JP5211307B2 - Photosensitive composition - Google Patents

Description

  The present invention relates to a photosensitive composition in which a film or a fine pattern excellent in heat resistance and solvent resistance can be obtained by performing exposure and heat treatment. The photosensitive composition of the present invention is a color filter, black matrix, color filter protective film, photo spacer, protrusion for liquid crystal alignment, micro lens, insulating film for touch panel, flexible film used for color liquid crystal display devices, color image pickup tube elements, etc. It can be used for an adhesive for an electronic material or an adhesive sheet around a printed wiring board.

  In general, for liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc., color filters, black matrixes, color filter protective films, photo spacers, protrusions for liquid crystal alignment, microlenses, insulating films for touch panels, etc. A pattern is provided. While these films or fine patterns are required to have optical properties such as transparency, they are required to have high heat resistance and chemical resistance when performing subsequent processes such as formation and assembly of other members. Therefore, it is known to form a film or a fine pattern excellent in heat resistance, chemical resistance and the like by adding a thermal crosslinking agent to the photosensitive composition in advance and performing photocuring and thermosetting.

  As the photosensitive composition, a resin having a carboxyl group may be used from the viewpoint of imparting alkali developability. When a resin having a carboxyl group is used as the resin, a crosslinking agent having a functional group capable of reacting with the carboxyl group is used. Examples of the functional group include an isocyanate group, a blocked isocyanate group, an epoxy group, and a β-hydroxyalkylamide group.

  When a crosslinking agent having an isocyanate group is used, the isocyanate group and the carboxyl group are said to react at 130 ° C. or higher. However, since isocyanate groups are more reactive with OH groups, water, and alcohol in the resin, they react with carboxyl groups when alcohol is used as a solvent during mixing or when a solvent containing water is used. It cannot be used because it reacts with water and alcohol before it is used. In addition, since long-term storage after blending also reacts with moisture in the air, it is difficult to make a single solution.

  There is an example in which blocked isocyanate is used in order to solve the above problem, but the blocking agent remains in the cured product, which may adversely affect insulation properties. Further, depending on the blocking agent, the blocking agent may be scattered in the air at the time of heat-curing, so that there is a concern that the optical characteristics are deteriorated or the worker or the environment is adversely affected.

  Moreover, the crosslinking agent which has an epoxy group is used universally when bridge | crosslinking the resin which has a carboxyl group along with isocyanate, and many kinds are marketed. There is no by-product in the reaction of the epoxy group and the carboxyl group, and it is considered that no adverse effect such as a blocking agent for blocked isocyanate occurs. The reaction does not proceed so much without a catalyst, but it can be cured at a temperature of 150 ° C. or lower by adding a tertiary amine or a quaternary ammonium salt as a catalyst. However, there is a problem that the reaction proceeds little by little at room temperature due to the influence of the catalyst to be added, and the storage stability is poor.

The β-hydroxyalkylamide group is also a crosslinking agent that reacts with a carboxyl group. The only by-product during the reaction is water, and there is little effect on the cured product, and there is a merit that there is no effect on the worker or the environment. Further, it can be cured at 150 ° C., and the reaction does not proceed at room temperature and the storage stability is good.

  As a cross-linking agent having a β-hydroxyalkylamide group that is currently available on the market, Primid XL-552 manufactured by Ems Chemie is listed, which is mainly used as a cross-linking agent for powder coatings. Examples in which a photosensitive composition is combined with a resin containing a photopolymerizable functional group (Patent Document 1), and examples in which a photopolymerizable functional group is added to β-hydroxyalkylamide to form a photosensitive composition (Patent Document) 2) However, in any case, β-hydroxyalkylamide has poor solubility in the composition and does not become a uniform coating agent. There is a problem that the optical characteristics are deteriorated.

  Although the photosensitive composition is usually an organic solvent system, it is effective to lower the polarity of β-hydroxyalkylamide, which is originally water-soluble, in order to increase the solubility thereof. As a method of changing from water-soluble to water-insoluble, a method of increasing the molecular weight of β-hydroxyalkylamide is known (Patent Document 3). Further, according to the study by the present inventors, modifying β-hydroxyalkylamide with an isocyanate compound (Patent Document 4) is also effective in increasing the solubility in an organic solvent. In any case, only the use as a powder coating is known, and no example used for an organic solvent-based photosensitive composition is known.

JP 2005-512116 A Special Table 2001-509200 JP 2008-255197 A JP 2001-11147 A

  This invention is made | formed in view of said present condition, and it aims at providing the photosensitive composition containing (beta) -hydroxyalkylamide soluble in an organic solvent. Thereby, a film or a fine pattern satisfying heat resistance, chemical resistance, smoothness, and optical characteristics can be formed.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and imparted solubility in organic solvents by using β-hydroxyalkylamides having a specific structure. As a result, the present invention has been completed.
That is, the present invention comprises a β-hydroxyalkylamide (A) represented by the general formula (1), a polymer (B) containing a carboxyl group, a photopolymerization initiator (C), and an organic solvent. The present invention relates to a photosensitive composition containing a photopolymerizable functional group as an essential component in the composition.
General formula (1)
here,
X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen;
n is an integer of 2-6,
R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or the general formula (3) Wherein at least one of the one or more R ¹ and R ² bonded to one or more nitrogen atoms is a group represented by the general formula (2), and at least one is general It is group represented by Formula (3) .
General formula (2)
General formula (3)
Here, R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group,
R ⁷ represents a residue of a compound having a functional group capable of reacting with a hydroxyl group.

Further, the present invention is characterized in that at least one of β-hydroxyalkylamide (A) represented by the general formula (1) or a polymer (B) containing a carboxyl group contains a photopolymerizable functional group. It is related with the said photosensitive composition.
Moreover, this invention relates to the said photosensitive composition containing a photopolymerizable monomer (D).
In the present invention, in the compound having a functional group capable of reacting with the hydroxyl group, the functional group capable of reacting with the hydroxyl group includes a carboxyl group, an isocyanate group, a carboxylic acid anhydride group, an acid halide group, a carboxylic acid group. It is at least 1 sort (s) chosen from the group which consists of a primary alkylester group, a hydroxymethylamino group, an alkoxy silyl group, and an epoxy group, It is related with the said photosensitive composition characterized by the above-mentioned.
Moreover, this invention relates to the said photosensitive composition whose compound which has a functional group which can react with the said hydroxyl group is monofunctional isocyanate or monofunctional carboxylic acid.

In the present invention, the compound having a functional group capable of reacting with the hydroxyl group is represented by at least one selected from the group consisting of the following general formula (4), general formula (5) and general formula (6). It is related with the said photosensitive composition characterized by being a compound.
General formula (4)

[Wherein R ⁸ is a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]
General formula (5)

[Wherein R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or an aromatic hydrocarbon group. R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]
General formula (6)

[Wherein R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a formula

^{[N 1} is an integer of 1-2. ] Or a group represented by

[R ¹⁴ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group or an aromatic hydrocarbon group,, R ¹⁵ is a straight chain having 6 to 13 carbon atoms Or a branched alkylene group, a divalent alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]. ]

The present invention also relates to the photosensitive composition, wherein the compound having a functional group capable of reacting with the hydroxyl group has a photopolymerizable functional group.
The present invention also relates to the above photosensitive composition, wherein an atom directly bonded to a carbonyl group in X in the general formula (1) is a carbon atom not contained in an aromatic ring.
The present invention also relates to the above photosensitive composition, wherein X in the general formula (1) is an n-valent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 6 or more carbon atoms.
In the present invention, the β-hydroxyalkylamide (A) represented by the general formula (1) is
(A-1) An amidation of a carboxylic acid having a valence of 2 or more or a derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position (a-3) β -The above photosensitive composition, which is a compound obtained by reacting a part of hydroxyl groups of hydroxyalkylamide with a compound (a-4) having one or more functional groups capable of reacting with hydroxyl groups Related to things.
Furthermore, this invention relates to the said photosensitive composition in which (beta) -hydroxyalkylamide (A) represented by the said General formula (1) is soluble in an organic solvent.

Furthermore, this invention relates to the coating agent for touchscreen interlayer insulation films containing the said photosensitive composition.
Furthermore, this invention relates to the photosensitive composition for color filters containing the said photosensitive composition and a pigment.
Furthermore, this invention relates to the photosensitive soldering resist ink containing the said photosensitive composition and a flame retardant.
The present invention relates to a dry film you being formed from the photosensitive solder resist ink.
Furthermore, this invention relates to the insulating film for touchscreens formed from the said coating agent for touchscreen interlayer insulation films.
In addition, the present invention relates to a color filter comprising a filter segment or a black matrix formed from the above photosensitive composition for a color filter on a transparent substrate.

 According to the present invention, a photosensitive composition containing β-hydroxyalkylamide that is soluble in an organic solvent can be provided. As a result, a film or fine pattern satisfying heat resistance, chemical resistance, smoothness, and optical characteristics could be formed.

  The present invention is described in detail below.

<< Photosensitive composition >>
First, the combination of the elements constituting the photosensitive composition of the present invention will be described.

The characteristics of the photosensitive composition of the present invention are as follows:
1. 1. A fine pattern can be formed when the photosensitive composition has alkali developability due to a carboxyl group. A uniform cross-linked structure is obtained by heat curing in which a β-hydroxyalkylamide group and a carboxyl group undergo a condensation reaction and photocuring in which a photopolymerizable functional group is polymerized by a photopolymerization initiator in a uniform composition. Is formed, and a film and a pattern excellent in heat resistance and chemical resistance are formed.
In addition, the photosensitive composition of this invention can also be used for forming a fine pattern by solvent image development, or forming as a film | membrane or a molding without developing. In that case, the carboxyl group is utilized for the cross-linking of Feature 2.

In order to embody it, the photosensitive composition of the present invention comprises a β-hydroxyalkylamide (A) that is soluble in an organic solvent, a polymer (B) containing a carboxyl group, a photopolymerization initiator (C ) And an organic solvent as essential constituents , and a photopolymerizable monomer (D) as constituents if necessary. Of these components, at least one of the components must contain a photopolymerizable functional group.

  When (beta) -hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group contain both photopolymerizable functional groups, when any one is included, all the cases where neither is included belong to this invention. . Only when the β-hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group do not contain any photopolymerizable functional group, the photopolymerizable monomer (D) is further added as an essential component. To do.

  That is, the constituents of the photosensitive composition of the present invention include the following combinations (1) to (7).

(1) β-hydroxyalkylamide (A) containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
A photopolymerization initiator (C) , an organic solvent (2) a β-hydroxyalkylamide (A) containing a photopolymerizable functional group,
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
A photopolymerization initiator (C);
A photopolymerizable monomer (D) , an organic solvent (3) a β-hydroxyalkylamide (A) containing a photopolymerizable functional group,
A polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group;
A photopolymerization initiator (C) , an organic solvent (4) a β-hydroxyalkylamide (A) containing a photopolymerizable functional group,
A polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group;
A photopolymerization initiator (C);
A photopolymerizable monomer (D) , an organic solvent (5) a β-hydroxyalkylamide (A) not containing a photopolymerizable functional group,
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
A photopolymerization initiator (C) , an organic solvent (6) β-hydroxyalkylamide (A) not containing a photopolymerizable functional group,
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
A photopolymerization initiator (C);
A photopolymerizable monomer (D) , an organic solvent (7) β-hydroxyalkylamide (A) not containing a photopolymerizable functional group,
A polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group;
A photopolymerization initiator (C);
Photopolymerizable monomer (D) and organic solvent

Next, each component of the photosensitive composition of this invention is demonstrated.
In the present invention, (meth) acrylate means acrylate and / or methacrylate, and (meth) acrylic acid means acrylic acid and / or methacrylic acid.

<Organic solvent>
The β-hydroxyalkylamide (A) that is soluble in the organic solvent of the present invention and soluble in the organic solvent means that it is 25 with respect to at least one organic solvent among isopropanol, methyl ethyl ketone, ethyl acetate, and toluene. It means that the solubility at 5 ° C. is 5% by weight or more. The organic solvent that can be used in the present invention is not particularly limited, but methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, acetic acid Examples include ethyl, propyl acetate, butyl acetate, benzene, toluene, ethylbenzene, xylene, cyclohexane, hexane, octane, cyclomethane, chloroform, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, and the like. These can be used alone or in combination of two or more.
Among them, it is preferable to use a ketone-based, ester-based, or ether-based solvent because other components have good solubility.

  The amount of the organic solvent used is preferably an amount that makes the solid content concentration of the photosensitive composition 5 to 50% by weight. By setting the solid content concentration of the photosensitive composition within such a range, it is possible to provide a highly smooth film or fine pattern having a more uniform thickness. That is, if the solid content concentration exceeds 50% by weight, the leveling property when applying the photosensitive composition, the smoothness of the resulting film or fine pattern, and the transparency may be lowered. This is because if the solid content concentration is less than 5% by weight, a film and pattern having a predetermined thickness may not be obtained.

  The structure of β-hydroxyalkylamide (A) will be described in detail later.

<Photopolymerizable functional group>
The photopolymerizable functional group of the present invention is a functional group that undergoes radical polymerization, cationic polymerization, anionic polymerization, addition reaction, etc. by the photopolymerization initiator, or the photopolymerizable functional group itself is excited by light irradiation to cause the addition reaction. It means the functional group that occurs. For example,
Photopolymerizable functional groups that undergo radical polymerization include acryloyl, methacryloyl, styryl, maleimide, alkenyl, and alkynyl photopolymerizable functional groups that undergo cationic polymerization such as epoxy, alicyclic epoxy, and oxetanyl. Photopolymerizable functional groups that undergo anionic polymerization such as epoxy groups, vinyl ether groups, episulfide groups, ethyleneimine groups, and hydroxyl groups, and photopolymerizable functional groups that undergo an addition reaction such as epoxy groups, ene groups, mercapto groups (ene-thiol addition) , Styryl group, maleimide group (photodimerization), vinyl group, maleimide group (photoinitiator-free system) and the like.
In view of reactivity and material selectivity, it is preferable to use an acryloyl group or a methacryloyl group in the case of radical polymerization. In the case of cationic polymerization, it is preferable to use an epoxy group, an oxetanyl group, or a vinyl ether group, and it is more preferable to use an epoxy group or an oxetanyl group.

<Polymer containing carboxyl group (B)>
The carboxyl group-containing polymer (B) of the present invention is used for the purpose of imparting alkali developability to the photosensitive composition and thermosetting reaction with β-hydroxyalkylamide (A). It is a polymer having a carboxyl group at the terminal and / or side chain. It may or may not contain a photopolymerizable functional group. The polymer may be linear, branched or star-shaped, and may be thermoplastic or thermosetting.
Examples of the polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group include, for example, carboxy-terminated polyester, polyamide, polyesteramide, polyetherester, acrylic, polybutadiene, polyisoprene, and carboxyl group side chain polyurethane, Examples thereof include carboxylic acid-added cellulose, (meth) acrylate copolymer containing a carboxyl group, and a carboxylic acid anhydride adduct of a phenol resin.
In the case of the polymer (B) containing a carboxyl group containing a photopolymerizable functional group, radically polymerizable, cationically polymerizable, and anionic polymerizable photopolymerizable functional groups can be introduced. It is preferable to contain a polymerizable photopolymerizable functional group. For example, for example,
(B-1) A method of introducing a photopolymerizable functional group into a polymer containing a carboxyl group (B-2) A method of introducing a photopolymerizable functional group into a polymer not containing a carboxyl group, and introducing a carboxyl group. Can be mentioned. Moreover, it is not limited about the polymer which has these functional groups, It is possible to use each polymer, such as an acrylic type, a urethane type, a polyester type, a polyolefin type, a polyether type, a natural rubber, a block copolymer rubber, and a silicone type. it can.

As a method of introducing the photopolymerizable functional group used in (B-1) and (B-2),
(B-11) A carboxyl group, a hydroxyl group, a mercapto group, an amino group, an active methylene group, etc. in a polymer containing a carboxyl group, a hydroxyl group, a mercapto group, an amino group, an active methylene group, etc., an epoxy group, an isocyanate group, an aldehyde A method of reacting an epoxy group, an isocyanate group, an aldehyde group or the like in a compound containing a group or the like and a photopolymerizable functional group,
(B-12) Epoxy groups, isocyanate groups, aldehyde groups, and the like in polymers containing epoxy groups, isocyanate groups, aldehyde groups, carboxyl groups, hydroxyl groups, mercapto groups, amino groups, active methylene groups, and the like, and photopolymerizability. Examples thereof include a method of reacting a carboxyl group, a hydroxyl group, a mercapto group, an amino group, an active methylene group and the like in a compound containing a functional group.
As a method of introducing the carboxyl group used in (B-2),
(B-13) A method in which an acid anhydride group in a polybasic acid anhydride is reacted with a hydroxyl group, an amino group, or the like in a polymer containing a hydroxyl group, an amino group, or the like.
As a method of simultaneously introducing a photopolymerizable functional group and a carboxyl group used in (B-2),
(B-14) A method in which an acid anhydride group in a polymer containing a carboxylic acid anhydride group is reacted with a hydroxyl group or the like in a compound containing a photopolymerizable functional group (B-15) Examples thereof include a method of reacting an acid anhydride group in a compound containing a photopolymerizable functional group with a hydroxyl group or amino group in a polymer containing a group.

  The polymer (B) containing a carboxyl group can be used alone or in combination of two or more. The ratio of the carboxyl group in the polymer (B) containing a carboxyl group and the hydroxyl group in the β-hydroxylamide group is preferably 10/1 to 1/10 in terms of molar ratio, and more preferably 3/1 to 1/3. Further, 1.5 / 1 to 1 / 1.5 is preferable. When it is out of the range of 10/1 to 1/10, the hydroxyl group in the carboxyl group or β-hydroxyalkylamide group is excessive in the cured film or fine pattern, and the chemical resistance and heat resistance are insufficient. There is a risk.

  The concentration of the carboxyl group in the polymer (B) containing a carboxyl group is preferably an acid value of 10 to 250 mgKOH / g, more preferably 20 to 200 mgKOH / g, and further preferably 40 to 100 mgKOH / g. If it is less than 10 mgKOH / g, the functional group (carboxyl group) that can react with the hydroxyl group in β-hydroxyalkylamide (A) decreases, and chemical resistance and heat resistance may not be obtained satisfactorily. If it exceeds 250 mgKOH / g, the viscosity of the coating agent is high, and the storage stability may deteriorate.

  In addition to the carboxyl group, an active methylene group such as a phenolic hydroxyl group, an aromatic mercapto group, or a β-diketone can be used as the functional group capable of reacting with the β-hydroxyalkylamide (A). The functional group can be introduced into the polymer (B) containing a carboxyl group. You may contain in (beta) -hydroxyalkylamide (A) and a photopolymerizable monomer (D).

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) of the present invention is a compound that initiates polymerization of a photopolymerizable functional group by generating radicals, cations, and anions upon irradiation with light.
As a thing generating a radical among photoinitiators (C),
For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenone compounds such as butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin compounds such as ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. Thioxanthone compounds, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4 Triazine compounds such as' -methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, an electron-withdrawing substitution on the phenyl group described in Japanese Patent Application No. 2010-054456 Oxime ester compounds such as N-phenylcarbazole skeleton oxime ester having a group, phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p Examples include imidazole compounds such as -methylphenyl) biimidazole, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, and titanocene compounds.

As a thing generating a cation among photoinitiators (C),
Examples include onium salt compounds. Examples of onium salt compounds include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, diazonium salt compounds, pyridinium salt compounds, benzothiazolium salt compounds, sulfoxonium salt compounds, and ferrocene compounds. These structures are not particularly limited, and may have a polyvalent cation structure such as a dication, and known counter anions can be appropriately selected and used.
Acid generators other than onium salts include nitrobenzyl sulfonates, alkyl or aryl-N-sulfonyloxyimides, optionally halogenated alkyl sulfonate esters, 1,2-disulfones, oxime sulfonates Benzoin tosylates, β-ketosulfones, β-sulfonylsulfones, bis (alkylsulfonyl) diazomethanes, iminosulfonates, imidosulfonates, trihaloalkyltriazines and other compounds having a trihaloalkyl group, etc. It can be mentioned, but is not limited to these.
Specific examples include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium, p-toluenesulfonate, N, N-dimethyl-N-benzylanilinium. Antimony hexafluoride, N, N-dimethyl-N-benzylanilinium tetrafluoride, N, N-dimethyl-N-benzylpyridinium antimony hexafluoride, N, N-diethyl-N-benzyltrifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoride antimony, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony, Tiltriphenylphosphonium antimony hexafluoride, antimony tetrabutylphosphonium hexafluoride, boron triphenylsulfonium tetrafluoride, antimony triphenylsulfonium hexafluoride, arsenic triphenylsulfonium hexafluoride, tri (4-methoxyphenyl) sulfonium hexa Arsenic fluoride, diphenyl (4-phenylthiophenyl) sulfonium arsenic hexafluoride, Adekaoptomer SP-150 (manufactured by ADEKA Corporation, counter ion: PF6), Adekaoptomer SP-170 (manufactured by ADEKA Corporation) Counter ion: SbF6), Adekaoptomer CP-66 (manufactured by ADEKA Corporation, counter ion: SbF6), Adekaoptomer CP-77 (manufactured by ADEKA Corporation, counter ion: SbF6), Sun-Aid SI-60L (three Shin Chemical Co., Ltd. Made by a company, counter-ion: SbF6), Sun-Aid SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd., counter-ion: SbF6), Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd., counter-ion: SbF6), Sun-Aid SI -150 (manufactured by Sanshin Chemical Industry Co., Ltd., counter ion: SbF6), CYRACURE UVI-6974 (manufactured by Union Carbide, counter ion: SbF6), CYRACURE UVI-6990 (manufactured by Union Carbide, counter ion: PF6) , UVI-508 (manufactured by General Electric), UVI-509 (manufactured by General Electric), FC-508 (manufactured by Minnesota Mining and Manufacturing), FC-509 (Minnesota Mining and Manufacturing) Ring Corporation), CD-1010 (Cert CD-1011 (manufactured by Sartomer) and CI series (manufactured by Nippon Soda Co., Ltd., counterions: PF6, SbF6), diphenyliodonium hexafluoroarsenide, di-4-chlorophenyliodonium hexafluoroarsenide, di -4-Bromophenyliodonium arsenic hexafluoride, phenyl (4-methoxyphenyl) iodonium arsenic hexafluoride, UVE series manufactured by General Electric, FC series manufactured by Minnesota Mining & Manufacturing, Toshiba Silicone UV-9310C (counter ion: SbF6) manufactured by Rhodia and Photoinitiator 2074 (counter ion: (C6F5) 4B) manufactured by Rhodia, etc. can be mentioned, but are not limited thereto.

  Examples of the photopolymerization initiator (C) that generate anions include o-nitrobenzoin carbamate, benzoin carbamate, α, α-dimethylbenzyloxycarbamoylamine, o-acyloxime, formanilide derivatives, α-ammonium acetophenone. Etc.

  As these photopolymerization initiators (C), those generating radicals, cations and anions can be used alone or in combination. Moreover, it can be used 1 type or in mixture of 2 or more types by arbitrary ratios as needed. The photopolymerization initiator (C) is preferably 0.01 to 60 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.03 in 100 parts by weight of the solid content in the photosensitive composition. ~ 7 parts by weight. If the amount is less than 0.01 part by weight, the photocuring reactivity may be poor and polymerization may not proceed. If the amount exceeds 10 parts by weight, transparency may deteriorate due to the yellowing of the initiator.

  Furthermore, the photosensitive composition of the present invention can contain a sensitizer. Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained. The sensitizer may contain two or more sensitizers in any ratio.

The sensitizer is preferably used in an amount of 0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the photopolymerization initiator (C) in the photosensitive composition. Is more preferable.

<Photopolymerizable monomer (D)>
The photopolymerizable monomer (D) of the present invention is a compound containing a photopolymerizable functional group, and the structure thereof may or may not have a carboxyl group.
Among the photopolymerizable monomers (D), those that do not have a carboxyl group and undergo radical polymerization include, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Tricyclodecanyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylic acid esters and methacrylic acid esters such as acrylate,
Epoxy (meth) acrylates such as 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, and polyester (meth) Acrylates, urethane (meth) acrylates, methylolated melamine (meth) acrylates,
Reactive substituents such as isocyanate groups, aldehyde groups, epoxy groups, hydroxyl groups, carboxyl groups, amino groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, isocyanate groups, aldehyde groups, and epoxy groups Polymers made of (meth) acrylic compounds and cinnamic acid having
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether,
(Meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

Among the photopolymerizable monomers (D), those that do not have a carboxyl group and undergo cationic polymerization include, for example,
Examples of the compound having an epoxy group include bisphenol A type epoxy resin, glycidyl ether type epoxy resin, phenol novolac type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolac type epoxy resin, glycidyl amine type epoxy resin, Alcohols such as naphthalene type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, polyfunctional epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin, hydrogenated bisphenol A type epoxy resin Epoxy resin, halogenated epoxy resin such as brominated epoxy resin, rubber modified epoxy resin, urethane modified epoxy resin, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene A block copolymer, an epoxy group-containing polyester resin, an epoxy group-containing polyurethane resin, an epoxy group-containing acrylic resin, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point 71 ° C.), etc. These epoxy resins may be liquid or solid at room temperature, and epoxy group-containing oligomers can also be suitably used, for example, bisphenol A type epoxy oligomers (for example, oil (Epicoat 1001, 1002, etc., manufactured by Kasei Shell Epoxy Co., Ltd.) Furthermore, addition polymers of the above epoxy group-containing monomers and oligomers may be used, for example, glycidylated polyester, glycidylated polyurethane, glycidylated acrylic. Etc.

  Examples of the compound having an alicyclic epoxy group include 1,2: 8,9-diepoxy limonene, 4-vinylcyclohexene monoepoxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, (3,4-epoxy). Cyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, bis- (3,4-epoxycyclohexyl) adipate, norbornene monoepoxide, adamantyl monoepoxide, limonene monoepoxide, 2- (3,4-epoxycyclohexyl-5,5 -Spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis- (3,4-epoxycyclohexylmethylene) adipate, bis- (2,3-epoxycyclopentyl) ether, (2,3-epoxy 6-methylcyclohexylmethyl) adipate, dicyclopentadiene dioxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane and the like.

  Specific examples of the aliphatic epoxy resin include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, and propylene. Glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl Ether, trimethylolpropane monoglycidyl ether, trimethylolpropane triglyceride Jill ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and the like.

  Examples of the compound having an oxetanyl group include phenoxymethyl oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3- Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, oxetanyl Examples include silsesquioxane, phenol novolac oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like.

  Examples of the compound having a vinyl ether group include hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, and the like. Other examples include compounds having an episulfide group, an ethyleneimine group, and a hydroxyl group.

  Examples of the photopolymerizable monomer (D) that does not have a carboxyl group and undergoes anion polymerization include compounds having the above-described epoxy group.

Moreover, as what has a carboxyl group among photopolymerizable monomers (D), for example,
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) Acryloyloxypropyl hexahydrophthalate, ethylene oxide modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, ω-carboxypolycaprolactone (meth) acrylate, crotonic acid, α- (hydroxymethyl) acrylic acid, α -(Hydroxymethyl) methacrylic acid, etc. can be used.

  These photopolymerizable monomers (D) can be used alone or in admixture of two or more.

<Β-Hydroxyalkylamide (A)>
From here, the structure of β-hydroxyalkylamide (A) will be described in detail.

  The β-hydroxyalkylamide (A) of the present invention is a compound represented by the general formula (1).

General formula (1)

In the formula, X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, and n is an integer of 2-6. Specific examples of X include an n-valent aliphatic hydrocarbon group having 2 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group having a hetero atom.

  Examples of the halogen include fluorine, chlorine, bromine and iodine, and fluorine is preferable from the viewpoint of transparency. From the viewpoint of imparting flame retardancy, chlorine and bromine are preferred.

An n-valent group is a group obtained by removing n hydrogen atoms from a compound. Hereinafter, this is referred to as an n-valent group derived from the compound.

  Examples of the n-valent aliphatic hydrocarbon group include n-valent groups derived from alkanes, alkenes, and alkynes.

  Alkanes include ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, heptadecane, hexadecane, octadecane, nonadecane, icosane, heicossan, docosane, isobutane, isopentane, Neopentane, methylpentane, dimethylpentane, ethylmethylpentane, diethylpentane, methylhexane, tetramethylheptane, and the like. As the n-valent group derived from alkane, for example, 1,6-hexyl group, 1,7-heptyl group, 1,8-octyl group, 1,9-nonyl group, 1,10-decyl group, 1,11 -Undecyl group, 1,12-dodecyl group, 1,13-tridecyl group, 1,14-tetradecyl group, 1,15-pentadecyl group, 1,16-hexadecyl group, 1,17-heptadecyl group, 1,18- Octadecyl group, 1,19-nonadecyl group, 1,3,6-hexyl group, 1,4,7-heptyl group, 1,2,8-octyl group, 1,3,9-nonyl group, 1,3, Examples include 4,6-hexyl group, 1,4,6,7-heptyl group, 1,4,5,6,7-heptyl group and 1,2,3,4,5,6-hexyl group.

  Alkenes include ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, docene, tridecene, tetracene, pentadecene, heptadecene, hexadecene, octadecene, nonadecene, icosene, heicocene, dococene, methylpentene, etc. Is mentioned. Examples of the n-valent group derived from an alkene include a 1,6- (2-hexenyl) group, a 1,7- (2-heptenyl) group, a 1,8- (2-octenyl) group, and a 1,9- (2-nonenyl) group, 1,10- (2-decenyl) group, 1,11- (2-undecenyl) group, 1,12- (2-dodecenyl) group, 1,13- (2-tridecenyl) group 1,14- (2-tetradecenyl) group, 1,15- (2-pentadecenyl) group, 1,16- (2-hexadecenyl) group, 1,17- (2-heptadecenyl) group, 1,18- ( 2-octadecenyl) group, 1,19- (2-nonadecenyl) group, 1,3,6- (2-hexenyl) group, 1,4,7- (3-heptenyl) group, 1,2,8- ( 4-octenyl) group, 1,3,9- (5-nonenyl) group, 1,3,4,6- (2-hex) ) Group, 1,4,6,7- (3-Hepuseniru) group, 1,4,5,6,7- (3- Hepuseniru) group.

  Examples of alkynes include ethyne, propyne, butyne, pentyne, hexyne, peptin, octyne, nonin, decyne, undecine, dodecin, tridecine, icosin, heicosin, docosin, and the like. Examples of the n-valent group derived from alkyne include 1,6- (2-hexynyl) group, 1,7- (2-hepsinyl) group, 1,8- (2-oxynyl) group, 1,9- (2-nonyl) group, 1,10- (2-decynyl) group, 1,11- (2-undecynyl) group, 1,12- (2-dodecynyl) group, 1,13- (2-tridecynyl) group 1,14- (2-tetradecynyl) group, 1,15- (2-pentadecynyl) group, 1,16- (2-hexadecynyl) group, 1,17- (2-heptadecynyl) group, 1,18- ( 2-octadecynyl) group, 1,19- (2-nonadecynyl) group, 1,3,6- (2-hexynyl) group, 1,4,7- (3-hepsinyl) group, 1,2,8- ( 4-octynyl) group, 1,3,9- (5-nonyl) group, 1,3,4,6- (2-hexini) ) Group, 1,4,6,7- (3-Hepushiniru) group, and 1,4,5,6,7- (3- Hepushiniru) group.

  Examples of the n-valent alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclohexene, methylcyclohexene, norbornane, norbornene, and bicyclo And n-valent groups derived from octene, decahydronaphthalene, adamantane, dimethyladamantane, and the like. For example, 1,1-cyclohexyl group, 1,2-cyclohexyl group, 1,3-cyclohexyl group, 1,4-cyclohexyl group, 1,2,4-cyclohexyl group, 1,3,5-cyclohexyl group, 1, Examples include 2,4,5-cyclohexyl group, 1,2,3,4,5,6-cyclohexyl group, 2,6-decahydronaphthyl group, 1,3-adamantyl group, 1,3,5-adamantyl group. .

  Examples of n-valent aromatic hydrocarbon groups include n-valent aromatic hydrocarbon groups derived from benzene, naphthalene, biphenyl, anthracene, toluene, xylene, ethylbenzene, tert-butylbenzene, diphenylethane, diphenylacetylene, 9,9-diphenylfluorene, and the like. Groups. For example, examples of the group in which an aromatic ring contains a carbon atom bonded to a carbonyl group include a phenylene group and a tolylene group. Examples of the group in which the carbon atom bonded to the carbonyl group is not contained in the aromatic ring include toluene-α, α-diyl group, ethylbenzene-α, β-diyl group, ethylbenzene-β, β-diyl group, 1,2-diphenyl. And ethane-1,2-diyl group.

  N-valent groups having heteroatoms (oxygen, sulfur, nitrogen, halogen atoms) include ethanol, ethylene glycol, ethylene diacetate, ethylene dipivalate, ethylene dibenzoate, ethylene bis (methyl benzoate), ethylene bis (methoxy Benzoate), propanol, isopropanol, ethyl acetate, erythritol, ethylene oxide, acetaldehyde, acetone, dipropyl ketone, γ-pentadecanolactone, 1,2-cyclohexane, γ-butyrolactone, ethylamine, ethylmethylamine, propylamine, N- Propylacetamide, ethanethiol, ethanedithiol, tetrafluoroethane, dibromoethane, hexafluoropropane, octofluorobutane, dodecafluorohexane, hexadecaf Fluorooctane, 1,2,3,4,7,7-hexachloronorbornene, anisole, fluorobenzene, tetrafluorobenzene, trifluoromethylbenzene, chlorobenzene, dichlorobenzene, tetrafluorobenzene, bromobenzene, tetrabromobenzene, nitrobenzene, phenol Aniline, benzenesulfonic acid, anthraquinone, butanephosphonic acid, triethyltriazine, tripropyltriazine, triethylisocyanurate, tripropylisocyanurate, benzophenone, thiophene, diethylsulfide, diphenylsulfone, 2,2-diphenyl-1,1,1 , 3,3,3-hexafluoropropane, diphenyl ether, and the like.

Among these, as X, from the viewpoint of reactivity, it is preferable that the atom in X that is directly bonded to the carbonyl group is a carbon atom that is not included in the aromatic ring. Further, a linear aliphatic hydrocarbon group having 6 to 18 carbon atoms or an alicyclic hydrocarbon group is preferable, and more preferably a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms, or It is an alicyclic hydrocarbon group, More preferably, it is a C6-C12 linear aliphatic hydrocarbon group.

In the formula, R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or a general formula In the group represented by (3), at least one of one or more R ¹ and R ² bonded to one or more nitrogen atoms is a group represented by the general formula (2), and at least 1 One is a group represented by the following general formula (3) .

General formula (2)

General formula (3)

  Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group , Dodecyl group, pentadecyl group, and octadecyl group.

  Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group and 1-octadecenyl group. Groups.

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. .

  The alicyclic hydrocarbon group includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-indeno group, decahydronaphthyl group, adamantyl group, dicyclopenta And a cycloalkyl group such as a nyl group.

Examples of the aromatic hydrocarbon group include a single ring, a condensed ring, and a ring assembly aromatic hydrocarbon group.
The monocyclic aromatic hydrocarbon group includes monocyclic aromatic groups such as phenyl group, benzyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group and mesityl group. Group hydrocarbon group.
As the condensed ring aromatic hydrocarbon group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, Examples thereof include condensed ring aromatic hydrocarbon groups such as 2-azurenyl group, 1-pyrenyl group and 2-triphenylyl group.
Examples of the ring-assembled aromatic hydrocarbon group include ring-assembled aromatic hydrocarbon groups such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group.

Among them, R ¹ and R ² other than those represented by formulas (2) and (3) are preferably aliphatic hydrocarbon groups, alicyclic hydrocarbons, or monocyclic aromatic hydrocarbon groups, and more preferably An aliphatic hydrocarbon group and an alicyclic hydrocarbon, and more preferably an aliphatic hydrocarbon group having 4 or more carbon atoms.

R ^{3 to} R ^{6 in the} groups represented by formulas (2) and (3) each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group partially substituted with a hydroxyl group, and R ⁷ represents a hydroxyl group. Represents a residue of a compound having a functional group capable of reacting with.

The hydrocarbon groups are the same as those described above for R ¹ and R ² . Examples of the hydrocarbon group substituted with a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxyphenyl group, a hydroxycyclohexyl group, and the like.

  The residue of the compound having a functional group capable of reacting with a hydroxyl group is not particularly limited, but isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol ester, amino Examples thereof include resins, compounds having an epoxy, and the like, and isocyanates, carboxylic acids, carboxylic acid halides, and carboxylic anhydrides are preferable, and monofunctional isocyanates or monofunctional carboxylic acids are more preferable.

Among these, from the viewpoint of easy production, it is more preferable that R ⁷ in the general formula (3) is obtained as a β-hydroxyalkylamide (A) represented by the following general formula (4).

General formula (4)

here,
R ¹⁶ comprises a single bond, a (m ¹ +1) valent hydrocarbon group, or at least one of a urethane bond, a urea bond, an allophanate bond, a biuret bond, and an isocyanurate ring, and a carbon atom or a hydrogen atom (m ¹ +1) represents a valent group,
A ¹ represents a single bond, a urethane bond or a urea bond,
R ¹⁷ represents a divalent hydrocarbon group,
A ² represents an ether bond or an ester bond,
R ¹⁸ represents a monovalent hydrocarbon group,
m ¹ represents an integer of ¹ to 5,
p ¹ represents an integer of 0 to 100.

From the viewpoint of easy production, it is more preferable to obtain β-hydroxyalkylamide (A) in which R ⁷ in the general formula (3) is represented by the following general formula (5).

General formula (5)

here,
R ¹⁹ represents a single bond, a (m ² +1) valent hydrocarbon group, or a (m ² +1) valent group consisting of a carbon atom, a hydrogen atom, or an oxygen atom,
A ³ represents a single bond, an ester bond or an amide bond,
R ²⁰ represents a divalent hydrocarbon group,
A ⁴ represents an ether bond or an ester bond,
R ²¹ represents a monovalent hydrocarbon group,
m ² represents an integer of 1 to 5,
p ² is an integer of 0 to 100.

(Method for producing β-hydroxyalkylamide (A))
Although the compound represented by the general formula (1) can be produced by various methods, main production methods [1] to [ 3 ] are listed below.

When at least one of R ¹ and R ² is a group represented by the general formula (3):

[1] A product obtained by amidating (a-1) a divalent or higher carboxylic acid or derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position (a- 3) A part of the hydroxyl group of β-hydroxyalkylamide is reacted with a compound having (a-4) one or more functional groups capable of reacting with the hydroxyl group.

[2] (a-2) (a-4) having at least one functional group capable of reacting with a hydroxyl group as part of the hydroxyl group of a primary or secondary amine having at least one hydroxyl group at the β-position After reacting the compound, (a-1) amidation with a divalent or higher carboxylic acid or derivative thereof is performed.

[3] (a-2) A compound having one or more functional groups capable of reacting with a hydroxyl group by protecting the amino group of a primary or secondary amine having one or more hydroxyl groups at the β-position React. After removing the protecting group of this compound, (a-1) amidation with a divalent or higher carboxylic acid or derivative thereof is performed.

The method [1] is preferable in view of production cost, ease of reaction, and the like.

(A-3) When β-hydroxyalkylamide is available, (a-1) a divalent or higher carboxylic acid or derivative thereof, and (a-2) 1 having one or more hydroxyl groups at the β-position (A-3) a compound having at least one functional group capable of reacting with a hydroxyl group as a part of the hydroxyl group of (a-3) β-hydroxyalkylamide without undergoing a reaction of a secondary or secondary amine; The method of making it react may be sufficient.

[4] Amidation of (a-1) a divalent or higher carboxylic acid or derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position.

  β-hydroxyalkylamide (A) may or may not contain a photopolymerizable functional group. (A-1) a divalent or higher carboxylic acid or derivative thereof, (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position, or (a-4) a functional group capable of reacting with a hydroxyl group. A photopolymerizable functional group can be introduced by using a compound containing a photopolymerizable functional group as a compound having one or more groups. In view of stability during synthesis, (a-4) it is preferable to contain a photopolymerizable functional group in the compound having one or more functional groups capable of reacting with a hydroxyl group.

(A-1) Among divalent or higher carboxylic acids or derivatives thereof, examples of divalent or higher carboxylic acids include the following. (Hereinafter, “” is used to indicate an alias for the same compound.)
Linear saturated aliphatic dicarboxylic acids: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid , Pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid,

 Branched saturated aliphatic dicarboxylic acids: methyl malonic acid, dimethyl malonic acid, ethyl malonic acid, dipropyl malonic acid, isopropyl malonic acid, methyl succinic acid, dimethyl succinic acid, butyl succinic acid, octyl succinic acid, decyl succinic acid, dodecyl succinic acid, tetra Decyl succinic acid, hexadecyl succinic acid, octadecyl succinic acid, methyl glutaric acid, dimethyl glutaric acid, ethyl methyl glutaric acid, diethyl glutaric acid, methyl adipic acid, tetramethyl pimelic acid,

 Unsaturated aliphatic dicarboxylic acids: allyl succinic acid, methallyl succinic acid, hexenyl succinic acid, octenyl succinic acid, dodecenyl succinic acid, dococenyl succinic acid, decadiene-1,2-dicarboxylic acid, fumaric acid, maleic acid, acetylenedicarboxylic acid, muconic acid, itaconic acid Citraconic acid, mesaconic acid,

 Alicyclic dicarboxylic acids: cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, camphoric acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, methylcyclohexenedicarboxylic acid, norbornanedicarboxylic acid, norbornenedicarboxylic acid, bicyclo [2.2.2] Oct-5-ene-2,3-dicarboxylic acid, adamantanedicarboxylic acid, cyclopentylmalonic acid, cyclopentanediacetic acid, cyclohexanediacetic acid, adamantanediacetic acid,

 Aliphatic dicarboxylic acid having an aromatic ring (the carbon atom bonded to the carboxyl group does not form an aromatic ring): phenylmalonic acid, benzylmalonic acid, thiophenmalonic acid, phenylsuccinic acid, diphenylsuccinic acid,

 Aliphatic or cycloaliphatic carboxylic acids containing oxygen atoms in addition to carboxyl groups: tartaric acid, diacetyltartaric acid, dipivaloyltartaric acid, dibenzoyltartaric acid, ditoluoyltartaric acid, di (p-anisoyl) tartaric acid, malic acid, acetylmalic acid, citric acid, citramal Acid, hydroxymethylglutaric acid, galactaric acid, epoxysuccinic acid, oxalacetic acid, oxoglutaric acid, oxoazelaic acid, 4,5-dicarboxy-γ-pentadecanolactone, 3,6-epoxy-1,2,3 6-hexahydrophthalic acid, butyrolactone dicarboxylic acid,

 Aliphatic or alicyclic dicarboxylic acids containing nitrogen atom: aspartic acid, N-methylaspartic acid, N- (tert-butoxycarbonyl) -aspartic acid, N- (benzyloxycarbonyl) aspartic acid, N-carbamoylaspartic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] aspartic acid, glycylaspartic acid, 3-hydroxyaspartic acid, glutamic acid, N-acetylglutamic acid, N- (tert-butoxycarbonyl) -glutamic acid, N- (benzyl Oxycarbonyl) glutamic acid, N-benzoylglutamic acid, N- (4-aminobenzoyl) glutamic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] glutamic acid, methylglutamic acid, glycylglutamic acid Grayed azide Nino glutaric acid, N- phthalyl glutamic acid, amino adipic acid, aminopimelic acid, diaminopimelic acid, aminosuberic acid, folic acid, methotrexate,

 Aliphatic or alicyclic dicarboxylic acids containing sulfur atoms: dimercaptosuccinic acid, thiomalic acid,

 Aliphatic or alicyclic dicarboxylic acid containing a halogen atom: tetrafluorosuccinic acid, dibromosuccinic acid, hexafluoroglutaric acid, octafluoroadipic acid, dodecafluorosuberic acid, hexadecafluorosebacic acid, chlorendic acid «Het acid»,

Aromatic dicarboxylic acids: phthalic acid, methylphthalic acid, tert-butylphthalic acid, ethynylphthalic acid, (phenylethynyl) phthalic acid, methoxyphthalic acid, fluorophthalic acid, tetrafluorophthalic acid, trifluoromethylphthalic acid, chlorophthalic acid, dichloro Phthalic acid, tetrachlorophthalic acid, bromophthalic acid, tetrabromophthalic acid, nitrophthalic acid, hydroxyphthalic acid, aminophthalic acid, sulfophthalic acid, isophthalic acid, methylisophthalic acid, tert-butylisophthalic acid, methoxyisophthalic acid, tetrafluoroisophthalic acid , Bromoisophthalic acid, nitroisophthalic acid, hydroxyisophthalic acid, aminoisophthalic acid, aminotriiodoisophthalic acid, sulfoisophthalic acid, terephthalic acid, dimethylterephthalic acid, tetrafluoro Terephthalic acid, dichloro terephthalic acid, tetrachlorophthalic terephthalic acid, bromo terephthalic acid, tetrabromophthalic terephthalic acid, nitroterephthalic acid, dihydroxy terephthalic acid, aminoterephthalic acid, sulfoterephthalic acid,
Naphthalenedicarboxylic acid, anthracene dicarboxylic acid, anthraquinone dicarboxylic acid, 1,3-dibenzyl-2-oxo-4,5-imidazolidine dicarboxylic acid, thiophene dicarboxylic acid,

 Aliphatic or alicyclic tricarboxylic acid: 1,2,3-propanetricarboxylic acid «tricarballylic acid», anicotic acid, butenetricarboxylic acid, cyclohexanetricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 3- Butene-1,2,3-tricarboxylic acid, cyclohexanetricarboxylic acid, pentanetricarboxylic acid, tris (2-carboxyethyl) -1,3,5-triazine, tris (3-carboxypropyl) -1,3,5-triazine , Isocyanuric acid tris (2-carboxyethyl), isocyanuric acid tris (3-carboxypropyl),

 Aromatic tricarboxylic acid: trimellitic acid, hemimellitic acid, benzene-1,3,5-tricarboxylic acid, benzophenone tricarboxylic acid,

 Aliphatic or alicyclic tetracarboxylic acid: butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, thiodisuccinic acid, tetrahydrofurantetracarboxylic acid, bicyclo [2.2.2] oct-7 -Ene-2,3,5,6-tetracarboxylic acid, 5- (1,2-dicarboxyethyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 4- (1,2-dicarboxylic acid) Carboxyethyl) 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid,

 Aromatic tetracarboxylic acid: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenylsulfonetetracarboxylic acid, oxydiphthalic acid, hexafluoroisopropylidenediphthalic acid, naphthalenetetracarboxylic acid, fluorene-9,9-bisphthalate acid,

 Aliphatic or cycloaliphatic pentacarboxylic acid or hexacarboxylic acid: cyclohexane hexacarboxylic acid,

 Aromatic pentacarboxylic acid or hexacarboxylic acid: benzene pentacarboxylic acid, merit acid,

 In addition, as a divalent or higher carboxylic acid, polyester, polybutadiene, polyisoprene, acrylic oligomer having a carboxylic acid at the terminal and / or side chain, or polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, poly It is obtained by modifying polyols such as acrylic polyol with acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Also included are compounds.

  Examples of carboxylic acid derivatives include acid anhydrides, acid chlorides, acid bromides, methyl esters, ethyl esters, phenyl esters, and tert-butyl esters of the above carboxylic acids.

  (A-2) Examples of the primary or secondary amine having one or more hydroxyl groups at the β-position include the following.

 Primary amine: ethanolamine, 1-amino-2-propanol <isopropanolamine>, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-2-phenyl-ethanol, 2-amino-2 -Methyl-1-propanol, isoleucinol << 2-amino-3-methyl-1-pentanol >>, 2-isopropylamino-3-methyl-1-butanol, leucinol << 2-amino-4-methyl-1-pentanol , Tert-leucinol << 2-amino-3,3-dimethyl-1-butanol >>, phenylalaninol << 2-amino-3-phenyl-1-propanol >>, 1-amino-2-butanol, 2-amino- 1-phenylethanol, 2-amino-1-phenyl-1-propanol,

 One of the substituents on the nitrogen atom is a hydrocarbon group and the other is a secondary amine represented by the general formula (2): N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N- tert-butylethanolamine, 3-tert-butylamino-1,2-propanediol, N-cyclohexylethanolamine, N-phenylethanolamine, N-benzylethanolamine,

Secondary amines in which both substituents on the nitrogen atom are represented by the general formula (2): diethanolamine, diisopropanolamine,
R ^{3 to} R ⁶ include a hydroxyl group-substituted hydrocarbon group: 2-[(hydroxymethyl) amino] ethanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1 , 3-propanediol, tris (hydroxymethyl) aminomethane, 3-amino-1,2-propanediol, 3- (methylamino) -1,2-propanediol, N-methylglucamine << 6- (methylamino ) -1,2,3,4,5-hexanepentaol, 1,3-bis [tris (hydroxymethyl) methylamino] propane, 2-amino-1-phenyl-1,3-propanediol, phenylephrine << 1- (3-hydroxyphenyl) -2- (methylamino) ethanol, ethylephrine << 2-ethylamino-1- (3-hydroxypheny ) Ethanol ",
Other than the above: 2- (2-aminomethylaminoethanol), 2-amino-1- (4-nitrophenyl) -1,3-propanediol, serine, serine methyl ester, N- (2,4-dinitrophenyl) Serine, methioninol << 2-amino-4-methylthio-1-butanol >>, N- (5-nitro-2-pyridyl) alaninol, pyrrolinol << 2- (hydroxymethyl) piperidine >>, 4-amino-3-hydroxybutyric acid, 3-hydroxypiperidine, isoserine, 2-aminocyclohexanol, threonine, 1-amino-2-indanol, glucosamine, 1,3-diamino-2-propanol, atenolol, adrenaline, α, α-diphenyl-2-pyrrolidinemethanol.

(A-4) Examples of compounds having at least one functional group capable of reacting with a hydroxyl group are isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol ester, amino Examples thereof include resins and compounds having an epoxy group. Among these, from the viewpoint of reactivity, an isocyanate group, a carboxyl group, a carboxylic acid anhydride group, and a carboxylic acid halide group are particularly preferable, and a carboxyl group and an isocyanate group are more preferable.

 Examples of the isocyanate include the following.

 Monofunctional isocyanate: methyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, lauryl isocyanate, stearyl isocyanate, phenyl isocyanate, cyclopropyl isocyanate, phenethyl isocyanate, tosyl isocyanate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate 2- (2-acryloyloxyethyloxy) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 1,1-bis (methacryloyloxymethyl) Ethyl isocyanate,

 Bifunctional isocyanates: tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, trizine diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate Isopropylidenebis (cyclohexyl isocyanate), 3- (2′-isocyanatocyclohexyl) propyl isocyanate, dianisidine isocyanate, diphenyl ether diisocyanate, dimer isocyanate, tetramethylxylylene diisocyanate,

 Trifunctional isocyanate: lysine triisocyanate, tris (isocyanatophenyl) methane, tris (isocyanatophenyl) thiophosphate,

 Further, biurets, uretdiones, isocyanurates, and adducts of the above polyfunctional isocyanates are also included.

 Isocyanate selected from the above-mentioned polyfunctional isocyanate, biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct, methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, methyl Activities such as amine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone Compounds obtained by reacting a silicon compound may be mentioned.

 Among the above, considering the solubility, storage stability, ease of production, etc., the above monofunctional isocyanate, or one of the polyfunctional isocyanate or biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct It is preferable to use a monofunctional isocyanate which is obtained by leaving a group and reacting the remainder with an active hydrogen compound.

Among them, since the photosensitivity is improved, that R ₇ is obtained represented by β- hydroxyalkylamide the general formula (4) (A) with a compound represented by the following general formula (6) preferable.

General formula (6)

[Wherein R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a formula

^{[N 1} is an integer of 1-2. ] Or a group represented by

[R ¹⁴ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group or an aromatic hydrocarbon group,, R ¹⁵ is a straight chain having 6 to 13 carbon atoms Or a branched alkylene group, a divalent alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]. ]

Examples of the carboxylic acid, that is, the compound having a carboxyl group include the following.
Aliphatic saturated monofunctional carboxylic acids: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid <pentanoic acid>, 2-methylbutyric acid, isovaleric acid <3-methylbutyric acid>, pivalic acid <2,2-dimethyl Propionic acid, caproic acid <hexanoic acid>, methylvaleric acid, dimethylbutyric acid, ethylbutyric acid, enanthic acid <heptanoic acid>, caprylic acid <octanoic acid>, 2-ethylhexanoic acid, pelargonic acid <nonanoic acid>, capric acid << decanoic acid >>, undecanoic acid, lauric acid << dodecanoic acid >>, tridecanoic acid, myristic acid << tetradecanoic acid >>, pentadecanoic acid, palmitic acid << hexadecanoic acid >>, margaric acid << heptadecanoic acid >>, stearic acid << octadecanoic acid >>, isostearic acid Acid "2-heptylundecanoic acid", nonadecanoic acid, arachidic acid "icosanoic acid", henicosa Acid, behenic acid "docosanoate", tricosanoic acid, lignoceric acid "tetracosanoic acid", pentacosanoic acid, cerotic acid "hexacosanoic acid", heptacosanoic acid, montanic acid "octacosanoic", nonacosanoic acid, melissic acid "triacontanoic"

 Aliphatic unsaturated monofunctional carboxylic acids: acrylic acid, methacrylic acid, crotonic acid, undecenoic acid, palmitoleic acid <9-hexadecenoic acid>, petrothelic acid <6-octadecenoic acid>, oleic acid <9-octadecenoic acid>, elaidic acid << 9-octadecenoic acid >>, vaccenic acid, linoleic acid << 9,12-octadecadienoic acid >>, linolenic acid << 9,12,15-octadecatrienoic acid >>, gamma-linolenic acid << 6,9,12-octa Decatrienoic acid, eleostearic acid, araguidonic acid << 5,8,11,14-eicosatetraenoic acid >>, 5,8,11,14,17-eicosapentaenoic acid, erucic acid << 13-docosenoic acid >> Docosahexaenoic acid, 22-tricosenoic acid, 15-tetracosenoic acid, nervonic acid,

 Aromatic monofunctional carboxylic acids: benzoic acid, toluic acid, dimethyl benzoic acid, trimethyl benzoic acid, ethyl benzoic acid, propyl benzoic acid, isopropyl benzoic acid, butyl benzoic acid, tert-butyl benzoic acid, vinyl benzoic acid, fluorobenzoic acid , Chlorobenzoic acid, bromobenzoic acid, iodobenzoic acid, trifluoromethylbenzoic acid, cyanobenzoic acid, hydroxybenzoic acid, hydroxymethylbenzoic acid, aminobenzoic acid, mercaptobenzoic acid, naphthoic acid, methylnaphthoic acid, hydroxynaphthoic acid Anthonic acid << anthracenecarboxylic acid >>, pyrenecarboxylic acid,

 Alicyclic monofunctional carboxylic acids: cyclopropanecarboxylic acid, dimethylcyclopropanecarboxylic acid, tetramethylcyclopropanecarboxylic acid, mercaptomethylcyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentylacetic acid, aminocyclopentanecarboxylic acid , Cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexylpropionic acid, cyclohexylbutyric acid, methylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, tert-butylcyclohexanecarboxylic acid, hydroxycyclohexanecarboxylic acid , (Hydroxymethyl) cyclohexanecarboxylic acid, cyclohexenecarbo Acid, norbornene carboxylic acid, norbornane carboxylic acid, noradamantane carboxylic acid, adamantane carboxylic acid,

 Monofunctional carboxylic acid having an oxygen atom in addition to the carboxyl group: glycolic acid, lactic acid, hydroxypalmitic acid, ricinoleic acid, hydroxystearic acid, alloyed acid <trihydroxyhexadecanoic acid>, jasmonic acid <3-oxo-2- (2- Pentenyl) cyclopentaneacetic acid, cucurbic acid << 3-hydroxy-2- (2-pentenyl) cyclopentaneacetic acid >>, 3-oxobutanoic acid and the like, and (a-1) a divalent or higher valent acid And compounds listed as carboxylic acids.

 Examples of the carboxylic acid, that is, a compound having a carboxyl group, include compounds obtained by esterifying or amidating a part of a compound mentioned as a divalent or higher carboxylic acid or a derivative thereof with an alcohol or an amine. For example, methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Such as (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, methylamine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone, etc. Alcohol, amine, and (a-1) a compound enumerated with a divalent or higher carboxylic acid are partially esterified to leave a single carboxyl group in the molecule. Ability carboxylic acid, and the like. In particular, it is preferable to use a cyclic carboxylic acid anhydride of a divalent carboxylic acid because one carboxyl group is generated after reacting with a hydroxyl group or an amino group in a 1: 1 ratio.

 Further, acid anhydrides, acid halides, methyl esters, ethyl esters, phenyl esters, and tert-butyl esters of the above compounds having a carboxyl group are also included.

 Among the above, in consideration of solubility, storage stability, ease of production, etc., some of the monofunctional carboxylic acid, acid halide, acid anhydride, or polyfunctional carboxylic acid or derivative thereof Monofunctional carboxylic acid or derivative thereof in which carboxylic acid is reacted with alcohol or amine to leave one carboxyl group, or monofunctional carboxylic acid produced by reacting monofunctional alcohol or amine with a cyclic acid anhydride of divalent carboxylic acid Is preferably used.

  Especially, since it is easy to provide the solubility to an organic solvent, it is preferable to use the compound represented by following General formula (7), and since photocurability becomes favorable, in following General formula (8) It is preferable to use the compound represented.

  General formula (7)

[Wherein R ⁸ is a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]

  General formula (8)

[Wherein, R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is a linear or branched alkylene group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 2 to 8 carbon atoms, R ¹¹ is a C 2-8 linear or branched alkylene group, alicyclic hydrocarbon group, or aromatic hydrocarbon group. ]
These compounds may be used alone or in combination.

  Silanol is a compound having a Si—OH structure in the molecule, and OH in the silanol reacts with a hydroxyl group. Further, alkoxysilane, sulfuric acid of silanol, sulfonic acid ester, and halogenated silane (hereinafter collectively referred to as “silanol derivatives”) generate silanol by hydrolysis, and thus can be used in the same manner as silanol. A silanol derivative is commercially available from the viewpoint of storage stability.

 The following are mentioned as a silanol derivative.

 Monofunctional silanol derivatives: trimethylsilyl triflate, triethylsilyl triflate, tert-butyldimethylsilyl triflate, diethylisopropylsilyl triflate, tripropylsilyl triflate, bis (trimethylsilyl) sulfate, chlorotrimethylsilane, chlorotriethylsilane, trimethylmethoxysilane,

 Multifunctional silanol derivatives: dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane , Vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycosoxypropyltriethoxy Silane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxy Propylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminomethyl) -3-aminopropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, 3-chloro B pills trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane,

 Among these, considering the solubility, storage stability, ease of production, etc., it is preferable to use the monofunctional silanol derivative.

  An amino resin is a compound having a hydroxymethylamino group in which an electron-withdrawing group is bonded to a nitrogen atom, and reacts with a hydroxyl group to form an ether bond. Examples of the electron withdrawing group include a carbonyl group, a thiocarbonyl group, and a triazine ring. A compound having an alkoxymethylamino group in which the hydroxyl group is capped with an alcohol can also be used because it generates a hydroxyl group by hydrolysis.

 The following are mentioned as an amino resin.

 Monofunctional amino resin: N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, N-hydroxymethylacetamide, N-hydroxymethylurea, 1- (hydroxymethyl) -5,5-dimethylhydantoin, N- (hydroxymethyl) nicotinamide,

 Multifunctional amino resin: N, N′-dimethylolurea, 1,3-bis (hydroxymethyl) -5- [1,3-bis (hydroxymethyl) ureido] hydantoin, 1,3,4,6-tetrakis (methoxy) Methyl) glycoluril, hexamethylolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc., nitrogen, hydroxyl, methoxymethyl, butoxymethyl groups are substituted, urea, melamine, benzoguanamine, glycoluril, etc. Is mentioned.

 Among the above, in consideration of solubility, storage stability, ease of production, etc., it is preferable to use the monofunctional amino resin.

  Examples of the compound having an epoxy group include the following.

 Monofunctional epoxy: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, phenyl glycidyl ether, phenylphenol glycidyl ether, sec-butylphenol monoglycidyl ether, polyethylene glycol monophenyl ether monoglycidyl ether, N-glycidyl phthalimide, styrene oxide 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexane-1-carboxylic acid ester, 3,4-epoxycyclohexane-1-methanol, 3,4-epoxycyclohexane-1-carbaldehyde, 4, 5-epoxy-1,2-dicarboxylic acid ester,

 Multifunctional epoxy: sorbitol polyglycidyl ether, polyglycerin polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerin polyglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether 1,6-hexanediol polyglycidyl ether, bis (hydroxycyclopropyl) propane diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tert-butylphenol glycidyl ether, polybutadiene diglycidyl ether, diglycidyl phthalate, cyclohexane Dicarboxylic acid Glycidyl terephthalate, hydroquinone diglycidyl ether, dibromophenol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, condensate of bisphenol A and epichlorohydrin, condensate of bisphenol F and epichlorohydrin, phenol novolac poly Glycidyl ether, cresol novolac polyglycidyl ether, condensate of brominated bisphenol A and epichlorohydrin, N, N, N ′, N′-tetraglycidyl bis (aminophenyl) methane, diglycidyl dimer, hydrogenated bisphenol A and Epichlorohydrin condensate, di-tert-butylhydroquinone diglycidyl ether, tetramethylbisphenol F diglycidyl ether, bis (N, N-diglycidylamino) Chill) benzene, bis (N, N-diglycidyl aminomethyl) cyclohexane, and the like.

 Among the above, in consideration of solubility, storage stability, ease of production, etc., it is preferable to use the above monofunctional epoxy.

(Amidation)
There are various methods for amidating (a-1) a divalent or higher carboxylic acid or derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position. -1) The reaction can proceed by removing water when the divalent or higher carboxylic acid or derivative thereof is a carboxylic acid, removing alcohol in the case of a carboxylic acid ester, and removing acid in the case of a carboxylic acid anhydride or halide. . In the case of water or alcohol, it is prepared to be removed from the reaction system by heating. In the case of acid, triethylamine, tributylamine, dimethylbenzylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. The basic compound can be removed.

 A catalyst can be used in the amidation. For example, acid catalysts such as sulfuric acid, hydrochloric acid, methanesulfonic acid and p-toluenesulfonic acid, base catalysts such as sodium hydroxide, sodium carbonate and sodium methoxide (hereinafter referred to as “base catalyst”), triethylamine, tributylamine, Amine catalysts such as octylamine, tetramethylethylenediamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, N-methylimidazole (hereinafter referred to as “amine catalyst”) Summarize), salts and complexes containing metal ions such as iron (III), zirconium (IV), scandium (III), titanium (IV), tin (IV), hafnium (IV), diphenylammonium triflate, pentafluorophenylammonium Ammonium salts such as Rifurato, and the like.

 A solvent can be used in the amidation reaction. The solvent to be used can be used as long as it is other than a solvent that reacts with a reaction substrate such as alcohol, amine, or carboxylic acid. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc. It is done.

 In particular, the amidation with carboxylic acid can be performed using a condensing agent. A condensing agent activates a carboxylic acid or an amine, and the esterification reaction can be carried out under mild conditions. At the same time, the by-product water is combined with the condensing agent to form another compound. And a compound having a water removing action. Such condensing agents include, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, p-toluenesulfonyl chloride, 1-ethyl-3- (N, N-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldiimidazole, ethyl chloroformate, chloroformate Acid isobutyl, 2,4,6-trichlorobenzoic acid chloride, 2-methyl-6-nitrobenzoic anhydride, O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′— Examples thereof include tetramethyluronium hexafluorophosphate.

(Denaturation)
(A-3) When reacting a part of the hydroxyl group of β-hydroxyalkylamide with a compound having one or more functional groups capable of reacting with (a-4) hydroxyl group, What is necessary is just to make it react on suitable conditions.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is an isocyanate, the reaction proceeds by adding a non-catalyst or an appropriate catalyst and heating. Suitable catalysts include, for example, amines such as triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and salts thereof, tetrabutyl titanate, dibutyltin dilaurate, tin octylate. And metal salts and complexes.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is a carboxylic acid, the dehydration condensation reaction proceeds by heating to 100 ° C. or higher, preferably 140 ° C. or higher without a catalyst. Alternatively, the reaction can be allowed to proceed at a lower temperature by adding an appropriate catalyst. The catalysts, condensing agents, etc. described for the amidation reaction can be used for this reaction.

(A-4) When the compound having at least one functional group capable of reacting with a hydroxyl group is a carboxylic acid anhydride or a carboxylic acid halide, a base catalyst or an amine catalyst is added and reacted at 0 to 100 ° C. preferable. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is silanol, it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is an amino resin, methanesulfonic acid, p-toluenesulfonic acid, ammonium salt or amine salt thereof is used as a catalyst, and 0 It is preferable to make it react at -200 degreeC.

(A-4) When the compound having at least one functional group capable of reacting with a hydroxyl group is an epoxy group, potassium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium hydride, etc. It is preferable to use a strong base catalyst or a metal catalyst such as tetrafluoroboric acid or tin (IV) chloride and react at 0 to 200 ° C.

  When the compound represented by the general formula (1) contains a photopolymerizable functional group, a gas having a polymerization inhibitory effect is introduced into the reaction system during the reaction, or a polymerization inhibitor is added. May be. By introducing a gas having a polymerization inhibition effect into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented.

  Examples of the gas having an effect of inhibiting radical polymerization include a gas containing oxygen that does not enter the explosion range of the substance in the system, for example, air.

  As the radical polymerization inhibitor, known ones can be used and are not particularly limited. For example, hydroquinone, methoquinone, 2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), phenothiazine and the like. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor to be used is preferably 0.005 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the total solids in the reaction system. Most preferred is 1.5 parts by weight. If the polymerization inhibitor is less than 0.005 parts by weight, the polymerization inhibition effect may not be sufficient. On the other hand, if it exceeds 5 parts by weight, the exposure sensitivity may decrease. Moreover, it is more preferable to use a gas having a polymerization inhibiting effect in combination with the polymerization inhibitor because the amount of the polymerization inhibitor to be used can be reduced or the polymerization inhibiting effect can be enhanced.

<Polymer not containing carboxyl group>
The photosensitive composition of this invention may contain the polymer which does not contain a carboxyl group as needed. Examples of the polymer not containing a carboxyl group include thermoplastic resins and thermosetting resins.
Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.
Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

<Additives>
The photosensitive composition of the present invention further includes a curing agent, a leveling agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an inorganic filler, an adhesion-imparting agent, and a surface active agent that are used in combination with the thermosetting resin as necessary. Additives such as adhesion improvers such as agents, storage stabilizers, dyes, and silane coupling agents may be added. These additives can be added in any amount as long as the purpose of the resin composition is not impaired.

<Curing method>
β-hydroxyalkylamide (A), carboxyl group-containing polymer (B), photopolymerization initiator (C), organic solvent, and photopolymerizable monomer (D) as required A photosensitive composition is prepared by mixing and stirring the components. The obtained photosensitive composition is applied to one or both surfaces of various base materials, or molded using a mold, etc., dried by heating as necessary, irradiated with active energy rays, and developed as necessary. And the target hardened | cured material can be obtained by making it heat-harden at 100-200 degreeC.
Examples of the substrate include glass, ceramic, polycarbonate, polyester, urethane, acrylic, polyacetate cellulose, polyamide, polyimide, polystyrene, epoxy resin, polyolefin, polycycloolefin, polyvinyl alcohol, various metals such as stainless steel, and the like. It is done.
Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays and the like, and ultraviolet rays are particularly preferable. When ultraviolet rays are used, it is preferable to use a light source such as a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, or an excimer lamp.
Development can be performed by immersing in a solvent or an alkaline developer, or by spraying the developer with a spray or the like to remove uncured portions and form a desired fine pattern.

<< Coating agent for touch panel interlayer insulation film >>
Since the photosensitive composition of this invention can form the film | membrane and pattern excellent in heat resistance and chemical resistance as above-mentioned, it can also be used as a coating agent for touchscreen interlayer insulation films. Below, the coating agent for touchscreen interlayer insulation films is demonstrated.

  The touch panel interlayer insulating film is provided to protect the ITO electrodes that are members of the touch panel and to maintain insulation between the ITO electrodes. The coating agent for touch panel interlayer insulation film of this invention contains the photosensitive composition of this invention as an essential component, and can satisfy | fill required physical properties, such as chemical resistance, heat resistance, insulation, hardness, and adhesiveness. The components are as described above, but particularly preferred ranges are described below.

<Organic solvent>
The interlayer insulating film is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 10 μm. An organic solvent is used to facilitate this. As the organic solvent, those mentioned above can be used, and 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, , 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropionic acid Ethyl, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol Monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether , Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol Monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl Ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate Benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters and the like are preferably used. These can be used alone or in combination.

In particular, considering the drying property of the organic solvent, in the die coating method, the screen printing method, the offset printing method, the gravure printing method and the like, it is preferable to include a high boiling point solvent of 160 ° C. or higher,
For example, 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1,3-butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1, 3-propanediol (bp 213 ° C.), diisobutyl ketone (bp 168.1 ° C.), ethylene glycol monobutyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5) ° C), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monomethyl ether (bp 194.0 ° C.), diethylene glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188. ° C), diethylene glycol monoisopropyl ether (bp 207.3 ° C), propylene glycol monobutyl ether (bp 170.2 ° C), propylene glycol diacetate (bp 190.0 ° C), dipropylene glycol monomethyl ether (bp 187.2 ° C), dipropylene Glycol monoethyl ether (bp 197.8 ° C), dipropylene glycol monopropyl ether (bp 212.0 ° C), dipropylene glycol dimethyl ether (bp 175 ° C), tripropylene glycol monomethyl ether (bp 206.3 ° C), 3-ethoxypropionic acid Ethyl (bp 169.7 ° C.), 3-methoxybutyl acetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyro Kuton (bp204 ° C), N, N-dimethylacetamide (bp166.1 ° C), N-methylpyrrolidone (bp202 ° C), p-chlorotoluene (bp162.0 ° C), o-diethylbenzene (bp183.4 ° C), m -Diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8 ° C), o-dichlorobenzene (bp180.5 ° C), m-dichlorobenzene (bp173.0 ° C), n-butylbenzene (bp183.3 ° C) ), Sec-butylbenzene (bp 178.3 ° C.), tert-butylbenzene (bp 169.1 ° C.), cyclohexanol (bp 161.1 ° C.), cyclohexyl acetate (bp 173 ° C.), methylcyclohexanol (bp 174 ° C.) and the like. High boiling point solvents above 160 ° C 5 to 50% by weight as a quasi-is preferable.
The organic solvent can be used in an amount of 200 to 4000 parts by weight with respect to 100 parts by weight of the total solid content in the coating agent for touch panel interlayer insulating film.

<Β-Hydroxyalkylamide (A)>
The β-hydroxyalkylamide (A) of the present invention is as described above, but when used as a coating agent for a touch panel interlayer insulating film, in order to improve chemical resistance, heat resistance, and hardness, It is preferable that at least one of X, R ¹ and R ^{2 in} the formula (1) contains a photopolymerizable functional group.

<Polymer containing carboxyl group (B)>
The polymer (B) containing a carboxyl group of the present invention is as described above, but when used as a coating agent for a touch panel interlayer insulating film, high transparency is required, so that it is in the visible light region. A polymer having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm is used. From the viewpoint of transparency, a (meth) acrylic copolymer containing a carboxyl group is preferably used.

((Meth) acrylic copolymer containing carboxyl group)
As a method of obtaining a (meth) acrylic copolymer containing a carboxyl group, a method of copolymerizing (meth) acrylic acid or a (meth) acrylate containing a carboxyl group with another monomer, or a hydroxyl group (meta ) A method of reacting a hydroxyl group in a polymer obtained by copolymerizing an acrylate with another monomer with an acid anhydride group in a polybasic acid anhydride.

Moreover, as a method of obtaining the (meth) acrylate copolymer containing a photopolymerizable functional group and a carboxyl group, there are the methods (B-1) and (B-2) described above.
(B-16) a method of reacting a part of the carboxyl group in the (meth) acrylic copolymer containing a carboxyl group with the epoxy group in the (meth) acrylate containing an epoxy group;
(B-17) A hydroxyl group produced by reacting an epoxy group in a (meth) acrylic copolymer containing an epoxy group with a carboxyl group in a (meth) acrylate containing (meth) acrylic acid or a carboxyl group A method of reacting an acid anhydride group of a polybasic acid anhydride;
(B-18) A hydroxyl group in a (meth) acrylic copolymer containing a carboxyl group and a hydroxyl group is reacted with an isocyanate group or an acid anhydride group in an (meth) acrylate or unsaturated acid anhydride containing an isocyanate group. The method of making it, etc. are mentioned.

Examples of the (meth) acrylate containing a carboxyl group include acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethylhexa. Examples include hydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, and ω-carboxypolycaprolactone (meth) acrylate.
Itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) acrylic acid, α- (hydroxymethyl) methacrylic acid, p-vinylbenzoic acid and the like can also be used.
(Meth) acrylic acid is preferred from the viewpoints of copolymerizability and availability.

Examples of the (meth) acrylate containing an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidiether, 3,4-epoxybutyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5 , 6-epoxyhexyl (meth) acrylate, α-ethyl acrylate glycidyl, allyl glycidyl ether, crotonyl glycidyl ale, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate,
Further, examples of the aromatic compound containing an epoxy group include N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether. , Α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyl Oxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2, 3,6-trig Glycidyloxy-methylstyrene, 3,4,5-glycidyloxy-methylstyrene, etc. 2,4,6 glycidyloxymethyl styrene. Glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether are preferred from the viewpoint of easy availability of industrial products, and the concentration of ethylenically unsaturated groups can be increased and formed from a photosensitive composition. Glycidyl (meth) acrylate is more preferable in that UV curing in the coating film is easy to proceed.

Examples of the (meth) acrylate containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1 , 4-Cyclohexanedimethanol mono (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) phthalate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) Acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol) Ru-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, glycerol (meth) acrylate, etc. It is done.
2-hydroxyethyl (meth) acrylate is preferable from the viewpoints of copolymerizability and availability.

  Examples of the polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride And polybasic acid anhydrides. From the viewpoint of solvent solubility, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferred.

Examples of the (meth) acrylate containing an isocyanate group include (meth) acryloyl isocyanate, 1,1-bis ((meth) acryloylmethyl) ethyl isocyanate, m- (meth) acryloylphenyl isocyanate, and 2- (meth) acryloyl. Examples include oxyethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 2- (meth) acryloyloxyethoxyethyl isocyanate.
2-Methacryloyloxyethyl isocyanate is preferred because the concentration of the ethylenically unsaturated group can be increased, ultraviolet curing in the coating film formed from the photosensitive composition is easy to proceed, and it is easily available.

  Examples of the unsaturated acid anhydride include maleic anhydride and itaconic anhydride.

  In the (meth) acrylic copolymer containing a carboxyl group, other monomers such as copolymerizable (meth) acrylate can be copolymerized, and known ones can be used without limitation. .

  From the viewpoint of transparency, it is preferable to use a compound represented by the following general formula (9). When a (meth) acrylate containing a compound represented by the general formula (9) is copolymerized to obtain a resin, the cyclization reaction of the compound represented by the general formula (9) proceeds simultaneously with the polymerization, and tetrahydro A pyran ring structure is formed.

General formula (9)

In General Formula (9), R ²² and R ²³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t -Linear or branched alkyl groups such as amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, And alicyclic groups such as 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a hydrocarbon group which is difficult to be removed by heat are preferable from the viewpoint of heat resistance. R ²² and R ²³ may be the same or different.

  Specific examples of the compound represented by the general formula (9) include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)]. Bis-2-propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2- Propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di ( t-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2- Lopenoate, di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, (T-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, Di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl- 2,2 '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate and the like can be mentioned. Among these, from the viewpoint of heat resistance, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl -2,2 '-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate are preferable, and only one kind may be used. There may be more than species.

  The ratio at the time of polymerizing the compound represented by the general formula (9) is not particularly limited, but is 2 to 60 parts by weight, preferably 5 to 55 parts by weight, in 100 parts by weight of all monomer components used for the polymerization. More preferably, it is 5 to 50 parts by weight. When the amount of the compound represented by the general formula (9) is more than 60 parts by weight, it may be difficult to obtain a low molecular weight product during copolymerization or may be easily gelled. If the amount is less than 2 parts by weight, the coating film performance such as transparency and heat resistance may be insufficient.

  As for the weight average molecular weight (Mw) of the polymer (B) containing a carboxyl group, 2000-25000 are preferable, More preferably, it is 4000-15000. When the weight average molecular weight (Mw) is less than 2,000, the heat resistance may be deteriorated, and when the weight average molecular weight (Mw) exceeds 25,000, the viscosity becomes high and coating may be difficult.

  The polymer (B) containing a carboxyl group should be used in an amount of 10 to 60 parts by weight in a total of 100 parts by weight of the solid content of the coating agent for an interlayer insulating film for touch panel from the viewpoint of adhesion, hardness, and transmittance. Is preferred.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) of the present invention is as described above. However, when it is used as a coating agent for a touch panel interlayer insulating film, it is necessary to satisfy both hardness and adhesion. It is preferable to use a photopolymerization initiator in combination with a cationic polymerizable photopolymerization initiator.

For radical polymerizable initiators, examples are given above, but when used as a coating agent for touch panel interlayer insulation films, acetophenone photopolymerization initiators and oxime ester photopolymerization initiators have high sensitivity, Since the addition amount may be small, the transmittance increases, so that it is preferably used.
Among acetophenone photopolymerization initiators and oxime ester photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1 , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], especially 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)] has a high transmittance as an insulating film because it does not turn yellow during the heating step, and particularly has a transmittance around 400 nm. This is more preferable because a photosensitive resin composition having a high value can be provided.

  The photopolymerization initiator (C) is preferably used in an amount of 1 to 30 parts by weight in a total of 100 parts by weight of the solid content of the photosensitive composition, and is used in an amount of 1 to 10 parts by weight from the viewpoint of transmittance. It is more preferable.

  Further, a sensitizer can be used in combination, and those exemplified above can be used. The amount of the sensitizer used is preferably 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (C).

<Photopolymerizable monomer (D)>
The photopolymerizable monomer (D) of the present invention is as described above. However, when it is used as a coating agent for a touch panel interlayer insulating film, it is necessary to satisfy both hardness and adhesion. It is preferable to use a polymerizable photopolymerizable monomer and a cationic polymerizable photopolymerizable monomer in combination.

  The photopolymerizable monomer (D) is usually photocured by irradiating with ultraviolet rays or an electron beam [adding a photopolymerization initiator (C) if necessary]. If necessary, a thermal polymerization initiator may be added] to cause thermosetting.

  Examples of the radical polymerizable photopolymerizable monomer have been given above, but when used as a coating agent for a touch panel interlayer insulating film, 7 per molecule are used to increase hardness and solvent resistance. It is preferable to include a monomer containing the above radical polymerizable photopolymerizable functional group. Moreover, it is preferable to contain the photopolymerizable monomer containing 7-14 pieces, Preferably 8-10 photopolymerizable functional groups from viewpoints, such as maintenance of a transmittance | permeability and the balance of hardness and adhesiveness.

  As a monomer having seven or more photopolymerizable functional groups, for example, a group consisting of tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, and a compound represented by the following general formula (10) It is preferable that it is at least one or more selected.

General formula (10)

In the general formula (10), R ²⁴ represents a divalent organic group excluding an oxygen atom, and R ²⁵ represents a hydrogen atom or a methyl group.

  Examples of the divalent organic group include alkylene groups such as methylene group, ethylene group and propylene group, arylene groups such as phenylene group, tolylene group and xylylene group, ether group, carbonyl group, sulfonyl group and ester group. A structure represented by the following general formula (11) is preferable.

Formula (11)

In the general formula (11), R ²⁶ represents an aliphatic, alicyclic or aromatic structure.

  Examples of the compound represented by the general formula (10) include compounds obtained by reacting dipentaerythritol penta (meth) acrylate and polyfunctional isocyanate, dipentaerythritol penta (meth) acrylate and tetrabasic acid dianhydride. And compounds obtained by reacting dipentaerythritol penta (meth) acrylate and polyfunctional epoxy compounds.

Specific examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
Specific examples of tetrabasic acid dianhydrides include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride. , Cyclopentanetetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexylene tetracarboxylic acid A dianhydride etc. can be mentioned.
Specific examples of the polyfunctional epoxy compound include tris (glycidylphenyl) methane, triglycidyl isocyanurate, bis (3,4-epoxycyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl). Examples thereof include adipate, methylene bis (3,4-epoxycyclohexane), bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and novolak type epoxy resin.

  When used as a coating agent for a touch panel interlayer insulation film, tripentaerythritol hepta (meth) acrylate or tripentaerythritol octa (meth) acrylate is preferable as the photopolymerizable monomer (D), and these are mixed. It may be included. As such a photopolymerizable monomer (D), commercially available products include, for example, Biscoat # 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.). it can.

  The photopolymerizable monomer (D) may include a polyfunctional monomer having an acidic group. For example, free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid, and dicarboxylic acids An esterified product of a polycarboxylic acid and a monohydroxyalkyl (meth) acrylate can be used. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

  The content of the photopolymerizable monomer (D) is preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight, in a total of 100 parts by weight of the solid content of the coating agent for the touch panel interlayer insulating film. . If the amount is less than 5 parts by weight, the hardness and chemical resistance may be insufficient. If the amount is more than 80 parts by weight, the transmittance and adhesiveness may be decreased.

<Additives>
The above-mentioned additive may be added to the photosensitive composition of the present invention as necessary. However, when used as a coating agent for a touch panel interlayer insulating film, the adhesive property with a glass substrate, ITO, etc. Since it is necessary, it is preferable to contain an adhesion improver such as a silane coupling agent.
Adhesion improvers include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-amino Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 -Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane , 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like.

  Among these, inclusion of a silane-based additive is preferable because adhesion to a glass substrate or ITO is improved, and 3-methacryloxypropyltrimethoxysilane is more preferable, 3-glycidoxypropyltrimethoxysilane, 3-mercapto. Propyltrimethoxysilane is particularly preferred.

  The adhesion improver is preferably used in an amount of 0.1 to 10 parts by weight in a total of 100 parts by weight of the solid content of the photosensitive composition. If the amount is less than 0.1 parts by weight from the viewpoint of adhesion, the adhesion promoting effect may not be obtained because the amount of adhesion promoting additive is small. If it exceeds 10 parts by weight, β-hydroxylalkyl in the photosensitive composition may not be obtained. Since the amide (A), the polymer (B) containing a carboxyl group, the photopolymerization initiator (C) and the like are relatively decreased, characteristics such as hardness may be deteriorated.

  Moreover, since the coating agent for touch panel interlayer insulation films needs hardness, it is preferable to contain inorganic oxide microparticles. The inorganic oxide fine particles are formed of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium, from the viewpoint of the colorlessness of the cured film of the resulting curable composition. Oxide particles are preferred. Of these, from the viewpoint of transmittance, oxide particles of silicon, zirconium, or aluminum are preferable, and silicon oxide particles are particularly preferable.

  The inorganic oxide fine particles have an affinity with a binder component such as a polymer (B) or a photopolymerizable monomer (D) containing a carboxyl group in order to stabilize dispersion in a dispersion or coating solution. In order to improve the properties and bonding properties, physical surface treatment such as plasma discharge treatment or corona discharge treatment, and chemical surface treatment with a surfactant or a coupling agent may be performed.

  The average primary particle diameter of the inorganic oxide particles is preferably 1 nm to 1000 nm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 30 nm. If the average primary particle diameter exceeds 1000 nm, the transparency of the cured product may decrease, or the surface state of the coating may deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

  The average primary particle diameter of the inorganic oxide fine particles is measured using, for example, the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of volume to surface area is calculated using the specific gravity of the inorganic oxide, and the particles are assumed to be true spheres. There is a method of obtaining the particle diameter from these ratios to obtain the average primary particle diameter.

  The inorganic oxide particles are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  Commercially available products as silicon oxide fine particle dispersions particularly preferably used in the present invention include MA-ST-MS, IPA-ST, IPA-ST-MS, and IPA-ST- manufactured by Nissan Chemical Industries, Ltd. L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., hollow silica CS60-IPA manufactured by Catalyst Kasei Kogyo Co., Ltd., etc. Can be mentioned. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Examples of products that are commercially available as zirconia oxide fine particle dispersions preferably used in the present invention include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH manufactured by Nissan Chemical Industries, Ltd., Sumitomo Osaka Cement ( HXU-110JC manufactured by Co., Ltd. can be mentioned.

  Commercially available products as aluminum oxide fine particle dispersions preferably used in the present invention include alumina sol-100, alumina sol-200, alumina sol-520 manufactured by Nissan Chemical Industries, Ltd. and AS- manufactured by Sumitomo Osaka Cement Co., Ltd. 150I, AS-150T.

  In addition, inorganic oxide fine particle dispersions preferably used in the present invention are shown below. Antimony oxide fine particle dispersions include Celnax CX-Z330H manufactured by Nissan Chemical Industries, Ltd., and oxide fine particle dispersions of aluminum, titanium, tin, indium, zinc, etc. be able to.

  The amount of the inorganic oxide fine particles added is preferably 10 to 40 parts by weight, more preferably 15 to 35 parts by weight, based on 100 parts by weight of the total solid content in the coating agent for a touch panel interlayer insulating film. When the addition amount is less than 10 parts by weight, the effect such as improvement in hardness may not be obtained. On the other hand, when the addition amount exceeds 40 parts by weight, problems such as a decrease in adhesion may occur.

The coating agent for a touch panel interlayer insulating film can contain a storage stabilizer. By containing a storage stabilizer, the viscosity with time of the composition can be stabilized. Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid. Used alone or in combination.
The usage-amount of a storage stabilizer can be used in the quantity of 0.1-5 weight part in the total 100 weight part of the coating agent for touchscreen interlayer insulation films.

  In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coating agent for a touch panel interlayer insulating film. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination.

As a particularly preferred leveling agent, it is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and it has a hydrophilic group but has low solubility in water and is added to a coating agent for a touch panel interlayer insulating film. In that case, it has the characteristics of low surface tension lowering ability, and even though the surface tension lowering ability is low, it is useful to have good wettability to the glass plate, resulting in the appearance of coating film defects due to foaming. Those which can sufficiently suppress the chargeability with the added amount not used can be preferably used.
As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  The amount of the leveling agent used is preferably 0.003 to 0.5 parts by weight in a total of 100 parts by weight of the coating agent for the touch panel interlayer insulating film.

  The coating agent for a touch panel interlayer insulating film can contain an antioxidant in order to suppress a decrease in transmittance due to yellowing or the like due to a heating process. The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.

<Method for producing coating agent for touch panel interlayer insulating film>
The coating agent for a touch panel interlayer insulating film of the present invention comprises a β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, a photopolymerization initiator (C), an organic solvent, and a photopolymerizable monomer as required. It can be obtained by stirring and mixing the monomer (D) and the like , and if necessary, inorganic oxide fine particles.
The coating agent for a touch panel interlayer insulating film of the present invention is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more coarse by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove particles, mixed dust and foreign matter.

<Method for manufacturing touch panel interlayer insulating film>
Next, a method for producing a touch panel interlayer insulating film using the coating agent for a touch panel interlayer insulating film of the present invention will be described.
The thickness when producing the touch panel interlayer insulating film is preferably 0.005 to 30 μm in a dry state, more preferably 0.01 to 20 μm, and particularly preferably 0.1 to 10 μm. preferable. By setting the thickness in such a range, an appropriate mechanical strength and heat resistance can be obtained, and the light transmittance is less likely to be impaired.

  In addition, the method for applying the coating agent for the touch panel interlayer insulating film of the present invention to a glass substrate, ITO, metal film, organic film or the like is not particularly limited. For example, dipping method, spray method, roll coating method, die coating For example, a coating method such as a screen coating method, an offset printing method, or a gravure printing method can be used. It is also possible to form a pattern by photolithography.

  Furthermore, the drying method after applying the coating agent for a touch panel interlayer insulating film of the present invention to a glass substrate or the like is not particularly limited. For example, an oven or an infrared heater can be used. is there. And although the heating conditions can also be changed depending on the kind of each component used in the photosensitive composition, the addition amount (blending amount), etc., the temperature is usually in the range of 50 to 300 ° C. Heat curing is preferably performed under a condition of 10 to 10 hours, and more preferably a temperature of 100 to 250 ° C. and a heat curing condition of 0.5 to 5.0 hours.

The photocuring method is not particularly limited. For example, it is possible to irradiate ultraviolet rays using a high pressure mercury lamp, a metal halide lamp or the like as a light source. And although the irradiation conditions can also be changed according to the kind of each component used in the photosensitive composition, the addition amount (blending amount), etc., the irradiation amount of ultraviolet rays is usually 10 to 500 mJ / cm ^2. More preferably, it is 20-300 mJ / cm < ² >. After photocuring, it may be thermally cured by further heating.

  Regarding the thermosetting performed after photocuring, the carboxyl group in the polymer (B) containing a carboxyl group can be changed depending on the kind of each component used in the photosensitive composition and the amount added (blending amount). And the hydroxyl group in β-hydroxyalkylamide (A) is preferably subjected to a crosslinking reaction, and is preferably cured by heating under a condition of 0.1 to 10 hours in a temperature range of 50 to 300 ° C. Is a heat curing condition in which the temperature is in the range of 100 to 250 ° C. for 0.2 to 5.0 hours, more preferably in the range of 100 to 200 ° C. for 0.2 to 2 hours.

  The coating agent for a touch panel interlayer insulating film of the present invention may be used for any of insulating film use, protective film use, and flat film use.

<< Photosensitive composition for color filter >>
Since the photosensitive composition of this invention can form the film | membrane and pattern excellent in heat resistance and chemical resistance as above-mentioned, it can also be used as a photosensitive composition for color filters. Below, the photosensitive composition for color filters is demonstrated.

<Pigment>
Since the photosensitive composition for color filters is required to be colored, it contains the photosensitive composition of the present invention and a colorant such as a pigment. Below, the pigment preferably used for the photosensitive composition for color filters is demonstrated.

As a pigment contained in the photosensitive composition for color filters, an organic or inorganic pigment can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the photosensitive composition for color filters of this invention is shown by a color index number.

  Examples of the red photosensitive composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, Red pigments such as 255, 264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive composition.

Examples of yellow pigments that can be used in combination with the red photosensitive composition include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Or the like can be used 5,176,177,179,180,181,182,185,187,188,193,194,199,213,214.
Moreover, these yellow pigments can be used for the yellow photosensitive composition for forming a yellow filter segment individually or in combination of 2 or more types.

Examples of the orange pigment that can be used in combination with the red photosensitive composition include C.I. I. Orange pigments such as Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 can be used.
Moreover, these orange pigments can be used for the orange photosensitive composition for forming an orange filter segment individually or in combination of 2 or more types.

Examples of the green photosensitive composition for forming the green filter segment include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37 and 58 can be used. The yellow pigment described above can be used in combination with the green photosensitive composition.
Examples of the blue photosensitive composition for forming the blue filter segment include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and 80 can be used. Blue photosensitive compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

Examples of the cyan photosensitive composition for forming the cyan filter segment include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 80 can be used.
Examples of the magenta color photosensitive composition for forming the magenta color filter segment include C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 81, 144, 146, 177, and 169, and red pigments can be used. A yellow pigment can be used in combination with the magenta photosensitive composition.

  Examples of the black photosensitive composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, and perylene black pigment, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. For the black photosensitive composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black photosensitive composition.

Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The photosensitive composition for color filters can contain a dye within a range that does not decrease the heat resistance for color matching.

  From the viewpoint of obtaining sufficient color reproducibility, the preferable concentration of the pigment component is 10% by weight or more, more preferably 15% by weight or more, based on the total nonvolatile components of the photosensitive composition for color filters (100% by weight). And most preferably 20% by weight or more. Further, since the stability of the photosensitive composition for color filters is improved, the concentration of the preferred pigment component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less. .

<Organic solvent>
The photosensitive composition for color filters is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 10 μm. An organic solvent is used to facilitate this. As the organic solvent, those mentioned above can be used, and in particular, the solvents described in the section of the coating agent for touch panel interlayer insulating film can be preferably used.
The organic solvent is preferably used in an amount of 100 to 10000 parts by weight, preferably 500 to 5000 parts by weight, with respect to 100 parts by weight of the pigment in the photosensitive composition for color filters.

<Β-Hydroxyalkylamide (A)>
The β-hydroxyalkylamide (A) of the present invention is as described above, and when used as a photosensitive composition for a color filter, in order to improve chemical resistance, heat resistance and hardness, the above general formula It is preferable that at least one of X, R ¹ and R ² in (1) contains a photopolymerizable functional group.

<Polymer containing carboxyl group (B)>
The carboxyl group-containing polymer (B) of the present invention is as described above. However, when used as a photosensitive composition for a color filter, high transparency is required. It is preferable to use a polymer having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region as described in the film coating agent. From the viewpoint of transparency, a (meth) acrylic copolymer containing a carboxyl group is preferably used.

  The total amount of the β-hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group is 1 to 400 parts by weight, preferably 1 to 250 parts per 100 parts by weight of the pigment in the color filter photosensitive composition. It can be used in parts by weight.

<Polymer not containing carboxyl group>
Further, if the polymer has a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region, a thermoplastic resin containing no carboxyl group and thermosetting if necessary. A functional resin may be used in combination. In order to improve peeling and chipping during development of a fine pattern, an epoxy resin is preferably used in combination as a thermosetting resin.

  As the epoxy resin, known ones can be used. Among the photopolymerizable monomers (D), compounds having an epoxy group, compounds having an alicyclic epoxy group, aliphatic compounds described as those that undergo cationic polymerization. An epoxy resin, a compound having an oxetanyl group, a compound described as a compound having an epoxy group among the compounds (a-4) having one or more functional groups capable of reacting with a hydroxyl group, and the like can be used. Examples of products that are preferably used when used as a photosensitive composition for a color filter include the following.

Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256, JER 1032H60, JER 157S65, JER 157S70 , JER152, JER154 (above are trade names; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (trade names; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H, EPPN-501H, EPPN-201, EOCN-102S , EOCN-103S, EOCN-104S, EOCN-1020, XD-1000, NC-3000, (trade name; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-315 , EHPE-3150CE (trade name; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-901, EX-810, EX-830, EX-851, EX-611, EX-512, EX-421, EX-411 , EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation).

  The content can be in a range that does not impair the effects of the present invention. The total amount of the β-hydroxyalkylamide (A), the polymer (B) containing a carboxyl group, and the polymer not containing a carboxyl group is 1 to 400 weights with respect to 100 parts by weight of the pigment in the photosensitive composition for color filters. Parts, preferably 1 to 250 parts by weight.

<Photopolymerization initiator (C) and photopolymerizable monomer (D)>
The photopolymerization initiator (C) of the present invention is as described above, but when used as a photosensitive composition for a color filter, a radical polymerizable photopolymerization initiator is used from the viewpoint of reactivity. It is preferable. The photopolymerization initiator (C) is preferably used in an amount of 1 to 200 parts by weight, more preferably 1 to 150 parts by weight, with respect to 100 parts by weight of the pigment in the color filter photosensitive composition.

  The photopolymerizable monomer (D) of the present invention is as described above, but when used as a color filter photosensitive composition, it is a radical polymerizable photopolymerizable monomer from the viewpoint of reactivity. It is preferable to use a monomer. The photopolymerizable monomer (D) is preferably used in an amount of 10 to 300 parts by weight, more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the pigment in the photosensitive composition for color filter.

In the photosensitive composition for color filters, the ratio [Ia / M] of the weight [Ia] of the photopolymerization initiator (C) to the weight [M] of the photopolymerizable monomer (D) is 0.03 to 0.03. It is preferable that it is 1.00, and it is more preferable that it is 0.04-0.95.
Furthermore, when the photosensitive composition for color filters contains a sensitizer, the total weight [Ib] of the photopolymerization initiator (C) and the sensitizer and the weight of the photopolymerizable monomer (D) [ The ratio [Ib / M] to M] is preferably 0.04 to 1.50, more preferably 0.05 to 1.45.
When [Ia / M] is 0.03 or more and [Ib / M] is 0.04 or more, the sensitivity is high and good. Moreover, when [Ia / M] is 1.00 or less and [Ib / M] is 1.50 or less, the linearity and resolution of the pattern shape are more excellent.

<Additives>
The photosensitive composition for color filters can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol is used together with a radical polymerizable compound among the above-mentioned photopolymerization initiators (C), a thiyl radical that acts as a chain transfer agent in the radical polymerization process after light irradiation and is not easily inhibited by polymerization by oxygen. Since it generate | occur | produces, the photosensitive composition for color filters obtained becomes high sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaeryth Tallhexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- ( N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like.
These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

  The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment. By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. By using a thiol having a plurality of thiol (SH) groups, development resistance can be improved.

The photosensitive composition for color filters can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.
Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like. Or in a mixture used. Examples of the polymerization inhibitor include methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, t-butylcatechol and the like. Hydroquinone derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxyl Min such nitroso compounds and their ammonium salts or aluminum salts and the like, and used alone or in combination.

The ultraviolet absorber and the polymerization inhibitor are preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the pigment in the color filter photosensitive composition.
By using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

  The photosensitive composition for color filters can contain a storage stabilizer. As the storage stabilizer, those mentioned in the section of the coating agent for touch panel interlayer insulation film can be used.

The storage stabilizer is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the pigment in the color filter photosensitive composition.
By using 0.01 parts by weight or more of the storage stabilizer, the temporal stability of the color filter photosensitive composition is improved.

The color filter photosensitive composition preferably contains an adhesion improver such as a silane coupling agent in order to enhance adhesion to the transparent substrate. As the silane coupling agent, those described in the section of the coating agent for a touch panel interlayer insulating film can be preferably used.
The silane coupling agent is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the pigment in the color filter photosensitive composition.

The photosensitive composition for a color filter preferably contains an amine compound having a function of reducing dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Method for Producing Photosensitive Composition for Color Filter>
The photosensitive composition for color filters finely disperses pigments and dyes in a pigment carrier such as a resin and / or a solvent using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. To produce a pigment dispersion, and β-hydroxyalkylamide (A), a polymer containing a carboxyl group (B), a photopolymerization initiator (C), an organic solvent, and a photopolymerization agent as necessary. monomer (D), the sensitizer by cases, polyfunctional thiol, an ultraviolet absorber, polymerization inhibitor, a storage stabilizer, can be prepared by stirring and mixing the other ingredients. Further, the photosensitive coloring composition containing two or more kinds of pigments is obtained by mixing each pigment dispersion separately finely dispersed in a dye carrier and / or a solvent, and further adding β-hydroxyalkylamide (A), The polymer (B) containing a carboxyl group, a photopolymerization initiator (C), an organic solvent , and a photopolymerizable monomer (D) as necessary can be mixed and stirred.
You may use (beta) -hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group as a pigment | dye carrier at the time of manufacturing a pigment dispersion.

When the pigment is dispersed in a dye carrier such as a resin and / or a solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, the photosensitivity for a color filter formed by dispersing the pigment in a resin and / or solvent using the dispersion aid. When the composition is used, a color filter having excellent transparency can be obtained.
The dispersion aid is preferably used in an amount of 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and acts to stabilize the dispersion of the pigment on the dye carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Ethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as nolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

  The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

The photosensitive composition for a color filter can be prepared in the form of a solvent development type or alkali development type colored resist material. The colored resist material comprises β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, a photopolymerization initiator (C), an organic solvent, and a photopolymerizable monomer ( if necessary) A pigment is dispersed in a composition containing D) .

  The photosensitive coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

<Color filter manufacturing method>
Next, a method for producing a color filter using the color filter photosensitive composition will be described.
The color filter includes a filter segment or a black matrix formed from a photosensitive composition for a color filter on a transparent substrate, and a general color filter includes at least one red filter segment and at least one green filter. A segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. Although the heating conditions can also be changed depending on the types of components used in the photosensitive composition for color filters, the addition amount (blending amount), etc., the temperature is usually in the range of 50 to 300 ° C. Heat curing is preferably performed under a condition of 10 to 10 hours, and more preferably a temperature of 100 to 250 ° C. and a heat curing condition of 0.5 to 5.0 hours.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the photosensitive film composition for color filters prepared as a solvent development type or alkali development type colored resist material has a dry film thickness on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 0.2-10 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than printing methods such as a screen printing method, an offset printing method, and a gravure printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, after applying and drying the photosensitive composition for color filter, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. Ultraviolet exposure can also be performed after forming a film.

<< Photosensitive solder resist ink >>
Since the photosensitive composition of this invention can form the film | membrane and pattern excellent in heat resistance and chemical resistance as above-mentioned, it can also be used as a photosensitive soldering resist ink. Hereinafter, the photosensitive solder resist ink will be described.

The photosensitive solder resist ink is unnecessary in the soldering process performed when protecting the wiring (circuit) pattern formed on the substrate from the external environment or mounting the electronic component on the printed wiring board. It is provided in order to protect the solder from adhering to the portion. The photosensitive solder resist ink contains the photosensitive composition of the present invention as an essential component, so that it is a cured coating obtained through photosensitivity to active energy rays, developability to dilute alkaline aqueous solution, and post-curing (post-cure) process. The required characteristics such as flexibility, insulation, adhesion, solder heat resistance, coating film resistance, and flame resistance of the film can be satisfied.

<Flame Retardant>
Since the photosensitive solder resist ink is required to have flame retardancy, it contains the photosensitive composition of the present invention and a flame retardant. Below, the flame retardant preferably used for photosensitive solder resist ink is demonstrated.

Examples of the flame retardant include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate. Phosphate compounds and polyphosphate compounds, red phosphorus, organophosphate compounds, phosphazene compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, Phosphinic acid compounds such as aluminum methylbutylphosphinate and aluminum aluminum phosphinate, phosphine oxide compounds, phosphorane compounds, phosphoramidation Phosphorus-based flame retardants such things;
Nitrogen-based flame retardants such as melamine, melam, melem, melon, melamine cyanurate and other triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea;
Silicon-based flame retardants such as silicone compounds and silane compounds;
Halogenated flame retardants such as halogenated bisphenol A, halogenated epoxy compounds, halogenated phenoxy compounds and other low molecular halogen-containing compounds, halogenated oligomers and polymers; aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydroxylated Metal hydroxides such as barium and calcium hydroxide;
Inorganic flame retardants such as tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, hydrated glass, etc. Is mentioned.

In view of the environmental impact, which has been taken in recent years, it is desirable to use non-halogen flame retardants such as phosphorus flame retardants and nitrogen flame retardants. It is preferable to use a phosphazene compound, a phosphinic acid compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, etc. that are more effective in terms of flammability. These flame retardants can be used alone or in combination.
The flame retardant is preferably 5 to 200 parts by weight and more preferably 20 to 150 parts by weight with respect to 100 parts by weight of the polymer (B) containing a carboxyl group in the photosensitive solder resist ink.

<Organic solvent>
In the case of using a photosensitive solder resist ink, as the organic solvent, those listed in the section of the coating agent for the touch panel interlayer insulating film can be used, but the coating to the substrate such as the storage process and the coating process is completed. In the meantime, since it is preferable that the solvent does not volatilize for handling, the solvent used at the time of resin synthesis and the dilution solvent at the time of ink preparation are preferably those having the above high boiling points. Of these, carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone and the like are particularly preferable. In addition, in the case of liquid resist inks, there are also two-component types that are stored in advance separately from the curing agent in consideration of storage stability and handling, and mixed with a curing agent as necessary before coating. is there. In the case of the present invention, it can also be used as a two-component type, for example, by storing separately from the others as necessary.
On the other hand, when used as a dry film type photosensitive solder resist, first, after coating a photosensitive composition dissolved in a solvent on a film substrate with good releasability such as a separate film, by drying the solvent, Create a dry film resist. In this case, unlike the above-described photosensitive solder resist ink, the solvent to be used is preferably a low boiling point solvent because it is necessary to dry the solvent completely in a short time. For example, it is particularly preferable to use methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol, or the like.
The organic solvent can be used in an amount of 100 to 1000 parts by weight with respect to 100 parts by weight of the total solid content in the photosensitive solder resist ink.

<Β-Hydroxyalkylamide (A)>
The β-hydroxyalkylamide (A) of the present invention is as described above, and when used as a photosensitive solder resist ink, the flexibility of the cured coating, adhesion and solder heat resistance, coating resistance, difficulty In order to achieve both flammability, X in the general formula (1) is preferably a hydrocarbon group having 6 or more carbon atoms.

<Polymer containing carboxyl group (B)>
The carboxyl group-containing polymer (B) of the present invention is as described above, but when used as a photosensitive solder resist ink, it satisfies photosensitivity to active energy rays and developability to dilute alkaline aqueous solution. Therefore, it is preferable to use a polymer containing a carboxyl group containing a photopolymerizable functional group. More preferably, a polymer having a double bond equivalent of 200 to 5000 g / eq and an acid value of 10 to 200 mgKOH / g is preferably used. Specifically, (meth) acrylic copolymers as described in the section of the coating agent for touch panel interlayer insulation film can be used, but urethane resin, addition type ester resin, phenoxy resin, etc. are used. You can also

(Urethane resin containing a carboxyl group) As a method for obtaining a urethane resin containing a carboxyl group, for example, a compound having two hydroxyl groups in the molecule, a carboxylic acid compound having two hydroxyl groups in the molecule, There is a method of reacting with a diisocyanate compound.
Moreover, as a method for obtaining a urethane resin containing a photopolymerizable functional group and a carboxyl group, there are the methods (B-1) and (B-2) described above.
(B-19) a method of reacting a part of the carboxyl group in the carboxyl group-containing urethane resin with the epoxy group in the (meth) acrylate containing an epoxy group;
(B-20) The hydroxyl group in the hydroxyl group-containing urethane resin produced after reacting part or all of the carboxyl group in the carboxyl group-containing urethane resin with the epoxy group in the (meth) acrylate containing the epoxy group And a method of reacting with a polybasic acid anhydride.

The compound having two hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two hydroxyl groups in the molecule, but has a repeating unit having a polymerization degree of 2 or more in its structure (polyol compound). And those that do not have (diol compounds).

Examples of the polyol compound include polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol Polyether polyols such as
A polyester polyol which is a condensate of a polyhydric alcohol or polyether polyol and a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
A polycarbonate polyol obtained by a reaction of glycol or bisphenol with a carbonic acid ester or a reaction of phosgene with glycol or bisphenol in the presence of an alkali;
Examples include caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin-based polyol, polybutadiene-based polyol such as hydrogenated polybutadiene polyol, and silicone-based polyol.
Of these, polyether polyols are preferred from the viewpoints of developability for dilute alkaline aqueous solutions and flexibility of the cured coating film.

Examples of the diol compound include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1 , 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1 , 8-octanediol, 3,3′-dimethylolheptane, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pen Tandiol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, cyclohexane Aliphatic or alicyclic diols such as diol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol, hydrogenated bisphenol A, spiroglycol and the like;
1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4, 4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropylidenephenol, 1,2-indanediol, 1,3 -Naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol, 9,9'-bis (4-hydroxyphenyl) fluorene, 9,9'-bis (3-methyl-4-hydroxyphenyl) fluorene, etc. Aromatic diols and the like.
Other examples include phosphorus atom-containing diols, sulfur atom-containing diols, bromine atom-containing diols, and fluorine atom-containing diols.

The carboxylic acid compound having two hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two hydroxyl groups and one or more carboxyl groups in the molecule. For example, dimethylol butanoic acid, dimethylol Propionic acid and derivatives thereof (caprolactone adduct, ethylene oxide adduct, propylene oxide adduct, etc.), 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4-cyclohexanedimethanol Etc.
Among these, dimethylolbutanoic acid and dimethylolpropionic acid are preferable in the present invention in that the concentration of carboxyl groups in the resin can be increased.

Examples of the diisocyanate compound include aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and the like.

(Addition type ester resin containing carboxyl group) As a method for obtaining an addition type ester resin containing a carboxyl group, for example, a compound having two carboxyl groups in the molecule and two epoxy groups in the molecule are used. There is a method of synthesizing a side chain hydroxyl group-containing addition-type ester resin by reacting with a compound having, and then modifying the hydroxyl group to a carboxyl group with a polybasic acid anhydride. Moreover, as a method for obtaining an addition-type ester resin containing a photopolymerizable functional group and a carboxyl group, there are methods (B-1) and (B-2) described above.
(B-21) A method of reacting a part of the carboxyl group in the carboxyl group-containing addition-type ester resin with the epoxy group in the (meth) acrylate containing an epoxy group;
(B-22) A hydroxyl group-containing addition-type ester resin produced after reacting a part or all of the carboxyl groups in a carboxyl group-containing addition-type ester resin with an epoxy group in a (meth) acrylate containing an epoxy group. And a method of reacting a hydroxyl group therein with a polybasic acid anhydride.

The compound having two carboxyl groups in the molecule is not particularly limited as long as it is a compound having two carboxyl groups in the molecule, and the compounds listed above for (a-1) divalent or higher carboxylic acids, etc. Is mentioned.

The compound having two epoxy groups in the molecule is not particularly limited as long as it is a compound having two epoxy groups in the molecule. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichloro Hydrine type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexa Hydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type e Xy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol full orange glycidyl ether 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, JP 2004-156024 A, JP 2004-315595 A, An epoxy compound excellent in flexibility disclosed in JP-A No. 2004-323777 and represented by the following formulas (12) to (14) And an epoxy compound having a structure as described above.

Formula (12)

Formula (13)

Formula (14)

Among them, 1,6-hexanediol diglycidyl ether is preferable from the viewpoint of flexibility of the cured coating film, and bisphenol A / epichlorohydrin type epoxy resin is preferable from the viewpoint of heat resistance of the cured coating film. These can be selected according to the purpose, and may be used alone or in combination.

(Phenoxy resin containing carboxyl group)
As a method for obtaining a phenoxy resin containing a carboxyl group, for example, a compound having two phenolic hydroxyl groups in the molecule and a compound having two epoxy groups in the molecule are reacted to form a side chain hydroxyl group-containing phenoxy. There is a method of modifying a hydroxyl group to a carboxyl group with a polybasic acid anhydride after synthesizing the resin.
In addition, as a method for obtaining an addition-type ester resin containing a photopolymerizable functional group and a carboxyl group, there is the method (B-1) or (B-2) described above.
(B-23) A method in which a part of the carboxyl group in the carboxyl group-containing phenoxy resin is reacted with the epoxy group in the (meth) acrylate containing an epoxy group;
(B-24) After reacting a part or all of the carboxyl groups in the carboxyl group-containing phenoxy resin with the epoxy groups in the (meth) acrylate containing an epoxy group, And a method of reacting with a polybasic acid anhydride.

The compound having two phenolic hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two phenolic hydroxyl groups in the molecule. For example, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is a representative example.
Bisphenols in which a hydrogen atom is bonded to a central carbon such as bis (4-hydroxyphenol) methane (also known as bisphenol F);
Bisphenols in which one methyl group is bonded to the central carbon such as 2,2-bis (4-hydroxyphenyl) -n-butane;
Bisphenols in which two methyl groups are bonded to a central carbon such as 2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly called bisphenol C);
Bisphenols which are diphenylmethane derivatives such as bis (4-hydroxyphenyl) -1,1-diphenylmethane;
Bisphenols which are cyclohexane derivatives such as 1,1-bis (4-hydroxyphenyl) cyclohexane (commonly called bisphenol Z);
Bisphenols which are -3,3,5-trimethylcyclohexane derivatives such as 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane;
Bisphenols which are fluorene derivatives such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene;
Bisphenols that are cycloalkane derivatives such as 1,1-bis (4-hydroxyphenyl) -cyclopentane;
Biphenols directly linked with aromatic rings such as 4,4′-biphenol;
Bisphenols which are sulfone derivatives such as bis (4-hydroxyphenyl) sulfone;
Bisphenols having an ether bond such as bis (4-hydroxyphenyl) ether;
Bisphenols having a sulfide bond such as bis (4-hydroxyphenyl) sulfide;
Bisphenols which are sulfoxide derivatives such as bis (4-hydroxyphenyl) sulfoxide;
Bisphenols having a heteroatom-containing aliphatic ring such as phenolphthalein;
Examples thereof include bisphenols having a carbon-fluorine bond, such as 2,2-bis (4-hydroxyphenyl) hexafluoropropane.
And dihydroxybenzenes such as hydroquinone, resorcinol, catechol, methylhydroquinone;
Examples thereof include dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

  Among these, 2,2-bis (4-hydroxyphenyl) propane is preferable from the viewpoints of production cost, ease of reaction, and heat resistance of the cured coating film.

  The urethane resin containing carboxyl group, addition type ester resin, and phenoxy resin shown above are 100 parts by weight to 1000 parts by weight with respect to 100 parts by weight of β-hydroxyalkylamide (A) in the photosensitive solder resist ink. It is preferable to add at a ratio of 100 parts by weight, and it is more preferable to add at a ratio of 100 parts by weight to 500 parts by weight.

<Polymer not containing carboxyl group>
Moreover, you may use together the thermoplastic resin and thermosetting resin which do not contain a carboxyl group as needed in the range which does not impair the physical property of photosensitive soldering resist ink. Specifically, epoxy resin or blocked isocyanate is preferably used as a thermosetting resin in order to satisfy the required properties such as flexibility, insulation, adhesion, solder heat resistance, coating resistance, and flame resistance of the cured coating. A group-containing compound is used in combination.

As an epoxy resin, said epoxy resin can be used suitably. For example, when improving the adhesive strength to polyimide or copper, it is preferable to use an isocyanurate ring-containing epoxy compound such as trishydroxyethyl isocyanurate triglycidyl ether or triglycidyl isocyanurate. Moreover, when improving the heat resistance of a cured coating film, it is preferable to use polyfunctional epoxy compounds, such as a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, and a biphenol epichlorohydrin type epoxy resin.

  The blocked isocyanate group-containing compound is not particularly limited as long as the isocyanate group in the isocyanate group-containing compound is a blocked isocyanate group-containing compound protected with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol or the like. Is not to be done. For example, in order to improve storage stability, adhesion strength to polyimide and copper, and solder heat resistance, hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole may be used. preferable.

  In this case, the thermosetting resin containing no carboxyl group is 1 part by weight to 100 parts by weight of the polymer (B) containing β-hydroxyalkylamide (A) and carboxyl group in the photosensitive solder resist ink. It is preferably added at a rate of 50 parts by weight, and more preferably added at a rate of 5 to 30 parts by weight.

<Photopolymerization initiator (C) and photopolymerizable monomer (D)>
The photopolymerization initiator (C) is as described above, but when used as a photosensitive solder resist ink, it is preferable to use a radical polymerizable photopolymerization initiator from the viewpoint of reactivity. The photopolymerization initiator (C) is preferably added in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the solid content in the photosensitive solder resist ink.
Moreover, a well-known organic amine can also be added as a sensitizer. It is preferably used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerizable initiator (C).

  The photopolymerizable monomer (D) is as described above, but when used as a photosensitive solder resist ink, use a radical polymerizable photopolymerizable monomer from the viewpoint of reactivity. Is preferred. 10-1000 weight part is preferable with respect to a total of 100 weight part of (B) -hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group, More preferably, it is 50-800 weight part.

<Additives> Adhesion improvers such as dyes, pigments, storage stabilizers, silane coupling agents and the like can be further added as optional components to the photosensitive resin composition as long as the purpose is not impaired. As these, those described in the section of the above-mentioned photosensitive composition for color filter and coating agent for touch panel interlayer insulating film can be preferably used.
The storage stabilizer is preferably used in an amount of 0.1 to 5 parts by weight in a total of 100 parts by weight of the photosensitive solder resist ink.

<Method for producing photosensitive solder resist ink>
Next, the manufacturing method of the photosensitive soldering resist ink of this invention is demonstrated.
The photosensitive solder resist ink is finely divided by using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor in a polymer (B) solution containing a carboxyl group. A dispersion is produced by dispersion, and β-hydroxyalkylamide (A), a photopolymerization initiator (C), an organic solvent, a polymer not containing a carboxyl group as necessary, a photopolymerizable monomer (D), the sensitizer by cases, a polymerization inhibitor, a storage stabilizer, can be prepared by stirring and mixing the other ingredients.

It is preferable that the photosensitive solder resist ink removes coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and mixed dust and foreign matters by means of centrifugal separation, sintered filter, membrane filter and the like. Thereby, the required characteristics, such as high photosensitivity requested | required of the photosensitive soldering resist, the flexibility of a cured coating film, bendability, insulation, and a flame retardance, can be satisfy | filled.
The photosensitive solder resist ink having the above composition is used by adjusting the solution to a viscosity suitable for each coating method as required and applying the solution to a printed wiring board on which a circuit is formed.
Examples of the coating method include dipping, spraying, spin coater, roll coater, curtain coater, and screen printing.

<Dry film type photosensitive solder resist>
Next, the dry film type photosensitive solder resist will be described.
The dry film type photosensitive solder resist can be prepared by applying the above photosensitive solder resist ink on a separate film and then drying the solvent.

  The coating method on the separate film is not particularly limited, and examples thereof include dipping method, spray, spin coater, roll coater, curtain coater, or screen printing, and the solution is adjusted to a viscosity suitable for the coating method. It is applied to a printed wiring board on which a circuit is formed.

The dry film produced on the separate film is bonded to a copper circuit or the like formed on the polyimide, and thereafter, bubbles and the like are removed and adhered to the circuit by lamination or vacuum lamination. After this pasting step, there may be a case where the radiation curing is performed through a separate film, or a case where the development pattern is brought into contact after the separation film is peeled to perform the radiation curing. When radiation curing is performed by bringing the development pattern into contact, if the dry film has tack, the development pattern may be contaminated. Therefore, a dry film type photosensitive solder resist that requires less dry film tack is required. Is done.

For the radiation curing, a known radiation curing method can be used. For example, an electron beam, ultraviolet rays, or visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) for ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

  Furthermore, the dry film type photosensitive solder resist forms a pattern by developing after radiation curing, and forms a film having excellent resistance by thermosetting as post-cure. The post cure is preferably 30 to 2 hours at 100 to 200 ° C. Further, in order to further improve the resistance of the coating film, radiation irradiation can be performed as necessary even after the post cure. By performing radiation irradiation after post cure, solder heat resistance and the like can be further improved.

<< Other uses >>
The use of the photosensitive composition of the present invention is not particularly limited. In addition to the touch panel interlayer insulating film, color filter, black matrix, and photosensitive solder resist described above, a color filter protective film, a photo spacer, and a liquid crystal It can be used to produce alignment protrusions, microlenses, optical hard coats, UV inks, photosensitive lithographic printing plates, various coatings, and the like.
Further, it can also be used for reinforcing plate adhesives, interlayer adhesives, coating agents, electromagnetic wave shielding adhesives, photosensitive optical waveguides, photothermal dual-curing potting agents and the like used for flexible printed wiring boards.

  The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”. In the following examples, the molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

All NMR measurements in the examples were performed in DMSO-d6 using 1H-NMR measurement using JNM-ECX400P manufactured by JEOL. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values in terms of polystyrene measured by GPC-8020 manufactured by Tosoh Corporation.

  All IR measurements in the examples were performed using Spectrum One manufactured by PerkinElmer.

<< Synthesis of β-hydroxyalkylamide (A) >>
Synthesis example 1
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was carried out, and the integration ratio of the methylene group of the ester bond (near δ = 4.1) and the methyl group derived from 2-ethylhexanoic acid (near δ = 0.85) was 2: 6. From this, it was confirmed that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A1 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A2 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 3
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 216 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A3 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 4
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 288 parts of 2-ethylhexanoic acid was dripped in this over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A4 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 5
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 72 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A5 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 6
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. A mixture of 320 parts of this product and 83 parts of isophthalic acid was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A6 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 7
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 266 parts of diisopropanolamine, 10 parts of potassium hydroxide and 202 parts of sebacic acid were placed at 120 ° C. for 4 hours. Heated. 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 433 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 72 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A7 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 8
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, 210 parts of diethanolamine and 10 parts of sodium methoxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 230 parts of dimethyl sebacates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was carried out, and the integration ratio of the methylene group of the ester bond (near δ = 4.1) and the methyl group derived from 2-ethylhexanoic acid (near δ = 0.85) was 2: 6. From this, it was confirmed that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A8 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 9
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 266 parts of diisopropanolamine, 10 parts of potassium hydroxide and 202 parts of sebacic acid were placed at 120 ° C. for 4 hours. Heated. 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 433 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 211 parts of lauryl isocyanate was dripped over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A9 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 10
In a reaction vessel equipped with a stirrer, thermometer, dripping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of 2-amino-2-methyl-1,3-propanediol and 10 parts of potassium hydroxide are placed. After heating to 60 ° C., 100 parts of succinic anhydride was added little by little over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 260 parts of this product was placed in the reaction vessel again and melted by heating to 150 ° C. In this, 89 parts of phenyl isocyanate was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A10 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 11
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 242 parts of tris (hydroxymethyl) aminomethane, 10 parts of potassium hydroxide, 2,4-diethylglutaric acid 188 A portion was added and heated at 120 ° C. for 4 hours. 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 394 parts of this product, 396 parts of pyridine, and 2674 parts of dichloromethane were again placed in the reaction vessel and cooled on ice. In this, 547 parts of lauroyl chloride was dripped from the dripping apparatus over 1 hour. After dropping, the reaction was completed by stirring at 25 ° C. for 5 hours. The dichloromethane solution was washed with 2000 parts of 10% hydrochloric acid, 2000 parts of a saturated aqueous sodium hydrogen carbonate solution and 2000 parts of saturated brine, and then dried over anhydrous magnesium sulfate. After removing the solvent dichloromethane with a rotary evaporator, 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A11 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 12
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 334 parts of 2-amino-1-phenyl-1,3-propanediol and 10 parts of potassium hydroxide are placed. After heating to 60 ° C., 98 parts of maleic anhydride was added little by little over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 414 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 284 parts of isostearic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A12 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 13
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide are placed, heated to 60 ° C., and then 148 parts of phthalic anhydride. Was added in portions over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 340 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 88 parts of butyric acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A13 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 14
266 parts of diisopropanolamine, 10 parts of potassium hydroxide, and 166 parts of isophthalic acid are placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube at 120 ° C. for 4 hours. Heated. 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 396 parts of this product, 285 parts of pyridine, and 1802 parts of dichloromethane were placed in the reaction vessel again and cooled on ice. In this, 184 parts of acetic anhydride was dripped from the dripping apparatus over 1 hour. After dropping, the reaction was completed by stirring at 25 ° C. for 5 hours. The dichloromethane solution was washed with 2000 parts of 10% hydrochloric acid, 2000 parts of a saturated aqueous sodium hydrogen carbonate solution and 2000 parts of saturated brine, and then dried over anhydrous magnesium sulfate. After removing the solvent dichloromethane with a rotary evaporator, 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A14 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 15
A reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube was charged with 203 parts of terephthalic acid dichloride, 316 parts of pyridine, and 1459 parts of dichloromethane and stirred on ice. 210 parts of diethanolamine was added dropwise from the dropping device over 2 hours. Then, it stirred at 25 degreeC for 5 hours, and reaction was completed. The dichloromethane solution was washed with 2000 parts of 10% hydrochloric acid, 2000 parts of a saturated aqueous sodium hydrogen carbonate solution and 2000 parts of saturated brine, and then dried over anhydrous magnesium sulfate. The dichloromethane of the solvent was removed with a rotary evaporator, and the product was recovered. 340 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 284 parts of stearic acid was added over 1 hour. After stirring at 150 ° C. for 1 hour, 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A15 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 16
Into a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 363 parts of tris (hydroxymethyl) aminomethane and 10 parts of potassium hydroxide were placed and heated to 60 ° C. 192 parts of trimellitic anhydride were added in portions over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 520 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. To this, 1795 parts of palmitic acid was added over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A16 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 17
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 469 parts of N-butylethanolamine, 10 parts of potassium hydroxide, 1,2,3,4-butanetetra After charging 234 parts of carboxylic acid and heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, and the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 631 parts of this product was again put into the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 122 parts of benzoic acid was added over 1 hour. After stirring at 150 ° C. for 1 hour, 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A17 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 18
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 357 parts of N-ethylethanolamine and 10 parts of potassium hydroxide are placed, heated to 60 ° C. and then anhydrous. 218 parts of pyromellitic acid was added in portions over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 539 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. To this, 178 parts of 4-tert-butylbenzoic acid was added over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A18 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 19
In a reaction vessel equipped with a stirrer, thermometer, dripping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 533 parts of diisopropanolamine and 10 parts of potassium hydroxide are placed, heated to 60 ° C., and then 3 or 3 294 parts of ', 4,4'-biphenyltetracarboxylic anhydride were added in portions over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 791 parts of this product was placed in the reaction vessel again and melted by heating to 150 ° C. with stirring. To this, 513 parts of cyclohexanecarboxylic acid was added over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A19 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 20
A reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube was charged with 315 parts of diethanolamine, 10 parts of potassium hydroxide, and 192 parts of citric acid, and the temperature was raised to 120 ° C. 4 After heating for 100 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 453 parts of this product, 316 parts of pyridine, and 2429 parts of dichloromethane were placed in the reaction vessel again and cooled on ice. Into this, 445 parts of trimethylsilyl trifluoromethanesulfonate was dropped from a dropping device over 1 hour. After dropping, the reaction was completed by stirring at 25 ° C. for 5 hours. The dichloromethane solution was washed with 2000 parts of 10% hydrochloric acid, 2000 parts of a saturated aqueous sodium hydrogen carbonate solution and 2000 parts of saturated brine, and then dried over anhydrous magnesium sulfate. After removing the solvent dichloromethane with a rotary evaporator, 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A20 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 21
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, 703 parts of 2-amino-4-methyl-1-pentanol, 10 parts of potassium hydroxide, cyclohexane-1 , 2,3,4,5,6-hexacarboxylic acid 348 parts, heated to 120 ° C. and heated for 4 hours, 500 parts toluene was added, the Dean-Stark tube was filled with toluene, and azeotroped with toluene The generated water was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 943 parts of this product, 373 parts of 2-ethylhexyl glycidyl ether, and 20 parts of zinc tetrafluoroborate were added and reacted at 100 ° C. for 6 hours. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A21 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 22
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried.
In a second reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 130 parts of 2-ethylhexanol, 228 parts of ε-caprolactone and 0.1 part of tetrabutyl titanate were added. The reaction was further carried out at 160 ° C. for 8 hours. Thereafter, 100 parts of succinic anhydride was added, and the mixture was further reacted for 3 hours. 320 parts of the above slurry product was added to the second reaction vessel and reacted at 150 ° C. for 2 hours. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A22 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 23
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. A mixture of 144 parts of 2-ethylhexanoic acid, 270 parts of 2-acryloyloxyethyl hexahydrophthalate (light acrylate HOA-HH manufactured by Kyoeisha Chemical Co., Ltd.), and 0.4 part of methoquinone was added to the dropping apparatus while blowing dry air. From about 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A23 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 24
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 119 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic-N), 2-acryloyloxyethyl succinic acid (HO-MS, Kyoeisha Chemical Co., Ltd.) A mixture of 173 parts and methoquinone 0.3 part was added dropwise from a dropping device over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A24 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 25
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 133 parts of Ricacid DDSA (manufactured by Shin Nippon Chemical Co., Ltd.) was dropped into the reactor over 1 hour. After the dropping, a mixture of 78 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was added dropwise over 1 hour from the dropping device. After dropping, the mixture was stirred at 150 ° C. for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A25 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 26
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 361 parts of n-octanoic acid was dripped over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. A mixture of 636 parts of this liquid product, 49 parts of maleic anhydride, 4 parts of dimethylbenzylamine and 0.4 part of methoquinone was heated again to 100 ° C. while blowing dry air and stirred for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A26 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 27
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. To 447 parts of this liquid product, a mixture of 141 parts of 2-acryloyloxyethyl isocyanate (Karenz AOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was dropped from a dropping device over 1 hour. It stirred at 100 degreeC after dripping for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A27 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 28
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 158 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic-N) was added dropwise from the dropping device over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off.
In a second reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, gas introduction tube, 222 parts of isophorone diisocyanate, 116 parts of 2-hydroxyethyl acrylate, 0.1 part of tetrabutyl titanate The reaction was carried out at 60 ° C. for 8 hours while blowing dry air. 461 parts of the above slurry product was added to the second reaction vessel and reacted at 60 ° C. for 8 hours. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A28 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 29
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 266 parts of diisopropanolamine and 10 parts of potassium hydroxide are placed, heated to 60 ° C., and then 4-cyclohexene. 152 parts of -1,2-dicarboxylic anhydride were added in portions over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 401 parts of this product was placed in the reaction vessel again and melted by heating to 150 ° C. with stirring. In this, 282 parts of oleic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A29 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 30
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 60 ° C., and then cyclohexane-1,2 -154 parts of dicarboxylic anhydride were added in portions over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 346 parts of this product was placed in the reaction vessel again and melted by heating to 150 ° C. with stirring. In this, 280 parts of linoleic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A30 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 31
A reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube was charged with 400 parts of diisopropanolamine, 10 parts of potassium hydroxide, and 176 parts of tricarballylic acid, and the temperature was raised to 120 ° C. After heating and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 522 parts of this product was again put into the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 557 parts of linolenic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, and 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A31 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 32
A reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube was charged with 210 parts of diethanolamine, 10 parts of potassium hydroxide, and 561 parts of dimer acid, and the temperature was raised to 120 ° C. After heating for 100 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 735 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. To this, 138 parts of norbornene carboxylic acid was added over 1 hour. After stirring at 150 ° C. for 1 hour, the temperature was lowered to 60 ° C. and 1H-NMR measurement was performed to confirm that the desired product was produced. Further, the structure was confirmed by IR. Cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A32 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 33
After putting 421 parts of 2-amino-1-butanol and 10 parts of potassium hydroxide into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, and heating to 60 ° C. 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride 322 parts was added in portions over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 707 parts of this product, 152 parts of N-methylolacrylamide, 2 parts of ammonium p-toluenesulfonate, and 2 parts of p-methoxyphenol were added and stirred at 100 ° C. for 6 hours, followed by 1H-NMR measurement to obtain the desired product. Was confirmed to be generated. Further, the structure was confirmed by IR. The temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A33 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

<< Synthesis of Polymer (B) Containing Carboxyl Group >>
Synthesis Example 34
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 20 parts of methacrylic acid at the same temperature, A mixture of 10 parts of methyl methacrylate, 55 parts of n-butyl methacrylate, 15 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of dropping, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. Got. After cooling to room temperature, a polymer solution P-1 containing a carboxyl group not containing a photopolymerizable functional group having a solid content of 20% was obtained by diluting with cyclohexanone. The weight average molecular weight was 40,000.

Synthesis Example 35
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 25 parts of methacrylic acid at the same temperature, A mixture of 20 parts of 2-hydroxyethyl methacrylate, 30 parts of methyl methacrylate, 25 parts of styrene and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, the temperature of the reaction vessel was cooled to 70 ° C., and dry air was further introduced into the reaction vessel, and 24 parts of 2-methacryloyloxyethyl isocyanate, 36 parts of cyclohexanone, 0.1 part of dibutyltin dilaurate, 0.1 part of methoquinone 0.1 Then, stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the polymer solution P-2 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group was obtained by diluting with cyclohexanone. The weight average molecular weight was 42,000.

Synthesis Example 36
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 40 parts of methacrylic acid at the same temperature, A mixture of 25 parts of methyl methacrylate, 12.5 parts of styrene, 17.5 parts of n-butyl methacrylate, 5 parts of 2-methoxyethyl acrylate, and 4 parts of 2,2′-azobisisobutyronitrile is added dropwise over 1 hour. The polymerization reaction was carried out. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 25 parts of glycidyl methacrylate, 37 parts of cyclohexanone, 1 part of dimethylbenzylamine, and 0.1 part of methoquinone were charged, and stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the polymer solution P-3 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group was obtained by diluting with cyclohexanone. The weight average molecular weight was 41000.

Synthesis Example 37
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 74 parts of glycidyl methacrylate at the same temperature, A mixture of 11 parts of methyl methacrylate, 7.5 parts of n-butyl methacrylate, 7.5 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 37.5 parts of acrylic acid, 56 parts of cyclohexanone, 1 part of dimethylbenzylamine and 0.1 part of methoquinone were charged, and stirring was continued for 10 hours at the same temperature. Further, 52 parts of succinic anhydride was charged, and stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the polymer solution P-4 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group was obtained by diluting with cyclohexanone. The weight average molecular weight was 44,000.

Synthesis Example 38
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 13,000 and an actually measured resin solid acid value of 98 mgKOH / g.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-reduced weight average molecular weight of 14800 and an actually measured resin solid acid value of 8 mgKOH / g. Next, 63 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. By diluting with cyclohexanone, a polymer solution P-5 containing a urethane resin containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group was obtained. The weight average molecular weight was 15400.

Synthesis Example 39
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 40.08 parts of PEG # 250 (manufactured by NOF Corporation, ethylene glycol), Ricacid TH (Nippon Nippon Chemical Co., Ltd.) Made of tetrahydrophthalic anhydride), 1.66 parts of triphenylphosphine, 1.66 parts of N, N-dimethylbenzylamine as a catalyst, and 100 parts of cyclohexanone as a solvent. The temperature was raised to ° C. and reacted for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, 65.14 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) and 65 parts of cyclohexanone are charged into this flask, and the temperature is raised to 110 ° C. with stirring in a nitrogen stream for 8 hours. I let you. Next, 57.94 parts of Ricacid TH (manufactured by Shin Nippon Rika Co., Ltd., tetrahydrophthalic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air, while stirring, 27.05 parts of Bremmer G (manufactured by NOF Corporation, glycidyl methacrylate), and hydroquinone as a polymerization inhibitor in an amount of 0. 13 parts was added and reacted at 80 ° C. for 8 hours. After cooling to room temperature, by diluting with cyclohexanone, a polymer solution P-6 containing an addition-type ester resin containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group was obtained. The weight average molecular weight was 14500.

Synthesis Example 40
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 64.8 parts of bisphenol A, 57.1 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether) 128.1 parts, 1.25 parts triphenylphosphine as catalyst, 1.25 parts N, N-dimethylbenzylamine, 250 parts cyclohexanone as solvent The mixture was heated to 110 ° C. with stirring under a nitrogen stream and reacted for 8 hours to obtain a hydroxyl group-containing resin. Next, 54.6 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 55.2 parts of Bremmer G (manufactured by NOF Corporation: glycidyl methacrylate), hydroquinone as a polymerization inhibitor 18 parts were added and reacted at 80 ° C. for 8 hours. After cooling to room temperature, it was diluted with cyclohexanone to obtain a polymer solution P-7 containing a photopolymerizable functional group having a solid content of 20% and a phenoxy resin containing a carboxyl group. The weight average molecular weight was 25100.

Comparative Synthesis Example 1
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dripping device, reflux condenser, and gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature 2-hydroxyethyl methacrylate A mixture of 55.5 parts, 10 parts of methyl methacrylate, 19.5 parts of n-butyl methacrylate, 15 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. After completion of dropping, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. Got. After cooling to room temperature, the solution was diluted with cyclohexanone to obtain a polymer solution P-8 containing a hydroxyl group having a solid content of 20%. The weight average molecular weight was 38000.

<Coating agent for touch panel interlayer insulation film>
[Examples 1 to 21 , Comparative Examples 1 to 7]
The compositions shown in Tables 1 and 2 and the mixture of the blended amounts were stirred and mixed so as to be uniform, and then filtered through a 1 μm filter, and the photosensitive properties corresponding to Examples 1 to 21 and Comparative Examples 1 to 7, respectively. A composition was obtained.
In Table 1 and Table 2, the amount of A1 to 31 and P-1 to P-8 is the value of the solution.

Abbreviations in Tables 1 and 2 are shown below.
Photopolymerizable monomer (D)
V # 802: Biscoat # 802 (manufactured by Osaka Organic Chemical Co., Ltd.) Mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate M402: Aronix M-402 (manufactured by Toa Gosei Co., Ltd.) Dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate Photopolymerization initiator (C): Irgacure OXE-01 (manufactured by Ciba Japan) 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
Silane coupling agent: KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3-mercaptopropyltrimethoxysilane filler: PMA-ST (manufactured by Nissan Chemical Co., Ltd.) Propylene glycol monomethyl ether acetate dispersion of silicon oxide fine particles (solid content 30) %)
PGMAc: Propylene glycol monomethyl ether acetate MEK: Methyl ethyl ketone IPA: isopropanol
Its other resins XD-1000: manufactured by Nippon Kayaku Co., Ltd. dicyclopentanyl skeleton-containing novolak epoxy resin BL3175: SUMIDUR BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd.) blocked isocyanate isocyanurate type MEK oxime-blocked DBU: 1. 8-Diazabicyclo [5.4.0] undec-7-ene

  The obtained photosensitive composition was used as a coating agent for a touch panel interlayer insulating film, and the transparency, chemical resistance, hardness, adhesion, insulation, patterning suitability, and storage stability over time were evaluated by the following methods. The results are shown in Tables 3 and 4.

[Measurement of transmittance]
The photosensitive compositions of Examples 1 to 21 and Comparative Examples 1 to 7 were heated at 150 ° C. for 20 minutes using a spin coater on a 100 mm × 100 mm, 0.7 mm thick glass substrate (Corning Glass Eagle 2000). A substrate coated so as to have a finished film thickness of 2.0 μm was obtained. Next, after drying under reduced pressure, UV exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . The coated substrate was heated at 230 ° C. for 20 minutes and allowed to cool, and then the transmittance at a wavelength of 400 nm of the obtained coating film was determined using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).
○: Transmittance 97% or more: Good level Δ; Transmittance 95% or more and less than 97%: Inferior to ○, but practical level ×; Transmittance less than 95%: Level not suitable for practical use

[Evaluation of chemical resistance]
The thickness of the substrate obtained by the same method as that prepared for measuring transmittance was measured. The substrate was immersed in aqua regia (nitric acid: hydrochloric acid = 1/3) for 5 minutes at room temperature, then washed with ion-exchanged water and air-dried. Thereafter, the substrate was visually observed and the film thickness was measured, and the change rate of the film thickness was calculated. The film thickness was measured with a stylus type film thickness meter DEKTAK-3 manufactured by ULVAC. The rank of evaluation is as follows.
○: Appearance and color are not changed, and the absolute value of the film thickness change rate is less than 5%
: Good level Δ: No change in appearance and color, and the absolute value of the rate of change in film thickness is 5% to less than 10%
: Inferior to ○, but practical level ×: Appearance, color change, and / or thickness change rate absolute value is 10% or more
: Level not suitable for practical use

[Measurement of pencil hardness]
About the board | substrate obtained by the same method as what was produced for the measurement of the transmittance | permeability, the surface hardness of the insulating film was measured by the scratch hardness (pencil method) test according to JISK5600-5-4.
○: 4H or more: good level Δ; 3H: minimum practical hardness x; 2H or less: level not suitable for practical use

[Measurement of adhesion to glass]
About the substrate obtained by the same method as that prepared for the measurement of the transmittance, the adhesion of the coating film was evaluated by an adhesion (cross-cut method) test according to JIS K5600-5-6. The number of peeled pieces was counted.
○: Number of cross-cuts peeled less than 2: Good level Δ; Number of cross-cuts peeled 2 or more and 10 or less: Inferior to ○, but practical level ×; Number of cross-cuts peeled over 10: Level not suitable for practical use

[Insulation evaluation]
About the board | substrate obtained by the same method as what was produced for the measurement of the transmittance | permeability, the surface resistance value was measured with the digital ultrahigh resistance / micro ammeter R8340A (Daiichi Kagaku company make, probe URS, applied voltage 5V). .
○: 1 × 10 ^{12 to} 3 × 10 ¹⁶ Ω / □
×: Less than 1 × 10 ¹² Ω / □

[Sensitivity at the time of patterning]
After coating the photosensitive compositions of Examples 1 to 21 and Comparative Examples 1 to 7 on a 10 cm × 10 cm glass substrate by spin coating, the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven, A coating film of about 2 μm was obtained. Next, after cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask having a stripe pattern of 100 μm width (pitch: 200 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 150 ° C. for 30 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive composition, and this was set as an appropriate development time. The film thickness of the coating film is Dektak
3030 (manufactured by Nippon Vacuum Technology Co., Ltd.) was used. The pattern film thickness at the formed 100 μm photomask portion was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure amount, the higher the sensitivity and the better the photosensitive composition. The rank of evaluation is as follows.
○: Less than 50 mJ / cm ² : Good level Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² : Inferior to ○, but practical level ×: 100 mJ / cm ² or more: Level not suitable for practical use

[Storage stability evaluation]
The photosensitive compositions of Examples 1 to 21 and Comparative Examples 1 to 7 were evaluated by measuring the initial viscosity and the viscosity after one month at room temperature, and calculating the degree of increase in viscosity relative to the initial viscosity. The rank of evaluation is as follows.
○: Viscosity increase ratio is less than 5%, good: Good level Δ: Viscosity increase ratio is 5% or more and less than 10%: Inferior to ○, but practical level ×: Viscosity increase ratio is 10% Above: Level not suitable for practical use

As shown in Tables 3 and 4, all of the photosensitive compositions of Examples 1 to 21 had good transmittance, chemical resistance, pencil hardness, adhesion, insulation, patterning sensitivity, and storage stability. It was.
The photosensitive composition of Examples 1 17, for containing photopolymerizable monomer and (D), the sensitivity at the time of patterning was superior.
The photosensitive composition ratio Comparative Examples 1-7, any of the above properties become poor outcome, all is not obtained satisfy the practical level.
Since Comparative Example 1 did not contain a photopolymerizable functional group and Comparative Example 2 did not contain a photopolymerization initiator (C), patterning could not be performed. Moreover, since photocuring did not occur, the results were inferior in heat resistance and chemical resistance.
Since Comparative Example 3 did not contain a hydroxyl group having a β-hydroxyalkylamide structure, the curing reaction did not proceed, resulting in poor chemical resistance and pencil hardness. In Comparative Example 4, an epoxy resin was added instead of β-hydroxyalkylamide (A), but since there was no catalyst, thermosetting did not proceed sufficiently, resulting in poor chemical resistance and pencil hardness. In Comparative Example 5, since the catalyst was further added, the thermosetting reaction proceeded, but the storage stability was lowered. In Comparative Example 6, since blocked isocyanate was added, the deblocking agent generated during thermosetting lowered the transmittance and insulation. In Comparative Example 7, since the polymer (B) containing a carboxyl group was not included, patterning was not possible, and the thermosetting reaction did not proceed, resulting in poor chemical resistance and pencil hardness.

<Photosensitive composition for color filter>
[Preparation of red pigment dispersion]
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion PR was prepared.
Diketopyrrolopyrrole pigment (CI Pigment Red 254) 6.82 parts ("Irga Four Red B-CF" manufactured by Ciba Japan)
1.08 parts of anthraquinone pigment (CI Pigment Red 177) (“Chromoval Red A2B” manufactured by Ciba Japan)
Nickel azo complex pigment (CI Pigment Yellow 150) 0.88 parts ("E4GN" manufactured by LANXESS)
Resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol) 1.74 parts Diketopyrrolopyrrole pigment derivative 2.05 parts

Polymer solution P-1 5.83 parts Cyclohexanone 81.60 parts

[Preparation of green pigment dispersion]
A green pigment dispersion PG was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
Halogenated copper phthalocyanine pigment (CI Pigment Green 36) 8.93 parts ("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150) 2.74 parts ("E4GN" manufactured by LANXESS)
Resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol Corporation) 2.80 parts Polymer solution P-1 5.53 parts Cyclohexanone 80.00 parts

[Preparation of blue pigment dispersion]
A blue pigment dispersion P-B was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 12.88 parts (“Heliogen Blue L-6700F” manufactured by BASF)
Resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol Co., Ltd.) 5.62 parts Polymer solution P-1 1.50 parts Cyclohexanone 80.00 parts

[Preparation of black pigment dispersion]
A black pigment dispersion P-K was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
Carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation) 11.67 parts Resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol Corporation) 2.80 parts Polymer solution P-1 5.53 parts Cyclohexanone 80.00 parts

[Examples 22 to 73 and Comparative Examples 8 to 14]
[Preparation of photosensitive composition for color filter]
Each material was mixed and stirred with the compositions and blending amounts shown in Tables 5 and 6, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

Abbreviations in Tables 5 and 6 are shown below.
Photopolymerizable monomer (D): Aronix M-402 (manufactured by Toa Gosei Co., Ltd.) Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate Photopolymerization initiator (C): Irgacure 907 (manufactured by Ciba Japan) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one polyfunctional thiol: TEMB (manufactured by Showa Denko) Trimethylolethane tris (3-mercaptobutyrate)
Epoxy resin: XD-1000: manufactured by Nippon Kayaku Co., Ltd. dicyclopentanyl skeleton-containing novolak epoxy resin amine catalysts: dimethylbenzylamine organic solvent: cyclohexanone
Others 1: "XD-1000" manufactured by Nippon Kayaku Co., Ltd. dicyclopentanyl skeleton-containing novolak epoxy resin Others 2: BL3175: (manufactured by Sumika Bayer Urethane Co., Ltd.) SUMIDUR BL3175 blocked isocyanate isocyanurate MEK oxime-blocked the amount of A1 to 33 and P-1 to P-8 in Table 5 and 6 is a value as a solution.

  About the obtained photosensitive composition for color filters, transparency, chemical resistance, hardness, adhesion, insulation, patterning suitability, and storage stability over time were evaluated by the following methods. The results are shown in Tables 7 and 8.

[Evaluation of transparency (haze measurement)]
The photosensitive compositions for color filters of Examples 22 to 73 and Comparative Examples 8 to 14 were applied to a glass substrate of 100 mm × 100 mm and a thickness of 0.7 mm (Corning Glass Eagle 2000) at 150 ° C. using a spin coater. The board | substrate apply | coated so that the finished film thickness after minute heating might be set to 2.0 micrometers was obtained. Next, after drying under reduced pressure, UV exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . The coated substrate was heated at 150 ° C. for 20 minutes and allowed to cool, and then the haze value was measured using a haze meter NDH-2000 (manufactured by Tokyo Denshoku). The rank of evaluation is as follows.
○: Haze value less than 0.5%: Good level Δ; Haze value 0.5% or more and less than 1.5%: Inferior to ○, but practical level ×; Haze value 1.5% or more: Practical use Is not suitable level

[Evaluation of chemical resistance]
The chromaticity of the substrate obtained by the same method as that prepared for measuring haze was measured. The substrate was immersed in an N-methylpyrrolidone solution at room temperature for 30 minutes, then washed with ion exchange water and air dried. Thereafter, the chromaticity of the substrate was measured, and the color difference ΔE was calculated. The chromaticity was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) using a C light source. The rank of evaluation is as follows.
○: ΔE ≦ 1.5: good level Δ: 1.5 <ΔE ≦ 3: level inferior to ○, but practical level ×: 3 <ΔE: level not suitable for practical use

[Heat resistance evaluation]
The chromaticity of the substrate obtained by the same method as that prepared for measuring haze was measured. Further, after heating and cooling the substrate at 250 ° C. for 60 minutes, the chromaticity of the substrate was measured again, and the color difference ΔE was calculated. The rank of evaluation is as follows.
○: ΔE ≦ 1.5: good level Δ: 1.5 <ΔE ≦ 3: level inferior to ○, but practical level ×: 3 <ΔE: level not suitable for practical use

[Measurement of adhesion to glass]
About the board | substrate obtained by the same method as what was produced for the measurement of haze, the adhesiveness (cross-cut method) test according to JIS K5600-5-6 evaluated the adhesiveness of a coating film, The number of peels was counted.
○: Number of cross-cuts peeled less than 2: Good level Δ; Number of cross-cuts peeled 2 or more and 10 or less: Inferior to ○, but practical level ×; Number of cross-cuts peeled over 10: Level not suitable for practical use

[Sensitivity at the time of patterning]
Using the photosensitive compositions for color filters of Examples 22 to 73 and Comparative Examples 8 to 14, the sensitivity was evaluated in the same manner as the coating agent for touch panel interlayer insulating film.

[Evaluation of pattern peeling]
About the board | substrate produced for the said sensitivity evaluation, it observed and evaluated using the optical microscope about the pattern in a 100 micrometer photomask part. The rank of evaluation is as follows.
○: Good without peeling or chipping: Good level △: No peeling but partial chipping: Inferior to ○, but practical level ×: Many peelings and chipping: Unsuitable level for practical use

[Storage stability evaluation]
The color filter photosensitive composition for Examples 22 to 73 and Comparative Examples 8 to 14, the storage stability was evaluated similarly to the touch panel interlayer insulating film coating agent.

As shown in Tables 7 and 8, all of the photosensitive compositions for color filters of Examples 22 to 73 have transparency, chemical resistance, heat resistance, adhesion, patterning sensitivity, pattern peeling, and storage stability. It was good.
Since the photosensitive compositions of Examples 22 to 52 , 56 to 62 , and 64 to 72 contained the photopolymerizable monomer (D), the sensitivity at the time of patterning was more excellent. Further, in Examples 23 , 36 , 42 , 57 , and 66 , the peeling of the pattern is suppressed by the addition of the epoxy resin, and may be used as long as the storage stability is not hindered .
The photosensitive composition ratio Comparative Examples 8 to 14, any of the above properties become poor outcome, all is not obtained satisfy the practical level.
Since Comparative Example 8 did not contain a photopolymerizable functional group and Comparative Example 9 did not contain a photopolymerization initiator (C), patterning could not be performed. Moreover, since photocuring did not occur, the results were inferior in heat resistance and chemical resistance.
Since Comparative Example 10 did not contain a hydroxyl group having a β-hydroxyalkylamide structure, the curing reaction did not proceed, resulting in poor chemical resistance and heat resistance.
In Comparative Example 11, epoxy resin was added instead of β-hydroxyalkylamide (A), but since there was no catalyst, thermosetting did not proceed sufficiently, resulting in poor chemical resistance and heat resistance. In Comparative Example 12, since the catalyst was further added, the thermosetting reaction proceeded, but the storage stability decreased. In Comparative Example 13, since blocked isocyanate was added, the transparency was lowered by the deblocking agent generated at the time of thermosetting. In Comparative Example 14, since the polymer (B) containing a carboxyl group was not included, patterning was not possible, and the thermosetting reaction did not proceed, resulting in poor chemical resistance and heat resistance.

<Photosensitive solder resist ink>

[Examples 74 to 85 , Comparative Examples 15 to 19]
In the composition and amount shown in Tables 9 and 10, β-hydroxyalkylamide (A) and a polymer (B) containing a carboxyl group were blended, and Epicoat 1031S (manufactured by Mitsubishi Chemical Corporation, polyfunctional glycidyl ether) Type epoxy resin) 5 parts, BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate type block isocyanate), Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd., 2-methyl-1- [4- (methylthio) ) Phenyl] -2-morpholino-1-propane) 2.5 parts, DETX-S (manufactured by Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone) 0.25 parts, Aronix M-310 (manufactured by Toagosei Co., Ltd.) , Trimethylolpropane PO-modified triacrylate)) 8 parts, green paste (GREE 2 parts of pigment / base resin (phenolic resin) / solvent (carbitol acetate) = 28/12/60), 8 parts of SPB-100 (manufactured by Otsuka Chemical Co., Ltd., phosphazene flame retardant), PHOSMEL-100 (Nissan Chemical Industries) After mixing 8 parts STABACE MC-5S (manufactured by Sakai Chemical Industry Co., Ltd., melamine cyanurate) and kneading the mixture with three rolls so as to be uniform, 1 μm The photosensitive compositions corresponding to Examples 74 to 85 and Comparative Examples 15 to 19 were obtained.
The amount of A1 to 27 and P-1 to P-7 in Table 9 and 10 is the value as a solution.

The resulting photosensitive composition was used as a photosensitive solder resist ink to evaluate developability, resolution, solder heat resistance, flexibility, and flame retardancy by the following methods. The results are shown in Tables 11 and 12.

[Preparation of Sample A]
Photosensitive solder resist inks obtained in Examples 74 to 85 and Comparative Examples 15 to 19 so that the film thickness after drying was 20 μm on the release surface of a 38 μm-thick separator PET film on which one side was peeled. Was coated and dried, and then cooled to room temperature. Next, the photosensitive resin composition surface on this film and a 25 μm-thick PET film are laminated to create a dry film type photosensitive solder resist of the photosensitive resin composition in which both surfaces are sandwiched by the PET film. did.
Next, from this dry film, the separator PET film is peeled off, and the photosensitive resin composition surface exposed on the surface and the copper foil surface of the copper-clad laminate (thinning the copper surface by etching) are laminated together, It was stuck by vacuum lamination (60 ° C., 0.2 MPa = 2 kg / cm 2). Subsequently, a negative film having a resist pattern [φ70 μm hole, 21 steps, solid line / space = 100/60 (μm / μm)] is brought into close contact with the PET film, and an ultraviolet exposure device (EXM-1201F manufactured by ORC Corporation, short-circuited). (Arc lamp) was used to irradiate ultraviolet rays (400 mJ / cm ² ). Next, the PET film was peeled off, and developed with a 1% sodium carbonate aqueous solution at a spray pressure of ² kg / cm ² for 60 seconds. Thereafter, heat curing was performed with a hot air dryer at 150 ° C. for 1 hour to prepare Sample A.

[Developability]
For sample A, the number of steps where the negative film having 21 steps is in close contact with the developer is swollen by the developer, and the number of steps where the coating is washed away with the developer is the peel step. did. It can be said that the lower the number of peeling steps, the faster the development speed and the better the developability. The developability was judged according to the following criteria using the number of peeling steps.
○ ・ ・ ・ Number of peeling steps ≦ 5
Δ: number of peeling steps = 6 to 10
X ... number of peeling steps ≥ 11

[Resolution]
For sample A, observe the hole of φ70μm with a magnifying glass, measure the diameter of the part where the resist layer is developed and the copper surface is exposed (the part where the hole is opened), and resolve it according to the following criteria: Judging sex. It can be said that the closer the diameter of this hole is to 70 μm, the more faithfully the pattern is formed and the better the resolution.
○ ・ ・ ・ Diameter 60μm or more Δ ・ ・ ・ Diameter 40μm or more to 59μm or less × ・ ・ ・ Diameter 39μm or less

[Solder heat resistance]
Weakly active rosin flux (manufactured by Nippon Alpha Metals Co., Ltd., trade name: RM-615) was applied to Sample A, and immersed in a solder bath (JIS C6481) at 260 ° C. for 10 seconds. This was repeated as 2 cycles, and the state of the coating film was determined as follows.
○… There is no abnormality in the appearance of the coating film, and there is no swelling or peeling.
Δ: The coating film is partially swollen or peeled off.
X: The whole coating film has swelling or peeling.

[Preparation of Sample B]
After the photosensitive solder resist inks obtained in Examples 74 to 85 and Comparative Examples 15 to 19 were uniformly coated on a 38 μm-thick separator PET film so that the dry film thickness was 20 μm and dried, Cooled to room temperature. Next, after irradiating ultraviolet rays with an integrated light quantity of 400 mJ / cm ² with the same ultraviolet exposure apparatus used when preparing Sample A, it was cured with a hot air dryer at 150 ° C. for 1 hour. The obtained cured film was cooled to room temperature, and the cured coating film was peeled off from the separator film. This is designated as sample B.

[Flexibility]
Sample B was folded 180 degrees and the same part was folded 180 degrees on the opposite side. The state of the coating film at that time was judged according to the following criteria.
○: No cracks are observed on the film surface Δ: Slight cracks are observed on the film surface ×: The film is cracked and cracks are clearly seen on the film surface

[Preparation of Sample C]
For the photosensitive solder resist inks obtained in Examples 74 to 85 and Comparative Examples 15 to 19, except that the negative film having a resist pattern was not used in the preparation process of Sample A, but ultraviolet irradiation (entire exposure) was performed. Sample C was prepared in the same manner as sample A.

[Flame retardance]
Sample C was evaluated for flame retardancy in accordance with the UL Subject 94V method, and the results were judged according to the following criteria.
○ ・ ・ ・ VTM-0
△ ・ ・ ・ VTM-1
× ・ ・ ・ VTM-2 or less (including complete combustion)

As can be seen from the results in Table 11, the photosensitive compositions of Examples 74 to 85 all have good developability, resolution, solder heat resistance, flexibility, and flame retardancy, and are flexible printed wiring boards. It has been shown that it is excellent as a flexible insulating protective film used for such as .
Hand, as can be seen from the results in Table 12, it was not obtained satisfy the practical level in the comparative example. For example, Comparative Examples 15 to 17 did not contain β-hydroxyalkylamide (A), and thus the heat resistance of the cured coating film was inferior. In Comparative Examples 18 and 19, since the polymer (B) containing a carboxyl group was not included, developability and resolution could not be satisfied.

The photosensitive composition of the present invention can be used as long as it is cured by light and heat. In addition to the touch panel interlayer insulating film, color filter, black matrix, photosensitive solder resist described above, It can be used to produce filter protective films, photo spacers, liquid crystal alignment protrusions, micro lenses, optical hard coats, UV inks, photosensitive lithographic printing plates, various coatings, and the like.
Further, it can also be used for reinforcing plate adhesives, interlayer adhesives, coating agents, electromagnetic wave shielding adhesives, photosensitive optical waveguides, photothermal dual-curing potting agents and the like used for flexible printed wiring boards.

Claims (17)

Photosensitive composition containing (beta) -hydroxyalkylamide (A) represented by General formula (1), the polymer (B) containing a carboxyl group, a photoinitiator (C), and an organic solvent . A photosensitive composition comprising a photopolymerizable functional group as an essential component in the composition.
General formula (1)
here,
X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen;
n is an integer of 2-6,
R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or the general formula (3) Wherein at least one of the one or more R ¹ and R ² bonded to one or more nitrogen atoms is a group represented by the general formula (2), and at least one is general It is group represented by Formula (3) .
General formula (2)
General formula (3)
Here, R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group,
R ⁷ represents a residue of a compound having a functional group capable of reacting with a hydroxyl group.   The β-hydroxyalkylamide (A) represented by the general formula (1) or at least one of the polymer (B) containing a carboxyl group contains a photopolymerizable functional group. Photosensitive composition.   The photosensitive composition of Claim 1 or 2 containing a photopolymerizable monomer (D).   In the compound having a functional group capable of reacting with the hydroxyl group, the functional group capable of reacting with the hydroxyl group is a carboxyl group, an isocyanate group, a carboxylic acid anhydride group, an acid halide group, a carboxylic acid tertiary alkyl ester group, The photosensitive composition according to claim 3, which is at least one selected from the group consisting of a hydroxymethylamino group, an alkoxysilyl group, and an epoxy group.   The photosensitive composition according to claim 4, wherein the compound having a functional group capable of reacting with a hydroxyl group is a monofunctional isocyanate or a monofunctional carboxylic acid. The compound having a functional group capable of reacting with the hydroxyl group is a compound represented by at least one selected from the group consisting of the following general formula (4), general formula (5) and general formula (6). The photosensitive composition according to claim 5.
General formula (4)
[Wherein, R ⁸ represents a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]
General formula (5)
[Wherein R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or an aromatic hydrocarbon group. R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]
General formula (6)
[Wherein R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a formula
[N ¹ is an integer of 1-2. ] Or a group represented by
[R ¹⁴ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group or an aromatic hydrocarbon group,, R ¹⁵ is a straight chain having 6 to 13 carbon atoms Or a branched alkylene group, a divalent alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]. ]   The photosensitive composition according to claim 1, wherein the compound having a functional group capable of reacting with a hydroxyl group has a photopolymerizable functional group.   The photosensitive composition according to any one of claims 1 to 7, wherein an atom directly bonded to a carbonyl group in X in the general formula (1) is a carbon atom not contained in an aromatic ring.   8. The photosensitive composition according to claim 1, wherein X in the general formula (1) is an n-valent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 6 or more carbon atoms. . Β-hydroxyalkylamide (A) represented by the general formula (1) is
(A-1) An amidation of a carboxylic acid having a valence of 2 or more or a derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position (a-3) β A compound obtained by reacting a part of the hydroxyl group of -hydroxyalkylamide with (a-4) a compound having one or more functional groups capable of reacting with a hydroxyl group. 9. The photosensitive composition in any one of 9.   The photosensitive composition according to any one of claims 1 to 10, wherein the β-hydroxyalkylamide (A) represented by the general formula (1) is soluble in an organic solvent.   The coating agent for touchscreen interlayer insulation films containing the photosensitive composition in any one of Claims 1-11.   The photosensitive composition for color filters containing the photosensitive composition in any one of Claims 1-11, and a pigment.   The photosensitive soldering resist ink containing the photosensitive composition in any one of Claims 1-11, and a flame retardant. A photosensitive solder resist ink according to claim 14. Yfilm.   The insulating film for touchscreens formed from the coating agent for touchscreen interlayer insulation films of Claim 12. A color filter comprising a filter segment or a black matrix formed from the photosensitive composition for a color filter according to claim 13 on a transparent substrate.