JP2011225683A - Curable composition and usage of the same, and curing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition from which a cured film can be formed, the film having favorable adhesiveness to a copper substrate, a polyimide film or the like and also having excellent adhesiveness to a plating layer.SOLUTION: The curable composition contains a compound (A) expressed by general formula (1) and an epoxy resin (B). In formula (1), Rand Reach independently represent an organic group having 1 to 100 carbon atoms; and Rrepresents a divalent group expressed by -CH=CH-.

Description

  The present invention relates to a curable composition suitably used for producing an electronic circuit board, its use, and a curing agent suitably used as a component of the curable composition.

  Epoxy resin composition as a protective film that protects conductor surfaces such as metal wiring having a predetermined circuit pattern when manufacturing electronic circuit boards (eg, printed wiring boards, flexible wiring boards, semiconductor package boards), etc. The cured film obtained from is used. However, a cured film obtained from the epoxy resin composition has been considered to be unsuitable for use as an interlayer insulating film of a multilayer substrate because of low adhesion to a plating layer formed on the cured film.

  In recent technology, there is a report that a cured film having high adhesion to a plating layer can be obtained by using a bisphenol A type epoxy resin having a phosphaphenanthrene structure (see, for example, Patent Document 1). However, in order to achieve a practical peel strength between the cured film and the plating layer, the surface of the cured film needs to be rough, and therefore a surface roughening process is necessary, so the manufacturing process Becomes complicated.

JP 2008-074929 A

  An object of the present invention is to provide a cured film suitable for a material of an interlayer insulating film of a multilayer substrate, which can form a cured film having good adhesion to a copper substrate, a polyimide film, etc. and excellent adhesion to a plating layer. It is to provide a sex composition.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by using a curable composition containing a compound (A) having a specific structure and an epoxy resin (B), thereby completing the present invention.

  That is, the present invention has the following configuration.

  [1] A curable composition containing a compound (A) represented by the following general formula (1) and an epoxy resin (B).

[In formula (1), R ¹ and R ³ are each independently an organic group having 1 to 100 carbon atoms, and R ² is a divalent group represented by any one of the following formulas (a) to (g). It is. ]

[2] R ¹ in the formula (1) may be substituted aryl having 6 to 20 carbon atoms, optionally substituted cycloalkyl having 5 to 20 carbon atoms, or the following general formula ( The curable composition according to [1], which is a monovalent group represented by 2).

[In Formula (2), R ⁴ is alkylene having 1 to 20 carbon atoms, R ⁵ is hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 0 to 20. ]
[3] In the above [2], R ⁴ in the formula (2) is alkylene having 2 to 8 carbon atoms, R ⁵ is alkyl having 1 to 18 carbon atoms, and n is an integer of 0 to 10. The curable composition as described.

[4] In the formula (2), R ⁴ is alkylene having 2 to 8 carbon atoms, R ⁵ is hydrogen or a monovalent group represented by the following general formula (3), and n is 1 to 10 The curable composition according to [2], which is an integer.

[In formula (3), R ⁶ is a divalent group represented by any of the following formulas (a) to (g). ]

[5] The curable composition according to any one of [1] to [4], wherein R ³ in the formula (1) is a monovalent group represented by the following general formula (4). .

[In Formula (4), R ⁷ is alkylene having 1 to 20 carbon atoms, R ⁸ is hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 0 to 20. ]
[6] In the above [5], R ⁷ in the formula (4) is alkylene having 2 to ⁸ carbon atoms, R ⁸ is alkyl having 1 to 18 carbon atoms, and n is an integer of 0 to 10. The curable composition as described.

[7] In the formula (4), R ⁷ is alkylene having 2 to 8 carbon atoms, R ⁸ is hydrogen or a monovalent group represented by the following general formula (5), and n is 1 to 10 The curable composition according to [5], which is an integer.

[In formula (5), R ⁹ is a divalent group represented by any one of the following formulas (a) to (g). ]

[8] R ² in the formula (1), R ⁶ in the formula (3), and R ⁹ in the formula (5) are represented by any of the following formulas (a) to (c) The curable composition according to [7], which is a group.

  [9] The compound [A] represented by the formula (1) is at least one compound selected from the group consisting of compounds represented by the following formulas (A1) to (A6). ] The curable composition as described in above.

[In the formulas (A1) to (A6), R is ethylene, propylene or butylene, and n is an integer of 1 to 10. ]
[10] The epoxy resin (B) is a phenol novolak epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, or a hydrogenated bisphenol F epoxy resin. Bisphenol S type epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-di Glycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and at least selected from the group consisting of epoxy resins represented by the following formulas (B1) to (B4) [1] to [9], which is one compound The curable composition according to one or Re.

[In formula (B1), n is an integer of 1-50. ]
[11] The curable composition according to any one of [1] to [10], further including a thermosetting compound (C) other than the epoxy resin (B).

  [12] The curable composition according to any one of [1] to [11], further including a radical polymerizable compound (D) and a photopolymerization initiator (E).

  [13] The curable composition according to any one of [1] to [12], further including a flame retardant (F).

  [14] The curable composition according to [13], wherein the flame retardant (F) is a compound having a structure represented by the following formula (F-1).

  [15] The curable composition according to [13], wherein the flame retardant (F) is a compound represented by the following general formula (F-2).

[Wherein, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 3. ]
[16] An inkjet ink comprising the curable composition according to any one of [1] to [15].

  [17] A curing agent containing the compound (A) represented by the following general formula (1).

[In formula (1), R ¹ and R ³ are each independently an organic group having 1 to 100 carbon atoms, and R ² is a divalent group represented by any one of the following formulas (a) to (g). It is. ]

[18] The compound (A) represented by the formula (1) was obtained by further reacting an acid anhydride with an addition compound obtained by reacting an amino-containing compound with maleic anhydride. The curing agent according to [17], which is a compound.

  [19] The above-mentioned [17], wherein the compound (A) represented by the formula (1) is at least one compound selected from the group consisting of compounds represented by the following formulas (A1) to (A6). ] Or the curing agent according to [18].

[In the formulas (A1) to (A6), R is ethylene, propylene or butylene, and n is an integer of 1 to 10. ]
[20] A cured film formed from the curable composition according to any one of [1] to [15] or the inkjet ink according to [16].

  [21] A substrate with a cured film, comprising a substrate and the cured film according to [20] formed on the substrate.

  [22] An electronic circuit board comprising the substrate with a cured film as described in [21].

  According to the curable composition of the present invention, it is possible to form a cured film having good adhesion to a copper substrate, a polyimide film and the like and excellent adhesion to a plating layer. Therefore, the curable composition of the present invention is suitable for the material of the interlayer insulating film of the multilayer substrate, and can produce a highly reliable multilayer substrate.

Hereinafter, the curable composition of the present invention, a cured film formed from the composition, a substrate with a cured film having the cured film, an electronic circuit substrate comprising the substrate, and a component contained in the composition are suitably used. The curing agent will be described in detail.
1. Curable composition The curable composition of this invention contains the compound (A) represented by General formula (1), and an epoxy resin (B). The curable composition of the present invention may contain a thermosetting compound (C) other than the epoxy resin (B), a radical polymerizable compound (D), a photopolymerization initiator (E), and a flame retardant (F). In addition, a colorant, a solvent, a surfactant, a polymerization inhibitor, and the like may be contained as necessary.

The curable composition of the present invention may be colorless or colored.
1.1 Compound (A) represented by Formula (1)
The curable composition of this invention contains the compound (A) represented by following General formula (1).

In formula (1), R ¹ and R ³ are each independently an organic group having 1 to 100 carbon atoms; R ² is a divalent group represented by any of the following formulas (a) to (g). It is preferable that it is a divalent group represented by any one of the following formulas (a) to (c), and is represented by the following formula (b). A divalent group is particularly preferred.

<For R ^1>
R ¹ in the above formula (1) is an aryl having 6 to 20 carbon atoms which may have a substituent, a cycloalkyl having 5 to 20 carbon atoms which may have a substituent, or the following general formula (2). A monovalent group represented by the following general formula (2) is particularly preferred in that a cured film excellent in flexibility can be obtained.

The aryl is preferably phenyl, and the cycloalkyl is preferably cyclohexyl. Examples of the substituent in the aryl and cycloalkyl include carboxyl, hydroxyl, alkyl having 1 to 14 carbon atoms, and the like.

In formula (2), R ⁴ is alkylene having 1 to 20 carbon atoms, R ⁵ is hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 0 to 20. Examples of the organic group include alkyl having 1 to 20 carbon atoms and monovalent groups represented by the following general formula (3). R ⁵ is preferably hydrogen or a monovalent group represented by the following general formula (3) in that a cured film excellent in adhesion with the substrate and the plating layer can be obtained.

In the formula (3), R ⁶ is a divalent group represented by any one of the above formulas (a) to (g), and the above formula (a) is obtained in that a cured film excellent in flexibility can be obtained. It is preferable that it is a bivalent group represented by any one of-(c), and it is especially preferable that it is a bivalent group represented by the said Formula (b).

In the above formula (2), R ⁴ is alkylene having 2 to 8 carbon atoms, R ⁵ is alkyl having 1 to 18 carbon atoms, and n is preferably an integer of 0 to 10; flexibility and adhesion R ⁴ is an alkylene having 2 to ⁴ carbon atoms, R ⁵ is an alkyl having 1 to 18 carbon atoms, and n is an integer of 2 to 8 in that an excellent cured film is obtained due to the balance of properties. Is more preferable.

In the above formula (2), R ⁴ is alkylene having 2 to 8 carbon atoms, R ⁵ is hydrogen or a monovalent group represented by the above formula (3), and n is an integer of 1 to 10. It is also preferable that R ⁴ has 2 to ⁴ carbon atoms in that an excellent cured film is obtained by a balance between flexibility and adhesion.
R ⁵ is hydrogen or a monovalent group represented by the above formula (3), and n is 2
More preferably, it is an integer of ˜8.

<For R ^3>
R ³ in the above formula (1) is preferably a monovalent group represented by the following general formula (4) in that a cured film excellent in flexibility can be obtained.

In formula (4), R ⁷ is alkylene having 1 to 20 carbon atoms, R ⁸ is hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 0 to 20. Examples of the organic group include alkyl having 1 to 20 carbon atoms and monovalent groups represented by the following general formula (5). R ⁸ is preferably hydrogen or a monovalent group represented by the following general formula (5) in that a cured film excellent in adhesion with the substrate and the plating layer can be obtained.

In the formula (5), R ⁹ is a divalent group represented by any one of the above formulas (a) to (g), and the above formula (a) is obtained in that a cured film excellent in flexibility can be obtained. It is preferable that it is a bivalent group represented by any one of-(c), and it is especially preferable that it is a bivalent group represented by the said Formula (b).

In the above formula (4), R ⁷ is alkylene having 2 to ⁸ carbon atoms, R ⁸ is alkyl having 1 to 18 carbon atoms, and n is preferably an integer of 0 to 10; flexibility and adhesion R ⁷ is alkylene having 2 to 4 carbon atoms, R ⁸ is alkyl having 1 to 18 carbon atoms, and n is an integer of 2 to 8 in that an excellent cured film can be obtained due to the balance of properties. Is more preferable.

In the above formula (4), R ⁷ is alkylene having 2 to 8 carbon atoms, R ⁸ is hydrogen or a monovalent group represented by the above formula (5), and n is an integer of 1 to 10. It is also preferable that R ⁷ has 2 to 4 carbon atoms in that a cured film excellent in balance between flexibility and adhesion can be obtained.
R ⁸ is hydrogen or a monovalent group represented by the above formula (5), and n is 2
More preferably, it is an integer of ˜8.

R ² in the above formula (1), R ⁶ in the above formula (3), and R ⁹ in the above formula (5) are divalent groups represented by any of the above formulas (a) to (c). It is preferable that it is a divalent group represented by the above formula (b).

  As the compound (A), at least one compound selected from the compounds represented by the following formulas (A1) to (A6) is preferable in that a cured film excellent in balance of flexibility and adhesion can be obtained. Particularly preferred is at least one compound selected from compounds represented by the following formulas (A4) to (A6).

  In formulas (A1) to (A6), R is ethylene, propylene or butylene, n is an integer of 1 to 10, preferably an integer of 2 to 10, and more preferably an integer of 2 to 8. .

The cured film obtained from the curable composition of the present invention containing the compound (A) has high flexibility, adhesion to the substrate on which the cured film is formed, and a plating layer formed on the cured film; Excellent adhesion. In particular, since the compound (A) has a structure containing nitrogen atoms, the cured film obtained from the curable composition of the present invention is excellent in adhesion to a plating layer or a metal substrate. Further, like the compounds represented by the above formulas (A1) to (A6), R ¹ and / or in the above formula (1)
Alternatively, if R ³ has a structure having a hydroxyl group or a carboxyl, a cured film excellent in adhesion to the substrate and the plating layer can be obtained.

In the curable composition of the present invention, the compound (A) is usually 10 to 300 parts by weight, preferably 20 to 250 parts by weight, more preferably 40 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin (B). Included in range. When the content of the compound (A) is in the above range, a cured film excellent in adhesion to the substrate and the plating layer is obtained, and in terms of balance such as flexibility, it is preferable. 1.2 Production Method of Compound (A) Represented by General Formula (1) The compound (A) represented by the general formula (1) includes, for example, (i) a compound having amino and maleic anhydride. It can be obtained by performing a step of reacting, and (ii) a step of further reacting an acid anhydride with the addition compound obtained in step (i).

<Process (i)>
In the step (i), a compound having amino and maleic anhydride react to form maleimide by dehydration cyclization (maleimide forming reaction), and a compound having amino has double reaction such as maleic anhydride. Reaction to add to the bond (addition reaction to double bond) proceeds. These reactions may proceed simultaneously or sequentially. For example, maleic anhydride may be reacted with a compound having amino to obtain maleimide by dehydration cyclization, and then the compound having amino may be added to the double bond of the maleimide. In addition, these reactions can proceed in the presence of a solvent. Alternatively, maleimide may be used as a raw material, and an amino-containing compound may be reacted with maleimide to obtain an addition compound in which an amino-containing compound is added to a maleimide double bond.

  In step (i), the charge ratio of the amino-containing compound and maleic anhydride is not particularly limited, but the amino-containing compound: maleic anhydride (molar ratio) is usually 2.5: 1 to 2: 1. Preferably, it may be 2.2: 1 to 2: 1.

  The reaction temperature in the maleimide formation reaction and the addition reaction to the double bond is usually 70 to 250 ° C., preferably 120 to 200 ° C., and the reaction time is usually 0.5 to 20 hours, preferably 1 to 10 hours.

In the maleimide production reaction, the amino-containing compound is a compound represented by H ₂ N—R ¹ ′. R ¹ ′ is an organic group having 1 to 100 carbon atoms, aryl having 6 to 20 carbon atoms which may have a substituent, cycloalkyl having 5 to 20 carbon atoms which may have a substituent, or the following general group A monovalent group represented by the formula (2 ′) is preferable.

In formula (2 ′), R ⁴ is alkylene having 1 to 20 carbons, R ⁵ is hydrogen or an organic group having 1 to 20 carbons, and n is an integer of 0 to 20. Examples of the organic group include alkyl having 1 to 20 carbon atoms. Preferred embodiments of R ⁴ and n in the formula (2 ') is the same as R ⁴ and n in the above formula (2).

  The maleimide production reaction proceeds, for example, as shown in the following formula.

In the addition reaction to the double bond, the compound having amino added to the maleic anhydride or the double bond of the maleimide is a compound represented by H ₂ N—R ³ ′.
R ³ ′ is an organic group having 1 to 100 carbon atoms, and is preferably a monovalent group represented by the following general formula (4 ′).

In formula (4 ′), R ⁷ is alkylene having 1 to 20 carbons, R ⁸ is hydrogen or an organic group having 1 to 20 carbons, and n is an integer of 0 to 20. Examples of the organic group include alkyl having 1 to 20 carbon atoms. Preferred embodiments of R ⁷ and n in the formula (4 ') is the same as R ⁷ and n in the formula (4).

  The addition reaction of the maleimide to the double bond proceeds, for example, as shown in the following formula.

<Process (ii)>
In step (ii), the acid anhydride is further reacted with the addition compound obtained in step (i).

  The acid anhydride is a compound represented by the following general formula.

Wherein, R ² has the same meaning as R ² in the formula (1). Examples of the acid anhydride include succinic acid anhydride, maleic acid anhydride, citraconic acid anhydride, phthalic acid anhydride, cyclohexane dicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride, and trimellitic acid anhydride. Succinic anhydride, maleic anhydride, and citraconic anhydride are preferable, and maleic anhydride is particularly preferable in that a cured film having excellent properties can be obtained.

  This reaction can also proceed in the presence of a solvent.

  In step (ii), the amount ratio of the addition compound and the acid anhydride is not particularly limited, but the sum of amino and hydroxyl in the addition compound: the acid anhydride (molar ratio) is usually 1: 0. .5 to 1: 1, preferably 1: 0.8 to 1: 1.

Moreover, the reaction temperature in process (ii) is 70-200 degreeC normally, Preferably it is 100-16.
It is 0 degreeC and reaction time is 0.5 to 20 hours normally, Preferably it is 1 to 10 hours.

  The reaction in step (ii) proceeds, for example, as shown in the following formula.

In the case where R ¹ ′ or R ³ ′ in the compound obtained in step (i) has a group capable of reacting with the acid anhydride (eg, hydroxyl), R ¹ ′ and / or R ³ ′ and the above Reaction with acid anhydrides can also occur.

Specifically, when R ¹ ′ is a monovalent group represented by the above formula (2 ′) and R ⁵ is hydrogen, R ¹ ′ is represented by the above formula ( It is a monovalent group represented by 2), and R ⁵ can be converted to a monovalent group represented by the above formula (3).

When R ³ ′ is a monovalent group represented by the above formula (4 ′) and R ⁸ is hydrogen, R ³ ′ is represented by the above formula (4) by reaction with the acid anhydride. A monovalent group represented by R ⁸ can be converted to a monovalent group represented by the above formula (5).

As described above, the compound (A) represented by the above formula (1) can be obtained.
1.2 Epoxy resin (B)
The curable composition of the present invention contains an epoxy resin (B). When the curable composition of the present invention containing an epoxy resin (B) is used, a cured film having excellent adhesion to various substrates (eg, copper substrate, polyimide film) can be obtained.

  Examples of the epoxy resin (B) include phenol novolak type, cresol novolak type, bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, hydrogenated bisphenol F type, bisphenol S type, trisphenol methane type, and tetraphenol ethane. Type, bixylenol type or biphenol type epoxy resin; alicyclic or heterocyclic epoxy resin; epoxy resin having a dicyclopentadiene type or naphthalene type structure.

  Examples of the epoxy resin (B) include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N. , N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane.

Various commercially available products can be used as the epoxy resin (B), such as TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), Epicoat 828, 834, 1001 and 1004 (trade name; Japan Epoxy Resin). Epiclon 840, 850, 1050, 1050, 2055 (trade name; manufactured by DIC), Epotot YD-011, YD-013, YD-127, YD-128 (trade name; Toto Kasei Co., Ltd.) Manufactured), D.E.R.317
331, 661, 664 (trade name; manufactured by Dow Chemical Co., Ltd.), Araldide 6071, 6084, GY250, GY260 (trade name; manufactured by Ciba Specialty Chemicals), Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (trade name; manufactured by Sumitomo Chemical Co., Ltd.), A.E.R. 330, 331, 661,
Bisphenol A type epoxy resin such as 664 (trade name; manufactured by Asahi Kasei Kogyo Co., Ltd.);
Epicoat 152, 154 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), D.E.R.4
31, 438 (trade name; manufactured by Dow Chemical), Epicron N-730, N-770, N-865 (trade name; manufactured by DIC), Epototo YDCN-701, YDCN-704 (trade name; Manufactured by Toto Kasei), Araldide ECN1235, ECN1273, ECN1299 (trade name; manufactured by Ciba Specialty Chemicals), XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 (product) Name: Nippon Kayaku Co., Ltd.), Sumi-epoxy ESCN-195X, ESCN-220 (trade name; manufactured by Sumitomo Chemical Co., Ltd.), AER ECN-235, ECN-299 (trade name; ADEKA) Novolac type epoxy resin, etc .;
Epicron 830 (trade name; manufactured by DIC), JER807 (trade name; manufactured by Japan Epoxy Resin), Epototo YDF-170 (trade name; manufactured by Tohto Kasei), YDF-175, YDF-2001, YDF-2004, Araldide Bisphenol F type epoxy resin such as XPY306 (trade name; manufactured by Ciba Specialty Chemicals); Hydrogenated bisphenol A such as Epototo ST-2004, ST-2007, ST-3000 (trade name; manufactured by Toto Kasei) Type epoxy resin;
An alicyclic epoxy resin such as Celoxide 2021 (trade name; manufactured by Daicel Chemical Industries), Araldide CY175, CY179, and CY184 (trade names; manufactured by Ciba Specialty Chemicals);
Trihydroxyphenylmethane type epoxy resins such as YL-933 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-501, EPPN-502 (trade name; manufactured by Dow Chemical Co.); YL-6056, YX-4000, YL- 6121 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.) and other bixylenol type or biphenol type epoxy resins or mixtures thereof;
Bisphenol S type epoxy resin such as EBPS-200 (trade name; manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (trade name; manufactured by ADEKA), EXA-1514 (trade name; manufactured by DIC); JER157S (trade name; Tetraphenylolethane type such as YL-931 (trade name; made by Japan Epoxy Resin), Araldide 163 (trade name; made by Ciba Specialty Chemicals), etc. Epoxy resin;
Heterocyclic epoxy resins such as Araldide PT810 (trade name; manufactured by Ciba Specialty Chemicals) and TEPIC (trade name; manufactured by Nissan Chemical Industries); HP-4032, EXA-4750, EXA-4700 (trade name; DIC) Naphthalene-containing epoxy resins such as HP-7200, HP-7200H, and HP-7200HH (trade name; manufactured by DIC), and the like, and epoxy resins having a dicyclopentadiene skeleton.

Among these epoxy resins, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type Epoxy resin, trisphenolmethane type epoxy resin, tetraphenolethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Preferred are cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and epoxy resins represented by the following formulas (B1) to (B4);
N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4, 4′-diaminodiphenylmethane and epoxy resins represented by the following formulas (B1) to (B4) are particularly preferable in that a cured film having excellent chemical resistance can be obtained.

  In formula (B1), n is an integer of 1-50.

  An epoxy resin (B) may be used by 1 type, and may use 2 or more types together.

The epoxy resin (B) is preferably contained in an amount of 20 to 80% by weight in terms of high adhesion of the obtained cured film to various substrates with respect to the total amount of the curable composition excluding the solvent; From the viewpoint of the balance between the chemical properties and the chemical resistance, it is more preferably 22 to 70% by weight, particularly preferably 25 to 60% by weight.
1.3 Thermosetting compounds other than epoxy resin (B) (C)
The curable composition of the present invention may contain a thermosetting compound (C) other than the epoxy resin (B), for example, in order to improve heat resistance. The thermosetting compound (C) is not particularly limited as long as it is a compound having a functional group that can be thermally cured, and examples thereof include bismaleimide, a phenol resin, a melamine resin, and an epoxy curing agent.

When using the thermosetting compound (C), in the curable composition of the present invention, the thermosetting compound (C) is 100 parts by weight in total of the compound (A) and the epoxy resin (B). Usually, it is contained in the range of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, more preferably 15 to 40 parts by weight. When the content of the thermosetting compound (C) is in the above range, a cured film excellent in chemical resistance, flexibility and heat resistance can be obtained.
1.3.1 Examples of bismaleimide bismaleimide include compounds represented by the following general formula (6). The bismaleimide represented by the following general formula (6) is, for example, a compound obtained by reacting a diamine with an acid anhydride.

In formula (6), R ¹⁰ and R ¹² are each independently hydrogen or methyl, and are preferably hydrogen from the viewpoint of excellent heat resistance of the cured film obtained from the curable composition; R ¹¹ is the number of carbon atoms. It is a 1-100 divalent organic group, and it is preferable that it is a bivalent group represented by following General formula (7) at the point from which the softness | flexibility of the cured film obtained becomes high.

In formula (7), each of R ¹³ and R ¹⁴ independently represents an alkylene having 1 to 18 carbon atoms in which arbitrary methylene that is not continuous may be replaced by oxygen, or an aromatic ring that may have a substituent. It is a cycloalkylene which may have a valent group or a substituent. Examples of the substituent in the aromatic ring and cycloalkylene include carboxyl, hydroxyl, alkyl having 1 to 5 carbons, and alkoxy having 1 to 5 carbons. From the viewpoint of high heat resistance of the obtained cured film, R ¹³ and R ¹⁴ are each preferably a divalent group represented by any one of the following formulas.

  In formula (7), X is a divalent group represented by any of the following formulas.

A bismaleimide may be used by 1 type and may use 2 or more types together.
1.3.2 Phenolic resins As phenolic resins, novolak resins obtained by condensation reaction of aromatic compounds having phenolic hydroxyl groups and aldehydes, vinylphenol homopolymers (including hydrogenated products), vinylphenols and A vinylphenol copolymer (including a hydrogenated product) with a compound copolymerizable therewith is 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, o-xylenol, 2,3-xylenol, 2,4-xylenol, 2,5-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, β-naphthol, etc. I can get lost.

  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, acrylonitrile and the like.

  Specific examples of the phenol resin include Resitop PSM-6200 (trade name; manufactured by Gunei Chemical Co., Ltd.), Shonor BRG-555 (trade name; manufactured by Showa Polymer Co., Ltd.), Marca Linker MS-2P, Marca Linker CST70, Marca A linker PHM-C (trade name; manufactured by Maruzen Petrochemical Co., Ltd.) can be mentioned.

A phenol resin may be used by 1 type and may use 2 or more types together.
1.3.3 Melamine Resin Melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde, methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, etherified methylol benzoguanamine, and Examples thereof include condensates thereof. Among these, etherified methylol melamine is preferable in terms of good chemical resistance.

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

A melamine resin may be used by 1 type and may use 2 or more types together.
1.3.4 Epoxy Curing Agent The curable composition of the present invention may contain an epoxy curing agent in terms of further improving its chemical resistance. As the epoxy curing agent, an acid anhydride curing agent, a polyamine curing agent, a catalytic curing agent and the like are preferable.

Acid anhydride curing agents include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, trimellit Examples thereof include acid anhydrides and styrene-maleic anhydride copolymers.

  Examples of polyamine curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, and 1,3-bis (amino). Methyl) cyclohexane, N-aminoethylpiperazine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, diaminodiphenylsulfone and the like.

  The epoxy curing agent may be used alone or in combination of two or more.

Examples of the catalyst-type curing agent include tertiary amine compounds and imidazole compounds.
1.4 Radical polymerizable compound (D)
The curable composition of the present invention may contain a radical polymerizable compound (D).

  The radically polymerizable compound (D) is not particularly limited as long as it is a compound having any one or more of (meth) acryloyl, allyl, and vinyl. From the viewpoint of photopolymerization, a compound having (meth) acryloyl is used. Particularly preferred.

  The compounds having (meth) acryloyl include isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, penta Erythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycidyl (meth) acrylate, 3 , 4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, (meth) acrylic acid, methyl (meth) acrylate , Ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Benzyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, bisphenol F type ethylene oxide modified diacrylate, bisphenol A type ethylene oxide modified diacrylate , Polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexa Diol diacrylate, 1,9-nonanediol diacrylate, 1,4-cyclohexanedimethanol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, 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 Rate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified phosphate tri (meth) acrylate, urethane (meth) acrylate, ε-caprolactone-modified tris (acryloyloxyethyl) isocyanate Examples include nurate.

  A radically polymerizable compound (D) may be used by 1 type, and may use 2 or more types together.

When the radically polymerizable compound (D) is used, the radically polymerizable compound (D) in the curable composition of the present invention is usually used with respect to a total of 100 parts by weight of the compound (A) and the epoxy resin (B). It is contained in the range of 10 to 200 parts by weight, preferably 15 to 150 parts by weight, more preferably 20 to 100 parts by weight. When content of a radically polymerizable compound (D) exists in the said range, the viscosity of a composition can be adjusted according to a use.
1.5 Photopolymerization initiator (E)
The curable composition of the present invention may contain a photopolymerization initiator (E) in order to impart photocurability thereto. The photopolymerization initiator (E) is not particularly limited as long as it is a compound capable of generating radicals upon irradiation with ultraviolet rays or visible light, but alkylphenone-based, acylphosphine oxide-based, and titanocene-based photopolymerization initiators may be used. From the viewpoint of photocurability, acylphosphine oxide photopolymerization initiators are particularly preferred.

Specific examples of the photopolymerization initiator (E) include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2 -Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzi 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) 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-butylpe) Ruoxycarbonyl) benzophenone,
2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2,6-di ( Trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4′-methoxyphenyl) − - triazine,
2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin),
2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ′ -Tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,4) 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, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ − 2,4-cyclopentadiene-1-
Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2,4,6- And trimethylbenzoyldiphenylphosphine oxide.

  A photoinitiator (E) may be used by 1 type, and may use 2 or more types together.

When the photopolymerization initiator (E) is used, the photopolymerization initiator (E) in the curable composition of the present invention is usually 5 to 70 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (D). Preferably it is contained in the range of 10 to 60 parts by weight, more preferably 20 to 50 parts by weight. When the content of the photopolymerization initiator (E) is within the above range, it is preferable in that the composition becomes highly sensitive to the amount of light irradiation.
1.6 Flame retardant (F)
The curable composition of the present invention may contain a flame retardant (F). Although it will not specifically limit as a flame retardant (F) if it is a compound which can provide a flame retardance, It is preferable to use an organophosphorus flame retardant from a viewpoint of low toxicity, low pollution property, and safety.

  Examples of the organophosphorus flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 Oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide and the like Can be mentioned.

  Among the flame retardants (F), when the cured film obtained from the curable composition is exposed to a high temperature state, there is no bleed out of the flame retardant, and the following formula (F-1) which is an organophosphorus flame retardant It is preferable to use a compound having the structure represented. As a compound having a structure represented by the following formula (F-1), HFA-3003 (trade name; Showa Polymer Co., Ltd.) which is condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide It is more preferable to use a compound represented by the following general formula (F-2) such as

  In the formula, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 3. Preferably, m is 1 or 2, n is 1 or 2, and m + n is 3.

  A flame retardant (F) may be used by 1 type and may use 2 or more types together. In addition, the flame retardant (F) demonstrated above can be manufactured by a well-known method, and is also marketed like the above-mentioned HFA-3003 by Showa Polymer Co., Ltd.

When the flame retardant (F) is used, in the curable composition of the present invention, the flame retardant (F) is usually 10 to 50 with respect to 100 parts by weight of the total of the compound (A) and the epoxy resin (B). Part by weight, preferably 15 to 40 parts by weight, more preferably 20 to 30 parts by weight. When the content of the flame retardant (F) is in the above range, it is preferable in terms of a good balance with other characteristics and excellent flame retardancy.
1.7 Other components The curable composition of the present invention may contain a colorant, a solvent, a surfactant, a polymerization inhibitor and the like in order to further improve various properties.
1.7.1 Colorant The curable composition of the present invention may contain a colorant , for example, in order to facilitate discrimination from the substrate when examining the state of the cured film. As the colorant, dyes and pigments are preferable.

  A coloring agent may be used by 1 type and may use 2 or more types together.

In the case of using a colorant, the content is preferably 0.01 to 10% by weight with respect to the total amount of the curable composition, considering the point that the inspection of the cured film is easy and the balance with other characteristics. Preferably it is 0.05 to 5 weight%, More preferably, it is the range of 0.1 to 1 weight%.
1.7.2 Solvent The curable composition of the present invention may contain a solvent, for example, in order to improve the film surface uniformity of the obtained cured film. In addition, when the curable composition of the present invention is used as an inkjet ink, if the ink contains a low-boiling solvent, the solvent volatilizes and the viscosity of the ink increases to clog the nozzle head of the inkjet head. May end up. For this reason, a solvent having a boiling point of 100 to 300 ° C. is particularly preferable.

Solvents having a boiling point of 100 to 300 ° C. include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, and methyl ethoxyacetate. , Ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-oxy Methyl propionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl onate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvic acid Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene Glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Cetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether Acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xyle , Anisole, γ-butyrolactone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone and the like.

  A solvent may be used by 1 type and may use 2 or more types together.

The content of the solvent is preferably 0 to 85% by weight, more preferably 0 to 80% by weight, considering the balance between the ejection property as an inkjet ink and other characteristics with respect to the total amount of the curable composition. More preferably, it is the range of 0 to 75 weight%.
1.7.3 Surfactant The curable composition of the present invention may contain a surfactant , for example, in order to improve wettability to the base substrate and film surface uniformity of the obtained cured film. . Examples of the surfactant include a silicon-based surfactant, an acrylic surfactant, and a fluorine-based surfactant.

  Examples of commercially available silicon surfactants include Byk-300, 306, 335, 310, 341, 344, and 370 (trade names; manufactured by BYK Chemie). Examples of commercially available acrylic surfactants include Byk-354, 358, and 361 (trade names; manufactured by Big Chemie). Examples of commercially available fluorosurfactants include DFX-18, Footgent 250, 251 (trade name; manufactured by Neos), MegaFace F-479 (trade name; manufactured by DIC), and the like.

  Surfactant may be used by 1 type and may use 2 or more types together.

In the case of using a surfactant, the content is preferably 0.001 to 1% by weight, more preferably the total amount of the curable composition, considering the balance with the film surface uniformity and other characteristics of the cured film. Is in the range of 0.005 to 0.1% by weight, more preferably 0.01 to 0.05% by weight.
1.7.4 Polymerization inhibitor The curable composition of the present invention may contain a polymerization inhibitor in order to improve storage stability. Examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, phenothiazine and the like. Among these, phenothiazine is preferable in that the change in viscosity is small even during long-term storage.

  A polymerization inhibitor may be used by 1 type and may use 2 or more types together.

When a polymerization inhibitor is used, its content is preferably 0.01 to 1% by weight with respect to the total amount of the curable composition, taking into account the small change in viscosity even during long-term storage and the balance with other properties. More preferably, it is in the range of 0.04 to 0.5% by weight.
2. Preparation method of curable composition The curable composition of this invention can be prepared by mixing each component used as a raw material by a well-known method. In particular, the curable composition of the present invention is a mixture of the components (A) to (B) and the components (C) to (F) and other components as necessary, and the resulting solution is filtered. It is preferable to prepare it. For the filtration, for example, a fluororesin membrane filter is used.
3. Viscosity of curable composition The curable composition of the present invention is preferably adjusted to a viscosity range suitable for a desired coating method. The viscosity of the curable composition is preferably adjusted, for example, by optimizing the type and content of the solvent or radical polymerizable compound (D).

  When the curable composition of the present invention is used as an inkjet ink, the viscosity measured with an E-type viscometer at a discharge temperature (preferably 10 to 120 ° C.) is preferably 1 to 30 mPa · s, and 2 to 25 mPa · s. Is more preferable, and 3 to 20 mPa · s is particularly preferable.

  When a curable composition having a viscosity at 25 ° C. of 30 mPa · s or more is used as an inkjet ink, more stable ejection becomes possible by heating the inkjet head to lower the viscosity during ejection.

When the inkjet head is heated, it is preferable to use an ink that does not contain a solvent, because the viscosity may increase due to the volatilization of the solvent. In that case, the viscosity of the ink is preferably adjusted by optimizing the type and content of the radical polymerizable compound (D).
4). Storage of curable composition When the curable composition of the present invention is stored at -20 to 20 ° C, the viscosity change during storage is small and the storage stability is good.
5. Application of Curable Composition by Inkjet Coating Method The curable composition of the present invention can be applied using a known inkjet coating method or the like. As an inkjet coating method, for example, a method in which mechanical energy is applied to ink to eject (apply) ink from an inkjet head (so-called piezo method), or a method in which thermal energy is applied to ink to apply ink (so-called bubble) Jet (registered trademark) system.

  By using the inkjet coating method, the curable composition can be applied in a predetermined pattern. As a result, ink can be applied only to necessary portions, and the cost can be reduced as compared with the photolithography method. That is, by using the curable composition of the present invention as an inkjet ink, the amount of capital investment can be reduced and the loss of materials can be reduced.

  As a preferable application device, for example, energy corresponding to the application signal is applied to the ink in the ink jet head chamber having the ink storage portion in which the ink is stored, and ink droplets are generated by the energy. An apparatus for performing a corresponding application (drawing) can be mentioned.

Examples of the inkjet head include those having a heat generating part wetted surface containing a metal and / or a metal oxide. Specific examples of the metal and / or metal oxide include metals such as Ta, Zr, Ti, Ni, and Al, and oxides of these metals.

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 integrated so as not to be separated. In addition, the ink storage unit is integrated with the ink jet head so as to be separable or non-separable and mounted on the carriage, and is provided at a fixed portion of the apparatus, and the ink jet head via an ink supply member, for example, a tube The ink may be supplied to the ink.
6). Cured film The cured film of the present invention is formed from the above-described curable composition of the present invention. Since the cured film of the present invention has good adhesion to various substrates (eg, copper substrate, polyimide film) and excellent adhesion to the plating layer, it is suitable as an interlayer insulating film for coverlay films and multilayer substrates. Can be used.

  The cured film of the present invention is obtained by applying the curable composition of the present invention to the substrate surface by a known method such as an inkjet coating method, and then irradiating the coating film with light (eg, irradiation with ultraviolet rays or visible light) and / or Or it is obtained by heating and curing the coating film.

In the case of curing by light irradiation, the exposure amount to the coating film is about 10 to 10,000 mJ / cm ^{2 as} measured by an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC. Is preferably about ²⁰ to 5,000 mJ / cm ² , more preferably about 40 to 2,000 mJ / cm ² . Moreover, the wavelength of the irradiated light is 250-5.
00 nm is preferable, and 300 to 450 nm is more preferable.

  The exposure machine is not particularly limited as long as it can irradiate light in the range of 250 to 500 nm, including a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a halogen lamp, and the like.

  When curing by heating, the heating device may be any of a hot plate, oven, far-infrared oven, etc., and the heating temperature and heating time are preferably 100 to 350 ° C. for 10 minutes to 6 hours, and 150 to 300 ° C. for 30 minutes to 2 hours is more preferable.

The coating film may be further heated after being cured by light irradiation, in which case it is preferably heated at 100 to 250 ° C. for 10 minutes to 3 hours, and heated at 150 to 250 ° C. for 30 minutes to 2 hours. More preferably. By reducing the fluidity of the coating film by light irradiation and then heating it, a hardened film having the same pattern size as that at the time of drawing can be obtained.
7). The board | substrate with a cured film of this invention has a board | substrate and the cured film of this invention formed on this board | substrate. The board | substrate with which the cured film of this invention is formed will not be specifically limited if it can become the object by which the curable composition of this invention is apply | coated. The shape of the substrate is not limited to a flat plate shape, and may be a curved surface shape.

The substance constituting the substrate is not particularly limited. For example, plastic film, cellophane, acetate, metal foil, laminated film of polyimide and metal foil, glassine paper having a sealing effect, parchment paper, and polyethylene, clay binder, polyvinyl Examples thereof include paper and glass that have been treated with alcohol, starch, carboxymethyl cellulose (CMC), or the like. Examples of the plastic film include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
Examples thereof include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, fluororesins, acrylic resins, polyamides, polycarbonates, and polyimides.

  The substance constituting the substrate may further include a pigment, a dye, an antioxidant, a deterioration inhibitor, a filler, an ultraviolet absorber, an antistatic agent, an electromagnetic wave inhibitor, etc., as long as the effect of the present invention is not adversely affected. An additive may be contained. In addition, a layer made of a material different from that of the substrate (for example, a coverlay or a solder resist film) may be formed on a part of the substrate surface.

  Although the thickness of a board | substrate is not specifically limited, Usually, it is about 10 micrometers-2 mm, and is suitably adjusted with the objective to use. Although the thickness of a cured film is not specifically limited, Usually, it is 3-50 micrometers, and is suitably adjusted with the objective to use.

  If necessary, the surface on which the cured film of the substrate is to be formed may be subjected to easy adhesion treatment such as water repellent treatment, corona treatment, plasma treatment, blast treatment, or an easy adhesion layer or a color filter protective film. May be.

  The use of the substrate with a cured film of the present invention is not particularly limited, but the cured film obtained from the curable composition of the present invention is excellent in chemical resistance and heat resistance, and therefore an electronic circuit substrate having metal wiring on the substrate surface It is preferable to be used for production of the above.

  Although the metal which forms wiring is not specifically limited, Gold, silver, copper, aluminum, and ITO (indium tin oxide) are preferable. A cured film obtained by applying the curable composition of the present invention to a substrate on which a metal wiring is formed in a predetermined pattern using an inkjet apparatus and curing the substrate functions well as a coverlay film for protecting the wiring. . In addition, since the cured film has excellent adhesion to the plating layer and the substrate, it functions well as an interlayer insulating film in the case of a multilayer substrate.

By mounting an IC chip, a capacitor, a resistor, a fuse, or the like on the electronic circuit substrate formed of the substrate with a cured film of the present invention, for example, an electronic component for a liquid crystal display element can be manufactured.
8). Curing Agent The curing agent of the present invention contains the compound (A) represented by the above formula (1). The curing agent can be suitably used as a curing agent for various resins (eg, epoxy resin, oxetane compound, benzoxazine, oxazole, oxazoline). Moreover, the said hardening | curing agent can also be used in combination with a conventionally well-known hardening | curing agent suitably.

  The cured film formed using the curing agent of the present invention has good adhesion to various substrates (eg, copper substrate, polyimide film) and also excellent adhesion to the plating layer. It can be suitably used as an interlayer insulating film of a substrate.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. In addition, the symbol used in an Example represents the following.
EDM: Diethylene glycol methyl ethyl ether AEE: 2- (2-aminoethoxy) ethanol MAA: Maleic anhydride VGL: TECHMORE VG3101L
(Mitsui Chemicals, Inc. epoxy resin, epoxy resin represented by the above formula (B2))
HPH: HP-7200H
(Epoxy resin manufactured by DIC Corporation, epoxy resin represented by the above formula (B1))
BM1: bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane ARM: Aronix M-327 (acrylic monomer manufactured by Toagosei Co., Ltd., ε-caprolactone-modified tris (acryloyloxyethyl) isocyanurate)
TPO: DAROCUR (trade name) TPO (photopolymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide manufactured by Ciba Specialty Chemicals Co., Ltd.)
[Synthesis Example 1]
A 100 mL four-necked flask was charged with 50.0 g of EDM, 10.0 g of AEE, and 5.0 g of MAA, and stirred at 30 ° C. for 30 minutes. Thereafter, the temperature was raised and the mixture was stirred at 160 ° C. for 2 hours, and water produced was distilled off together with EDM. The distilled liquid was 6.1 g. After cooling the reaction solution to 100 ° C., 10.0 g of MAA was added, and the mixture was stirred at 115 ° C. for 2 hours. A 36.3% by weight solution (hereinafter referred to as “(A-1) solution”) of the compound represented by (A6) (which is a mixture of R = ethylene and n = 2) was obtained.

[Synthesis Example 2]
A 200 mL four-necked flask was charged with 71.1 g of EDM, 10.5 g of AEE and 17.3 g of N-phenylmaleimide, and stirred at 130 ° C. for 2 hours. Thereafter, the mixture was cooled to 100 ° C., 19.6 g of MAA was added, and the mixture was stirred at 115 ° C. for 2 hours. The compound (A) represented by the general formula (1) (specifically, represented by the above formula (A1)) A 40 wt% solution of the compound (R = ethylene, n = 2) (hereinafter referred to as “(A-2) solution”) was obtained.

[Example 1]
After mixing 2.7548 g of the (A-1) solution as the compound (A), 1.0000 g of VGL as the epoxy resin (B), and 1.9595 g of EDM as the solvent, the resulting mixture was filtered with a 1 μm PTFE membrane filter. Then, a curable composition 1 was prepared. It was 10.2 mPa * s (25 degreeC) when the viscosity was measured using the E-type viscosity meter (TV-22 by Toki Sangyo Co., Ltd., the same hereafter).

  The curable composition 1 is injected into an ink jet cartridge, and this is mounted on an ink jet apparatus (DMP-2811 manufactured by FUJIFILM Dimatix), using a head for 10 pl, an ejection voltage (piezo voltage) of 16 V, a head temperature of 30 ° C. Of a substrate [(Mitsui Chemicals Co., Ltd.) Neoflex NEX-13FE (trade name)] on which a copper foil (thickness: 12.5 μm) is laminated on polyimide under a discharge condition of a drive frequency of 5 kHz and a coating frequency of once. A square pattern of 40 mm × 40 mm was formed on the copper foil surface. Then, it dried for 10 minutes on an 80 degreeC hotplate, and also baked for 30 minutes in 250 degreeC oven, and obtained the cured film with a film thickness of 3.2 micrometers.

[Example 2, Comparative Examples 1-2]
In the same manner as in Example 1, curable compositions having the compositions shown in Table 1 were prepared. The curable composition was injected into an ink jet cartridge, and a cured film having a film thickness described in Table 1 was obtained in the same manner as in Example 1.

[Board adhesion]
A cross-cut peel test (JIS K 5400 (1990)) was performed on the cured film obtained above, and the substrate was peeled off after peeling the adhesive tape (Sumitomo 3M “Polyester tape: adhesive strength; 5.5 N / cm”) The adhesion of the cured film to the substrate was evaluated by observing the state of the cured film remaining on the top. The evaluation criteria are as follows.
◯: The cured film was not changed at all Δ: Part of the cured film was peeled off x: All of the cured film was peeled off

[Plating adhesion, peel strength]
The cured film obtained above was subjected to electroless copper plating using an electroless copper plating solution PEA manufactured by Uemura Kogyo Co., Ltd., and the adhesion of the plating was observed according to the following evaluation criteria. The results are shown in Table 1.
○: Plating adhered on the cured film.
X: The cured film was dissolved and no plating adhered.

A 20 μm thick copper plating layer was formed on the cured film after electroless copper plating using an electrolytic copper plating solution EPL manufactured by Uemura Kogyo Co., Ltd. A 2 mm × 30 mm cut was made in this copper plating layer with a cutter, and the copper plating-cured film interface at the cut end was peeled off to obtain a sample for peel test. This sample was set on a tensile tester EZGraph manufactured by Shimadzu Corporation and the peel strength was measured. The results are shown in Table 1.

* In the column for compound (A), the numerical value in parentheses indicates the content of compound (A).

[Examples 3 to 4]
In the same manner as in Example 1, curable compositions having the compositions shown in Table 2 were prepared.

[5% weight loss temperature]
The curable composition 1 or the curable composition 5 was applied to a 10 cm × 10 cm glass substrate by spin coating at 500 rpm / 10 seconds, and this substrate was dried on a hot plate at 80 ° C. for 10 minutes, and then 250 ° C. Baked in the oven for 30 minutes. The obtained cured film was scraped off with a cutter, and the thermogravimetric measurement was performed using a TG / DTA apparatus (TG / DTA6200 manufactured by SII Nano Technology). The evaluation was made at a temperature at a 5% weight loss. The results are shown in Table 2.

[Line pattern]
The curable composition 1 or the curable composition 6 is injected into an ink jet cartridge, and this is mounted on an ink jet apparatus (DMP-2811 manufactured by FUJIFILM Dimatix), and a discharge voltage (piezo voltage) using a head for 10 pl. A line pattern with a width of 1 mm and a length of 100 mm is formed on a 100 μm-thick Kapton film substrate (polyimide film manufactured by Toray DuPont Co., Ltd.) under a discharge condition of 16 V, a head temperature of 35 ° C., a drive frequency of 5 kHz, and a coating frequency of once. Ten pieces were formed at intervals of 1 mm.

  In the case of the curable composition 1: This substrate was dried on an 80 ° C. hot plate for 10 minutes and further baked in an oven at 250 ° C. for 30 minutes to obtain a cured film having a line pattern. The width of the line pattern was measured using a 50 × optical microscope.

In the case of the curable composition 6: The substrate was irradiated with ultraviolet light having a wavelength of 365 nm at a UV exposure amount of 2000 mJ / cm ² and then baked in an oven at 250 ° C. for 30 minutes to obtain a cured film having a line pattern. The width of the line pattern was measured using a 50 × optical microscope.

* In the column for compound (A), the numerical value in parentheses indicates the content of compound (A).

  The heat resistance of the cured film obtained from the curable composition 5 to which bismaleimide was added was further improved. The cured film obtained by adding the radical polymerizable compound (D) and the photopolymerization initiator (E) and irradiating with ultraviolet rays further improved the pattern formability.

Claims (22)

The curable composition containing the compound (A) represented by following General formula (1), and an epoxy resin (B).

[In formula (1), R ¹ and R ³ are each independently an organic group having 1 to 100 carbon atoms, and R ² is a divalent group represented by any one of the following formulas (a) to (g). It is. ]

R ¹ in the formula (1) is an aryl having 6 to 20 carbon atoms which may have a substituent, a cycloalkyl having 5 to 20 carbon atoms which may have a substituent, or the following general formula (2). The curable composition according to claim 1 which is a monovalent group represented.

[In Formula (2), R ⁴ is alkylene having 1 to 20 carbon atoms, R ⁵ is hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 0 to 20. ] The curability according to claim 2, wherein R ⁴ in the formula (2) is alkylene having 2 to 8 carbon atoms, R ⁵ is alkyl having 1 to 18 carbon atoms, and n is an integer of 0 to 10. Composition. R ⁴ in the formula (2) is alkylene having 2 to 8 carbon atoms, R ⁵ is hydrogen or a monovalent group represented by the following general formula (3), and n is an integer of 1 to 10. The curable composition according to claim 2.

[In formula (3), R ⁶ is a divalent group represented by any of the following formulas (a) to (g). ]

R ³ in the formula (1) is a monovalent group represented by the following general formula (4).
The curable composition as described in any one of -4.

[In Formula (4), R ⁷ is alkylene having 1 to 20 carbon atoms, R ⁸ is hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 0 to 20. ] The curability according to claim 5, wherein R ⁷ in the formula (4) is alkylene having 2 to ⁸ carbons, R ⁸ is alkyl having 1 to 18 carbons, and n is an integer of 0 to 10. Composition. R ⁷ in the formula (4) is alkylene having 2 to 8 carbon atoms, R ⁸ is hydrogen or a monovalent group represented by the following general formula (5), and n is an integer of 1 to 10. The curable composition according to claim 5.

[In formula (5), R ⁹ is a divalent group represented by any one of the following formulas (a) to (g). ]

R ² in the formula (1), R ⁶ in the formula (3), and R ⁹ in the formula (5) are divalent groups represented by any of the following formulas (a) to (c). The curable composition according to claim 7.

The compound (A) represented by the formula (1) is at least one compound selected from the group consisting of compounds represented by the following formulas (A1) to (A6). Curable composition.

[In the formulas (A1) to (A6), R is ethylene, propylene or butylene, and n is an integer of 1 to 10. ] The epoxy resin (B) is a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin, or a bisphenol S. Type epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) ) At least one selected from the group consisting of cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and epoxy resins represented by the following formulas (B1) to (B4) The compound according to any one of claims 1 to 9, which is a compound. The curable composition.

[In formula (B1), n is an integer of 1-50. ]   Furthermore, the curable composition as described in any one of Claims 1-10 containing thermosetting compounds (C) other than the said epoxy resin (B).   Furthermore, the curable composition as described in any one of Claims 1-11 containing a radically polymerizable compound (D) and a photoinitiator (E).   Furthermore, the curable composition as described in any one of Claims 1-12 containing a flame retardant (F). The curable composition according to claim 13, wherein the flame retardant (F) is a compound having a structure represented by the following formula (F-1).

The curable composition according to claim 13, wherein the flame retardant (F) is a compound represented by the following general formula (F-2).

[Wherein, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 3. ]   An ink-jet ink comprising the curable composition according to any one of claims 1 to 15. The hardening | curing agent containing the compound (A) represented by following General formula (1).

[In formula (1), R ¹ and R ³ are each independently an organic group having 1 to 100 carbon atoms, and R ² is a divalent group represented by any one of the following formulas (a) to (g). It is. ]

  The compound (A) represented by the formula (1) is a compound obtained by further reacting an acid anhydride with an addition compound obtained by reacting an amino-containing compound with maleic anhydride. The curing agent according to claim 17. The compound (A) represented by the formula (1) is at least one compound selected from the group consisting of compounds represented by the following formulas (A1) to (A6). The curing agent described.

[In the formulas (A1) to (A6), R is ethylene, propylene or butylene, and n is an integer of 1 to 10. ]   The cured film formed from the curable composition as described in any one of Claims 1-15, or the inkjet ink of Claim 16.   The board | substrate with a cured film which has a board | substrate and the cured film of Claim 20 formed on this board | substrate.   The electronic circuit board which consists of a board | substrate with a cured film of Claim 21.