KR101523160B1 - Photocurable／thermosetting inkjet composition, and printed wiring board using same - Google Patents

Abstract

According to the present invention, there is provided a process for producing a photopolymerizable composition comprising a monomer having a (meth) acryloyl group and a glycidyl group in a molecule and having a viscosity at 25 DEG C of 10 mPa.s or less, an acrylate monomer having three or more functional groups, Wherein the photo-curable thermosetting composition for inkjet is provided. Further, there is provided a photocurable thermosetting composition containing titanium oxide in the above composition, which is used for patterning on a resin insulating layer formed on a printed wiring board.

Description

TECHNICAL FIELD [0001] The present invention relates to a photocurable thermosetting composition for inkjet, and a printed circuit board using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a photo-curable thermosetting composition for use in forming a resin insulating layer, which is suitable for directly drawing an insulating layer or a pattern as a marking on a substrate for a printed circuit board by using an inkjet printer, And a resin insulating layer formed using the resin insulating layer.

As a manufacturing method of a printed wiring board using an ink jet printer, there is a method of forming a conductor circuit in which an etching resist is formed by using, for example, an ink jet printer on a metal foil on a plastic substrate and subjected to an etching treatment (Japanese Patent Application Laid- Japanese Patent Application Laid-open No. 56-157089, Japanese Patent Laid-Open Nos. 58-50794 and 6-237063). This method directly draws the pattern on the metal foil in accordance with the CAD data. Therefore, compared with the case of patterning by the photographic developing method using a photosensitive resin in which a photomask is essential and patterning the resist ink by the screen printing method, The labor and time required for the manufacturing process can be greatly shortened, and consumption of a developing solution, a resist ink, a cleaning solvent, and the like can be reduced.

In addition, a method of forming a resin insulating layer such as a solder resist for protecting a conductor circuit formed on a printed wiring board using an inkjet printer has already been proposed (Japanese Patent Laid-Open Nos. 7-263845 and 9-18115 Reference). The forming method is the same as the above-described method of forming the etching resist. Even when the inkjet method is used, the number of steps, time, and consumables can be reduced as compared with the photographic developing method and the screen printing method. Further, the ink tank of the ink jet printer is divided into each of the ink for the etching resist, the solder resist ink, the marking ink, and the curing agent thereof, and provided in the inkjet printer so that a plurality of processes can be performed by one inkjet printer (See Japanese Patent Application Laid-Open No. 8-236902).

However, the ink used for the ink-jet printer needs to have a viscosity of about 20 mPa · s or less at the time of application. On the other hand, the viscosity of the ink used for screen printing is around 20,000 mPa · s, and there is a large difference in the viscosity of both. Therefore, even when the resist ink for screen printing is diluted with a large amount of diluent, it is difficult to lower the viscosity of the ink for use in an inkjet printer. Further, even if the viscosity of the resist ink can be lowered to 20 mPa 占 퐏, for example, the physical properties such as heat resistance and chemical resistance required for the resin insulating layer such as solder resist are significantly deteriorated. In addition, when the resist ink is diluted with a volatile solvent, the nonvolatile content becomes very small, so that it becomes difficult to secure a predetermined film thickness when the resist ink is applied to a substrate. As a method for forming the resin insulating layer of the printed wiring board, there is no resin composition such as a resist ink for forming a practical resin insulating layer, which can be used in an inkjet printer without departing from the idea of the inkjet method.

With respect to this prior art, a resin composition containing a monomer having a (meth) acryloyl group and a thermosetting functional group, a photoreactive diluent having a weight average molecular weight of 700 or less, and a photopolymerization initiator and having a viscosity of 150 mPa · s or less at 25 ° C A photo-curable and thermosetting composition for ink jet which solves the above problems is known (International Publication WO2004 / 099272). According to this inkjet photocurable and thermosetting composition, an inkjet composition having heat resistance required as a solder resist can be obtained in spite of a low viscosity. In this resin composition, the adhesion property, chemical resistance, low temperature curability And further improvement was desired in terms of

Further, in recent years, the demand for white marking ink used in the above-mentioned inkjet method is increasing, but when the titanium oxide suitable as a white pigment is blended, the viscosity of the marking ink increases. As a countermeasure, it is common to employ a method of lowering the molecular weight of the resin composition, so that the adhesion between the marking pattern and the resin insulating layer is lowered and the marking pattern is peeled off from the resin insulating layer. As a result, there was no practical white marking ink usable in an ink jet printer.

Japanese Patent Application Laid-Open No. 56-66089 Japanese Patent Application Laid-Open No. 56-157089 Japanese Patent Laid-Open No. 58-50794 Japanese Patent Laid-Open No. 6-237063 Japanese Patent Application Laid-Open No. 7-263845 Japanese Patent Laid-Open No. 9-18115 Japanese Patent Application Laid-Open No. 8-236902 International Publication WO2004 / 099272

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the conventional art described above. The first problem is to provide a photo-curable thermosetting composition for use in forming a resin insulating layer, Curable thermosetting composition capable of directly drawing a resin insulating layer pattern.

A second object of the present invention is to provide a photocurable thermosetting composition for inkjet comprising titanium oxide which is suitable for directly drawing a pattern as a marking by using an inkjet printer on a resin insulating layer such as solder resist formed on a printed wiring board .

A third object of the present invention is to provide a printed wiring board having a resin insulating layer formed by directly drawing a pattern on a substrate for a printed wiring board by using an inkjet printer using the photo-curable thermosetting composition for inkjet and curing the pattern have.

A fourth object of the present invention is to provide a printed wiring board having a marking pattern formed by forming a pattern of the above-mentioned photocurable thermosetting composition using an inkjet printer on a resin insulating layer formed on a printed wiring board and hardening the pattern.

More specifically, the first problem described above is a viscosity that can be used in an inkjet printer, and is excellent in heat resistance, chemical resistance, and the like required for the resin insulating layer, Curable thermosetting composition capable of thermosetting at a low temperature of 170 占 폚 or lower, preferably 150 占 폚 or lower.

More specifically, the second problem is a viscosity that can be used in an inkjet printer. The second problem is that the photocurable thermosetting composition capable of forming a pattern having good adhesion to the resin insulating layer formed on the printed wiring board even if titanium oxide is blended .

In order to solve the first problem, the inkjet photocurable thermosetting composition of the present invention comprises a monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 ° C of 10 mPa · s or less, Acrylate monomer, a thermosetting catalyst, and a photopolymerization initiator.

Another feature of the inkjet photocurable thermosetting composition of the present invention is that the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 DEG C of 10 mPa.s or less is glycidyl methacrylate or 4 - hydroxybutyl acrylate glycidyl ether.

Another characteristic feature of the ink-jet photo-curable thermosetting composition of the present invention is that in the ink-jet photo-curable thermosetting composition, the ink has a (meth) acryloyl group and a glycidyl group in the molecule and has a viscosity at 25 ° C of 10 mPa · s or less When the monomer is 100 parts by mass, 15 to 400 parts by mass, preferably 20 to 300 parts by mass of the trifunctional or higher functional acrylate monomer, 0.1 to 5 parts by mass, preferably 0.5 to 4 parts by mass of the thermosetting catalyst ≪ / RTI >

Here, the viscosity refers to the viscosity measured according to JIS K2283. The viscosity of the photo-curable thermosetting composition for inkjet is 150 mPa 占 퐏 or less at room temperature (25 占 폚). As described above, the viscosity of the ink used in the ink jet printer is required to be about 20 mPa s or less at the temperature at the time of coating. However, if the viscosity is 150 mPa 占 퐏 or less at room temperature, the above conditions can be satisfied by heating before or during coating. In the following description, the viscosity is used in the above-mentioned meaning.

In order to solve the second problem, the ink-jet photo-curable thermosetting composition for inkjet according to the present invention comprises a monomer having a (meth) acryloyl group and a glycidyl group in a molecule and having a viscosity at 25 ° C of 10 mPa · s or less, A photocurable thermosetting composition comprising an acrylate monomer, titanium oxide, a thermosetting catalyst, and a photopolymerization initiator, and is used for patterning on a resin insulating layer formed on a printed wiring board.

Another feature of the inkjet photocurable thermosetting composition of the present invention is that the photocurable thermosetting composition for inkjet comprising the titanium oxide is characterized in that it has a (meth) acryloyl group and a glycidyl group in the molecule and has a viscosity Is 10 mPa · s or less is glycidyl methacrylate or 4-hydroxybutyl acrylate glycidyl ether.

Another feature of the inkjet photocurable thermosetting composition of the present invention is that the photocurable thermosetting composition for inkjet comprising the titanium oxide is characterized in that it has a (meth) acryloyl group and a glycidyl group in the molecule and has a viscosity Is in the range of 15 to 400 parts by mass, preferably 20 to 300 parts by mass, and the thermosetting catalyst is used in an amount of 0.1 to 5 parts by mass, preferably 0.1 to 5 parts by mass, 0.5 to 4 parts by mass.

The printed wiring board of the present invention is characterized by having a resin insulating layer formed by drawing a pattern on a substrate by an inkjet printer using the photo-curable thermosetting composition for inkjet and curing the pattern.

The printed wiring board of the present invention is characterized by having a pattern formed by patterning the ink-jet photocurable thermosetting composition using an inkjet printer on a resin insulating layer formed on a printed wiring board and curing the pattern.

The photo-curable thermosetting composition for inkjet of the present invention comprises a monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 ° C of 10 mPa · s or less and a trifunctional or higher-functional acrylate monomer, Heat resistance, chemical resistance and adhesion of the resin insulating layer can be improved. Particularly, in a conventional inkjet resin composition, a photosensitive monomer (or a photosensitive thermosetting monomer) having a high viscosity is used, and in order to lower the composition to the predetermined viscosity (20 mPa · s), a monofunctional photosensitive It was common to form monomers. On the other hand, in the present invention, by using a monomer having a low viscosity, a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚 as the photosensitive thermosetting monomer, heat resistance, chemical resistance and adhesion It has become possible to blend an acrylate monomer having three or more functionalities with high viscosity.

Further, by incorporating a thermosetting catalyst, the photo-curable thermosetting composition for inkjet of the present invention can be cured at a heating temperature of 170 占 폚 or less, preferably 150 占 폚 or less, at the time of producing a printed wiring board. Thereby, the resin insulating layer can be formed without affecting the characteristics of the printed wiring board.

Further, the photo-curable thermosetting composition for inkjet of the present invention can be obtained by combining a monomer having a (meth) acryloyl group and a glycidyl group in a molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚 and an acrylate monomer having three or more functional groups, The adhesion of the marking pattern to the resin insulating layer formed on the printed wiring board can be improved even when titanium oxide is blended as the pigment. In particular, since the conventional inkjet resin composition uses a photosensitive monomer (or a photosensitive thermosetting monomer) having a high viscosity, the viscosity of the composition is further increased by adding titanium oxide as a white pigment thereto. Therefore, in order to lower the composition to the predetermined viscosity (20 mPa 占 퐏), a large amount of a monofunctional photosensitive monomer having a low viscosity must be blended, and a marking pattern having sufficient adhesion can not be formed. On the other hand, in the present invention, by using a monomer having a low viscosity, a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚 as the photosensitive thermosetting monomer, heat resistance, chemical resistance and adhesion It is possible to form a trifunctional or higher acrylate monomer having a high viscosity and to realize a viscosity of the composition and to form a marking pattern having sufficient adhesion.

Further, by incorporating a thermosetting catalyst, the photo-curable thermosetting composition for inkjet of the present invention can be cured at a heating temperature of 170 占 폚 or less, preferably 150 占 폚 or less, at the time of producing a printed wiring board. Thereby, the marking pattern can be formed without affecting the characteristics of the printed wiring board.

Hereinafter, a first embodiment of the present invention will be described in detail. In this embodiment, a printed circuit board using the photo-curable thermosetting composition as a means for solving the above-mentioned first problem will be described.

That is, this composition is a viscosity that can be used in an ink jet printer, and is excellent in heat resistance, chemical resistance, and the like required for the resin insulating layer, and has good adhesion, and is preferably 170 ° C or less, Is a photocurable thermosetting composition that can be thermally cured at a low temperature of 150 ° C or lower. Needless to say, the present invention is not limited to this embodiment.

As described above, the photocurable thermosetting composition for inkjet of the present invention can directly draw a predetermined pattern on a substrate for a printed wiring board by using an inkjet printer, primary-curing it by irradiating it with an active energy ray , And then heating and curing it again, a resin insulating layer excellent in heat resistance, chemical resistance, adhesion, and the like can be formed. In addition, since the composition contains a thermosetting catalyst, it is possible to sufficiently cure the thermosetting resin at a temperature lower than the heating temperature at the time of producing the printed wiring board in the thermosetting. In this case, the irradiation condition of the active energy ray is preferably 100 mJ / cm 2 or more, and more preferably 300 mJ / cm 2 to 2,000 mJ / cm 2. The heat curing is preferably carried out at 140 to 170 占 폚 for 20 minutes or more, preferably 150 to 170 占 폚 for 20 to 60 minutes.

The irradiation of the active energy ray is carried out after drawing of the pattern by the ink jet printer and the method is performed in parallel with the pattern drawing. The latter method is preferable from the viewpoint of time and shortening of the process. Examples of the method of conducting the irradiation of the active energy ray in parallel with the pattern drawing include a method of irradiating active energy rays from the side or bottom of the substrate during patterning. 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 ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like can be used. In addition, electron beams,? Rays,? Rays,? Rays, X rays, neutron rays, etc. can also be used.

Next, the ink-jet photocurable thermosetting composition according to the first embodiment of the present invention will be described.

Examples of the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚 include glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like Examples of commercially available products include Nichiyu Brenma G and Kyoeisha Chemical Lite Esters G, and the like. In the present specification, the term "(meth) acryloyl group" generally refers to an acryloyl group and a methacryloyl group, and the same applies to other similar expressions.

Examples of the trifunctional or higher functional acrylate monomers include polyethylene glycol diacrylate such as triethylene glycol diacrylate and tetraethylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolmethane triacrylate , Ethylene oxide modified trimethylol propane triacrylate, propylene oxide modified trimethylol propane triacrylate, epichlorohydrin modified trimethylol propane triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, Tetramethylolmethane tetraacrylate, ethylene oxide modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, Are polyfunctional acrylates represented by silsesquioxane-modified products thereof, or methacrylate monomers corresponding thereto, trifunctional methacrylate esters,? -Caprolactone-modified tris (acroxyethyl) isocyanurate And the like. The blending amount of the trifunctional or higher functional acrylate monomer is preferably 15 to 400 parts by mass when 100 parts by mass of a monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 DEG C of 10 mPa.s or less is used Is 20 to 300 parts by mass.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator.

As the photo radical polymerization initiator, any compound that generates a radical by light, laser, electron beam or the like and initiates a radical polymerization reaction can be used. Examples of the photo radical polymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- - amino acetophenones such as N, N, N-dimethylaminoacetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutyrate; Thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; Organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, and tribromomethylphenyl sulfone; Benzophenones such as benzophenone and 4,4'-bisdiethylaminobenzophenone, or xanthones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.

The photoradical polymerization initiator may be used singly or in combination of a plurality of species. In addition to these, in addition to these, tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine Additional initiating adjuvants may be used. Further, a titanocene compound such as CGI-784 (manufactured by BASF Japan) having absorption in the visible light region and the like can also be added to the photo radical polymerization initiator to promote the photoreaction. The component added to the photo radical polymerization initiator is not limited to these, and if it absorbs light in ultraviolet light or in the visible light region to radically polymerize an unsaturated group such as a (meth) acryloyl group, a photopolymerization initiator, But they may be used singly or in combination.

As the photo cationic polymerization initiator, any compound that initiates cationic polymerization reaction by light, laser, electron beam or the like can be used. Examples of the photo cationic polymerization initiator that generates cationic species by light include diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts, pyridinium salts and the like Onium salts; Halogenated compounds such as tris (trihalomethyl) -s-triazine and its derivatives; 2-nitrobenzyl ester of sulfonic acid; Iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; N-hydroxyimide = sulfonate; Tri (methanesulfonyloxy) benzene derivatives; Bis-sulfonyldiazomethanes; Sulfonylcarbonylalkanes; Sulfonylcarbonyldiazomethanes; Disulfone compounds and the like. Examples of commercially available photo cationic polymerization initiators include Cyracure UVI-6970, UVI-6974, UVI-6990 and UVI-6950 (trade names, manufactured by UCC Co., Ltd.), Irgacure 261 (Trade name, manufactured by Asahi Denka Kogyo K.K.), DAICAT II (trade name, manufactured by Daicel Chemical Industries, Ltd.), UVAC 1591 (manufactured by Daicel Chemical Industries, Ltd.) (Trade name, manufactured by Nippon Soda Co., Ltd.), PI-2074 (trade name, manufactured by Lo Fran Co., Ltd.), FFC509 (trade name, manufactured by Nippon Soda Co., Ltd.), CI-2734, CI-2855, CI- Rhodorsil photoinitiator 2074 (trade name, manufactured by Rhodia), BBI-102, BBI-101 (trade name, manufactured by Midori Kagaku Co., Ltd.) CD-1012 (trade name, manufactured by Sartomer), and the like.

Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4- Imidazole derivatives such as cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. Examples of commercially available thermosetting catalysts include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., U-CAT 3503N, DBT, DBN, U-CATSA102, and U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like can be given as examples of CAT3502T (all of the block isocyanate compounds of dimethylamine). These may be used alone or in combination of two or more. The blending amount of the thermal curing catalyst is 0.1 to 5 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of a monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 DEG C of 10 mPa.s or less, 4 parts by mass.

A diluting solvent may be added to the ink-jet photo-curable thermosetting composition of the first embodiment of the present invention for the purpose of adjusting the viscosity. Examples of the diluting solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Of glycol ethers; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

Further, the photo-curable thermosetting composition according to the first embodiment of the present invention may contain a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, carbon black and naphthalene black, hydroquinone, hydroquinone monomethyl Based antifoaming agents and / or leveling agents such as silicone, fluorine, and high molecular weight, imidazole-based, thiazole-based, triazole-based, silane couple And an adhesion-imparting agent such as a lixing agent.

[Example]

Hereinafter, the present invention will be described in detail with reference to Examples of the ink-jet photo-curable thermosetting composition according to the first embodiment of the present invention, but the present invention is not limited to these Examples. Unless specifically stated below, " parts " means parts by mass.

For each of Examples 1 to 5 and Comparative Examples 1 to 6, each component was blended at the ratios shown in Table 1, stirred with a dissolver, and filtered through a 1 占 퐉 disk filter to obtain respective compositions.

≪ Monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 캜 of 10 mPa> or less>

GMA: glycidyl methacrylate (viscosity 2 mPa 占 퐏 (25 占 폚))

4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (viscosity 7 mPa s (25 캜))

&Quot; Monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚>

EA-1010N: Compound obtained by adding acrylic acid to one epoxy group of a bisphenol A type epoxy resin (viscosity: 22,000 mPa 揃 s (25 属 C) manufactured by Shin-Nakamura Chemical Co., Ltd.)

AGE: allyl glycidyl ether having allyl group and glycidyl group (viscosity 1 mPa 占 퐏 (25 占 폚))

4HBA: 4-hydroxybutyl acrylate (viscosity 10 mPa 占 퐏 (25 占 폚))

DPGDA: dipropylene glycol diacrylate (viscosity 12 mPa 占 퐏 (25 占 폚))

M-100: Compound having 3,4-epoxycyclohexylmethyl methacrylate meta-chromate and alicyclic epoxy group Diacetate crosslinking agent (viscosity 10 mPa · s (25 ° C))

≪ Trifunctional acrylate monomer >

PETA: pentaerythritol triacrylate

TMPTA: trimethylolpropane triacrylate

SR9011: Trifunctional methacrylate ester Satomase

M327:? -Caprolactone-modified tris (acroxyethyl) isocyanurate (manufactured by Doagosei Co., Ltd.)

<Thermal curing catalyst>

2E4MZ: 2-ethyl-4-methylimidazole

<Photopolymerization initiator>

IRG819: BASF priest Irgacure 819

Each of the above compositions was subjected to the following characteristic tests. The results are shown in Table 2.

&Lt; Coatability >

(Epson Format A4) using a Dimatix Materials Printer DMP-2831, an inkjet printer manufactured by Fuji Photo Film Co., Ltd., with each composition having a width of 100 mu m and a length of one side of 20 mm L-type lines were printed. The L-shaped line was observed with a magnifying glass, and the shape of the line was evaluated as follows.

○: Line is drawn without any scratches or kinks.

X: The line can not be confirmed, or scratches or kinks occur in the line.

<Photocurability>

(FR-4, thickness: 1.6 mm, size: 150 mm x 95 mm) was printed with a rectangular pattern having a size of 10 x 20 mm by each of the above compositions on a printed circuit board laminate (FR-4, thickness 150 mm x 95 mm) using a DMI- . Immediately thereafter, the printed laminated plate was subjected to UV irradiation at a cumulative light quantity of 300 mJ / cm 2 using a high-pressure mercury lamp. With respect to the rectangular pattern, the cured state after UV irradiation was evaluated as follows.

∘: Cured and maintained in shape.

X: Not cured.

&Lt; Adhesion >

(FR-4, thickness: 1.6 mm, size: 150 mm x 95 mm) was printed with a rectangular pattern having a size of 10 x 20 mm by each of the above compositions on a printed circuit board laminate (FR-4, thickness 150 mm x 95 mm) using a DMI- Was printed so as to have a film thickness of 15 mu m. Immediately thereafter, the printed laminated plate was subjected to UV irradiation at a cumulative light quantity of 300 mJ / cm 2 using a high-pressure mercury lamp. Subsequently, the laminated plate subjected to the UV irradiation was heated in a hot-air circulating type drying oven at 150 DEG C for 30 minutes to thermally cure the pattern to obtain test pieces. A rectangular pattern of each of the test pieces was cut one by one vertically and horizontally by a cutter knife. Peeling was performed with a cellophane tape, and the peeling was evaluated as follows.

○: Almost no peeling was observed.

X: There is peeling which is largely transferred to Cellotape (registered trademark).

<Chemical resistance>

For each of the above compositions, each test piece was produced by the same method as described in the above adhesion test. Each of the test pieces was immersed in propylene glycol monomethyl ether acetate at room temperature for 30 minutes, taken out, and then dried. With respect to each test piece after drying, the state of the coating film was visually evaluated as follows.

○: No change in the state of the coating film

X: Exposed to the coating film and peeled

<Heat resistance>

For each of the above compositions, each test piece was produced by the same method as described in the above adhesion test. For each of the test pieces, a rosin-based flux was applied and immersed in a solder bath at 260 캜 for 10 seconds, taken out and naturally cooled. After this test was repeated three times, the state of the coating film of each test piece was visually evaluated as follows.

○: No change in the state of the coating film

X: Exposed to the coating film and peeled

<Insulation>

The compositions of Examples 1 to 5 were prepared by the same method as described in the adhesion test except that the interdigital electrode B coupon of the IPC B-25 test pattern was used in place of the copper clad laminate, Each test piece was produced. A bias of 500 V DC was applied to the test piece to measure the insulation resistance value. When the value was 100 G? Or more, it was rated?, And when it was less than 100 G?

From the above, the photo-curable thermosetting composition for inkjet according to the present invention can be used to draw a pattern directly on a substrate for a printed wiring board by using an inkjet printer and can form a resin insulation Layer can be formed.

Next, the ink-jet photocurable thermosetting composition according to the second embodiment of the present invention will be described in detail. In this embodiment, a printed wiring board using the composition and a method for the ink-jet photocurable thermosetting composition suitable for forming a marking pattern as a means for solving the above-mentioned second problem will be described.

The ink-jet photo-curable thermosetting composition for inkjet according to the second embodiment can directly form a predetermined marking pattern on a resin insulating layer formed on a printed wiring board using an inkjet printer, And then heating and curing it again, a marking pattern excellent in heat resistance, chemical resistance, adhesion, and the like can be formed. In addition, since the composition contains a thermosetting catalyst, it is possible to sufficiently cure the thermosetting resin at a temperature lower than the heating temperature at the time of producing the printed wiring board in the thermosetting. In this case, the irradiation condition of the active energy ray is preferably 100 mJ / cm 2 or more, and more preferably 300 mJ / cm 2 to 2,000 mJ / cm 2. The heat curing is preferably carried out at 140 to 170 占 폚 for 20 minutes or more, preferably 150 to 170 占 폚 for 20 to 60 minutes.

As described in the description of the first embodiment, the irradiation of the active energy ray is preferably performed in parallel with the patterning of the pattern by the inkjet printer. As this method, for example, there is a method of irradiating an active energy ray from a side portion or a bottom portion of a substrate at the time of patterning, for example, as described above. 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 ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like can be used. In addition, electron beams,? Rays,? Rays,? Rays, X rays, neutron rays, etc. can also be used.

Examples of the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚 as in Embodiment 1 include glycidyl methacrylate, 4-hydroxybutyl acrylate Glycidyl ether and the like. Commercially available products include Nichiyu Brenma G, Kyoeisha Chemical Co., Ltd. Light Ester G, and the like.

As the acrylate monomers having three or more functional groups, monomers similar to those of the first embodiment can be mentioned. However, the blending amount of the trifunctional or higher functional acrylate monomer is preferably in the range of 15 to 400 parts by weight, based on 100 parts by weight of the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa.s or less at 25 DEG C , Preferably 20 to 300 parts by mass.

As the titanium oxide, both anatase type titanium oxide and rutile type titanium oxide can be used. From the standpoint of suppressing photo deterioration of the marking pattern, it is particularly preferable to use rutile titanium oxide. The anatase type titanium oxide is more preferable as the white pigment from the viewpoints of the whiteness and the reflectance because the anatase type titanium oxide has a higher reflectance near the boundary between the ultraviolet ray region and the visible light region as compared with the rutile type titanium oxide. However, since the anatase type titanium oxide has photocatalytic activity, there is a case where the resin included in the photocurable thermosetting composition causes discoloration due to the photoactivity. On the other hand, the rutile titanium oxide has a slightly lower whiteness than the anatase type titanium oxide, but has almost no photocatalytic activity, so that deterioration of the resin can be suppressed and a stable marking pattern can be obtained.

Specific examples of the rutile-type titanium oxide include Teapac R-820, Taipei R-830, Taipei R-930, Taipei R-550, Taipei R-630, Taipei R-670, Taipei KR-80, Taipei KR-80, Taipei CR-50, Taipei CR-57, Taipei CR-80, Taipei CR-90, Taipei CR-93, Taipei CR-95, Taipei CR-97, Taipei CR-60, Taipei CR-63, Taipei CR-67, Taipei CR-58, ), Tie Pure R-101, Tie Pure R-102, Tie Pure R-103, Tie Pure R-104, Tie Pure R-105, (TITON) R-25, TITON R-21 (trade name, manufactured by DuPont), Titan R-901, TITON R-7N, TITON R-61N, TITON R-62N, TITON R-4N, TITON R-45, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D-918, TITON TCR-29, TITON TCR-52, TITON FTR-700 Manufactured by Cai Kagaku Kogyo Co., Ltd.).

As the anatase type titanium oxide, TA-100, TA-200, TA-300, TA-400 and TA-500 (manufactured by Fuji Titanium High Co., 220, Taipei W-10 (manufactured by Ishihara Sangyo Co., Ltd.), TITANIX JA-1, Titanix JA-3, Titanix JA-4, Titanix JA- A-100, A-100, A-100, K-10, Kronos KA-15, Kronos KA-20 and Kronos KA-30 manufactured by Titan Kogyo Co., SA-1, and SA-1L (all manufactured by SAKAI KAGAKU KOGYO CO., LTD.).

The blending amount of titanium oxide is preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass based on the total amount of the whole composition. If the blending amount of titanium oxide exceeds 30 parts by mass based on the total amount, the viscosity of the photocurable thermosetting composition of the present invention becomes high, and the photocurability is lowered and the depth of curing is lowered. On the other hand, if the blending amount of titanium oxide is less than 3 parts by mass based on the total amount, the hiding power of the photocurable thermosetting composition becomes small, and a white marking pattern can not be obtained.

Since the thermosetting catalyst is the same as that of the first embodiment, a detailed description thereof will be omitted.

As the photopolymerization initiator, as in the first embodiment, a photo radical polymerization initiator and a photo cation polymerization initiator can be mentioned.

The photoradical polymerization initiator is the same as that of the first embodiment, and thus a detailed description thereof will be omitted.

Since the photocationic polymerization initiator is the same as that of the first embodiment, detailed description thereof will be omitted.

In the ink-jet photo-curable thermosetting composition for inkjet of the present invention, a diluting solvent may be added for the purpose of adjusting the viscosity, similarly to the first embodiment, but detailed description is omitted in order to avoid duplication.

The photo-curable thermosetting composition of the present invention may contain, as necessary, antifoaming agents such as known polymerization inhibitors, silicones, fluorides, and polymers, and / or leveling agents, imidazoles, thiazoles, An adhesion promoter such as a silane coupling agent, etc. may be added.

[Example]

Hereinafter, the photocurable thermosetting composition according to the second embodiment of the present invention will be described in detail with reference to examples. Unless otherwise stated, &quot; part &quot; means the part by mass, as described above in the following.

For each of Examples 1 to 5 and Comparative Examples 1 to 8, each component was blended at the ratios shown in Table 3, stirred with a dissolver, and filtered with a disc filter of 1 mu m to obtain respective compositions.

&Lt; Monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 캜 of 10 mPa> or less>

GMA: glycidyl methacrylate (viscosity 2 mPa 占 퐏 (25 占 폚))

4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (viscosity 7 mPa s (25 캜))

&Quot; Monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚>

EA-1010N: Compound obtained by adding acrylic acid to one epoxy group of a bisphenol A type epoxy resin (viscosity: 22,000 mPa 揃 s (25 属 C) manufactured by Shin-Nakamura Chemical Co., Ltd.)

AGE: allyl glycidyl ether having allyl group and glycidyl group (viscosity 1 mPa 占 퐏 (25 占 폚))

4HBA: 4-hydroxybutyl acrylate (viscosity 10 mPa 占 퐏 (25 占 폚))

DPGDA: dipropylene glycol diacrylate (viscosity 12 mPa 占 퐏 (25 占 폚))

M-100: Compound having 3,4-epoxycyclohexylmethyl methacrylate meta-chromate and alicyclic epoxy group Diacetate crosslinking agent (viscosity 10 mPa · s (25 ° C))

&Lt; Trifunctional acrylate monomer >

PETA: pentaerythritol triacrylate

TMPTA: trimethylolpropane triacrylate

SR9011: Trifunctional methacrylate ester Satomase

M327:? -Caprolactone-modified tris (acroxyethyl) isocyanurate (manufactured by Doagosei Co., Ltd.)

<Titanium oxide>

CR-95: Ishihara acid titanium oxide

<Barium sulfate>

B-30: barium sulfate &lt; RTI ID = 0.0 &gt;

<Thermal curing catalyst>

2E4MZ: 2-ethyl-4-methylimidazole

<Photopolymerization initiator>

IRG819: BASF priest Irgacure 819

Each of the above compositions was subjected to the following characteristic tests. The results are shown in Table 4.

&Lt; Coatability >

(SUNHAYATO PF-10R-A4) using the above-mentioned composition, letters A to Z were printed in a square size of 2 mm on each side using a DIMMTIC MULTI PRINTER DMP-2831, an inkjet printer manufactured by Fuji Photo Film Co., Printed. For each character, the shape of the character was observed with a magnifying glass and evaluated as follows.

○: There are no scratches or kinks in the characters, and no protruding parts are wasted.

X: The character can not be confirmed, or the character has scratches or kinks, or has jumped out to a useless part.

<Photocurability>

The solder resist PSR-4000G24 manufactured by Daiei Ink Manufacturing Co., Ltd. was printed on the copper-clad laminate for printed wiring boards (FR-4 thickness 1.6 mm in size 150 mm 95 mm) by screen printing with a screen printing method so as to have a dry film thickness of 20 탆. Then, it was dried at 80 DEG C for 30 minutes, and exposed at 300 mJ / cm2 in a pattern in which a coating film remained entirely on the laminate. The exposed laminate was developed with 30 wt% 1 wt% Na ₂ CO ₃ and washed with water. This was further cured at 150 DEG C for 30 minutes to prepare a test substrate. Then, a rectangular pattern having a size of 10 x 20 mm was printed on each of the test substrates by using a DMI-2831, a DIMMatic material printer, an inkjet printer manufactured by Fuji Photo Film. Each test substrate immediately after printing was subjected to UV irradiation at a cumulative light quantity of 300 mJ / cm 2 using a high-pressure mercury lamp.

With respect to the rectangular pattern, the cured state after UV irradiation was evaluated as follows.

∘: Cured and maintained in shape.

X: Not cured.

&Lt; Adhesion >

Each test substrate was produced by the same method as described in the above-described photocuring property test. Then, a rectangular pattern with a size of 10 x 20 mm was printed on each of the above-mentioned test substrates using a DMI-2831 manufactured by Fuji Film's Inkjet printer so as to have a film thickness of 15 mu m . Immediately after printing, each test substrate was subjected to UV irradiation using a high-pressure mercury lamp at an integrated light quantity of 300 mJ / cm 2. Subsequently, each of the test substrates after the UV irradiation was heated in a hot-air circulation type drying furnace at 150 DEG C for 30 minutes to thermally cure the test pieces. Thereafter, a rectangular pattern of each test piece was formed by inserting one by one longitudinally and horizontally by a cutter knife, and then peeling was performed with a cellophane tape. The peeling was evaluated as follows.

○: Almost no peeling was observed.

X: There is peeling which is largely transferred to Cellotape (registered trademark).

<Chemical resistance>

For each of the above compositions, each test piece was produced by the same method as described in the above adhesion test. Each of the test pieces was immersed in propylene glycol monomethyl ether acetate at room temperature for 30 minutes, taken out, and then dried. With respect to each test piece after drying, the state of the coating film was visually evaluated as follows.

○: No change in the state of the coating film

X: Exposed to the coating film and peeled

<Heat resistance>

For each of the above compositions, each test piece was produced by the same method as described in the above adhesion test. For each of the test pieces, a rosin-based flux was applied and immersed in a solder bath at 260 캜 for 10 seconds, taken out and naturally cooled. After this test was repeated three times, the state of the coating film of each test piece was visually evaluated as follows.

○: No change in the state of the coating film

X: Exposed to the coating film and peeled

<Visibility>

Each test substrate was produced by the same method as described in the above-described photocuring property test. Alphabet A to E were printed on each of the test substrates by using the above-mentioned respective compositions with a square size of 3 mm on each side using a DIMMTIC MATERIAL PRINTER DMP-2831, an ink jet printer manufactured by Fuji Photo Film. For each character, the contrast with the naked eye was evaluated as follows.

○: The contrast is so large that the characters can be clearly recognized.

X: The contrast is small and the distinction between text and characters is ambiguous.

As described above, the ink-jet photo-curable thermosetting composition for inkjet according to the second embodiment of the present invention is capable of directly patterning a resin insulating layer formed on a printed wiring board by using an inkjet printer and has excellent adhesiveness, , A marking pattern excellent in heat resistance can be formed. In particular, a marking pattern having high adhesion to the resin insulating layer can be formed. The photocurable thermosetting composition can be used as a marking composition which requires harsh characteristics including printed wiring boards.

Claims (10)

A monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚,
A trifunctional or higher acrylate monomer,
A thermosetting catalyst,
A photopolymerization initiator,
Wherein the amount of the thermosetting catalyst is 0.1 to 5 parts by mass based on 100 parts by mass of the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and a viscosity at 25 DEG C of 10 mPa.s or less. Curable thermosetting composition for inkjet. The positive resist composition according to claim 1, wherein the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚 is glycidyl methacrylate or 4-hydroxybutyl acrylate glycidyl Wherein the photo-curable thermosetting composition is an ether. The process according to claim 2, wherein the amount of the trifunctional or higher acrylate monomer is in the range of 15 to 400 parts by mass relative to 100 parts by mass of the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 DEG C of 10 mPa.s or less. By mass based on the total amount of the thermosetting thermosetting composition. delete A printed wiring board characterized by having a resin insulating layer formed by drawing a pattern on a substrate by an inkjet printer using the inkjet photo-curable thermosetting composition according to any one of claims 1 to 3 and curing the pattern. A monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚,
A trifunctional or higher acrylate monomer,
Titanium oxide,
A thermosetting catalyst,
A photopolymerization initiator,
Wherein the blending amount of the thermosetting catalyst is 0.1 to 5 parts by mass relative to 100 parts by mass of the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 캜 of 10 mPa 이하 or less, Wherein the curable composition is used for patterning on an insulating layer. The composition of claim 6, wherein the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity of 10 mPa 占 퐏 or less at 25 占 폚 is glycidyl methacrylate or 4-hydroxybutyl acrylate glycidyl Wherein the photo-curable thermosetting composition is an ether. [Claim 8] The method according to claim 7, wherein the blending amount of the trifunctional or higher acrylate monomer is 15 to 400 parts by mass based on 100 parts by mass of the monomer having a (meth) acryloyl group and a glycidyl group in the molecule and having a viscosity at 25 DEG C of 10 mPa.s or less. By mass based on the total amount of the thermosetting thermosetting composition. delete There is provided a pattern forming method comprising the steps of patterning a photocurable thermosetting composition for inkjet according to any one of claims 6 to 8 on a resin insulating layer formed on a printed wiring board using an inkjet printer, Printed wiring board.