TWI509033B - A photohardenable thermosetting composition for inkjet and a printed circuit board using the same - Google Patents

Description

Photocurable thermosetting composition for inkjet and printed circuit board using the same

The present invention relates to a photocurable thermosetting composition for forming a resin insulating layer, which is capable of directly drawing light as an insulating layer or a pattern on a substrate for a printed circuit board using an ink jet printer. A curable thermosetting composition and a printed circuit board having the resin insulating layer formed using the same.

A method of manufacturing a printed circuit board using an ink jet printer, for example, a method of forming a conductor circuit by performing an etching process after forming an etching resist using an ink jet printer on a metal foil on a plastic substrate (refer to Japan) JP-A-56-66089, JP-A-56-157089, JP-A-58-50794, and JP-A-6-237063. This method is based on CAD data to directly draw a pattern on a metal foil, patterned with a photographic imaging method using a photosensitive resin that requires a photomask, or a photoresist ink by screen printing. Compared with the case of patterning, it has the advantage that the procedure or time for manufacturing the printed circuit board can be greatly shortened, and consumables such as a developing solution, a photoresist ink, and a cleaning solvent can be reduced.

Further, regarding the resin insulating layer of the solder resist formed on the protective conductor circuit on the printed circuit board, there is also a method of forming an ink jet printer (refer to Japanese Patent Laid-Open No. Hei 7-263845, No. 9-18115, Japan) ). This formation method is the same as the method of forming the above-described etching photoresist. When using this inkjet method, the step can be reduced compared to the photolithography or screen printing method. Number of steps, time, consumables. Further, it is further proposed that the ink tanks of the ink jet printer having the ink jet printer are separated into, for example, an etch resist ink, a solder resist ink, a marking ink, and the like, and may be only one. A method in which a plurality of ink jet printers can perform a plurality of steps (refer to Japanese Patent Laid-Open No. Hei 8-236902).

However, the ink used in inkjet printers must have a viscosity of about 20 mPa when applied. s below. On the other hand, the viscosity of the ink used in screen printing is 20,000 mPa. Before and after s, the viscosity of the two is very different. Therefore, even when the photoresist ink for screen printing is diluted with a large amount of diluent, it is difficult to reduce it to a viscosity which can be used for an ink jet printer. Moreover, if the viscosity of the photoresist ink can be reduced to 20 mPa. s, the physical properties of heat resistance and chemical resistance required for the resin-resistant resin-like insulating layer are also greatly reduced. Further, when the resist ink is diluted with a volatile solvent, the amount of non-volatile matter is extremely small, and it becomes difficult to secure a predetermined film thickness required for application to the substrate. Therefore, as a method of forming a resin insulating layer of a printed circuit board, the ink jet method is only a field of concept, and there is no photoresist ink for forming a practical resin insulating layer which can be used by an ink jet printer. Resin composition.

In contrast to the prior art, it is known to use a photoreactive diluent having a (meth)acrylonium group and a thermosetting functional group in a molecule, a weight average molecular weight of 700 or less, and photopolymerization. Starting agent, and the viscosity is 150mPa at 25 °C. s The following resin composition, to solve the above problems, the photocurability of inkjet. Thermosetting composition (International Publication WO2004/099272). According to this inkjet light hardenability. Thermosetting composition The inkjet composition having the heat resistance required for the solder resist can be obtained even at a low viscosity, but it is still desired to have the adhesion, chemical resistance, and low-temperature hardening required for the solder resist in the resin composition. There can be an improvement in the level of sex.

Further, in recent years, the need for the white marking ink used in the above-described ink jet method has been gradually increased. However, when a titanium oxide suitable as a white pigment is blended, the viscosity of the marking ink increases. Further, in the corresponding strategy, the resin composition is generally made to have a low molecular weight, and the adhesion between the marking pattern and the resin insulating layer is lowered, and the marking pattern is peeled off by the resin insulating layer. Therefore, there is no practical white marking ink that can be used with an ink jet printer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 56-66089

[Patent Document 2] Japanese Patent Laid-Open No. 56-157089

[Patent Document 3] Japanese Patent Laid-Open No. 58-50794

[Patent Document 4] Japanese Patent Laid-Open No. 6-237063

[Patent Document 5] Japanese Patent Laid-Open No. 7-263845

[Patent Document 6] Japanese Patent Laid-Open No. 9-18115

[Patent Document 7] Japanese Patent Laid-Open No. 8-236902

[Patent Document 8] International Publication WO2004/099272

The present invention has been made in order to solve the problems of the prior art, and the first object of the invention is to provide a photocurable thermosetting composition for inkjet, which is a photocurable thermosetting composition for forming a resin insulating layer. The article can be used to draw a resin insulating layer pattern directly on a substrate for a printed circuit board using an ink jet printer.

A second object of the present invention is to provide a photocurable thermosetting composition for inkjet comprising titanium oxide, which is suitable for use in a resin insulating layer such as a solder resist formed on a printed circuit board, and an ink jet printer is used. The pattern that is marked as a marker can be directly drawn.

A third object of the present invention is to provide a printed circuit board having a pattern directly formed on a substrate for a printed circuit board by an ink jet printer using the photocurable thermosetting composition for inkjet. A resin insulating layer that is hardened.

A fourth aspect of the present invention provides a printed circuit board having a pattern formed on a resin insulating layer formed on a printed circuit board and using the ink jet printer to form the photocurable thermosetting composition. Hardened marking pattern.

More specifically, the first object of the present invention provides a photocurable thermosetting composition which is excellent in heat resistance and chemical resistance required for a resin insulating layer, and can be used for an ink jet printer. Further, the adhesion is also excellent, and the heating temperature at the time of producing a printed circuit board is 170 ° C or lower, and preferably at a low temperature of 150 ° C or lower, which is thermally hardened.

More specifically, the second object described above provides a photocurable thermosetting composition which can use the viscosity of an ink jet printer and even if it is blended The titanium oxide can still form a pattern having good adhesion to the resin insulating layer formed on the printed circuit board.

In order to solve the above-mentioned first problem, the photocurable thermosetting composition for inkjet according to the present invention is characterized in that it has a (meth)acryl fluorenyl group and a propylene group in a molecule and has a viscosity of 10 mPa at 25 ° C. s The following monomer, a trifunctional or higher acrylate monomer, a thermosetting catalyst, and a photopolymerization initiator.

Further, the photocurable thermosetting composition for inkjet according to the present invention is characterized in that the (meth)acrylonyl group and the epoxy group are contained in the molecule and the viscosity at 25 ° C is 10 mPa. The monomers below s are epoxypropyl methacrylate or 4-hydroxybutyl acrylate glycidyl ether.

Another feature of the photocurable thermosetting composition for inkjet according to the present invention is that the photocurable thermosetting composition for inkjet has a (meth)acryl fluorenyl group and an epoxy in the molecule. The propyl group has a viscosity of 10 mPa at 25 ° C. When the monomer of s or less is 100 parts by mass, the trifunctional or higher acrylate monomer is contained in an amount of 15 to 400 parts by mass, preferably 20 to 300 parts by mass, and the thermosetting catalyst is contained in an amount of 0.1 to 5 parts by mass. It contains 0.5 to 4 parts by mass.

Here, the above viscosity means a viscosity measured in accordance with JIS K2283. Further, the viscosity of the photocurable thermosetting composition for inkjet is 150 mPa at room temperature (25 ° C). s below. As mentioned above, the viscosity of the ink used in the inkjet printer must be about 20 mPa in the temperature at the time of coating. s below. However, if it is 150mPa at normal temperature. s below the viscosity, by coating before or The above conditions can be satisfied by the heating at the time of coating. In the following description, the viscosity is set to use the above definition.

In order to solve the second problem, the photocurable thermosetting composition for inkjet according to the present invention comprises a (meth)acrylonyl group and a glycidyl group in the molecule and has a viscosity of 10 mPa at 25 ° C. a photocurable thermosetting composition of a monomer having s or less, a trifunctional or higher acrylate monomer, a titanium oxide, a thermosetting catalyst, or a photopolymerization initiator, which is characterized in that it can be used for forming on a printed circuit board. Graphical depiction on the resin insulation layer.

Moreover, the photocurable thermosetting composition for inkjet according to the present invention is characterized in that the photocurable thermosetting composition for inkjet containing titanium oxide has (meth)acrylic acid in the molecule. The base is epoxy propyl and has a viscosity of 10 mPa at 25 ° C. The monomers below s are epoxypropyl methacrylate or 4-hydroxybutyl acrylate glycidyl ether.

Further, in another feature of the photocurable thermosetting composition for inkjet according to the present invention, the photocurable thermosetting composition for inkjet containing titanium oxide has (meth)acryl in the molecule. The sulfhydryl group and the epoxy propyl group have a viscosity of 10 mPa at 25 ° C. The monomer having s or less is 100 parts by mass, and the trifunctional or higher acrylate monomer is contained in an amount of 15 to 400 parts by mass, preferably 20 to 300 parts by mass, and the thermosetting catalyst is contained in an amount of 0.1 to 5 parts by mass. Contains 0.5 to 4 parts by mass.

The printed circuit board of the present invention is characterized in that it has a resin insulating layer which is formed by patterning on a substrate by an ink jet printer using the photocurable thermosetting composition for inkjet.

Furthermore, the printed circuit board of the present invention is characterized by having a shape The photocurable thermosetting composition for inkjet was patterned and hardened on a resin insulating layer formed on a printed circuit board by using an ink jet printer.

The photocurable thermosetting composition for inkjet according to the present invention has a (meth) acrylonitrile group and an epoxy propyl group in a molecule and has a viscosity of 10 mPa at 25 ° C. s The following monomer or a trifunctional or higher acrylate monomer can improve the heat resistance, chemical resistance, and adhesion of the resin insulating layer which is cured. In particular, in the conventional resin composition for inkjet, a high-viscosity photosensitive monomer (or a photosensitive thermosetting monomer) is used, and in order to reduce the composition to the predetermined viscosity (20 mPa·s), it is generally With a low viscosity monofunctional photosensitive monomer. In another aspect, the present invention has a low viscosity in the molecule having a (meth) acrylonitrile group and an epoxy propyl group and a viscosity of 10 mPa at 25 ° C. The monomer having s or less is a photosensitive thermosetting monomer, and is a acrylate monomer having a high viscosity of three or more functional groups which is excellent in heat resistance, chemical resistance, and adhesion.

Moreover, the photocurable thermosetting composition for inkjet according to the present invention can be cured at a heating temperature of 170 ° C or less, preferably 150 ° C or less, in the production of a printed wiring board by blending a thermosetting catalyst. Thereby, the resin insulating layer can be formed without affecting the characteristics of the printed circuit board.

Further, the photocurable thermosetting composition for inkjet according to the present invention has a (meth)acryl fluorenyl group and a propylene group in a molecule and has a viscosity of 10 mPa at 25 ° C. s below monomer and trifunctional or higher acrylate monomer Even if the titanium oxide of the white pigment is blended, the adhesion of the resin insulating layer formed on the printed circuit board to the mark pattern can be improved. In particular, in the conventional resin composition for inkjet, since a photosensitive monomer (or a photosensitive thermosetting monomer) having a high viscosity is used, if the titanium oxide of the white pigment is blended, the viscosity of the composition is further increased. rise. Therefore, in order to lower the composition to the above-mentioned predetermined viscosity (20 mPa·s), it is necessary to mix a low-viscosity monofunctional photosensitive monomer in a large amount, and it is impossible to form a mark pattern having sufficient adhesion. In another aspect, the present invention has a low viscosity in the molecule having a (meth) acrylonitrile group and an epoxy propyl group and a viscosity of 10 mPa at 25 ° C. The monomeric photosensitive thermosetting monomer of s or less is compatible with a high-viscosity trifunctional or higher acrylate monomer which is excellent in heat resistance, chemical resistance, and adhesion, and can achieve not only the viscosity of the composition. It is also possible to form a mark pattern with sufficient adhesion.

Furthermore, the photocurable thermosetting composition for inkjet according to the present invention can be cured at a heating temperature of 170 ° C or lower, preferably 150 ° C or lower, at the time of producing a printed wiring board by blending a thermosetting catalyst. Thereby, the mark pattern can be formed without affecting the characteristics of the printed circuit board.

Hereinafter, the first embodiment of the present invention will be described in detail. In this embodiment, a photocurable thermosetting composition as a means for solving the above first problem will be described, and a printed circuit board in which the composition and the composition are used will be described.

That is, the composition is a viscosity that can be used with an inkjet printer, a tree The grease insulating layer is excellent in heat resistance and chemical resistance, and has good adhesion. The heating temperature of the printed circuit board can be 170 ° C or less, and preferably 150 ° C or less. A sclerosing thermosetting composition. Furthermore, the present invention is not limited to the embodiment at all.

As described above, the photocurable thermosetting composition for inkjet according to the present invention can directly draw a predetermined pattern on a substrate for a printed circuit board using an ink jet printer, and irradiate the active energy ray once. After hardening, it is further cured by heat to form a resin insulating layer which is excellent in heat resistance, chemical resistance, adhesion, and the like. Further, the above composition contains a thermosetting catalyst, and in the above-described heat curing, it is sufficiently cured even at a low temperature at a heating temperature at the time of producing a printed circuit board. In this case, the irradiation condition of the active energy ray is preferably 100 mJ/cm ² or more, and preferably 300 mJ/cm ² to 2000 mJ/cm ² . Further, the conditions for heat curing are 20 minutes or longer at 140 to 170 ° C, preferably 20 to 60 minutes at 150 to 170 ° C.

Although the irradiation of the active energy ray is carried out in parallel with the drawing, the method of performing the drawing by the inkjet printer is preferred, but the method of the latter is preferably shortened by time or steps. . As a method of performing the irradiation of the active energy ray in parallel with the pattern drawing, for example, there is a method of irradiating an active energy ray from a side portion or a bottom portion of a substrate or the like at the time of pattern drawing. The active light source illumination source may be 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. Others may also use an electron line, an alpha line, a beta line, a gamma line, an X line, a neutral line, and the like.

Next, the light hardening for inkjet according to the first embodiment of the present invention will be described. A thermosetting composition.

The above has a (meth) acrylonitrile group and a propylene group in the molecule and has a viscosity of 10 mPa at 25 ° C. Examples of the monomer of s or less include, for example, a glycidyl methacrylate or a 4-hydroxybutyl acrylate glycidyl ether. Commercially available products include Blemmer G, manufactured by Nippon Oil Co., Ltd. Ester G and the like. Further, in the present specification, the terms (meth)acryloyl group-based acryl-alkyl group and methacryl oxime group have the same performances.

Examples of the trifunctional or higher acrylate monomer include polyethylene glycol diacrylate such as triethylene glycol diacrylate or tetraethylene glycol diacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate. , trimethylol methane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide denatured trimethylolpropane triacrylate, epichlorohydrin derivatized trimethylolpropane triacrylate , pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylol methane tetraacrylate, ethylene oxide modified phosphoric acid triacrylate, epichlorohydrin modified triglyceride, dipentaerythritol hexaacrylate, dipentaerythritol a monofunctional hydroxy acrylate, or a polyfunctional acrylate represented by such a sesquioxane denature or the like, or a methacrylate monomer, a trifunctional methacrylate ester, ε- Caprolactone denatured ginseng (propylene oxyethyl) trimeric isocyanate or the like. It will have a (meth) acrylonitrile group and an epoxy propyl group in the molecule and a viscosity of 10 mPa at 25 ° C. When the monomer of s or less is 100 parts by mass, the amount of the trifunctional or higher acrylate monomer is from 15 to 400 parts by mass, preferably from 20 to 300 parts by mass.

The photopolymerization initiator may be a photoradical polymerization initiator or a photo-cation Ionic polymerization initiator.

The photoradical polymerization initiator can be used as long as it is a compound which generates a radical due to light, a laser, an electron beam or the like and starts a radical polymerization reaction. Examples of the photoradical polymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethyl Acetophenones such as oxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.; 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)- Aminoacetophenones such as butan-1-one, N,N-dimethylaminoacetophenone, etc.; 2-methyloxime, 2-ethylhydrazine, 2-t-butylhydrazine, Anthraquinone such as 1-chloroindole; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthene a thioxanthone such as a ketone; a ketal such as acetophenone dimethyl ketal or benzyl diethyl ketal; a 2,4,5-triarylimidazole dimer; riboflavin tetrabutyl acrylate; a mercaptan compound such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole; 2,4,6-para-s-triazine, 2,2,2-tribromoethanol, Organic halogen compound such as tribromomethylphenylhydrazine; benzophenone, 4,4'-bisdiethylamine The benzophenone benzophenone or oxygen onion ketone; 2,4,6-trimethylbenzyl diphenyl acyl phosphine oxide.

The above photoradical polymerization initiator may be used singly or in combination of plural kinds. Further, and in addition to these, ethyl N,N-dimethylamino benzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylamino group can also be used. A light-starting aid such as a tertiary amine such as a benzyl ester, triethylamine or triethanolamine. Also, in order to promote the photoreaction, it may be added The ferrocene compound of CGI-784 or the like (manufactured by BASF JAPAN Co., Ltd.) having absorption in the light field is equal to the photoradical polymerization initiator. Further, the component to be added to the photoradical polymerization initiator is not limited thereto, and as long as the ultraviolet light or the visible light field absorbs light to cause an unsaturated radical polymerization of a (meth)acryl fluorenyl group or the like, that is, It is limited to a photopolymerization initiator and a photoinitiator, and may be used singly or in combination.

The photocationic polymerization initiator may be a compound which initiates cationic polymerization by light, laser, electron beam or the like. Examples of the photocationic polymerization initiator which generates a cationic species by light include, for example, a diazonium salt, a phosphonium salt, a bromine sulfonium salt, a chloranium salt, a phosphonium salt, a selenium salt, a pyrylium salt, a thiopyranium salt, a phosphonium salt of pyridinium or the like; a halogenated compound of a hydrazine (trihalomethyl)-s-triazine and a derivative thereof; a 2-nitrobenzyl sulfonate; an imidosulfonate; Base-2-diazonaphthoquinone-4-sulfonate derivative; N-hydroxyquinone imide=sulfonate; tris(methanesulfonyloxy)benzene derivative; bissulfonyl diazomethane; sulfonate Mercaptocarbonylols; sulfonylcarbonyldiazomethanes; diterpenoids and the like. Commercially available photocationic polymerization initiators include CYRACURE UVI-6970, UVI-6974, UVI-6990, UVI-6950 (trade name, manufactured by UCC Corporation), and IRGACURE 261 (trade name manufactured by BASF JAPAN Co., Ltd.). ), SP-150, SP-152, SP-170 (above, trade name of Asahi Denki Kogyo Co., Ltd.), DAICATII (trade name of Dell Chemical Industry Co., Ltd.), and UVAC1591 (DAICEL CYTEC) Trade name), CI-2734, CI-2855, CI-2823, CI-2758 (above, the product name of Japan's Soda Co., Ltd.), PI-2074 (trade name of Rhône-Poulenc (share)), FFC509 (trade name of 3M (share)), RHODORSIL photopolymerization initiator 2074 ( ROHDIA (trade name), BBI-102, BBI-101 (trade name of Green Chemical Co., Ltd.), CD-1012 (trade name of SARTOMER).

The above thermosetting catalyst may, for example, be imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole or 1-cyano group. Imidazole derivatives such as ethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanamide, benzyldimethylamine, 4-( Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine An amine compound such as an amine compound, diammonium adipate or diammonium phthalate; a phosphorus compound such as triphenylphosphine; and the like. For example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemicals Co., Ltd., and U-made by San-Apro Co., Ltd., may be mentioned. -CAT3503N, U-CAT3502T (all trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic guanidine compounds and salts thereof). These may be used singly or in combination of two or more. It will have a (meth) acrylonitrile group and an epoxy propyl group in the molecule and a viscosity of 10 mPa at 25 ° C. When the monomer below s is 100 parts by mass, the amount of the thermosetting catalyst is 0.1 to 5 parts by mass, and is added to 0.5 to 4 parts by mass.

In the photocurable thermosetting composition for inkjet according to the first embodiment of the present invention, a diluent solvent may be added for the purpose of adjusting the viscosity. Examples of the diluent solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, seed, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and card. Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate Acetate such as carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; ethanol, propanol, ethylene glycol, An alcohol such as propylene glycol; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, petroleum brain, hydrogenated petroleum brain or solvent oil.

Further, the photocurable thermosetting composition according to the first embodiment of the present invention may be blended with phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, carbon black, naphthalene black, etc., if necessary. Conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, gallic phenol, phenothiazine, etc., polyfluorene, fluorine, polymer, etc. An antifoaming agent and/or a leveling agent, and an additive such as an imidazole imparting agent such as an imidazole-based, a thiazole-based, a triazole-based or a decane coupling agent.

[Examples]

In the following, an embodiment of the photocurable thermosetting composition for inkjet according to the first embodiment of the present invention will be described, and the present invention will be specifically described. However, the present invention is not limited to the embodiments. In addition, the following "parts" means the parts by mass unless otherwise defined.

In each of Examples 1 to 5 and Comparative Examples 1 to 6, the respective components were blended in the ratio shown in Table 1, and the mixture was stirred by a dissolver and further filtered by a 1 μm disk filter to obtain each composition.

<In the molecule, there is (meth)acryloyl group and epoxypropyl group and the viscosity at 25 ° C is 10 mPa. s below monomer>

GMA: Epoxypropyl methacrylate (viscosity 2mPa.s (25°C))

4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (viscosity 7mPa.s (25 ° C))

<A monomer other than a 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 ° C>

EA-1010N: epoxide-added propylene to bisphenol A type epoxy resin Acidic acid compound (Nippon Nakamura Chemical Industry Co., Ltd. (viscosity 22,000mPa.s (25°C))

AGE: allyl epoxypropyl ether with allyl and epoxy propyl (viscosity 1mPa.s (25 ° C))

4HBA: 4-hydroxybutyl acrylate (viscosity 10mPa.s (25 ° C))

DPGDA: dipropylene glycol diacrylate (viscosity 12mPa.s (25 ° C))

M-100: 3,4-epoxycyclohexylmethyl methacrylate Compound having methacryl fluorenyl group and alicyclic epoxy group Manufactured by Dale Chemicals Co., Ltd. (viscosity 10 mPa.s (25 ° C))

<3-functional acrylate monomer>

PETA: pentaerythritol triacrylate

TMPTA: Trimethylolpropane triacrylate

SR9011: 3-functional methacrylate ester manufactured by SARTOMER

M327: ε-caprolactone denatured ginseng (propylene oxyethyl) trimeric isocyanate (manufactured by Toagosei Co., Ltd.)

<Thermal hardening catalyst>

2E4MZ: 2-ethyl-4-methylimidazole

<Photopolymerization initiator>

IRG819: IRGACURE 819 manufactured by BASF

Each of the above compositions was subjected to a characteristic test as shown below. The results are shown in Table 2.

<Coating property>

Each of the above-described compositions was printed on an inkjet printing paper (Epson paper A4) using an Fujifilm inkjet printer, Dimatix Materials Printer DMP-2831, to form an L-shaped line having a width of 100 μm and a length of 20 mm on one side. The L-shaped line was observed with a magnifying glass, and the shape of the line was evaluated as follows.

○: The line is not blurred or distorted and is correctly drawn.

×: The confirmation cannot be confirmed, or the line is blurred or distorted.

<Photohardenability>

The above composition was printed to a size of 10×20 mm on a printed circuit board copper-clad laminate (FR-4 thickness 1.6 mm size 150×95 mm) using a Fujifilm inkjet printer Dimatix Materials Printer DMP-2831. The rectangular pattern. Immediately thereafter, the above printed laminate was irradiated with UV at a cumulative light amount of 300 mJ/cm ² using a high pressure mercury lamp. Regarding the rectangular pattern, the hardened state after the UV irradiation was evaluated as follows.

○: It has been hardened and kept in shape.

×: Not hardened.

<adhesiveness>

Using the Fujifilm inkjet printer Dimatix Materials Printer DMP-2831, the above-mentioned respective compositions were made to have a film thickness on a copper-clad laminate for printed circuit boards (FR-4 thickness: 1.6 mm, size: 150 × 95 mm). It is printed in a rectangular pattern of 10 × 20 mm in a size of 15 μm. Immediately thereafter, the above printed laminate was irradiated with UV light at a cumulative light amount of 300 mJ/cm ² using a high pressure mercury lamp. Next, the UV-irradiated laminate was heated at 150 ° C for 30 minutes in a hot air circulating drying oven to thermally harden the pattern to obtain each test piece. The rectangular pattern of each test piece was cut by a cutting blade on the vertical and horizontal axes by a cutting blade, and peeling of the cellophane tape was performed thereon, and the peeling was evaluated as follows.

○: Almost no peeling was observed.

×: There is a large transfer peeling on Cellotape (registered trademark).

<Chemical resistance>

Each of the above-mentioned compositions was prepared into the respective test pieces in the same manner as the method described in the above adhesion test. Each test piece was immersed in propylene glycol monomethyl ether acetate at room temperature for 30 minutes, taken out, and dried. The state of the coating film was evaluated by visual observation of each test piece after drying.

○: The state of the coating film has not changed.

×: The coating film is floated and peeled off.

<heat resistance>

Each of the above-mentioned compositions was prepared into the respective test pieces in the same manner as the method described in the above adhesion test. Each of the test pieces was coated with a rosin-based flux, and immersed in a flux bath at 260 ° C for 10 seconds, and taken out, and then naturally cooled. After the test was repeated three times, the state of the coating film for each test piece was evaluated by visual observation as follows.

○: The state of the coating film has not changed.

×: The coating film is floated and peeled off.

<insulation>

The composition of the above Examples 1 to 5 was the same as the method described in the adhesion test except that the comb-shaped electrode B sample of the IPC B-25 test pattern was used instead of the copper-clad laminate, and the film thickness was 40 μm. The test piece was prepared by the method. A bias voltage of DC500V was applied to the test piece to measure the insulation resistance value. If the value is 100 GΩ or more, it is ○, and if it is less than 100 GΩ, it is ×.

As described above, the photocurable thermosetting composition for inkjet according to the present invention can directly draw a pattern on a substrate for a printed circuit board using an ink jet printer, and has no problem of coating property. Next, a resin insulating layer excellent in adhesion, chemical resistance, and heat resistance is formed.

Next, the photocurable thermosetting composition for inkjet according to the second embodiment of the present invention will be described in detail. In this embodiment, the description is about It is preferable to form a photo-curable thermosetting composition for inkjet printing which is suitable for forming a mark pattern, and a method for producing the same, and a printed circuit board using the same.

The photocurable thermosetting composition for inkjet according to the second embodiment can directly draw a predetermined mark pattern on an insulating resin layer formed on a printed circuit board by using an ink jet printer. The active energy ray is irradiated to be hardened once, and thereafter, by heating and hardening, a pattern of heat resistance, chemical resistance, adhesion, and the like can be formed. Further, the composition contains a thermosetting catalyst, and can be sufficiently cured even at a low temperature of the heating temperature at the time of manufacturing the printed wiring board in the heat curing. In this case, the irradiation condition of the active energy ray is preferably 100 mJ/cm ² or more, and preferably 300 mJ/cm ² to 2000 mJ/cm ² . Further, the conditions for heat curing are 20 minutes or longer at 140 to 170 ° C, preferably 20 to 60 minutes at 150 to 170 ° C.

The irradiation of the above-mentioned active energy ray is preferably carried out in parallel with the case of drawing a pattern using an ink jet printer as described in the description of the first embodiment. As described above, the method is, for example, a method of irradiating an active energy ray from a side portion or a bottom portion of a substrate or the like when drawing a pattern. The active light source illumination source can utilize 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. Others may also use an electron beam, an alpha line, a beta line, a gamma line, an X line, a neutral line, or the like.

In the same manner as in the first embodiment, the (meth)acryloyl group and the epoxy group are contained in the molecule and the viscosity at 25 ° C is 10 mPa. The monomer below s, for example, may be exemplified by epoxy propyl methacrylate or 4-hydroxybutyl acrylate epoxide A commercially available product may be a Blemmer G manufactured by Nippon Oil Co., Ltd. or a light ester G produced by Kyoeisha Chemical Co., Ltd., or the like.

The above-mentioned trifunctional or higher acrylate single system may be the same as the monomer of the first embodiment. However, it will have a (meth) acrylonitrile group and an epoxy propyl group in the molecule and a viscosity of 10 mPa at 25 ° C. When the amount of the monomer below s is 100 parts by mass, the amount of the trifunctional or higher acrylate monomer is from 15 to 400 parts by mass, preferably from 20 to 300 parts by mass.

As the titanium oxide, any of anatase type titanium oxide and rutile type titanium oxide can be used. From the viewpoint of suppressing photodegradation of the mark pattern, it is particularly preferable to use rutile-type titanium oxide. Compared with rutile-type titanium oxide, anatase-type titanium oxide has a high reflectance near the boundary between the ultraviolet field and the visible light field, and an anatase titanium oxide is used on the whiteness and reflectance side. White pigments are ideal. However, the anatase-type titanium oxide has a photocatalytic activity, and thus it is photoactive to cause discoloration of the resin contained in the photohardenable thermosetting composition. On the other hand, the rutile-type titanium oxide has a slightly lower whiteness than the anatase-type titanium oxide, but since it has almost no photocatalytic activity, deterioration of the resin can be suppressed, and a stable mark pattern can be obtained. .

Specific examples of the rutile-type titanium oxide include TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-670, TIPAQUE R-680, and TIPAQUE R- 780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUE CR-80, TIPAQUE CR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUE CR-67, TIPAQUE CR-58, TIPAQUE CR-85, TIPAQUE UT771 (above, Ishihara Sangyo Co., Ltd.), Ti-Pure R-100, Ti-Pure R- 101, Ti-Pure R-102, Ti-Pure R-103, Ti-Pure R-104, Ti-Pure R-105, Ti-Pure R-108, Ti-Pure R-900, Ti-Pure R-902 , Ti-Pure R-960, Ti-Pure R-706, Ti-Pure R-931 (above, DuPont), TITON R-25, TITON R-21, TITON R-32, TITON R-7E , TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D-918 , TITON TCR-29, TITON TCR-52, TITON FTR-700 (above, 堺Chemical Industry Co., Ltd.).

Further, the anatase-type titanium oxide may, for example, be TA-100, TA-200, TA-300, TA-400, TA-500 (above, manufactured by Fuji Titanium Industries Co., Ltd.), TIPAQUE A-100, TIPAQUE A-220, TIPAQUE W-10 (above, Ishihara Industry Co., Ltd.), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5 (above, TAYCA (share) system), KRONOS KA -10, KRONOS KA-15, KRONOS KA-20, KRONOS KA-30 (above, Titanium Industry Co., Ltd.), A-100, A-100, A-100, SA-1, SA-1L (above,堺Chemical Industry (shares) system, etc.

The amount of the titanium oxide is preferably from 3 to 30 parts by mass, more preferably from 5 to 20 parts by mass, based on the total amount of the total composition. When the amount of the titanium oxide is more than 30 parts by mass, the viscosity of the photocurable thermosetting composition of the present invention is high and the photocurability is lowered, and the hardening is deep. The degree is not good. On the other hand, when the amount of the titanium oxide is less than 3 parts by mass, the concealing force of the photocurable thermosetting composition is small, and the white marking pattern cannot be obtained.

Since the above-mentioned thermosetting catalyst is the same as that of the first embodiment, it will be described in detail herein.

The photopolymerization initiator is a photoradical polymerization initiator or a photocationic polymerization initiator as in the first embodiment.

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

Since the photocationic polymerization initiator is still the same as that of the first embodiment, it will be described in detail herein.

The photocurable thermosetting composition for inkjet according to the present invention is the same as that of the first embodiment, and a diluent solvent may be added for the purpose of adjusting the viscosity. However, detailed description thereof will be omitted in order to avoid redundancy.

Further, in the same manner as in the first embodiment, the photocurable thermosetting composition of the present invention may be blended with a conventionally known polymerization inhibiting agent, a polyfluorene-based, fluorine-based or polymeric antifoaming agent. And/or a leveling agent, an additive such as an imidazole imparting agent such as an imidazole-based, a thiazole-based, a triazole-based or a decane coupling agent.

[Examples]

Hereinafter, the photocurable thermosetting composition according to the second embodiment of the present invention will be specifically described. Similarly to the above, unless otherwise defined, "parts" means parts by mass.

In each of Examples 1 to 5 and Comparative Examples 1 to 8, the components were blended in the proportions shown in Table 3, and the dissolver was stirred, and further filtered by a 1 μm disk filter to obtain each composition.

<In the molecule, there is (meth)acryloyl group and epoxypropyl group and the viscosity at 25 ° C is 10 mPa. s below monomer>

GMA: Epoxypropyl methacrylate (viscosity 2mPa.s (25°C))

4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (viscosity 7mPa.s (25 ° C))

<"In the molecule, it has a (meth)acryloyl group and an epoxy group and is sticky at 25 ° C. The degree is 10mPa. Monomers other than the monomer below s>

EA-1010N: a compound of a single epoxy group of bisphenol A type epoxy resin. New Nakamura Chemical Co., Ltd. (viscosity 22,000 mPa.s (25 ° C))

AGE: allyl epoxypropyl ether with allyl and epoxy propyl (viscosity 1mPa.s (25 ° C))

4HBA: 4-hydroxybutyl acrylate (viscosity 10mPa.s (25 ° C))

DPGDA: dipropylene glycol diacrylate (viscosity 12 mPa.s (25 ° C))

M-100: 3,4-epoxycyclohexylmethyl methacrylate with methyl propyl Alkene-based and alicyclic epoxy-based compounds manufactured by Dell Chemical Industry (viscosity 10mPa.s (25°C))

<3-functional acrylate monomer>

PETA: pentaerythritol triacrylate

TMPTA: Trimethylolpropane triacrylate

SR9011: 3-functional methacrylate ester manufactured by SARTOMER

M327: ε-caprolactone denatured ginseng (propylene oxyethyl) trimeric isocyanate (manufactured by Toagosei Co., Ltd.)

<titanium oxide>

CR-95: Titanium industry titanium oxide

<Barium sulfate>

B-30: Barium sulfate produced by bismuth chemical

<Thermal hardening catalyst>

2E4MZ: 2-ethyl-4-methylimidazole

<Photopolymerization initiator>

IRG819: IRGACURE 819 manufactured by BASF

Each of the above compositions was subjected to a characteristic test as shown below. The results are shown in Table 4.

<Coating property>

Using the Fujifilm inkjet printer Dimatix Materials Printer DMP-2831, the inkjet sheet for inkjet printers (Sunhayato PF-10R-A4) was used to print the English letters A~ in the size of 2 mm square. Z. The shape of the character was observed with a magnifying glass, and each character was evaluated as follows.

○: The text is not blurred or distorted, and there is no flying to the extra part.

×: The text cannot be confirmed, or the text is blurred or distorted, or there is a portion that flies to the excess.

<Photohardenability>

For copper-clad laminates for printed circuit boards (FR-4 thickness: 1.6 mm, size: 150 × 95 mm), solar ink is made into a solder resist PSR-4000G24 so that the dried coating film can be screen-printed at 20 μm. Full-page printing. This was dried at 80 ° C for 30 minutes, and the coating film was entirely exposed to the pattern of the above laminate, and exposed at 300 mJ/cm ² . The exposed laminate was developed at 30 ° C 1 wt% Na ₂ CO ₃ and washed with water. Further, it was hardened at 150 ° C for 30 minutes to prepare a test substrate. Further, each of the above-described compositions was printed into a rectangular pattern of a size of 10 × 20 mm on each of the test substrates using Dimatix Materials Printer DMP-2831, an inkjet printer manufactured by Fujifilm. Further, after printing, UV was irradiated to each test substrate using a high-pressure mercury lamp at a cumulative light amount of 300 mJ/cm ² .

Regarding the above rectangular pattern, the hardened state after UV irradiation was evaluated as follows.

○: It has been hardened and kept in shape.

×: Not hardened.

<adhesiveness>

Each test substrate was prepared in the same manner as the method described in the above photocurability test. Further, using the Fujifilm Film Printer Dimatix Materials Printer DMP-2831, each of the above-described compositions was printed in a rectangular shape of 10 × 20 mm in a film thickness of 15 μm on each of the above test substrates. type. Immediately after the printing, UV was irradiated to each test substrate using a high-pressure mercury lamp at a cumulative light amount of 300 mJ/cm ² . Next, each test substrate after UV irradiation was heated at 150 ° C for 30 minutes in a hot air circulation type drying furnace to be thermally cured, and each test piece was obtained. Thereafter, each of the rectangular patterns of the test pieces was cut by a cutting knife on the vertical and horizontal axes, and then peeling test was performed with a cellophane tape, and evaluation of peeling was performed as follows.

○: Almost no peeling was observed.

×: There is a large transfer peeling on Cellotape (registered trademark).

<Chemical resistance>

Each of the above-mentioned compositions was prepared into the respective test pieces in the same manner as the method described in the above adhesion test. Each test piece was immersed in propylene glycol monomethyl ether acetate at room temperature for 30 minutes, taken out, and dried. The state of the coating film was evaluated by visual observation of each test piece after drying.

○: The state of the coating film has not changed.

×: The coating film is floated and peeled off.

<heat resistance>

Each of the above-mentioned compositions was prepared into the respective test pieces in the same manner as the method described in the above adhesion test. Each of the test pieces was coated with a rosin-based flux, and immersed in a flux bath at 260 ° C for 10 seconds, and taken out, and then naturally cooled. After the test was repeated three times, the state of the coating film for each test piece was evaluated by visual observation as follows.

○: The state of the coating film has not changed.

×: The coating film is floated and peeled off.

<identification>

It is made in the same manner as the method described in the above photocurability test. Each test substrate. Further, the above-mentioned respective compositions were printed with English letters A to E on the respective test substrates in a size of 3 mm square using a Fujifilm sheet-type inkjet printer Dimatix Materials Printer DMP-2831. Regarding each character, the comparison with the substrate was visually evaluated as follows.

○: The contrast is large and the text can be clearly recognized.

×: The contrast is small and the difference between the base and the text is blurred.

As described above, the photocurable thermosetting composition for inkjet according to the second embodiment of the present invention can directly draw a pattern on a resin insulating layer formed on a printed circuit board using an ink jet printer. And without the problem of coating properties, it can form a marking pattern with excellent adhesion, chemical resistance and heat resistance. In particular, it is possible to form a mark pattern having a high adhesion to the above-mentioned resin insulating layer. Further, the photocurable thermosetting composition can be used as a marking composition which requires a severe characteristic as a printed circuit board.

Claims (8)

A photocurable thermosetting composition for inkjet for low temperature curing at 150 ° C or lower, which comprises a (meth)acryl fluorenyl group and an epoxy propyl group in a molecule and having a viscosity of 10 mPa at 25 ° C. s or less monomer, trifunctional or higher acrylate monomer, thermosetting catalyst, photopolymerization initiator; having a (meth) acrylonitrile group and an epoxy propyl group in the molecule and having a viscosity of 25 ° C relative to the above The amount of the thermosetting catalyst is 0.1 to 5 parts by mass based on 100 parts by mass of the monomer of 10 mPa·s or less. The photocurable thermosetting composition for inkjet according to claim 1, wherein the monomer having a (meth)acrylonium group and a glycidyl group in the molecule and having a viscosity at 25 ° C of 10 mPa·s or less is a ring. Oxypropyl methacrylate or 4-hydroxybutyl acrylate glycopropyl ether. The photocurable thermosetting composition for inkjet according to claim 2, wherein the monomer having a (meth)acrylonium group and a glycidyl group in the molecule and having a viscosity at 25 ° C of 10 mPa·s or less is used. The amount of the above-mentioned trifunctional or higher acrylate monomer is from 15 to 400 parts by mass per 100 parts by mass. A printed circuit board characterized by having a photocurable thermosetting composition for inkjet according to any one of claims 1 to 3, wherein a pattern is drawn on a substrate by an ink jet printer, and Hardened resin insulation. A photocurable thermosetting composition for inkjet for low temperature curing at 150 ° C or lower, which is used for patterning on a resin insulating layer formed on a printed circuit board, and is characterized by being contained in a molecule (A) a monomer having a propylene fluorenyl group and a propylene group and having a viscosity at 25 ° C of 10 mPa·s or less, a trifunctional or higher acrylate monomer, a titanium oxide, a thermosetting catalyst, and a photopolymerization initiator; 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) acrylonitrile group and a glycidyl group in the molecule and a viscosity at 25 ° C of 10 mPa ‧ or less. The photocurable thermosetting composition for inkjet according to claim 5, wherein the monomer having a (meth)acrylonium group and a glycidyl group in the molecule and having a viscosity at 25 ° C of 10 mPa·s or less is a ring. Oxypropyl methacrylate or 4-hydroxybutyl acrylate glycopropyl ether. The photocurable thermosetting composition for inkjet according to claim 6, wherein the monomer having a (meth)acrylonium group and a glycidyl group in the molecule and having a viscosity at 25 ° C of 10 mPa·s or less is used. The amount of the above-mentioned trifunctional or higher acrylate monomer is from 15 to 400 parts by mass per 100 parts by mass. A printed circuit board characterized by having a photocurable thermosetting composition for inkjet according to any one of claims 5 to 7 using an ink jet printer on a resin insulating layer which has been formed on a printed circuit board. The object is depicted in a pattern, And make it hardened into a pattern.