JP2005068280A - Photo-curable/heat-curable composition for inkjet and printed wiring board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat resistant photo-curable/heat-curable composition that permits direct writing, as solder resist ink, on a printed wiring board with use of an inkjet printer; to provide its cured product; and to provide a printed wiring board with a solder resist pattern formed thereon using it. <P>SOLUTION: The photo-curable/heat curable composition for inkjet contains (A) an acid anhydride, (B) a liquid compound having a cyclic ether group such as oxirane group or oxetanyl group, (C) a photoreactive diluent, and (D) a photopolymerization initiator, and has viscosity of ≤150 mPa s at 25°C. Using the composition the solder resist pattern is directly drawn on the printed wiring board with the inkjet printer, which is primarily cured by irradiation of an active energy ray and then further heat cured. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a heat-resistant photocurable and thermosetting composition suitable for direct drawing using an ink jet printer as a solder resist ink, a cured product thereof, and a solder resist pattern drawn directly using the same. It is related with the printed wiring board which has.

  As a method of manufacturing a printed wiring board using an ink jet printer, it has already been proposed to form an etching resist by drawing a conductor circuit pattern on a metal foil on a plastic substrate using an ink jet printer and perform an etching process. (See Patent Documents 1 to 4). Since this method draws directly in accordance with CAD data, it takes more steps than patterning by a photographic development method that requires a photomask using a photosensitive resin or patterning resist ink by a screen printing method. This has the advantage that labor and time can be greatly reduced, and consumables such as developer, resist ink, and cleaning solvent can be reduced.

In addition, a solder resist for protecting a conductor circuit formed on a printed wiring board has already been proposed to be formed by an ink jet method (see Patent Documents 5 and 6), and its construction method is the same as that of an etching resist. is there. Also in this case, the number of steps, time, and consumables can be reduced as compared with the photographic development method and the screen printing method. Furthermore, it has also been proposed to draw out the advantages of the ink jet system by dividing the etching resist, solder resist, marking ink and ink tanks of those curing agents and sharing the printer (see Patent Document 7).
JP-A-56-66089 (Claims) JP-A-56-157089 (Claims) JP 58-50794 (Claims) JP-A-6-237063 (Claims) JP-A-7-263845 (Claims) Japanese Patent Laid-Open No. 9-18115 (Claims) JP-A-8-236902 (Claims)

  However, there is a restriction that the ink for ink jet needs to have a viscosity of about 20 mPa · s or less at the time of application, which is far from the viscosity of about 20,000 mPa · s which is the viscosity of the ink used for screen printing. Even if diluted with a large amount of diluent, it does not decrease to the target viscosity. Even if the viscosity is reduced, the physical properties such as heat resistance and chemical resistance required as a solder resist are greatly reduced. Furthermore, when diluted with a volatile solvent, the non-volatile content becomes very small and it is difficult to ensure the film thickness. In addition, since thermal sagging of the pattern occurs during thermosetting, it is difficult to obtain a desired coating film shape. For this reason, the above-described ink jet system has not come out of idea as a solder resist for printed wiring boards, and there has been no practical solder resist ink that can be used in an ink jet printer.

The present invention has been made to solve the above-described problems of the prior art, and its main purpose is to provide heat-resistant light that can be directly drawn as a solder resist ink using an inkjet printer on a printed wiring board. It is intended to provide a curable / thermosetting composition and a cured product thereof.
Furthermore, the objective of this invention is providing the printed wiring board which formed the heat resistant soldering resist pattern drawn directly using this photocurable and thermosetting composition.

In order to achieve the object, according to the present invention, (A) an acid anhydride, (B) a liquid compound having a cyclic ether group, (C) a photoreactive diluent, and (D) a photopolymerization initiator. And a viscosity of 150 mPa · s or less at 25 ° C. is provided, which is a heat-resistant photocurable / thermosetting composition for inkjet. In a preferred embodiment, (E) a curing accelerator is further contained.
Viscosity here means the viscosity measured at normal temperature (25 degreeC) according to JISK2283. As described above, in the case of the ink jet system, the viscosity of the ink needs to be about 20 mPa · s or less at the temperature at the time of application. This condition can be satisfied.

  The photocurable / thermosetting composition for inkjet according to the present invention may have a viscosity at 25 ° C. of 150 mPa · s or less as a whole composition. In a more preferred embodiment, the component (A) and ( It is preferable that both the components B) satisfy this condition. That is, according to a preferred embodiment of the present invention, (A) an acid anhydride having a viscosity at 25 ° C. of 150 mPa · s or less, (B) an oxirane group having a viscosity at 25 ° C. of 150 mPa · s or less, oxetanyl A liquid compound having a cyclic ether group such as a group, (C) a photoreactive diluent having a weight average molecular weight of 700 or less, and (D) a photopolymerization initiator, and having a viscosity of 150 mPa · s or less at 25 ° C. There is provided a heat-curable photocurable / thermosetting composition for inkjet which is characterized by the above.

  The blending ratio of each component of the photocurable / thermosetting composition may be any ratio as long as the viscosity of the composition at 25 ° C. is 150 mPa · s or less, but in general, the oxirane group, The liquid compound (B) having a cyclic ether group such as an oxetanyl group is suitably in the range of 20 to 300 parts by mass per 100 parts by mass of the acid anhydride (A). The mixing ratio of the photoreactive diluent (C) is suitably in the range of 20 to 1,000 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. . On the other hand, the blending ratio of the photopolymerization initiator (D) is suitably in the range of 0.1 to 10% by mass of the entire composition.

  Further, according to the present invention, the heat-resistant photocurable / thermosetting composition for inkjet is used, and is cured by irradiating active energy rays at the same time or after application by the inkjet method, and then thermosetting. To provide a cured product formed in a predetermined pattern, and has a solder resist pattern drawn directly by an inkjet printer using the heat-resistant photocurable / thermosetting composition for inkjet. A printed wiring board is also provided.

  The photocurable / thermosetting composition for inkjet according to the present invention contains an acid anhydride (A) as a curing agent for the liquid compound (B) having a cyclic ether group such as the oxirane group or oxetanyl group. The first feature. Thereby, while thermosetting is accelerated | stimulated more rapidly, volatilization of the said compound (B) which is a thermosetting monomer can be reduced, and it becomes possible to obtain a desired film thickness. And the volatilization amount of the said compound (B) can further be reduced by using together a hardening accelerator (E). The second feature is that the photoreactive diluent (C) is used in combination with the polymerization initiator (D). As a result, primary curing by irradiation with active energy rays prior to thermal curing suppresses sagging during coating and curing, and it is required as a solder resist despite its low viscosity so that it can be jetted with an inkjet method. The cured film pattern having a desired shape having physical properties such as heat resistance and chemical resistance can be formed. Therefore, using the photocurable / thermosetting composition for inkjet of the present invention, the solder resist pattern is directly drawn with an inkjet printer, and the primary curing is performed by irradiating with active energy rays, thereby preventing the pattern from sagging. Then, by further heat-curing, a fine pattern excellent in various properties such as heat resistance, solder heat resistance, chemical resistance, hardness, electrical insulation, and electroless plating resistance can be formed.

  As a result of intensive studies on heat-curable photocurable / thermosetting compositions that can be directly drawn as a solder resist ink using an inkjet printer on a printed wiring board, the present inventors have found that the oxirane group, oxetanyl group, etc. A liquid compound (B) having a cyclic ether group is used as a thermosetting base monomer, and an acid anhydride (A) is blended as the curing agent, and a photoreactive diluent (C) and a polymerization initiator (D) are added. The compounded photocurable and thermosetting composition was found to have practical properties such as heat resistance and chemical resistance as a solder resist that can be applied with an ink jet printer, and led to the completion of the present invention. is there.

  That is, the photocurable / thermosetting composition for inkjet according to the present invention is an acid anhydride as a curing agent for the liquid compound (B) having a cyclic ether group such as the oxirane group or oxetanyl group, which is a thermosetting component. The first feature is that it contains (A), whereby the ring-opening polymerization of the compound (B) occurs more rapidly, the thermal curing is accelerated, and the compound is a thermosetting monomer. It is possible to reduce volatilization of (B) and obtain a desired film thickness. That is, since acid anhydrides, particularly acid anhydrides that are liquid at room temperature, have low viscosity, they are optimal as curing agents for the liquid compound (B) having the cyclic ether group, and contain these as thermosetting components. The composition can achieve a reduction in viscosity, which has not been achieved conventionally as an ink jet composition. However, since an acid anhydride tends to volatilize at the time of thermosetting, there exists a difficulty that a desired cured film thickness cannot be obtained.

  Therefore, the second feature of the photocurable / thermosetting composition for inkjet according to the present invention is that a photoreactive diluent (C) that is liquid at room temperature as a photocurable component is used in combination with a polymerization initiator (D). There is. This hardens the coating film by primary curing by irradiation with active energy rays prior to thermal curing, effectively preventing acid anhydride volatilization during thermal curing, and suppresses sagging during coating and curing. The cured film pattern having a desired film thickness is obtained by caulking. In addition, the photoreactive diluent (C) that is liquid at room temperature is advantageous for achieving a low viscosity as an ink jet composition.

The photocurable / thermosetting composition of the present invention having the above-described composition has heat resistance, chemical resistance, and the like required as a solder resist despite being so low in viscosity that it can be jetted by an inkjet method. The pattern of the cured film having the physical properties can be formed. For example, by using the photocurable / thermosetting composition for ink jet of the present invention, a solder resist pattern is directly drawn on a printed wiring board with an ink jet printer, and primary curing is performed by irradiating with an active energy ray. By preventing sagging and then heat-curing, a fine pattern excellent in various properties such as heat resistance, solder heat resistance, chemical resistance, hardness, electrical insulation, and electroless plating resistance can be formed. At this time, the irradiation conditions of the active energy rays, 100 mJ / cm ² or more, preferably it is desirable to ^{300mJ / cm 2 ~2000mJ / cm 2} . Further, the heat curing conditions are 80 to 200 ° C. for 10 minutes or longer, preferably 140 to 180 ° C. for 20 to 60 minutes.

  The irradiation of the active energy ray can be performed after pattern drawing by the ink jet printer, but it is preferable to perform the irradiation simultaneously, for example, by irradiating the active energy ray from the side or the lower side in parallel with the pattern drawing by the ink jet printer. As the irradiation source of the active energy ray, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, electron beams, α rays, β rays, γ rays, X rays, neutron rays, and the like can also be used.

Hereinafter, the photocurable and thermosetting composition for inkjet according to the present invention will be described in detail.
First, as the acid anhydride (A), a solid or liquid acid anhydride can be used at room temperature, but in the case of a solid acid anhydride such as trimellitic anhydride or pyromellitic anhydride, the composition can be used. From the viewpoint of dispersibility, it is necessary to make the maximum particle size 1 μm or less. Since there is no such difficulty, a liquid acid anhydride, particularly a liquid acid anhydride having a viscosity at 25 ° C. of 150 mPa · s or less is most preferable. Specific examples of such acid anhydrides include methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: Epicron B570 / manufactured by Dainippon Ink and Chemicals), methyl-hexahydro anhydride. Phthalic acid (trade name: Epicron B650 / manufactured by Dainippon Ink and Chemicals), methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (trade name: Hymic anhydride / Hitachi) Kasei Kogyo Co., Ltd.), 4-methylhexahydrophthalic anhydride (trade name: Ricacid MH-700 / Shin Nihon Rika Co., Ltd.), citraconic anhydride, dodecene succinic anhydride (trade name: Ricacid DDSA / New) Nippon Rika Co., Ltd.), glycerol bis (anhydrous trimellitate) monoacetate (trade name: Ricacid MTA-10 / manufactured by Shin Nippon Rika Co., Ltd.) Examples of commercially available products (trade name / Nippon Zeon Co., Ltd.) Quinn hard -200, there is an Epicure YH-306 (trade name / manufactured by Japan Epoxy Resins Co., Ltd.), and the like.
The acid anhydride (A) can be used alone or in combination.

  The compound (B) having a cyclic ether group is preferably a compound having an oxirane group or oxetanyl group, particularly a liquid compound having a viscosity at 25 ° C. of 150 mPa · s or less. Specific examples of such compounds include glycidyl methacrylate, (meth) acryloyl group-containing alicyclic epoxy resins (trade names: cyclomers M100, A200, A2000) and the like as compounds having an oxirane group. . In addition, ethylene glycol diglycidyl ether (trade name: Epolite 40E / Kyoeisha Chemical Co., Ltd.), diethylene glycol diglycidyl ether (trade name: Epolite 100E / Kyoeisha Chemical Co., Ltd.), polyethylene glycol diglycidyl ether (trade name: Epolite 200E, 400E / manufactured by Kyoeisha Chemical Co., Ltd.), propylene glycol diglycidyl ether (trade name: Epolite 70P / manufactured by Kyoeisha Chemical Co., Ltd.), tropropylene glycol diglycidyl ether (trade name: Epolite 200P / Kyoeisha Chemical Co., Ltd.) ), Polypropylene glycol diglycidyl ether (trade name: Epolite 400P / manufactured by Kyoeisha Chemical Co., Ltd.), neopentyl glycol diglycidyl ether (trade name: Epolite 1500NP / Kyoeisha Chemical Co., Ltd.) ), 1,6-hexanediol diglycidyl ether (trade name: Epolite 1600 / manufactured by Kyoeisha Chemical Co., Ltd.), glycerin diglycidyl ether (trade name: Epolite 80MF / manufactured by Kyoeisha Chemical Co., Ltd.), trimethylolpropane triglycidyl Ether (trade name: Epolite 100MF / manufactured by Kyoeisha Chemical Co., Ltd.), resorcinol diglycidyl ether (trade name: Denacol EX-201), hydrogenated bisphenol A diglycidyl ether (trade name: Epolite 4000 / manufactured by Kyoeisha Chemical Co., Ltd.) ), 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, phenol novolac type epoxy resin (trade names: Epicron N-730S, N-740 / manufactured by Dainippon Ink and Chemicals, Inc.), t-butyl Catechol-modified epoxy resin (trade name: Epiclone HP-820), alicyclic epoxy resin (trade name: Celoxide 2021, 2080, 3000, Epolide GT301), cardo modified epoxy resin (trade name: BPEF-G / Osaka Gas ( Etc.).

On the other hand, as a liquid compound having an oxetanyl group, 3-ethyl-3-hydroxymethyloxetane (trade name OXT-101), 1,4-bis [[(3-ethyl-3-oxetanyl) methoxy] methyl] benzene (Trade name OXT-121), 3-ethyl-3- (phenoxymethyl) oxetane (trade name OXT-211), di [1-ethyl (3-oxetanyl)] methyl ether (trade name OXT-221), 3- Ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name OXT-212), 4,4'-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl (trade name ETERNACOLL OXBP / Ube Industries ( ), Silsesquioxane-modified oxetane (trade name OX-SQ / manufactured by Toa Gosei Co., Ltd.), oxetane (me And acrylate (trade name: OXE-10, 30 / manufactured by Osaka Organic Chemical Co., Ltd.).
The compound (B) having a cyclic ether group can be used alone or in combination.

The photoreactive diluent (C) is liquid at room temperature, and for that purpose, the weight average molecular weight is preferably 700 or less, and the photoreactive group is typically a (meth) acryloyl group. Is mentioned. In the present specification, the (meth) acryloyl group is a generic term for an acryloyl group and a methacryloyl group, and the same applies to other similar expressions.
Specific examples of the monomer having one (meth) acryloyl group in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) ) Acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylates such as glycidyl methacrylate, and acryloylmorpholine. it can.

Specific examples of the polyfunctional monomer having two or more (meth) acryloyl groups in the molecule include, for example, polyethylene glycol diacrylate such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, or polyurethane. Diacrylates and their corresponding methacrylates, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylol methane triacrylate, ethylene oxide modified trimethylol propane triacrylate, propylene oxide modified trimethylol propane triacrylate, epichlorohydrin modified tri Methylolpropane triacrylate, pentaerythritol tetraacrylate, pentae Thritol tetramethacrylate, tetramethylolmethane tetraacrylate, ethylene oxide-modified phosphate triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, bisphenol fluorenedihydroxyhydroxyacrylate, bisphenol fluorenedimethacrylate, or these And polyfunctional acrylates typified by silsesquioxane-modified products, etc., or methacrylate monomers corresponding to these.
In addition, polyfunctional (meth) acrylates in which acrylate groups are introduced by esterification and amidation reaction of butanediol monoacrylate, polyethylene glycol acrylate, etc. to carboxyl group-containing polymers such as polymethacrylic acid, polyacrylic acid, and polymaleic acid are used. You can also

Other photoreactive diluents (C) include vinyl ethers, ethylene derivatives, styrene, chloromethylstyrene, α-methylstyrene, maleic anhydride, dicyclopentadiene, norbornadiene, N-vinylpyrrolidone, N-vinylformamide, and the like. And compounds having an unsaturated double bond.
The photoreactive diluent (C) can be used alone or in combination.

As the photopolymerization initiator (D) used in the present invention, a radical photopolymerization initiator can be suitably used. Any radical photopolymerization initiator can be used as long as it is a compound that generates radicals by light, laser, electron beam or the like and initiates radical polymerization reaction.
Specific examples of the radical photopolymerization initiator include, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, Acetophenones such as 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- Aminoacetophenones such as 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, Anthraquinones such as chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,5-triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s- Organohalogen compounds such as triazine, 2,2,2-tribromoethanol and tribromomethylphenylsulfone; benzophenones such as benzophenone and 4,4′-bisdiethylaminobenzophenone Sandtons; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine can be added. In addition, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction. The photopolymerization initiator and the photoinitiator aid are not particularly limited to these, as long as they absorb light in the ultraviolet or visible light region and radically polymerize unsaturated groups such as (meth) acryloyl groups. Not limited, it can be used alone or in combination.

  It is preferable to add a hardening accelerator (E) to the photocurable / thermosetting composition of the present invention in addition to the above components. Specific examples of the curing accelerator include imidazole derivatives, guanamines, polyamines and organic acid salts and / or epoxy adducts thereof, triazine derivatives, tertiary amines, organic phosphines, phosphonium salts, quaternary ammonium salts. , Copper, lead, tin, manganese, nickel, iron, chromium, zinc, cobalt, lithium, sodium, potassium, etc. of aliphatic or aromatic organic acids such as octylic acid, stearic acid, oleic acid, lauric acid, naphthenic acid Metal salts, U-CAT 5002 (manufactured by San Apro Co., Ltd.), Novacure HX-3612, 3613, 3741, 3742 (manufactured by Asahi Kasei Kogyo Co., Ltd.), cure adduct (Shikoku Kasei Kogyo Co., Ltd.) and the like. It can be used alone or in any combination of two or more.

  The addition amount of the curing accelerator is not particularly limited, but is preferably in the range of 0.01 to 25 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (C). The range of 1 to 15 parts by mass is more preferable. If the addition amount of the curing accelerator is less than 0.01, it may take a long time to increase the uncured part and cure, and may cause volatilization of the cured composition. On the other hand, if it exceeds 25 parts by mass, it is stable over time. There is a risk of deteriorating the properties and properties of the coating film.

  Furthermore, the photocurable / thermosetting composition of the present invention is a curable compound other than the components (A) to (C), in addition to the above components, in a quantitative ratio that does not impair the effects of the present invention. For example, vinyl group-containing compounds such as diethylene glycol divinyl ether, allyl group-containing compounds such as triallyl isocyanate, hydrogenated products of bisphenol A and bisphenol A, hydroxyl group-containing compounds such as phenol novolac resins, and isocyanate groups such as xylylene diisocyanate -Containing compounds, amino group-containing compounds such as melamine, mercapto group-containing compounds such as methanedithiol, oxazoline group-containing compounds such as 1,3-phenylenebisoxazoline, carboxyl group-containing compounds such as malonic acid, succinic acid and chic acid, phenol Solid at room temperature such as novolak oxetane An oxetanyl group-containing compound, an epoxy group-containing compound such as an alicyclic epoxy resin or a glycidyl ether type epoxy resin, a methoxymethyl group-containing compound, an imino group-containing compound, or an ethoxymethyl group-containing compound as a thermosetting component Can do. The photocurable / thermosetting composition for inkjet containing such a thermosetting component, the compound serves as a cross-linking agent, and the crosslink density of the cured film is increased, so that heat resistance, hardness, solder heat resistance, Various properties such as chemical resistance, electrical insulation and electroless plating resistance can be further improved.

  As described above, since the components (A) to (C) have a low viscosity in the photocurable / thermosetting composition for inkjet of the present invention, the addition of a diluting solvent is basically unnecessary. A dilution solvent can also be added for the purpose of adjustment. Examples of the diluent solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol Glycol ethers such as monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol Acetic acid ester such as 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, limonene, etc. Terpenes and the like.

  Furthermore, the photo-curable / thermosetting composition of the present invention can be used as necessary, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, Known and conventional fillers such as aluminum oxide, aluminum hydroxide, and mica powder, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and the like Known and usual polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, etc., defoamers and / or leveling agents such as silicones, fluorines and polymers, imidazoles, thiazoles, tones It may be blended azole, known conventional additives, such as adhesion imparting agents such as a silane coupling agent. However, when these additives are solid, the maximum particle size is preferably 1 μm or less.

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

Examples 1 to 14 and Comparative Examples 1 and 2
The blending components shown in Table 1 are mixed at the blending ratios shown in Table 2, and dispersed with Dispermat CA-40 and Milling System (manufactured by Getmann) for 20 minutes, filtered through a 1.0 μm filter, and used for inkjet. A photocurable and thermosetting composition was obtained.

Using each of the photocurable and thermosetting compositions thus obtained, the test substrate was prepared by drawing on the substrate with an ink jet printer under the following conditions, followed by UV curing and further thermosetting. It was.
<Drawing conditions by inkjet printer>:
Film thickness: 20 μm
Device: Uses a piezo inkjet printer (head temperature: 50 ° C)
<Conditions for UV curing>:
Exposure amount: 1000 mJ / cm ²
<Thermal curing conditions>:
180 ° C x 30 minutes

  About the test substrate produced as mentioned above, each characteristic shown in Table 3 was tested and evaluated. The results are shown in Table 3.

表３に示されるように、本発明に係る実施例１〜１４のインクジェット用光硬化性・熱硬化性組成物は、インクジェット方式で噴射可能なほど低粘度であるにも拘らず、ソルダーレジストとして要求される耐薬品性、はんだ耐熱性、無電解金めっき耐性に優れた硬化皮膜のパターンを形成できたが、本発明の（Ａ）〜（Ｃ）成分を含有しない比較例２ではこれらの特性に劣っており、また本発明の（Ｃ）成分を含有しない比較例１では充分満足できる特性は得られなかった。また、本発明に係る実施例１と１４によれば、硬化促進剤を添加することで、さらに揮発量を低減することができた。

As shown in Table 3, although the photocurable / thermosetting composition for inkjet of Examples 1 to 14 according to the present invention has a low viscosity so that it can be jetted by an inkjet method, it is used as a solder resist. Although the cured film pattern excellent in the required chemical resistance, solder heat resistance, and electroless gold plating resistance could be formed, these characteristics were obtained in Comparative Example 2 which does not contain the components (A) to (C) of the present invention. In Comparative Example 1 which does not contain the component (C) of the present invention, sufficiently satisfactory characteristics were not obtained. Moreover, according to Examples 1 and 14 which concern on this invention, the amount of volatilization could be reduced further by adding a hardening accelerator.

In addition, the evaluation method of each characteristic shown in Table 3 is as follows.
<Viscosity>
It measured based on the measuring method of JIS K-2283. The measurement temperature is 25 ° C.

<Coating hardness>
It measured based on JIS K-5400.

<Volatilization amount>
Each photocurable / thermosetting composition was applied to a glass plate (110 mm × 160 mm) having a thickness of 1.1 mm using an applicator so as to have a film thickness of 100 μm, and this was applied to a precision balance (manufactured by Mettler). Use and weigh precisely, and let the mass be w1. Then, after exposure at 1000 mJ / cm ^{2 with} a UV irradiator and then curing in a hot air circulating drying oven at 180 ° C. for 60 minutes, the weight was precisely measured using a precision balance in the same manner as described above. The amount of volatilization (%) was calculated by the following formula with w2.
Volatilization amount (%) = {(w1-w2) ÷ w1} × 100

<Solvent resistance>
The state of the coating film after visually immersing the cured coating film in acetone for 30 minutes was visually observed and evaluated according to the following criteria.
○: No change is observed at all.
Δ: Slightly changed (whitened).
X: Swelling or peeling of the coating film is observed.

<Chemical resistance>
5 wt. The state of the coating film after immersing in a 10% sulfuric acid aqueous solution for 10 minutes was observed and evaluated according to the following criteria.
○: No change is observed at all.
Δ: Slightly changed (whitened).
X: Swelling or peeling of the coating film is observed.

<Solder heat resistance>
Based on the method of JIS C-6481, the cured coating film was immersed in a solder bath at 260 ° C. for 10 seconds, and then the state of the coating film was visually observed after a peeling test using a cellophane adhesive tape. It was evaluated with.
○: No change in coating film.
Δ: The coating film has changed.
X: The film peeled off.

<Electroless plating resistance>
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating was performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the surface state of the cured coating film was observed. Judgment criteria are as follows.
○: No change at all.
Δ: There is a slight change.
X: Significant whitening or clouding occurred.

<Curing property>
The cured coating film was wiped off 50 times with a waste cloth containing acetone, and the coating film state was visually observed and evaluated according to the following criteria.
○: No change in coating film.
Δ: The coating film has changed.
X: The film peeled off.

The inkjet photocurable / thermosetting composition of the present invention is useful as a solder resist for printed wiring boards, and is directly cured by drawing a solder resist pattern directly on an inkjet printer and irradiating with active energy rays. Prevents the pattern from sagging and then further heat cures to form fine patterns with excellent properties such as heat resistance, solder heat resistance, chemical resistance, hardness, electrical insulation, and electroless plating resistance. . Moreover, since the photocurable / thermosetting composition for inkjet of the present invention has heat resistance, it is useful as a marking ink or the like that requires heat resistance.

Claims (4)

(A) An acid anhydride, (B) a liquid compound having a cyclic ether group, (C) a photoreactive diluent, and (D) a photopolymerization initiator, and having a viscosity of 150 mPa · s or less at 25 ° C. A heat-curable photocurable and thermosetting composition for inkjet, characterized by being. Furthermore, (E) hardening accelerator is contained, The photocurable and thermosetting composition for inkjets of Claim 1 characterized by the above-mentioned. Using the heat-resistant photocurable / thermosetting composition for inkjet according to claim 1 or 2, the composition is cured by irradiating with active energy rays simultaneously with or after application by the inkjet method, and then heat A cured product formed into a predetermined pattern by curing. A printed wiring board having a solder resist pattern drawn directly by an ink jet printer using the heat-resistant photocurable / thermosetting composition for ink jet according to claim 1.