JP6248506B2 - Composition for forming cured film - Google Patents

Description

  The present invention relates to a composition for forming a cured film capable of forming a cured film whose surface free energy is changed by ultraviolet irradiation.

  Conventionally, a photolithography method has been used to form wirings used for printed wiring boards and semiconductor package substrates. However, the photolithography method requires expensive equipment and high manufacturing costs due to long and complicated processes. In recent years, various electronic parts such as printed wiring boards have been formed by directly drawing fine wiring patterns using various printing methods such as the ink jet method as an alternative to the photolithography method, which has a high manufacturing cost. The method to do is attracting attention. On the other hand, a printing method such as an ink jet method has a problem that the accuracy of a drawn pattern is lower than that of a photolithography method due to ink wetting and liquid accumulation.

  As one of the methods for solving the above problems, a wettability changing layer made of a wettability changing material capable of changing the surface free energy by applying energy is formed on the substrate, and the wettability changing layer is formed on the substrate. A method has been proposed in which a fine pattern consisting of a lyophobic part and a lyophilic part in which a wiring pattern is reflected in advance is formed on a substrate before a fine wiring pattern is drawn by applying a certain active energy. (For example, refer to Patent Document 1).

  The conditions for drawing a fine wiring pattern using the wettability changing layer are that the contact angle of water on the thin film before ultraviolet irradiation is 90 ° or more and that the surface free energy difference before and after ultraviolet irradiation is as much as possible. It is large, for example, 15 mN / m or more. By satisfying these conditions, when ink is applied on the wettability changing layer, it is possible to paint using the difference between the low surface free energy part and the high surface free energy part, thereby realizing high-accuracy pattern drawing. it can.

Patent Document 2 discloses a polymer material containing polyimide having a hydrophobic group whose critical surface tension is changed by application of energy. According to Patent Document 2, these polyimides are applied onto a substrate and dried at 180 ° C. to form a cured film, and further irradiated with ultraviolet light having a wavelength of 250 nm to change the wettability of the cured film. ing. In the example of Patent Document 2, the contact angle of water exceeds 90 ° when not irradiated and is hydrophobic (water repellent), but when irradiated with ultraviolet rays at an irradiation dose of 10 J / cm ² or more, 20 Further, it is described that the surface free energy is decreased by 18 ° and the surface free energy is changed from 18 to 28 mN / m before irradiation to 41 to 44 mN / m after irradiation.

However, in the method of Patent Document 2, when the water contact angle is changed from hydrophobicity exceeding 90 ° to hydrophilicity where the water contact angle is 20 °, ultraviolet treatment with an irradiation amount of 10 J / cm ² or more is performed. is necessary. As described in Patent Document 2, when the intensity of 250 nm light is adjusted to 5 mW / cm ² using a UV lamp, the irradiation time is 2000 sec, that is, a long time of about 33 minutes is required. . Also, if a flexible substrate such as a film made of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), or PC (polycarbonate), which is easily deformed by heat, is used, the substrate may be bent or distorted by irradiation with ultraviolet rays for a long time. There is a problem that it is easily generated and deformed.

Patent Document 3 discloses a polyimide precursor that can largely change hydrophilicity / hydrophobicity by ultraviolet light irradiation, and a polyimide obtained by dehydrating and ring-closing the polyimide precursor. In the example of Patent Document 3, the cured film made of such a polyimide precursor or polyimide is irradiated with ultraviolet rays of 40 J / cm ² near 254 nm, so that the contact angle of water exceeds 90 ° when not irradiated. It is described that the contact angle of water has changed to hydrophilicity of 25 ° or less.

However, in the method of Patent Document 3, the irradiation dose required for changing the water contact angle from the hydrophobicity exceeding 90 ° to the hydrophilicity where the water contact angle is 25 ° or less is a huge 40 J / cm. ^{Since 2} is required, it is assumed to be difficult for actual application.

JP 2002-164635 A JP 2006-60113 A International Publication No. 2009/113549 Pamphlet

  An object of the present invention is a composition for forming a fine wiring pattern on an electronic circuit board or the like, which has a low surface free energy and high liquid repellency by being applied onto a substrate and heated and dried. Forming a cured film that can form a lyophilic region having a high surface free energy by irradiating the cured film with ultraviolet rays at a dose smaller than that of the prior art It is to provide a composition for use.

  As a result of intensive studies to solve the above problems, the present inventor has achieved the wettability of a cured film with a smaller amount of ultraviolet irradiation by using a composition containing an amide derivative having a specific structure or an imidized product thereof. It was found that it can be easily changed. That is, the cured film made of the composition has low surface free energy and high liquid repellency, but by selectively irradiating the cured film surface with ultraviolet light, the surface free energy of the irradiated region is increased, and the lyophilic liquid It has been found that a wettable region can be easily formed and a wettability changing layer for forming a desired fine wiring pattern can be obtained. The present invention includes, for example, the following matters.

[1] Amide derivative (A1) obtained by reacting acid anhydride (a1) having a partial structure represented by the following formula (1) with amine (a2) having a hydrophobic group, and imidized product (A2) A composition comprising at least one compound (A) selected from the group consisting of:
For forming a cured film used in a method of forming a surface free energy portion higher than the surface free energy of the unirradiated portion on the cured film surface by irradiating at least part of the cured film obtained from the composition with ultraviolet rays Composition.

式（１）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ水素または炭素数１〜１０のアルキルである。

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each hydrogen or alkyl having 1 to 10 carbons.

  [2] The composition for forming a cured film according to item [1], wherein the acid anhydride (a1) is an acid anhydride represented by the following formula (2-1) or (2-2).

式（２−１）および（２−２）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ独立に水素または炭素数１〜１０のアルキルであり、Ｒ⁵は単結合、炭素または炭素数１〜５０の２〜４価の有機基であり、ｍは１または２であり、ｎは１または２である。

In formulas (2-1) and (2-2), R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or alkyl having 1 to 10 carbons, and R ⁵ is a single bond, carbon or A divalent to tetravalent organic group having 1 to 50 carbon atoms, m is 1 or 2, and n is 1 or 2.

  [3] Item [1] or [3], wherein the acid anhydride (a1) is at least one compound selected from the group consisting of tetracarboxylic dianhydrides represented by the following formulas (3) to (5): The composition for forming a cured film as described in 2].

［４］ アミン（ａ２）が、メチレン基を含み、かつ、疎水性基を有するモノアミンおよびジアミンからなる群より選ばれる少なくとも一種の化合物である、項［１］〜［３］のいずれか１項に記載の硬化膜形成用組成物。

[4] Any one of Items [1] to [3], wherein the amine (a2) is at least one compound selected from the group consisting of a monoamine and a diamine having a methylene group and having a hydrophobic group. The composition for forming a cured film as described in 1.

  [5] The composition for forming a cured film according to any one of items [1] to [4], wherein the amine (a2) is a compound represented by the following formula (6).

式（６）中、Ｔ、ＵおよびＶは、それぞれ独立してベンゼン環またはシクロヘキサン環であり、これらの環上の任意の水素は、炭素数１〜３のアルキル、炭素数１〜３のフッ素置換アルキル、フッ素、塩素またはシアノで置き換えられてもよく、ｈは０〜５の整数であり、ｉおよびｊは、それぞれ０〜２の整数であり、ｐは０または１であり、ｑは１または２であり、Ｒは水素、フッ素、塩素、シアノまたは炭素数１〜３０の１価の有機基である。

In formula (6), T, U and V are each independently a benzene ring or a cyclohexane ring, and any hydrogen on these rings is alkyl having 1 to 3 carbon atoms, fluorine having 1 to 3 carbon atoms May be substituted with substituted alkyl, fluorine, chlorine or cyano, h is an integer from 0 to 5, i and j are each an integer from 0 to 2, p is 0 or 1 and q is 1; Or 2, and R is hydrogen, fluorine, chlorine, cyano, or a monovalent organic group having 1 to 30 carbon atoms.

  [6] The composition for forming a cured film according to any one of items [1] to [5], wherein the amine (a2) is a compound represented by the following formula (7).

式（７）中、ＵおよびＶは、それぞれ独立してベンゼン環またはシクロヘキサン環であり、ｈは０または１であり、ｉおよびｊは、それぞれ０〜２の整数であり、ｐは０または１であり、Ｒは水素、フッ素または炭素数１〜２０の１価の有機基である。

In Formula (7), U and V are each independently a benzene ring or a cyclohexane ring, h is 0 or 1, i and j are each an integer of 0 to 2, and p is 0 or 1 R is hydrogen, fluorine or a monovalent organic group having 1 to 20 carbon atoms.

  [7] The composition for forming a cured film according to any one of items [1] to [6], further including a solvent (B).

  The composition of the present invention can be easily applied by various methods such as spin coating and printing, and can form a cured film exhibiting excellent liquid repellency. In addition, by irradiating the cured film with ultraviolet rays with a smaller dose than in the prior art, the liquid-repellent film surface can be easily changed to a highly lyophilic film surface. A cured film having a desired lyophilic region having a large difference in wettability between the hydrophilic regions can be obtained. Therefore, the present invention can be applied not only to a glass substrate but also to a flexible substrate such as a film such as PET, PEN, or PC that is easily deformed by heat.

  The composition of the present invention can form an insulating film having excellent insulating properties and solvent resistance by changing the curing method as needed after being applied to a substrate. It can also be used as a constituent material. In this case, since the step of applying a surface treatment agent or the like to the insulating film and performing the liquid repellent treatment can be omitted, the manufacturing process can be simplified and the manufacturing cost can be reduced.

Hereinafter, the composition for forming a cured film according to the present invention (simply referred to as “the composition of the present invention”) will be described in detail.
In this specification, ink is a solution used when drawing a circuit pattern using various printing techniques, and is a material such as a conductor or semiconductor that constitutes an electronic component regardless of color or colorless. Refers to a solution containing dissolved or dispersed or the like.

[Composition for forming cured film]
The composition of this invention contains the compound (A) mentioned later, and may further contain a solvent (B) as needed. The composition of the present invention is a method for forming a surface free energy part higher than the surface free energy of the part not irradiated with ultraviolet rays on the cured film surface by irradiating at least part of the cured film obtained from the composition with ultraviolet rays. Used for.

<Compound (A)>
The compound (A) includes an amide derivative (A1) obtained by reacting an acid anhydride (a1) having a structure represented by the following formula (1) with an amine (a2) having a hydrophobic group, and an imide thereof And at least one compound selected from the group consisting of compound (A2).

式（１）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ水素または炭素数１〜１０のアルキルである。

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each hydrogen or alkyl having 1 to 10 carbons.

  Examples of the alkyl having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n- Examples include octyl, n-nonyl, and n-decyl.

1. Acid anhydride (a1)
The acid anhydride (a1) is not particularly limited as long as it is an acid anhydride having the structural unit of the formula (1). For example, an acid anhydride represented by the following formula (2-1) or (2-2) Thing is preferable and the acid anhydride represented by Formula (2-1) is more preferable.

式（２−１）および（２−２）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ独立に水素または炭素数１〜１０のアルキル、好ましくは水素または炭素数１〜８のアルキル、より好ましくは水素であり、Ｒ⁵は単結合、炭素または炭素数１〜５０の２〜４価の有機基、好ましくは単結合、炭素または炭素数１〜３０の有機基、より好ましくは単結合、炭素または炭素数１〜２０の有機基であり、ｍは１または２であり、ｎは１または２である。

In formulas (2-1) and (2-2), R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or alkyl having 1 to 10 carbons, preferably hydrogen or having 1 to 8 carbons. Alkyl, more preferably hydrogen, and R ⁵ is a single bond, carbon or a divalent to tetravalent organic group having 1 to 50 carbon atoms, preferably a single bond, carbon or an organic group having 1 to 30 carbon atoms, more preferably It is a single bond, carbon or an organic group having 1 to 20 carbon atoms, m is 1 or 2, and n is 1 or 2.

  Preferable examples of the acid anhydride represented by the formula (2-1) include tetracarboxylic dianhydrides represented by the following formulas (3) to (5).

２．アミン（ａ２）
アミン（ａ２）は、疎水性基を有するアミンであれば特に限定されないが、メチレン基を含み、かつ、疎水性基を側鎖に有するモノアミンおよびジアミンからなる群より選ばれる少なくとも一種の化合物が好ましく、下記式（６）で表される化合物がより好ましく、下記式（７）で表わされる化合物が特に好ましい。

2. Amine (a2)
The amine (a2) is not particularly limited as long as it is an amine having a hydrophobic group, but is preferably at least one compound selected from the group consisting of a monoamine and a diamine containing a methylene group and having a hydrophobic group in the side chain. The compound represented by the following formula (6) is more preferred, and the compound represented by the following formula (7) is particularly preferred.

式（６）中、Ｔ、ＵおよびＶは、それぞれ独立してベンゼン環またはシクロヘキサン環であり、これらの環上の任意の水素は、炭素数１〜３のアルキル、炭素数１〜３のフッ素置換アルキル、フッ素、塩素またはシアノで置き換えられてもよく、ｈは０〜５の整数であり、ｉおよびｊは、それぞれ０〜２の整数であり、ｐは０または１であり、ｑは１または２であり、Ｒは水素、フッ素、塩素、シアノまたは炭素数１〜３０の１価の有機基である。なお、ｉ＝２の場合、複数あるＵは、それぞれ同一でも異なっていてもよく、ｊ＝２の場合、複数あるＶは、それぞれ同一でも異なっていてもよい。

In formula (6), T, U and V are each independently a benzene ring or a cyclohexane ring, and any hydrogen on these rings is alkyl having 1 to 3 carbon atoms, fluorine having 1 to 3 carbon atoms May be substituted with substituted alkyl, fluorine, chlorine or cyano, h is an integer from 0 to 5, i and j are each an integer from 0 to 2, p is 0 or 1 and q is 1; Or 2, and R is hydrogen, fluorine, chlorine, cyano, or a monovalent organic group having 1 to 30 carbon atoms. When i = 2, the plurality of U may be the same or different, and when j = 2, the plurality of V may be the same or different.

式（７）中、ＵおよびＶは、それぞれ独立してベンゼン環またはシクロヘキサン環であり、ｈは０または１であり、ｉおよびｊは、それぞれ０〜２の整数であり、ｐは０または１であり、Ｒは水素、フッ素または炭素数１〜２０の１価の有機基である。

In Formula (7), U and V are each independently a benzene ring or a cyclohexane ring, h is 0 or 1, i and j are each an integer of 0 to 2, and p is 0 or 1 R is hydrogen, fluorine or a monovalent organic group having 1 to 20 carbon atoms.

  Examples of the monovalent organic group in R include, for example, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, and carboxylic acid ester at any site of these organic groups. Examples thereof include an organic group having at least one bond selected from the group consisting of a bond, a sulfonate bond, an amide bond, a phosphonic acid bond, an ether bond, a sulfide bond, and an imide bond.

  Preferable embodiments of the compound represented by the formula (7) include diamines represented by the following formulas (8) to (10).

式（８）〜（１０）中、Ｖはベンゼン環またはシクロヘキサン環であり、ｊは０〜２の整数であり、Ｒは炭素数１〜２０のアルキルである。

In formulas (8) to (10), V is a benzene ring or a cyclohexane ring, j is an integer of 0 to 2, and R is alkyl having 1 to 20 carbons.

3. Other raw materials When synthesizing the compound (A), other raw materials may be used in combination with the acid anhydride (a1) and the amine (a2) described above. Examples of other raw materials include tetracarboxylic dianhydrides and diamines that can be used as normal polyimide raw materials, and dicarboxylic anhydrides and monoamines that can be used as normal end-capping agents. Specific examples include tetracarboxylic dianhydride (a3), diamine (a4), dicarboxylic anhydride (a5), and monoamine (a6), which will be described later. The compounds described in Documents 2 and 3 can also be used.

(1) Tetracarboxylic dianhydride (a3)
Specific examples of tetracarboxylic dianhydride (a3) include pyromellitic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 3,3 ′, 4,4 '-Benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3' , 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether Tetracarboxylic acid Water, 2,2′-bis [(dicarboxyphenoxy) phenyl] propanoic dianhydride, 2,2-bis [(3,4-dicarboxyphenyl)] hexafluoropropanoic dianhydride, ethylene glycol bis (Anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Examples include ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride. Tetracarboxylic dianhydride (a3) may be used alone or in combination of two or more.

(2) Diamine (a4)
Specific examples of the diamine (a4) include 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, and 2,2′-diaminodiphenyl. Propane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, benzidine, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1 -Bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, 1,1 -Bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) ) Phenyl] methane, 1,3-bis (4-aminophenoxy) benzene, diethylene glycol bis (3-aminopropyl) ether. Diamine (a4) may be used alone or in combination of two or more.

(3) Dicarboxylic anhydride (a5)
Specific examples of the dicarboxylic acid anhydride (a5) include phthalic anhydride, trimellitic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 4-tert-butylphthalic anhydride, and 3-fluorophthalic acid. Anhydride, 4-fluorophthalic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, tetrafluorophthalic anhydride, succinic anhydride, butyl succinic anhydride, n-octyl succinic acid Anhydride, dodecyl succinic anhydride, tetrapropenyl succinic anhydride, tetradecenyl succinic anhydride, octadecenyl succinic anhydride, allyl succinic anhydride, 2-buten-1-yl succinic anhydride, 2-dodecen-1-ylsuccinic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, glutaric anhydride, Conic anhydride, citraconic anhydride, allyl nadic acid anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, cis-4-cyclohexene-1, 2-dicarboxylic acid anhydride, methylcyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 1,3-cyclohexanedicarboxylic acid anhydride, p- (trimethoxysilyl) ) Phenyl succinic anhydride, p- (triethoxysilyl) phenyl succinic anhydride, m- (trimethoxysilyl) phenyl succinic anhydride, m- (triethoxysilyl) phenyl succinic anhydride, trimethoxysilylpropyl Succinic anhydride and triethoxy It includes the Lil propyl succinate anhydrase hydride. Only one kind of dicarboxylic acid anhydride (a5) may be used, or two or more kinds may be used in combination.

(4) Monoamine (a6)
Specific examples of the monoamine (a6) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-aminobutyltrimethoxysilane. 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane , M-aminophenyltrimethoxysilane, m-aminophenylmethyldiethoxysilane, 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutyne, 4-aminobutyne, 5-aminopentyne 4 Aminopenchin, allylamine, 7 Aminohepuchin, m- aminostyrene, p- aminostyrene, m- amino -α- methyl styrene, and 3-aminophenyl acetylene and 4-aminophenyl acetylene. Monoamine (a6) may be used alone or in combination of two or more.

4). Method for Synthesizing Compound (A) The compound (A) can be synthesized according to a general method for synthesizing amide derivatives or imides.

(1) Method for synthesizing amide derivative (A1) The amide derivative (A1) comprises an acid anhydride (a1) having a structure of the formula (1), an amine (a2) having a hydrophobic group, an amino group, It can be synthesized by reacting under mild reaction conditions in which an acid anhydride group reacts to form an amic acid. Further, in order to improve the solubility of the amide derivative, the film forming property when forming a cured film, and the properties such as transparency in the cured film, tetracarboxylic dianhydride (a3), dicarboxylic acid anhydride (a5) ), A diamine (a4), and a monoamine (a6), at least one compound selected from the group consisting of monoamine (a6) may be further used for the reaction.

  The above mild reaction conditions are, for example, a temperature of 20 to 60 ° C., a reaction time of 0.2 to 20 hours under normal pressure, and the acid anhydride group was ring-opened by the reaction without using a catalyst. The condition is that the reaction is performed without activating the carboxyl group. The activation of the carboxyl group is, for example, conversion to acid chloride.

  Under such mild reaction conditions, the carboxyl group produced by the reaction of the acid anhydride group with the amino group further has an amine (a2), diamine (a4) and / or monoamine (a6) having a hydrophobic group. Therefore, an amic acid derivative having a free carboxyl group is obtained.

(2) Synthesis method of imidized product (A2) The imidized product (A2) can be obtained by imidizing the amic acid derivative (A1). Specifically, the imidized product (A2) is a method of imidizing an amic acid derivative by a thermal method or a chemical method using a dehydration catalyst and a dehydrating agent, and preferably has few impurities and is not subjected to a purification treatment. A method of imidizing by a thermal method that can be used in the process. More preferably, the acid anhydride (a1) having the structure of the formula (1) and the amine (a2) having a hydrophobic group, and other raw materials as necessary are reacted in a reaction solvent, and then refluxed. It can be obtained by a method of imidization. Refluxing is preferably carried out at 140 to 230 ° C. for 1.5 to 10 hours, although the conditions vary depending on the reaction solvent used. When the reflux temperature is within the above range, a cured film having sufficiently high imidization and high insulation resistance can be formed. Moreover, even if it uses a solvent with a comparatively high boiling point, it can reflux.

(3) Reaction solvent The reaction solvent used for synthesizing the amic acid derivative (A1) or its imidized product (A2) is not particularly limited as long as it can synthesize the amic acid derivative or its imidized product.

  Specific examples of the reaction solvent include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol Cole monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol divinyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl Ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetramethylene glycol monovinyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, methyl benzoate, ethyl benzoate, anisole, cyclohexanone, Clopentanone, γ-butyrolactone, 1,3-dioxolane, 1,4-dioxane, 2-pyrrolidone, 1-methyl-2-pyrrolidone (abbreviation: NMP), 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 1-acetyl-2-pyrrolidone, N-methyl-ε-caprolactam, N, N-dimethylacetamide, N, N-diethyl Acetamide, N, N-dimethylpropionamide, N, N-dimethylformamide and 1,3-dimethyl-2-imidazolidinone.

  Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, cyclopentanone, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether acetate, γ-butyrolactone, 2-pyrrolidone, 1 -Methyl-2-pyrrolidone (abbreviation: NMP), 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 1 -Acetyl-2-pyrrolidone, N-methyl-ε-caprolactam, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide N, N-dimethylformamide and 1,3-dimethyl-2-imidazolidinone are preferred in terms of solubility.

  Only one reaction solvent may be used, or two or more reaction solvents may be mixed and used. In addition, other solvents other than the above reaction solvent can be mixed with the reaction solvent. The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total amount of raw material compounds used in the reaction, since the reaction proceeds smoothly.

5). Example of Compound (A) The compound (A) is not limited as long as it is an amic acid derivative and / or an imide compound having the structure of the formula (1).

Preferable examples of the compound (A) include a polyamic acid derivative obtained by using a compound having two or more acid anhydride groups and a diamine, or an imidized product thereof.
Specific examples of the amic acid derivative (A1) include a compound having a structural unit represented by the following formula (11) (hereinafter referred to as “compound (11)”), but are not limited thereto. Specific examples of the imidized product (A2) include, but are not limited to, the imidized product of the compound (11).

式（１１）中、Ｇ₁は、酸無水物（ａ１）、例えば前記式（３）〜（５）で表わされるテトラカルボン酸二無水物の残基１〜１００モル％と、酸無水物（ａ３）および（ａ５）に由来する芳香族基、脂肪族基、脂環式基およびシロキサン基からなる群より選ばれる１種以上の基を有する酸無水物の残基０〜９９モル％とからなり、Ｇ₂は、アミン（ａ２）、例えば前記式（６）で表わされるアミンの残基１〜１００モル％と、アミン（ａ４）および（ａ６）に由来する芳香族基、脂肪族基、脂環式基およびシロキサン基からなる群から選ばれる１種以上の基を有するアミンの残基０〜９９モル％とからなる。Ｒ₁は水素または１価の有機基であり、２個のＲ₁は同じでも異なっていてもよい。ｓは正の整数である。

In Formula (11), G ₁ represents an acid anhydride (a1), for example, a residue of 1 to 100 mol% of a tetracarboxylic dianhydride represented by the above formulas (3) to (5), an acid anhydride ( From residues 0 to 99 mol% of an acid anhydride having one or more groups selected from the group consisting of aromatic groups, aliphatic groups, alicyclic groups and siloxane groups derived from a3) and (a5) G ₂ is an amine (a2), for example, 1 to 100 mol% of an amine residue represented by the formula (6), an aromatic group derived from the amines (a4) and (a6), an aliphatic group, It consists of 0 to 99 mol% of amine residues having one or more groups selected from the group consisting of alicyclic groups and siloxane groups. R ₁ is hydrogen or a monovalent organic group, and two R ₁ may be the same or different. s is a positive integer.

6). Content of Compound (A) From the viewpoint of obtaining a cured film and appropriately adjusting the viscosity of the composition, the composition of the present invention contains 0.0% of compound (A) with respect to 100 parts by weight of the total amount of the composition. 1 to 99.9 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight. When the compound (A) is contained in an amount within the above range, it is possible to form a relatively thin film (film thickness is 1 μm or less) when forming a cured film.

<Solvent (B)>
The composition of the present invention can be adjusted in viscosity by containing the solvent (B), and can be applied to various printing methods such as an inkjet method, a gravure method, a spin coating method, a dip coating method, a screen method, and a flexo method. . The viscosity is not particularly limited, but it is important to adjust to a viscosity suitable for the desired printing method.

  The solvent (B) is not particularly limited as long as it can dissolve the compound (A). In addition, even if the solvent alone does not dissolve the compound (A), such a mixed solvent can be used as the solvent (B) as long as the compound (A) can be dissolved by mixing with another solvent. Is possible.

  The boiling point of the solvent (B) is preferably 50 to 300 ° C, more preferably 100 to 250 ° C. When the boiling point is 100 ° C. or higher, the composition can be prevented from being dried at the time of application by the ink jet printing method.

  Specific examples of the solvent (B) include ethanol, benzyl alcohol, cyclohexanol, 1,4-butanediol, glycerin, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, polyethylene Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene Glycol dimethyl ether, triethylene glycol divinyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol Monophenyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, triethylene glycol Coal, tripropylene glycol, tripropylene glycol methyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetramethylene glycol monovinyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3 -Methoxybutanol, 3-methoxybutyl acetate, methyl 2-hydroxyisobutyrate, i-propyl 2-hydroxyisobutyrate, i-butyl 2-hydroxyisobutyrate, n-butyl 2-hydroxyisobutyrate, butyl acetate, butyl propionate , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethyl 3-methoxypropionate, Methyl acetate, ethyl acetoacetate, ethyl lactate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl benzoate, ethyl benzoate, dioxane, toluene, xylene, anisole, cyclohexanone, cyclopentanone, γ-butyrolactone, 1 , 3-dioxolane, 1,4-dioxane, 2-pyrrolidone, 1-methyl-2-pyrrolidone (abbreviation: NMP), 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2- Pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 1-acetyl-2-pyrrolidone, N-methyl-ε-caprolactam, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethyl Propionamide, N, N-dimethylformamide and 1,3-dimethyl Ru-2-imidazolidinone.

  Among these, from the viewpoint of solubility and film-forming property of the compound (A), ethyl lactate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, cyclopentanone, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether Diethylene glycol dimethyl ether and diethylene glycol monobutyl ether acetate are preferably included as the solvent (B).

  Among the above exemplified solvents, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1- (2-hydroxyethyl)- 2-pyrrolidone, 2-pyrrolidone, 1-methyl-2-pyrrolidone (abbreviation: NMP), 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide An amide solvent such as N, N-dimethylformamide and N-methyl-ε-caprolactam is preferably contained in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the solvent (B). More preferably, it is contained in an amount of not more than parts, and it is even more preferred that the solvent (B) is a non-amide solvent.

  As described above, a reaction solvent is used for the synthesis of the compound (A). Therefore, when the reaction solvent remains when the synthesis of the compound (A) is completed, the reaction solvent can also be used as the solvent (B).

  A solvent (B) may use only 1 type, or may mix and use 2 or more types. Moreover, the composition of this invention is 0.1-99.9 weight part of solvent (B) with respect to the total amount of 100 weight part of a composition from a viewpoint of adjusting the viscosity of a composition appropriately, Preferably it is 50. It is contained in an amount of ˜99 parts by weight, more preferably 80 to 99 parts by weight. When the content of the solvent (B) is within the above range, it is possible to form a relatively thin film (film thickness is 1 μm or less) when forming a cured film.

  The viscosity of the composition of the present invention is preferably 3 to 200 mPa · s, more preferably 5 to 100 mPa · s, and particularly preferably 10 to 50 mPa · s from the viewpoint of increasing the discharge accuracy, for example, when coating is performed by an inkjet method. s. In this specification, “viscosity” is the viscosity at 25 ° C. measured using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS C 2103 5.3. .

<Surfactant (C)>
The composition of this invention can contain surfactant (C) in the range which does not impair the effect of this invention for the improvement of the applicability | paintability of a composition. The surfactant (C) is not particularly limited as long as it can improve the coating property of the composition of the present invention. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), Disperbeek 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by BYK Japan, Inc.), KP-341, KP-358, KP-368, KF-96-50CS, KF- 50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 51, FTX-218 (trade name, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, manufactured by Mitsubishi Materials Corporation) ), Mega Fuck F-470, Mega Fuck F-471, Mega Fuck F-475, Mega Fuck R-08, Mega Fuck F-477, Mega Fuck F-479, Mega Fuck F-553, Mega Fuck F-554 ( (Trade name, manufactured by DIC Corporation), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, diglycerin tetrakis ( Fluoroalkyl group Oxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, Polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan Stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthylate , Alkyl benzene sulfonates and alkyl diphenyl ether disulfonates can be used.

  Only 1 type may be used for surfactant (C), or 2 or more types may be mixed and used for it. In addition, the content of the surfactant (C) in the composition of the present invention is usually 0 to 1 part by weight, preferably 100 parts by weight with respect to the total amount of the composition, from the viewpoint of improving the applicability of the composition. Is 0 to 0.5 parts by weight.

<Other components (D)>
The composition of the present invention is effective for improving the coating properties and storage stability of the composition, the ejection properties when applied by the inkjet printing method, the durability of the resulting cured film, the insulation properties, etc. In the range which does not impair, other component (D) can be included.

  Examples of other components (D) include colorants, antistatic agents, coupling agents, pH adjusters, rust inhibitors, preservatives, antifungal agents, antioxidants, reduction inhibitors, evaporation accelerators, chelates. And a water-soluble polymer. These components may be a single compound or a mixture of two or more different compounds.

<Preparation of composition>
The composition of the present invention can be prepared by mixing the compound (A) and the solvent (B) and, if necessary, the surfactant (C) and / or other component (D) by a known method. . The solution obtained by mixing is more preferably degassed after filtration from the viewpoint of preventing impurities from being mixed during coating. For the filtration, for example, a fluororesin membrane filter is used.

[Curing film]
The cured film of the present invention can be formed by applying the composition of the present invention to a substrate and heating and drying. In this specification, the cured film thus obtained is referred to as a “first cured film”.

  Examples of the coating method include generally known coating methods such as spin coating, dip coating, ink jet printing, screen printing, gravure printing, flexographic printing, and the like.

  The heating / drying method is not particularly limited, but is preferably performed on a hot plate or in an oven. The heating temperature is not particularly limited, but it is preferably 80 to 300 ° C., more preferably 80 to 250 ° C. from the viewpoint of sufficient drying, and when it is necessary to improve the insulation depending on the purpose of use, amide In order to further promote imidization of the acid derivative, the temperature is preferably 150 to 400 ° C, more preferably 200 to 400 ° C. The heating time is preferably 10 to 240 minutes, more preferably 30 to 120 minutes. The cured film thus obtained is sufficiently dried and cured, and the stickiness of the film surface disappears.

A board | substrate will not be specifically limited if it can become the object by which the composition of this invention is apply | coated, The shape is not restricted to flat form, A curved surface form may be sufficient.
The material and form of the substrate that can be used are not particularly limited. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, and fluorine resins. Plastic film such as acrylic resin, polyamide, polycarbonate, polyimide; cellophane; acetate; metal foil; laminated film of polyimide and metal foil; glassine paper or parchment paper with sealing effect; polyethylene, clay binder, polyvinyl alcohol, Examples of the paper include a glass treated with starch, carboxymethyl cellulose, and the like; The substances constituting these substrates include pigments, dyes, antioxidants, anti-degradation agents, fillers, ultraviolet absorbers, antistatic agents and anti-radioactive agents as long as the effects of the present invention are not adversely affected. Such additives may be included.

  Although the thickness of a board | substrate is not specifically limited and is suitably adjusted with the objective to use, Preferably it is about 10 micrometers-2 mm, More preferably, it is 20 micrometers-1.5 mm, More preferably, it is 50 micrometers-1 mm. If necessary, the surface of the substrate on which the cured film is formed may be subjected to an easy adhesion treatment such as a corona treatment, a plasma treatment, or a blast treatment, or may be provided with an easy adhesion layer.

The surface of the first cured film obtained as described above is highly lyophobic due to the hydrophobic group derived from the amine (a2), and its surface free energy is low.
The contact angle of pure water at 25 ° C. on the surface of the first cured film is usually 80 degrees or more, preferably 80 to 110 degrees, more preferably 90 to 110 degrees. In addition, the contact angle in this specification measured the value after 1 second of water droplet (pure water) landing at 25 ° C. using a contact angle meter “DropMaster 500” (trade name) manufactured by Kyowa Interface Chemical Co., Ltd. It is.

Moreover, the surface free energy of a 1st cured film is 45 mN / m or less normally, Preferably it is 20-40 mN / m, More preferably, it is 30-40 mN / m. In this specification, the surface free energy is obtained by using CH ₂ I ₂ having a known value of the dispersion force component and the hydrogen bonding force component of the surface free energy and the above-described pure water droplets, such as the first cured film. The contact angle was measured on the solid surface and calculated by the method of Owens. That is, the surface free energy of the solid surface is the sum of the dispersion force component and the hydrogen bonding force component of the surface free energy of the solid surface, calculated by the following simultaneous equations. In addition, about the thing with the meaning of each symbol and a known value, the value is shown in following Table 1.

<Formation of lyophilic region>
By irradiating the necessary part of the liquid-repellent first cured film obtained as described above with ultraviolet light, the part irradiated with ultraviolet light becomes lyophilic, and the surface free energy of the ultraviolet irradiated part is not irradiated with ultraviolet light. A cured film higher than the surface free energy of the part can be obtained. In this specification, such a partially lyophilic cured film is referred to as a “second cured film”.

Although the wavelength of the ultraviolet-ray to irradiate is not specifically limited, From a viewpoint made fully lyophilic, Preferably it is 150-400 nm, More preferably, it is 200-350 nm. Although the exposure amount depends on the composition of the composition, it is preferably 100 to 3,000 mJ / cm ² , more preferably measured by a UV intensity meter “UVC-254” (trade name) manufactured by Custom Co., Ltd. 500-2600 mJ / cm ² . The second cured film thus obtained maintains the liquid repellency of the UV-irradiated part and the UV-irradiated part becomes lyophilic, so that wetting and spreading when ink droplets are placed on the irradiated part. Becomes better.

  As described above, a cured film having a film surface in which a liquid repellent region and a lyophilic region are mixed can be formed by irradiating a necessary portion with ultraviolet rays. In the second cured film of the present invention, the difference in the contact angle of pure water at 25 ° C. (hereinafter also referred to as “contact angle difference”) between the liquid repellent part and the lyophilic part is preferably 30 ° or more, and more Preferably it is 35-60 degrees, Most preferably, it is 40-55 degrees. If it is this range, the ink application will be favorable. In addition, a contact angle difference is calculated | required by following formula (e).

Formula (e); contact angle difference (degree) = contact angle of liquid repellent part (degree) −contact angle of lyophilic part (degree)
By applying the ink material only or entirely to the lyophilic portion of such a film, the ink material does not remain in the lyophobic portion but accumulates in the lyophilic portion, so that the ink pattern can be easily formed. The film patterned in this manner may be further dried as necessary.

The surface free energy difference between the lyophobic part and the lyophilic part in the second cured film of the present invention is preferably 10 mN / m or more, more preferably 12 to 10 when irradiated with ultraviolet rays at an exposure dose of 2500 mJ / cm ^2. 30 mN / m, particularly preferably 15 to 25 mN / m. If it is this range, the ink application will be favorable.

<Characteristics of cured film>
1. Film thickness The film thickness of the 2nd cured film of this invention will not be specifically limited if the effect of this invention is acquired, What is necessary is just to adjust suitably according to the intended purpose. For example, when used as a wettability changing layer, the film thickness is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, still more preferably 0.2 to 1 μm, and further used as an insulating film. In this case, the film thickness is preferably 0.1 to 100 μm, more preferably 0.5 to 20 μm, and still more preferably 1 to 10 μm from the viewpoint of insulation. In addition, a film thickness is an average value when three places of the said cured film are measured using the stylus type film thickness meter "P-15" (brand name) by KLA-Tencor Japan Co., Ltd. .

2. Insulating film The second cured film of the present invention can also be used as an insulating film capable of changing wettability. If it is an insulating film, it can be used as a constituent material of the laminated pattern circuit of an electronic component. In this specification, the “insulating film” means a volume resistivity measured in accordance with JIS-K-6911 using a resistivity meter “R8340” (trade name) manufactured by ADC Co., Ltd. A film that is × 10 ¹⁴ Ω · cm or more. In the present invention, the volume resistivity of the insulating film is preferably 1.0 × 10 ¹⁴ Ω · cm or more, more preferably 1.0 × 10 ¹⁵ Ω · cm or more.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.
<Reagent>
The reagents used in Examples and Comparative Examples are as follows.
TAPQ; tetracarboxylic dianhydride represented by the above formula (3) (manac Co., Ltd.)
BSAA; 2,2′-bis [(dicarboxyphenoxy) phenyl] propanoic dianhydride (manufactured by Air Water Co., Ltd.)
TMAH: tetracarboxylic dianhydride represented by the following formula (12) (manac)
p-TAPA; tetracarboxylic dianhydride having an amide structure represented by the following formula (13) (manufactured by Nippon Seika Co., Ltd.)
PMDA: pyromellitic dianhydride (Wako Pure Chemical Industries, Ltd.)
4-FPA; 4-fluorophthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
TFPA: Tetrafluorophthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
BAPP; 2,2-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd.)
DA5HP; 5-((4- (4- (4-pentylcyclohexyl) cyclohexyl) phenyl) methyl) -1,3-diaminobenzene DA16P represented by the following formula (14); 5- represented by the following formula (15) (4-hexadecylbenzyl) benzene-1,3-diamine DA7PPE; 4′-heptyl- (1,1′-biphenyl) -4-yl represented by the following formula (16) 4- (3,5-diaminobenzyl ) Benzoate DA5HP was synthesized by the synthesis method described in JP-A No. 2002-162630, and DA16P and DA7PPE were synthesized based on the synthesis method of DA5HP.

<Synthesis Example 1>
In a 500 mL four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, 6.6484 g (0.01536 mol) DA5HP, 2.052 g (0.00512 mol) BAPP and 87 .91 g of dehydrated NMP was added and dissolved by stirring in a dry nitrogen atmosphere. While maintaining the temperature of the reaction system in the range of 5 to 70 ° C, 13.442 g (0.02048 mol) of TAPQ was added, and the mixture was further reacted at 70 ° C for 3 hours. Then, it cooled to room temperature and obtained about 110 g of polyamic acid derivative solutions with a solid content concentration of 20.0 wt%. The polyamic acid contained in this polyamic acid derivative solution is referred to as PA acid 1.

<Synthesis Example 2>
PA acid 1 was synthesized in the same manner as in Synthesis Example 1 and reacted at 70 ° C. for 3 hours. Then, instead of cooling to room temperature, the heating temperature was increased, water was removed, and the reaction temperature was 170 ° C. for 5 hours. Reacted for hours. Thereafter, the mixture was cooled to room temperature to obtain about 110 g of a partially imidized polyamic acid derivative solution having a solid content concentration of 20.0 wt%. The polyamic acid derivative contained in this partially imidized polyamic acid derivative solution is referred to as PA acid 2.

<Synthesis Example 3>
In a 500 mL four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, put 8.648 g (0.02048 mol) of DA5HP and 87.91 g of dehydrated NMP in a dry nitrogen atmosphere. Stir to dissolve. While maintaining the temperature of the reaction system in the range of 5 to 70 ° C, 13.442 g (0.02048 mol) of TAPQ was added, and the mixture was further reacted at 70 ° C for 3 hours. Then, it cooled to room temperature and obtained about 110 g of polyamic acid derivative solutions with a solid content concentration of 20.0 wt%. The polyamic acid derivative contained in this polyamic acid derivative solution is referred to as PA acid 3.

<Synthesis Example 4>
PA acid 3 was synthesized in the same manner as in Synthesis Example 3 and reacted at 70 ° C. for 3 hours. Then, instead of cooling to room temperature, the heating temperature was increased, water was removed, and the reaction temperature was 170 ° C. for 5 hours. Reacted for hours. Then, it cooled to room temperature and obtained about 110 g of polyamic acid derivative solutions with a solid content concentration of 20.0 wt%. The polyamic acid derivative contained in this polyamic acid derivative solution is referred to as PA acid 4.

<Synthesis Example 5>
About 110 g of a polyamic acid derivative solution having a solid content concentration of 20.0 wt% was obtained in the same manner as in Synthesis Example 3 except that DA16P (8.650 g, 0.02048 mol) was used instead of DA5HP. The polyamic acid derivative contained in this polyamic acid derivative solution is referred to as PA acid 5.

<Synthesis Example 6>
About 110 g of a polyamic acid derivative solution having a solid content concentration of 20.0 wt% was obtained in the same manner as in Synthesis Example 1, except that DA7PPE (10.919 g, 0.02048 mol) was used instead of DA5HP. The polyamic acid derivative contained in this polyamic acid derivative solution is referred to as PA acid 6.

<Synthesis Example 7>
About 110 g of a polyamic acid derivative solution having a solid content concentration of 20.0 wt% was obtained in the same manner as in Synthesis Example 1, except that BSAA (10.552 g, 0.02048 mol) was used instead of TAPQ. The polyamic acid derivative contained in this polyamic acid derivative solution is referred to as PA acid 7.

<Synthesis Example 8>
About 110 g of a polyamic acid derivative solution having a solid content concentration of 20.0 wt% was obtained in the same manner as in Synthesis Example 1 except that p-TAPA (9.340 g, 0.02048 mol) was used instead of TAPQ. It was. The polyamic acid derivative contained in this polyamic acid derivative solution is referred to as PA acid 8.

<Synthesis Example 9>
About 110 g of a polyamic acid derivative solution having a solid content concentration of 20.0 wt% was obtained in the same manner as in Synthesis Example 1, except that TMAH (9.380 g, 0.02048 mol) was used instead of TAPQ. The polyamic acid derivative contained in this polyamic acid derivative solution is referred to as PA acid 9.

<Synthesis Example 10>
A polyamic acid derivative solution having a solid content concentration of 20.0 wt% was obtained in the same manner as in Synthesis Example 1 except that PMDA (4.464 g, 0.02048 mol), which is an acid anhydride, was used instead of TAPQ. 110 g was obtained. The polyamic acid derivative contained in this partial polyamic acid derivative solution is referred to as PA acid 10.

<Synthesis Example 11>
In a 500 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, 6.6484 g (0.02048 mol) of DA5HP and 87.91 g of dehydrated NMP were placed in a dry nitrogen atmosphere. Stir to dissolve. While maintaining the temperature of the reaction system in the range of 5 to 70 ° C., 3.402 g (0.02048 mol) of 4-FPA was added, and further reacted at 70 ° C. for 3 hours. Thereafter, the mixture was cooled to room temperature to obtain about 110 g of an amic acid derivative solution having a solid content concentration of 20.0 wt%. The amic acid derivative contained in this amic acid derivative solution is referred to as PA acid 11.

<Synthesis Example 12>
In a 500 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, 6.6484 g (0.02048 mol) of DA5HP and 87.91 g of dehydrated NMP were placed in a dry nitrogen atmosphere. Stir to dissolve. While maintaining the temperature of the reaction system in the range of 5 to 70 ° C, 4.505 g (0.02048 mol) of TFPA was added, and the mixture was further reacted at 70 ° C for 3 hours. Thereafter, the mixture was cooled to room temperature to obtain about 110 g of an amic acid derivative solution having a solid content concentration of 20.0 wt%. The amic acid derivative contained in this amic acid derivative solution is referred to as PA acid 12.

[Preparation of composition]
(Measurement of viscosity)
The viscosity of the composition is measured at a temperature of 25 ° C. using an E-type viscometer “TV-22” (trade name) manufactured by Toki Sangyo Co., Ltd. according to JIS C 2103 5.3. did.

<Preparation Example 1>
Mix and dissolve 1.0 g of the NMP solution of PA acid 1 (solid content 20.0 wt%) obtained in Synthesis Example 1 and 3 g of cyclopentanone, and then filter with a fluororesin membrane filter (0.5 μm). Thus, composition 1 was obtained. The viscosity of Composition 1 obtained was 2.2 mPa · s.

<Preparation Example 2>
A composition 2 was obtained in the same manner as in Preparation Example 1 except that an NMP solution of PA acid 2 (solid content 20.0 wt%) was used instead of an NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of Composition 2 obtained was 2.5 mPa · s.

<Preparation Example 3>
A composition 3 was obtained in the same manner as in Preparation Example 1, except that an NMP solution of PA acid 3 (solid content 20.0 wt%) was used instead of the NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 3 was 2.0 mPa · s.

<Preparation Example 4>
A composition 4 was obtained in the same manner as in Preparation Example 1, except that an NMP solution of PA acid 4 (solid content 20.0 wt%) was used instead of an NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 4 was 2.0 mPa · s.

<Preparation Example 5>
Composition 4 was obtained in the same manner as in Preparation Example 1, except that an NMP solution of PA acid 5 (solid content 20.0 wt%) was used instead of an NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 5 was 2.5 mPa · s.

<Preparation Example 6>
Composition 6 was obtained in the same manner as in Preparation Example 1, except that an NMP solution of PA acid 6 (solid content 20.0 wt%) was used instead of the PA acid 1 NMP solution (solid content 20.0 wt%). It was. The viscosity of the obtained composition 6 was 2.8 mPa · s.

<Comparative Preparation Example 1>
A composition 7 was obtained in the same manner as in Preparation Example 1 except that an NMP solution of PA acid 7 (solid content 20.0 wt%) was used instead of the NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 7 was 5.2 mPa · s.

<Comparative Preparation Example 2>
A composition 8 was obtained in the same manner as in Preparation Example 1 except that an NMP solution of PA acid 8 (solid content 20.0 wt%) was used instead of the NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 8 was 3.2 mPa · s.

<Comparative Preparation Example 3>
A composition 9 was obtained in the same manner as in Preparation Example 1 except that an NMP solution of PA acid 9 (solid content 20.0 wt%) was used instead of an NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 9 was 2.2 mPa · s.

<Comparative Preparation Example 4>
A composition 10 was obtained in the same manner as in Preparation Example 1 except that an NMP solution of PA acid 10 (solid content 20.0 wt%) was used instead of an NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 10 was 2.3 mPa · s.

<Comparative Preparation Example 5>
A composition 11 was obtained in the same manner as in Preparation Example 1 except that an NMP solution of PA acid 11 (solid content 20.0 wt%) was used instead of an NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 11 was 2.0 mPa · s.

<Comparative Preparation Example 6>
A composition 12 was obtained in the same manner as in Preparation Example 1, except that an NMP solution of PA acid 12 (solid content 20.0 wt%) was used instead of the NMP solution of PA acid 1 (solid content 20.0 wt%). It was. The viscosity of the obtained composition 12 was 2.0 mPa · s.

[Examples 1-6 and Comparative Examples 1-6]
Each composition obtained in Preparation Examples 1-6 and Comparative Preparation Examples 1-6 was adjusted with a spin coater so that the film thickness was 1 μm, and the glass substrate “EAGLE XG” manufactured by Corning was used. It was applied on (trade name, thickness 0.7 mm). Next, the substrate coated with the composition was dried on a hot plate at 100 ° C. for 2 minutes, and a test substrate having a first cured film was produced. A test substrate having a second cured film was produced by irradiating the entire surface of the obtained test substrate with ultraviolet rays under the following conditions. In addition, Table 2 and Table 3 show the rotation speed of the spin coater in each example and each comparative example.

(UV irradiation conditions)
Ultraviolet irradiation device: “PHOTO SURFACE PROCESSOR PL2003N-12” (product name) manufactured by Sen Special Light Source Co., Ltd.
Exposure light source: Low-pressure mercury lamp Exposure: 2500 mJ / cm ² (measured with a custom-made UV intensity meter “UVC-254” (trade name))
In addition, the water contact angle before and behind ultraviolet irradiation and the surface free energy were measured by the method described in this specification.

<Evaluation>
About the board | substrate which has the obtained 2nd cured film, the following characteristic was measured and evaluated. The results are shown in Tables 2-4.

(Film thickness)
Using a “stylus type film thickness meter P-15” (trade name) manufactured by KLA-Tencor Japan, three locations of the second cured film were measured, and the average value was taken as the film thickness.

(Dielectric constant)
The dielectric constant of the second cured film was measured at a measurement frequency of 1 MHz by using “LCR meter 4284A” (trade name) manufactured by Agilent Technologies to create electrodes on the upper and lower sides of the second cured film.

(Volume resistivity)
The volume resistivity of the second cured film was measured at 25 ° C. in accordance with JIS-K-6911 using a resistivity meter “E4980A” (trade name) manufactured by Agilent Technologies.

  As shown in Tables 2 and 3, the cured films of the examples had a higher water contact angle before ultraviolet irradiation, and a larger contact angle difference and surface free energy difference before and after ultraviolet irradiation than the comparative examples. Moreover, the desired lyophilic part was appropriately formed by ultraviolet irradiation. Furthermore, as shown in Table 4, the cured films of the examples showed high insulation properties.

  As is clear from the above, the cured film of the present invention exhibits high liquid repellency, can easily form a lyophilic part by ultraviolet irradiation, and is lyophilic between the lyophobic part and the lyophilic part. The difference is big. Therefore, since ink is selectively placed on the lyophilic portion, the ink can be applied separately, and fine circuit pattern formation (patterning) can be facilitated. Moreover, since the cured film obtained from the composition of the present invention maintains a sufficient volume resistivity and has a low dielectric constant, it can be effectively used as an insulating film material capable of changing wettability.

Claims (5)

An amide derivative (A1) obtained by reacting an acid anhydride (a1) having a partial structure represented by the following formula (1) with an amine (a2) represented by the following formula (6 ) and its imidized product ( A composition comprising at least one compound (A) selected from the group consisting of A2),
For forming a cured film used in a method of forming a surface free energy portion higher than the surface free energy of the unirradiated portion on the cured film surface by irradiating at least part of the cured film obtained from the composition with ultraviolet rays Composition.

[In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each hydrogen or alkyl having 1 to 10 carbon atoms. ]

[In Formula (6), T, U, and V are each independently a benzene ring or a cyclohexane ring, and arbitrary hydrogen on these rings is alkyl having 1 to 3 carbon atoms, or having 1 to 3 carbon atoms. Fluorine-substituted alkyl, fluorine, chlorine or cyano may be substituted, h is an integer of 0 to 5, i and j are each an integer of 0 to 2, p is 0 or 1, and q is 1 or 2, and R is hydrogen, fluorine, chlorine, cyano, or a monovalent organic group having 1 to 30 carbon atoms. ] The composition for forming a cured film according to claim 1, wherein the acid anhydride (a1) is an acid anhydride represented by the following formula (2-1) or (2-2).

[In the formulas (2-1) and (2-2), R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or alkyl having 1 to 10 carbon atoms, R ⁵ is a single bond, carbon Or it is a C1-C50 divalent to tetravalent organic group, m is 1 or 2, and n is 1 or 2. ] The curing according to claim 1 or 2, wherein the acid anhydride (a1) is at least one compound selected from the group consisting of tetracarboxylic dianhydrides represented by the following formulas (3) to (5). Film forming composition.

The composition for cured film formation of any one of Claims 1-3 whose amine (a2) is a compound represented by following formula (7).

[In Formula (7), U and V are each independently a benzene ring or a cyclohexane ring, h is 0 or 1, i and j are each an integer of 0 to 2, and p is 0 or 1 and R is hydrogen, fluorine or a monovalent organic group having 1 to 20 carbon atoms. ] The composition for forming a cured film according to any one of claims 1 to 4 , further comprising a solvent (B).