JP5504769B2 - Polymerizable composition - Google Patents

Description

  In the present invention, after printing using a predetermined method such as an ink jet printing method, a screen printing method, a gravure printing method, an offset printing method, etc., it is cured in an exposure and baking process, and a display element for liquid crystal, EL, etc. The present invention relates to a curable composition used for manufacturing electronic circuit boards such as printed wiring boards, flexible wiring boards, and semiconductor package boards, and more specifically, a coverlay and a solder for protecting a metal wiring surface forming a predetermined circuit pattern. The present invention relates to a curable composition suitable for a resist or the like.

  Until now, when manufacturing electronic circuit boards such as printed wiring boards, flexible wiring boards, and semiconductor package boards, polymer-based coverlay films have been used as protective films to protect conductive surfaces such as metal wiring that form a predetermined circuit pattern. Have been used.

  As a method of adhering the cover lay film to the conductor surface, one surface of the cover lay film is processed into a predetermined shape, an adhesive is applied to this surface, and this is overlaid on the electronic circuit board for alignment. Then, a method of thermocompression bonding with a press or the like is common. Thereafter, a protective film having a predetermined pattern is formed by patterning and etching using a photoresist.

  In forming a protective film using such a polymer-based coverlay film, when processing the coverlay film before bonding, applying an adhesive, or patterning (microfabrication) using a photoresist Requires a large number of steps such as photoresist application, exposure, development, etching, resist stripping, and the operation is complicated.

  Therefore, conventionally, for the purpose of improving workability and position accuracy, a method of forming a protective layer by applying a photosensitive coverlay film to a conductor surface has been proposed (for example, Japanese Patent Application Laid-Open No. 45-115541 (patent). Reference 1), Japanese Patent Application Laid-Open No. 51-40922 (Patent Document 2)). However, the formation of a protective film using such a photosensitive coverlay film requires patterning of the film by pattern exposure and development of the film, and also for the production of a photomask necessary for the pattern exposure. It takes a long time and a lot of money.

  In recent years, polyimide resins soluble in organic solvents have been developed. This soluble polyimide is used in a pattern formed by using a predetermined method such as an ink jet printing method, a screen printing method, a gravure printing method, or an offset printing method (for example, JP 2000-154346 A (Patent Document). 3), JP-A-2002-94232 (Patent Document 4), JP-A-2000-47212 (Patent Document 5)). However, since such a soluble polyimide is dissolved in an organic solvent, at the time of use, the organic solvent is evaporated and cured in the firing step. Therefore, it tends to be avoided from the environmental and manufacturing aspects. Moreover, depending on the organic solvent which can be dissolved, it will invade the apparatus and the member of manufacturing equipment, and versatility will become narrow.

  On the other hand, many raw materials for resins formed by curing acrylic monomers exist as liquids at room temperature, and do not need to be dissolved in a solvent. Most of them can be dissolved, and it is not necessary to use a solvent. For this reason, there is no concern about adverse effects on the environment and manufacturing during use, and there is no risk of damaging the devices and manufacturing members used, so the versatility is wide.

  However, it is necessary to add a flame retardant in a resin cured using only an acrylic monomer in order to impart flame retardancy. Conventionally, various halogen compounds have been used to impart flame retardancy. However, in recent years, generation of dioxins during combustion has been regarded as a problem, and a flame retardant that does not use a halogen-based compound has been demanded, and phosphorus-based compounds are often used. Furthermore, recent electronic parts are required to have improved heat resistance. For this purpose, a flame retardant having a reactive functional group is required. Under such circumstances, various reactive flame retardants have been proposed (for example, Patent Documents 1 and 2, JP-A-2001-213889 (Patent Document 6), JP-A-2002-121245 (Patent Document). 7), Japanese Patent Application Laid-Open No. 2004-91683 (Patent Document 8) and the like).

  It is necessary to increase the content of the phosphorus compound in the ink in order to impart flame retardancy. When the phosphorus-based compound in the ink has a high content, it is difficult to sufficiently satisfy all other performances such as plating resistance, solder heat resistance, and flexibility. Therefore, it is desirable to make the content of the phosphorus compound as small as possible.

On the other hand, a cured film having flame resistance as well as heat resistance, chemical resistance, and bending resistance using imide (meth) acrylate and soluble polyimide has been proposed (for example, Patent 3914800 (Patent Document 9). )). However, in this case, since polyimide diluted with a solvent or the like is used, it is avoided from the environmental aspect and the manufacturing process.

  In addition, as the characteristics of imide (meth) acrylate, weather resistance and abrasion resistance (for example, Japanese Patent Application Laid-Open No. 2001-172336 (Patent Document 10), Japanese Patent No. 3880735 (Patent Document 11), Japanese Patent Application Laid-Open No. 2001-254070 (Patent Document 12). ), JP-A 2006-307203 (Patent Document 13)), high adhesiveness (for example, JP-A-11-140108 (Patent Document 14), JP-A 2000-239616 (Patent Document 15), JP-A 2004-189790 (Patent Document 16). JP, 2007-238802, A (patent documents 17)) is known.

  However, there was no curable composition having a solid content of 100%, having heat resistance, chemical resistance and bending resistance, and having flame retardancy.

Japanese Patent Laid-Open No. 60-161993 JP 2001-106766 A JP 2000-154346 A JP 2002-94232 JP JP 2000-47212 A JP 2001-213889 A Japanese Laid-Open Patent Publication No. 2002-121245 JP 2004-91683 A Patent 3914800 JP 2001-172336 A Japanese Patent No. 3807035 Japanese Patent Laid-Open No. 2001-254070 JP 2006-307203 A JP-A-11-140108 JP 2000-239616 A JP 2004-189790 A JP 2007-238802 A

  Provided is a curable composition capable of forming a cover lay or a solder resist having an excellent balance of flame retardancy, adhesion, chemical resistance, heat resistance, flex resistance, and the like under the above circumstances. There is.

The inventors of the present invention have a curable composition containing an imide (meth) acrylate (A) having a specific structure and a flame retardant (B), which has plating resistance, solder heat resistance, adhesion, and flame retardancy. Based on this finding, it was found that a film can be formed, and that the above-mentioned properties are further improved by adding a diluent (C), a thermosetting resin (D), and a photopolymerization initiator (E). The present invention has been completed. Furthermore, the present invention provides such a curable composition, a cured film obtained from the curable composition, a method for forming the same, and the like.

（式中、Ｒ^１は水素又はメチルであり、Ｒ^２は炭素数１〜１００の有機基であり、Ｒ^３、Ｒ^４は、それぞれ独立して、水素又はメチルであるか、Ｒ^３とＲ^４が結合して環状構造を示す炭化水素環又は該炭化水素環にメチルが１〜４つ結合した炭化水素環誘導体であり、ｎは１〜６の整数である） The present invention includes the following items.
[1] A curable composition comprising an imide (meth) acrylate (A) represented by formula (1) and a flame retardant (B).

Wherein R ¹ is hydrogen or methyl, R ² is an organic group having 1 to 100 carbon atoms, and R ³ and R ⁴ are each independently hydrogen or methyl, or R ³ and R 4 A hydrocarbon ring in which ⁴ is bonded to form a cyclic structure or a hydrocarbon ring derivative in which 1 to 4 methyls are bonded to the hydrocarbon ring, and n is an integer of 1 to 6)

（式中、Ｒ^１は水素又はメチルであり、Ｒ^２は炭素数１〜１００の有機基であり、ｎは１〜６の整数である） [2] The curable composition according to [1], wherein the imide (meth) acrylate (A) is a compound represented by the formula (2).

(Wherein R ¹ is hydrogen or methyl, R ² is an organic group having 1 to 100 carbon atoms, and n is an integer of 1 to 6)

[3] The curable composition according to [1] or [2], wherein the imide (meth) acrylate (A) is a compound represented by the formula (3).

（式中、Ｒは水素、ヒドロキシまたは炭素数１〜１００の有機基であり、ｎは１〜２０の整数である。） [4] The curable composition according to any one of [1] to [3], wherein the flame retardant (B) is represented by the formula (4).

(In the formula, R is hydrogen, hydroxy, or an organic group having 1 to 100 carbon atoms, and n is an integer of 1 to 20)

[5] The curable composition according to any one of [1] to [4], wherein R in Formula (4) has at least one radical polymerizable double bond.

（式（５）中、ａ、ｂ及びｃはそれぞれ独立して０〜１０の整数であり、Ｘはそれぞれ独立して炭素数１〜５の直鎖または分岐のアルキレンであり、ｍはそれぞれ独立して０または１であり、３つのＲ^６のうち１〜２個は式（５−１）で表される基であり、残りは式（５−２）で表される基であり、Ｒ^７は水素またはメチルである。）

（式（６）中、ａ、ｂ及びｃはそれぞれ独立して０〜１０の整数であり、Ｘはそれぞれ独立して炭素数１〜５の直鎖または分岐のアルキレンであり、ｍはそれぞれ独立して０または１であり、３つのＲ^６のうち１〜２個は式（６−１）で表される基であり、残りは式（６−２）で表される基であり、Ｒ^７は水素またはメチルである。）

（式（７）中、ａ、ｂ、ｃ及びｄはそれぞれ独立して０〜１０の整数であり、Ｘはそれぞれ独立して炭素数１〜５の直鎖または分岐のアルキレンであり、ｍはそれぞれ独立して０または１であり、４つのＲ^６のうち１〜３個は式（７−１）で表される基であり、残りは式（７−２）で表される基であり、Ｒ^７は水素またはメチルである。）

（式（８）中、ａ、ｂ、ｃ、ｄ、ｅ及びｆはそれぞれ独立して０〜１０の整数であり、Ｘはそれぞれ独立して炭素数１〜５の直鎖または分岐のアルキレンであり、ｍはそれぞれ独立して０または１であり、６つのＲ^６のうち１〜５個は式（８−１）で表される基であり、残りは式（８−２）で表される基であり、Ｒ^７は水素またはメチルである。） [6] The curing according to any one of [1] to [5], wherein the flame retardant (B) is at least one selected from the group of compounds represented by formulas (5) to (8). Sex composition.

(In formula (5), a, b and c are each independently an integer of 0 to 10, X is independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is each independently. 0 to 1 and 1 to 2 of the three R ⁶ are groups represented by the formula (5-1), and the rest are groups represented by the formula (5-2). ⁷ is hydrogen or methyl.)

(In Formula (6), a, b and c are each independently an integer of 0 to 10, X is independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is each independently. And 1 to 2 of the three R ⁶ are groups represented by the formula (6-1), and the rest are groups represented by the formula (6-2). ⁷ is hydrogen or methyl.)

(In formula (7), a, b, c and d are each independently an integer of 0 to 10, X is independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is Each independently 0 or 1, and 1 to 3 of the four R ⁶ are groups represented by the formula (7-1), and the rest are groups represented by the formula (7-2). R ⁷ is hydrogen or methyl.)

(In the formula (8), a, b, c, d, e and f are each independently an integer of 0 to 10, and X is independently a linear or branched alkylene having 1 to 5 carbon atoms. Each of m is independently 0 or 1, and 1 to 5 of ⁶ R ⁶ are groups represented by the formula (8-1), and the rest are represented by the formula (8-2). And R ⁷ is hydrogen or methyl.)

[7] The curable composition according to any one of [1] to [6], further including a diluent (C).

[8] The curable composition according to [7], wherein the diluent (C) has a viscosity at 25 ° C of 0.1 to 100 mPa · s.

[9] The curable composition according to [7] or [8], wherein the diluent (C) is a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate.

[10] The curable composition according to any one of [1] to [9], further including a thermosetting resin (D).

[11] The curable composition according to any one of [1] to [10], further including a photopolymerization initiator (E).

[12] The curable composition according to [11], wherein the photopolymerization initiator (E) is at least one compound selected from the group consisting of acylphosphine oxides and alkylphenone compounds.

[13] The imide (meth) acrylate (A) is 3,4,5,6-tetrahydrophthalimidoethyl acrylate represented by the formula (3), and the flame retardant (B) is condensed 9,10-dihydro-9-. It is oxa-10-phosphaphenanthrene-10 oxide, the diluent (C) is dipropylene glycol diacrylate, the thermosetting resin (D) is a melamine resin, and the photopolymerization initiator (E) is 2, The curable composition according to [11] or [12], which is 4,6-trimethylbenzoyldiphenylphosphine oxide and contains phenothiazine as a polymerization inhibitor.

[14] The curable composition according to any one of [1] to [13], which is an ink composition.

[15] The curable composition according to any one of [1] to [14], which is an inkjet ink.

[16] A cured film forming method in which the curable composition according to any one of [1] to [15] is applied and a cured film is formed by irradiating the applied curable composition with light.

[17] A cured film forming method of forming a cured film by further heating the cured film obtained by light irradiation according to [16].

[18] A cured film obtained from the curable composition according to any one of [1] to [15].

[19] The cured film according to [18], which is formed on the pattern.

[20] An electronic circuit board in which the cured film according to [18] or [19] is formed on a substrate.

[21] An electronic component having the electronic circuit board according to [20].

[22] A display element comprising the electronic circuit board according to [20] or the electronic component according to claim 21.

According to the curable composition which concerns on the preferable aspect of this invention, the curable composition excellent in the sclerosis | hardenability of film | membrane, adhesiveness, chemical resistance (plating resistance), heat resistance, a flexibility, and a flame retardance. Can be provided.

  The curable composition of the present invention contains an imide (meth) acrylate (A) having a specific structure and a flame retardant (B), and a cured film having plating resistance, solder heat resistance, adhesion, and flame retardancy. It can be formed. Furthermore, the above-mentioned characteristic can be improved more by adding a diluent (C), a thermosetting resin (D), and a photoinitiator (E). A cured film having plating resistance, solder heat resistance, adhesion, and flame retardancy can be formed, and at the same time, it can be used for printing methods such as an ink jet printing method, a screen printing method, a gravure printing method, and an offset printing method. However, there is an optimum ink viscosity for each printing method. Therefore, in the following embodiments and examples, it is appropriate to generally consider that there is no influence on the performance of the cured film except that the properties such as the viscosity of the curable composition before curing are different. Therefore, although the ink used by an inkjet printing system is mentioned as an example as this invention, it is set as the curable composition applicable also to other printing systems.

1. Curable composition of the present invention The curable composition of the present invention contains an imide (meth) acrylate (A) and a flame retardant (B). As needed, you may contain a diluent (C), a thermosetting resin (D), and a photoinitiator (E). The curable composition of the present invention may be colorless or colored.

  Moreover, the curable composition of this invention can further contain an epoxy hardening | curing agent, surfactant, a coloring agent, a polymerization inhibitor, or a solvent as needed.

  The weight average molecular weight in the present specification is a value in terms of polystyrene determined by GPC method (column temperature: 35 ° C., flow rate: 1 ml / min) using a THF column manufactured by POLYMER Laboratories as a column. The GPC apparatus used was LC-10AT system, RID-6A (RI detector), CTO-6A (column oven) manufactured by Shimadzu Corporation, and the column was a PLgel 5 μm MIXED-D column. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

1.1 Imido (meth) acrylate (A)
The curable composition of the present invention contains an imide (meth) acrylate (A).
In the present invention, the imide (meth) acrylate (A) is a compound represented by the formula (1). The imidoacrylate (A) has one (meth) acryloyl and one imide in each molecule.

In Formula (1), R ¹ is hydrogen or methyl, R ² is an organic group having 1 to 100 carbon atoms, and R ³ and R ⁴ are each independently hydrogen or methyl, or R ³ And R ⁴ is a hydrocarbon ring having a cyclic structure or a hydrocarbon ring derivative in which 1 to 4 methyls are bonded to the hydrocarbon ring, and n is an integer of 1 to 6.

  In the present invention, the imidoimide acrylate (A) is not limited as long as it has (meth) acryloyl and imide represented by the formula (1). Specific examples of the imide (meth) acrylate (A) include 3,4,5,6-tetrahydrophthalimidoethyl (meth) acrylate, 3,4,5,6-tetrahydrophthalimidopropyl (meth) acrylate, 3,4, 5,6-tetrahydrophthalimide isopropyl (meth) acrylate, 3,4,5,6-tetrahydrophthalimide butyl (meth) acrylate, 3,4,5,6-tetrahydrophthalimide isobutyl (meth) acrylate, 3,4,5 6-tetrahydrophthalimidohydroxyethyl (meth) acrylate, 3,4,5,6-tetrahydrophthalimidohydroxybutyl (meth) acrylate, 4-methyl3,4,5,6-tetrahydrophthalimidoethyl (meth) acrylate, 3,4 -Dimethyl 3, 4, 5, 6 Tetrahydrophthalimide ethyl (meth) acrylate, maleimide ethyl (meth) acrylate, methyl maleimide ethyl (meth) acrylate, dimethyl maleimide (meth) acrylate. Among them, (meth) acrylate having 3,4,5,6-tetrahydrophthalimide as represented by the formula (2) is preferable, and 3,4,5,6- represented by the formula (3). Tetrahydrophthalimidoethyl acrylate is more preferred.

  3,4,5,6-tetrahydrophthalimidoethyl acrylate represented by the formula (3) is commercially available as TO-1534 from Toagosei Co., Ltd.

  These imide (meth) acrylates (A) may be a single compound or a mixture of two or more compounds.

  The content of the imide (meth) acrylate (A) is preferably 5 to 50% by weight of the solid content of the ink because the balance of plating resistance, heat resistance, adhesion, and flame retardancy is improved, and more preferably 10 -40% by weight, more preferably 15-25% by weight.

  Since the curable composition of the present invention contains the imide (meth) acrylate (A), the curable composition has sufficient flame retardancy even if the content of the phosphorus compound as a flame retardant is low. In the curable composition of the present invention, since the content of the phosphorus compound can be kept low, the cover lay and solder resist can be used without reducing other performance such as plating resistance, solder heat resistance, and flexibility. The required performance can be fully satisfied.

1.2 Flame retardant (B)
The curable composition of this invention contains a flame retardant (B). The flame retardant (B) is not particularly limited, such as an inorganic flame retardant and an organic flame retardant (phosphorus compound, halogen compound, etc.), but an organic flame retardant from the viewpoint of low toxicity, low pollution and safety. Of these, it is preferable to use a phosphorus compound.

  Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, antimony trioxide, borate, zinc stannate, molybdenum oxide, zinc molybdate, calcium molybdate, guanidine nitride, and antimony pentoxide.

  Examples of halogen compounds include tetrabromobisphenol A, decabromodiphenyl oxide, hexabromocyclodecane, 2,4,6-tribromophenol, ethylenebistetrabromophthalimide, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated Epoxy resins, brominated (meth) acrylates, chlorinated paraffins, cycloaliphatic chlorinated compounds and the like are listed.

  Preferred examples of the phosphorus compound include compounds represented by the above formula (4). In the formula (4), R is hydrogen, hydroxy, or an organic group having 1 to 100 carbon atoms, where the “organic group having 1 to 100 carbon atoms” is preferably an organic group having 4 to 90 carbon atoms, More preferably, it is a C10-C80 organic group, More preferably, it is a C15-70 organic group. Further, it is preferably an organic group having a radical polymerizable double bond, and the radical polymerizable double bond is a carbon-carbon double bond, specifically, acryloyl, methacryloyl, styryl, maleimide, vinyl, Examples include double bonds such as allyl, and acryloyl is particularly preferable.

  n is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and further preferably an integer of 1 to 6.

  The compound represented by the formula (4) is more preferably a compound represented by the above formula (5), (6), (7) or (8).

In the formula (5), a, b and c are each independently preferably an integer of 0 to 10, more preferably an integer of 0 to 3, and further preferably an integer of 0 to 1.
X in Formula (5) is each independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is independently 0 or 1.
Three ^{R 6} in the formula (5) is consists of a group represented by one or two groups of the formula (5-1) and 2 or one of formula (5-2) , Preferably composed of one group represented by the formula (5-1) and two groups represented by the formula (5-2).
R ⁷ in formula (5-1) and formula (5-2) may be either hydrogen or methyl, but is preferably hydrogen.

In the formula (6), the ratio of the group represented by the formula (6-1) and the group represented by the formula (6-2) that constitutes a, b and c, X, m, and R ⁶ , and R ⁷ The thing similar to the thing of the said Formula (5) is mentioned, The same thing is preferable.

A, b, c and d in Formula (7) are each independently preferably an integer of 0 to 10, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 1. .
X in Formula (7) is each independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is independently 0 or 1.
The four R ⁶ in the formula (7) are composed of 1 to 3 groups represented by the formula (7-1) and 3 to 1 groups represented by the formula (7-2). And preferably composed of 1 to 2 groups represented by the formula (7-1) and 3 to 2 groups represented by the formula (7-2), more preferably one formula (7 -1) and three groups represented by formula (7-2).
R ⁷ in Formula (7-1) and Formula (7-2) may be either hydrogen or methyl, but is preferably hydrogen.

A, b, c, d, e and f in Formula (8) are each independently preferably an integer of 0 to 10, more preferably an integer of 0 to 3, and further preferably 0 to 1. Is an integer.
X in Formula (8) is each independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is independently 0 or 1.
Six ^{R 6} in the formula (8) is composed of a group represented by the group and 5 to one of the formulas represented by 1-5 Formula (8-1) (8-2) , Preferably composed of 1 to 4 groups represented by formula (8-1) and 5 to 2 groups represented by formula (8-2), more preferably 2 to 4 formulas. A group represented by (8-1) and a group represented by 4 to 2 formulas (8-2), more preferably 4 groups represented by formula (8-1); It consists of two groups represented by the formula (8-2).
R ⁷ in formula (8-1) and formula (8-2) may be either hydrogen or methyl, but is preferably hydrogen.

As an example of a compound represented by Formula (5), Showa Polymer Co., Ltd. HFA-3003 (in Formula (5), a = 0, b = 0, c = 0, Formula (5-1) And a group represented by one (R ⁷ is hydrogen) and two groups (R ⁷ is hydrogen) represented by the formula (5-2)).
Moreover, the compound of Formula (8) is Showa High Polymer Co., Ltd. product HFA-6127 (in Formula (8), a = 1, b = 1, c = 1, d = 1, e = 1, f = 1. , All m are 1, all X are — (CH ₂ ) ₅ —, four groups represented by formula (8-1) (R ⁷ is hydrogen), and represented by formula (8-2) Commercially available as a compound having two groups (R ⁷ is hydrogen).

  Specific examples of the phosphorus compound 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.

なお、難燃剤（Ｂ）は、上述した化合物から選ばれる１種の化合物であってもよく、またこれらの２種以上の化合物の混合物であってもよい。 Among these flame retardants, in particular, condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide (produced by Showa Polymer Co., Ltd.), which is a compound represented by the following formula (B-1) HFA-3003 (trade name)) is preferable because the viscosity of the curable composition can be lowered, and is particularly suitable for an ink jet ink. Further, the cured film obtained from the curable composition is exposed to a high temperature state. Even if it is, it is preferable because there is no bleed out of the flame retardant.

The flame retardant (B) may be one compound selected from the above-described compounds, or may be a mixture of these two or more compounds.

  When the flame retardant (B) is 1 to 50% by weight of the total amount of the curable composition, the cured film obtained from the curable composition exhibits high flame resistance (equivalent to UL94 flame test method VTM-0 standard), Furthermore, it is preferable because it has a good balance with adhesion, plating resistance and solder heat resistance, more preferably 2 to 40% by weight, still more preferably 3 to 30% by weight, and particularly preferably 5 to 20% by weight. is there.

1.3 Diluent (C)
The curable composition of the present invention may contain a diluent (C) in order to improve and maintain various properties. Although the diluent (C) of the present invention is not particularly limited, it is preferable that the viscosity at 25 ° C. is 0.1 to 100 mPa · s as long as it is used as an inkjet ink, and a monomer having radical polymerization properties. And solvents. As the monomer having radical polymerizability, monofunctional (meth) acrylate or polyfunctional (meth) acrylate is preferable.

1.3 (1) Monofunctional polymerizable monomer The diluent (C) may be a monofunctional polymerizable monomer.

Specific examples of the monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N -Hydroxyethyl (meth) acrylamide, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl- 3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-yl Methyl ether, -Phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (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, benzyl (meth) ) Acrylate, styrene, methyl styrene, chloromethyl styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, vinyltoluene, tricyclo [5.2.1.0 ^{2 , 6} ] Decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, tetrahydrofurfuryl ( (Meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid , Fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl] , Mono [2- (meth) acryloyloxyethyl maleate], mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate, (meth) acrylamide, N, N-dimethyl (meth) Examples include acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-acryloylmorpholine, N-phenylmaleimide, and N-cyclohexylmaleimide. it can.

  These monofunctional polymerizable monomers may be a single compound or a mixture of two or more compounds.

  Among them, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, etc. This is more preferable because it improves the solubility and solubility of the ink solid component.

  The content of the monofunctional polymerizable monomer as the diluent (C) is preferably 2 to 40% by weight of the total amount of the curable composition because it can be adjusted to a viscosity suitable for the intended use. Considering the balance, it is more preferably 4 to 30% by weight, further preferably 6 to 25% by weight, and particularly preferably 8 to 20% by weight.

1.3 (2) Polyfunctional polymerizable monomer The diluent (C) may be a polyfunctional polymerizable monomer.

  Specific examples of the polyfunctional polymerizable monomer include acid-modified epoxy (meth) acrylate, acid-modified (meth) acrylate, bisphenol F ethylene oxide-modified diacrylate, bisphenol A ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified diacrylate, polyethylene glycol di Acrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol Diacrylate, 1,4-cyclohexanedimethanol diacrylate, 2-n-butyl-2-ethyl-1,3-pro Diol diacrylate, trimethylolpropane diacrylate, dipentaerythritol diacrylate, modified isocyanuric acid ethylene oxide modified di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, pentaerythritol tri (Meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, polyester Lenglycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol 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, epichlorohydride Modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified triphosphate Mention may be made of (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, urethane (meth) acrylate. Among them, dipropylene glycol diacrylate and acid-modified epoxy (meth) acrylate have good film properties such as plating resistance, heat resistance, and adhesion.

  Since the content of the polyfunctional (meth) acrylate as the diluent (C) is 20 to 80% by weight of the total amount of the curable composition, the balance between plating resistance, heat resistance, adhesion, and flame retardancy is improved. Preferably, it is 30 to 70% by weight, more preferably 35 to 65% by weight, and particularly preferably 40 to 60% by weight.

  The diluent (C) may be a single compound or a mixture of two or more compounds. For example, the diluent (C) may be a mixture of monofunctional (meth) acrylate and polyfunctional (meth) acrylate.

1.3 (3) Solvent Any solvent may be used as the diluent (C) as long as it does not attack each member of the apparatus used. For example, when using an inkjet printing method to heat an inkjet head, if the ink contains a low-boiling solvent, the solvent volatilizes and the viscosity of the ink increases and the nozzle head of the inkjet head is clogged. Sometimes. Therefore, a solvent having a boiling point of 100 to 300 ° C. is particularly preferable.

  Specific examples of the solvent 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, and butyl methoxyacetate. , Methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl toxipropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, 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, tri Propylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monome Ether ether, 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, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, polyethylene N-glycol methyl ethyl ether, toluene, xylene, anisole, γ-butyrolactone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, or dimethylimidazolidinone.

  These solvents may be a single compound or a mixture of two or more compounds.

  The content of the solvent as the diluent (C) is not particularly limited. For example, when used in an inkjet printing method, 0.1 to 10% by weight of the total amount of the curable composition is used in the inkjet printing method. The balance between jetting and other characteristics is good, more preferably 0.2 to 8% by weight, still more preferably 0.5 to 6% by weight, and particularly preferably 1 to 5% by weight.

  The diluent (C) may be a single compound or a mixture of two or more compounds. For example, a mixture of a monofunctional polymerizable monomer and a solvent may be used.

1.4 Thermally reactive resin (D)
The curable composition of the present invention may contain a thermally reactive resin (D) in order to improve and maintain various properties. “Thermal reactivity” of the thermally reactive resin (D) means, for example, a property of causing a crosslinking reaction by heat, but is not limited thereto.

  Examples of the thermally reactive resin (D) include an epoxy resin, a melamine resin, a polymer of a radical polymerizable monomer having a thermally reactive functional group (for example, a phenol resin), or a radical polymerizable monomer having a thermally reactive functional group. And other radically polymerizable monomers. Among these, it is preferable to use a melamine resin from the viewpoints of heat resistance and chemical resistance, and a polymer of a radical polymerizable monomer having a heat-reactive functional group from the viewpoint of the peelability of the cured film from an alkaline aqueous solution and an acidic aqueous solution. It is preferable to use (for example, phenol resin).

  Specific examples of the melamine resin include melamine, methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, etherified methylol benzoguanamine, and condensates thereof. Of these, etherified methylol melamine is preferred because of its good chemical resistance, and a mixture of etherified methylol melamine and its condensate is commercially available as Nicalak MW-30 (trade name) manufactured by Sanwa Chemical Co., Ltd. ing.

  Specific examples of the “polymer of radically polymerizable monomer having a thermoreactive functional group” include phenol resins such as polyvinyl alcohol and polyvinylphenol, poly (glycidyl (meth) acrylate), poly (3,4-epoxycyclohexyl ( (Meth) acrylate), poly (methylglycidyl (meth) acrylate), poly (3-methyl-3- (meth) acryloxymethyloxetane), poly (3-ethyl-3- (meth) acryloxymethyloxetane), poly (3-methyl-3- (meth) acryloxyethyl oxetane), poly (3-ethyl-3- (meth) acryloxyethyl oxetane), poly (p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether) , Poly (2-phenyl-3- (meth) acryloxymethyloxetane), Examples include li (2-trifluoromethyl-3- (meth) acryloxymethyloxetane), poly (4-trifluoromethyl-2- (meth) acryloxymethyloxetane), poly (meth) acrylic acid, and the like. . Among them, a phenol resin such as polyvinylphenol is preferable because it improves the peelability of the cured film from an alkaline aqueous solution, and is commercially available as Maruka Linker MS-2P (trade name) manufactured by Maruzen Petrochemical Co., Ltd.

  When the heat-reactive resin (D) is contained in the curable composition in an amount of 1 to 20% by weight, the chemical resistance of the resulting cured film is preferably increased, and more preferably 2 to 15% by weight. More preferably, it is contained in an amount of 3 to 10% by weight.

1.5 Photopolymerization initiator (E)
The curable composition of the present invention may contain a photopolymerization initiator (E) in order to impart photocurability thereto. A photoinitiator (E) will not be specifically limited if it is a compound which generate | occur | produces a radical by irradiation of an ultraviolet-ray or visible light.

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, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), 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- [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-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 ( , 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, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Examples include titanium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Can.

  The photopolymerization initiator (E) may be a single compound or a mixture of two or more compounds.

  The content of the photopolymerization initiator (E) is preferably 0.5 to 20% by weight of the total amount of the curable composition, because when used as an ink, it becomes highly sensitive to ultraviolet rays, and more preferably 1 to 1%. It is 20% by weight, more preferably 2 to 20% by weight.

1.6 Other Components The curable composition of the present invention may contain an epoxy resin, an epoxy curing agent, a surfactant, a colorant, a polymerization inhibitor and the like in order to further improve various properties.

1.6 (1) Epoxy Resin The curable composition of the present invention may contain an epoxy resin, for example, in order to improve plating resistance and heat resistance.

  Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, and alicyclic epoxy resin.

  Examples of commercially available epoxy resins include Epicoat 807, 815, 825, 827, 828, 190P, 191P, 1004, and 1256 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), Araldite CY177, CY184 (trade name; manufactured by Nippon Ciba-Geigy Co., Ltd.), Celoxide 2021P, EHPE-3150 (trade name; manufactured by Daicel Chemical Industries, Ltd.), or Techmore VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.) Can do.

  The epoxy resin used in the curable composition may be a single compound or a mixture of two or more compounds.

  The content of the epoxy resin is preferably 1 to 20% by weight of the solid content in the curable composition because etching resistance or plating resistance is improved, more preferably 1 to 10% by weight, and still more preferably. Is 1-7% by weight.

  When the curable composition contains an epoxy resin, for example, an epoxy curing agent may be further contained in order to further improve the plating resistance or etching resistance of the cured film. As the epoxy curing agent, an acid anhydride curing agent, a polyamine curing agent, a catalytic curing agent, and the like are preferable.

  Specific examples of the acid anhydride curing agent include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, A merit acid anhydride or a styrene-maleic anhydride copolymer may be mentioned.

  Specific examples of the polyamine curing agent include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, 1,3- Bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, or diaminodiphenylsulfone. Specific examples of the catalyst type curing agent include a tertiary amine compound or an imidazole compound.

  Specific examples of polycarboxylic acid-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloro Examples include endomethylenetetrahydrophthalic anhydride or methyl-3,6-endomethylenetetrahydrophthalic anhydride.

The epoxy curing agent used in the curable composition may be a single compound or a mixture of two or more compounds.
The content of the epoxy curing agent is preferably 0.5 to 50% by weight of the total amount of the curable composition because etching resistance or plating resistance is improved, and more preferably 0 in view of balance with other characteristics. 0.5 to 40% by weight, and more preferably 0.5 to 30% by weight.

1.6 (2) Surfactant The curable composition of the present invention may contain a surfactant in order to improve wettability to the base substrate and film surface uniformity of the cured film, for example. As the surfactant, a silicon surfactant, an acrylic surfactant, a fluorine surfactant, or the like is used.

  Examples of commercially available surfactants include silicon surfactants such as Byk-300, 306, 335, 310, 341, 344, and 370 (trade names; manufactured by Big Chemie Japan Co., Ltd.). , Byk-354, 358, and 361 (trade name; manufactured by Big Chemie Japan Co., Ltd.) and the like, DFX-18, Footage 250, or 251 (trade name; Neos Co., Ltd.) And Fluorosurfactant such as MegaFuck F-479 (trade name; manufactured by DIC Corporation).

  The surfactant used in the curable composition may be a single compound or a mixture of two or more compounds.

  The content of the surfactant is preferably 0.001 to 1% by weight of the solid content in the curable composition because the film surface uniformity of the cured film is improved, and more considering the balance with other characteristics, Preferably it is 0.001-0.1 weight%, More preferably, it is 0.001-0.05 weight%.

1.6 (3) 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.

  The colorant used in the curable composition may be a single compound or a mixture of two or more compounds.

  When the content of the colorant is 0.1 to 5% by weight of the solid content in the curable composition, it is preferable because the cured film can be easily inspected, and more preferably 0 in view of the balance with other characteristics. 0.1 to 1% by weight, more preferably 0.1 to 0.5% by weight.

1.6 (4) Polymerization inhibitor The curable composition of the present invention may contain a polymerization inhibitor, for example, in order to improve storage stability. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, or phenothiazine. Among these, phenothiazine is preferable because the change in viscosity is small even during long-term storage.

  The polymerization inhibitor used in the curable composition may be a single compound or a mixture of two or more compounds.

  The content of the polymerization inhibitor is preferably 0.01 to 1% by weight of the solid content in the curable composition because the change in viscosity is small even in long-term storage, and considering the balance with other properties, More preferably, it is 0.01 to 0.5 weight%, More preferably, it is 0.01 to 0.1 weight%.

1.7 Viscosity of Curable Composition The curable composition of the present invention is preferably used at a viscosity suitable for each printing method. For example, in the case of application by an ink jet printing method, 25 measured with an E-type viscometer A viscosity at 2 ° C. of 2 to 200 mPa · s is preferable because application characteristics (such as jetting accuracy) by ink jet printing are improved. The viscosity of the curable composition at 25 ° C. is more preferably 5 to 180 mPa · s, and further preferably 7 to 150 mPa · s.

  For example, when using an ink jet printing method and using an ink having a viscosity of 30 mPa · s or higher at 25 ° C., the ink jet head is heated to lower the viscosity at the time of ejection, thereby enabling more stable ejection. When jetting by heating the inkjet head, the viscosity of the inkjet ink at a heating temperature (preferably 40 to 120 ° C.) is preferably 1 to 30 mPa · s, more preferably 2 to 25 mPa · s. ˜20 mPa · s is particularly preferred.

  For example, when an inkjet head is heated using an inkjet printing method, it is preferable to use an ink that does not contain a solvent. In that case, the viscosity of the ink is preferably adjusted by appropriately selecting the type and content of the diluent (C). When the inkjet head is not heated, the viscosity of the curable composition (ink) can be adjusted by adding a solvent of 10% by weight or less of the total amount of the ink.

1.8 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.

2. Application of curable composition by inkjet printing method The curable composition of the present invention can be applied using a known inkjet printing method. 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), and a coating 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, the curable composition can be applied only to necessary portions, and the cost can be reduced as compared with the photolithography method.

  A preferable application unit for performing application using the curable composition of the present invention includes, for example, an ink jet unit provided with an ink containing portion containing these curable compositions and an ink jet head. Examples of the ink jet unit include an ink jet unit that causes thermal energy corresponding to a coating signal to act on ink and generates ink droplets by the energy.

  As an inkjet head, for example, it has a heating part liquid contact 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.

  As a preferable coating apparatus for performing coating using the curable composition of the present invention, for example, energy corresponding to a coating signal is given to ink in an ink jet head chamber having an ink storage section in which ink is stored, An apparatus for generating ink droplets by the energy is mentioned.

  The ink jet coating apparatus is not limited to the 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. The ink container is integrated with the ink jet head in a separable or non-separable manner and mounted on the carriage, and is provided at a fixed portion of the apparatus so that the ink is supplied to the ink jet head through an ink supply member, for example, a tube. It may be in the form of supplying.

  Moreover, 10-120 degreeC is preferable for the discharge (application | coating) temperature of an inkjet, and it is preferable that the viscosity of the curable composition in application | coating temperature is 1-200 mPa * s.

3. Formation of Cured Film The cured film of the present invention is obtained by applying the curable composition described above to the substrate surface by an ink jet printing method, and then irradiating the ink with light such as ultraviolet rays or visible rays as necessary.

When irradiating with ultraviolet rays, the amount of ultraviolet rays to be irradiated depends on the composition of the curable composition, but is measured with an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by Ushio Electric Co., Ltd. 10~1,000mJ / cm ² approximately by weight, and more preferably about 20~800mJ / cm ^2, about 40~500mJ / cm ² is more preferred. Moreover, 200-450 nm is preferable, the wavelength of the ultraviolet-ray to irradiate is more preferable, 220-430 nm is more preferable, 250-400 nm is further more preferable.

  In addition, if necessary, the cured film cured by light irradiation may be further heated and fired. In particular, it is preferable to heat at 100 to 250 ° C. for 10 to 60 minutes, and at 120 to 230 ° C. for 10 to 10 minutes. Heating for 60 minutes is more preferable, and heating at 150 to 200 ° C. for 10 to 60 minutes is more preferable.

  The “substrate” that can be used in the present invention is not particularly limited as long as it can be a target to which the curable composition is applied, and the shape is not limited to a flat plate shape, and may be a curved surface shape.

  The material of the substrate is not particularly limited. For example, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, fluororesins, acrylic resins, Plastic film such as polyamide, polycarbonate, polyimide, cellophane, acetate, metal foil, laminated film of polyimide and metal foil, glassine paper, parchment paper or polyethylene, clay binder, polyvinyl alcohol, starch, carboxymethyl cellulose ( CMC) and the like can be mentioned as paper and glass.

  The substances constituting these substrates may be further added to pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents and / or electromagnetic waves, as long as the effects of the present invention are not adversely affected. An additive such as an inhibitor may be included. Further, a material different from the substrate may be formed on a part of the surface of the substrate.

  The use of the substrate is not particularly limited, but the cured film obtained from the ink jet ink of the present invention is excellent in plating resistance, heat resistance, flame retardancy, adhesion, and flexibility, so that a metal circuit is formed on the substrate surface. It is preferably used for the production of an electronic circuit board or the like having Although the metal which forms a circuit is not specifically limited, Gold, silver, copper, aluminum, or ITO is preferable.

  Although the thickness of a board | substrate is not specifically limited, Usually, it is about 10 micrometers-2 mm, Although it adjusts suitably by the objective to use, 15-500 micrometers is preferable and 20-200 micrometers is more preferable.

  If necessary, a liquid-repellent component or a lyophilic component may be applied to the surface of the substrate on which the cured film is formed to improve the ink application property to the substrate, and corona treatment, plasma treatment, blast treatment, etc. Adhesion treatment may be applied, or an easy adhesion layer or a color filter protective film may be provided on the surface.

4). Flame retardancy of cured film The cured film of the present invention has excellent flame retardancy. Its flame retardancy is VTM-2, VTM-1 or VTM-0 in the UL94VTM vertical combustion test. As for the film thickness of a test piece, 10-50 micrometers is preferable. More preferably, it is 15-40 micrometers, More preferably, it is 20-35 micrometers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

<Preparation of curable composition and cured film pattern-formed substrate>
First, the curable composition concerning Examples 1-2 and Comparative Examples 1-4 and the cured film pattern formation board | substrate obtained from it are demonstrated.

[Example 1]
As imide (meth) acrylate (A), TO-1,534 (trade name; manufactured by Toagosei Co., Ltd.) which is 3,4,5,6-tetrahydrophthalimidoethyl acrylate, as a flame retardant (B), condensation 9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10 oxide HFA-3003 (trade name; manufactured by Showa Polymer Co., Ltd.), Diluent (C), 4-hydroxybutyl acrylate, dipropylene glycol di SR-508 (trade name; Sartomer), which is an acrylate, Nicalac MW-30 (trade name; manufactured by Sanwa Chemical Co., Ltd.), which is a melamine resin, as a thermoreactive resin (D), a photopolymerization initiator (E) DAROCUR TPO (trade name; Ciba-Ja), which is 2,4,6-trimethylbenzoyldiphenylphosphine oxide As a polymerization inhibitor, phenothiazine was mixed and dissolved in the following composition ratio, and then filtered through a PTFE membrane filter (1 μm) to prepare an inkjet ink 1.
(A) TO-1534 20.00 g
(B) HFA-3003 12.00g
(C) 4-hydroxybutyl acrylate 12.50 g
(C) SR-508 42.50 g
(D) Nicarak MW-30 5.00g
(E) DAROCUR TPO 4.00g
(Others) Phenothiazine 0.05g
Using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd., hereinafter the same), the viscosity of ink-jet ink 1 at 25 ° C. was measured and found to be 127 mPa · s.

(1) Ink discharge conditions Ink 1 is injected into an ink jet cartridge, and this is attached to an ink jet apparatus (DMP-2831 manufactured by FUJIFILM Dimatix), and a 10 pl head (DMC-11610) is used to discharge ink ( (Piezo voltage) 16V, head temperature 70 ° C, drive frequency 5kHz, discharge conditions of 1 application, a predetermined pattern on the copper surface of Neoflex NEX-3FE (Mitsui Chemicals), which is a flexible printed circuit board Formed.

(2) Curing conditions of the coating film A substrate on which the ink 1 is patterned is exposed to UV (40 mJ / cm ² ), further baked at 190 ° C. for 30 minutes, and cured to a thickness of 10 μm. A substrate 1 on which a film pattern was formed was obtained. The light source used for UV exposure was an ultra-high pressure mercury lamp, and the exposure amount was measured with an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC.

(3) Evaluation of Adhesiveness of Cured Film to Copper Substrate In order to evaluate the adhesiveness of the cured film to copper, it was examined whether peeling occurred using a cross-cut method (JIS K5400). The test was performed under conditions of a temperature of 25 ° C. and a humidity of 65%. The results were as shown in Table 1, where “◯” indicates that no peeling occurred and “×” indicates that peeling occurred.

(4) Evaluation of the resistance of the cured film to the plating solution In order to evaluate the resistance of the cured film to the plating solution, the produced test substrate was treated with a 30 ° C palladium aqueous solution (trade name: KAT-450, Pd concentration of 12 mg / L, Uemura). After immersion for 1 minute in Kogyo Co., Ltd. and washing with water, in an electroless nickel plating solution (trade name: Nimden NPR-4, Ni concentration 4.5 g / L, manufactured by Uemura Kogyo Co., Ltd.) at 80 ° C. Immerse for 30 minutes and wash with water, then soak in water for 10 minutes in an electroless gold plating solution (trade name: Goblite TAM-55, Au concentration 1 g / L, manufactured by Uemura Kogyo Co., Ltd.) at 80 ° C. Thus, a plating film was formed. “○” indicates that no penetration of the plating solution into the cured film or peeling of the cured film occurs during this process, and “×” indicates that the penetration of the plating solution into the cured film or peeling of the cured film occurs. It was. The results are shown in Table 1.

(5) Evaluation of solder heat resistance of cured film In order to evaluate the solder heat resistance of the cured film, rosin flux (trade name: NS-829, manufactured by Nippon Superior Co., Ltd.) is applied to the surface of the cured film of the test substrate. Then, it was immersed in a solder bath at 260 ° C. for 30 seconds to examine whether peeling or swelling occurred. The case where no peeling or swelling occurred was indicated by “◯”, and the case where slight peeling or swelling occurred was indicated by “X”. The results are shown in Table 1.

(6) Evaluation of flame retardancy In order to evaluate the flame retardancy of a cured film obtained from the curable composition, on Kapton 200H (made by Toray DuPont Co., Ltd.) which is a polyimide film (thickness 50 μm). The ink was coated on the surface with an applicator to a film thickness of 25 μm, UV exposed (40 mJ / cm ² ), and baked at 190 ° C. for 30 minutes to form a cured film. Further, a cured film was prepared on the back surface in the same manner as the front surface, and a test sheet was prepared. The light source used for UV exposure was an ultra-high pressure mercury lamp, and the exposure amount was measured with an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC. The prepared test sheet was cut into a size of 50 mm in width and 200 mm in length, and the test sheet was wound into a cylindrical shape in accordance with UL94 VTM test to prepare a sample for combustion test. When a flame of 20 mm is brought close to this sample for combustion test for 3 seconds, the flame is extinguished within 10 seconds after the flame is released, and when the flame does not reach the height of 125 mm, “◯” is given. The case where it took more than a second or the flame reached to a height of 125 mm was defined as “x”. The results are shown in Table 1. In addition, the said evaluation is evaluated according to the vertical combustion test of the thin material of UL94, and the case of "(circle)" is equivalent to VTM-0. The results are shown in Table 1.

[Example 2]
Ink jet ink 2 was prepared in the same manner as in Example 1 except that the composition ratio was as follows.
(A) TO-1534 20.00 g
(B) HFA-3003 5.60 g
(C) 4-hydroxybutyl acrylate 9.90 g
(C) SR-508 42.50 g
(D) Nicarak MW-30 5.00g
(E) DAROCUR TPO 4.00g
(Others) Phenothiazine 0.05g
Using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd., the same shall apply hereinafter), the viscosity of the ink-jet ink 2 at 25 ° C. was measured and found to be 102 mPa · s.
A substrate 2 on which a cured film pattern having a thickness of 10 μm was formed was obtained in the same manner as in Example 1 using the inkjet ink 2. Moreover, the ink 2 and its cured film were evaluated by the above-mentioned method. The results are shown in Table 1.

[Comparative Example 1]
Inkjet ink 3 was prepared in the same manner as in Example 1, except that M-140 (trade name; manufactured by Toagosei Co., Ltd.), which is hexahydrophthalimidoethyl acrylate, was used instead of TO-1534.
(A) M-140 20.00 g
(B) HFA-3003 12.00g
(C) 4-hydroxybutyl acrylate 12.50 g
(C) SR-508 42.50 g
(D) Nicarak MW-30 5.00g
(E) DAROCUR TPO 4.00g
(Others) Phenothiazine 0.05g
Using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd., the same applies hereinafter), the viscosity of the ink-jet ink 3 at 25 ° C. was measured and found to be 128 mPa · s.
A substrate 3 on which a cured film pattern having a thickness of 10 μm was formed was obtained in the same manner as in Example 1 using the inkjet ink 3. Moreover, the ink 3 and its cured film were evaluated by the above-mentioned method. The results are shown in Table 1.

[Comparative Example 2]
Ink for inkjet recording, in the same manner as in Example 1, except that UVT-302 (trade name; manufactured by Toagosei Co., Ltd.), which is an acrylic polymer having TO-1534 in the side chain, was used instead of TO-1534. 4 was prepared.
(A) UVT-302 20.00 g
(B) HFA-3003 12.00g
(C) 4-hydroxybutyl acrylate 12.50 g
(C) SR-508 42.50 g
(D) Nicarak MW-30 5.00g
(E) DAROCUR TPO 4.00g
(Others) Phenothiazine 0.05g
Using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd., the same shall apply hereinafter), the viscosity of the ink-jet ink 4 at 25 ° C. was measured and found to be 105 mPa · s.
A substrate 4 on which a cured film pattern having a thickness of 10 μm was formed was obtained in the same manner as in Example 1 using the inkjet ink 4. Moreover, the ink 4 and its cured film were evaluated by the above-mentioned method. The results are shown in Table 1.

[Comparative Example 3]
Inkjet ink 5 was prepared in the same manner as in Example 1 except for TO-1534 in the same composition as in Example 1.
(B) HFA-3003 12.00g
(C) 4-hydroxybutyl acrylate 12.50 g
(C) SR-508 42.50 g
(D) Nicarak MW-30 5.00g
(E) DAROCUR TPO 4.00g
(Others) Phenothiazine 0.05g
Using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd., the same shall apply hereinafter), the viscosity of the ink-jet ink 5 at 25 ° C. was measured and found to be 86 mPa · s.
A substrate 5 on which a cured film pattern having a thickness of 10 μm was formed was obtained in the same manner as in Example 1 using the inkjet ink 5. Moreover, the ink 5 and its cured film were evaluated by the above-mentioned method. The results are shown in Table 1.

[Comparative Example 4]
Inkjet ink 6 was prepared in the same manner as in Example 1 with the same composition as in Example 1 except for HFA-3003.
(A) TO-1534 20.00 g
(C) 4-hydroxybutyl acrylate 12.50 g
(C) SR-508 42.50 g
(D) Nicarak MW-30 5.00g
(E) DAROCUR TPO 4.00g
(Others) Phenothiazine 0.05g
Using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd., the same shall apply hereinafter), the viscosity of the inkjet ink 6 at 25 ° C. was measured and found to be 77 mPa · s.
A substrate 6 on which a cured film pattern having a thickness of 10 μm was formed was obtained in the same manner as in Example 1 using the inkjet ink 6. Moreover, the ink 6 and its cured film were evaluated by the method described above. The results are shown in Table 1.

  As is apparent from the results shown in Table 1, in Examples 1 to 2 and Comparative Examples 1, 2, and 4 according to the present invention, the liquid column during jetting is ejected in the vertical direction, no satellite is generated, and the ink The dischargeability of was good. In Comparative Example 2 containing a polymer component, since satellites were generated, the subsequent evaluation on the substrate was stopped.

  In Comparative Example 3 containing no imide (meth) acrylate (A), adhesion was poor and almost peeled off from the substrate 5, and peeling of the cured film was also observed in the plating resistance and solder heat resistance tests.

  In Comparative Example 1 containing hexahydrophthalimidoethyl acrylate instead of TO-1534, the adhesion was good, but in the evaluation of plating resistance, penetration of the plating solution into the cured film was observed.

  As is apparent from the results shown in Table 1, in the evaluation of flame retardancy, in Examples 1 and 2 and Comparative Example 2, the flame was extinguished within 10 seconds, and the flame was extinguished without reaching a height of 125 mm. The property was good. However, in Comparative Examples 3 and 4, since the flame reached a height of 125 mm or more within 3 seconds, the test was stopped. In Comparative Example 1, the test was stopped because it took 10 seconds or more to extinguish.

  As described above, according to the present invention, it is possible to obtain a curable composition having excellent ink ejection properties, adhesion, plating resistance, solder heat resistance, and flame retardancy.

Claims (19)

The imide (meth) acrylate (A) represented by the formula (1), the flame retardant (B) and the diluent (C) represented by the formula (4), and the diluent (C) is monofunctional (meth) A curable composition which is an acrylate or a polyfunctional (meth) acrylate .

Wherein R ¹ is hydrogen or methyl, R ² is an organic group having 1 to 100 carbon atoms, and R ³ and R ⁴ are each independently hydrogen or methyl, or R ³ and R 4 A hydrocarbon ring in which ⁴ is bonded to form a cyclic structure or a hydrocarbon ring derivative in which 1 to 4 methyls are bonded to the hydrocarbon ring, and n is an integer of 1 to 6)

(In the formula, R is hydrogen, hydroxy, or an organic group having 1 to 100 carbon atoms, and n is an integer of 1 to 20) The curable composition of Claim 1 whose imide (meth) acrylate (A) is a compound represented by Formula (2).

(Wherein R ¹ is hydrogen or methyl, R ² is an organic group having 1 to 100 carbon atoms, and n is an integer of 1 to 6) The curable composition of Claim 1 or 2 whose imide (meth) acrylate (A) is a compound represented by Formula (3).

The curable composition according to any one of claims 1 to 3 , wherein R in the formula (4) has at least one radical polymerizable double bond. The curable composition according to any one of claims 1 to 4 , wherein the flame retardant (B) is at least one selected from the group of compounds represented by formulas (5) to (8).

(In formula (5), a, b and c are each independently an integer of 0 to 10, X is independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is each independently. 0 to 1 and 1 to 2 of the three R ⁶ are groups represented by the formula (5-1), and the rest are groups represented by the formula (5-2). ⁷ is hydrogen or methyl.)

(In Formula (6), a, b and c are each independently an integer of 0 to 10, X is independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is each independently. And 1 to 2 of the three R ⁶ are groups represented by the formula (6-1), and the rest are groups represented by the formula (6-2). ⁷ is hydrogen or methyl.)

(In formula (7), a, b, c and d are each independently an integer of 0 to 10, X is independently a linear or branched alkylene having 1 to 5 carbon atoms, and m is Each independently 0 or 1, and 1 to 3 of the four R ⁶ are groups represented by the formula (7-1), and the rest are groups represented by the formula (7-2). R ⁷ is hydrogen or methyl.)

(In the formula (8), a, b, c, d, e and f are each independently an integer of 0 to 10, and X is independently a linear or branched alkylene having 1 to 5 carbon atoms. Each of m is independently 0 or 1, and 1 to 5 of ⁶ R ⁶ are groups represented by the formula (8-1), and the rest are represented by the formula (8-2). And R ⁷ is hydrogen or methyl.) The curable composition as described in any one of Claims 1-5 whose 25 degreeC viscosity of a diluent (C) is 0.1-100 mPa * s. Furthermore, the curable composition as described in any one of Claims 1-6 containing a heat- reactive resin (D). Further, a photopolymerization initiator containing (E), the curable composition according to any one of claims 1-7. The curable composition according to claim 8 , wherein the photopolymerization initiator (E) is at least one compound selected from the group consisting of acylphosphine oxides and alkylphenone compounds. Imide (meth) acrylate (A) as a 3,4,5,6-tetrahydrophthalic phthalimidoethyl acrylated DOO, condensation 9,10-dihydro-9-oxa-10-phospha-phenanthrene -10 oxy de as a flame retardant (B) , dipropylene glycol di acrylated preparative as the diluent (C), melamine resins as heat reactive resin (D), photopolymerization initiator as (E) 2,4,6-trimethyl benzoyl diphenyl phosphine oxa i de, and containing phenothiazine as a polymerization inhibitor, hardening compositions. The curable composition according to any one of claims 1 to 10 , which is an ink composition. The curable composition according to any one of claims 1 to 11 , which is an inkjet ink. The curable composition according to any one of claims 1 to 12 applied to form a cured film by irradiating light to the curable composition applied, cured film forming method. The cured film formation method of forming a cured film by further heating the cured film obtained by the light irradiation of Claim 13 . Cured film obtained from the curable composition according to any one of claims 1 to 12. The cured film of Claim 15 currently formed in pattern shape. An electronic circuit board on which the cured film according to claim 15 or 16 is formed. An electronic component comprising the electronic circuit board according to claim 17 . A display element comprising the electronic circuit board according to claim 17 or the electronic component according to claim 18 .