JP2022055206A - Radiation sensitive composition, insulation film for display device, display device, manufacturing method of insulation film for display device, and polymer - Google Patents

Abstract

To provide a radiation-sensitive composition that has sufficient lithographic property, has sufficient hardness also by heating at a relatively low temperature, can form a hardened film difficult to generate warp after heat treatment, is lower in generation of an out gas when the hardened film formed from the radiation-sensitive composition is used in the display device, and can reduce inconvenience due to out gas.SOLUTION: A radiation-sensitive composition of the present invention is a radiation-sensitive composition comprising a polymer of at least one member selected from a polymer having a structural site represented by a formula (1) and a polymer having a structural site represented by formula (2), and (B) a radiation-sensitive composition containing a radiation-sensitive compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to a radiation-sensitive composition, an insulating film for a display device, a display device, a method for forming an insulating film for a display device, and a polymer.

As one of the light emitting devices being developed in recent years, an organic electroluminescence (EL) device having a laminated structure including an anode layer, an organic light emitting layer and a cathode layer is known. As a display device having an organic EL element, an organic EL device with a touch panel provided with a touch panel on the front surface of the device is known (see Patent Document 1).

An organic EL device with a touch panel is manufactured by, for example, attaching a touch panel to a substrate on which an organic EL element is formed via an adhesive layer or an adhesive layer. A touch panel is usually manufactured by providing a touch panel member such as a sensor electrode on a touch panel support substrate.

JP 2015-161806A

As described above, when the touch panel is attached to the substrate on which the organic EL element is formed via the adhesive layer or the adhesive layer, the thickness of the entire organic EL device with the touch panel becomes large. In the case of a device with a large thickness, breakage or functional deterioration is likely to occur when the device is bent. Further, in various display devices, thinning itself is desired. Therefore, it is considered that the thickness of the entire display device such as an organic EL device with a touch panel can be reduced by directly providing the touch panel on the substrate on which the organic EL element is formed by a method such as lithography or etching. ..
However, in the conventional method using a material containing polyfunctional (meth) acrylate or the like as a curable component, the insulating film for forming the touch panel is cured by heating at a temperature of more than 100 ° C, preferably more than 120 ° C. is required. When the insulating layer is formed on the substrate on which the organic EL element is formed, there is a disadvantage that the organic light emitting layer is deteriorated by heating above 100 ° C., particularly above 120 ° C.
On the other hand, when the insulating film is formed by heating at 120 ° C. or lower, particularly 100 ° C. or lower using a conventional material, the obtained insulating film cannot withstand the etching chemical solution for wiring formation and oxygen ashing. It tends to be difficult to fabricate the touch panel structure. Not only in the insulating film for organic EL devices with a touch panel, but also in various applications such as insulating films for other display devices, it is possible to obtain a cured film having sufficient etching chemical resistance and oxygen ashing resistance even by heating at a relatively low temperature. The development of a radiation-sensitive composition is desired.

The present invention has been made based on the above circumstances, and the radiation-sensitive composition of the present invention has sufficient lithography performance, and has sufficient hardness even when heated at a relatively low temperature. It is possible to form a cured film in which cracks such as cracks do not easily occur, and it is possible to form a cured film in which warpage does not easily occur after heat treatment. It is an object of the present invention that when a cured film formed from the radiation-sensitive composition is used in a display device, outgas is less generated and defects caused by outgas can be reduced.
Suitable as an insulating film for a display device and a display device obtained by using the radiation-sensitive composition, a method for forming an insulating film for a display device using the radiation-sensitive composition, and a component of the radiation-sensitive composition. An object of the present invention is to provide a polymer.

（式（１）中、Ｒ^１、Ｒ^２は炭素数１から１２の炭化水素基、Ｒ^３はカルボキシル基、（メタ）アクリロイル基、酸無水物構造のいずれかを有する１価の有機基、Ｒ^４は炭素数１から１２のアルカンジイル基、フェニル基、または脂環式炭化水素を有する２価の有機基を示す。ｎは２から１００の整数、ａ、ｂはそれぞれ、１から１２の整数を示す。
式（２）中、Ｒ^５、Ｒ^６は炭素数１から１２の炭化水素基、Ｒ^７はカルボキシル基、（メタ）アクリロイル基、酸無水物構造のいずれかを有する１価の有機基、Ｒ^８は炭素数１から１２のアルカンジイル基、フェニル基、または脂環式炭化水素を有する２価の有機基を示す。ｍは２から１００の整数、ｃ、ｄはそれぞれ、１から１２の整数を示す。） The invention made to solve the above problems is at least one selected from (A) a polymer having a structural moiety represented by the following formula (1) or a polymer having a structural moiety represented by the following formula (2). It is a radiation-sensitive composition containing one of the polymers, (B) a radiation-sensitive compound.

(In the formula (1), R ¹ and R ² are hydrocarbon groups having 1 to 12 carbon atoms, R ³ is a carboxyl group, a (meth) acryloyl group, and a monovalent organic group having any of an acid anhydride structure. ^R4 represents a divalent organic group having an alcandiyl group, a phenyl group, or an alicyclic hydrocarbon having 1 to 12 carbon atoms. N is an integer of 2 to 100, and a and b are 1 to 12, respectively. Indicates an integer.
In formula (2), R ⁵ and R ⁶ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁷ is a carboxyl group, a (meth) acryloyl group, and a monovalent organic group having any of an acid anhydride structure, R. Reference numeral ⁸ indicates a divalent organic group having an alcandiyl group, a phenyl group, or an alicyclic hydrocarbon having 1 to 12 carbon atoms. m is an integer from 2 to 100, and c and d are integers from 1 to 12, respectively. )

Another invention made to solve the above problems is an insulating film for a display device formed from the radiation-sensitive composition.

Yet another invention made to solve the above problems is a display device having an insulating film for the display device.

Yet another invention made to solve the above problems is a step of directly or indirectly forming a coating film on a substrate, a step of irradiating at least a part of the coating film with radiation, and a step of developing the coating film. This is a method for forming an insulating film for a display device, which comprises a step of heating the coating film in this order, and forms the coating film with the radiation-sensitive composition.

（式（３）中、Ｘは炭素数１から１２のアルカンジイル基を示す。ｎは２から１００の整数を示す。） Yet another invention made to solve the above problems is a polymer having a structural moiety represented by the following formula (3).

(In formula (3), X represents an arcandyl group having 1 to 12 carbon atoms, and n represents an integer of 2 to 100.)

（式（４）中、Ｘは炭素数１から１２のアルカンジイル基を示す。ｍは２から１００の整数を示す。） Yet another invention made to solve the above problems is a polymer having a structural moiety represented by the following formula (4).

(In formula (4), X represents an alkanediyl group having 1 to 12 carbon atoms. M represents an integer from 2 to 100.)

The radiation-sensitive composition of the present invention has sufficient lithography performance, has sufficient hardness even when heated at a relatively low temperature, and can form a cured film in which cracks such as cracks do not easily occur. It is possible to form a cured film that is less likely to warp after heat treatment. When the cured film formed from the radiation-sensitive composition is used in a display device, outgas is less generated, and defects caused by outgas can be reduced.
Suitable as an insulating film for a display device and a display device obtained by using the radiation-sensitive composition, a method for forming an insulating film for a display device using the radiation-sensitive composition, and a component of the radiation-sensitive composition. A polymer can be provided.

FIG. 1 is a cross-sectional view schematically showing an organic EL device with a touch panel according to an embodiment of the present invention.

<Radiation-sensitive composition>
The radiation-sensitive composition according to one embodiment of the present invention contains (A) a polymer and (B) a radiation-sensitive compound. The radiation-sensitive composition may contain at least one of (C) (meth) acrylic compound and epoxy compound. Each component will be described in detail.

The polymer (A) in the radiation-sensitive composition is at least one selected from a polymer having a structural moiety represented by the following formula (1) or a polymer having a structural moiety represented by the following formula (2). It is one of the polymers.

In formula (1), R ¹ and R ² are hydrocarbon groups having 1 to 12 carbon atoms, R ³ is a carboxyl group, a (meth) acryloyl group, and a monovalent organic group having any of an acid anhydride structure, R. Reference numeral ⁴ indicates a divalent organic group having an alcandiyl group, a phenyl group, or an alicyclic hydrocarbon having 1 to 12 carbon atoms. n is an integer from 2 to 100, and a and b are integers from 1 to 12, respectively.
In formula (2), R ⁵ and R ⁶ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁷ is a carboxyl group, a (meth) acryloyl group, and a monovalent organic group having any of an acid anhydride structure, R. Reference numeral ⁸ indicates a divalent organic group having an alcandiyl group, a phenyl group, or an alicyclic hydrocarbon having 1 to 12 carbon atoms. m is an integer from 2 to 100, and c and d are integers from 1 to 12, respectively.

An example of synthesis of a polymer having a structural site represented by the formula (1) is shown.
As shown by the following formula (5), it is synthesized by polycondensation with a silicone oil modified with aminos at both ends and a compound having isocyanate groups at both ends. It has a urea bond due to the reaction between the amino group and isocyanate.
Then, the compound obtained by the formula (5) is reacted with an acid chloride having an acid anhydride structure in the presence of an amine to obtain a compound into which a group having an acid anhydride structure is introduced (formula (6)).
Further, the compound obtained by the formula (6) can be hydrolyzed in the presence of an acid to express a carboxyl group (formula (7)).

As the silicone oil modified with aminos at both ends, a compound having an amino group introduced at both ends of the polysiloxane can be used, and a commercially available product can be used. Such available silicone oils with both terminal amino modifications include PAM-E, KF-8010, X-22-161A, X-22161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

Compounds having isocyanate groups at both ends include 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, and 4,4'-diphenyldiisocyanate. Aromatic diisocyanates such as 1,5-naphthalenediocyanate, 4,4'-toluidin diisocyanate, 4,4'-diphenyl ether diisocyanate, etc., 1,3- or 1,4-xylylene diisocyanate, or a mixture thereof. Diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butyrene diisocyanate, 2,3-butyrene diisocyanate, 1,3-butyrene diisocyanate, 2,4, Alius diisocyanate such as 4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate , 3-Isocyanate Methyl-3,5,5-trimethylcyclohexamethylene diisocyanate, 4,4'-methylene bis (cyclohexamethylene diisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis (Isocyanate methyl) Alicyclic diisocyanate such as cyclohexane can be used. Of these, hexamethylene diisocyanate is preferably used because of its reactivity and availability.

Examples of the acid chloride having an acid anhydride structure include trimellitic anhydride, acid chloride of hydrogenated trimellitic anhydride, and the like.
When reacting an acid chloride having an acid anhydride structure, a base can be added if necessary. Examples of the base include trimethylamine, triethylamine, tripropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, sodium hydroxide, potassium hydroxide and the like, and triethylamine is preferable.

The weight average molecular weight of the polymer having the structural moiety represented by the formula (1) is preferably in the range of 1,000 to 500,000.

マイケル付加反応に用いられる塩基としては、トリメチルアミン、トリエチルアミン、トリプロピルアミン、イミダゾール、ジアザビシクロウンデセン、ピリジン、モルホリン、ピペラジン、ピペリジン、水酸化ナトリウム、水酸化カリウム等を挙げることができ、トリエチルアミンが好ましい。 An example of synthesis of a polymer having a structural site represented by the formula (2) is shown.
As shown by the following formula (8), it is synthesized by a Michael addition reaction with a silicone oil modified with amino at both ends and a compound having a (meth) acryloyl group at both ends.
Then, a carboxyl group can be introduced by reacting the compound obtained by the formula (8) with an acid anhydride (formula (9)).

Examples of the base used for the Michael addition reaction include trimethylamine, triethylamine, tripropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, sodium hydroxide, potassium hydroxide and the like. preferable.

As the silicone oil modified with aminos at both ends, a compound having an amino group introduced at both ends of the polysiloxane can be used, and a commercially available product can be used. Such available silicone oils with both terminal amino modifications include PAM-E, KF-8010, X-22-161A, X-22161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

Examples of the compound having a (meth) acryloyl group include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, and diethylene glycol. Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 9-Nonandiol di (meth) acrylate, 1,9-nonandiol di (meth) acrylate, tricyclodendimethanol diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-hydroxyethoxy) Phenyl] Full orange acrylate and the like can be mentioned.
The acid anhydrides include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, pyromellitic anhydride, trimellitic anhydride, and trimellitic anhydride. And so on. Of these, succinic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, and hydrogenated trimellitic anhydride are preferable from the viewpoint of reactivity.

The weight average molecular weight of the polymer having the structural moiety represented by the formula (2) is preferably in the range of 1,000 to 500,000.

The polymer having the structural moiety represented by the formula (1) or the polymer having the structural moiety represented by the formula (2) may be used alone or in combination.

(B) Radiation-sensitive compound The (B) radiation-sensitive compound contained in the radiation-sensitive composition of the embodiment of the present invention is a compound capable of generating radicals and initiating polymerization in response to radiation (that is, (B). -1) Photoradical polymerization initiator) or a compound that generates acid in response to radiation (that is, (B-2) photoacid generator). The radiation-sensitive composition of the present embodiment can have (B) radiation-sensitive by containing (B) a radiation-sensitive compound, and for example, depending on the type of the radiation-sensitive compound, positive-type radiation-sensitive or It can have negative radiation sensitivity.

Examples of the (B-1) photoradical polymerization initiator of the radiation-sensitive composition of the present embodiment include an O-acyloxime compound, an acetophenone compound, and a biimidazole compound. These compounds may be used alone or in combination of two or more.

Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9.H.-carbazole-3-yl) -octane-1-one oxime- O-acetyl, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, ethane-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl) } -9. H. -Carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned.

Of these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), etanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime) or etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl) } -9. H. -Carbazole-3-yl] -1- (O-acetyloxime) is preferable.

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1-(. Examples thereof include 4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and the like.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1-one. , 4- (2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone and the like.

As the acetophenone compound, an α-aminoketone compound is preferable, and in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-dimethylamino-2- (4-methylbenzyl) are preferable. ) -1- (4-Morphorin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one are preferable.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,). 4-Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole is preferred, of which 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'- Biimidazole is more preferred.

(B-1) As described above, the photoradical polymerization initiator can be used alone or in combination of two or more. The content ratio of the (B-1) photoradical polymerization initiator is preferably 1 part by mass to 40 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the component [A]. (B-1) By using 1 part by mass to 40 parts by mass of the photoradical polymerization initiator, the radiation-sensitive composition has high solvent resistance, high hardness and high hardness even at a low exposure dose. A cured film having adhesiveness can be formed. As a result, it is possible to provide an insulating film according to an embodiment of the present invention, which is excellent in such characteristics. When a photoradical polymerization initiator is used, it can be a negative type radiation-sensitive composition.

Next, examples of the (B-2) photoacid generator of the radiation-sensitive composition of the present embodiment include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, and a sulfonic acid. Examples thereof include ester compounds, carboxylic acid ester compounds, and quinone diazide compounds. These (B-2) photoacid generators may be used alone or in combination of two or more.

Specific examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-iriden)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2- Iliden)-(2-Methylphenyl) acetonitrile, (Camfersulfonyloxyimino-5H-thiophen-2-iriden)-(2-Methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2- Examples thereof include iriden)-(2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like, and these can be obtained as commercial products.

Examples of the above-mentioned onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, benzylsulfonium salt and the like.

As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylsulfonium hexafluoro Phosphate is more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is even more preferred.

Examples of the sulfoneimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (kanfasulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, and N- (2-trifluoromethylphenylsulfonyl). Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (kanfasulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, Examples thereof include N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (kanfasulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide and the like.

Preferable examples of the sulfonic acid ester compound include haloalkyl sulfonic acid esters, and more preferred examples include N-hydroxynaphthalimide-trifluoromethane sulfonic acid esters.

Examples of the quinone diazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter, also referred to as “matrix”) and 1,2-naphthoquinone diazide sulfonic acid halide or 1,2-naphthoquinone diazido sulfonic acid amide. Can be used.

Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei other than the mother nucleus.

As a specific example of the above-mentioned mother nucleus, for example,
Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone;
As tetrahydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4 , 2'-Tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
Examples of the pentahydroxybenzophenone include 2,3,4,2', 6'-pentahydroxybenzophenone;
As hexahydroxybenzophenone, 2,4,6,3', 4', 5'-hexahydroxybenzophenone, 3,4,5,3', 4', 5'-hexahydroxybenzophenone and the like;
As (polyhydroxyphenyl) alkanes, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl) Etan, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-4) Hydroxyphenyl) -3-phenylpropane, 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4) -Hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6', 7'-hexanol, 2,2,4-trimethyl-7,2', 4'-trihydroxyflaban, etc .;
Can be mentioned.

Examples of the above other mother nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman and 1- [1- (3- {1). -(4-Hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl) -1-methylethyl } -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene and the like.

Among these, the mother nuclei are 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4'-[1- [4- [4]. 1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

Further, as the above-mentioned 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazido sulfonic acid chloride is preferable, 1,2-naphthoquinone diazido-4-sulfonic acid chloride, 1,2-naphthoquinone diazido-5-. Sulfonic acid chloride is more preferred, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is even more preferred.

As the above-mentioned 1,2-naphthoquinone diazide sulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide is preferable.

In the condensation reaction between the above-mentioned phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol with respect to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halides corresponding to% or more and 85 mol% or less, more preferably 50 mol% or more and 70 mol% or less can be used. The condensation reaction can be carried out by a known method.

As the above (B-2) photoacid generator, an oxime sulfonate compound, an onium salt, a sulfonimide compound and a quinone diazide compound are preferable, and an oxime sulfonate compound and a quinone diazide compound are more preferable.

(B-2) By using the above-mentioned compound as the photoacid generator, the radiation-sensitive composition of the present embodiment containing the compound can improve the sensitivity and solubility. Among the photoacid generators, a positive radiation-sensitive composition can be obtained, especially when a quinonediazide compound is used.

The content of the (B-2) photoacid generator is preferably 0.1 part by mass to 50 parts by mass, and more preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the component (A). (B-2) By setting the content of the photoacid generator in the above range, the sensitivity of the radiation-sensitive composition of the present embodiment can be optimized, and a cured film having a high surface hardness can be formed, which is excellent in such characteristics. An insulating film according to an embodiment of the present invention can be provided.

(C) (Meta) Acrylic Compound and Epoxy Compound The radiation-sensitive composition of the present invention may contain at least one of the (C) (meth) acrylic compound and the epoxy compound.
As the (meth) acrylic compound, a polyfunctional (meth) acrylic acid ester such as a bifunctional (meth) acrylic acid ester or a trifunctional or higher functional (meth) acrylic acid ester can be used.
Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetra. Examples thereof include ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate.

Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylol propanetriacrylate, trimethylolpropanetrimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol penta. Acrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, tri (2-acryloyloxy) In addition to ethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylate, it has a linear alkylene group and an alicyclic structure, and 2 It is obtained by reacting a compound having one or more isocyanate groups with a compound having one or more hydroxy groups in the molecule and having three, four or five (meth) acryloyloxy groups. Examples thereof include polyfunctional urethane acrylate compounds.

The content of the polyfunctional acrylate in the radiation-sensitive composition is not particularly limited, but the lower limit with respect to 100 parts by mass of the component [A] is preferably 20 parts by mass, more preferably 30 parts by mass. On the other hand, as the upper limit, 150 parts by mass is preferable, and 100 parts by mass is more preferable. By setting the content of the polyfunctional acrylate in the radiation-sensitive composition within the above range, various properties of the obtained cured film can be more effectively enhanced.

Epoxy compounds also include compounds having an oxetanyl group.
Both high molecular weight epoxy resins and low molecular weight epoxy compounds can be used. For example, bisphenol type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol A type epoxy resin and bisphenol F type epoxy resin, alkylene oxide modified products thereof, and hydrides thereof; 3, 3', 5 , 5'-Tetramethyl-4,4'-biphenol type epoxy resin and 4,4'-biphenol type epoxy resin and other biphenyl type epoxy resins; , Novolak type epoxy resin such as dicyclopentadiene novolac type epoxy resin, biphenyl novolak type epoxy resin; 3,4,3', 4'-diepoxybicyclohexane, 3,4-epoxycyclohexylmethyl (3,4-epoxy) Alicyclic epoxy resin such as cyclohexanecarboxylate; 1,3,5-triazine nucleus derivative represented by tris (2,3-epoxypropyl) isocyanurate and tris (α-methylglycidyl) isocyanurate Triazine such as epoxy resin Derivative epoxy resins; examples include naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenylol ethane type epoxy resin, and urethane modified epoxy resin.

Examples of low molecular weight epoxy compounds include 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3', 4'-epoxycyclohexanemethyl 3,4-epoxycyclohexanecarboxylate, 2-. (3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy) Cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxiside, ethylene glycol Examples thereof include compounds such as di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), pentaerythritol tetraglycidyl ether, and trimethylolpropane triglycidyl ether.

Examples of the compound having an oxetanyl group include a compound having two or more oxetanyl groups per molecule. Specifically, 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4- Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanyl) methyl] Methoxy) methyl] propane, bis [1-ethyl (3-oxetanyl)] methyl ether, bis (3-ethyl-3-oxetanylmethyl) ether, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene Glycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycolbis (3-ethyl-3-oxetanylmethyl) ether, 1,3-bis (3-ethyl-3-oxetanylmethoxy) propane, 1,4 -Bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, 1,4-bis (3-ethyl-3-oxetanylmethoxymethyl) benzene, 1 , 3-Bis (3-ethyl-3-oxetanylmethoxymethyl) benzene, 1,2-bis (3-ethyl-3-oxetanylmethoxymethyl) benzene, 4,4'-bis (3-ethyl-3-oxetanylmethoxy) Methyl) biphenyl, 2,2'-bis (3-ethyl-3-oxetanylmethoxymethyl) biphenyl, 3-[(3-ethyloxetane-3-yl) methoxy] hydrolysis condensate of propyltrialkoxysilane, 3- Examples thereof include a condensation reaction product of ethyloxetane-3-ylmethanol and a silanetetraol polycondensate.

The organic solvent used in the radiation-sensitive composition of the present invention is not particularly limited, and examples thereof include an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, and an amide solvent. The organic solvent may be used alone or in combination of two or more.
Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-. Alcohols such as 2-propanol and diacetone alcohol;
Examples include aromatic alcohols such as benzyl alcohol.
Examples of the ether solvent include ethylene glycol monoalkyl ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether;
Examples thereof include dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether.
Examples of the ester solvent include carboxylic acid esters such as ethyl acetate, i-propyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate;
Polyhydric alcohol carboxylate solvent such as propylene glycol diacetate;
Examples thereof include polyhydric alcohol partially ether carboxylate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.
Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone and the like.
Among these, an ether solvent and an ester solvent are preferable, an ester solvent is more preferable, and a polyhydric alcohol partially ether carboxylate solvent is further preferable. Among the ether-based solvent and the ester-based solvent, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate are preferable.

The content of the organic solvent in the radiation-sensitive composition is not particularly limited, but it is preferably prepared so that the solid content concentration is within the following range. The lower limit of the solid content concentration in the radiation-sensitive composition is preferably 5% by mass, more preferably 10% by mass, still more preferably 20% by mass. On the other hand, the upper limit of the solid content concentration is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass.

(Other ingredients)
The radiation-sensitive composition may further contain components other than the above-mentioned (A) polymer, (B) radiation-sensitive compound, (C) (meth) acrylic compound, epoxy compound, and organic solvent. .. Examples of such other components include curing agents, curing accelerators, adhesion aids, antioxidants, surfactants and the like. However, the content ratio of the components other than the (A) polymer, (B) radiation-sensitive compound, (C) (meth) acrylic compound, epoxy compound, and organic solvent in the radiation-sensitive composition is 10. It may be preferably mass% or less, and may be more preferably 1 mass% or less.

(Curing temperature)
As described above, the radiation-sensitive composition can obtain a cured film having sufficient resistance to etching chemicals and oxygen ashing even by heating at a relatively low temperature. The radiation-sensitive composition is preferably a composition that can be cured by heating in a temperature range of 60 ° C. or higher and 120 ° C. or lower, and is a composition that can be cured by heating in a temperature range of 60 ° C. or higher and 100 ° C. or lower. It is more preferable to have.

(Method for preparing radiation-sensitive composition)
The radiation-sensitive composition can be prepared by mixing each component in a predetermined ratio and dissolving it in (C) an organic solvent. The prepared composition is preferably filtered with, for example, a filter having a pore size of about 0.2 μm.

<Insulating film for display devices>
The insulating film for a display device according to an embodiment of the present invention is a cured film formed from the radiation-sensitive composition. The insulating film for the display device may be a patterned film. Since the insulating film for the display device is formed of a radiation-sensitive composition capable of obtaining a cured film having sufficient etching chemical resistance and oxygen ashing resistance even by heating at a relatively low temperature, the yield is high and the durability is high. It is also excellent in sex.

The insulating film for the display device is suitable as an interlayer insulating film, and may also be used as a flattening film, a spacer, a protective film, or the like. The insulating film for a display device can be used for a display device (liquid crystal display device) including a liquid crystal display element, a display device (organic EL device) including an organic EL element, and a display device such as electronic paper. Further, as will be described later, the insulating film for the display device is suitable as an interlayer insulating film for a touch panel in a display device with a touch panel such as an organic EL device with a touch panel.

Even when the insulating film for the display device is relatively thick, cracks are unlikely to occur. Therefore, the insulating film for the display device can be made thicker. The lower limit of the average thickness of the insulating film for the display device may be, for example, 0.1 μm, preferably 0.5 μm, more preferably 1 μm, and even more preferably 2 μm. On the other hand, the upper limit of this average thickness is, for example, 10 μm, 6 μm, or 4 μm.

<Display device>
The display device according to the embodiment of the present invention has an insulating film for the display device. Examples of the display device include a liquid crystal display device, an organic EL device, an electronic paper, and the like. Among these, the display device according to the embodiment of the present invention is preferably an organic EL device.

The organic EL device includes an organic EL element. The organic EL element usually has a laminated structure including an anode layer, an organic light emitting layer, and a cathode layer. The organic EL device preferably has a touch panel laminated on a substrate having an organic EL element. It is preferable that the insulating film for a display device according to the embodiment of the present invention is used for at least a part of the insulating film in the touch panel. In particular, it is preferable that the insulating film for a display device according to one embodiment of the present invention is used as the insulating film of the touch panel laminated on the substrate having the organic EL element without the intervention of the adhesive layer or the adhesive layer. By doing so, the touch panel can be directly laminated on the substrate on which the organic EL element is formed, so that the organic EL device with the touch panel can be made thinner. Further, since the radiation-sensitive composition can obtain a cured film having sufficient etching chemical solution resistance and oxygen ashing resistance even by heating at a relatively low temperature, deterioration of the organic EL element in the manufacturing process can be suppressed. It is possible to increase the yield. Further, as described above, by forming the insulating film by heating at a relatively low temperature using the radiation-sensitive composition, deterioration of the organic EL element in the manufacturing process can be suppressed, so that the organic EL device with a touch panel can be suppressed. The radiation-sensitive composition can be particularly preferably used for forming an insulating film in various organic EL devices including organic EL devices other than the above.

FIG. 1 shows a form of an organic EL device with a touch panel. The organic EL device 10 with a touch panel of FIG. 1 includes an organic EL display substrate 20 and a touch panel 30. The organic EL display substrate 20 has a structure in which a support substrate 21, an anode layer 22, an organic light emitting layer 23, a cathode layer 24, an adhesive layer 25, and a sealing substrate 26 are laminated in this order. At least the anode layer 22, the organic light emitting layer 23, and the cathode layer 24 constitute an organic EL element. As the organic light emitting layer 23, for example, a structure in which a hole injection layer, a hole transport layer, an organic EL light emitting layer, an electron transport layer, and an electron injection layer are laminated in this order from the anode layer 22 side is adopted. Can be done.

The touch panel 30 is of a capacitance type in which the first sensor electrode 31, the interlayer insulating film 33, and the second sensor electrode 32 are laminated in this order. The touch panel 30 has a first sensor electrode 31, a second sensor electrode 32 arranged facing the first sensor electrode 31, an interlayer insulating film 33, and a transparent substrate 34 arranged on the outermost surface. In the present embodiment, the first sensor electrode 31 is directly formed on the sealing substrate 26 of the organic EL display substrate 20. The interlayer insulating film 33 is a transparent insulating film that insulates the first sensor electrode 31 and the second sensor electrode 32, and is formed of the radiation-sensitive composition. The touch panel is not limited to such a capacitance type touch panel.

<Method of forming an insulating film for display devices>
The method for forming an insulating film for a display device according to an embodiment of the present invention is a step of directly or indirectly forming a coating film on a substrate (hereinafter, also referred to as a “coating film forming step”), or at least the above-mentioned coating film. A step of partially irradiating (exposing) radiation (hereinafter, also referred to as “radiation irradiation step”), a step of developing the coating film (hereinafter, also referred to as “development step”), and heating of the coating film. The steps (hereinafter, also referred to as “heating step”) are provided in this order, and the coating film is formed by the radiation-sensitive composition according to the embodiment of the present invention. The forming method may include, as an optional step, a step of heating the coating film (hereinafter, also referred to as “PEB step”) between the irradiation step and the developing step.

According to the forming method, since the above-mentioned radiation-sensitive composition is used, the insulating film can be patterned into a good shape and has sufficient etching chemical resistance and oxygen ashing resistance even when heated at a relatively low temperature. Can be obtained. Further, even if the substrate on which the coating film is formed contains an organic EL element, deterioration of the organic EL element can be suppressed by performing the heating step at a relatively low temperature. Hereinafter, each step will be described.

(Coating film forming process)
In this step, after the radiation-sensitive composition is applied directly on the substrate or via another layer, the coated surface is preferably heated (prebaked) to remove the organic solvent and the like to form a coating film. do. Examples of the material of the substrate include glass, quartz, silicon, resin and the like. Specific examples of the resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, an addition polymer of a cyclic olefin, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof. Be done.

The substrate may include an organic EL element or the like. Further, the substrate may be provided with electrodes, wiring, etc. on the coated surface. As such a substrate, the organic EL display substrate 20 in FIG. 1 described above on which the first sensor electrode 31 is formed can be exemplified.

The method for applying the radiation-sensitive composition is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method, or a bar coating method should be adopted. Can be done. Among these coating methods, the spin coating method and the slit die coating method are particularly preferable. The prebaking conditions vary depending on the type of each component, the mixing ratio, and the like, but for example, the heating time may be 1 minute or more and 10 minutes or less at a temperature of 60 ° C. or higher and 120 ° C. or lower, more preferably 100 ° C. or lower.

(Irradiation process)
In this step, at least a part of the coating film formed in the coating film forming step is irradiated with radiation. Usually, when irradiating a part of the coating film with radiation, it is irradiated through a photomask having a predetermined pattern. As the radiation, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used. Among these radiations, radiation having a wavelength in the range of 190 nm or more and 450 nm or less is preferable, and radiation containing ultraviolet rays having a wavelength of 365 nm is more preferable.

As the lower limit of the exposure amount in this step, 10 mJ / cm ² is preferable, and 50 mJ / cm ² is preferable as a value measured by an illuminance meter (“OAI model 356” of OAI Optical Associates Inc.) at a wavelength of 365 nm of radiation. More preferred. The upper limit of the exposure amount is preferably 2,000 mJ / cm ² and more preferably 1,000 mJ / cm ² as a value measured by the illuminance meter.

(PEB process)
When the PEB step is provided, the PEB conditions vary depending on the type of each component, the mixing ratio, etc., but for example, the heating time is 1 minute or more and 10 minutes or less at a temperature of 60 ° C. or higher and 120 ° C. or lower, more preferably 100 ° C. or lower. And it is sufficient.

(Development process)
In this step, a predetermined pattern is formed by developing the coating film after irradiation with a developing solution. An alkaline developer is preferable as the developer. The alkaline developer is alkaline in which at least one alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, or tetraethylammonium hydroxide is dissolved. Examples include aqueous solution. Further, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer in an appropriate amount.

As the developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, and a spraying method can be adopted. The development time varies depending on the composition of the radiation-sensitive composition, but is, for example, 10 seconds or more and 180 seconds or less. A desired pattern can be formed by, for example, washing with running water for a treatment time of 30 seconds or more and 90 seconds or less after such a development treatment, and then air-drying with compressed air or compressed nitrogen, for example.

(Heating process)
In this step, the developed and patterned coating film is heated (post-baked) using a heating device such as a hot plate or an oven to obtain an insulating film for a display device having a desired pattern. The coating film may be irradiated with radiation such as ultraviolet rays between the developing step and the heating step. The exposure amount at this time can be, for example, 100 mJ / cm ² or more and 2,000 mJ / cm ² or less. The lower limit of the heating temperature is preferably 60 ° C, and may be 80 ° C. By setting the heating temperature to the above lower limit or higher, a sufficiently cured insulating film can be obtained. On the other hand, the upper limit of the heating temperature is preferably 120 ° C, more preferably 100 ° C. By setting the heating temperature to the above lower limit or higher, it is possible to obtain a sufficiently cured insulating film while suppressing deterioration of the organic EL element provided on the substrate, for example. Further, by setting the heating temperature to the above upper limit or less, it is possible to suppress the generation of excessive stress such as sudden film shrinkage, so that the generation of cracks can be suppressed. As described above, in the heating step, it is preferable to perform heating in a temperature range of 60 ° C. or higher and 120 ° C. or lower. The heating time varies depending on the type of heating device, but may be, for example, 5 minutes or more and 30 minutes or less when heating on a hot plate, and 10 minutes or more and 90 minutes or less when heating in an oven. The heating may be performed in the air or in an atmosphere of an inert gas such as nitrogen or argon. It is also possible to use a step baking method in which two or more heating steps are performed.

(Other processes)
In the case of manufacturing a touch panel or the like having the insulating film for the display device, in order to form further electrodes, wiring and the like (for example, the second sensor electrode 32 in the touch panel 30 of FIG. 1) after forming the insulating film for the display device. Other steps such as are performed. Examples of such a step include an electrode forming step, a wiring forming step, an etching step, an ashing step, and the like. A known method such as printing or vapor deposition can be adopted for forming the electrodes and wiring. Etching can be performed using a known etching agent such as an amine-based solution. Ashing can be performed by a known ashing method such as oxygen ashing. When manufacturing the touch panel or the like, the forming of the insulating film, the forming of the electrodes, the wiring, and the like may be performed a plurality of times.

式（３）中、Ｘは炭素数１から１２のアルカンジイル基を示す。ｎは２から１００の整数を示す。炭素数１から１２のアルカンジイル基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基が特に好ましい。
また、下記式（４）で示される構造部位を有する重合体である。

式（４）中、Ｘは炭素数１から１２のアルカンジイル基を示す。ｍは２から１００の整数を示す。炭素数１から１２のアルカンジイル基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基が特に好ましい。
上記重合体は、本発明の感放射線性組成物に好適に用いられる。 <Polymer>
It is a polymer having a structural part represented by the following formula (3).

In formula (3), X represents an alkanediyl group having 1 to 12 carbon atoms. n represents an integer from 2 to 100. As the alkanediyl group having 1 to 12 carbon atoms, a methylene group, an ethylene group, a propylene group, a butylene group and a hexamethylene group are particularly preferable.
Further, it is a polymer having a structural portion represented by the following formula (4).

In formula (4), X represents an alkanediyl group having 1 to 12 carbon atoms. m represents an integer from 2 to 100. As the alkanediyl group having 1 to 12 carbon atoms, a methylene group, an ethylene group, a propylene group, a butylene group and a hexamethylene group are particularly preferable.
The polymer is suitably used for the radiation-sensitive composition of the present invention.

The polymer can be suitably used as a component of a radiation-sensitive composition for forming an insulating film for a display device. The polymer is a preferred form of the polymer (A) in the radiation-sensitive composition according to the embodiment of the present invention described above.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

<Measurement of weight average molecular weight (Mw)>
In the polymer synthesis examples shown below, the weight average molecular weight (Mw) of the obtained polymer was measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: Showa Denko's "GPC-101"
Column: Showa Denko's "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" connected mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow velocity: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection amount: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

An example of synthesizing the polymer (A) is shown below. (A) The polymer is not limited to the following synthetic examples. The product names of the compounds used in the synthesis examples are shown below.
PAM-E: Silicone diamine made by Shinetsu Silicone, functional group equivalent = 130 g / mol
KF8010: Silicone diamine made by Shinetsu Silicone, functional group equivalent = 430 g / mol
A-BPEF: Bifunctional fluorene acrylate manufactured by Shin-Nakamura Chemical A-BPE-2: Bifunctional bisphenol A acrylate manufactured by Shin-Nakamura Chemical

(Synthesis Example 1)
8.77 g (10.2 mmol) of KF8010 (silicone diamine made by Shinetsu Silicone, functional group equivalent = 430 g / mol) as silicone oil with amino-modified ends in a 100 mL three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube. 35.1 g of tetrahydrofuran was charged and cooled with water. Next, 1.68 g (10.0 mmol) of hexamethylene diisocyanate and 6.72 g of 1-methyl-2-pyrrolidone were added to the dropping funnel as compounds having isocyanate groups at both ends so that the internal temperature was 40 ° C. or lower. Was slowly added dropwise to the mixture, and the mixture was stirred at room temperature for 8 hours.
Next, 4.21 g (20.0 mmol) of trimellitic anhydride chloride and 16.8 g of 1-methyl-2-pyrrolidone were charged in the dropping funnel. The mixture was slowly added dropwise while cooling with ice so that the internal temperature was 30 ° C. or lower, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the mixture was poured into 500 mL of water and reprecipitated, and the removal of the supernatant was repeated twice. The precipitate was then dissolved in 140 g of 1-methyl-2-pyrrolidone and concentrated to a solid content concentration of 20%. The obtained polymer (A-1) was used. The weight average molecular weight of (A-1) measured by GPC was 8,000.

(Synthesis Example 2)
2.6 g (10. mmol) of PAM-E (Shinetsu Silicone Silicone Diamine, functional group equivalent = 130 g / mol) and 5 of 1-methyl-2-pyrrolidone in a 100 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube. .2g was charged and cooled with water. Next, 5.47 g (10.0 mmol) of 9,9-bis [4- (2-hydroxyethoxy) phenyl] full orange acrylate (A-BPEF, bifunctional fluorene acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to the dropping funnel. 10.9 g of -methyl-2-pyrrolidone was charged, slowly added dropwise so that the internal temperature was 40 ° C. or lower, and the mixture was stirred at room temperature for 3 hours. Next, 2.0 g (20.0 mmol) of succinic acid anhydride and 4.0 g of 1-methyl-2-pyrrolidone were charged, slowly added dropwise so that the internal temperature was 30 ° C. or lower, and stirred at 100 ° C. for 4 hours. gone. After completion of the reaction, 1-methyl-2-pyrrolidone was added to adjust the solid content concentration to 20%. The obtained polymer (A-2) was used. The weight average molecular weight of (A-2) measured by GPC was 3,900.

表中「－」は、使用しなかったことを示す。 (Synthesis Examples 3 to 7)
As shown in the composition of Table 1, synthesis was carried out in the same manner as in Synthesis Example 1. The results are shown in Table 1.
The measurement result of ^{1 1} H-NMR of the polymer (A-1) and (A-4) is shown. ^{1 1} H-NMR (400 MHz) was measured using DMSO-d ⁶ as a solvent and an apparatus manufactured by JEOL.
(A-1): An aromatic ring was confirmed around 7.6 to 8.2 ppm, an alkylene was confirmed around 0.2 to 3.8 ppm, and a peak of a proton derived from Si-CH ₃ was confirmed near 0 ppm.
(A-4): An aromatic ring was confirmed around 6.7 to 7.9 ppm, an alkylene was confirmed around 1.2 to 4.5 ppm, and a peak of a proton derived from Si-CH ₃ was confirmed around 0 ppm.

"-" In the table indicates that it was not used.

(Comparative synthesis example 1)
After adding 390 g of γ-butyrolactone (γ-BL) as a polymerization solvent to a three-necked flask, 120 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as a diamine compound was added to the polymerization solvent. added. After dissolving the diamine compound in the polymerization solvent, 71 g of 4,4'-oxydiphthalic acid dianhydride was added as an acid dianhydride. Then, after reacting at 60 degreeC for 1 hour, 19 g of maleic anhydride as an end-sealing agent was added. After further reacting at 60 ° C. for another 1 hour, the temperature was raised and the reaction was carried out at 180 ° C. for 4 hours to obtain about 600 g of a γ-BL solution containing the polymer (A-8) and having a solid content concentration of 35% by mass. rice field. The Mw of the obtained polymer (A-8) was 8000.

(Comparative synthesis example 2)
A flask equipped with a cooling tube and a stirrer was charged with 5.2 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 160 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 10 parts by mass of methacrylic acid, 15 parts by mass of glycidyl methacrylate, 15 parts by mass of cyclohexylmaleimide, 10 parts by mass of 4-isopropenylphenol, 25 parts by mass of methylmethacrylate, and 0.5 parts by mass of α-methylstyrene dimer were charged and nitrogen was charged. After the replacement, gentle stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain an acrylic polymer solution containing the polymer (A-9). The Mw of the polymer (A-9) was 11,000.

(Comparative synthesis example 3)
125 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was charged in the reaction vessel, and the temperature was raised to 80 ° C. In this reaction vessel, 12 parts by mass of methacrylic acid, 45 parts by mass of benzyl methacrylate, 20 parts by mass of N-phenylmaleimide, 5 parts by mass of styrene, 18 parts by mass of 2-hydroxymethacrylate, and 2,2'-azobis- as a polymerization initiator ( A solution obtained by mixing 5 parts by mass of 2,4-dimethylvaleronitrile) and 25 parts by mass of PGMEA was added dropwise to the reaction solution over 2 hours each. After the dropping, the mixture was heated at 80 ° C. for 2 hours and at 100 ° C. for 1 hour. An acrylic polymer solution containing the polymer (A-10) was obtained. The Mw of the polymer (A-10) was 12,000.

The composition was adjusted and evaluated by the following procedure. The results are shown in Table 2.
(Adjustment of radiation-sensitive composition)
The components (A) to (G) were blended and adjusted with the compositions shown in Table 2. The compounds used are as follows.
(B) Radical compound B-1: 4,4'-[1- [4- [1 [(4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1 , 2-Naftquinone diazide-5-Sulfonic acid chloride (3.0 mol) condensate B-2: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2- Condensate with naphthoquinone diazide-5-sulfonic acid chloride (3.0 mol) B-3: Photoradical polymerization initiator NCI-930 (manufactured by ADEKA)
(C) (Meta) acrylate compound, epoxy compound C-1: pentaerythritol tetraglycidyl ether C-2: trimethylolpropane triglycidyl ether, trade name "Denacol EX-321L" (manufactured by Nagase ChemteX Corporation)
C-3: Dipentaerythritol acrylate, trade name "A-DPH" (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
C-4: Pentaerythritol tetraacrylate, trade name "A-TMMT" (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
C-5: Trimethylolpropane triacrylate, trade name "Aronix M-309" (manufactured by Toagosei Co., Ltd.)

(Evaluation of outgas)
The outgas of the cured film was measured by P & T GC-MS. Each composition was spin-coated on a Si wafer and prebaked at 100 ° C. for 2 minutes. Using an aligner (manufactured by Suss Microtec, model "MA-100"), the entire surface of the coating film was irradiated so that the exposure amount of ultraviolet rays (wavelength 365 nm) from a high-pressure mercury lamp was 300 mJ / cm ² . After that, for Examples 10 and 11 and Comparative Example 3, development was carried out in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds by a liquid filling method, and washing with ultrapure water for 60 seconds was performed. It was dried.
Then, it was heated at 250 ° C. for 30 minutes. Then, the substrate piece cut out to a certain area was sealed in a glass tube, heated at 250 ° C. for 15 minutes, and the generated gas was analyzed by a GC-MS apparatus. The total amount of gas generated was measured and evaluated according to the following criteria.
◎: The generated gas is less than 200 ppm with respect to the weight of the cured film 〇: The generated gas is 200 ppm or more and less than 1000 ppm with respect to the weight of the cured film ×: The generated gas is 1000 ppm or more with respect to the weight of the cured film ◎: The generated gas is the weight of the cured film 〇: The generated gas is 200 ppm or more and less than 1000 ppm with respect to the weight of the cured film ×: The generated gas is 1000 ppm or more with respect to the weight of the cured film

(Evaluation of crack resistance)
A film was formed by spin-coating on a Kapton film having a thickness of 125 μm and then prebaking at 100 ° C. for 2 minutes. Using an aligner (manufactured by Suss Microtec, model "MA-100"), the entire surface of the coating film was irradiated with ultraviolet rays from a high-pressure mercury lamp so that the exposure amount was 300 mJ / cm ² at a wavelength of 365 nm. After that, for Examples 10 and 11 and Comparative Example 3, development was carried out in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds by a liquid filling method, and washing with ultrapure water was carried out with running water for 60 seconds. It was dried.
Subsequently, the film was post-baked at 250 ° C. for 30 minutes under air and nitrogen to prepare a cured film having a film thickness of 2.5 μm. The film with the cured film was fixed to the core material so as to have a radius of curvature of 350 μm, and the state of the film after bending was observed by SEM.
◎: No cracks even without a core material 〇: No cracks with a core material with a radius of curvature of 350 μm ×: Cracks with a core material with a radius of curvature of 350 μm

(Evaluation of resolution)
After applying each of the prepared radiation-sensitive resin compositions on a silicon substrate by spin coating,
A coating film having a film thickness of 2.5 μm was formed by prebaking on a hot plate at 100 ° C. for 2 minutes.
On the obtained coating film, a square pattern with a side of 2 μm is arranged at intervals of 6 μm with an exposure amount of 300 mJ / cm ² at a wavelength of 365 nm using an exposure machine (manufactured by Aligner SusS Microtec, model “MA-100”). The exposure was performed through the mask. Then, development was carried out in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds by a liquid filling method.
Then, it was washed with running water for 60 seconds with ultrapure water and dried to form a pattern on a silicon substrate. The cross-sectional shape of the square pattern having a side of 2 μm thus obtained was observed at a magnification of 1500 times using a scanning electron microscope (S-4200 manufactured by Hitachi, Ltd.). The resolution was evaluated according to the evaluation criteria shown below.
〇: The pattern opening is formed without a residual. ×: There is a residual in the pattern opening.

(Evaluation of warpage)
Each composition was applied onto a substrate with a release material, and then heated at 100 ° C. for 2 minutes using a hot plate to prepare a uniform coating film having a thickness of 10 μm. Next, using an aligner (manufactured by Suss Microtec, model "MA-100"), the entire surface of the coating film was irradiated with ultraviolet rays from a high-pressure mercury lamp so that the exposure amount was 300 mJ / cm ² at a wavelength of 365 nm. After that, for Examples 10 and 11, Comparative Example 3 was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds by a liquid filling method, washed with ultrapure water for 60 seconds, and dried. I let you.
It was then heated in an oven at 250 ° C. for 30 minutes.
The coating film after the heat treatment was cut into 5 cm squares, and the height of peeling of the film at the end was measured.
It was evaluated according to the following evaluation criteria.
〇: When the height of the peeling of the film at the end is 10 mm or less ×: When the height of the peeling of the film at the end is 10 mm or more

As shown in Table 2, Examples 1 to 11 generate less outgas, have good crack resistance, and have excellent resolution. Furthermore, good results were shown in the evaluation of warpage.

The radiation-sensitive property of the present invention can be suitably used as a material for forming an insulating film or the like of a display device.

10 Organic EL device with touch panel 20 Organic EL display substrate 21 Support substrate 22 Anode layer 23 Organic light emitting layer 24 Cathode layer 25 Adhesive layer 26 Encapsulation substrate 30 Touch panel 31 First sensor electrode 32 Second sensor electrode 33 Interlayer insulating film 34 Transparent substrate

Claims (14)

(A) At least one polymer selected from a polymer having a structural moiety represented by the following formula (1) or a polymer having a structural moiety represented by the following formula (2).
(B) A radiation-sensitive composition containing a radiation-sensitive compound.

(In the formula (1), R ¹ and R ² are hydrocarbon groups having 1 to 12 carbon atoms, R ³ is a carboxyl group, a (meth) acryloyl group, and a monovalent organic group having any of an acid anhydride structure. ^R4 represents a divalent organic group having an alcandiyl group, a phenyl group, or an alicyclic hydrocarbon having 1 to 12 carbon atoms. N is an integer of 2 to 100, and a and b are 1 to 12, respectively. Indicates an integer.
In formula (2), R ⁵ and R ⁶ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁷ is a carboxyl group, a (meth) acryloyl group, and a monovalent organic group having any of an acid anhydride structure, R. Reference numeral ⁸ indicates a divalent organic group having an alcandiyl group, a phenyl group, or an alicyclic hydrocarbon having 1 to 12 carbon atoms. m is an integer from 2 to 100, and c and d are integers from 1 to 12, respectively. ) In the polymer having the structural moiety represented by the formula (1) or the polymer having the structural moiety represented by the formula ( ² ), R3 is selected from the groups represented by the following formulas (1a) to (1c). The radiation-sensitive composition according to claim 1, wherein R ⁷ is a group represented by the following formulas (2a) to (2b).

(In the formula, Ra represents a hydrogen atom or a methyl group, and R ^b represents ^a hydrocarbon group having a divalent ring having 2 to 12 carbon atoms or an aromatic ring having 6 to 10 carbon atoms *. Indicates the bond position.) The radiation-sensitive composition according to claim 1 or 2, wherein the radiation-sensitive compound is at least one of a photoacid generator and a photoradical polymerization initiator. The radiation-sensitive composition according to claim 1 to 3, further comprising (C) at least one of a (meth) acrylic compound and an epoxy compound. The radiation-sensitive composition according to claim 1 to claim 4, which can be cured by heating in a temperature range of 60 ° C. or higher and 120 ° C. or lower. An insulating film for a display device formed from the radiation-sensitive composition according to any one of claims 1 to 5. A display device having an insulating film for the display device according to claim 6. The display device according to claim 7, which is an organic electroluminescence device. The display device according to claim 8, which is an organic electroluminescence device with a touch panel. The process of forming a coating film directly or indirectly on a substrate,
The step of irradiating at least a part of the coating film with radiation,
A display device comprising the steps of developing the coating film and heating the coating film in this order, and forming the coating film with the radiation-sensitive composition according to any one of claims 1 to 5. How to form an insulating film. The method for forming an insulating film for a display device according to claim 10, wherein the substrate includes an organic electroluminescence element. The method for forming an insulating film for a display device according to claim 10 or 11, wherein the heating is performed in a temperature range of 60 ° C. or higher and 120 ° C. or lower. A polymer having a structural site represented by the following formula (3).

(In formula (3), X represents an alkanediyl group having 1 to 12 carbon atoms, and n represents an integer from 2 to 100.) A polymer having a structural site represented by the following formula (4).

(In formula (4), X represents an alkanediyl group having 1 to 12 carbon atoms. M represents an integer from 2 to 100.)

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