JP2012172083A - Polyrotaxane and curable composition - Google Patents

Abstract

The present invention provides a curable composition capable of producing a pattern having excellent resolution and solvent resistance, and a polyrotaxane from which the curable composition can be obtained.
A polyrotaxane comprising a cyclic compound (A) and a linear polymer (B) penetrating through the cavity of the cyclic compound,
The cyclic compound is a compound obtained by adding an unsaturated compound having an isocyanato group to the hydroxy group of the cyclic compound (A ′) having a plurality of hydroxy groups,
A polyrotaxane in which the linear polymer is a polymer having N-substituted amino groups at both ends, and a curable composition containing the polyrotaxane.
[Selection figure] None

Description

  The present invention relates to a polyrotaxane and a curable composition containing the polyrotaxane.

In recent liquid crystal display panels and the like, a pattern obtained from a curable composition is usually used on a substrate surface in order to form a transparent film such as a coat layer, a photo spacer, a pixel of a color filter, and the like.
As such a curable composition, a resin obtained by adding glycidyl methacrylate to a copolymer of benzyl methacrylate, methacrylic acid, and monomethacrylate having a tricyclodecane skeleton, together with a pigment, dipentaerythritol hexaacrylate, and a polymerization initiator. The curable composition containing is known (for example, patent document 1).

Japanese Patent Laying-Open No. 2005-157311

  When a pattern is formed on a substrate with low heat resistance such as a plastic substrate, and the pattern is used for applications such as a color filter, the substrate deforms the pattern having the resolution and chemical resistance required for the application. Therefore, a curable composition capable of forming such a pattern is required.

The present invention provides the following [1] to [6].
[1] A polyrotaxane comprising a cyclic compound (A) and a linear polymer (B) penetrating through the cavity of the cyclic compound,
The cyclic compound is a compound obtained by adding an unsaturated compound having an isocyanato group to the hydroxy group of the cyclic compound (A ′) having a plurality of hydroxy groups,
A polyrotaxane, wherein the linear polymer is a polymer having N-substituted amino groups at both ends.
[2] The polyrotaxane according to [1], wherein the N-substituted amino group is an N-arylamino group.
[3] A curable composition comprising the polyrotaxane according to [1] or [2] and a polymerization initiator.
[4] The curable composition according to [3], further including a colorant.
[5] A pattern formed from the curable composition according to [3] or [4].
[6] A display device including the pattern according to [5].

  According to the polyrotaxane of the present invention, a curable composition capable of producing a pattern with high resolution can be obtained. Moreover, even if it is a pattern produced from the curable composition at a temperature at which the plastic substrate does not deform, it exhibits high solvent resistance.

  A polyrotaxane is a polymer of a molecule (rotaxane) in which a rotor and an axis are combined, and a cyclic compound is attached to both ends of a linear polymer compound in which a large number of cyclic compounds are intercalated. Is a compound having a structure provided with a large substituent that acts so as not to leave.

  The polyrotaxane of the present invention comprises a cyclic compound (A) and a linear polymer (B) penetrating through the cavity of the cyclic compound (A). The cyclic compound (A) constituting the polyrotaxane of the present invention has an isocyanato group on the hydroxy group of the cyclic compound (A ′) having a plurality of hydroxy groups (hereinafter sometimes referred to as “cyclic compound (A ′)”). The straight chain polymer (B) is a polymer having N-substituted amino groups at both ends.

  The cyclic compound (A ′) is not particularly limited as long as it is a cyclic compound having a plurality of hydroxy groups, and known compounds can be used. Examples thereof include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Of these, α-cyclodextrin is preferred.

  Examples of the unsaturated compound (C) having an isocyanato group include (meth) acryloyloxyisocyanate, 2- (meth) acryloyloxyphenyl isocyanate, 2- (p-vinylphenyl) propan-2-yl isocyanate, 2- ( (Meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 6- (meth) acryloyloxyhexyl isocyanate, 8- (meth) acryloyloxyoctyl isocyanate, 10- ( (Meth) acryloyloxydecyl isocyanate, 1,1- [bis (meth) acryloyloxymethyl] ethyl isocyanate, 1,1,1- [tris (meth) acryloyloxymethyl] methyl ester Cyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, 2- [2- (2-isocyanatoethoxy) ethoxy] ethyl (meth) acrylate, 2- [2- [2- [2-] 2- (meth) acrylate (2-isocyanatoethoxy) ethoxy] ethoxy] ethyl, 2- (2-isocyanatepropoxy) ethyl (meth) acrylate, 2- [2- (2-isocyanatepropoxy) propoxy] ethyl (meth) acrylate, and the like. .

  Among these, 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, (meth) methacrylic acid 2- (2-isocyanatoethoxy) ethyl from the point of reactivity with the cyclic compound (A ′). 1,1- [bis (meth) acryloyloxymethyl] ethyl isocyanate is preferred.

  Among such compounds, as a commercial product of 2-acryloyloxyethyl isocyanate, Karenz AOI (manufactured by Showa Denko KK) under the trade name, and as a commercial product of 2-methacryloyloxyethyl isocyanate, Karenz MOI (Showa as a commercial product). As a commercial product of 2- (2-isocyanatoethoxy) ethyl methacrylate, a commercial name of Karenz MOI-EG (manufactured by Showa Denko), 1,1- (bisacryloyloxymethyl) ethyl As a commercial product of isocyanate, Karenz BEI (manufactured by Showa Denko KK) or the like can be used under the trade name.

  The addition amount of the unsaturated compound (C) having an isocyanato group is preferably 1 to 10000 mol, more preferably 2 to 1000 mol, per 1 mol of the cyclic compound (A ′). When the amount of the unsaturated compound (C) having an isocyanato group is in the above range, the resulting pattern tends to be excellent in resolution and solvent resistance, which is preferable.

  In the polyrotaxane of the present invention, the number of unsaturated bonds derived from the unsaturated compound (C) having an isocyanato group is preferably 1 to 2400, more preferably 10 to 1200, and more preferably 1 molecule per polyrotaxane. The number is preferably 10 to 600. When the number of unsaturated bonds derived from an unsaturated compound having an isocyanato group is in the above range, the resulting pattern tends to be excellent in resolution and solvent resistance, which is preferable.

  The cyclic compound (A) is a compound obtained by adding an unsaturated compound (C) having an isocyanato group to the cyclic compound (A ′). Specifically, for example, the hydroxy group of α-cyclodextrin is N- (methacryloyl). Oxyethyl) a compound substituted with an aminocarbonyloxy group, a compound in which the hydroxy group of α-cyclodextrin is substituted with an N- (acryloyloxyethyl) aminocarbonyloxy group, and a hydroxy group of α-cyclodextrin is N- {1 , 1-bis (acryloyloxymethyl) ethyl} aminocarbonyloxy group, and the like. Among them, the cyclic compound (A) constituting the polyrotaxane of the present invention is preferably a compound in which the hydroxy group of α-cyclodextrin is substituted with an N- (acryloyloxyethyl) aminocarbonyloxy group.

The weight average molecular weight in terms of polystyrene of the cyclic compound (A) is preferably from 100 to 10,000, and particularly preferably from 100 to 5,000. When the weight average molecular weight of a cyclic compound (A) exists in the said range, the pattern obtained tends to be excellent in resolution and solvent resistance, and is preferable.
In addition, the cyclic compound (A) is preferably one that dissolves in water because purification becomes easy.

  The introduction amount of the cyclic compound (A) in the polyrotaxane of the present invention is preferably 2 to 1000 molecules, more preferably 5 to 100 molecules, per 1 molecule of the linear polymer (B). When the amount of the cyclic compound (A) introduced is in the above range, the resulting pattern tends to be excellent in resolution and solvent resistance, which is preferable.

  A well-known thing can be used as a linear polymer (B). For example, polyethers (for example, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, etc.), polyolefins (for example, polyethylene, polypropylene, polyisoprene, polyisobutylene, polybutadiene, etc.), celluloses (for example, carboxymethyl cellulose, hydroxypropyl cellulose, etc.), siloxane (Polydimethylsiloxane). Of these, polyethers are preferable, and polyethylene glycol is particularly preferable. These linear polymer compounds may be used alone or in combination of two or more.

  The weight average molecular weight in terms of polystyrene of the linear polymer (B) is preferably 1,000 or more and 100,000 or less, more preferably 1,000 or more and 50,000 or less, and 1,000. It is especially preferable that it is above 30,000. When the weight average molecular weight of the linear polymer is in the above range, the resulting pattern is preferred because it tends to be excellent in resolution and solvent resistance.

The linear polymer (B) constituting the polyrotaxane of the present invention has N-substituted amino groups as end-capping groups at both ends. As the N-substituted amino group, those having bulkiness and / or ionicity are preferable. Here, the bulky group is selected depending on the size of the opening of the cyclic compound, and the ionic group is selected based on the electronic state of the opening of the cyclic compound.
Specific examples of the N-substituted amino group that the linear polymer (B) has include, for example, an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-butylamino group, an N- -Benzylamino group, N-acetylamino group, N-benzoylamino group, N-methoxycarbonylamino group, N- (2,4-dinitrophenyl) amino group, N- (2,4,6-trinitrophenyl) N-monosubstituted amino groups such as amino group, N-tritylamino group, N-dansylamino group;
Examples thereof include N, N-disubstituted amino groups such as N, N-dimethylamino group, N, N-diethylamino group, and N, N-dibutylamino group. Among them, N-substituted amino groups include N- (2,4-dinitrophenyl) amino group, N- (2,4,6-trinitrophenyl) amino group, N-tritylamino group, and N-dansylamino group. N-arylamino groups such as are preferred. By having these groups in the linear polymer penetrating the cyclic compound, the penetrating linear polymer can be prevented from leaving the cyclic compound, and the penetrating state can be maintained.

  The polyrotaxane of the present invention reacts a cyclic compound (A ′) with a linear polymer (B), and a compound in which the linear polymer (B) penetrates the cavity of the cyclic compound (A ′) ( a ′), a polyrotaxane (a) having an N-amino group introduced into both ends of the linear polymer of the compound using an end-capping agent is obtained, and the polyrotaxane (a) is further obtained. The unsaturated compound (C) having an isocyanato group can be added to the hydroxy group of the cyclic compound (A ′).

  More specifically, for example, the cyclic compound (A ′) is 1 part or more and 10 parts or less (preferably 1 part or more and 5 parts or less) with respect to 1 part of the linear polymer (B). Is stirred and mixed in water, for example, in the temperature range of room temperature to 90 ° C. for about 10 minutes to 3 hours. If the linear polymer is difficult to dissolve in water, the polymer may be stirred while applying ultrasonic waves. Then, it cools at the temperature of 0 degreeC-10 degreeC for 1 hour-24 hours, and the produced | generated deposit and water are isolate | separated. Examples of the separation method at this time include filtration, centrifugal separation, membrane separation using an ultrafiltration membrane, and vacuum distillation. Further, after separating the generated precipitate and water, if necessary, drying may be performed under reduced pressure. When drying, it is preferable to dry at a temperature of 0 ° C. to 100 ° C. for 1 hour to 24 hours. Thereby, the compound (P ′) in which the linear polymer (B) penetrates the cavity of the cyclic compound (A ′) can be obtained.

  Next, an end-capping group is introduced at the end of the linear polymer passing through the cavity of the cyclic compound. Specifically, for example, a compound (P ′) in which a linear polymer passes through a cavity of a cyclic compound is dissolved in a solvent to prepare a solution, and a terminal blocking agent is added to the solution, for example, Stir in suspension at 10-30 ° C. for 30 minutes to 5 hours.

  Examples of the solvent include N, N-dimethylformamide. The usage-amount of a solvent is about 100-2000 mass parts normally with respect to 100 mass parts of terminal blockers.

  The end-capping agent is used to introduce N-substituted amino groups at both ends of the linear polymer (B). Examples of the end-capping agent include 2,4-dinitrophenyl. Examples include fluoride, 2,4,6-trinitrophenyl fluoride, trityl bromide, dansyl chloride and the like.

  The amount of the end-capping agent used is preferably 2 to 50 mol, more preferably 2 to 20 mol, relative to 1 mol of the compound (P ′) in which the linear polymer passes through the cavity of the cyclic compound. .

  By purifying the suspension, a polyrotaxane (P) (hereinafter referred to as “polyrotaxane (P) in which an N-substituted amino group is introduced as a terminal blocking group at the end of a linear polymer penetrating through a cavity of a cyclic compound”. ) ”In some cases.

Examples of the purification method include centrifugation, silica gel force ram chromatography, a method of separating the upper layer from the lower layer using a separatory funnel, recrystallization, and washing with an organic solvent. Centrifugation is preferred from the viewpoint of ease of operation and high purification efficiency.
When performing purification by centrifugation, for example, after washing with a solvent (preferably water) in which the cyclic compound (A ′) is dissolved, washing with a solvent in which the end capping agent is dissolved is preferable. Centrifugation is preferably performed at a rotational speed of 1 to 10,000 rpm for about 1 minute to 1 hour. After the purification, when there is a lot of moisture, a drying treatment with a desiccant such as anhydrous magnesium sulfate or anhydrous sodium sulfate or a vacuum drying treatment may be performed. The drying treatment with a desiccant is performed by adding a desiccant to a solution obtained by dissolving the cyclic compound (A ′) in a solvent, and performing the treatment at a temperature of 0 to 50 ° C. for 1 minute to 24 hours, preferably 1 minute to 1 hour. preferable. Then, a polyrotaxane (P) is obtained by removing a desiccant and removing a solvent from the obtained filtrate. The vacuum drying treatment is preferably performed at a temperature of 0 to 100 ° C. for 1 minute to 48 hours, preferably 1 minute to 24 hours.

Next, the unsaturated compound (C) having an isocyanato group is added to the hydroxy group of the cyclic compound (A ′).
Specifically, for example, an unsaturated compound (C) having an isocyanato group is added to a solution in which polyrotaxane (P) is dissolved in a solvent (for example, dimethyl sulfoxide, etc.), for example, at a temperature of 30 ° C to 80 ° C. Stir for 1 to 24 hours. In order to accelerate this reaction, a catalyst may be used in combination. Then, the polyrotaxane of this invention can be obtained by refine | purifying the said stirring mixture.

  Examples of the catalyst include triethylamine, lauric acid, dibutyltin, and the like. The amount of the catalyst used is preferably 0.001 to 10% by mass with respect to the polyrotaxane (P).

Purification methods include centrifugation, silica gel force ram chromatography, separation of upper and lower layers using a separatory funnel, recrystallization, washing with organic solvents, etc. Centrifugation is more preferable from the viewpoint of height.
When purifying by centrifugation, for example, it is preferable to perform washing with a solvent in which the unsaturated compound (C) having an isocyanato group is dissolved. Centrifugation is preferably performed at a rotational speed of 1 to 10,000 rpm for about 1 minute to 1 hour. After the purification, if there is a lot of water, it may be dried with anhydrous magnesium sulfate, anhydrous sodium sulfate or the like. When drying is performed, it is preferably performed at a temperature of 0 to 50 ° C. for 1 minute to 24 hours, preferably 1 minute to 1 hour. Then, the polyrotaxane of this invention is obtained by removing a desiccant and removing a solvent from the obtained filtrate. If necessary, vacuum drying may be performed in the same manner as described above.

  The curable composition of this invention contains the polyrotaxane of this invention mentioned above and a polymerization initiator.

  The polymerization initiator contained in the curable composition of the present invention is not particularly limited, and a known polymerization initiator can be used. For example, biimidazole compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds are preferred. Moreover, you may use the photocationic polymerization initiator (For example, what is comprised from the onium cation and the anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Among them, it is preferable to use an oxime compound in terms of sensitivity. These polymerization initiators may be used alone or in combination of two or more.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2. -Benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1- (4-isopropenylphenyl) propan-1-one oligomers and the like Examples thereof include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. It is done. Commercial products such as Irgacure 369, 907 (above, manufactured by BASF Japan Ltd.) may be used.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Sulfonyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba Japan) may be used.

  Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one. 2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl- 6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, OXE-02 (manufactured by BASF Japan), N-1919 (manufactured by ADEKA) may be used.

  Furthermore, as polymerization initiators, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'- Benzophenone compounds such as methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Examples include quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (particularly amines) described later.

The curable composition of the present invention may further contain a polymerization initiation assistant. The polymerization initiation assistant is a compound or a sensitizer that is used in combination with a polymerization initiator and is used to promote polymerization of a polymerizable compound that has been polymerized by the polymerization initiator.
Examples of the polymerization initiation assistant include amine compounds, thiazoline compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the thiazoline compound include compounds represented by formula (III-1) to formula (III-3).

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  The content of the polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin. When the content of the polymerization initiator is within this range, a pattern can be formed with high sensitivity, and the chemical resistance, mechanical strength, and surface smoothness of the pattern tend to be good.

  When using a polymerization initiation aid, the amount used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the resin. Moreover, it is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol per mol of the polymerization initiator. When the amount of the polymerization initiation assistant is within this range, a pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

  Moreover, the curable composition of this invention may contain the polyfunctional thiol compound further. This polyfunctional thiol compound is a compound having two or more sulfanyl groups in the molecule. Especially, it is preferable to use a compound having two or more sulfanyl groups adjacent to the aliphatic hydrocarbon group because a pattern can be formed with high sensitivity.

  Polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate), ethylene glycol bis ( 3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanyl) Acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyltris ( - sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  The content of the polyfunctional thiol compound is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerization initiator. When the content of the polyfunctional thiol compound is in this range, the sensitivity tends to be high and the developability tends to be good.

The curable composition of the present invention may contain a colorant.
Examples of the colorant include pigments and dyes, but it is preferable to include a pigment in terms of heat resistance and light resistance.

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specific examples of the organic pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 242, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferable. These pigments may be used alone or in admixture of two or more.

  The pigment is optionally treated with rosin, surface treatment using a pigment derivative or pigment dispersant introduced with an acidic group or basic group, graft treatment on the pigment surface with a polymer compound, etc., sulfuric acid atomization Atomization treatment by a method or the like, cleaning treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

  Commercially available surfactants can be used as the pigment dispersant, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, non-ionic, amphoteric, polyester-based, polyamine-based, and acrylic-based. Surfactant etc. are mentioned. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.) ), Disperbyk (manufactured by Big Chemie) and the like. These can be used alone or in combination of two or more.

  When a pigment dispersant is used, the amount used is preferably 100% by mass or less, more preferably 5 to 50% by mass, based on the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in a uniform dispersion state tends to be obtained.

  The content of the colorant is preferably 5 to 60% by mass and more preferably 5 to 45% by mass with respect to the solid content of the curable composition. When the content of the colorant is within the above range, a desired spectrum and color density can be obtained. Here, solid content in this specification means the total amount of the component remove | excluding the solvent from the curable composition.

  The curable composition of the present invention may contain a resin (R). The resin used in the curable composition of the present invention is not particularly limited, and a resin generally used in the field can be used. A resin having a saturated bond, at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as “(a)”), (a) and 2 carbon atoms A monomer (c) having an unsaturated bond copolymerizable with a monomer having an cyclic ether of ˜4 and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”) (hereinafter referred to as “( c) ”may be copolymerized with a resin (R1) obtained by further reacting (b), and (b) and (c) may be copolymerized. Obtained by further reacting (a) with the resulting copolymer It can be used as resin (R2) and the like. Among these, it is particularly preferable to use (R1).

Specific examples of (a) constituting the resins (R1) and (R2) include acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid. Of unsaturated monocarboxylic acids;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.
Here, in this specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond. (B2) (hereinafter sometimes referred to as “(b2)”), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), and the like.

  Examples of (b1) include a monomer (b1-1) having a structure obtained by epoxidizing a chain olefin and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1-1)”), cycloalkene And a monomer (b1-2) having an epoxidized structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1-2)”).

  Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclone). Mer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), formula (II) ) And the like.

[In Formula (I) and Formula (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. May be substituted.
X ¹ and X ² each independently represent a single bond, —R ³ —, * —R ³ —O—, * —R ³ —S—, or * —R ³ —NH—.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

  (B2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Examples of (b-2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, and 3-methyl-3- (meth) acryloyloxyethyl. Examples include oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b-3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (c) include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta It is said to be nyl (meth) acrylate.
), (Meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

  Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among these, (c) is a compound (c1) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a tricyclodecene skeleton and an ethylenically unsaturated bond (hereinafter referred to as “(c1)”. It is preferable that the When (c) is (c1), the film loss of the pattern due to development can be suppressed.
Here, the “tricyclodecane skeleton” and the “tricyclodecene skeleton” in this specification refer to the following structures (respectively, the bond is an arbitrary position).

  Specific examples of (c1) include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. . These may be used alone or in combination of two or more.

  Resin (R1) and resin (R2) can be manufactured through a two-step process, for example. In this case, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972), JP-A-2001-89533. It can be produced with reference to the method described in the publication.

Resin (R1) first obtains a copolymer of (a) and (c) as the first step. Specifically, a method in which a predetermined amount of (a) and (c), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and oxygen is substituted with nitrogen, thereby deoxidizing, stirring, heating, and keeping warm. Is exemplified. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent described later can be used as a solvent for the curable composition.
As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

The ratio of the structural units derived from (a) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%)
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%)

Next, as a second step, the carboxylic acid (a) and a part of the carboxylic anhydride derived from the obtained copolymer are reacted with the cyclic ether (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b), and (b1-1) is more preferable.
Specifically, following the above, the atmosphere in the flask was replaced from nitrogen to air, and 5 to 80 mol% (b) of a reaction catalyst of a carboxy group and a cyclic ether with respect to the number of moles of (a) ( For example, tris (dimethylaminomethyl) phenol) is 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c), and a polymerization inhibitor (such as hydroquinone) is (a), 0.001-5 mass% is put in a flask with respect to the total amount of (b) and (c), and it is made to react at 60-130 degreeC for 1 to 10 hours, and resin (R1) can be obtained. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the number of moles of (b) is preferably 10 to 75 mole%, more preferably 15 to 70 mole%, with respect to the number of moles of (a). By setting the number of moles of (b) within this range, the balance between storage stability, solvent resistance and heat resistance tends to be good.

  Specific examples of the resin (R1) include a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate with glycidyl (meth) acrylate, (meth) acrylic acid / benzyl (meth) Resin obtained by reacting acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / cyclohexyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, (meth) acrylic acid / Resin obtained by reacting styrene copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / methyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, (meth) acrylic acid / N-cyclohexylmaleimide copolymer reacted with glycidyl (meth) acrylate , Glycidyl the copolymers of crotonic acid / dicyclopentanyl (meth) acrylate (meth) resins obtained by reacting an acrylate;

  Crotonic acid / benzyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / cyclohexyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / Styrene copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / Methyl crotonic acid copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / N-cyclohexylmaleimide copolymer Resin obtained by reacting glycidyl (meth) acrylate with the coalescence;

  Resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, and resin obtained by reacting maleic acid / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate , A resin obtained by reacting maleic acid / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, a resin obtained by reacting maleic acid / styrene copolymer with glycidyl (meth) acrylate, maleic acid / maleic acid A resin obtained by reacting a copolymer of methyl with glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of maleic acid / N-cyclohexylmaleimide with glycidyl (meth) acrylate;

  Resin obtained by reacting (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / benzyl (meth) Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of acrylate, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, Resin obtained by reacting a meth) acrylic acid / maleic anhydride / styrene copolymer with glycidyl (meth) acrylate, and a glycidyl (meth) acrylic acid / maleic anhydride / methyl (meth) acrylate copolymer Resin reacted with (meth) acrylate, (meth) acrylic acid / maleic anhydride / N-cyclohexylmale Glycidyl the copolymer of bromide (meth) resins obtained by reacting an acrylate;

  Resin obtained by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and (meth) acrylic acid / benzyl (meth) acrylate copolymer 3 , 4-Epoxycyclohexylmethyl methacrylate resin, (Meth) acrylic acid / cyclohexyl (meth) acrylate copolymer and 3,4-epoxycyclohexylmethyl methacrylate reaction resin, (Meth) acrylic acid / styrene A resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (4), a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / methyl (meth) acrylate, (Meth) acrylic acid / N-cyclohexyl male Resins obtained by reacting a copolymer in 3,4-epoxycyclohexylmethyl methacrylate bromide;

  Crotonic acid / dicyclopentanyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate; Crotonic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl Resin in which methacrylate is reacted, Resin in which crotonic acid / cyclohexyl (meth) acrylate copolymer is reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / styrene copolymer in 3,4-epoxycyclohexylmethyl Resin reacted with methacrylate, Crotonic acid / methyl crotonate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxycyclohexyl Methylme Resins obtained by reacting an acrylate;

  A resin obtained by reacting a maleic acid / dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and a maleic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl Resin reacted with methacrylate, Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate on maleic acid / cyclohexyl (meth) acrylate copolymer, 3,4-epoxycyclohexylmethyl on maleic acid / styrene copolymer Resin reacted with methacrylate, Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate on copolymer of maleic acid / methyl maleate, 3,4-epoxycyclohexyl on copolymer of maleic acid / N-cyclohexylmaleimide Methylme Resins obtained by reacting an acrylate;

  (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic anhydride / benzyl Resin obtained by reacting (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate; (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexyl Resin in which methyl methacrylate is reacted, Resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of (meth) acrylic acid / maleic anhydride / styrene, (meth) acrylic acid / maleic anhydride / Copolymer of methyl (meth) acrylate with 3,4-epoxycyclohexene Examples thereof include a resin obtained by reacting silmethyl methacrylate and a resin obtained by reacting a copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate.

Furthermore, the resin (R1) is a resin obtained by reacting (b) with a copolymer obtained by copolymerizing (a), (c1) and (c) other than (c1). It is more preferable. When resin (R1) is the said structure, the pattern obtained tends to be excellent in adhesiveness with a board | substrate and solvent resistance.
When the copolymer of (a) and (c) is composed of (c) other than (a), (c1) and (c1), it is derived from (c) other than (c1) and (c1) The ratio of structural units is preferably 10:90 to 60:40, more preferably 10:90 to 40:60, and even more preferably 10:90 to 30:70.

  Specific examples of the resin obtained by reacting (b) with a copolymer obtained by copolymerizing (a), (c1) and (c) other than (c1) include (meth) acrylic. Resin prepared by reacting glycidyl (meth) acrylate with a copolymer of acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meta ) A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of acrylate, a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene, A copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate is added to glycidyl (meth Resins obtained by reacting acrylate, (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N- cyclohexyl glycidyl the copolymer of maleimide (meth) resins obtained by reacting an acrylate;

  Crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer, resin obtained by reacting glycidyl (meth) acrylate, crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of the above, a resin obtained by reacting crotonic acid / dicyclopentanyl (meth) acrylate / styrene with a glycidyl (meth) acrylate, and crotonic acid / dicyclo A resin obtained by reacting a glycidyl (meth) acrylate with a copolymer of pentanyl (meth) acrylate / methyl crotonate, and a glycidyl (meth) acrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide ) Resin reacted with acrylate;

  Resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of the above, a resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate / styrene with a glycidyl (meth) acrylate, maleic acid / dicyclo A resin obtained by reacting a copolymer of pentanyl (meth) acrylate / methyl maleate with glycidyl (meth) acrylate, and a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide, ) Resin reacted with acrylate;

  (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride Resin / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) Resin obtained by reacting acrylate / styrene copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate copolymer Resin reacted with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / Cyclopentanyl (meth) acrylate / N- cyclohexyl glycidyl the copolymer of maleimide (meth) resins obtained by reacting an acrylate;

  A resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / dicyclopentanyl ( A resin obtained by reacting a copolymer of (meth) acrylate / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene. , 4-Epoxycyclohexylmethyl methacrylate reacted with 3,4-epoxycyclohexylmethyl methacrylate to (meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate copolymer Resin, (meth) acrylic acid / disi Ropentaniru (meth) acrylate / N- cyclohexyl maleimide copolymer resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate;

  A resin obtained by reacting a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl ( Resin of 3,4-epoxycyclohexylmethyl methacrylate reacted with meth) acrylate copolymer, 3,4-epoxycyclohexylmethyl methacrylate reacted with crotonic acid / dicyclopentanyl (meth) acrylate / styrene copolymer Resin, crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonic acid copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohex A resin obtained by reacting a copolymer of silmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;

  A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl ( Resin of 3,4-epoxycyclohexylmethyl methacrylate reacted with meth) acrylate copolymer, 3,4-epoxycyclohexylmethyl methacrylate reacted with maleic acid / dicyclopentanyl (meth) acrylate / styrene copolymer Resin, maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohex A resin obtained by reacting a copolymer of silmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;

  (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / A resin obtained by reacting a copolymer of maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic anhydride / di Resin prepared by reacting cyclopentanyl (meth) acrylate / styrene copolymer with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / (meta ) Copolymer of methyl acrylate with 3,4-epoxycyclohexane Resin reacted with silmethyl methacrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide copolymer, reacted with 3,4-epoxycyclohexylmethyl methacrylate Examples thereof include resins.

Resin (R2) obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin (R1) described above.
In this case, in the same manner as described above, the obtained copolymer may be used as it is as the solution after the reaction, or may be a concentrated or diluted solution, or a solid ( You may use what was taken out as a powder.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, in the same manner as in the production method of the resin (R1), the carboxylic acid or carboxylic anhydride possessed by (a) is added to the cyclic ether derived from (b) in the copolymer of (b) and (c). Can be obtained by reacting. A carboxylic acid anhydride may be further reacted with a hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol% with respect to the number of moles of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b), and (b1-1) is more preferable.

  Specific examples of the resin (R2) include a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, benzyl (meth) acrylate / glycidyl (meth) Resin in which (meth) acrylic acid is reacted with an acrylate copolymer, Resin in which (meth) acrylic acid is reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, styrene / glycidyl (meth) Resin in which (meth) acrylic acid is reacted with an acrylate copolymer, Resin in which (meth) acrylic acid is reacted with methyl (meth) acrylate / glycidyl (meth) acrylate copolymer, N-cyclohexylmaleimide / A resin obtained by reacting a copolymer of glycidyl (meth) acrylate with (meth) acrylic acid, Resin prepared by reacting lopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl ( Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, and (meth) acrylic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate , (Dicyclopentanyl (meth) acrylate / Methyl (meth) acrylate / Glycidyl (meth) acrylate copolymer) Resin obtained by reacting (meth) acrylic acid, Dicyclopentanyl (meth) acrylate / N- Copolymerization of cyclohexylmaleimide / glycidyl (meth) acrylate The (meth) resins obtained by reacting an acrylic acid;

  Resin obtained by reacting crotonic acid with dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer, resin obtained by reacting crotonic acid with benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin obtained by reacting crotonic acid with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, a resin obtained by reacting styrene / glycidyl (meth) acrylate copolymer with crotonic acid, methyl crotonate / glycidyl Resin obtained by reacting crotonic acid with copolymer of (meth) acrylate, resin obtained by reacting crotonic acid with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / Glycidyl (Meth) Ac Resin obtained by reacting crotonic acid with a copolymer of a rate, resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, dicyclopenta Resin obtained by reacting crotonic acid with a copolymer of nyl (meth) acrylate / styrene / glycidyl (meth) acrylate, croton into a copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / glycidyl (meth) acrylate A resin obtained by reacting an acid, a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;

  Resin made by reacting maleic acid with dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer, resin made by reacting maleic acid with benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin in which maleic acid is reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, a resin in which maleic acid is reacted with a copolymer of styrene / glycidyl (meth) acrylate, methyl maleate / glycidyl Resin in which maleic acid is reacted with copolymer of (meth) acrylate, resin in which maleic acid is reacted with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / Glycidyl (Meth) Ac Resin in which maleic acid is reacted with a copolymer of a rate, resin in which maleic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer maleic resin, dicyclopentanyl (meth) acrylate / methyl maleate / glycidyl (meth) acrylate copolymer A resin obtained by reacting an acid, a resin obtained by reacting a dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate copolymer with maleic acid;

  Resin obtained by reacting dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid and maleic anhydride, benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin in which (meth) acrylic acid and maleic anhydride are reacted with, cyclohexyl (meth) acrylate / glycidyl (meth) acrylate copolymer in which (meth) acrylic acid and maleic anhydride are reacted, styrene Resin prepared by reacting (meth) acrylic acid and maleic anhydride with a copolymer of glycidyl / glycidyl (meth) acrylate, and (meth) acrylic acid and a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate Resin reacted with maleic anhydride, (N-cyclohexylmaleimide / glycidyl A resin obtained by reacting a (meth) acrylate copolymer with (meth) acrylic acid and maleic anhydride, a dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer ( Resin obtained by reacting meth) acrylic acid and maleic anhydride, (meth) acrylic acid and maleic anhydride into dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, dicyclopentanyl (meth) Acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate Resin obtained by reacting polymer with (meth) acrylic acid and maleic anhydride, dimethypentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate copolymer with (meth) acrylic acid and maleic A resin reacted with an acid anhydride;

  Resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin in which (meth) acrylic acid is reacted with the polymer, Resin in which (meth) acrylic acid is reacted with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, styrene / 3,4-epoxy A resin obtained by reacting (meth) acrylic acid with a copolymer of cyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid with a copolymer of methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, N-cyclohexylmaleimide / 3,4-epo A resin obtained by reacting a copolymer of cyclocyclohexylmethyl methacrylate with (meth) acrylic acid, a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate (meta ) A resin obtained by reacting acrylic acid, a resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, Resin prepared by reacting a copolymer of pentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3 , 4-Epoxycyclohexylmethyl Resin of (meth) acrylic acid reacted with a copolymer of methacrylate, (meth) acrylic acid to a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate Reacted resin;

  A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, a copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate and croton Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, crotonic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer, croton Acid-reacted resin, Crotonic acid methyl / 3,4-epoxycyclohexylmethyl methacrylate copolymer, Crotonic acid-reacted resin, N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate copolymer A resin obtained by reacting crotonic acid, a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meta ) A resin obtained by reacting crotonic acid with a copolymer of acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting crotonic acid with copolymer, resin obtained by reacting crotonic acid with copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (Meta) acryle Resin obtained by reacting crotonic acid with a copolymer of carbonate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate;

  Dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid reacted, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, maleic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer Resin in which acid is reacted, Resin in which maleic acid is reacted with copolymer of methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate, Copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate A resin reacted with maleic acid, a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meta ) Resin prepared by reacting maleic acid with a copolymer of acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting maleic acid with copolymer, resin obtained by reacting maleic acid with copolymer of dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (Meta) acryle A resin obtained by reacting maleic acid with a copolymer of carbonate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate;

  Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, benzyl (meth) acrylate / 3,4-epoxycyclohexyl Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of methyl methacrylate, (meth) acrylic acid and maleic acid with a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexyl methyl methacrylate Resin in which anhydride is reacted, Resin in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of styrene / 3,4-epoxycyclohexylmethyl methacrylate, methyl (meth) acrylate / 3,4- Copolymerization of epoxycyclohexylmethyl methacrylate. A resin obtained by reacting (meth) acrylic acid and maleic anhydride, and a copolymer obtained by reacting a copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride. , A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, dicyclopentanyl ( Resin of (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer reacted with (meth) acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of tacrylate, copolymer of dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylic acid and maleic anhydride, and a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate to (meth) acrylic acid and Examples include resins reacted with maleic anhydride.

  The weight average molecular weight (Mw) in terms of polystyrene of the resins (R1) and (R2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weights of the resins (R1) and (R2) are in the above-mentioned range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel portion is easily removed during development. It tends to be good.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resins (R1) and (R2) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. It is. When the molecular weight distribution of the resins (R1) and (R2) is in the above range, the developability tends to be excellent.

  The acid values of the resins (R1) and (R2) are 20 to 150 mg-KOH / g, preferably 50 to 135 mg-KOH / g, more preferably 65 to 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resins (R1) and (R2), and can be determined by titration using an aqueous potassium hydroxide solution. it can.

  Content of resin (R) becomes like this. Preferably it is 0-80 mass% with respect to solid content of a curable composition, More preferably, it is 5-75 mass%, Most preferably, it is 10-70 mass%. In particular, when the curable composition of the present invention contains a colorant, the content is preferably 20 to 80% by mass, more preferably 30 to 60% by mass. When the content of the resin (R) is in the above range, developability, adhesion, solvent resistance, and mechanical properties tend to be good.

  The curable composition of the present invention may further contain a solvent. It does not specifically limit as a solvent, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like can be selected and used. These solvents may be used alone or in combination of two or more.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.

  The content of the solvent is preferably 60 to 95% by mass and more preferably 70 to 90% by mass with respect to the curable composition. In other words, the solid content of the curable composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. When the content of the solvent is in the above range, the flatness during application tends to be good.

  Moreover, the curable composition of this invention may contain surfactant. Examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and the like. By including the surfactant, the flatness during application tends to be good.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (DIC) ), Ftop (registered trademark) EF301, EF303, EF351, EF351, EF352 (manufactured by Mitsubishi Materials Denkasei), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) And E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  Surfactant is 0.001 mass% or more and 0.2 mass% or less with respect to curable composition, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, it is 0.01 mass. % Or more and 0.05% by mass or less. By containing the surfactant in this range, the flatness of the coating film can be improved.

  The colored photosensitive resin composition of the present invention may contain various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc., as necessary. May be included.

The curable composition of this invention can be prepared as follows, for example.
First, the pigment of the colorant is mixed with a solvent in advance, and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a pigment dispersant and some or all of resin (R) as needed. To the obtained pigment dispersion, polyrotaxane, the remainder of the resin (R), a polymerization initiator, other components used as necessary, and an additional solvent as necessary are added to a predetermined concentration. And the target curable composition can be obtained. When no colorant is included, the polyrotaxane, the resin (R), the polymerization initiator, and other components used as necessary are mixed to a predetermined concentration to obtain the desired curable composition. be able to.

  Examples of the method for obtaining the pattern include a photolithography method, an ink jet method, and a printing method. Of these, the photolithography method is preferable. The photolithography method is a method for obtaining a pattern by applying the curable composition to a substrate, drying, exposing through a photomask, and developing.

Examples of the substrate include glass, metal, plastic, and the like, and may be plate-shaped or film-shaped.
Examples of the plastic include polyolefins such as polyethylene, polypropylene, norbornene-based polymers, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylate, cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyetherketone, Examples include polyphenylene sulfide and polyphenylene oxide. Here, (meth) acrylic acid means at least one selected from the group consisting of acrylic acid and methacrylic acid. Structures such as a color filter, various insulating or conductive films, and a drive circuit may be formed on these substrates.
According to the curable composition of the present invention, since a pattern cured at a lower temperature can be formed, it is particularly useful when forming a pattern on a plastic substrate.

  Examples of the coating method on the substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Apply using a coating device such as a dip coater, roll coater, bar coater, spin coater, slit & spin coater, slit coater (sometimes called a die coater, curtain flow coater, or spinless coater) or inkjet. Also good. Especially, it is preferable to apply using a slit coater, a spin coater, a roll coater or the like.

Examples of the method for drying the film applied to the substrate include methods such as heat drying, natural drying, ventilation drying, and vacuum drying. A plurality of methods may be combined.
As drying temperature, 10-120 degreeC is preferable and 25-100 degreeC is more preferable. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
The vacuum drying is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
The film thickness of the coating film after drying is not particularly limited and can be appropriately adjusted depending on the material used, application, etc., and is, for example, 0.1 to 20 μm, preferably 1 to 6 μm.

The coating film after drying is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel light rays uniformly or the mask and the substrate can be accurately aligned.

After exposure, the coating film is brought into contact with a developer to dissolve a predetermined portion, for example, an unexposed portion, and developed, whereby a pattern can be obtained. As the developer, an organic solvent can be used, but it is preferable to use an aqueous solution of an alkaline compound because the exposed portion of the coating film is hardly dissolved or swollen by the developer and a pattern having a good shape can be obtained. .
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Inorganic alkaline compounds such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, mono Examples include organic alkaline compounds such as ethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Of these, potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium hydroxide are preferable.
The density | concentration in the aqueous solution of these inorganic and organic alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the alkaline compound may contain a surfactant.
Surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters , Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine;
Anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate;
And cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the aqueous solution of the alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.1 to 5% by mass.

  By further baking the pattern obtained as described above, a cured pattern can be obtained. The baking temperature is 25 ° C. or higher and 230 ° C. or lower, preferably 25 ° C. or higher and 200 ° C. or lower, more preferably 25 ° C. or higher and 160 ° C. or lower, and further preferably 25 ° C. or higher and 120 ° C. or lower. The baking time is 1 to 300 minutes, preferably 1 to 180 minutes, and more preferably 1 to 60 minutes.

  The pattern thus obtained is useful as, for example, a photospacer used in a liquid crystal display device, a patternable overcoat, and a color filter. In addition, the curable composition of the present invention can be suitably used for forming a coating film or a pattern to be a pixel of a liquid crystal display device or an image sensor. The present invention can be used for a color filter, an array substrate, and a display device including these color filters and / or an array substrate, for example, a liquid crystal display device, an organic EL device, a solid-state imaging device, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Example 1
To 1 part of polyoxyethylene bisamine (manufactured by Sigma) synthesized from polyethylene glycol having a weight average molecular weight of 3,350, 1.9 parts of α-cyclodextrin was added, dissolved in 30 parts of distilled water, and mixed. And stirred at 80 ° C. for 1 hour to obtain a transparent solution. Next, this transparent solution was cooled overnight in a refrigerator (5 ° C.) to obtain a white gel. The white gel was volatilized and removed under reduced pressure using an evaporator. The obtained white solid product was dissolved in 19 parts of N, N-dimethylformamide, and 3 parts of 2,4-dinitrophenyl fluoride was added thereto as an end-capping agent. Stir for hours. To the obtained reaction mixture, 55 parts of dimethyl sulfoxide was added and dissolved to obtain a transparent solution. Next, this transparent solution is transferred to a centrifuge cup, added with 300 parts of distilled water, centrifuged at 2600 rpm for 10 minutes using a multi-centrifuge (H700F type; manufactured by Kokusan), and then pipetted. The supernatant was removed. This operation was further performed twice with 300 parts of distilled water and three times with 300 parts of methanol. Polyrotaxane (P-1) 0 in which polyethylene glycol bisamine having a 2,4-dinitrophenyl group bonded to both ends is clathrated in an α-cyclodextrin by vacuum drying at 50 ° C. for 12 hours. .6 parts were obtained.

  Next, after dissolving 0.1 part of polyrotaxane (P-1) in 30 parts of dimethyl sulfoxide, 0.6 part of Karenz AOI (manufactured by Showa Denko) and 0.009 part of triethylamine are added and stirred at 60 ° C. for 6 hours. A clear solution was obtained. Subsequently, this transparent solution was transferred to a centrifuge cup, 300 parts of methanol was added, and centrifugation was performed at 2600 rpm for 10 minutes using a multi-centrifuge (H700F type; manufactured by Kokusan Co., Ltd.). Was removed. This operation was further performed twice with 300 parts of methanol. A polyrotaxane (P-2) in which a part of the hydroxy group of the α-cyclodextrin of the polyrotaxane (P-1) is substituted with an N- (acryloyloxyethyl) aminocarbonyloxy group by drying under vacuum at room temperature ) Was obtained. The structure of polyrotaxane (P-2) was confirmed by NMR (Varian400-MR).

Identification of polyrotaxane (P-2)
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 3.30-3.35 (m, 12H × 20), 3.51 (s, 4H × 82); 65-3.78 (m, 24H x 20, 2H x 37), 4.12 (d, 2H x 37), 4.45 (s, 6H x 20), 4.88 (s, 6H x 20), 5.48 (s, 6H × 20), 5.68 (s, 6H × 20), 5.92 (d, 1H × 37), 6.10-6.20 (m, 1H × 37), 6. 34 (d, 1H × 37), 7.15 (d, 2H), 8.30 (d, 2H), 8.88 (s, 2H)
¹³ C-NMR (100 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ): 38.87, 39.09, 39.29, 39.50, 39.71, 39.91, 40.13, 40.41, 48.62, 59.56, 62.98, 69.52, 69.79, 71.62, 72.14, 73.42, 81.74, 101.99, 128.22, 131. 78, 156.12, 165.50

From the above results, it was found that an average of 37 N- (acryloyloxyethyl) aminocarbonyloxy groups per molecule of polyrotaxane (P-2).
Moreover, it turned out that the number of the cyclic compounds which have included the linear polymer is an average of 20 molecules per linear polymer.

Synthesis example 1
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask from the dropping funnel over 2 hours, and further stirring at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin solution R (solid content: 35.1%) having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured under the following conditions using the GPC method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-5000, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Example 2
[Preparation of curable composition 1]
Pigment: C.I. I. 40 parts of Pigment Red 254,
15 parts of acrylic pigment dispersant,
Resin solution R 31 parts, propylene glycol monomethyl ether acetate 201 parts,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
232 parts of resin solution R,
Polyrotaxane (P-2): 40 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
2.7 parts,
Polymerization initiator: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF Japan Ltd.) 6.6 parts,
Polymerization initiation aid: diethylthioxanthone (KAYACURE DETX Nippon Kayaku Co., Ltd.) 2.7 parts,
Solvent: 26 parts of propylene glycol monomethyl ether acetate
Solvent: 403 parts of dimethyl sulfoxide and surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.02 part were mixed to obtain curable composition 1.

Example 3
[Preparation of curable composition 2]
Pigment: C.I. I. Pigment Green 58 35 parts,
7.0 parts of an acrylic pigment dispersant,
Resin solution R 40 parts, and propylene glycol monomethyl ether acetate 180 parts,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
Pigment: C.I. I. 20 parts of Pigment Yellow 138,
2.9 parts of acrylic pigment dispersant,
20 parts of resin solution R and 97 parts of propylene glycol monomethyl ether acetate
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
122 parts of resin solution R,
Polyrotaxane (P-2): 43 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
8.5 parts,
Solvent: 30 parts of propylene glycol monomethyl ether acetate Solvent: 395 parts of dimethyl sulfoxide, and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Product 2 was obtained.

Example 4
[Preparation of curable composition 3]
Pigment: C.I. I. Pigment Blue 15: 6 32 parts,
9.5 parts of acrylic pigment dispersant,
24 parts of resin solution R and 152 parts of propylene glycol monomethyl ether acetate are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
247 parts of resin solution R,
Polyrotaxane (P-2): 41 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
2.7 parts,
Polymerization initiator: 14 parts of bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (Irgacure 819; manufactured by BASF Japan Ltd.)
Polymerization initiation aid: diethylthioxanthone (KAYACURE DETX Nippon Kayaku Co., Ltd.) 6.8 parts,
Solvent: 77 parts of propylene glycol monomethyl ether acetate Solvent: 394 parts of dimethyl sulfoxide, and surfactant: 0.02 part of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
Were mixed to obtain a curable composition 3.

Example 5
[Preparation of curable composition 4]
Resin solution R 353 parts,
Polyrotaxane (P-2): 83 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
3.1 parts
Solvent: 87 parts of propylene glycol monomethyl ether acetate Solvent: 474 parts of dimethyl sulfoxide, and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Product 4 was obtained.

Example 6
[Preparation of curable composition 5]
Polyrotaxane (P-2): 124 parts,
Polymerizable compound: 83 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
3.1 parts
Solvent: 790 parts of dimethyl sulfoxide, and surfactant: 0.02 parts of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) were mixed to obtain a curable composition 5.

Comparative Example 1
[Preparation of curable composition 6]
Pigment: C.I. I. Pigment Green 36 5.51 parts Pigment: C.I. I. Pigment Yellow 150 2.43 parts Polyester pigment dispersant 1.20 parts Resin solution R 8.77 parts and propylene glycol monomethyl ether acetate 37.63 parts are mixed, and the pigment is sufficiently dispersed using a bead mill. Dispersion,
Binder resin: Resin solution R 10 parts,
Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.71 parts,
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (Irgacure 369; manufactured by BASF Japan Ltd.) 1.46 parts,
Photopolymerization initiator: 4,4′-di (N, N-diethylamino) -benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 0.49 parts,
Additive: Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Chemical Co., Ltd.)
0.61 part, and solvent: propylene glycol monomethyl ether acetate 26.19 parts,
Were mixed to obtain a curable composition 6.

<Pattern preparation>
A PET film (Toray Lumirror 75-T60) was bonded onto a 2-inch square glass plate to prepare a substrate. The curable composition was applied on the PET film side of the substrate by spin coating, dried under reduced pressure at an ultimate pressure of 66 Pa, and then pre-baked on a hot plate at 60 ° C. for 2 minutes. After allowing to cool, the distance between the substrate coated with the curable composition and the quartz glass photomask is set to 150 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ² (based on 365 nm). Note that a photomask having a line and space pattern of 10 to 100 μm was used. After irradiation with light, the pattern was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 40 seconds and washing with pure water. Got. Further, a cured pattern was obtained by heating (post-baking) at the temperature shown in Table 1 for 5 minutes. It was 2 micrometers when the film thickness of the obtained pattern or the hardened pattern was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

<Solvent resistance evaluation>
1 ml of propylene glycol monomethyl ether acetate is dropped on the pattern formed on the substrate or the cured pattern, and after standing still for 30 seconds, the spin coater is used to rotate at a rotation speed of 1000 rpm for 10 seconds, thereby propylene glycol monomethyl on the pattern. The ether acetate was shaken off.
The film thickness retention was calculated from the film thickness values measured before and after contact with propylene glycol monomethyl ether acetate according to the following formula. The higher the film thickness retention rate, the better the curability, and color mixing can be prevented when producing a color filter. The results are shown in Table 1.
(Thickness retention) (%) = (film thickness after contact) / (film thickness before contact)

<Resolution evaluation>
The obtained pattern was observed with a laser microscope (manufactured by Axio Imager MAT Carl Zeiss), and the minimum dimension resolved was taken as the resolution. The higher the resolution, the higher definition color filter can be produced. The results are shown in Table 1.

  According to the polyrotaxane of the present invention, a curable composition capable of producing a pattern with high resolution can be obtained. Moreover, the pattern produced from this curable composition shows high solvent resistance.

Claims (6)

A polyrotaxane comprising a cyclic compound (A) and a linear polymer (B) penetrating through the cavity of the cyclic compound,
The cyclic compound is a compound obtained by adding an unsaturated compound having an isocyanato group to the hydroxy group of the cyclic compound (A ′) having a plurality of hydroxy groups,
A polyrotaxane, wherein the linear polymer is a polymer having N-substituted amino groups at both ends.   The polyrotaxane according to claim 1, wherein the N-substituted amino group is an N-arylamino group.   A curable composition comprising the polyrotaxane according to claim 1 or 2 and a polymerization initiator.   Furthermore, the curable composition of Claim 3 containing a coloring agent.   The pattern formed with the curable composition of Claim 3 or 4.   A display device comprising the pattern according to claim 5.