresponding to 7.9 mol%), 15 parts by mass of tetrahydrofurfuryl methacrylate (corresponding to 12.3 mol%), 5 parts by mass of acryloylmorpholine (4.9 mol%) And 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were substituted with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and the polymerization was started when the reaction solution temperature reached 70 ° C. Thereafter, 3 parts by mass of N-cyclohexylmaleimide 30 minutes after the start of polymerization, and 3 parts by mass of N-cyclohexylmaleimide were added dropwise to the reaction solution 1 hour later. Thereafter, the polymer solution containing the copolymer (I-2) was obtained by maintaining for 3 hours. Copolymer I-2 had a polystyrene equivalent weight average molecular weight (Mw) of 9,000 and a molecular weight distribution (Mw / Mn) of 2.0.

<Synthesis Example of Compound 3>
<< Synthesis of MATHF >>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<< Synthesis of Compound 3 >>
PGMEA (propylene glycol monomethyl ether acetate) (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MAA (amount to be 9.5 mol% in all monomer components), MATHF (amount to be 43 mol% in all monomer components), MMA (47.5 mol% in all monomer components) ), V-65 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) was dissolved dropwise in PGMEA (89 g) at room temperature over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, a polymer compound 3 was obtained. In addition, it adjusted so that the density | concentration of components (referred to as solid content) other than a solvent might be 40 mass%. Mw was 15000.

<Synthesis Example of Compound 4>
According to the synthesis method described in Japanese Patent No. 5036269, Compound 4 (J-3) represented by the following structural formula was synthesized.

<Formulation of curable composition>
As shown in the following table, each component was blended and stirred to obtain a solvent solution, which was filtered through a polytetrafluoroethylene filter having a diameter of 0.3 μm to obtain a curable composition of the present invention. The unit of each component in the following table is parts by mass excluding the solid content concentration. Moreover, the mass part of solid content conversion is shown except an organic solvent.

<Evaluation of pencil hardness>
Each composition prepared above was spin-coated on a glass substrate and pre-baked at 90 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was formed by baking at 120 ° C. for 60 minutes in an oven.
The obtained cured film was subjected to a pencil hardness test by a method (load 750 g) based on JIS 5600 to evaluate the film strength. 2H or more is a practical range.

<Evaluation of transmittance>
Each of the prepared compositions was spin-coated on a glass substrate and pre-baked at 90 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was formed by baking at 120 ° C. for 60 minutes in an oven.
The total light transmittance was measured with respect to the obtained cured film using haze meter NDH7000 (made by Nippon Denshoku Industries Co., Ltd.). A total light transmittance of 90% or more is a practical range.

As is apparent from the above table, the composition of the present invention had high hardness even when cured at a low temperature.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter 110: Pixel substrate 140: Liquid crystal layer 120: Counter substrate 130: Sensor part 111: Polarizing plate 112: Transparent substrate 113: Common electrode 114: Insulating layer 115: Pixel electrode 116: Alignment film 121: Alignment film 122: Color filter 123: Transparent substrate 124: Retardation film 126: Adhesion layer 127: Polarizing plate

Claims (13)

1. I: an acrylic resin having an epoxy group and a styrene resin having at least one of an epoxy group,
   J: a compound having a carboxyl group and a weight average molecular weight of 1000 to 50,000; except for those corresponding to the above component I;
   C: alkoxysilane compound,
   D: an organic solvent, and E: at least one of inorganic particles having an average particle size of 1 to 200 nm and polymer particles having an average particle size of 1 to 200 nm, and voids in a cross-sectional image of the particles of the inorganic particles and the polymer particles by an electron microscope According to JIS-K-7136 of a curable composition having an average porosity of less than 10%, which is an arithmetic average of 200 area ratios between the portion and the particle cross section, and a film obtained by curing the curable composition A curable composition having a measured total light transmittance of 90% or more.
2. Furthermore, F: The curable composition of Claim 1 containing a crosslinking agent.
3. The curable composition according to claim 2, wherein the F: crosslinking agent contains a blocked isocyanate compound.
4. The curable composition according to claim 2 or 3, wherein the F: crosslinking agent contains a polyfunctional mercapto compound.
5. The curable composition according to any one of claims 1 to 4, wherein the solid content concentration of the curable composition is 20 to 40% by mass.
6. Applying the curable composition according to any one of claims 1 to 5 on a substrate;
   Removing the solvent from the applied curable composition;
   The manufacturing method of the cured film characterized by including the process of thermosetting.
7. The manufacturing method of the cured film of Claim 6 whose thermosetting temperature in the process to thermoset is 150 degrees C or less.
8. The method for forming a cured film according to claim 6 or 7, comprising a step of exposing the entire surface after the step of removing the solvent and before the step of thermosetting.
9. A cured film obtained by curing the curable composition according to any one of claims 1 to 5.
10. The cured film according to claim 9, which is a protective film.
11. The cured film of Claim 9 or 10 whose pencil hardness in the load of 750g measured according to JIS5600 is 2H or more.
12. An organic EL display device comprising the cured film according to any one of claims 9 to 11.
13. A liquid crystal display device comprising the cured film according to any one of claims 9 to 11.

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