JP2014141568A - Photocurable inkjet ink and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable inkjet ink which makes it possible to form a cured film having excellent flame resistance, folding resistance, plating resistance and the like in a balanced manner.SOLUTION: A photocurable inkjet ink contains a specific phosphorus-containing (meth) acrylate (A), a specific polyfunctional (meth) acrylate (B), a specific monofunctional (meth) acrylate (C), and a specific photopolymerization initiator (D).

Description

  The present invention relates to a photocurable ink-jet ink suitably used for producing an electronic circuit board such as a printed wiring board for forming a display element such as a liquid crystal display element or an EL (electroluminescence) display element. More specifically, the present invention relates to an ink jet ink suitable for a coverlay film for protecting a metal wiring surface forming a predetermined circuit pattern, a solder resist, or the like.

  Conventionally, a photolithography method using a photoresist has been used for manufacturing electronic circuit boards such as (flexible) printed wiring boards and semiconductor package boards. In this printed wiring board manufacturing method by photolithography, for example, a photoresist layer is formed on a copper foil of a copper-clad laminate, the layer is exposed through a photomask, and then an uncured portion is removed. Then, a resist pattern is formed. Next, a portion of the copper foil not covered with the resist pattern is removed by etching, and then the resist pattern is removed to obtain a printed wiring board.

  However, the method for manufacturing a printed wiring board as described above requires a large amount of capital investment because it takes a long time and a lot of cost to manufacture a photomask. Further, since pattern exposure using a photomask is required, the process is complicated and the operation is complicated.

  In recent years, in order to solve these problems, a method has been developed in which a photosensitive material is directly applied onto a substrate using an inkjet method to form a pattern (for example, Japanese Patent Laid-Open No. 56-66089 (Patent Document). 1), Japanese Patent Application Laid-Open No. 62-181490 (Patent Document 2), Japanese Patent Application Laid-Open No. 6-237063 (Patent Document 3) and Japanese Patent Application Laid-Open No. 7-131135 (Patent Document 4). This method is expected from the point that the amount of capital investment is small and the loss of material is small because the pattern exposure and development which are conventionally required are unnecessary.

  Examples of the photosensitive material used in such an ink jet method include coverlay ink, solder resist ink, and the like. Generally, cured films obtained from these inks are used for flexible printed wiring boards. Properties such as flame retardancy, folding resistance and plating resistance are required.

  As the photosensitive material, the applicant of the present application discloses a specific photocurable inkjet ink containing a monofunctional polymerizable monomer, a polyfunctional polymerizable monomer, and a photopolymerization initiator (for example, Japanese Patent Application Laid-Open No. 2010-2010). No. 143982 (see Patent Document 5).

JP 56-66089 A JP 62-181490 A JP-A-6-237063 JP 7-131135 A JP 2010-143982 A

However, when the ink described in Patent Document 5 is used, it may be impossible to obtain a cured product having excellent balance in flame retardancy, folding resistance, plating resistance, and the like.
In addition, for the purpose of imparting flame retardancy to the ink described in Patent Document 5, even if a conventionally known flame retardant is imparted, it is not possible to obtain a cured product excellent in balance in folding resistance, plating resistance, and the like. There was a case.

  The present invention has been made in view of such a situation, and an object of the present invention is to provide a photocurable inkjet ink capable of forming a cured film having excellent balance in flame retardancy, folding resistance, plating resistance, and the like. To do.

According to the ink comprising a phosphorus-containing (meth) acrylate having a specific structure, a polymerizable compound having a specific structure, and a photopolymerization initiator, the present inventors have flame retardancy, folding resistance and plating resistance. The present inventors have found that a cured film having excellent balance can be formed, and the present invention has been completed based on this finding.
The present invention includes the following items.

  [1] Phosphorus-containing (meth) acrylate (A) represented by formula (1), polyfunctional (meth) acrylate (B) represented by formula (2), monofunctional (3) represented by formula (3) A photocurable inkjet ink containing a (meth) acrylate (C) and a photopolymerization initiator (D).

［式（１）中、Ｒ¹は水素またはメチルであり、Ｒ²は炭素数１〜１０のアルキレンである。］

[In Formula (1), R < ¹ > is hydrogen or methyl, and R < ² > is C1-C10 alkylene. ]

［式（２）中、Ｒ³は独立に水素またはメチルであり、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に炭素数１〜１０のアルキレンであり、ａ、ｂおよびｃはそれぞれ独立に０〜１０の整数であり、ｄ、ｅおよびｆはそれぞれ独立に１〜１０の整数である。］

[In the formula (2), R ³ is independently hydrogen or methyl, R ⁴ , R ⁵ and R ⁶ are each independently alkylene having 1 to 10 carbon atoms, and a, b and c are each independently 0 Is an integer from 1 to 10, and d, e and f are each independently an integer from 1 to 10. ]

［式（３）中、Ｒ⁷は水素またはメチルであり、Ｒ⁸は単環式炭化水素基を含有する炭素数３〜１１の有機基であり、ｇは０〜５の整数である。］

Wherein (3), R ⁷ is hydrogen or methyl, R ⁸ is an organic group having a carbon number of 3 to 11 which contains a monocyclic hydrocarbon group, g is an integer of 0 to 5. ]

[2] The photocurable inkjet ink according to [1], wherein R ² in Formula (1) is alkylene having 1 to 5 carbon atoms.

[3] R ⁴ , R ⁵ and R ⁶ in formula (2) are each independently alkylene having 1 to 5 carbon atoms, a, b and c are each independently an integer of 0 to 5; d, e And the photocurable inkjet ink according to [1] or [2], wherein f and f are each independently an integer of 1 to 5.

[4] The photocurable inkjet ink according to any one of [1] to [3], wherein R ⁸ in Formula (3) is a group represented by Formula (4) or (5).

［式（４）および（５）中、Ｒ⁹は独立に水素または炭素数１〜５の有機基である。］

[In Formulas (4) and (5), R ⁹ is independently hydrogen or an organic group having 1 to 5 carbon atoms. ]

  [5] 15 to 45% by weight of phosphorus-containing (meth) acrylate (A), 5 to 40% by weight of polyfunctional (meth) acrylate (B), and monofunctional (meth) acrylate (100% by weight of the total amount of ink) The photocurable inkjet ink according to any one of [1] to [4], comprising 10 to 50% by weight of C) and 0.5 to 15% by weight of the photopolymerization initiator (D).

  [6] Further, a compound (E) having a radical polymerizable double bond other than phosphorus-containing (meth) acrylate (A), polyfunctional (meth) acrylate (B) and monofunctional (meth) acrylate (C). The photocurable inkjet ink according to any one of [1] to [5].

[7] A cured film obtained from the photocurable inkjet ink according to any one of [1] to [6].
[8] A substrate with a cured film having the cured film according to [7].

[9] An electronic component comprising the cured film according to [7] or the substrate with the cured film according to [8].
[10] A display element comprising the cured film according to [7] or the substrate with the cured film according to [8].

  The photocurable inkjet ink of the present invention is excellent in ejection properties, and according to the ink, a cured film having excellent balance in flame retardancy, folding resistance, plating resistance and the like can be formed.

1. Photocurable inkjet ink The photocurable inkjet ink of the present invention (hereinafter also referred to as “the ink of the present invention”) is a phosphorus-containing (meth) acrylate (A) represented by the following formula (1), and the following formula (2): ), A monofunctional (meth) acrylate (C) represented by the following formula (3), and a photopolymerization initiator (D).
Such an ink of the present invention is excellent in ejection properties, and a cured film obtained from the ink is excellent in balance in flame retardancy, folding resistance, plating resistance, and the like. These effects are achieved for the first time by including a specific compound (A), a specific polyfunctional (meth) acrylate (B), a specific monofunctional (meth) acrylate (C) and a photopolymerization initiator (D). can do.

In the present invention, “(meth) acrylate” is used to indicate both or one of acrylate and methacrylate.
In the present invention, “monofunctional compound” means a compound having one polymerizable group such as acryloyl group or methacryloyl group in one molecule, and “polyfunctional compound” means one molecule. A compound having a polymerizable group such as two or more acryloyl groups or methacryloyl groups therein.

1-1. Phosphorus-containing (meth) acrylate (A)
The phosphorus-containing (meth) acrylate (A) (hereinafter also referred to as “compound (A)”) is a compound having a structure represented by the following formula (1).
Since the ink of the present invention contains the compound (A), a cured film having excellent flame retardancy can be obtained.

［式（１）中、Ｒ¹は水素またはメチルであり、Ｒ²は炭素数１〜１０のアルキレンである。］

[In Formula (1), R < ¹ > is hydrogen or methyl, and R < ² > is C1-C10 alkylene. ]

R ² in Formula (1) is alkylene having 1 to 10 carbons, and is more preferably alkylene having 1 to 5 carbons because of ease of synthesis and availability of raw materials.
Examples of the alkylene having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, propane-2,2-diyl, butylene, tetramethylene, pentane-2,2-diyl, hexane-2,2-diyl and pentamethylene. Hexamethylene and heptamethylene, among which methylene, ethylene, trimethylene, propane-2,2-diyl, pentane-2,2-diyl are preferred, methylene, propane-2,2-diyl, pentane -2,2-diyl is more preferred.

Compound (A) may be a commercially available product, or may be one produced by a known production method, for example, the method described in Japanese Patent No. 3454544.
Specifically, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is reacted with ketones, and the resulting reaction product is reacted with (meth) acrylic acid. Can be synthesized.
The R ² can be adjusted by appropriately selecting ketones used at this time.

  The content of the compound (A) is preferably 15 to 45% by weight, more preferably 18 to 41% by weight, and further preferably 18 to 32% by weight with respect to 100% by weight of the total amount of the ink of the present invention. is there.

  Compound (A) may be a single compound or a mixture of two or more compounds.

1-2. Multifunctional (meth) acrylate (B)
The polyfunctional (meth) acrylate (B) (hereinafter also referred to as “compound (B)”) is a compound having the structure of the following formula (2). When the ink of the present invention contains the compound (B), a cured film having excellent folding resistance and plating resistance can be obtained.

［式（２）中、Ｒ³は独立に水素またはメチルであり、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に炭素数１〜１０のアルキレンであり、ａ、ｂおよびｃはそれぞれ独立に０〜１０の整数であり、ｄ、ｅおよびｆはそれぞれ独立に１〜１０の整数である。］

[In the formula (2), R ³ is independently hydrogen or methyl, R ⁴ , R ⁵ and R ⁶ are each independently alkylene having 1 to 10 carbon atoms, and a, b and c are each independently 0 Is an integer from 1 to 10, and d, e and f are each independently an integer from 1 to 10. ]

As C1-C10 alkylene in R < ⁴ >, R < ⁵ > and R < ⁶ >, C1-C5 alkylene is more preferable from points, such as the ease of a synthesis | combination and the availability of a raw material.
Examples of the alkylene having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, propane-2,2-diyl, tetramethylene, pentamethylene, hexamethylene, and heptamethylene. Among these, methylene, ethylene , Trimethylene is preferred, and ethylene is more preferred.

Said a, b, and c are each independently preferably an integer of 0-5, more preferably an integer such that a + b + c is 0-5.
The d, e and f are each independently preferably an integer of 1 to 5.

  Examples of the compound (B) include tris [2- (meth) acryloyloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and the like.

Compound (B) may be produced by a known production method or may be a commercially available product.
Examples of commercially available products include Aronix M-327 and Aronix M-315 (both trade names: Toagosei Co., Ltd.).

  The content of the compound (B) is preferably 5 to 40% by weight with respect to 100% by weight of the total amount of the ink of the present invention because a cured film having excellent folding resistance can be obtained, and considering the balance with other materials. Particularly preferably, it is 9 to 30% by weight.

  Compound (B) may be a single compound or a mixture of two or more compounds.

1-3. Single-capacity (meth) acrylate (C)
The single-capacity (meth) acrylate (C) (hereinafter also referred to as “compound (C)”) is a compound having the structure of the following formula (3). When the ink of the present invention contains the compound (C), an ink particularly excellent in ejection stability can be obtained, and according to the ink, a cured film excellent in plating resistance can be obtained.

In formula (3), R ⁷ is hydrogen or methyl, and R ⁸ is a C 3-11 organic group containing a monocyclic hydrocarbon group. g is an integer of 0 to 5, preferably an integer of 0 to 3.

Since R ⁸ is a group containing a monocyclic hydrocarbon group, the ink of the present invention containing the compound (C) can form a cured film particularly excellent in folding resistance and plating resistance. R ⁸ is preferably a C 3-11 organic group containing one monocyclic hydrocarbon group because these effects are further enhanced.

  Examples of the monocyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a benzene ring. Among these, a cyclopentane ring, a cyclohexane ring, and a benzene ring are preferable.

  The organic group having 3 to 11 carbon atoms is not particularly limited as long as it contains a monocyclic hydrocarbon group, and may be a group containing an oxygen atom or a nitrogen atom. From the point that a cured film having excellent properties can be formed, a hydrocarbon group having 5 to 9 carbon atoms is preferable, and a hydrocarbon group having 5 to 7 carbon atoms is more preferable.

R ⁸ is more preferably a group represented by the following formula (4) or (5) from the viewpoint that a cured film excellent in folding resistance and plating resistance can be formed.

In formulas (4) and (5), R ⁹ is independently hydrogen or an organic group having 1 to 5 carbon atoms, preferably hydrogen or an organic group having 1 to 3 carbon atoms, and more preferably hydrogen.

  Examples of the compound (C) include cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl], phenyl (meta ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenylthioethyl (meth) acrylate, and the like. Of these, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate are preferred.

Compound (C) may be produced by a known production method or may be a commercially available product.
As a commercial item, light ester CH, light ester BZ (all are brand names; Kyoeisha Chemical Co., Ltd.) etc. are mentioned.

  When the content of the compound (C) is 10 to 50% by weight with respect to 100% by weight of the total amount of the ink of the present invention, an ink having excellent ejection properties can be obtained, and in particular, a cured film having excellent plating resistance can be obtained. In consideration of the balance with other materials, it is particularly preferably 30 to 50% by weight.

  Compound (C) may be a single compound or a mixture of two or more compounds.

1-4. Photopolymerization initiator (D)
The ink of the present invention contains a photopolymerization initiator (D) (hereinafter also referred to as “compound (D)”).
The compound (D) is more preferably a compound capable of generating radicals by irradiation with ultraviolet rays or visible rays.

The photopolymerization initiator (D) capable of generating radicals upon irradiation with ultraviolet rays or visible rays is not particularly limited, but benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2 , 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -1,2-diphenylethane-1-one, camphorquinone, benzanthrone, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxyca) Bonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ -Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4, 3′-di (t-butylperoxycarbonyl) benzophenone, 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone, 2- (4′-methoxystyryl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloro) (Romethyl) -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- [p-N, 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- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptoben Thiazole, 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'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl- 2-dimethylaminopropionyl) carbazole, 3,6-bis (2 -Methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1) -Yl) -phenyl) titanium, 1-hydroxycyclohexyl phenyl ketone, 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-methyl-1-propanone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholino-1-propanone, 2- (dimethylamino) -1- (4-morpholinophenyl)- -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-trimethylbenzoyldiphenylphosphine ester, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2 -(O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzo) Le) -9H- carbazol-3-yl] - ethanone-1-(O-acetyl oxime), and the like.

  Among these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 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-methyl-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 is preferred.

  Compound (D) may be a single compound or a mixture of two or more compounds.

  The content of the compound (D) is preferably 0.5 to 15% by weight with respect to 100% by weight of the total amount of the ink of the present invention, because an ink highly sensitive to ultraviolet rays is obtained, more preferably 1 to 1%. It is 15% by weight, more preferably 2 to 15% by weight.

1-5. Compound (E) having a radical polymerizable double bond other than compound (A), compound (B) and compound (C)
The ink of the present invention is a compound having a radical polymerizable double bond other than the compound (A), the compound (B) and the compound (C) from the viewpoint of adjusting the viscosity within a range not impairing the properties of the ink. (E) (hereinafter also referred to simply as “compound (E)”) may be included.

Although it does not restrict | limit especially as a compound (E), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-hydroxyethyl (meth) acrylamide, glycidyl ( (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (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, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3 -(Meth) acryloxymethyl Xetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate Glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, ω-carboxy Licaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl], (meth) acrylamide, N, N-dimethyl (meta ) Acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, thioglycidyl (meth) acrylate, ethoxylation o-Phenylphenol (meth) acrylate, dicyclopentanyl (meth) acrylate, γ-butyrolactone (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxybuty (Meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 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-propanediol di (meth) Acrylate, trimethylolpropane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Bis [2- (meth) acryloyloxyethyl] hydroxyethyl isocyanurate, styrene, methylstyrene, chloromethylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, vinyltoluene, polystyrene macromonomer, crotonic acid, α-chloroacrylic acid , Cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipenta Erythritol hexa (meth) acrylate, ethylene oxide modified tri (meth) acrylate , Urethane (meth) acrylate, acid-modified epoxy (meth) acrylate, acid-modified (meth) acrylate, bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate and bisphenol S ethylene oxide modified di (meth) An acrylate etc. are mentioned.

  Among these, the most suitable compounds for reducing the viscosity of the ink within a range not impairing the properties of the ink of the present invention are 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and dicyclopentanyl. (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, bisphenol F ethylene oxide-modified di (meth) acrylate, and bisphenol A ethylene oxide-modified di (meth) acrylate.

  Compound (E) may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains the compound (E), the compounding amount of the compound (E) is preferably 1 to 50% by weight with respect to 100% by weight of the total ink of the present invention, and is used for the ink of the present invention. Considering the balance with other materials to be used, it is particularly preferably 5 to 30% by weight.

1-6. Other components The ink of the present invention may contain other components such as an organic solvent, a polymerization inhibitor, a thermosetting compound, a thermal polymerization initiator, an antioxidant, and a colorant as long as they do not impair the gist of the present invention. May be included.

1-6-1. Organic Solvent The ink of the present invention may contain an organic solvent for the purpose of adjusting ejection properties. By including the organic solvent, the viscosity and surface tension of the ink can be finely adjusted, and the discharge property can be adjusted.
Although it does not restrict | limit especially as said organic solvent, It is preferable that it is an organic solvent with a boiling point of 100-300 degreeC.

  Specific examples of the organic solvent having a boiling point of 100 to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropion. Acid methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, dioxane, 3-methoxybutanol 3-methoxybutyl acetate, methyl 2-hydroxyisobutyrate, i-propyl 2-hydroxyisobutyrate, i-butyl 2-hydroxyisobutyrate, n-butyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether , Diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol Diethylene glycol, propylene glycol, dipropylene glycol, benzyl alcohol, cyclohexanol, 1,4-butanediol, triethylene glycol, tripropylene glycol, tripropylene glycol methyl ether, tripropylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate Tate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone , N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.

  The organic solvent may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains an organic solvent, the content of the organic solvent is 0.1 to 20% by weight with respect to 100% by weight of the total amount of the ink of the present invention. Since good ink is obtained, it is preferable, more preferably 0.2 to 10% by weight, still more preferably 0.5 to 8% by weight, and particularly preferably 1 to 5% by weight.

1-6-2. Polymerization inhibitor The ink of the present invention may contain a polymerization inhibitor in order to improve storage stability. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, dibutylhydroxytoluene and phenothiazine. Among these, phenothiazine is preferable because an ink with a small increase in viscosity can be obtained even in long-term storage.

  The polymerization inhibitor may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 1% by weight relative to 100% by weight of the total amount of the ink of the present invention. In view of the balance with other characteristics, it is more preferably 0.01 to 0.5% by weight, and still more preferably 0.01 to 0.1% by weight.

1-6-3. Thermosetting Compound The ink of the present invention may contain a thermosetting compound. The thermosetting compound is not particularly limited as long as it is a compound having a functional group that can be thermally cured, and examples thereof include epoxy compounds, bismaleimides, phenol resins, resins containing phenolic hydroxyl groups, and melamine resins. It is done.

  The thermosetting compound may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains a thermosetting compound, the content of the thermosetting compound is 0.01 to 10% by weight with respect to 100% by weight of the total amount of the ink of the present invention. Since heat resistance improves, it is preferable, More preferably, it is 0.1-8 weight%, More preferably, it is 0.5-5 weight%.

1-6-3-1. Epoxy Compound The ink of the present invention may contain an epoxy compound in order to improve the strength of the obtained cured film or the like.
The epoxy compound is not particularly limited as long as it has at least one structure represented by the following formula (3-1) or formula (3-2) in one molecule.

  Specific examples of the epoxy compound include novolak type (phenol novolak type and cresol novolak type) epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type epoxy resins, hydrogenated bisphenol A type epoxy resins, and hydrogenated compounds. Bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetraphenylolethane type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, alicyclic or heterocyclic epoxy resin, and dicyclopentadiene skeleton or naphthalene skeleton Epoxy resin having a novolak type epoxy resin, preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin and trisphenol methane type epoxy resin

  As the epoxy compound, an epoxy resin produced by a known method may be used, or a commercially available product may be used.

Examples of commercially available products include jER828, 834, 1001, 1004 (all trade names: manufactured by Mitsubishi Chemical Corporation), Epicron 840, 850, 1050, 1050, 2055 (all trade names: DIC ( Co., Ltd.), Epototo YD-011, YD-013, YD-127, YD-128 (all trade names: Nippon Steel & Sumikin Chemical Co., Ltd.), D.E.R.317, 331, 661, 664 (both trade names: Dow Chemical Japan Co., Ltd.), Araldite 6071, 6084, GY250, GY260 (both trade names: Huntsman Japan Co., Ltd.), Sumi-Epoxy ESA- 011, ESA-014, ELA-115, ELA-115, ELA-128 (all trade names: Sumitomo Chemical Co., Ltd.), AER 330, 331, 661, 664 ( Deviation trade name: Asahi Kasei E-materials Corp.) Bisphenol A type epoxy resins and the like;
jER152, 154 (all trade names: Mitsubishi Chemical Corporation), D.E.R.431, 438 (all trade names: Dow Chemical Japan Co., Ltd.), Epicron N-730, N-770 N-865 (all trade names: DIC Corporation), Epototo YDCN-701, YDCN-704 (all trade names: Nippon Steel & Sumikin Chemical Co., Ltd.), Araldite ECN1235, ECN1273, ECN1299 (All trade names: Huntsman Japan Co., Ltd.), XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 (all trade names: Nippon Kayaku Co., Ltd.), Sumi -Epoxy ESCN-195X, ESCN-220 (both trade names: Sumitomo Chemical Co., Ltd.), AER ECN-235, E N-299 (trade names: Asahi Kasei E-Materials Co., Ltd.) novolak type such as an epoxy resin;
Epicron 830 (trade name: DIC Corporation), jER807 (trade name: Mitsubishi Chemical Corporation), Epototo YDF-170 (trade name: Nippon Steel & Sumikin Chemical Co., Ltd.), YDF-175, YDF-2001, Bisphenol F type epoxy resins such as YDF-2004 and Araldite XPY306 (both trade names: Huntsman Japan K.K.);
Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, and ST-3000 (all trade names: Nippon Steel & Sumikin Chemical Co., Ltd.);
An alicyclic epoxy resin such as Celoxide 2021P (trade name: Daicel Corporation), Araldite CY175, CY179 (both trade names: Huntsman Japan Co., Ltd.);
Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, YL-6121 (all trade names: manufactured by Mitsubishi Chemical Corporation) or mixtures thereof;
Bisphenol S type epoxy resins such as EBPS-200 (trade name: Nippon Kayaku Co., Ltd.), EPX-30 (trade name: ADEKA Corp.), EXA-1514 (trade name: DIC Corp.);
bisphenol A novolac epoxy resin such as jER157S (trade name: Mitsubishi Chemical Corporation);
Tetraphenylol ethane type epoxy resins such as YL-931 (trade name: Mitsubishi Chemical Corporation), Araldite 163 (trade name: Huntsman Japan Co., Ltd.);
Heterocyclic epoxy resins such as Araldite PT810 (trade name: Huntsman Japan Co., Ltd.), TEPIC (trade name: Nissan Chemical Industries, Ltd.);
Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names: DIC Corporation);
Epoxy resins having a dicyclopentadiene skeleton such as HP-7200, HP-7200H, HP-7200HH (all trade names: DIC Corporation);
TECHMORE VG3101L (trade name: Printec Co., Ltd.), YL-933 (trade name: Mitsubishi Chemical Corporation), EPPN-501, EPPN-502 (all trade names: Dow Chemical Japan Co., Ltd.), etc. A trisphenol methane type epoxy resin is mentioned.

Among these, jER828, 834, 1001 and 1004 (all trade names: Mitsubishi Chemical Corporation), TECHMORE VG3101L (trade name: Printec Co., Ltd.), EPPN-501, EPPN-502 (all Use of a trade name: Dow Chemical Japan Co., Ltd. is preferable because a cured film having high adhesion can be obtained.
The epoxy resin may be a single compound or a mixture of two or more compounds.

1-6-3-2. Bismaleimide Examples of the bismaleimide include a compound represented by the following formula (6).

In formula (6), R ¹⁰ and R ¹² are each independently hydrogen or methyl, and R ¹¹ is a divalent group represented by the following formula (7).

In the formula (7), R ¹³ and R ¹⁴ each independently have an alkylene having 1 to 18 carbon atoms and a substituent that may be substituted for any methylene that is not continuous (not adjacent) with oxygen. It is a divalent group having an aromatic ring or an optionally substituted cycloalkylene. Examples of the substituent in R ¹³ and R ¹⁴ include carboxyl, hydroxy, alkyl having 1 to 5 carbons, and alkoxy having 1 to 5 carbons. R ¹³ and R ¹⁴ are each preferably a single divalent group selected from the following group (a) in that a cured film having high heat resistance is obtained.

  In the formula (7), X is one divalent group selected from the following group (b).

1-6-3-3. As a phenol resin or a resin containing a phenolic hydroxyl group, a novolac resin obtained by a condensation reaction between an aromatic compound having a phenolic hydroxyl group and an aldehyde is preferably used. As a resin containing a phenolic hydroxyl group, A vinylphenol homopolymer (including a hydrogenated product) and a vinylphenol copolymer (including a hydrogenated product) of vinylphenol and a compound copolymerizable therewith are preferably used.

  Examples of aromatic compounds having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4 , 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, bisphenol A, bisphenol F, terpene skeleton-containing diphenol, gallic acid, gallic acid ester, α-naphthol and β-naphthol Etc.

  Specific examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and acetaldehyde.

  Examples of the compound copolymerizable with vinylphenol include (meth) acrylic acid or a derivative thereof, styrene or a derivative thereof, maleic anhydride, vinyl acetate and acrylonitrile.

  Specific examples of phenolic resins include Resitop PSM-6200 (trade name: Gunei Chemical Industry Co., Ltd.), Shounol BRG-555 (trade name: Showa Denko Co., Ltd.), and concrete examples of resins containing phenolic hydroxyl groups. Specific examples include Marca Linker MS-2G, Marca Linker CST70, and Marca Linker PHM-C (all trade names: Maruzen Petrochemical Co., Ltd.).

1-6-3-4. Melamine resin The melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde. It is done. Among these, a condensate of etherified methylol melamine is preferable in that the resulting cured film has good chemical resistance.

  Specific examples of the melamine resin include Nicalac MW-30, MW-30HM, MW-390, MW-100LM, MX-750LM (trade names: Sanwa Chemical Co., Ltd.).

1-6-4. Thermal polymerization initiator The ink of the present invention may contain a thermal polymerization initiator in order to improve the curability of the ink by the heating step. Specific examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, di-t-butyl peroxide, Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-180 (all trade names: Sanshin Chemical Industry Co., Ltd.) It is done. Among these, 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile) are preferable.

  The thermal polymerization initiator may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 10% by weight or less with respect to 100% by weight of the total amount of the ink of the present invention. From the viewpoint of the above, it is more preferably 0.005 to 10% by weight.

1-6-5. Antioxidant The ink of the present invention may contain an antioxidant in order to prevent oxidation of the resulting cured film or the like.

  Antioxidants include triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzyl Examples include hindered phenol compounds such as phosphonate diethyl ester, and amine compounds such as n-butylamine, triethylamine, and diethylaminomethyl methacrylate.

  The antioxidant may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains an antioxidant, the content of the antioxidant is preferably 3% by weight or less with respect to 100% by weight of the total amount of the ink of the present invention. Is more preferably 0.005 to 2% by weight.

1-6-6. Colorant The ink of the present invention may be colored or colorless, but when inspecting the state of a cured film obtained by applying the ink to a substrate and then curing it, the cured film and the substrate In order to facilitate the identification, a colorant may be included. As the colorant, dyes and pigments are preferable.

  The colorant may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains a colorant, the content of the colorant is 0.1 to 5 weights with respect to 100 parts by weight of the solid content (total of all components other than the organic solvent) in the ink of the present invention. Part is preferable in terms of easy inspection of the cured film obtained from the ink, and is preferably 0.1 to 1 part by weight, and more preferably 0 in view of balance with other characteristics. .1 to 0.5 parts by weight.

1-7. Ink Storage When the ink of the present invention is stored at 5 to 25 ° C., the viscosity change during storage is small and the storage stability is good.

1-8. Ink viscosity The viscosity of the ink of the present invention at 25 ° C. measured with an E-type viscometer is preferably 2 to 200 mPa · s. When the viscosity is in this range, the dischargeability by the ink jet device is good. The viscosity of the ink of the present invention at 25 ° C. is preferably 2 to 100 mPa · s.

1-9. Ink Preparation Method The ink of the present invention can be prepared by mixing each component as a raw material by a known method.
In particular, the ink of the present invention is prepared by mixing the compound (A), the compound (B), the compound (C) and the compound (D) and, if necessary, the compound (E) and other components, For example, it is preferably prepared by filtration using a fluororesin membrane filter and deaeration. The ink prepared in this way is excellent in dischargeability.

1-10. Application of Ink by Inkjet Method The ink of the present invention can be applied using a known inkjet method. Examples of the ink jet method include a piezo method in which mechanical energy is applied to the ink to eject the ink from the ink jet head, and a coating method in which thermal energy is applied to the ink to discharge the ink (so-called thermal method). .

  By using the inkjet method, the ink of the present invention can be easily applied in a predetermined pattern, and a uniform pattern can be formed on a large substrate.

  As an inkjet head, what has the heat-emitting part which consists of a metal and / or a metal oxide is mentioned, for example. Specific examples of the metal and / or metal oxide include metals such as Ta, Zr, Ti, Ni, and Al, and oxides of these metals.

  As a preferable coating device used when coating using the ink of the present invention, for example, energy corresponding to a coating signal is given to ink in an ink jet head having an ink storage portion in which ink is stored, and An apparatus that performs application (drawing) corresponding to the application signal while generating ink droplets can be used.

  The ink jet coating apparatus is not limited to one in which the ink jet head and the ink container are separated, and may be one in which they are inseparably integrated. Further, the ink storage unit may be integrated with the ink jet head so as to be separable or non-separable and mounted on the carriage, or may be provided at a fixed portion of the apparatus. In the latter case, ink may be supplied to the ink jet head via an ink supply member, for example, a tube.

2. Cured film The cured film of the present invention is formed from the ink of the present invention described above. Specifically, after the ink of the present invention is applied to the substrate surface by an inkjet method, light such as ultraviolet rays or visible light is irradiated. A film obtained by curing the coating film is preferred.

  Although the use of the cured film of the present invention is not particularly limited, the cured film obtained from the ink of the present invention is excellent in balance with respect to adhesion to a substrate such as metal or resin, flame retardancy, folding resistance and plating resistance. In particular, it is suitably used as a coverlay film for protecting a metal wiring surface forming a predetermined circuit pattern, a solder resist, or the like.

Case of irradiation with ultraviolet light or visible light, exposure to radiation may be appropriately selected depending on the composition of the ink, but preferably about 100~5,000mJ / cm ^2, about 150~2000mJ / cm ² is More preferably, about 180 to 1000 mJ / cm ² is more preferable. Moreover, 200-500 nm is preferable and, as for wavelengths, such as an ultraviolet-ray and visible light to irradiate, 250-450 nm is more preferable.
In the present invention, the exposure amount is a value measured with an integrating light meter UIT-201 (trade name) equipped with a photoreceiver UVD-365PD (trade name) manufactured by USHIO INC.

  In addition, as an exposure machine, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a halogen lamp, an electrodeless lamp, etc. are mounted, and an apparatus that irradiates ultraviolet rays, visible rays, etc. in the range of 200 to 500 nm It is preferable that

  If necessary, the cured film cured by light irradiation may be further heated and baked, and the cured film is cured more firmly by heating and baking at 80 to 250 ° C. for about 10 to 120 minutes. Can be made.

  The “substrate” in the present invention is not particularly limited as long as it can be applied with the ink of the present invention, and the shape thereof is not limited to a flat plate shape, and may be a curved surface shape.

  Although it does not specifically limit as a board | substrate which can be used for this invention, For example, the polyester-type resin substrate which consists of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc .; The polyolefin resin substrate which consists of polyethylene, a polypropylene, etc .; Polyvinyl chloride, fluorine Organic polymer film made of resin, acrylic resin, styrene resin, polyamide, polycarbonate and polyimide; substrate made of cellophane; metal foil; laminated film of resin substrate made of polyimide and metal foil; glass epoxy resin and metal Laminated board with foil; sealing treatment with glassine paper, parchment paper, polyethylene, clay binder, polyvinyl alcohol, starch or carboxymethylcellulose (CMC) Paper; and glass substrates.

In addition, these substrates are further in the range where the effects of the present invention are not adversely affected, and further, pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents, and / or electromagnetic wave inhibitors, etc. The additive may be included.
Further, at least a part of the surface of the substrate may be subjected to surface treatment such as water repellent treatment, corona treatment, plasma treatment, and / or blast treatment if necessary, or the surface may be subjected to an easily adhesive layer, a color filter protective film, A coat film may be provided.

  The thickness of the cured film of the present invention may be appropriately selected according to the desired application, but is preferably 1 μm to 50 μm, more preferably 5 μm to 20 μm.

  The cured film formed on the substrate can be peeled from the substrate and used as a material for an electronic component or the like, and can be cured as it is without peeling from the substrate, depending on the application and the substrate to be used. As a substrate with a film, it can be used as a material for an electronic component or the like.

Examples of the electronic circuit board include a rigid board, a flexible board, and a rigid flexible board.
As the flexible substrate, for example, the ink of the present invention is applied to the entire surface or a predetermined pattern (line shape, etc.) by a inkjet method on a film-like substrate such as a polyimide film in which wiring is formed in advance by the inkjet method or the like. And a substrate obtained by forming a coating film and then curing the coating film.

  Although the metal which forms the said wiring (circuit) is not specifically limited, Gold, silver, copper, aluminum, or indium tin oxide (ITO) is preferable. A cured film obtained by applying the ink of the present invention to a substrate on which these wirings are formed in a predetermined pattern with an ink jet device and curing the substrate functions as a coverlay film, a solder resist, or the like that protects the wirings. To do.

3. Electronic component and display element The electronic component and display element of the present invention include the cured film or the substrate with the cured film. According to the cured film or the substrate with the cured film using a film substrate as the substrate, flexible electronic components and display elements can be obtained.
For example, by mounting an IC chip, a capacitor, a resistor, a fuse, or the like on an electronic circuit board manufactured using the cured film of the present invention having excellent heat resistance, adhesion to the substrate, folding resistance, and flame retardancy For example, an electronic component for a liquid crystal display element can be produced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these. In the following, the photocurable inkjet ink obtained in the examples or comparative examples may be simply referred to as ink. That is, for example, the inkjet ink 1 may be referred to as ink 1.

[Synthesis Example 1] <Synthesis Example of Phosphorus-Containing (Meth) acrylate (A) PA-1>
To a 1 L reactor equipped with a stirrer, a thermometer and a reflux condenser, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: SANKO-HCA, Sanko Co., Ltd.) (Hereinafter also referred to as “HCA”) 300 g and 600 ml of acetone were added and dissolved. The solution was stirred for 2 hours and reacted under reflux. After the reaction, unreacted acetone was distilled off to obtain a white solid which was an acetone adduct of HCA.

Next, a 1 L reactor equipped with a stirrer, a thermometer and a reflux condenser was charged with 274 g of the obtained compound, 218 g of acrylic acid, 500 g of toluene, 1 g of methoquinone, and 17 g of paratoluenesulfonic acid, and 90 to 95 Dehydration condensation reaction was carried out at 15 ° C. for 15 hours. The obtained reaction solution was washed 3 times with 10% aqueous sodium carbonate solution and then 3 times with 20% brine, and then toluene was distilled under reduced pressure to obtain 262 g of a slightly yellow liquid (PA-1).
It is confirmed by ¹ H-NMR that 90% by weight or more of the compound in which R ^{2 of} formula (1) is propane-2,2-diyl and R ¹ is hydrogen is present in the obtained PA-1. did.

[Synthesis Example 2] <Synthesis Example of Phosphorus-Containing (Meth) acrylate (A) PA-2>
To a 1 L reactor equipped with a stirrer, a thermometer and a reflux condenser, 300 g of HCA and 600 ml of methyl propyl ketone were added and dissolved. The solution was stirred for 2 hours and reacted under reflux. After the reaction, unreacted methyl propyl ketone was distilled off to obtain a white solid as a methyl propyl ketone adduct of HCA.

Next, 151 g of the obtained compound, 108 g of acrylic acid, 250 g of toluene, 0.5 g of methoquinone, and 8.5 g of paratoluenesulfonic acid were charged into a 1 L reactor equipped with a stirrer, a thermometer and a reflux condenser. The dehydration condensation reaction was performed at 90 to 95 ° C. for 18 hours. The obtained reaction solution was washed 3 times with 10% aqueous sodium carbonate solution and then 3 times with 20% brine, and then toluene was distilled under reduced pressure to obtain 131 g of a slightly yellow liquid (PA-2).
It was confirmed by ¹ H-NMR that 90% by weight or more of the compound in which R ^{2 of} formula (1) is pentane-2,2-diyl and R ¹ is hydrogen is present in the obtained PA-2. did.

[Synthesis Example 3] <Synthesis Example of Phosphorus-Containing (Meth) acrylate PA-3>
In a 1 L reactor equipped with a stirrer, a thermometer and a reflux condenser, 300 g of HCA and 600 ml of ethyl octyl ketone were added and dissolved. The solution was stirred for 2 hours and reacted under reflux. After the reaction, unreacted ethyl octyl ketone was distilled off to obtain a white solid as an adduct of HCA with ethyl octyl ketone.

Next, 193 g of the obtained compound, 108 g of acrylic acid, 250 g of toluene, 0.5 g of methoquinone, and 8.5 g of paratoluenesulfonic acid were charged into a 1 L reactor equipped with a stirrer, a thermometer and a reflux condenser. The dehydration condensation reaction was performed at 90 to 95 ° C. for 20 hours. The obtained reaction solution was washed 3 times with 10% aqueous sodium carbonate solution and then 3 times with 20% brine, and then toluene was distilled under reduced pressure to obtain 170 g of a slightly yellow liquid (PA-3).
It is confirmed by ¹ H-NMR that 90% by weight or more of the compound in which R ^{2 in} formula (1) is undecane-3,3-diyl and R ¹ is hydrogen is present in the obtained PA-3. did.

[Example 1]
As phosphorus-containing (meth) acrylate (A), FRM-1000 (trade name; Nippon Kayaku Co., Ltd., compound in which R ^{2 in} formula (1) is methylene and R ¹ is hydrogen), polyfunctional (meta ) Aronix M-327 (trade name; Toagosei Co., Ltd.) which is caprolactone-modified tris (acryloxyethyl) isocyanurate as acrylate (B), and lite which is cyclohexyl methacrylate as monofunctional (meth) acrylate (C) Ester CH (trade name; Kyoeisha Chemical Co., Ltd.), photopolymerization initiator (D), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) IRGACURE 379EG (trade name; BASF Japan Ltd.) which is phenyl] -1-butanone, and phenoti as a photopolymerization inhibitor Gin (PT) were mixed in the following composition ratio, and filtered through a membrane filter (0.2 [mu] m), to give filtrate (inkjet ink 1).
(A) FRM-1000 20.00 g
(B) Aronix M-327 30.00g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00 g
(Others) PT 0.055g

  It was 44.4 mPa * s as a result of measuring the viscosity of the ink 1 in 25 degreeC using the E-type viscosity meter (Toki Sangyo Co., Ltd. product TV-22, the same hereafter).

[Example 2]
As monofunctional (meth) acrylate (C), light ester BZ (trade name; Kyoeisha Chemical Co., Ltd.), which is benzyl methacrylate, was used in place of light ester CH, and the following composition ratio was used. Thus, inkjet ink 2 was prepared.
(A) FRM-1000 20.00 g
(B) Aronix M-327 30.00g
(C) Light ester BZ 50.00g
(D) IRGACURE 379EG 10.00g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 2 at 25 ° C. using an E-type viscometer, it was 38.7 mPa · s.

[Example 3]
Example 1 except that Aronics M-208 (trade name; Toagosei Co., Ltd.), which is a bisphenol F ethylene oxide-modified diacrylate, was used as the compound (E) having a radical polymerizable double bond, and the following composition ratio was used. In the same manner, inkjet ink 3 was prepared.
(A) FRM-1000 20.00 g
(B) Aronix M-327 20.00g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00g
(E) Aronix M-208 10.00g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 3 at 25 ° C. using an E-type viscometer, it was 39.4 mPa · s.

[Example 4]
As polyfunctional (meth) acrylate (B), instead of Aronix M-327, Aronix M-315 (trade name; Toago Constituent Co., Ltd.) which is tris [2-acryloyloxyethyl] isocyanurate is used, and the following composition is used: An inkjet ink 4 was prepared in the same manner as in Example 3 except that the ratio was changed.
(A) FRM-1000 20.00 g
(B) Aronix M-315 10.00g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00g
(E) Aronix M-208 20.00g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 4 at 25 ° C. using an E-type viscometer, it was 34.0 mPa · s.

[Example 5]
Inkjet ink 5 was prepared in the same manner as in Example 1, except that the composition ratio was as follows.
(A) FRM-1000 18.00 g
(B) Aronix M-327 30.00g
(C) Light ester CH 52.00g
(D) IRGACURE 379EG 10.00g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 5 at 25 ° C. using an E-type viscometer, it was 38.1 mPa · s.

[Example 6]
Inkjet ink 6 was prepared in the same manner as in Example 1 except that the composition ratio was as follows.
(A) FRM-1000 35.00 g
(B) Aronix M-327 30.00g
(C) Light ester CH 35.00g
(D) IRGACURE 379EG 10.00g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 6 at 25 ° C. using an E-type viscometer, it was 51.1 mPa · s.

[Example 7]
Inkjet ink 7 was prepared in the same manner as in Example 1 except that propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent and the composition ratio was as follows.
(A) FRM-1000 53.00 g
(B) Aronix M-327 30.00g
(C) Light ester CH 17.00 g
(D) IRGACURE 379EG 10.00 g
(Others) PT 0.055g
(Others) PGMEA 22.00g

  As a result of measuring the viscosity of the ink 7 at 25 ° C. using an E-type viscometer, it was 74.5 mPa · s.

[Example 8]
Inkjet ink 8 was prepared in the same manner as in Example 1 except that PA-1 prepared in Production Example 1 was used as the phosphorus-containing (meth) acrylate (A) and the following composition ratio was used.
(A) PA-1 35.00 g
(B) Aronix M-327 30.00g
(C) Light ester CH 35.00g
(D) IRGACURE 379EG 10.00 g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 8 at 25 ° C. using an E-type viscometer, it was 51.4 mPa · s.

[Example 9]
Inkjet ink 9 was prepared in the same manner as in Example 1 except that PA-2 prepared in Production Example 2 was used as the phosphorus-containing (meth) acrylate (A) and the composition ratio was as follows.
(A) PA-2 35.00 g
(B) Aronix M-327 30.00g
(C) Light ester CH 35.00g
(D) IRGACURE 379EG 10.00 g
(Others) PT 0.055g

  The viscosity of the ink 9 at 25 ° C. was measured using an E-type viscometer, and it was 55.3 mPa · s.

[Comparative Example 1]
Inkjet ink 10 was prepared in the same manner as in Example 1 except that light ester THF (trade name; Kyoeisha Chemical Co., Ltd.), which is tetrahydrofurfuryl methacrylate, was used instead of light ester CH, and the following composition ratio was used. .
(A) FRM-1000 20.00 g
(B) Aronix M-327 30.00g
(D) IRGACURE 379EG 10.00 g
(E) Light ester THF 50.00g
(Others) PT 0.055g

  Using an E-type viscometer, the viscosity of the ink 10 at 25 ° C. was measured and found to be 46.5 mPa · s.

[Comparative Example 2]
Inkjet ink 11 was prepared in the same manner as in Example 1 except that Aronix M-208 was used instead of Aronix M-327 and the composition ratio was as follows.
(A) FRM-1000 20.00 g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00g
(E) Aronix M-208 30.00g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 11 at 25 ° C. using an E-type viscometer, it was 28.8 mPa · s.

[Comparative Example 3]
NK ester A-GLY-3E (trade name; Shin-Nakamura Scientific Co., Ltd.), which is ethylene oxide-modified (3 mol) glycerin triacrylate, was used in place of Aronix M-327, except that the following composition ratios were used. Inkjet ink 12 was prepared in the same manner as Example 1.
(A) FRM-1000 20.00 g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00g
(E) NK ester A-GLY-3E 30.00 g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 12 at 25 ° C. using an E-type viscometer, it was 20.5 mPa · s.

[Comparative Example 4]
Instead of Aronix M-327, KAYARAD DPCA-20 (trade name; Nippon Kayaku Co., Ltd.), which is caprolactone-modified dipentaerythritol hexaacrylate, was used, and the same composition ratio was used as in Example 1. Inkjet ink 13 was prepared.
(A) FRM-1000 20.00 g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00 g
(E) KAYARAD DPCA-20 30.00 g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 13 at 25 ° C. using an E-type viscometer, it was 36.5 mPa · s.

[Comparative Example 5]
Inkjet ink 14 was prepared in the same manner as in Example 1 except that FA-513M (trade name; Hitachi Chemical Co., Ltd.), which is dicyclopentanyl methacrylate, was used instead of light ester CH, and the following composition ratio was used. Prepared.
(A) FRM-1000 20.00 g
(B) Aronix M-327 30.00g
(D) IRGACURE 379EG 10.00g
(E) FA-513M 50.00 g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 14 at 25 ° C. using an E-type viscometer, it was 220.4 mPa · s.

[Comparative Example 6]
Ink-jet ink 15 was prepared in the same manner as in Example 1 except that 4HBA (trade name; Nippon Kasei Co., Ltd.), which is 4-hydroxybutyl acrylate, was used instead of light ester CH and the composition ratio was as follows.
(A) FRM-1000 20.00 g
(B) Aronix M-327 30.00g
(D) IRGACURE 379EG 10.00g
(E) 4HBA 50.00g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 15 at 25 ° C. using an E-type viscometer, it was 230 mPa · s.

[Comparative Example 7]
Ink jet ink 16 was prepared in the same manner as in Example 1 except that FRM-1000 was not used and the following composition ratio was used.
(B) Aronix M-327 50.00g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00 g
(Others) PT 0.055g

  The viscosity of the ink 16 at 25 ° C. measured using an E-type viscometer was 47.1 mPa · s.

[Comparative Example 8]
Inkjet ink 17 was prepared in the same manner as in Example 1 except that PA-3 prepared in Production Example 3 was used as the phosphorus-containing (meth) acrylate (A) similar compound, and the composition ratio was as follows.
(A similar) PA-3 20.00g
(B) Aronix M-327 30.00g
(C) Light ester CH 50.00g
(D) IRGACURE 379EG 10.00 g
(Others) PT 0.055g

  As a result of measuring the viscosity of the ink 17 at 25 ° C. using an E-type viscometer, it was 55.3 mPa · s.

<Evaluation of inkjet ink>
With respect to the inks 1 to 17 obtained above, the inkjet dischargeability, and the flame retardancy, folding resistance and plating resistance of the cured film were evaluated. Each evaluation method is as follows, and the evaluation results are shown in Table 1 or Table 2.
When inks 14 and 15 were used, the cured film was not evaluated, so the cured film was not evaluated.

(Evaluation of ink jetting properties)
Inks 1 to 17 obtained in each of the examples and comparative examples were respectively injected into an ink jet cartridge and mounted on an ink jet apparatus (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Inc.). Voltage) 20V, the head temperature is appropriately adjusted according to the viscosity of the ink, the printing resolution is set to 1016 dpi under the discharge condition of 5 kHz drive frequency and the number of times of coating, and the thickness of 35 μm obtained by laminating the copper foil on the polyimide film A square pattern coating film having a 3 cm square was drawn on the center of the copper surface of Viroflex (trade name: Toyobo Co., Ltd.), which is a copper-clad laminate.

Thereafter, the substrate was irradiated with ultraviolet rays at a UV exposure of 1,000 mJ / cm ² using a UV irradiation device (J-CURE 1500 (trade name) manufactured by JATEC Corporation), and further in an oven at 160 ° C. for 60 minutes. The coating film was cured by heating to obtain a substrate on which a cured film pattern having a thickness of 11 μm was formed.

The ink ejection properties were evaluated by observing disorder of the 3 cm square cured film pattern obtained in this way and faint printing. The evaluation criteria are as follows.
○: No pattern disturbance or print fading △: Pattern disorder or print faint many ×: Ink cannot be ejected well (pattern cannot be formed)

(Flame retardancy evaluation method)
About flame retardance, it judged based on UL94 specification. Specifically, the inks obtained in Examples and Comparative Examples were coated on both sides of a polyimide film (Kapton (registered trademark) 100H; Toray DuPont Co., Ltd.) substrate so that the thickness after curing would be 20-30 μm. Each was applied by the ink jet method under the same conditions as in the case of evaluating the ink jetting properties, and the coating film was irradiated with ultraviolet rays of 1000 mJ / cm ² using a UV irradiation device, and then heated and cured at 160 ° C. for 60 minutes. About the obtained cured film, the thin material perpendicular | vertical combustion test (VTM test) based on UL94 specification was done, and it evaluated based on UL94 specification. As a result, when the evaluation was VTM-2 or higher, the cured film was judged to have flame retardancy.

(Folding resistance evaluation method)
Fracture resistance is based on JIS-C5016, and cracks occur in the cured film under the conditions of R = 0.38 mm and load 0.5 kgf by MIT Folding Fatigue Folding Tester (D type, manufactured by Toyo Seiki Seisakusho). The number of times until was measured. The said test was done using the board | substrate with a cured film. The substrate with a cured film was prepared by the inkjet method under the same conditions as those for evaluating the inkjet discharge properties so that the ink obtained in Examples and Comparative Examples had a cured film thickness of 8 to 10 μm. After applying to a substrate and irradiating the coating film with ultraviolet rays of 1000 mJ / cm ² using a UV irradiation device, it was cured by heating at 160 ° C. for 60 minutes.

(Plating resistance evaluation method)
The cured film-coated substrate prepared for evaluating the inkjet dischargeability was immersed in a 30 ° C. aqueous palladium solution (trade name: KAT-450, Pd concentration: 12 mg / L, Uemura Kogyo Co., Ltd.) for 1 minute, then washed with water. , Immersed in an electroless nickel plating solution (trade name: Nimden NPR-4, Ni concentration 4.5 g / L, Uemura Kogyo Co., Ltd.) for 30 minutes, washed with water, and then electroless at 80 ° C. A plating film was formed on the substrate with the cured film by immersing in a gold plating solution (trade name: Goblite TAM-55, Au concentration 1 g / L, Uemura Kogyo Co., Ltd.) for 10 minutes and then washing with water. The board | substrate with a cured film in which this plating film was formed was evaluated visually according to the following evaluation criteria.
○: No penetration of the plating solution into the cured film or peeling of the cured film ×: Penetration of the plating solution into the cured film or peeling of the cured film occurred

  It turns out that the ink of Examples 1-9 can form the cured film which is excellent in balance with a flame retardance, folding resistance, plating resistance, etc. compared with the ink of Comparative Examples 1-8.

  As described above, the cured film obtained from the ink of the present invention is excellent in properties such as flame retardancy, bendability and plating resistance, and therefore can be used favorably as a material for an electronic circuit board.

Claims (10)

Phosphorus-containing (meth) acrylate (A) represented by formula (1), polyfunctional (meth) acrylate (B) represented by formula (2), monofunctional (meth) acrylate represented by formula (3) A photocurable inkjet ink containing (C) and a photopolymerization initiator (D).

[In Formula (1), R < ¹ > is hydrogen or methyl, and R < ² > is C1-C10 alkylene. ]

[In the formula (2), R ³ is independently hydrogen or methyl, R ⁴ , R ⁵ and R ⁶ are each independently alkylene having 1 to 10 carbon atoms, and a, b and c are each independently 0 Is an integer from 1 to 10, and d, e and f are each independently an integer from 1 to 10. ]

Wherein (3), R ⁷ is hydrogen or methyl, R ⁸ is an organic group having a carbon number of 3 to 11 which contains a monocyclic hydrocarbon group, g is an integer of 0 to 5. ] R ² is alkylene of 1 to 5 carbon atoms in the formula (1), the light-curable inkjet ink according to claim 1. R ⁴ , R ⁵ and R ⁶ in formula (2) are each independently alkylene having 1 to 5 carbon atoms, a, b and c are each independently an integer of 0 to 5, and d, e and f are The photocurable inkjet ink of Claim 1 or 2 which is an integer of 1-5 each independently. The photocurable inkjet ink of any one of Claims 1-3 whose R < ⁸ > in Formula (3) is group represented by Formula (4) or (5).

[In Formulas (4) and (5), R ⁹ is independently hydrogen or an organic group having 1 to 5 carbon atoms. ]   15 to 45% by weight of phosphorus-containing (meth) acrylate (A), 5 to 40% by weight of polyfunctional (meth) acrylate (B), and monofunctional (meth) acrylate (C) with respect to 100% by weight of the total amount of ink. The photocurable inkjet ink according to any one of claims 1 to 4, comprising 10 to 50% by weight and a photopolymerization initiator (D) in an amount of 0.5 to 15% by weight.   Furthermore, it contains a compound (E) having a radical polymerizable double bond other than phosphorus-containing (meth) acrylate (A), polyfunctional (meth) acrylate (B) and monofunctional (meth) acrylate (C). Item 6. The photocurable inkjet ink according to any one of Items 1 to 5.   The cured film obtained from the photocurable inkjet ink of any one of Claims 1-6.   The board | substrate with a cured film which has a cured film of Claim 7.   An electronic component comprising the cured film according to claim 7 or the cured film-coated substrate according to claim 8.   A display element comprising the cured film according to claim 7 or the substrate with a cured film according to claim 8.