JP2012214532A - Curable resin composition for inkjet, cured product thereof and printed wiring board having the cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for inkjet, which is used in an inkjet printer and has excellent heat resistance, chemical resistance, insulation properties and storage stability.SOLUTION: The curable resin composition for inkjet includes (A) a bisallylnadiimide compound represented by general formula (1) (wherein Ris 2-18C alkyl, aryl or aralkyl), a bismaleimide compound of a specific structure, (C) a diluent and (D) at least one of hydroquinone and a hydroquinone derivative, and has a viscosity at 25°C of ≤150 mPa s.

Description

  The present invention relates to a curable resin composition for inkjet which is useful for the production of a printed wiring board and has excellent heat resistance, a cured product thereof, and a printed wiring board having the cured product. More specifically, it is a curable resin composition used in the production of printed wiring boards such as solder resist inks and marking inks, and has a low viscosity, excellent workability and storage stability, and is further resistant to heat and resistance. The present invention relates to a curable resin composition for ink jet excellent in chemical properties, electroless gold plating resistance and insulation, a cured product thereof, and a printed wiring board using the cured product.

  In general, as a curable resin composition used for manufacturing some consumer printed wiring boards and industrial printed wiring boards, for example, solder resist ink, from the viewpoint of high accuracy and high density, a liquid development type solder A resist composition is used. This liquid development type solder resist composition is irradiated with ultraviolet rays on a coating film formed using this, and an image is formed by developing the film. A solder resist is formed by carrying out this hardening. At present, in consideration of environmental problems, among liquid development type solder resist compositions, it is the mainstream to use an alkali development type liquid solder resist composition using a dilute aqueous alkali solution as a developer. Examples of the alkali development type liquid solder resist composition using the dilute aqueous alkali solution include, for example, a carboxyl group-containing photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolac type epoxy resin and an unsaturated group-containing monocarboxylic acid, There exists a solder resist composition comprising a photopolymerization initiator, a diluent and an epoxy resin (see Patent Document 1).

  However, the alkali developing type liquid solder resist composition described above is highly reactive between the carboxyl group-containing photosensitive resin and the epoxy resin, and in order to prevent the two from reacting before use, the two are stored separately. It is necessary to adopt a liquid type configuration. Therefore, there exists a fault that these must be mixed before use and must be used within several days after mixing.

  Moreover, in order to form a solder resist using the above-mentioned liquid solder resist composition, it is necessary to go through many steps such as coating, drying, exposure, development and thermosetting, Since equipment such as a coating machine, a dryer, an exposure machine, a developing machine, and a thermosetting furnace is required, there is a drawback that the manufacturing cost is high.

  As a method for solving the above problems, a method of creating a solder resist pattern by drawing a pattern of a curable resin composition on a substrate using an ink jet printer and drying the pattern is proposed (patent) Reference 2). However, in the screen printing method conventionally used for forming the solder resist, the viscosity of the curable resin composition to be used is 2,000 to 15,000 mPa · s (25 ° C.), whereas an ink jet printer is used. In this case, the viscosity of the curable resin composition is as low as 10 to 150 mPa · s (25 ° C.), and the difference in viscosity is large. Therefore, when such a curable resin composition having a low viscosity is actually used in an ink jet printer, the viscosity is further reduced by heat applied in the drying process, and the formed pattern has a sufficient accuracy because it is blurred. A solder resist pattern cannot be obtained and has not been put to practical use.

  Further, as a method for reducing the viscosity of the curable resin composition, a method using a low molecular weight compound, for example, an epoxy resin such as trimethylolpropane triglycidyl ether or triallyl isocyanurate (TAIC) as a diluent may be considered. . However, in this case, there has been a problem that a cured product formed using the resin composition lacks heat resistance and curability.

  Therefore, for the purpose of imparting characteristics such as heat resistance to the cured product, a method of blending a bisallyl nadiimide compound having a relatively low molecular weight and heat resistance into the curable resin composition is also conceivable (see Patent Document 4). ). Here, since the resin composition containing the bisallylnadiimide compound generally needs to be cured at a high temperature of about 250 ° C., a method of curing the resin composition using a peroxide has been proposed (patent) Reference 3). However, when a cured product formed using a peroxide is used for a printed wiring board, oxidation of the metal surface such as a copper foil of the printed wiring board becomes intense, resulting in a problem that the physical properties are deteriorated.

 Moreover, when a bisallyl nadiimide compound is mix | blended with a resin composition, a resin composition may gelatinize with time.

JP-A 61-243869 JP-A-7-263845 JP-A-7-18031 International Publication WO2006 / 0756654

The problems to be solved by the present invention are low viscosity, excellent workability and storage stability, which are useful for the production of printed wiring boards, and further, heat resistance, chemical resistance, electroless gold plating resistance, and insulation. The object is to provide an excellent curable resin composition. Specifically, an object of the present invention is to provide an ink-jet curable resin composition that can prevent gelation with time that sometimes occurs when a bisallylnadiimide compound is blended.
As a result of various studies, the present inventors have inferred that the gelation is caused by the following reason. That is, the bisallylnadiimide compound may not be completely ring-closed during imidization, which is the synthesis process, and a bisallylnadiimide compound in which the amic acid is not completely ring-closed may be synthesized. . In addition, when a diamine is added to nadic acid and synthesized by dehydration, the dehydration reaction may be insufficient. Such a bisallylnadiimide compound is acidified because carboxylic acid remains, thereby causing an ene reaction and a Diels-Alder reaction.
From the above, the present inventors have inferred that gelation is likely to occur in the curable resin composition containing the bisallylnadiimide compound in which the above-mentioned amic acid is not ring-closed.

（式中、Ｒ^１は、炭素数２〜１８のアルキル基、アリール基又はアラルキル基を示す。）
（Ｂ）下記一般式（２）で示されるビスマレイミド化合物と、

（式中、Ｒ^２は、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）と、
（Ｃ）希釈剤と、
（Ｄ）ヒドロキノン及びヒドロキノン誘導体の少なくとも一方とを含有するインクジェット用硬化性樹脂組成物であって、
その粘度が２５℃で１５０ｍＰａ・ｓ以下であることを特徴とするインクジェット用硬化性樹脂組成物である。 In order to achieve the above object, the present invention has the following features.
That is, one of the features of the present invention is (A) a bisallylnadiimide compound represented by the following general formula (1):

(In the formula, R ¹ represents an alkyl group, aryl group or aralkyl group having 2 to 18 carbon atoms.)
(B) a bismaleimide compound represented by the following general formula (2);

(Wherein R ² represents an alkyl group having ^{2 to} 32 carbon atoms, an aryl group or an aralkyl group);
(C) a diluent;
(D) A curable resin composition for inkjet containing at least one of hydroquinone and a hydroquinone derivative,
It is a curable resin composition for inkjet, having a viscosity of 150 mPa · s or less at 25 ° C.

（式中、Ｒは、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）
及び下記一般式（４）で示される無水アリルナジック酸に下記一般式（５）で示されるジアミン化合物を付加し脱水反応させて得られるビスアリルナジイミド化合物（ａ−２）

（式中、Ｒは、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）
の少なくとも一方を含むインクジェット用硬化性樹脂組成物である。 Another feature of the present invention is that the bisallylnadiimide compound (a-1) is obtained by heating and dehydrating the amic acid compound represented by the following general formula (3).

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
And a bisallylnadiimide compound (a-2) obtained by adding a diamine compound represented by the following general formula (5) to the allyl nadic acid anhydride represented by the following general formula (4) to cause a dehydration reaction

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
It is the curable resin composition for inkjets containing at least one of these.

  Moreover, as a suitable aspect of this invention, it is the curable resin composition for inkjets whose said diluent (C) is at least one of an organic solvent (C-1) and a polymerizable monomer (C-2). Here, the polymerizable monomer (C-2) preferably has at least one of an acryloyl group and a methacryloyl group.

Moreover, in this invention, it is preferable to make each compounding quantity of the component of the curable resin composition for inkjets as follows.
That is, the blending amount of the bisallylnadiimide compound (A) is 30 with respect to the blending amount of the components of the curable resin composition for inkjet excluding the bisallylnadiimide compound (A) and the organic solvent (C). It is preferable that it is -96 mass%.
The bismaleimide compound (B) is preferably blended in an amount of 4 to 45 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A).
The diluent (C) is preferably blended in an amount of 25 to 1900 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A). In addition, when using the said polymerizable monomer (C-2) independently as said diluent (C), this is mix | blended 25-200 mass parts with respect to 100 mass parts of said bisallyl nadiimide compounds (A). It is preferable.
Further, at least one of the hydroquinone and the hydroquinone derivative (D) is preferably blended in an amount of 0.04 to 0.5 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A).

Furthermore, another feature of the present invention is that an ink jet printer is used to draw a pattern of the curable resin composition for ink jet on a printed wiring board substrate or a solder resist pattern formed on the printed wiring board. A printed wiring board having a cured product of a curable resin composition obtained by thermosetting this.
In addition, when using the said polymerizable monomer (C-2) as said organic solvent (C), it uses an inkjet printer on the board | substrate of a printed wiring board, or the solder resist pattern formed on a printed wiring board. The cured product can also be formed by drawing a pattern of the curable resin composition for inkjet and irradiating the pattern with ultraviolet rays, followed by photocuring and then thermosetting.

  Since the curable resin composition for inkjet of the present invention has a low viscosity, it is possible to draw a pattern on a substrate using an inkjet printer. Moreover, the hardened | cured material obtained by carrying out thermosetting etc. of the curable resin composition for inkjets of this invention is excellent in heat resistance, and can be used as a soldering resist for printed wiring boards, or marking ink. Furthermore, the curable resin composition for inkjet according to the present invention prevents gelation of the resin composition over time that sometimes occurs when a bisallylnadiimide compound is blended by blending hydroquinone or a hydroquinone derivative. be able to. And by being able to form a cured product of such a curable resin composition using an ink jet printer, productivity is improved by simplifying the manufacturing process of the printed wiring board, and the maintenance cost of manufacturing equipment is also reduced. Therefore, it can contribute to the reduction of the production cost of the printed wiring board.

  Hereinafter, an embodiment of the present invention will be described in detail. Of course, the present invention is not limited to this embodiment.

（式中、Ｒ^１は、炭素数２〜１８のアルキル基、アリール基又はアラルキル基を示す。）
（Ｂ）下記一般式（２）で示されるビスマレイミド化合物と、

（式中、Ｒ^２は、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）と、
（Ｃ）希釈剤と、
（Ｄ）ヒドロキノン及びヒドロキノン誘導体の少なくとも一方とを含有することにより、ソルダーレジストやマーキングインキに求められる耐熱性等の必要な特性を維持した状態で、インクジェットプリンターでパターンを描画できる粘度（２５℃で１５０ｍＰａ・ｓ以下）とすることが可能である。 The inkjet curable resin composition of the present invention includes (A) a bisallylnadiimide compound represented by the following general formula (1),

(In the formula, R ¹ represents an alkyl group, aryl group or aralkyl group having 2 to 18 carbon atoms.)
(B) a bismaleimide compound represented by the following general formula (2);

(Wherein R ² represents an alkyl group having ^{2 to} 32 carbon atoms, an aryl group or an aralkyl group);
(C) a diluent;
(D) By containing at least one of hydroquinone and a hydroquinone derivative, a viscosity (at 25 ° C.) that can draw a pattern with an ink jet printer while maintaining necessary characteristics such as heat resistance required for solder resist and marking ink. 150 mPa · s or less).

（式中、Ｒは、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）
及び下記一般式（４）で示される無水アリルナジック酸に下記一般式（５）で示されるジアミン化合物を付加し脱水反応させて得られるビスアリルナジイミド化合物（ａ−２）

（式中、Ｒは、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）
の少なくとも一方を含む場合であっても、ヒドロキノン又はヒドロキノン誘導体の少なくとも一方を配合することにより、上記ビスアリルナジイミド化合物（ａ−１）及び（ａ−２）を起因として発生すると推測される当該樹脂組成物のゲル化を防止することができると考えられる。 Moreover, the curable resin composition for inkjet according to the present invention is a bisallylnadiimide compound (A) obtained by heating and dehydrating the amic acid compound represented by the following general formula (3). a-1)

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
And a bisallylnadiimide compound (a-2) obtained by adding a diamine compound represented by the following general formula (5) to the allyl nadic acid anhydride represented by the following general formula (4) to cause a dehydration reaction

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
Even if it contains at least one of the above, it is presumed that the above bisallylnadiimide compounds (a-1) and (a-2) are generated due to the incorporation of at least one of hydroquinone or hydroquinone derivatives. It is considered that gelation of the resin composition can be prevented.

  That is, in this invention, heat resistance can be provided to the hardened | cured material of a curable resin composition by mix | blending a bisallyl nadiimide compound (A). However, the bisallylnadiimide compound (A) alone is not thermally cured unless heated to around 250 ° C. Therefore, by using the bismaleimide compound (B) represented by the general formula (2) and the bisallyl nadiimide compound (A), which is one of the features of the present invention, the curing temperature of the printed wiring board is adjusted. It becomes possible to make it 100-200 degreeC generally used by manufacture, Preferably it is 140-180 degreeC. Further, by using the bisallylnadiimide compound (A) and the bismaleimide compound (B) in combination, the crystallinity of the bismaleimide compound (B) is lowered, and further by adding a diluent (C), It becomes possible to provide a liquid curable resin composition having excellent storage stability with viscosity.

  Hereinafter, the curable resin composition for inkjet of the present invention will be described.

（式中、Ｒ^１は、炭素数２〜１８のアルキル基、アリール基又はアラルキル基を示す。）
特に好ましいものとしては、上記一般式（１）中のＲ^１が、下記式（６）、（７）及び（８）

で示される化合物である。具体的には、丸善石油化学社製のＢＡＮＩ−Ｍ、ＢＡＮＩ−Ｈ、ＢＡＮＩ−Ｘ（何れも製品グレード名）等が挙げられる。 <Bisallyl nadiimide compound (A)>
The bisallyl nadiimide compound (A) used in the present invention is a bisallyl nadiimide compound represented by the following general formula (1).

(In the formula, R ¹ represents an alkyl group, aryl group or aralkyl group having 2 to 18 carbon atoms.)
Particularly preferably, R ¹ in the above general formula (1) is represented by the following formulas (6), (7) and (8).

It is a compound shown by these. Specific examples include BANI-M, BANI-H, and BANI-X (all are product grade names) manufactured by Maruzen Petrochemical Co., Ltd.

（式中、Ｒは、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）
及び下記一般式（４）で示される無水アリルナジック酸に下記一般式（５）で示されるジアミン化合物を付加し脱水反応させて得られるビスアリルナジイミド化合物（ａ−２）

（式中、Ｒは、炭素数２〜３２のアルキル基、アリール基又はアラルキル基を示す。）
の少なくとも一方を含む。 Moreover, the bisallyl nadiimide compound (A) used for this invention is the bisallyl nadiimide compound (a-1) obtained by heat-dehydrating the amic acid compound shown by following General formula (3).

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
And a bisallylnadiimide compound (a-2) obtained by adding a diamine compound represented by the following general formula (5) to the allyl nadic acid anhydride represented by the following general formula (4) to cause a dehydration reaction

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
At least one of the above.

  These bisallylnadiimide compounds (A) may be used singly or in combination. Moreover, it is preferable that the compounding quantity is 30-96 mass% with respect to the compounding quantity of the component of the curable resin composition for inkjet except the said bisallyl nadiimide compound (A) and the organic solvent (C). Furthermore, if necessary, monoallyl nadiimide having a diluting effect, for example, ANI-HP (product grade name) manufactured by Maruzen Petrochemical Co., Ltd. can be used.

（式中、Ｒ^２は、炭素数２〜３２のアルキル基、アリール基、又はアラルキル基を示す。）
で示される化合物である。特に好ましいものとしては、Ｒ^２が、下記式（９）、（１０）、（１１）及び（１２）

で示される化合物である。具体的には、ケイ・アイ化成社製のＢＭＩ、ＢＭＩ−７０、ＢＭＩ−８０（何れも製品グレード名）、大和化成工業社製のＢＭＩ−１０００、ＢＭＩ−３０００、ＢＭＩ−４０００、ＢＭＩ−５０００（何れも製品グレード名）等が挙げられる。これらのビスマレイミド化合物（Ｂ）は、単独又は複数種を混合して用いても良い。また、その配合量は、前記ビスアリルナジイミド化合物（Ａ）１００質量部に対して、４〜４５質量部、好ましくは１５〜３５質量部である。当該ビスマレイミド化合物（Ｂ）の配合量が、前記ビスアリルナジイミド化合物（Ａ）１００質量部に対して４質量部未満の場合、硬化性樹脂組成物の硬化性が低下するため好ましくない。一方、前記ビスマレイミド化合物（Ｂ）の配合量が、前記ビスアリルナジイミド化合物（Ａ）１００質量部に対して４５質量部を超えた場合、硬化性樹脂組成物の耐熱性や硬化性が低下したり、更にはビスマレイミド化合物（Ｂ）の結晶性が強くなるためインクジェットノズルの目詰まりの原因となり、好ましくない。尚、必要に応じて、希釈効果のあるモノマレイミド化合物、例えばフェニルマレイミドやシクロヘキシルマレイミド、及び硬化性向上効果のあるアニリン樹脂から誘導される多官能マレイミド化合物、例えばＢＭＩ−２０００（製品グレード名）等を使用することもできる。 <Bismaleimide compound (B)>
The bismaleimide compound (B) used in the present invention has the following general formula (2)

(In the formula, R ² represents an alkyl group having ^{2 to} 32 carbon atoms, an aryl group, or an aralkyl group.)
It is a compound shown by these. Particularly preferably, R ² is represented by the following formulas (9), (10), (11) and (12).

It is a compound shown by these. Specifically, BMI, BMI-70 and BMI-80 (all are product grade names) manufactured by KAI Kasei Co., Ltd., BMI-1000, BMI-3000, BMI-4000, BMI-5000 manufactured by Daiwa Kasei Kogyo Co., Ltd. (Both are product grade names). These bismaleimide compounds (B) may be used singly or in combination. Moreover, the compounding quantity is 4-45 mass parts with respect to 100 mass parts of said bisallyl nadiimide compounds (A), Preferably it is 15-35 mass parts. When the blending amount of the bismaleimide compound (B) is less than 4 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A), the curability of the curable resin composition decreases, which is not preferable. On the other hand, when the blending amount of the bismaleimide compound (B) exceeds 45 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A), the heat resistance and curability of the curable resin composition are lowered. In addition, the crystallinity of the bismaleimide compound (B) becomes strong, which may cause clogging of the inkjet nozzle, which is not preferable. If necessary, a monomaleimide compound having a diluting effect, such as phenylmaleimide or cyclohexylmaleimide, and a polyfunctional maleimide compound derived from an aniline resin having an effect of improving curability, such as BMI-2000 (product grade name), etc. Can also be used.

<Diluent (C)>
Examples of the diluent (C) used in the present invention include an organic solvent (C-1) and a polymerizable monomer (C-2). Moreover, as a polymerizable monomer (C-2), what has at least one of an acryloyl group and a methacryloyl group is preferable.

  Examples of the organic solvent (C-1) include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbi Toluene, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl Carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Seteto, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha. These organic solvents (C-1) can be used individually or in combination of multiple types.

  Examples of the polymerizable monomer (C-2) include styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, and vinyl benzoate; vinyl isobutyl ether, vinyl-n-butyl ether. Vinyl ethers such as vinyl tert-butyl ether, vinyl n-amyl ether, vinyl isoamyl ether, vinyl n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxime (Meth) acrylamides such as ruacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate, diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, butoxyethyl (meth) acrylate, methyltriglycol ( (Meth) acrylate, cyclohexyl acrylate, 2-ethylhexyl carbitol acrylate, 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, methoxydiethyl Lenglycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, methoxypropylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 1,3-butylene glycol Di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 Hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2 Ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-isobutyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclohexylene 1,3-dioxolane, trimethylolpropane Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. In which one or more acryloyl groups and / or methacryloyl groups are contained in one molecule. Among these, a compound having at least one of 1 to 4 acryloyl groups and methacryloyl groups in one molecule is preferable. Furthermore, a compound having a viscosity of 300 mPa · s or less at 25 ° C. is particularly preferable. These polymerizable monomers (C-2) may be used alone or in combination of two or more.

  In the present specification, the term “(meth) acrylate” is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

The blending amount of the diluent (C) is preferably 25 to 1900 parts by mass, more preferably 40 to 400 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A).
When the blending amount of the diluent (C) is less than 25 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A), poor dissolution or curing of the bisallylnadiimide compound (A) occurs. This is not preferable because the adhesive resin composition becomes highly viscous and cannot be applied to a substrate or the like. Moreover, when using only the organic solvent (C-1) as a diluent (C), when the compounding quantity exceeds 1900 mass parts with respect to 100 mass parts of the said bisallyl nadiimide compounds (A), curable resin composition Since the solid content in the product is reduced, it is difficult to ensure the film thickness of the coating film when it is applied to a substrate or the like. Furthermore, when using only a polymerizable monomer (C-2) as a diluent (C), the compounding quantity shall be 25-200 mass parts with respect to 100 mass parts of the said bisallyl nadiimide compounds (A). preferable. When the compounding amount of the polymerizable monomer (C-2) exceeds 200 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A), a coating film is formed when the curable resin composition is cured. Since it becomes easy to break, it is not preferable.

<Hydroquinone, hydroquinone derivative (D)>
As at least one (D) of hydroquinone and hydroquinone derivative used in the present invention, hydroquinone, arbutin (hydroquinone-β-D-glucoside), hydroquinone monobenzyl ether, hydroquinone hydroquinone, hydroquinone monomethyl ether, hydroquinone dimethyl ether, hydroquinone monoethyl Ether, potassium hydroquinonesulfonate, dipotassium hydroquinone-2,5-disulfonate, hydroquinone mono-n-hexyl ether, hydroquinone monophenyl ether, p-methoxyphenol, 2-methylhydroquinone, 2,5 di-t-butylhydroquinone Etc. At least one (D) of these hydroquinones and hydroquinone derivatives may be used alone or in combination. Moreover, it is preferable that the compounding quantity of at least one (D) of the said hydroquinone and a hydroquinone derivative is 0.04-0.5 mass part with respect to 100 mass parts of said bisallyl nadiimide compounds (A). When the blending amount is less than 0.04 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A), the effect of preventing gelation and improving storage stability is not preferable. On the other hand, when the blending amount exceeds 0.5 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A), the coating properties of the cured product are deteriorated, which is not preferable.

<Other additives>
In order to improve curability, the curable resin composition of the present invention may contain a radical polymerization initiator that generates radicals by irradiation with heat or active energy rays. As such a radical polymerization initiator, a polymerization initiator excluding a peroxide that oxidizes a metal surface such as copper foil can be used. For example, benzoin and benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether can be used. Alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) ) Phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, aminoacetophenones such as N, N-dimethylaminoacetophenone ; 2-methylanthraki , 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones and xanthones such as benzophenone and 4,4′-bisdiethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-trichloromethyl Halomethyloxadiazoles such as -5-styryl-1,3,4-oxadiazole and 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole 2,4-bis (trichloromethyl) -6- (p-methoxy-phenylvinyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s- And halomethyl-s-triazine compounds such as triazine and 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine. These radical polymerization initiators may be used alone or in combination of two or more. The compounding quantity is 10 mass with respect to the compounding quantity of the component of the curable resin composition except the said organic solvent (C-1), when mix | blending an organic solvent (C-1) as said diluent (C). % Or less, preferably 0.5 to 5% by mass. When the blending amount exceeds 10% by mass, the coating film characteristics of the curable resin composition deteriorate, which is not preferable.

  The curable resin composition of the present invention includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. Polymerization initiation assistants such as tertiary amines can be added.

  Furthermore, the curable resin composition of the present invention may contain an ultrafine inorganic filler such as nano silica or an inorganic pigment such as titanium oxide. It is preferable that these compounding quantities are 30 mass parts or less with respect to 100 mass parts of non volatile matters of a curable resin composition. When the blending amount exceeds 30 parts by mass, the viscosity of the curable resin composition is increased, so that it is difficult to apply a pattern using an ink jet printer, and the curability of the resin composition is decreased. Absent.

  In addition to the above, the curable resin composition of the present invention includes guanamines such as dicyandiamide, o-tolylbiguanide, guanamine, acetoguanamine, and benzoguanamine, antioxidants such as melamine, anthraquinone, perylene, disazo, and isoazo. Various additives such as organic pigments such as indoline and phthalocyanine, antifoaming agents, adhesion-imparting agents, leveling agents, and pigment dispersants can be blended. The compounding quantity of these additives is 5 mass parts or less with respect to 100 mass parts of non volatile matters of curable resin composition. When the blending amount exceeds 5 parts by mass, the viscosity of the curable resin composition is increased, so that it is difficult to apply a pattern using an ink jet printer, and the curability of the resin composition is decreased. Absent.

The inkjet curable resin composition of the present invention and the printed wiring board having the cured product are produced, for example, by the following procedure.
That is, first, each component of the curable resin composition is uniformly mixed and dispersed using a stirrer or a disperser such as a roll mill, a sand mill, a ball mill, a bead mill, or an attritor. Then, the viscosity of the mixed and dispersed composition is adjusted with a diluent (C) so that it is 150 mPa · s or less, preferably 110 to 5 mPa · s at 25 ° C., and the curable resin composition for inkjet according to the present invention is used. Make a thing.

  And the pattern of the said curable resin composition is drawn on the printed wiring board surface in which the circuit was formed using the inkjet printer. Then, the resist pattern which is hardened | cured material excellent in heat resistance etc. can be obtained by thermosetting the said pattern at 100-200 degreeC, Preferably 140-180 degreeC for 10 to 60 minutes. Moreover, in the thermosetting resin composition for inkjets of the present invention, a polymerizable monomer (C-2) is used as the diluent (C), and further, the radical polymerization initiator that generates radicals upon irradiation with active energy rays is blended. In such a case, an ink jet printer is used to draw a pattern of the curable resin composition on the surface of the printed circuit board on which the circuit has been formed, and then the pattern is irradiated with active energy rays such as ultraviolet rays to photocure it. By doing so, it is possible to form a pattern with little blurring. And the resist pattern which is a hardened | cured material excellent in heat resistance can be obtained by thermosetting the said photocured pattern at 100-200 degreeC, Preferably it is 140-180 degreeC for 10 to 60 minutes.

  As the ink jet printer, an on-demand piezo ink jet printer can be used. When the ink jet printer is used, the nozzle can be applied by heating to a room temperature or about 60 ° C. or less.

  As the irradiation light source of the active energy ray, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is preferably used. Laser beams and the like can also be used as active energy rays.

  As described above, when a printed wiring board is produced using the curable resin composition for inkjet of the present invention, it does not require a complicated process as in the conventional alkali development type liquid solder resist composition. It is possible to provide a highly reliable printed wiring board that is inexpensive and has no adhesion of ionic substances or the like.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited only to these Examples. In the following, “part” means part by mass unless otherwise specified.

Selection of bisallylnadiimide compound (A) About the bisallylnadiimide-1 represented by the following general formula (13) from which a production lot differs, it mix | blended in the component and ratio which are shown in Table 1, and stirred this with the dissolver. The stirrer was filtered using a 1 μm disk filter to obtain the compositions of Examples 1 to 3.

ビスマレイミド−１：ビス（３−エチル−５−メチル−４−マレイミドフェニル）メタン
アクリレート−１：１，４−ブタンジオールジアクリレート
アクリレート−２：４−ヒドロキシブチルアクリレート
アクリレート−３：トリメチロールプロパントリアクリレート

Bismaleimide-1: bis (3-ethyl-5-methyl-4-maleimidophenyl) methane acrylate-1: 1,4-butanediol diacrylate acrylate-2: 4-hydroxybutyl acrylate acrylate-3: trimethylolpropane tri Acrylate

500 g of each of the compositions of Examples 1 to 3 was placed in a 500 ml brown glass bottle, and the stopper was completely closed and sealed. Next, after each glass bottle was stored in a storage cabinet at a temperature of 50 ° C. for 7 days, the glass bottle was returned to room temperature, and then the state of each composition was visually observed and evaluated as follows. The results are shown in Table 2.
○: No change such as thickening is observed Δ: Clear thickening is observed ×: Solidified

  As shown in Table 2, it can be seen that the composition in which the production lots of bisallylnadiimide-1 of Example 1 and Example 2 were blended did not show changes such as thickening, and had good storage stability. On the other hand, it can be seen that bisallylnadiimide-1 in the production lot of Example 3 had a problem in storage stability.

  Then, the composition and ratio which are shown in Table 3 using the bisallyl nadiimide-1 of the production lot 3 which produced the problem in storage stability, and the bisallyl nadiimide-1 of the production lot 1 with good storage stability. And the mixture was stirred with a dissolver. The agitated material was filtered using a 1 μm disk filter, and compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were obtained.

＜ビスマレイミド化合物（Ｂ）＞
ビスマレイミド−１：ビス（３−エチル−５−メチル−４−マレイミドフェニル）メタン
＜希釈剤（Ｃ）＞
アクリレート−１：１，４−ブタンジオールジアクリレート
アクリレート−２：４−ヒドロキシブチルアクリレート
アクリレート−３：トリメチロールプロパントリアクリレート
＜開始剤＞
開始剤−１：ＢＡＳＦ社製イルガキュア３７９
＜ヒドロキノン、ヒドロキノン誘導体（Ｄ）＞
ヒドロキノン誘導体−１：ｐ−メトキシフェノール
ヒドロキノン誘導体−２：２−メチルヒドロキノン
ヒドロキノン誘導体−３：２，５ジ−ｔ−ブチルヒドロキノン
＜添加剤＞
アミン−１：ジアザビシクロウンデセン（酸性を塩基性で中和する目的で添加）

<Bismaleimide compound (B)>
Bismaleimide-1: bis (3-ethyl-5-methyl-4-maleimidophenyl) methane <Diluent (C)>
Acrylate-1: 1,4-butanediol diacrylate acrylate-2: 4-hydroxybutyl acrylate acrylate-3: trimethylolpropane triacrylate <initiator>
Initiator-1: Irgacure 379 manufactured by BASF
<Hydroquinone, hydroquinone derivative (D)>
Hydroquinone derivative-1: p-methoxyphenol hydroquinone derivative-2: 2-methylhydroquinone hydroquinone derivative-3: 2,5 di-t-butylhydroquinone <additive>
Amine-1: Diazabicycloundecene (added for the purpose of neutralizing acidity with basicity)

500 g of each composition of Examples 1 to 6 and Comparative Examples 1 to 5 was placed in a 500 ml brown glass bottle, and the stopper was completely closed to make it sealed. Next, after each glass bottle was stored in a storage cabinet at a temperature of 50 ° C. for 7 days, the glass bottle was returned to room temperature, and then the state of each composition was visually observed and evaluated as follows. The results are shown in Table 4.
○: No change such as thickening is observed Δ: Clear thickening is observed ×: Solidified

<Heat and chemical resistance test>
Using Fujifilm inkjet printer Dimatix Materials Printer DMP-2831, copper-clad laminate for printed wiring board (FR-4 thickness 1.6 mm, size 150 × 95 mm), Examples 1 to 6 and Comparative Example 1 A rectangular pattern having a size of 10 × 20 mm was printed with the composition No. 5 so that the film thickness was 10 μm. Immediately thereafter, the pattern was irradiated with UV at a cumulative light quantity of 1000 mJ / cm ² using a high-pressure mercury lamp. Next, the UV-irradiated pattern was heated and cured at 180 ° C. for 30 minutes in a hot-air circulating drying oven to obtain each test piece.

In order to evaluate the heat resistance and chemical resistance of the heat-cured pattern, rosin flux was applied to each test piece, and this was immersed in a solder bath at 260 ° C. for 10 seconds. Thereafter, each test piece taken out from the solder bath was naturally cooled, and further immersed in propylene glycol monomethyl ether acetate for 10 minutes for cleaning. The state of the coating film (pattern) of each test piece after washing was visually evaluated as follows. The results are shown in Table 5.
○: No change is observed in the coating film Δ: Slightly floating, peeling is seen ×: Clear peeling is seen

<Insulation test>
The compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were the above except that the comb-type electrode B coupon of the IPC B-25 test pattern was used instead of the copper-clad laminate, and the film thickness was 40 μm. Each test piece was produced by the same method as described in the heat resistance / chemical resistance test. A DC 500 V bias was applied to each test piece, and the insulation resistance value was measured. When the insulation resistance value of each test piece was 100 GΩ or more, it was evaluated as ◯, and when it was less than 100 GΩ, it was rated as x. The results are shown in Table 5.

  As described above, the curable resin composition for inkjet of the present invention can form a cured product having excellent heat resistance, chemical resistance, and insulation. Moreover, the curable resin composition for inkjet of the present invention is a curable resin composition that can prevent gelation and has excellent storage stability regardless of the production lot of bisallylnadiimide.

Claims (13)

(A) a bisallylnadiimide compound represented by the following general formula (1);

(In the formula, R ¹ represents an alkyl group, aryl group or aralkyl group having 2 to 18 carbon atoms.)
(B) a bismaleimide compound represented by the following general formula (2);

(Wherein R ² represents an alkyl group having ^{2 to} 32 carbon atoms, an aryl group or an aralkyl group);
(C) a diluent;
(D) A curable resin composition for inkjet containing at least one of hydroquinone and a hydroquinone derivative,
A curable resin composition for inkjet, having a viscosity of 150 mPa · s or less at 25 ° C. The bisallylnadiimide compound (A-1) obtained by heating and dehydrating the amic acid compound represented by the following general formula (3) as the bisallylnadiimide compound (A)

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
And a bisallylnadiimide compound (a-2) obtained by adding a diamine compound represented by the following general formula (5) to the allyl nadic acid anhydride represented by the following general formula (4) to cause a dehydration reaction

(In the formula, R represents an alkyl group having 2 to 32 carbon atoms, an aryl group, or an aralkyl group.)
The curable resin composition for inkjet according to claim 1, comprising at least one of the following.   The curable resin composition for inkjet according to claim 1, wherein the diluent (C) is at least one of an organic solvent (C-1) and a polymerizable monomer (C-2).   The said polymerizable monomer (C-2) has at least one of an acryloyl group and a methacryloyl group, The curable resin composition for inkjets of Claim 3 characterized by the above-mentioned.   The blending amount of the bisallylnadiimide compound (A) is 30 to 96 with respect to the blending amount of the components of the curable resin composition for inkjet excluding the bisallylnadiimide compound (A) and the organic solvent (C). The curable resin composition for inkjet according to any one of claims 1 to 4, wherein the curable resin composition is for ink jetting.   The said bismaleimide compound (B) is 4 to 45 mass parts with respect to 100 mass parts of the said bisallyl nadiimide compound (A), It is for inkjets of any one of Claim 1 thru | or 5 characterized by the above-mentioned. Curable resin composition.   The curing for inkjet according to any one of claims 1 to 6, wherein the diluent (C) is blended in an amount of 25 to 1900 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A). Resin composition.   The polymerizable monomer (C-2) is blended in an amount of 25 to 200 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound (A), according to any one of claims 1 to 7. Curable resin composition for inkjet.   The at least one (D) of the said hydroquinone and a hydroquinone derivative is mix | blended 0.04-0.5 mass part with respect to 100 mass parts of said bisallyl nadiimide compounds (A), The Claim 1 thru | or 8 characterized by the above-mentioned. Curable resin composition for inkjet.   It is obtained by applying the curable resin composition for inkjet according to any one of claims 1 to 9 on a substrate by using an inkjet printer to form a coating film, and thermally curing the coating film. Hardened | cured material of the curable resin composition for inkjet characterized by these.   The ink-jet curable resin composition according to claim 4 is applied onto a substrate by using an ink-jet printer to form a coating film, and the coating film is irradiated with ultraviolet rays to be photocured and the photocured. A cured product of a curable resin composition for inkjet, which is obtained by thermally curing a coating film.   A solder resist pattern is formed on a printed wiring board, and the curable resin composition for inkjet according to any one of claims 1 to 9 is applied onto the solder resist pattern using an inkjet printer to form a coating film. A printed wiring board comprising a cured product obtained by forming and thermally curing the coating film.   A solder resist pattern is formed on the printed wiring board, and the curable resin composition for inkjet according to claim 4 is applied onto the solder resist pattern using an inkjet printer to form a coating film. A printed wiring board characterized by having a cured product obtained by irradiating ultraviolet rays to photocure it and thermally curing the photocured coating film.