JP5619368B2 - Curable resin composition for inkjet - Google Patents

Description

  The present invention relates to a curable resin composition for inkjet used in the production of printed wiring boards, the cured product thereof, and a printed wiring board using the same.

  At present, resist ink compositions for some consumer printed wiring boards and most industrial printed wiring boards, from the viewpoint of high accuracy and high density, form images by developing after irradiation with ultraviolet rays, heat and A liquid development type curable resin that undergoes final curing (main curing) by light irradiation is used. In consideration of environmental problems, an alkali development type liquid curable resin using a dilute alkaline aqueous solution as a developing solution has become mainstream. Examples of the alkali development type resist ink composition using such a 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 novolak type epoxy resin and an unsaturated group-containing monocarboxylic acid. A resist ink composition comprising a photopolymerization initiator, a diluent and an epoxy resin is disclosed (for example, see Patent Document 1).

  However, these curable resin compositions are two-component due to the high reactivity of the carboxyl group-containing photosensitive resin and the epoxy resin, and have the disadvantage that they must be mixed before use and used within a few days. is there.

  Further, these curable resin compositions require many steps such as coating, drying, exposure, development, and thermosetting. And these processes have the fault that manufacturing cost is required because equipment such as a coating machine, a dryer, an exposure machine, a developing machine, and a thermosetting furnace is required.

  For this reason, a method has been proposed in which a curable resin pattern is created by drawing with an inkjet printer and drying (see, for example, Patent Document 2). When drawing with such an ink jet printer, a complicated process such as an alkali developing type curable resin is not required, so the printed wiring board has high reliability and is inexpensive and free from adhesion of ionic substances. Can be provided. However, the viscosity of the ink of the screen printing method is 2,000 to 15,000 mPa · s (25 ° C.), whereas the viscosity of the ink jet ink is as low as 1 to 150 mPa · s (25 ° C.). Therefore, in such a method, since the viscosity of the ink is further lowered by heat during drying, blurring occurs, sufficient pattern formation accuracy cannot be obtained, and practical use has not been achieved.

  In order to reduce the viscosity, it is conceivable to mix a low molecular weight compound. However, for example, when an epoxy resin such as trimethylolpropane triglycidyl ether or triallyl isocyanurate (TAIC) is used as a diluent, sufficient heat resistance and curability cannot be obtained.

  A bisallylnadiimide compound can be used as a relatively low molecular weight compound having heat resistance, but it is usually necessary to cure at a high temperature of about 250 ° C. Thus, a method of curing using a peroxide has been proposed (see, for example, Patent Document 3). However, when a composition using a peroxide is used for a printed wiring board, oxidation of the metal surface such as copper foil becomes intense, resulting in a problem that the physical properties are lowered.

  Thus, there has been proposed a composition that lowers the curing temperature while realizing a viscosity applicable to ink jetting by using a combination of the bisallylnadiimide compound and a bismaleimide compound that is a low molecular weight compound (for example, Patent Document 4) reference).

  Such a composition can be patterned without blurring by using both photocuring and thermosetting, and has high reliability as an insulator of a wiring board using silver as an electric wiring material by increasing the crosslinking density. Can be obtained. In other words, silver is more likely to migrate than other metals for electrical wiring, such as copper. Although the resistance decreases, the occurrence of early migration is suppressed and a long life is obtained.

  However, since such a composition has a large cure shrinkage and the cured product is hard and brittle, it is difficult to apply it to a very thin material or a flexible material. Has the problem of cracking.

JP 61-243869 (Claims) JP-A-7-263845 (Claims) JP-A-7-18031 (Claims) WO2006 / 0775654 (Claims)

  The present invention has been made in view of such problems, and can be reduced in viscosity, excellent in workability and storage stability, and cured in excellent heat resistance, chemical resistance, migration resistance, and flexibility. It is in providing the curable resin composition for inkjet which can obtain, and its hardened | cured material and a printed wiring board using the same.

（式中、Ｒ^１は、炭素数２〜１８のアルキレン基、アリーレン基又はアラルキレン基を示す）
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のアルキレン基、アリーレン基又はアラルキレン基を示す）。 In order to achieve the above object, as a basic aspect of the present invention, a bisallylnadiimide compound represented by the following general formula (1):

(In the formula, ^{R 1,} an alkylene group having 2 to 18 carbon atoms, arylene group or represents an aralkyl alkylene group)
A bismaleimide compound represented by the following general formula (2);

(Wherein, ^{R 2} is alkylene group having 2 to 32 carbon atoms, arylene group or represents an aralkyl alkylene group).

（式中、Ｒ^３は、水素原子及び又はメチル基、Ｒ^４は、炭素数２〜１２のアルキレン基とシクロヘキシレン基を示す）
光重合開始剤を含み、粘度が２５℃で１〜１５０ｍＰａ・ｓの範囲であるインクジェット用硬化性樹脂組成物であって、前記光重合開始剤がヒドロキシアルキルフェノン系、アミノアルキルフェノン系、オキシム系のいずれか１種または２種以上からな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が提供される。 A hydroxy (meth) acrylate compound represented by the following general formula (3) and 300 to 3000 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound,

(Wherein, ^{R 3} is a hydrogen atom and or a methyl group, ^{R 4} represents an alkylene group and cycloalkylene hex alkylene group having 2 to 12 carbon atoms)
Includes a photopolymerization initiator, a viscosity of the inkjet curable resin composition is in the range of 1~150mPa · s at 25 ° C., the photopolymerization initiator hydroxycarboxylic alkyl phenone, aminoalkyl phenone, any one or jet curable resin composition characterized Rukoto such two or more oxime is provided.

With such a configuration, it is possible to apply by inkjet , and it is possible to obtain a cured product having excellent workability and storage stability, and excellent heat resistance, chemical resistance, migration resistance, and flexibility.

  By containing the said hydroxy (meth) acrylate compound, a flexibility can be provided to a composition and high heat resistance can be maintained. Moreover, since it is highly compatible with bisallylnadiimide and bismaleimide, good storage stability can be obtained without settling of the composition.

  As such a hydroxy (meth) acrylate compound, 4-hydroxybutyl acrylate is particularly preferable. Furthermore, as the photopolymerization initiator, it is preferable to use an acetophenone series, an oxime series, particularly an α-hydroxyacetophenone series from the viewpoint of the curing degree.

  According to still another aspect of the present invention, a cured product obtained by drawing the curable resin composition for inkjet in a desired pattern with an inkjet printer, irradiating with ultraviolet rays, photocuring, and heat treatment, and such A printed wiring board having an insulating layer made of a hardened material is provided.

  According to one embodiment of the present invention, the curable resin composition for inkjet has excellent storage stability and can be reduced in viscosity, so that it can be stably applied using an inkjet printer and can be obtained. In a product, sufficient heat resistance, chemical resistance, migration resistance, and flexibility can be obtained. In addition, it is possible to improve the productivity and reduce the cost of a printed wiring board manufactured using the curable resin composition for inkjet.

As a result of intensive studies to solve these problems, the present inventors have obtained a bisallylnadiimide compound represented by the general formula (1), a bismaleimide compound represented by the general formula (2), and a general formula (3). hydroxy (meth) acrylate compound represented, hydroxycarboxylic alkyl phenone, aminoalkyl phenone, comprising a photopolymerization initiator ing from any one or more of the oxime, a viscosity of 25 ℃ 1~150mPa -The composition which is the range of s finds that it can apply | coat with an inkjet in the state which maintained the characteristic required for the curable resin used for a printed wiring board, marking ink, and an insulating material for a flexible use, and this invention It has come to be completed.

  That is, the bisallyl nadiimide compound represented by the general formula (1) is excellent in heat resistance and has a relatively low molecular weight, so that it is required to have low viscosity in addition to heat resistance. It is suitable as a thermosetting resin component that constitutes an insulator for marking ink and other flexible applications.

  Furthermore, by using together with the bismaleimide compound represented by the general formula (2), 100 to 200 ° C., preferably 140 to 140 ° C., which is generally used in printed wiring boards from around 250 ° C. when the curing temperature is used alone. It becomes possible to make it 180 degreeC. Moreover, by using together with a bismaleimide compound, crystallization of the bismaleimide compound is lowered, and further, by adding a hydroxy (meth) acrylate compound, a liquid composition having low viscosity and excellent one-component stability is provided. It becomes possible.

  Furthermore, by adding 300 to 3000 parts by mass of a hydroxy (meth) acrylate compound to 100 parts by mass of the bisallylnadiimide compound, heat resistance, chemical resistance, migration required for insulating materials for printed wiring boards Despite having resistance, it is possible to provide flexibility that is difficult to be compatible with these. In addition, since the effect of reducing the crystallinity of the bisallylnadiimide compound and the bismaleimide compound is also obtained, an excellent stability composition can be obtained without crystallizing not only at room temperature but also in winter and storage in a refrigerator. It is done.

  In addition, by using a photopolymerization initiator, it is possible to instantly solidify or increase the viscosity of the composition by irradiating an active energy ray such as UV light after coating. The pattern can be held without flowing with time, and a high-definition pattern can be held even when heated in a subsequent process.

（式中Ｒ^１は炭素数２〜１８のアルキレン基、アリーレン基、又はアラルキレン基を示す）で示される化合物であり、特に好ましいものとしてＲ^１が下式（４）、（５）、（６）及び（７）

で示される化合物のいずれかであり、具体的には、ＢＡＮＩ−Ｍ、ＢＡＮＩ−Ｈ、ＢＡＮＩ−Ｘ、ＢＡＮＩ−Ｄ（いずれも丸善石油化学社製）等が挙げられる。これらビスアリルナジイミド化合物は単独又は２種類以上を混合して用いても良い。 Hereinafter, each component of the curable resin composition for inkjet according to the present embodiment will be described in detail. First, the bisallyl nadiimide compound used in this embodiment is

(Wherein ^{R 1} represents an alkylene group, arylene group, or an aralkyl alkylene group having 2 to 18 carbon atoms) is a compound represented by, ^{R 1} is the formula as particularly preferred (4), (5) , (6) and (7)

Specific examples thereof include BANI-M, BANI-H, BANI-X, and BANI-D (all manufactured by Maruzen Petrochemical Co., Ltd.). These bisallylnadiimide compounds may be used alone or in admixture of two or more.

（式中Ｒ^２は、炭素数２〜３２のアルキレン基、アリーレン基、又はアラルキレン基を示す）で示される化合物であり、特に好ましいものとしては、Ｒ^２が下記式（８）、（９）、（１０）、（１１）

で示される化合物のいずれかであり、具体的には、ＢＭＩ、ＢＭＩ−７０、ＢＭＩ−８０（いずれもケイ・アイ化成製）、ＢＭＩ−１０００、ＢＭＩ−３０００、ＢＭＩ−４０００、ＢＭＩ−５０００、ＢＭＩ−ＴＹＨ（いずれも大和化成工業社製）等が挙げられる。 The bismaleimide compound used in this embodiment is represented by the following general formula (2)

(Wherein ^{R 2} is an alkylene group having 2 to 32 carbon atoms, arylene group, or an aralkyl alkylene group) is a compound represented by, those particularly preferred, ^{R 2} is represented by the following formula (8), (9), (10), (11)

In particular, BMI, BMI-70, BMI-80 (all manufactured by KAI Chemical Industries), BMI-1000, BMI-3000, BMI-4000, BMI-5000, BMI-TYH (both manufactured by Daiwa Kasei Kogyo Co., Ltd.) and the like can be mentioned.

  These bismaleimide compounds may be used alone or in admixture of two or more, and the blending amount is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound. When the blend amount of the bismaleimide compound is less than 10 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound, the curability is lowered. When the amount exceeds 100 parts by mass, heat resistance and curability are lowered, crystallinity is increased, and clogging of the ink jet nozzle is caused. More preferably, it is 20-70 mass parts.

  If necessary, a polyfunctional maleimide compound derived from an aniline resin having an effect of improving curability, for example, BMI-2000 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) may be blended.

（式中、Ｒ^３は水素原子又はメチル基、Ｒ^４は２〜１２のアルキレン基又はシクロヘキシレン基を示す）であり、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシへキシル、（メタ）アクリル酸８−ヒドロキシオクチル、（メタ）アクリル酸１０−ヒドロキシデシル、（メタ）アクリル酸１２−ヒドロキシラウリル、（４−ヒドロキシメチルシクロへキシル）メチルアクリレートの如きヒドロキシル基含有モノマー等が挙げられる。特にＲ^３が水素原子で、Ｒ^４が２〜６のアルキル基及び又はシクロヘキシル基であるものが好ましい。より好ましいものは、4-ヒドロキシブチルアクリレートである。
The hydroxy (meth) acrylate compound used in this embodiment has the general formula (3)

(Wherein, ^{R 3} is a hydrogen atom or a methyl group, ^{R 4} represents a 2 to 12 alkylene group or a cyclohexyl alkylene group), 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 Hydroxypropyl, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (meth) acrylic 12 And hydroxyl group-containing monomers such as -hydroxylauryl and (4-hydroxymethylcyclohexyl) methyl acrylate. Particularly preferred are those wherein R ³ is a hydrogen atom and R ⁴ is an alkyl group and / or a cyclohexyl group of 2 to 6. More preferred is 4-hydroxybutyl acrylate.

  The compounding quantity of the said hydroxy (meth) acrylate compound needs to be 300-3000 mass parts with respect to 100 mass parts of said bisallyl nadiimide compounds. If it is less than 300, only a function as a diluent can be obtained, and a flexible cured product cannot be obtained. On the other hand, when it exceeds 3000, it becomes difficult to obtain sufficient heat resistance. Preferably it is 800-2000 mass parts.

  As these preparation methods, it is preferable to add so that a bisallyl nadiimide compound and a bismaleimide compound may be dissolved, and then add a hydroxy (meth) acrylate compound and a photoinitiator.

  In order to cure the curable resin composition for inkjet of this embodiment, a photopolymerization initiator that generates radicals by irradiation with active energy rays is blended. As such a photopolymerization initiator, known polymerization initiators can be used. For example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy- 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-1- {4- (2-hydroxy-2-methyl-propionyl) -2-methyl-propane- Acetophenones such as 1-one; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one, N, N-dimethylamino Aminoacetophenones such as acetophenone, 2- (dimethylamino) -2-{(4-methylphenyl) methyl} -1- {4- (4-morpholinyl) phenyl} -1-butanone; 2-methylanthraquinone, 2- Anthraquinones such as ethyl anthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone Ketals such as dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4′-bisdiethylaminobenzophenone or xanthones; 2,4,6-trimethylbenzoyldiphenylphosphine oxa And halomethyl oxames such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole Diazole compounds; 2,4-bis (trichloromethyl) -6- (p-methoxy-phenylvinyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl Halomethyl-s-triazine compounds such as -s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 1,2- Octanedione, 1-[-4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) 9H-cal Zone --3-yl] -1- (O-acetyl oxime), and the like.

  Among them, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl is used to instantly solidify or increase the viscosity of the composition. -Propan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, and photopolymerization of oximes An agent is desirable.

  It is preferable that such a photoinitiator is 10-500 mass parts with respect to 100 mass parts of bisallyl nadiimide compounds. If it is less than 10, it becomes difficult to solidify or increase the viscosity after irradiation with active energy rays. If it exceeds 500, absorption of the active energy ray of the photopolymerization initiator itself becomes large, and it becomes difficult to solidify or increase the viscosity. More preferably, it is 20-400.

  Further, an acrylate monomer may be added. By adding an acrylate monomer, solidification or high viscosity can be promoted when irradiated with active energy rays. Moreover, the function as a diluent can also be obtained by selecting a low-viscosity acrylate monomer.

  Such acrylate monomers include 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, methoxydiethylene glycol (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, 1,9-nonanediol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- ( T) Acryloyloxymethyl-2-isobutyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, trimethylolpropane tri (meth) acrylate, trimethylol Acryloyl group in one molecule such as propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like A compound having one or more methacryloyl groups can be mentioned, and these can be used alone or in combination of two or more. Among these, a compound having a viscosity of 300 mPa · s or less at 25 ° C. is preferable.

  An organic solvent may be added for the purpose of adjusting the viscosity. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; 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 acetate, charcoal Esters such as propylene, octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, petroleum solvents such as solvent naphtha, a known organic solvent can be used. These organic solvents can be used alone or in combination of two or more.

  Further, if necessary, guanamines such as dicyandiamide, o-tolylbiguanide, guanamine, acetoguanamine, benzoguanamine, and antioxidants such as melamine; organics such as anthraquinone, perylene, disazo, isoindoline, phthalocyanine Various additives such as a pigment, an antifoaming agent, an adhesion-imparting agent, a leveling agent, and a pigment dispersant may be blended.

  The ink-jet curable resin composition obtained by blending these components uses a stirrer or a disperser such as a dissolver, a planetary mixer, a roll mill, a sand mill, a ball mill, a bead mill, a homogenizer, or an attritor. And mixed and dispersed until uniform.

  Thus, the obtained curable resin composition for inkjets of this embodiment is further adjusted so that the viscosity may be 1-150 mPa * s at 25 degreeC. When adjusted to less than 1 mPa · s, the component of the diluent in the composition increases, and it becomes difficult to obtain the desired thickness of the cured product, and the heat resistance of the cured product may be inferior. When it exceeds 150 mPa · s, application with an ink jet printer becomes difficult. More preferably, it is 5-110 mPa * s.

  Using the ink-jet curable resin composition of the present embodiment prepared in this manner, for example, a desired pattern is drawn with an ink-jet printer on the surface of a printed wiring board on which a circuit is formed, and active energy rays such as ultraviolet rays are used. Is irradiated and photocured. Furthermore, a cured product can be obtained by thermosetting at 100 to 200 ° C., preferably 140 to 180 ° C. for 10 to 60 minutes.

  As the ink jet printer, an on-demand piezo ink jet printer is preferably used because the nozzle can be applied at room temperature or at a temperature of about 60 ° C. or lower. Thus, by heating the nozzle, if the viscosity of the composition is 150 mPa · s or less, the viscosity can be adjusted to 30 mPa · s or less that can be applied.

  Moreover, as the irradiation source of the active energy ray, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is suitable, and a laser beam or the like can also be used as the active energy ray.

  The cured product thus obtained is excellent in heat resistance, Ag migration resistance, and flexibility, and is also excellent in adhesion to resist ink and marking ink applied later, and an insulator for flexible use. And by applying by inkjet, it becomes possible to simplify the manufacturing process of the printed wiring board, improve the productivity, and also reduce the maintenance cost of the equipment, so the cost of the obtained printed wiring board can be reduced It becomes.

  Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited to these Examples. In the following description, “part” means part by mass unless otherwise specified.

このようにして得られた組成物について、以下のようにして評価を行った。 The blending components shown in Table 1 below were mixed and stirred, and filtered through a 1 μm filter to obtain a curable resin composition for inkjet.

The composition thus obtained was evaluated as follows.

(1) Viscosity measurement About each curable resin composition obtained as mentioned above, the viscosity was measured at 23 degreeC using the CBC Materials viscomate VM-100A probe L. As shown in FIG. The results are shown in Table 2. The viscosity is
Viscosity (mPa · s) = kinematic viscosity (mm ² / s) × specific gravity. As shown in Table 2, in Examples 1 to 8, good viscosity could be obtained. On the other hand, in Comparative Example 2 that does not contain hydroxymethacrylate and does not contain a low-viscosity acrylate monomer, it can be seen that a viscosity that can be applied by inkjet cannot be obtained.

(2) Low temperature storage property The obtained composition was left to stand in a refrigerator at 5 ° C. for 30 days, and the presence or absence of precipitates was confirmed at the bottom of the storage bottle, and evaluated according to the following criteria.
◯: No precipitate Δ: Some precipitate is seen ×: Cannot be stored at 5 ° C. The results are shown in Table 2. As shown in Table 2, in Examples 1 to 8, good low temperature storage properties could be obtained. On the other hand, in Comparative Examples 1 and 2 not containing hydroxymethacrylate, it can be seen that good low-temperature storage stability is not obtained.

Furthermore, for each composition, a circuit-formed polyimide printed wiring board with a thickness of 50 μm was uniformly applied to the entire surface with an on-demand piezo-type inkjet printer to a thickness of 20 μm, and accumulated in a UV conveyor furnace. After irradiating with a light amount of 2000 mJ / cm ² , a test piece was prepared by thermosetting at 180 ° C. for 30 minutes in a hot-air circulating drying furnace. The prepared test piece was evaluated as follows. In Comparative Example 2, a test piece could not be produced.

(3) Warpage A test piece was cut out to 5 cm x 5 cm, and the amount of warpage was measured with a vernier caliper on a horizontal table, and evaluated according to the following criteria.
○: Less than 5 mm Δ: 5 mm or more and less than 15 mm ×: 15 mm or more The results are shown in Table 2. As shown in Table 2, as shown in Table 2, in Examples 1 to 8, the amount of warping could be suppressed. On the other hand, in Comparative Example 1 containing no hydroxymethacrylate, it can be seen that the amount of warpage increases.

(4) Bending Resistance The bending resistance of the test piece was evaluated according to the following criteria under the condition of 1/8 inch diameter and 10 cycles according to IPC-SM-849BTM2.4.29.
○: The cured coating film has no cracks Δ: The cured coating film has some cracks ×: The cured coating film has cracks The results are shown in Table 2. As shown in Table 2, no crack was observed in the cured coating film in any of the test pieces.

(5) Pencil hardness The pencil hardness on the Kapton substrate was evaluated according to the test method of JISK5600-5-4. The results are shown in Table 2. As shown in Table 2, in Examples 1-8, good pencil hardness was obtained.

(6) After the solder heat-resistant cured coating film was immersed in a 260 ° C. solder bath for 5 seconds, the coating film state after a peeling test using a cellophane tape was evaluated according to the following criteria.
○: No change in the coating film Δ: The coating film is discolored, etc. ×: The coating film is peeled off The results are shown in Table 2. As shown in Table 2, in Examples 1 to 8, good solder heat resistance could be obtained.

(7) Rubbing test A rubbing test was conducted 50 times with a waste impregnated with an organic solvent (propylene glycol monomethyl ether acetate), and the following criteria were evaluated.
○: No peeling at all Δ: Thin peeling off ×: Completely peeling off Table 2 shows the results. As shown in Table 2, in Examples 1 to 8, good organic solvent resistance could be obtained.

(8) Electrical properties Uniformly applied to a 50 μm thick polyimide printed wiring board with IPC B-25 test pattern comb-shaped electrode B coupons to a thickness of 20 μm on the entire surface with an on-demand piezo inkjet printer. Then, after irradiation with a cumulative light quantity of 2000 mJ / cm ² in a UV conveyor furnace, a test piece was prepared by thermosetting at 180 ° C. for 30 minutes in a hot-air circulating drying furnace. A DC 500 V bias was applied to the test piece, and the insulation resistance value was measured. The results are shown in Table 2. As shown in Table 2, in Examples 1-8, it turns out that favorable insulation resistance is obtained.

Claims (4)

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

(In the formula, ^{R 1,} an alkylene group having 2 to 18 carbon atoms, arylene group or represents an aralkyl alkylene group)
A bismaleimide compound represented by the following general formula (2);

(Wherein, ^{R 2} is alkylene group having 2 to 32 carbon atoms, arylene group or represents an aralkyl alkylene group)
A hydroxy (meth) acrylate compound represented by the following general formula (3) and 300 to 3000 parts by mass with respect to 100 parts by mass of the bisallylnadiimide compound,

(Wherein, ^{R 3} is a hydrogen atom and or a methyl group, ^{R 4} represents an alkylene group and cycloalkylene hex alkylene group having 2 to 12 carbon atoms)
A curable resin composition for inkjet which contains a photopolymerization initiator and has a viscosity in the range of 1 to 150 mPa · s at 25 ° C.,
The photopolymerization initiator, hydroxycarboxylic alkyl phenone, aminoalkyl phenone, any one or jet curable resin composition characterized Rukoto such two or more oxime. The hydroxy (meth) acrylate compounds, jet hardening resin composition according to claim 1 which is 4-hydroxybutyl acrylate.   The hardened | cured material obtained by apply | coating the curable resin composition for inkjets of Claim 1 or Claim 2 with an inkjet printer, irradiating an ultraviolet-ray and carrying out photocuring, and also thermosetting.   The printed wiring board which has an insulating layer obtained by apply | coating the curable resin composition for inkjets of Claim 1 or Claim 2 with an inkjet printer, irradiating an ultraviolet-ray and carrying out photocuring, and also thermosetting.