JP2019139091A - Photosensitive composition - Google Patents

Abstract

To provide a composition which can be cured by heating at a low temperature of 100°C or lower, has good resistance to a resist stripping solution or the like, and is highly transparent, and to provide a use thereof.SOLUTION: Since a photocurable composition contains a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D) and a silane coupling agent (F), the photocurable composition can form a transparent cured film having good resistance to a resist stripping solution after curing at a low temperature of 100°C or lower by being irradiated with ultraviolet rays.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive composition, a cured film, a substrate with a cured film, and an electronic component. More specifically, the present invention relates to a photosensitive resin composition containing a specific compound, a cured film formed from the composition, a substrate with a cured film having the cured film, and an electronic component having the cured film or the substrate with a cured film. .

  In recent years, as an input device, a touch panel type input device in which a liquid crystal display device or an organic electroluminescence device and a position detection device are combined has become widespread. A touch panel type input device is an input device that detects a contact position when a finger or the tip of a pen is brought into contact with a display screen. There are various detection methods for touch panel type input devices, such as a resistance film method and a capacitance method.

  For example, the capacitance method uses a device having a structure in which X and Y electrodes are arranged in a matrix on a glass substrate, and detects a change in capacitance caused by contact of a fingertip or the like as a change in current. It is a method.

  When forming the electrodes, in order to recognize the X and Y positions, a jumper is formed of ITO (Indium Tin Oxide) or the like at the overlapping portion of the X and Y electrodes, and the X and Y electrodes are not in contact with each other. A transparent insulating film is provided. The transparent insulating film is required to have high hardness, high transparency, adhesion to glass or ITO, etc., and from the viewpoint of the process, when an electrode is formed on the insulating film by photolithography, it is resistant to a resist stripping solution. Required.

  In addition, the capacitive touch panel type input device may be provided with an insulating overcoat to flatten the X and Y electrodes, for example. In addition to flatness, this overcoat is required to prevent outgassing, have high hardness, high transparency, and adherence to glass and ITO.

  In the touch panel, a partial replacement or a total replacement from a conventionally used glass to a plastic such as PET (polyethylene terephthalate) has been studied for the purpose of reducing the manufacturing cost. In addition, in view of energy saving and cost reduction in production, a material that can be cured at a low firing temperature or a material that can be cured by a UV-LED light source is required.

Various compositions have been studied for highly transparent insulating materials that can be used for the transparent insulating film or overcoat.
For example, Patent Literature 1 discloses a thermosetting resin composition containing a polyester amide acid having a specific structure, an epoxy resin, an epoxy curing agent, and the like. Patent Document 2 discloses a thermosetting resin composition containing a polyester amide acid having a specific structure, an epoxy compound having a fluorene skeleton, and a curing agent. Patent Document 3 discloses a photosensitive composition containing a polyester amide acid having a specific structural unit, a compound having a double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent.

JP 2005-105264 A WO2015 / 012395 pamphlet JP, 2006-103010, A

  In replacing the substrate from glass to plastic, for example, when considering the heat resistance of PET (polyethylene terephthalate), which is a kind of plastic, the material used for the overcoat is a cured film by low-temperature baking at 100 ° C. or lower. Is required to be formed. The formed cured film needs to have desired properties such as transparency, chemical resistance, flatness, adhesion to a substrate and an electrode.

In the photocuring system, a high-pressure mercury lamp or a metal halide lamp is mainly used as a light source for excitation. However, since such a light source consumes a large amount of energy and has a long remaining heat time, the risk of damaging the plastic substrate increases and the load on the environment also increases.
The UV-LED light source is simple in operability and can be expected to improve production yield and reduce energy discharge in terms of low energy consumption compared to UV mercury lamps and metal halide lamps.

  Under the above circumstances, Patent Documents 1 and 2 describe compositions that can be used as a color filter protective film, a protective film for various optical materials, and a transparent insulating film. However, no study has been made on the low-temperature curability at 100 ° C. or lower of the composition, the physical properties of the cured film obtained by low-temperature curing, the chemical resistance, etc., which are important when using a plastic substrate.

  Patent Document 3 describes that the composition is heated at 120 ° C. for 2 minutes, then irradiated with UV, and finally heated at 230 ° C. for 30 minutes to obtain a cured film. However, the cured film obtained by heating the composition at 80 ° C. for 5 minutes and then by UV irradiation and finally heating at 100 ° C. for 1 hour has poor resistance to a resist stripping solution or the like. For this reason, the said composition is not suitable for using as a transparent insulating film of a plastic substrate, and improvement is calculated | required.

  When manufacturing a touch panel type input device, a resin composition that can be used for both the transparent insulating film and the overcoat is desirable from the viewpoint of simplifying the line and improving the yield. In addition, a resin composition that forms a cured product having resistance to a resist stripping solution or the like by UV-LED irradiation or low-temperature baking is considered desirable because it can be used for a plastic substrate. However, such a composition has not been realized yet.

  An object of the present invention is to provide a composition that can be cured by low-temperature heating at 100 ° C. or less, has good resistance to a resist stripping solution of the cured product, and provides a highly transparent cured product, and uses thereof. It is to provide.

  The present inventors have intensively studied to solve the above problems. As a result, a resist stripping solution after low-temperature curing at 100 ° C. or lower by using a composition containing polyester amic acid, an epoxy compound having a fluorene skeleton, a urethane compound having a double bond, a photopolymerization initiator and a silane coupling agent It has been found that a transparent cured film having good resistance to water can be formed. The present invention is based on the findings and has the following configuration.

  [1] Photosensitivity including polyester amic acid (A), epoxy compound (B) having a fluorene skeleton, urethane compound (C) having a double bond, photopolymerization initiator (D), and silane coupling agent (F) Sex composition.

  [2] The photosensitive composition according to [1], further comprising a reaction accelerator (E).

  [3] The photosensitive composition according to [2], wherein the reaction accelerator (E) is a compound having a thiol group in the molecule.

  [4] The content of the photopolymerization initiator (D) is 2.5 to 10 parts by weight with respect to 100 parts by weight of the total content of the urethane compound (C) having a double bond. [1] The photosensitive composition according to any one of [3].

  [5] The photosensitive composition according to any one of [1] to [4], wherein the silane coupling agent (F) is contained in an amount of 3 to 15% by weight in the total solid content of the photosensitive composition. .

  [6] The content of the reaction accelerator (E) is 0.1 to 1.6 parts by weight based on 100 parts by weight of the total content of the urethane compound (C) having an oxiranyl compound and a double bond. The photosensitive composition according to any one of [2] to [5].

  [7] The photosensitive composition according to any one of [1] to [6], wherein the urethane compound (C) having a double bond is a bifunctional or higher urethane acrylate.

  [8] The photosensitive composition according to any one of [1] to [7], wherein the bifunctional or higher functional urethane acrylate is contained in an amount of 10 to 60% by weight in a solid content of the photosensitive composition.

  [9] The photosensitive composition according to any one of [1] to [8], further comprising a surfactant (G).

  [10] A cured film obtained from the photosensitive composition according to any one of [1] to [9].

  [11] The cured film according to [10], wherein the cured film is obtained by an ultraviolet irradiation step of irradiating the photosensitive composition with ultraviolet rays, and a heating step after the ultraviolet irradiation step.

  [12] The cured film according to [11], wherein the temperature in the heating step is 110 ° C. or lower.

  [13] The cured film according to [11] or [12], wherein the ultraviolet irradiation step irradiates ultraviolet rays using a UV-LED.

  [14] A substrate with a cured film, comprising the cured film according to any one of [10] to [13].

  [15] An electronic component having the cured film according to any one of [10] to [13] or the substrate with the cured film according to [14].

  [16] The electronic component according to [15], which is a touch panel type input device.

  The photosensitive composition of the present invention contains a polyester amic acid, an epoxy compound having a fluorene skeleton, a urethane compound having a double bond, and a photopolymerization initiator. It is possible to form a transparent cured film having good resistance to. For this reason, the photosensitive composition of the present invention is very practical, and for example, it is possible to produce a transparent insulating film and an overcoat for a touch panel with high productivity, and is suitable for these uses. Can be used.

  Hereinafter, the photosensitive composition of the present invention (hereinafter also referred to as “composition”), a method for preparing the composition, a method for forming a cured film, a substrate with a cured film, and an electronic component will be described in detail.

1. Thermosetting resin composition The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D), and Contains a silane coupling agent (F). The composition of the present invention may contain additives in addition to the above components, and the additives may be colored or colorless. Hereinafter, the epoxy compound (B) having an fluorene skeleton and the epoxy compound (B) have the same meaning.
According to such a composition of the present invention, the cured film has good resistance to the resist stripping solution (hereinafter also referred to as “resist stripping solution resistance” as appropriate), and a highly transparent cured film can be obtained. For this reason, since a cured film can be used for both a transparent insulating film and an overcoat, it is possible to produce a transparent insulating film or an overcoat for a touch panel with high productivity.
Moreover, since it is not necessary to heat at high temperature in order to form a cured film, the composition of this invention can be used suitably for plastic substrates, such as PET.

The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D), and a silane coupling agent (F ), The above-mentioned effect is excellent only. In particular, low-temperature baking at 100 ° C. or lower is possible, and the resistance of the obtained cured film to the resist stripping solution becomes good.
Conventional compositions composed of polyester amic acid, and compositions composed of an epoxy compound having a fluorene skeleton and an epoxy curing agent can provide a cured film that can be baked at a low temperature of 100 ° C. or less and has good resistance to a resist stripping solution. I couldn't. In the case of a composition comprising a polyester amide acid, an epoxy compound, a compound having a double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent, for example, the composition is heated at 120 ° C. for 2 minutes and then irradiated with UV. A cured film can be obtained by heating at 230 ° C. for 30 minutes, but after heating the composition at 80 ° C. for 5 minutes, it is irradiated with a UV-LED having a maximum emission wavelength of 385 nm and finally 100 ° C. The cured film obtained by heating for 1 hour had poor resistance to the resist stripping solution and the like.
Therefore, the composition of the present invention exhibits an effect different from that of the conventional composition by using the components (A), (B), (C), (D) and (F).

1.1. Polyester amide acid (A)
The polyester amide acid (A) used in the present invention is not particularly limited, but is preferably a compound having an ester bond, an amide bond, and a carboxyl group, and specifically represented by formulas (3) and (4). It is more preferable that the compound has a structural unit.
Such polyester amic acid (A) is combined with an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D), and a silane coupling agent (F). For the first time, a cured product having sufficient resistance to a resist stripping solution or the like can be obtained by curing at a low temperature of 100 ° C. or lower. For example, the cured film obtained by heating the composition at 80 ° C. for 5 minutes, irradiating a UV-LED having a maximum emission wavelength of 385 nm and finally heating at 100 ° C. for 1 hour is a resist stripping solution. Good tolerance.
Polyester amide acid (A) may use only 1 type, and may mix and use 2 or more types.

(R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is a divalent organic group having 1 to 20 carbon atoms. Group.)

R ¹ is independently a tetravalent organic group having 2 to 25 carbon atoms from the viewpoint that a compound having good compatibility with other components in the composition is obtained and a highly transparent cured film is obtained. Preferably, it is a tetravalent organic group having 2 to 20 carbon atoms, and more preferably a group represented by the formula (5).

(In the formula (5), R ⁴ represents —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁵ — or —COO—R ⁵ —OCO— (R ⁵ represents Independently, it is an alkyl group having 1 to 4 carbon atoms.)

From the point that a compound having good compatibility with other components in the composition is obtained, and a cured film having high transparency and good adhesion to glass and ITO is obtained, R ² has 2 to 2 carbon atoms. A divalent organic group of 35 is preferable, a divalent organic group having 2 to 30 carbon atoms is more preferable, and a group represented by the formula (6) is more preferable.

(In the formula (6), R ⁶ represents —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ — or —O—ph—R ⁸ —ph—O—). (a ph is a benzene ^{ring, R} 8 _{is, -O -, - CO -,} - SO 2 -, - C (CF 3) 2 - or -R ⁷ -. a a) in which. Incidentally, ^{R 7} is Independently, it is an alkyl group having 1 to 4 carbon atoms.)

From the standpoint of obtaining a highly transparent cured film, R ³ is preferably a divalent organic group having 2 to 15 carbon atoms, and is a group represented by the formula (7): —R ¹⁰ —NR ¹¹ -R ¹² - ^{(R 10} and ^{R 12} are independently an alkylene having 1 to 8 carbon ^{atoms, R 11} is hydrogen or at least one hydrogen which may be the number 1 to 8 carbon substituted by hydroxyl An alkyl having 2 to 15 carbon atoms, or at least one hydrogen of alkylene having 2 to 15 carbon atoms may be substituted with hydroxyl, and may have -O-. More preferably, it is more preferably a divalent alkylene having 2 to 6 carbon atoms.

(In Formula (7), R ⁹ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ —, or —ph—R ⁸ —ph— (ph Is a benzene ring, and R ⁸ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ — or —R ⁷ —.) Note that R ⁷ is independently carbon (It is an alkyl group of formulas 1 to 4.)

The polyester amic acid (A) is a compound obtained by reacting a component containing a tetracarboxylic dianhydride (a1), a component containing a diamine (a2) and a component containing a polyvalent hydroxy compound (a3). Preferably obtained by reacting a component containing tetracarboxylic dianhydride (a1), a component containing diamine (a2), a component containing polyvalent hydroxy compound (a3) and a component containing monohydric alcohol (a4). It is also preferable that it is a compound obtained.
That is, in formulas (3) and (4), R ¹ is independently a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue. Is preferred.
In this reaction, a reaction solvent (a5) or the like may be used.
The component containing the tetracarboxylic dianhydride (a1) only needs to contain the tetracarboxylic dianhydride (a1), and may contain other compounds other than this compound. The same applies to the other components described above.
Each of these (a1) to (a5) may be used alone or in combination of two or more.

  When the polyester amic acid (A) has an acid anhydride group at the molecular end, it is preferably a compound obtained by reacting a monohydric alcohol (a4) if necessary. The polyester amide acid (A) obtained by using the monohydric alcohol (a4) tends to be a compound having excellent compatibility with the epoxy compound (B) and the thiol compound (E), and also has excellent coating properties. Tends to be obtained.

1.1.1. Tetracarboxylic dianhydride (a1)
Although it does not restrict | limit especially as tetracarboxylic dianhydride (a1), As a specific example, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetra Carboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2 , 2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl) ] Aromatic tetracarboxylic dianhydrides such as fluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.); cyclobutanetetracarboxylic dianhydride Alicyclic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride and butanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides are listed.

  Among these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether is used because a compound having good transparency can be obtained. Tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, New Japan Rika Chemical Co., Ltd.) is preferred, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride are particularly preferred.

1.1.2. Diamine (a2)
Although it does not restrict | limit especially as a diamine (a2), As a specific example, 4,4'- diamino diphenyl sulfone, 3,3'- diamino diphenyl sulfone, 3,4'- diamino diphenyl sulfone, bis [4- (4-amino Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4 -Aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane is mentioned.

  Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are preferable, and 3,3′-diaminodiphenylsulfone is preferable from the viewpoint of obtaining a compound having good transparency. Is particularly preferred.

1.1.3. Polyvalent hydroxy compound (a3)
The polyvalent hydroxy compound (a3) is not particularly limited as long as it is a compound having two or more hydroxy groups. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol having a molecular weight of 1,000 or less. , Propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2- Pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2 , 6- Xanthriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2 , 8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decane Examples include triol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine and triethanolamine.

  Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol are preferable, and 1,4- Butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferable from the viewpoint of good solubility in the reaction solvent (a5).

1.1.4. Monohydric alcohol (a4)
The monohydric alcohol (a4) is not particularly limited as long as it is a compound having one hydroxy group. Specific examples include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol. Monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool, Terpineol, dimethylbenzyl carbinol and 3-ethyl- - it includes hydroxymethyl oxetane.

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are preferable. Considering the compatibility of the resulting polyester amic acid (A) with the epoxy compound (B) and the thiol compound (E) and the applicability of the resulting composition on glass or ITO, a monovalent alcohol (a4 ) Is more preferably benzyl alcohol.

1.1.5. Reaction solvent (a5)
The reaction solvent (a5) is not particularly limited, but specific examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether. Examples include acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide.

Among these, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, methyl 3-methoxypropionate and N-methyl-2-pyrrolidone are preferable from the viewpoint of solubility.
Specific examples of the reaction solvent (a5) include these solvents, but if these solvents are in a proportion of 30% by weight or less with respect to the total amount of the solvent used in the reaction, other than the solvent A mixed solvent obtained by mixing other solvents can also be used.

<< Synthesis of Polyesteramide Acid (A) >>
The method for synthesizing the polyester amic acid (A) is not particularly limited, but the tetracarboxylic dianhydride (a1), the diamine (a2), the polyvalent hydroxy compound (a3), and, if necessary, the monohydric alcohol (a4). A method of reacting as an essential component is preferred, and this reaction is more preferably carried out in the reaction solvent (a5).

The order of adding each component during this reaction is not particularly limited. That is, the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3) may be simultaneously added to the reaction solvent (a5) to cause the reaction, or the diamine (a2) and the polyvalent hydroxy compound may be reacted. After (a3) is dissolved in the reaction solvent (a5), the reaction may be carried out by adding tetracarboxylic dianhydride (a1), or tetracarboxylic dianhydride (a1) and diamine ( After reacting a2) in advance, the polyhydroxy compound (a3) may be added to the reaction product for reaction, and either method can be used.
The monohydric alcohol (a4) may be added at any point in the reaction.

  Moreover, in the case of the said reaction, in order to enlarge the weight average molecular weight of the obtained polyester amide acid (A), you may add the compound which has 3 or more acid anhydride groups, and may perform a synthetic reaction. Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer.

  The polyester amide acid synthesized in this way contains the structural units represented by the above formulas (3) and (4), and the ends thereof are derived from the raw materials tetracarboxylic dianhydride, diamine or polyhydroxy compound, respectively. It is an acid anhydride group, an amino group or a hydroxy group, or a group derived from a component other than these compounds (for example, a monohydric alcohol residue).

When the amounts of tetracarboxylic dianhydride (a1), diamine (a2) and polyvalent hydroxy compound (a3) used in the reaction are X mol, Y mol and Z mol, respectively, X, Y and It is preferable that the relationship of Formula (1) and Formula (2) is established between Z. By using each component in such an amount, a polyester amide acid (A) having high solubility in the solvent (i) described later is obtained, a composition having excellent coatability is obtained, and a cured film having excellent flatness Can be obtained.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)

  The relationship of Formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. The relationship of the formula (2) is preferably 0.3 ≦ (Y + Z) /X≦1.2, and more preferably 0.4 ≦ (Y + Z) /X≦1.0.

  When the amount of the monohydric alcohol (a4) used in the reaction is Z ′ mol, the amount used is not particularly limited, but is preferably 0.1 ≦ Z ′ / X ≦ 5.0, more preferably Is 0.2 ≦ Z ′ / X ≦ 4.0.

  When the reaction solvent (a5) is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3), the reaction proceeds smoothly. Therefore, it is preferable.

  The reaction is preferably performed at 40 to 200 ° C. for 0.2 to 20 hours.

<< Physical properties and usage of polyester amide acid (A) >>
The weight average molecular weight measured by gel permeation chromatography (GPC) of the polyester amic acid (A) is from the viewpoint of obtaining a cured film having a balance of transparency, adhesion to glass and ITO, and chemical resistance. , Preferably from 2,000 to 30,000, and more preferably from 3,000 to 30,000.
Specifically, this weight average molecular weight can be measured by the method described in Examples described later.

  The viscosity of the polyester amic acid (A) is preferably from 5 to 200 mPa · s at 25 ° C. from the viewpoint of adjusting the handleability of the resulting polyester amic acid (A) and adjusting the weight average molecular weight to the above preferred range. Preferably it is 10-150 mPa * s, More preferably, it is 15-100 mPa * s.

  The content of the polyester amic acid (A) is such that a cured film having a high transparency and excellent resistance to a resist stripping solution can be obtained, and the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition). ) It is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, and further preferably 5 to 50% by weight with respect to 100% by weight.

1.2. Epoxy compound having a fluorene skeleton (B)
The epoxy compound (B) used in the present invention is not particularly limited as long as it is an epoxy compound having a fluorene skeleton. Such an epoxy compound (B) has a high decomposition temperature and excellent heat stability. For this reason, in addition to the said effects, such as high transparency, the cured film which has these effects together can be obtained.
The epoxy compound (B) may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy compound (B) is preferably 200 to 550 g / eq, more preferably 220 to 490 g / eq, and still more preferably 240 to 480 g from the viewpoint of obtaining a cured film having excellent chemical resistance. / Eq.
The epoxy equivalent of the epoxy compound (B) can be measured, for example, by the method described in JIS K7236.

The refractive index of the epoxy compound (B) is preferably 1.50 to 1.75, more preferably 1.52 to 1.73, from the viewpoint of obtaining a cured film having excellent high transparency. More preferably, it is 1.54-1.71.
The refractive index of the epoxy compound (B) can be measured by, for example, the method described in JIS K7105 or JIS K7142.

The epoxy compound (B) may be obtained by synthesis or may be a commercially available product.
As a commercially available product of the epoxy compound (B), for example, “OGSOL PG-100” (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.64, epoxy equivalent 260 g / eq), “OGSOL CG-500” (Trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.70, epoxy equivalent 310 g / eq), “OGSOL EG-200” (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.62, epoxy Equivalent 290 g / eq), “OGSOL EG-250” (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.58, epoxy equivalent 395 g / eq), “OGSOL EG-280” (trade name, Osaka Gas Chemical) Co., Ltd., refractive index 1.56, epoxy equivalent 460 g / eq), “OGSOL CG-400” (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.53 Epoxy equivalent 540 g / eq) and the like.

  The content of the epoxy compound (B) is the solid content of the composition of the present invention (from the composition) in terms of the resistance to the resist stripping solution and the cured film having a good balance in adhesion to glass and ITO. The residue excluding the solvent) is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, still more preferably 15 to 21 parts by weight, and 100 parts by weight of the polyester amic acid (A) with respect to 100 parts by weight. On the other hand, it is preferably 30 to 120 parts by weight, more preferably 50 to 100 parts by weight, and still more preferably 70 to 80 parts by weight.

1.3. Urethane compound having a double bond (C)
The urethane compound (C) having a double bond used in the present invention is not particularly limited as long as it has a double bond. The double bond functions as a polymerizable group. The urethane compound (C) having a double bond is 100% by weight of the epoxy compound (B) from the viewpoint of the balance between curability by ultraviolet irradiation and resistance to a resist stripping solution of a cured film obtained by heating at 100 ° C. for 60 minutes. The amount is preferably 100 to 400 parts by weight, more preferably 140 to 350 parts by weight, and still more preferably 160 to 320 parts by weight.

  As the urethane compound having a double bond, for example, a urethane compound having a (meth) acryloyl group or a vinyl group is preferable, a urethane compound having a (meth) acryloyl group is particularly preferable, and a phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer. And pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, and the like.

  Moreover, although the following commercial items can be used for the urethane compound which has a double bond, it is not limited to this. For example, “AT-600” (trade name, phenylglycidyl ether acrylate toluene diisocyanate urethane prepolymer, manufactured by Kyoeisha Chemical Co., Ltd.), “AH-600” (trade name, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, Kyoeisha) Chemical Co., Ltd.), "UA-306I" (trade name, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, manufactured by Kyoeisha Chemical Co., Ltd.), "UA-306I" (trade name, pentaerythritol triacrylate isophorone diisocyanate urethane) Prepolymer, manufactured by Kyoeisha Chemical Co., Ltd.), “EB1290”, “UP135”, “UP111”, “UP128” (trade name, manufactured by Cytec), “EBECRYL204”, “ “BECRYL210”, “EBECRYL220”, “EBECRYL230”, “EBECRYL270”, “EBECRYL4858”, “EBECRYL8200”, “EBECRYL8201EBECRYL”, “EBECRYL8402”, “EBECRYL8402”, “EBECRYL8402”, “EBECRYL8402” , "EBECRYL7735", "EBECRYL8296" (trade name, manufactured by Daicel Ornex), "UX-3204", "UX-4101", "UX-6100", "UX-6101", "UX-8101", "UX-8101" "UX-0937", "UXF-4001-M35", "UXF-4002", "DPHA-40H", "UX-5000", "UX-5 "02D-M20", "UX-51013D", "UX-5005" (trade name, manufactured by Nippon Kayaku Co., Ltd.), "UV-7640B", "UV-7605B", "UV-7630B", "UV- 7600B "," UV-7620EA "," UV-6300B "," UV-7650B "," UV-7610B "," UV-7550B "," UV-7510B "," UV-6330B "," UV-7000B " , “UV-7461TE”, “UV-3500BA”, “UV-3520TL”, “UV-3200B”, “UV-3000B”, “UV-6640B”, “UV-3300B”, “UV-3700B”, “ "UV-3310B", "UV-3210EA", "UV-2750B", "UV-2000B" (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.), "8932," "8940", "8965" , “8966A”, “8967A” (trade name, manufactured by Nippon Pika Co., Ltd.), “PU240”, “PU340” (trade name, manufactured by Toyo Chemicals Co., Ltd.), and the like.

Among urethane compounds (C) having a double bond, from the viewpoint of heat resistance and resistance to a resist stripping solution, it is preferable that two or more double bonds are contained in the molecule, more preferably 3 or more, and still more preferably 4 or more. It is.
The composition of this invention contains a photoinitiator (D). A photoinitiator (D) will not be specifically limited if it is a compound which generate | occur | produces a radical or an acid by irradiation of an ultraviolet-ray or visible light.

1.4. Photopolymerization initiator (D)
Specific examples of the photopolymerization initiator (D) include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2- Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (eg, “I GACURE 907 ”; trade name; BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (eg“ IRGACURE 369 ”; trade name; BASF Japan Ltd.) )), Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (for example, “IRGACURE OXE-01”; trade name; BASF Japan Ltd.), 2,4 , 6-Trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyrene) Ryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 ′ -Pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- ( -Dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl)- 1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis ( 2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5'-Te Raphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1- Hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1-hydroxycyclohexyl Phenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propanone, 2-hydroxy- 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2- Tyl-1-propanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1 -Butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, oxy-phenyl-acetic acid 2- [2-oxo 2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoylformate, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphe Nylphosphinic acid ester, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime)], 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -ethanone-1- (O-acetyloxime) and the like.

  A photoinitiator (D) may be used independently and may mix and use 2 or more. Among photopolymerization initiators, α-aminoalkylphenone-based and acylphosphine oxide-based photopolymerization initiators require an exposure amount required for a tack-free state by photocuring (as appropriate, “tack-free exposure amount”). "Is also preferable from the viewpoint of reducing.

  Among the photopolymerization initiators (D), 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are initiated. When it is 20 parts by weight or more with respect to the total weight (100 parts by weight) of the agent, the tack-free exposure amount due to photocuring is preferably small, and more preferably 50 parts by weight or more.

  The content of the photopolymerization initiator (D) is based on 100 parts by weight of the total (meth) acrylate in the composition from the viewpoint of reducing the tack-free exposure amount due to photocuring and increasing the transparency of the resulting cured film. The amount is preferably 2.5 parts by weight or more, more preferably 3 parts by weight or more, and still more preferably 5 parts by weight or more. The content of the photopolymerization initiator (D) is preferably based on 100 parts by weight of the total (meth) acrylate in the composition from the viewpoint of good resistance to the resist stripping solution of the cured film obtained by the photocuring reaction. Is 60 parts by weight or less, more preferably 40 parts by weight or less, and still more preferably 10 parts by weight or less.

1.5. Silane coupling agent (F)
The silane coupling agent (F) is not particularly limited, and a known coupling agent can be used. The silane coupling agent (F) is used by adding 3 to 15% by weight based on 100% by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent). It is more preferable to add and use it so that it may become 4 to 12 weight%. A silane coupling agent (F) may use only 1 type, and may mix and use 2 or more types.

  Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyl Triethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldi Toxisilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltri Ethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltri Ethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane (epoxy equivalent 194 g / eq), γ-glycidoxypropyl Examples include methyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropyltriethoxysilane.

  Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycol. Sidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropyltriethoxysilane are particularly preferred.

1.6. Other additives The composition of the present invention comprises a polyester amic acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, and a photopolymerization initiator, depending on the intended properties. (D) You may contain additives other than a silane coupling agent (F). Examples of the additive include a reaction accelerator (E), a surfactant (G), other epoxy compounds (h), a solvent (i), an epoxy curing agent (j), a polyimide resin, a polymerizable monomer, and an antistatic agent. Agents, pH adjusters, rust inhibitors, antiseptics, antifungal agents, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, and water-soluble polymers. Moreover, you may contain a pigment or dye according to a desired use. Only one type of additive may be used, or two or more types may be mixed and used.

1.6.1. Reaction accelerator (E)
The reaction accelerator (E) used in the present invention is not particularly limited as long as it promotes a double bond or epoxy reaction, but is preferably one having a thiol group. Furthermore, what contains the oxygen atom in addition to the thiol group is preferable. Formed by low-temperature heating at 100 ° C. or lower after UV irradiation by using reaction accelerator (E) in combination with polyesteramide acid (A) and epoxy compound (B) having a specific structure and urethane compound having a double bond The effect of enhancing the resistance of the cured film to the resist stripping solution is obtained. Moreover, the composition which can form the cured film provided with the balance with high transparency is obtained. When a compound having a thiol group is used as the reaction accelerator (E), it has both an effect of curing itself by reacting with an epoxy or a double bond and an effect of assisting the reaction of an epoxy or a double bond. Therefore, it can be said that it plays the role of a curing agent and a curing accelerator in the reaction of epoxy and double bonds. Only one type of reaction accelerator (E) may be used, or two or more types may be used.

Examples of reaction accelerators having a thiol group include pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobuty Ryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopro) Pionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and the following chemical formula ( 8) glycoluril derivatives .

  Among these, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate) are preferable because a composition having good storage stability can be obtained. Further, it is preferable because a cured film having a good balance with respect to the resist stripping solution can be obtained.

The thiol compound may be obtained by synthesis or a commercial product.
Examples of commercially available thiol compounds include “Karenz MT PE1”, “Karenz MT BD1”, “Karenz MT NR1”, “TPMB” (trade names, manufactured by Showa Denko KK), “DPMP”, “PEMP”. ”,“ TEMPIC ”,“ TMMP ”(trade name, manufactured by SC Organic Chemical Co., Ltd.),“ TS-G ”(trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.).

  The content of the reaction accelerator (E) is such that a low temperature curability of 100 ° C. or less, a tackless property of a cured film obtained by ultraviolet irradiation before heat curing, and a cured film excellent in resistance to a resist stripping solution can be obtained. From 100 parts by weight of the solid content of the composition according to the present embodiment (residue obtained by removing the solvent (solvent) from the composition), preferably 0.1 to 20 parts by weight, more preferably 0.15 to 18 parts by weight, more preferably 0.2 to 15 parts by weight.

  The content of the reaction accelerator (E) is preferably 0.1 to 35 parts by weight, more preferably 100 parts by weight based on the total of all the epoxy compounds and compounds having all double bonds contained in the solid content of the composition. Is 0.2 to 30 parts by weight, more preferably 0.3 to 25 parts by weight.

  When the composition contains an epoxy curing agent (j), the content of the reaction accelerator (E) is preferably 1 to 350 parts by weight, more preferably 2 to 2 parts per 100 parts by weight of the epoxy curing agent (j). 320 parts by weight, more preferably 3 to 300 parts by weight.

1.6.2. Surfactant (G)
When the composition of the present invention contains the surfactant (G), a composition having improved wettability, leveling property and coating property to the base substrate can be obtained. When the composition of the present invention contains a surfactant (G), the surfactant (G) may be used in an amount of 0.01 to 1% by weight with respect to 100% by weight of the composition of the present invention. preferable.
As the surfactant (G), only one type may be used, or two or more types may be mixed and used.

  As the surfactant (G), for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK-” can be used, for example, because the coating property of the composition of the present invention can be improved. 310 ”,“ BYK-341 ”,“ BYK-344 ”,“ BYK-370 ”(manufactured by Big Chemie Japan Co., Ltd.) and the like; trade names“ BYK-354 ”,“ BYK-358 ” Acrylic surfactants such as “BYK-361” (manufactured by Big Chemie Japan); trade names “DFX-18”, “Factent 250”, “Factent 251” (manufactured by Neos), Fluorosurfactants such as “Megafac RS-72-K” (manufactured by DIC Corporation) can be used.

1.6.3. Other epoxy compounds (h)
In the present invention, a compound having at least one oxirane ring or oxetane ring is referred to as an epoxy compound. In the present invention, the other epoxy compound (h) refers to an epoxy compound other than the epoxy compound corresponding to the epoxy compound (B) and the silane coupling agent (F). The epoxy compound corresponding to the epoxy compound (B) and the silane coupling agent (F) is a compound containing a silane coupling group and an epoxy group in the molecule, that is, a hydrolyzability that binds to an inorganic substance that is hydrolyzed to become a silanol group. An epoxy compound having a group and an epoxy group as a reactive function that binds to an organic substance.
Hereinafter, the other epoxy compound (h) and the epoxy compound (h) have the same meaning.
As the epoxy compound (h), a compound having two or more oxirane rings is preferably used, and the epoxy compound (h) may be used alone or in combination of two or more.

  Examples of the epoxy compound (h) include bisphenol A type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, silica fine particle-containing epoxy compounds, monomers having an oxirane ring, monomers having an oxirane ring, and others. And a copolymer with the above monomer.

Examples of the monomer having an oxirane ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and a compound represented by the following formula (9).
In the present invention, (meth) acrylate refers to acrylate and / or methacrylate, and (meth) acryl refers to acryl and / or methacryl.

In formula (9), R is independently a group selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl and arylalkyl; in alkyl having 1 to 45 carbon atoms, at least One hydrogen may be replaced with fluorine, and any non-adjacent —CH ₂ — may be replaced with —O— or —CH═CH—; the alkyl in the arylalkyl has 1 to 10 carbon atoms Any non-adjacent —CH ₂ — of the alkyl may be replaced by —O—; R ¹ and R ² are each independently selected from alkyl of 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl X ¹ is any one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl and oxetanylene. It is a group having one.

  Other monomers that copolymerize with monomers having an oxirane ring include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloro Examples include methylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

  Preferred examples of the polymer of the monomer having an oxirane ring and the copolymer of the monomer having an oxirane ring and another monomer include polyglycidyl methacrylate, a copolymer of methyl methacrylate and glycidyl methacrylate, benzyl methacrylate and glycidyl methacrylate. A copolymer of n-butyl methacrylate and glycidyl methacrylate, a copolymer of 2-hydroxyethyl methacrylate and glycidyl methacrylate, a copolymer of (3-ethyl-3-oxetanyl) methyl methacrylate and glycidyl methacrylate. Examples thereof include a polymer and a copolymer of styrene and glycidyl methacrylate. It is preferable that the composition of the present invention contains these epoxy compounds since the heat resistance of the cured film formed from the composition is further improved.

  Specific examples of the epoxy compound (h) include, for example, an epoxy compound “jER807” (epoxy equivalent 160 to 175 g / eq), “jER815”, “jER825” (epoxy equivalent 170 to 180 g / eq), “jER827” (epoxy 180-190 g / eq), “jER828” (epoxy equivalents 184-194 g / eq), “jER190P”, “jER191P”, “jER1001” (epoxy equivalents 450-500 g / eq), “jER1002” (epoxy equivalents 600- 700 g / eq), “jER1004” (epoxy equivalent 875-975 g / eq), “jER1004AF” (epoxy equivalent 875-975 g / eq), “jER1007” (epoxy equivalent 1750-2200 g / eq), “jER1010” (epoxy Equivalent 3000-5000 g / eq), “jER157S70” (epoxy equivalent 200-220 g / eq), “jER1032H60” (epoxy equivalent 163-175 g / eq), “jER1256” (epoxy equivalent 7500-8500 g / eq) , Manufactured by Mitsubishi Chemical Corporation), “Celoxide 2021P” (epoxy equivalent 128-145 g / eq), “Celoxide 3000”, “EHPE-3150” (epoxy equivalent 170-190 g / eq), “EHPE-3150CE” (epoxy) Equivalents 147 to 157 g / eq) (trade name, manufactured by Daicel Corporation), “TECHMORE VG3101L” (trade name, manufactured by Printec Co., Ltd., epoxy equivalent 210 g / eq), “HP7200” (epoxy equivalents 254 to 264 g) / Eq), "HP 7200H "(epoxy equivalent 272-284 g / eq)," HP7200HH "(epoxy equivalent 274-286 g / eq) (above trade name, manufactured by DIC Corporation)," NC-3000 "(epoxy equivalent 265-285 g / eq) "NC-3000H" (epoxy equivalent 280-300 g / eq), "EOCN-102S" (epoxy equivalent 205-217 g / eq), "EOCN-103S" (epoxy equivalent 209-219 g / eq), "EOCN-104S (Epoxy equivalents 213 to 223 g / eq), "EPPN-501H" (epoxy equivalents 162 to 172 g / eq), "EPPN-501HY" (epoxy equivalents 163 to 175 g / eq), "EPPN-502H" (epoxy equivalents 158 ~ 178g / eq), "EPPN-201" (epoxy 180-200 g / eq) (above trade name, manufactured by Nippon Kayaku Co., Ltd.), “TEP-G” (epoxy equivalent 160-180 g / eq) (above trade name, manufactured by Asahi Organic Materials Co., Ltd.), “MA -DGIC (epoxy equivalent 140 g / eq) "," DA-MGIC "(epoxy equivalent 265 g / eq)," TG-G "(epoxy equivalent 92 g / eq) (above trade name, manufactured by Shikoku Chemicals Co., Ltd.), "TEPIC-VL" (epoxy equivalent 125-145 g / eq) (trade name, manufactured by Nissan Chemical Industries, Ltd.), "NANOPOX C620" (trade name, manufactured by EVONIK, epoxy equivalent approximately 220 g / eq), "Adeka Resin EP- 4088S "(trade name, manufactured by ADEKA Corporation, epoxy equivalent 170 g / eq)," FLEP-50 "," FLEP-60 "," FLEP-65 " Le Fine Chemical Co., Ltd.), N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N′-tetraglycidyl-4,4′-diaminodiphenylmethane, γ-glycidoxypropyltrimethoxysilane (epoxy equivalent 194 g / eq), γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldi Examples include ethoxysilane and γ-glycidoxypropyltriethoxysilane. “NANOPOX C620” is a compound obtained by reacting Celoxide 2021P (60 parts by weight) with hydroxyl group-containing silica (40 parts by weight). Among these, compositions containing “FLEP-50”, “FLEP-60”, and “FLEP-65” are preferable because they have good adhesion to metals and glass.

  Although the density | concentration of the epoxy compound (h) in the composition of this invention is not specifically limited, From the point of obtaining the cured film which is excellent in heat resistance and the adhesiveness with respect to glass or ITO, the composition of this invention is obtained. The solid content (residue obtained by removing the solvent from the composition) is preferably contained in an amount of 0 to 50% by weight, and more preferably 0 to 40% by weight.

1.6.4. Solvent (i)
The composition of the present invention includes, for example, a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D), and a silane coupling agent. (F) can be obtained by dissolving in solvent (i). Accordingly, the solvent (i) is composed of polyester amide acid (A), epoxy compound (B) having a fluorene skeleton, urethane compound (C) having a double bond, photopolymerization initiator (D), and silane coupling agent ( A solvent capable of dissolving F) is preferred. Independently dissolves polyester amide acid (A), epoxy compound (B) having a fluorene skeleton, urethane compound (C) having a double bond, photopolymerization initiator (D), and silane coupling agent (F). Even if the solvent is not used, it may be possible to use it as the solvent (i) by mixing it with another solvent.
As the solvent (i), only one type may be used, or two or more types may be mixed and used.

  Examples of the solvent (i) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether. Acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene Glycol Nomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether (ECa), diethylene glycol monobutyl ether (DB) ), Ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl Ether, tetraethylene glycol dimethyl ether (MTEM), tetramethylene glycol monovinyl ether, 2-methoxyethanol, 2-ethoxyethanol, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, α-acetyl-γ-butyrolactone, ε-caprolactone, γ -Hexanolactone, δ-hexanolacto , Methyl ethyl sulfoxide, methyl 2-hydroxyisobutyrate (HBM), dimethyl sulfoxide and Idemitsu Kosan Co., Ltd. "Ekuamido" (trade name).

  Among these, dissolution of polyester amic acid (A), epoxy compound (B) having a fluorene skeleton, urethane compound (C) having a double bond, photopolymerization initiator (D), and silane coupling agent (F) In view of the properties, the composition of the present invention comprises ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, γ -Butyrolactone, diethylene glycol monoethyl ether (ECa), diethylene glycol monobutyl ether (DB), methyl 2-hydroxyisobutyrate (HBM), tetra Chi glycol dimethyl ether (MTEM), dimethyl sulfoxide and Idemitsu Kosan Co., Ltd. "Ekuamido" (trade name), at least one member selected from the group consisting of preferably includes a solvent (i).

1.6.5. Epoxy curing agent (i)
The composition of the present invention may contain an epoxy curing agent (j) that accelerates the curing reaction of epoxy by reacting itself. A cured film having excellent heat resistance and chemical resistance can be obtained by blending the epoxy curing agent (j). In the present invention, the reaction accelerator (E) is not included in the epoxy curing agent (j).
The epoxy curing agent (j) is a compound different from the polyester amide acid (A), and specific examples include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent. However, acid anhydride curing agents are preferred from the standpoint of color resistance and heat resistance.
As the epoxy curing agent (j), only one kind may be used, or two or more kinds may be mixed and used.

  Specific examples of the acid anhydride curing agent include, for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride (active hydrogen content equivalent of 64 0.0), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (active hydrogen content equivalent 77.5), 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (active hydrogen content) Equivalent 111.0), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (active hydrogen equivalent 75.0) And aromatic polycarboxylic acid anhydrides such as styrene-maleic anhydride copolymer. Among these, trimellitic anhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 4,4 ′ is obtained from the viewpoint that a composition excellent in solubility in the solvent (i) can be obtained. -(Hexafluoroisopropylidene) diphthalic anhydride is particularly preferred. Further, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride is particularly preferable from the viewpoint of obtaining a cured film having a high glass transition temperature.

  Specific examples of the carboxylic acid curing agent include maleic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and dimer acid.

  The dimer acid can be obtained, for example, by polymerizing an unsaturated fatty acid using a Lewis acid and a Bronsted acid as a catalyst. Dimer acid can be produced by a known method (eg, JP-A-9-12712).

  Examples of unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, eleostearic acid, Meade acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosepentaenoic acid, ozbond acid, succinic acid, tetracosapentaenoic acid, docosahexaenoic acid, nisic acid Is mentioned. Carbon number of unsaturated fatty acid is 4-24 normally, Preferably it is 14-20.

  For example, when dimer acid is produced using linoleic acid, the resulting mixture generally contains dimer acid having 36 carbon atoms as a main component, but monomer acid having 18 carbon atoms and trimer acid having 54 carbon atoms are also minor components. As a general rule, a small amount is included, and various structures derived from raw materials are included.

  The content of the epoxy curing agent (j) is the solid content of the composition of the present invention (excluding the solvent from the composition) from the standpoint that a cured film having high resistance to chemicals such as resist stripping solution and high transparency can be obtained. The remaining amount) is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight, and still more preferably 0 to 30 parts by weight with respect to 100 parts by weight, and preferably 0 to 100 parts by weight of the total epoxy compound. It is -300 weight part, More preferably, it is 0-200 weight part, More preferably, it is 0-100 weight part.

  Moreover, the ratio of the total epoxy compound to be used and the epoxy curing agent (j) is such that a composition having excellent solubility in the solvent (i) is obtained, and a cured film having high transparency, excellent heat resistance, chemical resistance, and low water absorption. The amount of groups capable of reacting with epoxy groups such as acid anhydride groups and carboxyl groups in the epoxy curing agent is 0 to 1.5 times the amount of epoxy groups in all epoxy compounds used. It is preferably an equivalent, more preferably 0 to 1.2 times equivalent, and more preferably 0 to 0.8 times equivalent, since the chemical resistance of the resulting cured film is further improved. In this case, for example, when 1 equivalent of a compound having one epoxy group is used as the total epoxy compound and 1 equivalent of a compound having one acid anhydride group is used as the epoxy curing agent (j), all the epoxy compounds It is assumed that the amount of the epoxy curing agent (j) is 2 times equivalent.

1.6.6. The polyimide resin is not particularly limited as long as it has an imide group.
A polyimide resin may use only 1 type and may mix and use 2 or more types.

  The polyimide resin can be obtained, for example, by imidizing polyamic acid obtained by reacting acid dianhydride and diamine. As an acid dianhydride, the tetracarboxylic dianhydride (a1) which can be used for the synthesis | combination of a polyester amide acid (A) is mentioned, for example. Examples of the diamine include diamine (a2) that can be used for the synthesis of polyester amic acid (A).

  When the composition of the present invention contains a polyimide resin, the concentration of the polyimide resin in 100% by weight of the composition of the present invention is not particularly limited, but a cured film having better heat resistance and chemical resistance can be obtained. From the viewpoint, 0.1 to 20% by weight is preferable, and 0.1 to 10% by weight is more preferable.

1.6.7. Polymerizable monomer Examples of the polymerizable monomer include monofunctional polymerizable monomers, bifunctional (meth) acrylates, and trifunctional or higher polyfunctional (meth) acrylates.
As the polymerizable monomer, only one type may be used, or two or more types may be mixed and used.

  When the composition of the present invention contains a polymerizable monomer, the concentration of the polymerizable monomer in the composition of the present invention is not particularly limited, but a cured film having a better chemical resistance and surface hardness can be obtained. From 10 to 80% by weight, preferably 20 to 70% by weight is contained in 100% by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition). Is more preferable.

Examples of the monofunctional polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decanyl (meth) acrylate, glycerol model (Meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl ( (Meth) acrylate, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl- 3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) Acryloxime Tyloxetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide , N-phenylmaleimide, (meth) acrylamide, N-acryloylmorpholine, polystyrene macromonomer, polymethylmethacrylate macromonomer, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid , Itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl] , And chlorohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl].

  Examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanedio Distearate (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol di (meth) acrylate.

  Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and epichlorohydrin modified tri Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta Rithritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified tri (meth) acrylate phosphate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and urethane (meth) acrylate.

1.6.8. The antistatic agent can be used to prevent the composition of the present invention from being charged. When the composition of the present invention contains an antistatic agent, 0 in 100% by weight of the composition of the present invention. It is preferably used in an amount of 0.01 to 1% by weight.
A known antistatic agent can be used as the antistatic agent. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; and quaternary ammonium salts.
Only one type of antistatic agent may be used, or a mixture of two or more types may be used.

1.6.9. Antioxidant When the composition of the present invention contains an antioxidant, it is possible to prevent deterioration when a cured film obtained from the composition is exposed to high temperature or light. When the composition of the present invention contains an antioxidant, the antioxidant is 0.1 parts by weight based on 100 parts by weight of the solid content of the composition excluding the antioxidant (residue obtained by removing the solvent from the composition). It is preferable to add ~ 3 parts by weight.
Only 1 type may be used for antioxidant and 2 or more types may be mixed and used for it.

  Examples of the antioxidant include hindered amine compounds and hindered phenol compounds. Specifically, “IRGAFOS XP40”, “IRGAFOS XP60”, “IRGANOX 1010”, “IRGANOX 1035”, “IRGANOX 1076”, “IRGANOX 1135”, “IRGANOX 1520L” (trade name, manufactured by BASF), “ "ADK STAB AO-20", "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-80", "ADK STAB AO-330" (above product names, ADEKA Corporation) Manufactured) and the like.

1.6.10. Examples of the pigment or dye pigment include silicon carbide, alumina, magnesia, silica, zinc oxide, low-order titanium oxide, and graphite.
Examples of the dye include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes. Examples of azo dyes include “VALIFAST BLACK 3810”, “VALIFAST BLACK 3820”, “VALIFAST RED 3304”, “VALIFAST RED 3320”, and “OIL BLACK 860” (trade names, manufactured by Orient Chemical Industry Co., Ltd.). It is done.
Each of the pigment and the dye may be used alone or in combination of two or more.

2. Preparation method of thermosetting resin composition The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D ), And a silane coupling agent (F) and, if necessary, an epoxy curing accelerator (E), a surfactant (G), an epoxy compound (h), a solvent (i), and other additives are mixed. Can be prepared.
In addition, the composition of the present invention is prepared by using the reaction solution and the mixed solution obtained during the synthesis of the polyester amide acid (A) as they are, the epoxy compound (B) having a fluorene skeleton, the urethane compound (C) having a double bond, Photopolymerization initiator (D), silane coupling agent (F), epoxy curing accelerator (E) and surfactant (G) used as necessary, epoxy compound (h), solvent (i), etc. It can also be prepared by mixing with other additives.

3. Forming method of cured film The cured film of the present invention is not particularly limited as long as it is a film obtained by curing the composition of the present invention. The cured film of the present invention can be obtained, for example, by applying the composition of the present invention on a substrate, irradiating with UV-LED after drying, and finally heating.
Hereinafter, the coating method and the curing method in the method for forming a cured film using the composition of the present invention will be described.

3.1. Application Method of Thermosetting Resin Composition Application of the composition of the present invention on a substrate can be performed by spray coating, spin coating, roll coating, dipping, slit coating, bar coating, gravure printing, flexographic printing. It can be performed by a conventionally known method such as a printing method, an offset printing method, a dispenser method, a screen printing method and an ink jet printing method.

  For example, from the composition of the present invention, in the case of forming a transparent insulating film provided so that the X and Y electrodes are not in contact with each other, a gravure printing method, a flexographic printing method, an offset printing method is used in that pattern formation is easy. Printing methods such as a dispenser method, a screen printing method and an ink jet printing method are preferred.

  Further, for example, in the case of forming an overcoat from the composition of the present invention, spin coating, slit coating, gravure printing, flexographic printing, offset printing, dispenser, A coating method such as a screen printing method is preferred.

The substrate is not particularly limited, and a known substrate can be used. For example, glass that conforms to various standards such as FR-1, FR-3, FR-4, CEM-3, or E668. Epoxy substrate, glass composite substrate, paper phenol substrate, paper epoxy substrate, green epoxy substrate, BT (bismaleimide triazine) resin substrate; copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or A substrate made of metal such as stainless steel (may be a substrate having a layer made of these metals on the surface); indium tin oxide (ITO), aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium Silicate (zircon), magnesium oxide (magnesia), titanium Aluminum, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia) ), Silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel or spojumen Substrates made of inorganic substances (may be substrates having a layer containing these inorganic substances on the surface); PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylene dimethylene) Terephthalate), PPS (polyphenylene sulfide), polycarbonate, polyacetal, polyphenylene ether, polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer Or a substrate made of a resin such as a liquid crystal polymer (may be a substrate having a layer containing these resins on its surface); a semiconductor substrate such as silicon, germanium, or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO, or ATO A substrate on which an electrode material (wiring) such as (antimony tin oxide) is formed; αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel) or γGEL (gamma gel) (above Gel sheet registered trademark) of Tayca; and the like.
The composition of the present invention is preferably applied on a glass substrate, an ITO substrate or a resin film substrate.

3.2. Curing method of composition After coating the composition of the present invention, the composition coated on the substrate is dried, irradiated with UV-LED, and finally heated to obtain a cured film. As a method for forming a cured film in this manner, preferably, after applying the composition of the present invention, the solvent is removed by heating (drying treatment) by heating with a hot plate or an oven, etc. Further, a method of further heating (curing treatment) is used.

  If the composition of the present invention is used, a cured product having good resist stripping solution resistance and high transparency can be obtained by a two-stage curing process including an ultraviolet irradiation process and a heating process.

  In the ultraviolet irradiation process, the composition formed in a predetermined shape on the surface of an object to be coated such as a substrate is irradiated with ultraviolet rays so that it does not adhere even when touched lightly with a fingertip (so-called “tack-free” state). It is the 1st hardening process of hardening a composition until.

  As a light source used in the ultraviolet irradiation process, a UV-LED (ultraviolet LED) is preferable in that the required amount of energy is small and the load on the environment is low and the possibility of damaging the substrate is small. The UV-LED is also excellent in that the operation is simple. As irradiation light, for example, those having a maximum radiation wavelength of 385 nm are preferable. Examples of the light source other than the UV-LED include a UV mercury lamp and a metal halide lamp.

  The heating process is a second curing process in which the composition cured to a tack-free state by the ultraviolet irradiation process is further cured. By combining the ultraviolet irradiation step and the heating step, curing can proceed at a lower temperature than when the composition is cured only by heating. Therefore, the heating process which makes the hardened | cured material provided with the property which can be used as a transparent insulating film and overcoat can be implemented at temperature lower than before.

The temperature of the heating step is preferably 50 to 150 ° C, more preferably 70 to 120 ° C, and still more preferably 80 to 110 ° C from the viewpoint of preventing deformation due to softening of the substrate made of plastic such as PET.
Although the time of a heating process changes with temperature conditions, the shape of the composition to harden | cure, etc., the longer one is preferable for improving the physical property of hardened | cured material, and the shorter one is convenient for improving productivity. For example, when an overcoat is formed at a heating step of 100 ° C., it is preferably 10 to 120 minutes, more preferably 20 to 90 minutes, and even more preferably 30 to 60 minutes.

  When the composition is cured to obtain a cured product, the above-described ultraviolet irradiation step and other steps of the heating step may be performed. For example, as described above, a drying step of drying the solvent in the composition to some extent may be performed before the ultraviolet irradiation step. When performing the drying process, the temperature is lower than that of the heating process and for a short time.

  The conditions for the drying treatment vary depending on the types and blending ratios of the components contained in the composition to be used, but the heating temperature is usually 70 to 120 ° C., and the heating time is 5 to 15 minutes for an oven and 1 for a hot plate. 10 minutes. By such a drying process, a coating film to the extent that the shape can be maintained can be formed on the substrate.

  After forming the coating film, a cured film can be obtained by a curing treatment in which heat treatment is performed for 10 to 120 minutes using an oven or the like. The curing treatment is not limited to heat treatment, and may be treatment such as ultraviolet ray, near infrared ray, far infrared ray, ion beam, electron beam or gamma ray irradiation.

  The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D), and a silane coupling agent (F ), The low-temperature curability is good. For this reason, the cured film excellent in chemical resistance etc. can be formed by low-temperature baking of 100 degrees C or less. Therefore, it is possible to form a cured film even on a resin film substrate such as PET that is difficult to perform the curing process at a high temperature.

4). Substrate with Cured Film The substrate with a cured film of the present invention is not particularly limited as long as it has the cured film of the present invention, but at least one selected from the group consisting of the above-mentioned substrates, particularly glass substrates, ITO substrates, and resin film substrates. It is preferable to have the above-mentioned cured film on a kind of substrate.
Such a substrate with a cured film, for example, on the substrate of glass, ITO, PET, PEN, etc., the composition of the present invention is applied to the entire surface or a predetermined pattern (line shape, etc.) by the coating method, Then, it can form by passing through the drying process and hardening process which were demonstrated above.

5. Electronic component An electronic component of the present invention is an electronic component having the above-described cured film or substrate with a cured film. Examples of such electronic components include color filters, various optical materials such as LED light emitting elements and light receiving elements, and touch panels.

The touch panel can be manufactured, for example, by combining a liquid crystal display device or an organic electroluminescence device and a position detection device.
Here, as the position detection device, for example, a cured film (transparent insulating film) of the present invention is formed on a substrate on which a wiring (X electrode) made of a conductive material such as ITO is formed so as to cover the wiring. Then, an apparatus in which a wiring (Y electrode) made of a conductive material such as ITO is formed so as to be orthogonal to the X electrode, and then an overcoat is formed with the cured film of the present invention so as to cover the entire surface of the substrate. It is done.

  In the production of such a device, the cured film (transparent insulating film) usually formed in a pattern by a printing method or the like by using the composition of the present invention, and usually the front surface by a coating method or the like. The overcoat formed can be formed of a single composition. Therefore, by using the composition of the present invention, it is possible to simplify the line and improve the yield when manufacturing electronic components.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. Epoxy compound (B) having a fluorene skeleton, other epoxy compound (h), urethane compound (C) having a double bond, photopolymerization initiator (D), reaction accelerator (E), silane used in Examples Coupling agent (F), reaction accelerator (E), solvent (i), surfactant (G), tetracarboxylic dianhydride (a1), diamine (a2) used for the synthesis of polyester amic acid (A) ), Polyhydric hydroxy compound (a3), monohydric alcohol (a4), reaction solvent (a5) and polyhydric acid anhydride (a6), and their abbreviations. These abbreviations are used in the following description.

<Polyester amide acid (A)>
<Tetracarboxylic dianhydride (a1)>
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride <Diamine (a2)>
DDS: 3,3′-diaminodiphenylsulfone <Polyvalent hydroxy compound (a3)>
BDOH: 1,4-butanediol <monohydric alcohol (a4)>
BzOH: benzyl alcohol <Reaction solvent (a5)>
MPM: methyl 3-methoxypropionate

<Epoxy compound having a fluorene skeleton (B)>
EG-200: OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.) (epoxy equivalent 290, weight average molecular weight 2,000 or less)

<Other epoxy compounds (h)>
FLEP-60: Polysulfide polymer having an epoxy group at the terminal FLEP-60 (trade name, all manufactured by Toray Fine Chemical)

<Silane coupling agent (F)>
S510: 3-glycidoxypropyltrimethoxysilane, Silaace S510 (trade name, manufactured by JNC Corporation)
S710: 3-acryloxypropyltrimethoxysilane, Silaace S710 (trade name, manufactured by JNC Corporation)

<Urethane compound having a double bond (C)>
UV-1700B: 10 functional group urethane acrylate, UV-1700B (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.))
UA-122P: 5-functional urethane acrylate, UA-122P (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.))

<Compound with double bond>
M402: Dipentaerythritol hexaacrylate (trade name, manufactured by Toagosei Co., Ltd.)
P-2M: Phosphoric acid-containing (meth) acrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)

<Photopolymerization initiator (D)>
Acylphosphine oxide photopolymerization initiator Irgacure TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name, manufactured by BASF Japan Ltd.)
Irgacure 819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
Alkylphenone-based photopolymerization initiator Irgacure 379EG: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name, BASF (Made by Japan)
Irgacure 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name, manufactured by BASF Japan Ltd.)
Oxime ester photopolymerization agent Irgacure OXE01: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name, manufactured by BASF Japan Ltd.)
Irgacure OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (trade name, manufactured by BASF Japan Ltd.)
Irgacure OXE03 (trade name, manufactured by BASF Japan Ltd.)
Irgacure OXE04 (trade name, manufactured by BASF Japan Ltd.)
DETX-S: 2,4-diethylthioxanthone, KAYA CURE DETX-S (trade name; Nippon Kayaku Co., Ltd.)

<Reaction accelerator (E)>
Kalenz MT PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karenz MT PE1, manufactured by Showa Denko KK)

<Solvent (i)>
DPMA: Dipropylene glycol methyl ether acetate Eca: Diethylene glycol monoethyl ether (ethyl carbitol (common name))

<Surfactant (G)>
RS-72K (Brand name Megafuck RS-72K, manufactured by DIC Corporation)

<Polyester amide acid (A)>
First, polyester amic acid was synthesized as shown below (Synthesis Example 1).
[Synthesis Example 1]
A 1000 ml separable flask equipped with a thermometer, a stirring blade, a raw material charging inlet and a nitrogen gas inlet was charged with 46.96 g of dehydrated and purified MP31.93 g of BDOH, 25.54 g of BzOH and 183.20 g of ODPA under a dry nitrogen stream. Stir at 130 ° C. for 3 hours. Thereafter, the reaction solution was cooled to 25 ° C., 29.33 g of DDS and 183.04 g of MPM were added, and the mixture was stirred at 20 to 30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour. Thereafter, by cooling to 30 ° C. or lower, a pale yellow transparent 30% by weight solution of polyester amic acid was obtained.

  The rotational viscosity of this solution was 28.2 mPa · s. Here, the rotational viscosity is a value measured at 25 ° C. using an E-type viscometer (trade name; TVE-22LT, manufactured by Toki Sangyo Co., Ltd.) (hereinafter the same).

Moreover, the weight average molecular weight of the obtained polyester amide acid was 4,200. The weight average molecular weight of the polyester amide acid was measured as follows.
The obtained polyester amide acid is diluted with N, N-dimethylformamide (DMF) so that the concentration of the polyester amide acid is about 1% by weight to prepare a diluted solution. GPC apparatus: manufactured by JASCO Corporation Using Chrom Nav (differential refractometer RI-2031 Plus), the diluted solution was measured by GPC method using a developing agent, and was calculated by polystyrene conversion. Three columns, GF-1G7B, GF-510HQ and GF-310HQ, manufactured by Showa Denko Co., Ltd., were connected in this order, and the column was measured under conditions of a column temperature of 40 ° C. and a flow rate of 0.5 ml / min. (same as below).

[Example 1]
A 1,000 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 16.7 g of the polyester amic acid (A) solution obtained in Synthesis Example 1 (the amount of the polyester amic acid (A) in the solution is 5.0 g), 10.0 g FLEP-60, 12.5 g EG-200, 4.0 g S710, 10.0 g UA-122P, 25.0 g M402, 1.0 g P-2M, Irgacure 1.0 g of TPO, 1.0 g of Irgacure 907, 12.5 g of DPMA, 138.0 g of Eca, and 0.44 g of RS-72K were charged. Then, it stirred at 25 degreeC (room temperature) for 1 hour, and dissolved each component uniformly. After stirring at 25 ° C. for 30 minutes, the mixture was filtered through a membrane filter (material: polypropylene, pore size: 0.22 μm) to obtain a photosensitive composition as a filtrate.

[Examples 2-35]
In Examples 2 to 35, photosensitive compositions were prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Tables 2 to 5. In addition, the preparation amount of each component in the table indicates weight (g) (the same applies to the following tables).

[Comparative Examples 1-5]
Comparative Examples 1-5 prepared the photosensitive composition like Example 1 except having changed the kind and preparation amount of each component as shown in Table 6.

Using the photosensitive compositions according to the above Examples and Comparative Examples, a coating film was formed under the following conditions and then dried to obtain a pre-cured substrate on which a coating film before temporary curing was formed.
Substrate: Glass, EagleXG (trade name, manufactured by Corning)
Application method: Spin coat Spin coater: MS-A150 (trade name, manufactured by Mikasa Corporation)
Drying: Hot plate 80 ° C for 5 minutes

(Ultraviolet irradiation process, first curing process, exposure; number of tackless passes)
Using a conveyor-conveying 385 nm LED irradiation device (trade name: ASM1503NM-UV-LED, manufactured by Asumi Giken Co., Ltd.), coating is performed on the pre-cured substrate formed as described above under the condition of 300 mJ / cm ² at 1 Pass. Cured until the film was tack free. Tables 2 to 6 show the number of passes required for each photosensitive composition to become tack-free (the number of tackless passes).

(Thermosetting process, second curing process, firing)
The coating film of the photosensitive composition cured until it becomes tack-free by the ultraviolet irradiation process is baked at 100 ° C. for 60 minutes using a circulation type clean oven (trade name: DT-610 manufactured by Yamato Scientific Co., Ltd.). did.

(Film thickness)
About the cured product obtained by curing the coating film of the photosensitive composition formed on the substrate by a thermosetting process, using a stylus type step meter P-16 + (trade name, manufactured by KLA-Tencor) The film thickness (A, μm) was measured.

[Evaluation method]
(Optical property measurement; 400 nm transmittance)
About the hardened | cured material obtained by the thermosetting process, 400 nm transmittance | permeability was measured using the ultraviolet visible spectrophotometer V-670 (brand name, JASCO Corporation make). The transmittance was measured using glass as a reference (reference).

(Chemical resistance measurement; N300 resistance remaining film rate, N300 resistance after remaining film rate)
The board | substrate with which the hardened | cured material obtained by the thermosetting process was formed was immersed in Nagase resist strip N-300 (brand name, product made by Nagase ChemteX) at 40 degreeC for 20 minute (s). After taking out the board | substrate after the said immersion and washing with water, the film thickness (B, micrometer) of the hardened | cured material after immersion was measured using the stylus type level difference meter.
Further, the substrate was heated on a hot plate at 100 ° C. for 5 minutes and dried, and then the thickness (C, μm) of the cured product after heating was measured.

Using the film thickness before treatment (A), the film thickness after immersion (B), and the film thickness after heating (C), the remaining film ratio (%) after the immersion treatment and after the heat treatment in the chemical resistance test is as follows: It calculated | required using the formula of.
Remaining film ratio after immersion treatment (N300 resistance remaining film ratio,%)
= [Film thickness after immersion (B) / film thickness before treatment (A)] × 100
Residual film ratio after immersion treatment and heat treatment (Residual film ratio after N300 resistance,%)
= [Film thickness after heating (C) / Film thickness before treatment (A)] × 100
Peeling: The cured film peeled after the test.
NA: Not measured.

(Adhesion measurement; adhesion after N300 resistance)
After the same treatment as chemical resistance (dipping in N300, washing with water, drying by heating), an adhesion test of the cured product to the substrate was performed. For the adhesion test, a cross-cut peel test was used.
In the cross-cut method, a line of 1 mm intervals is drawn with a cutter 11 by 11 in length and width, and 100 cross sections are prepared, and then the ratio of the cured film peeled off from the substrate surface by applying a tape is peeled off according to standard ASTM D3359. Based on the evaluation.
As the tape for peeling, Scotch # 610, manufactured by 3M: 402 N / 100 mm (longitudinal direction) was used.
Evaluation criteria based on the standard ASTM D3359 are as follows.
0B: 65% or more 1B: 35% or more, 65% or less 2B: 15% or more, 35% or less 3B: 5% or more, 15% or less 4B: 5% or less 5B: No peeling NA: Not measured.

The evaluation results of the examples are shown in Tables 2 to 5, and the evaluation results of the comparative examples are shown in Table 6. From these results, the following was found.
By blending the silane coupling agent (F), N300 resistance and adhesion are improved.
By mix | blending reaction accelerator (E), N300 tolerance and adhesiveness become favorable.
When one type of photopolymerization initiator is used, Irature TPO is preferred.
By adjusting the blending amount of the photopolymerizable initiator (D) with respect to the urethane compound (C) having a double bond, a cured product having good N300 resistance and adhesion can be obtained.
By adjusting the blending amount of the photopolymerizable initiator (D) with respect to the total amount of the epoxy compound (B) having a fluorene skeleton, the epoxy compound (h) and the urethane compound (C) having a double bond, N300 resistance and adhesion A cured product having good properties can be obtained.
If the amount of Irture TPO preferred when using one type of photopolymerization initiator is too large relative to the urethane compound (C) having a double bond, the adhesion tends to decrease. However, adhesiveness improves by increasing the compounding quantity of a silane coupling agent (F).

Since the photosensitive composition of the present invention can form a transparent cured film having good resistance to a resist stripper after low-temperature curing at 100 ° C. or lower, it forms a transparent insulating film or overcoat that can also be used for a plastic substrate. Can be used.

Claims (16)

  Photosensitive composition containing polyester amic acid (A), epoxy compound (B) having a fluorene skeleton, urethane compound (C) having a double bond, photopolymerization initiator (D), and silane coupling agent (F) .   The photosensitive composition according to claim 1, further comprising a reaction accelerator (E).   The photosensitive composition of Claim 2 whose said reaction accelerator (E) is a compound which has a thiol group in a molecule | numerator.   Content of the said photoinitiator (D) is 2.5-10 weight part with respect to 100 weight part of sum total of content of the urethane compound (C) which has the said double bond. 4. The photosensitive composition according to any one of 3 above.   The photosensitive composition of any one of Claims 1-4 in which the said silane coupling agent (F) is contained 3 to 15weight% in the total solid of a photosensitive composition.   Content of the said reaction accelerator (E) is 0.1-1.6 weight part with respect to 100 weight part of sum total of content of the urethane compound (C) which has an oxiranyl compound and a double bond, Item 6. The photosensitive composition according to any one of Items 2 to 5.   The photosensitive composition of any one of Claims 1-6 whose urethane compound (C) which has the said double bond is a bifunctional or more than urethane acrylate.   The photosensitive composition according to any one of claims 1 to 7, wherein the bifunctional or higher urethane acrylate is contained in an amount of 10 to 60% by weight in a solid content in the photosensitive composition.   Furthermore, the photosensitive composition of any one of Claims 1-8 containing surfactant (G).   The cured film obtained from the photosensitive composition of any one of Claims 1-9. The cured film is
The cured film of Claim 10 obtained by the ultraviolet irradiation process which irradiates an ultraviolet-ray to the said photosensitive composition, and the heating process after the said ultraviolet irradiation process.   The cured film of Claim 11 whose temperature of the said heating process is 110 degrees C or less.   The cured film of Claim 11 or 12 whose ultraviolet irradiation process irradiates an ultraviolet-ray using UV-LED.   The board | substrate with a cured film which has a cured film of any one of Claims 10-13.   The electronic component which has a cured film of any one of Claims 10-13, or a board | substrate with a cured film of Claim 14.   The electronic component according to claim 15, which is a touch panel type input device.