JP6488149B2 - Photo-curable thermosetting resin composition, cured product thereof, and printed wiring board - Google Patents

Description

  The present invention relates to a photocurable thermosetting resin composition, a cured product thereof, and a printed wiring board. Specifically, the present invention relates to a photocurable thermosetting resin composition excellent in both sensitivity and solder heat resistance, a cured product thereof, and a printed wiring board.

  The solder resist used in the production of printed wiring boards is a liquid alkaline development type solder resist that forms an image by developing after exposure and heat-cures to form a coating film from the viewpoint of high accuracy and high density. Has been.

  In recent years, since lead contained in solder is harmful to the environment and the human body, the use of so-called lead-free solder that does not contain lead has been actively studied. As for this lead-free solder, the soldering temperature that has been standard at 220 ° C. to 230 ° C. has become as high as about 290 ° C. Under such circumstances, a solder resist composition using an inorganic silane compound in addition to the conventional organic materials has been proposed in order to improve solder heat resistance against the solder resist.

  For example, in Patent Document 1, in order to obtain a solder resist film excellent in PCT resistance and cooling cycle resistance in addition to solder heat resistance, (A) a novolak phenol resin (1) and an alkoxysilane partial condensate (2) are partially In particular, a solder resist composition containing an alkoxy group-containing silane-modified phenol resin, (B) an epoxy resin, and (C) a solvent, which is obtained by subjecting the alcohol to an alcohol-free condensation reaction, has been proposed.

  Moreover, in patent document 2, it consists of the partial hydrolyzate of an alkoxysilane compound, and an organic solvent from a viewpoint of improving heat resistance and being able to endure high temperature mounting by lead-free solder at the time of component mounting. In the two-component type solder resist coating, in which the first and second liquids composed of the first liquid and the second liquid composed of alkoxy titanium and an organic solvent are mixed and cured, the first liquid and / or the second liquid A two-component type solder resist coating containing potassium titanate fibers has been proposed.

  On the other hand, Patent Document 3 discloses an ethylenic unsaturated group having a hydroxyl group and two or more (meth) acryloyl groups in order to increase sensitivity to laser light and improve storage stability over time and adhesion to a substrate. It has been proposed to use an organic-inorganic composite (organic-inorganic hybrid resin) formed by chemically bonding silica and / or silicate to a compound.

JP 2002-40663 A (Claims etc.) Japanese Patent No. 3928136 (claims, etc.) Japanese Patent No. 4501402 (Claims etc.)

  In the solder resist composition, high solder heat resistance and the like can be obtained by using the organic-inorganic hybrid resin proposed so far, but there is still room for improvement in balance with sensitivity.

  Therefore, an object of the present invention is to provide a photocurable thermosetting resin composition excellent in both sensitivity and solder heat resistance, a cured product thereof, and a printed wiring board.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor uses a specific carboxyl group-containing photosensitive organic-inorganic hybrid resin varnish as a resin component, so that the above-mentioned component can be used without using an epoxy resin as a composition component. The present inventors have found that the problems can be solved and have completed the present invention.

  That is, in the photocurable thermosetting resin composition of the present invention, the unsaturated monocarboxylic acid (a2) is reacted with the epoxy group of the polyfunctional epoxy resin (a1), and the reaction product has hydroxyl groups. At least a silane compound having a (meth) acryloyl group with respect to the hydroxyl group of the photosensitive resin (A-1) containing a carboxyl group obtained by reacting the polybasic acid anhydride (a3) so that a part thereof remains. A carboxyl group-containing photosensitive organic-inorganic hybrid resin varnish (A) obtained by partially reacting a compound (A-2) obtained by subjecting one kind of silane compound to hydrolysis condensation reaction, and a photopolymerization initiator (B And an organic nitrogen compound (C).

  In the photocurable thermosetting resin composition of the present invention, the polyfunctional epoxy resin (a1) is preferably a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, or a cresol novolac type epoxy resin. The unsaturated monocarboxylic acid (a2) is preferably (meth) acrylic acid. Furthermore, the organic nitrogen compound (C) is preferably at least one of dicyandiamide, melamine or a derivative thereof.

  In addition, the cured product of the present invention is obtained by applying the photocurable thermosetting resin composition to a substrate and photocuring it by irradiation with active energy rays.

  Furthermore, the printed wiring board of the present invention has a cured coating film obtained by photocuring a coating film formed by applying the photocurable thermosetting resin composition on a substrate in a pattern. It is a feature.

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable thermosetting resin composition excellent in both a sensitivity and solder heat resistance, its hardened | cured material, and a printed wiring board can be provided. Moreover, according to this invention, since such an effect can be acquired, without using an epoxy resin, it becomes possible to set it as the one-component type photocurable thermosetting resin composition.

  Hereinafter, each component of the photocurable thermosetting resin composition of this invention is demonstrated in detail.

<Carboxyl group-containing photosensitive organic-inorganic hybrid resin varnish (A)>
Carboxyl group-containing photosensitive organic-inorganic hybrid resin varnish (A) (hereinafter referred to as “organic-inorganic hybrid resin varnish (A)” used in the photocurable thermosetting resin composition (hereinafter also referred to as “resin composition”) of the present invention. Is also referred to as “
Unsaturated monocarboxylic acid (a2) is reacted with the epoxy group of polyfunctional epoxy resin (a1), and polybasic acid anhydride (a3) is added to the reaction product so that a part of the hydroxyl group remains. A step (1) of obtaining a photosensitive resin (A-1) containing a carboxyl group in which a hydroxyl group is allowed to react;
A silane compound containing at least one silane compound having a (meth) acryloyl group is added to the photosensitive resin (A-1) containing a carboxyl group in which a hydroxyl group is left as a reaction product in the step (1). The compound (A-2) obtained by the decomposition condensation reaction is obtained by a production method including a step (2) for mixing or partially reacting in this order.

  First, the organic-inorganic hybrid resin varnish (A) uses a polyfunctional epoxy resin (a1) as a starting material. Typical examples include dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, etc. A compound which can be obtained by reacting with epichlorohydrin can be used. From the viewpoint of sensitivity and solder heat resistance, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, and cresol novolac type epoxy resin are preferable.

  In the step (1), a part of the hydroxyl group remains with respect to the reaction product generated by the esterification reaction between the epoxy group of the polyfunctional epoxy resin (a1) and the carboxyl group of the unsaturated monocarboxylic acid (a2). The polybasic acid anhydride (a3) was reacted as described above, and a number of free carboxyl groups were added to the side chain of the backbone polymer produced by the former esterification reaction by the latter reaction. Therefore, development with an aqueous alkali solution is possible.

The unsaturated monocarboxylic acid (a2) is a reaction product of acrylic acid, methacrylic acid, cinnamic acid, saturated or unsaturated dibasic acid anhydride and (meth) acrylates having one hydroxyl group in one molecule. These can be used singly or in combination of two or more. From the viewpoint of photocurability, acrylic acid or methacrylic acid is preferable, and acrylic acid is more preferable.
In the present specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  The polybasic acid anhydride (a3) is typically maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride. Dibasic acid anhydrides such as phthalic acid, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid Aromatic polyhydric carboxylic anhydrides such as dianhydrides; and other incidental examples such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Such polycarboxylic acid anhydride derivatives can be used.

In the step (2), at least one silane compound having a (meth) acryloyl group is prepared with respect to the photosensitive resin (A-1) containing a carboxyl group in which the hydroxyl group that is the reaction product of the step (1) is left. In this step, the compound (A-2) obtained by subjecting the seed-containing silane compound to hydrolysis condensation reaction is mixed or partially reacted. In this step, for the hydrolysis in the hydrolysis condensation reaction, for example, when an alkoxysilane compound having a (meth) acryloyl group is used, it is preferable to add about 1 equivalent of water to 3 equivalents of alkoxysilane. The reason for this is that if the amount of water is less than this ratio, hydrolysis does not proceed sufficiently, and if it is large, it is necessary to remove excess water from the system. If water remains, condensation does not proceed easily, and the fluidity of the resin is low. Because it will be lost. In addition, the hydrolysis in the hydrolysis condensation reaction proceeds by stirring at room temperature, but if the stirring time is short, sufficient hydrolysis does not occur, so stirring for 30 minutes or more, preferably 3 hours or more is required. is there. On the other hand, the condensation reaction in the hydrolysis-condensation reaction occurs partially at room temperature at the same time as the hydrolysis, but the reaction can be carried out by raising the temperature in order to shorten the time. The condensation reaction at a high temperature is preferably a reaction at 100 ° C. or lower because the acrylic component causes gelation.
In the present invention, by partially hybridizing the photosensitive resin (A-1) containing a carboxyl group in which the hydroxyl group which is the reaction product of the step (1) is left in the step (2). A photo-curable thermosetting resin composition excellent in both sensitivity and solder heat resistance can be obtained.

In the present invention, a silane compound having at least a (meth) acryloyl group is used during the synthesis of the organic-inorganic hybrid resin varnish (A). Specific examples of such a silane compound having a (meth) acryloyl group include, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) And alkoxysilane compounds having a (meth) acryloyl group such as acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane. These can be used singly or in combination of two or more. Among them, from the viewpoint of sensitivity and solder heat resistance, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane Is preferred.
Moreover, as a silane compound that can be used in combination with a silane compound having a (meth) acryloyl group, a silane compound generally known as a silane coupling agent can be used, for example, methyltrimethoxysilane, methyltriethoxysilane. Dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane and the like.

  In this specification, the organic-inorganic hybrid resin varnish is a silane containing at least one silane compound having a photosensitive resin (A-1) containing a carboxyl group in which a hydroxyl group remains and a (meth) acryloyl group. Let it be a mixture or a partial reaction product with the compound (A-2) obtained by carrying out a hydrolysis condensation reaction of a compound.

<Photoinitiator (B)>
The photocurable initiator composition (B) is used in the photocurable thermosetting resin composition of the present invention. As the photopolymerization initiator, one or more photopolymerization initiators selected from the following group can be used.

  Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2 , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2 Acetophenones such as morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tarsha Reeve Le anthraquinone, 1-chloro anthraquinone, 2-anthraquinone such as amyl anthraquinone; like benzophenone or xanthone such as benzophenone; acetophenone dimethyl ketal, ketal such as benzil dimethyl ketal. The preferred range of the amount of the photopolymerization initiator used is preferably 0.2 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the organic-inorganic hybrid resin varnish (A). It is a ratio.

<Organic nitrogen compound (C)>
Examples of the organic nitrogen compound (C) include dicyandiamide, melamine and derivatives thereof. In this invention, discoloration of copper foil can be prevented by using this organic nitrogen compound. In particular, by adding melamine, it is possible to reduce yellowing of the coating film and a decrease in reflectance even after a deterioration test in which the coating film is irradiated with UV or given a thermal history.
Melamine is 2,4,6-triamino-1,3,5-triazine, and as its main application, it is used as a raw material for melamine resin. By reacting melamine with formalin, methylol melamine can be obtained. By heating this using a catalyst, methylol melamine becomes a methylene bond, and a melamine resin can be produced. As a main production method of melamine, there is a method of reacting urea under high pressure of ammonia. Melamine is industrially made by this process. Moreover, as another manufacturing method of melamine, it can synthesize | combine also from lime nitrogen, dicyandiamide, and hydrocyanic acid. Furthermore, melamine derivatives such as methylol melamine may be used.
Examples of melamine derivatives include monoacetyl melamine, diacetyl melamine, triacetyl melamine, and more specifically, stearic acid anhydride, palmitic acid anhydride, myristic acid anhydride, lauric acid anhydride, capric acid anhydride, Substitutes such as caprylic anhydride, butyric anhydride, acetic anhydride and the like are known. In JP-A-8-193073, melamine-lactate, melamine-malonate, melamine-mono (2-methacryloyloxyethyl) acid phosphate Salt, melamine-toluenesulfonic acid, and melamine-tetrahydrophthalic acid have been evaluated as solder resists.
The preferable compounding quantity of such an organic nitrogen compound is 0.5-15 mass% with respect to 100 mass% of solid content of the said photosensitive resin (A-1) containing a carboxyl group, More preferably, 1- 10% by mass. When the blending amount is 0.5% by mass or more, the effect becomes clear, and when it is 15% by mass or less, storage stability, developability, water resistance of the coating film and the like are improved.

  The photocurable thermosetting resin composition of the present invention may further include, as necessary, known and commonly used fillers such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, phthalocyanine blue, phthalocyanine green, titanium oxide. Various known additives such as carbon black and other known colorants, antifoaming agents, adhesion-imparting agents or leveling agents, or known conventional polymerizations such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butyl catechol, and phenothiazine. Inhibitors may be added.

  The photocurable thermosetting resin composition of the present invention is applied to the entire surface of a printed wiring board substrate by, for example, a screen printing method, a roll coater method, or a curtain coater method, and active energy rays are applied through a resist pattern film. After irradiation and curing of the necessary portion, the unexposed portion is dissolved with an alkaline aqueous solution, and then heat-cured to form the intended solder resist film.

  As the alkaline aqueous solution used for the development, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. As the irradiation light source for photocuring, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable. In addition, a laser beam or the like can be used as an actinic ray for exposure.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following, “parts” and “%” are based on mass unless otherwise specified.

[Synthesis Example 1 (Synthesis of Resin 1 by Step (1))]
108 g of cresol novolak type epoxy resin (DIC-made N-695, epoxy equivalent 215 g / eq, softening point 96 ° C.) was weighed into a 500 cc three-necked separable flask, and 135 g of diethylene glycol monoethyl ether acetate was added and dissolved by heating. . Thereafter, 39.6 g (1.1 equivalents) of acrylic acid, 0.10 g of phenothiazine and 0.15 g of tetramethylammonium chloride were added, and the mixture was refluxed at 105 ° C. while blowing 0.5 L / min to prevent gelation. Stir for 8 hours. Furthermore, 45.6 g of tetrahydrophthalic anhydride (0.6 equivalent with respect to the hydroxyl group) was added, and the mixture was stirred at 100 ° C. for 4 hours to obtain Resin 1. Resin 1 obtained by synthesis was liquid at room temperature, and had a nonvolatile content of 60% and an acid value of 58 mKOH / g.

[Synthesis Example 2 (Synthesis of Resin 2 by Step (1))]
In a 500 cc three-neck separable flask, 104 g of dicyclopentadiene type epoxy resin was weighed, and 104 g of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Thereafter, 31.7 g (1.1 equivalents) of acrylic acid, 0.10 g of phenothiazine and 0.15 g of tetramethylammonium chloride were added, and the mixture was refluxed at 105 ° C. while blowing 0.5 L / min to prevent gelation. Stir for 8 hours. Furthermore, 36.5 g of tetrahydrophthalic anhydride (0.6 equivalent to the hydroxyl group) was added, and the mixture was stirred at 100 ° C. for 4 hours to obtain Resin 2. Resin 2 obtained by synthesis was liquid at room temperature, and had a non-volatile content of 66% and an acid value of 47.5 mKOH / g.

[Synthesis Example 3 (Synthesis of Resin 3 by Step (1))]
In a 500 cc three-neck separable flask, 82.0 g of a naphthalene type epoxy resin was weighed, and 104 g of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Thereafter, 39.6 g (1.1 equivalents) of acrylic acid, 0.10 g of phenothiazine and 0.15 g of tetramethylammonium chloride were added, and the mixture was refluxed at 105 ° C. while blowing 0.5 L / min to prevent gelation. Stir for 4 hours. Furthermore, 45.6 g of tetrahydrophthalic anhydride (0.6 equivalent to the hydroxyl group) was added, and the mixture was stirred at 100 ° C. for 1 hour to obtain Resin 3. Resin 3 obtained by synthesis was liquid at room temperature, had a nonvolatile content of 63% and an acid value of 59.1 mKOH / g.

[Synthesis Example 1-1 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-1-1 by Step (2))]
In a 500 cc three-necked separable flask, 37.4 g of 3-acryloxypropyltrimethoxysilane (KBE-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), 3.74 g of distilled water and 0.37 g of dibutyltin dilaurate were weighed and replaced with nitrogen. And stirring at 130 rpm for 3 hours.
Next, 60.0 g of the resin 1 (acrylic anhydride adduct of cresol novolak type epoxy resin) obtained in Synthesis Example 1 is added, and the mixture is stirred at 80 ° C. for 1 hour while blowing 0.5 L / min of air under reflux conditions. did. Thereafter, the reflux tube was removed, and stirring and heating were performed at 100 ° C. for 1 hour to obtain a mixture of the resin 1 and the organic-inorganic hybrid acrylic oligomer. Let this mixture be organic-inorganic hybrid resin varnish A-1-1.

[Synthesis Example 1-2 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-1-2 by Step (2))]
In a 500 cc three-necked separable flask, 38.1-acryloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical Co., Ltd.) 28.1 g, tetraethoxysilane (TEOS) 8.32 g, distilled water 3.64 g, dibutyltin dilaurate 0.36 g was weighed out and replaced with nitrogen, followed by stirring at room temperature at 130 rpm for 3 hours.
Next, 60.0 g of the resin 1 (acrylic anhydride adduct of cresol novolak type epoxy resin) obtained in Synthesis Example 1 is added, and the mixture is stirred at 80 ° C. for 1 hour while blowing 0.5 L / min of air under reflux conditions. did. Thereafter, the reflux tube was removed, and stirring and heating were performed at 100 ° C. for 1 hour to obtain a mixture of the resin 1 and the organic-inorganic hybrid acrylic oligomer. Let this mixture be organic-inorganic hybrid resin varnish A-1-2.

[Synthesis Example 1-3 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-1-3 by Step (2))]
Synthesis Example 1 except that 28.1 g of 3-acryloxypropyltrimethoxysilane (KBE-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 18.73 g and tetraethoxysilane (TEOS) 8.32 g was changed to 16.64 g. -2 The mixture which changed the ratio of resin 1 and an organic inorganic hybrid acrylic oligomer was obtained by the same method. Let this mixture be organic-inorganic hybrid resin varnish A-1-3.

[Synthesis Example 1-4 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-1-4 by Step (2))]
37.4 g of 3-acryloxypropyltrimethoxysilane (KBE-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), 33.28 g of tetraethoxysilane (TEOS), 3.74 g of distilled water to 3.33 g, and dilauryl A mixture of Resin 1 and an organic-inorganic hybrid oligomer containing no acryloyl group was obtained in the same manner as in Synthesis Example 1-1 except that 0.37 g of dibutyltin acid was changed to 0.33 g. Let this mixture be organic-inorganic hybrid resin varnish A-1-4.

[Synthesis Example 1-5 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-1-5 by Step (2))]
37.4 g of 3-acryloxypropyltrimethoxysilane (KBE-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 38.40 g of phenyltriethoxysilane (PEOS, KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.), and 3.74 g of distilled water is 3 Organic-inorganic hybrid oligomer containing resin 1 and an aromatic ring and no acryloyl group in the same manner as in Synthesis Example 1-1 except that .84 g and 0.37 g of dibutyltin dilaurate were changed to 0.38 g A mixture with was obtained. Let this mixture be organic-inorganic hybrid resin varnish A-1-5.

[Synthesis Example 2-1 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-2-1 by Step (2))]
In a 500 cc three-necked separable flask, 28.1 g of 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), 8.32 g of tetraethoxysilane (TEOS), 3.64 g of distilled water and dibutyltin dilaurate 0.36 g was weighed out and replaced with nitrogen, followed by stirring at room temperature at 130 rpm for 3 hours.
Next, 55.6 g of the resin 2 (acrylated anhydride adduct of dicyclopentadiene type epoxy resin) obtained in Synthesis Example 2 was added, and the mixture was refluxed at 80 ° C. for 1 hour while blowing 0.5 L / min. Stir. Thereafter, the reflux tube was removed, and stirring and heating were performed at 100 ° C. for 1 hour to obtain a mixture of the resin 2 and the organic-inorganic hybrid acrylic oligomer. This mixture is designated as organic-inorganic hybrid resin varnish A-2-1.

[Synthesis Example 2-2 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-2-2 by Step (2))]
In the same manner as in Synthesis Example 2-1, except that 8.32 g of tetraethoxysilane (TEOS) was changed to 9.60 g of phenyltriethoxysilane (PEOS, KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.), resin 2 and A mixture with an organic-inorganic hybrid acrylic oligomer containing an aromatic ring was obtained. This mixture is designated as organic-inorganic hybrid resin varnish A-2-2.

[Synthesis Example 3-1 (Synthesis of Organic-Inorganic Hybrid Resin Varnish A-3-1 by Step (2))]
In a 500 cc three-necked separable flask, 28.1 g of 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), 8.32 g of tetraethoxysilane (TEOS), 3.64 g of distilled water and dibutyltin dilaurate 0.36 g was weighed out and replaced with nitrogen, followed by stirring at room temperature at 130 rpm for 3 hours.
Next, 57.8 g of the resin 3 (acrylate anhydride anhydride adduct of naphthalene type epoxy resin) obtained in Synthesis Example 3 was added, and the mixture was stirred at 80 ° C. for 1 hour while blowing 0.5 L / min of air under reflux conditions. . Thereafter, the reflux tube was removed, and stirring and heating were performed at 100 ° C. for 1 hour to obtain a mixture of the resin 3 and the organic-inorganic hybrid acrylic oligomer. This mixture is designated as organic-inorganic hybrid resin varnish A-3-1.

<Preparation of the photocurable thermosetting resin composition of Examples 1-6 and Comparative Examples 1-6>
The following Table 1 other than the organic-inorganic hybrid resin varnishes A-1-1 to A-3-1, resins 1 to 3 and propylene glycol methyl ether acetate which are solvents for viscosity adjustment before printing obtained in the above synthesis examples Each component shown in 2 was blended in the ratio (parts by mass) described in the table, and each component was dispersed with a three-roll mill manufactured by Inoue Seisakusho.
Next, the organic-inorganic hybrid resin varnish A-1-1 to A-3-1 obtained in the above synthesis example, 10 parts by mass of the photosensitive resin solid content of the resins 1 to 3 (A-1-1-1 in the table) In the components of A-3-1 and resins 1 to 3, the photosensitive resin solids are all 10 parts by mass.), Organic-inorganic hybrid resin varnishes A-1-1-1 to A-3-1, resins 1 to 1 3 and 2.8 parts by mass of a dispersion other than propylene glycol methyl ether acetate, which is a solvent for adjusting viscosity before printing, were mixed to prepare a photocurable thermosetting resin composition.

＊１：有機無機ハイブリッド樹脂ワニスＡ−１−１（シラン化合物；ＫＢＭ−５１０３のみ）
＊２：有機無機ハイブリッド樹脂ワニスＡ−１−２（シラン化合物の質量比；ＫＢＭ−５１０３：ＴＥＯＳ＝３：１）
＊３：有機無機ハイブリッド樹脂ワニスＡ−１−３（シラン化合物の質量比；ＫＢＭ−５１０３：ＴＥＯＳ＝１：１）
＊４：有機無機ハイブリッド樹脂ワニスＡ−１−４（シラン化合物；ＴＥＯＳのみ）
＊５：有機無機ハイブリッド樹脂ワニスＡ−１−５（シラン化合物；ＰＥＯＳのみ）
＊６：有機無機ハイブリッド樹脂ワニスＡ−２−１（シラン化合物の質量比；ＫＢＭ−５１０３：ＴＥＯＳ＝３：１）
＊７：有機無機ハイブリッド樹脂ワニスＡ−２−２（シラン化合物の質量比；ＫＢＭ−５１０３：ＰＥＯＳ＝３：１）
＊８：有機無機ハイブリッド樹脂ワニスＡ−３−１（シラン化合物の質量比；ＫＢＭ−５１０３：ＴＥＯＳ＝３：１）
＊９：樹脂１（シラン化合物；含まない）
＊１０：樹脂２（シラン化合物；含まない）
＊１１：樹脂３（シラン化合物；含まない）
＊１２：光重合開始剤、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン（ＢＡＳＦジャパン社製）
＊１３：熱硬化性化合物
＊１４：ジペンタエリスリトールヘキサアクリレート（日本化薬社製）
＊１５：消泡・レベリング剤（共栄社化学社製）
＊１６：有機溶剤
＊１７：クレゾールノボラック型エポキシ樹脂（ＤＩＣ社製Ｎ−６９５）６０ｇをジエチレングリコールモノエチルエーテルアセテート（ＥＣＡ）４０ｇで溶解させた樹脂

* 1: Organic-inorganic hybrid resin varnish A-1-1 (silane compound; KBM-5103 only)
* 2: Organic / inorganic hybrid resin varnish A-1-2 (mass ratio of silane compound; KBM-5103: TEOS = 3: 1)
* 3: Organic / inorganic hybrid resin varnish A-1-3 (mass ratio of silane compound; KBM-5103: TEOS = 1: 1)
* 4: Organic / inorganic hybrid resin varnish A-1-4 (silane compound; TEOS only)
* 5: Organic / inorganic hybrid resin varnish A-1-5 (Silane compound; PEOS only)
* 6: Organic-inorganic hybrid resin varnish A-2-1 (mass ratio of silane compound; KBM-5103: TEOS = 3: 1)
* 7: Organic-inorganic hybrid resin varnish A-2-2 (mass ratio of silane compound; KBM-5103: PEOS = 3: 1)
* 8: Organic / inorganic hybrid resin varnish A-3-1 (mass ratio of silane compound; KBM-5103: TEOS = 3: 1)
* 9: Resin 1 (silane compound; not included)
* 10: Resin 2 (silane compound; not included)
* 11: Resin 3 (silane compound; not included)
* 12: Photopolymerization initiator, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (manufactured by BASF Japan)
* 13: Thermosetting compound * 14: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
* 15: Antifoam / leveling agent (manufactured by Kyoeisha Chemical Co., Ltd.)
* 16: Organic solvent * 17: Resin obtained by dissolving 60 g of cresol novolac epoxy resin (N-695 manufactured by DIC) with 40 g of diethylene glycol monoethyl ether acetate (ECA)

  About each photocurable thermosetting resin composition of the said Examples 1-6 and Comparative Examples 1-6, it tested about each following item and evaluated. The results of each evaluation are shown in Tables 3 and 4. The evaluation test method is shown below.

<Sensitivity>
The photocurable thermosetting resin compositions obtained in the above Examples 1 to 6 and Comparative Examples 1 to 6 were respectively applied by screen printing onto a copper foil of a glass epoxy substrate, and then heated in a hot air circulation type drying furnace. C. for 30 minutes. On these substrates, Kodak No. 2 step tablets were applied, exposed at 200 mJ / cm ² , developed with a 1% by weight Na ₂ CO ₃ aqueous solution with a spray pressure of 0.2 MPa for 1 minute, and the number of steps where the coating film remained completely was evaluated.
◎: Number of remaining stages 14 to 12 O: Number of remaining stages 11 to 9 △: Number of remaining stages 8 to 6 stages ×: Number of remaining stages 5 to 3 stages XX: Number of remaining stages 2 to 0 stages

<Solder heat resistance>
The photocurable thermosetting resin compositions obtained in the above Examples 1 to 6 and Comparative Examples 1 to 6 were respectively applied to the printed wiring board on which the circuit was formed by screen printing, and then heated in a hot air circulation drying oven. C. for 30 minutes. A negative film on which a solder resist pattern is drawn is applied to these substrates, exposed under an exposure condition of an exposure amount of 800 mJ / cm ² , and developed with a 1 mass% Na ₂ CO ₃ aqueous solution with a spray pressure of 0.2 MPa for 1 minute. A resist pattern was formed. This substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate.
A rosin-based flux is applied to the evaluation substrate and immersed in a solder bath set at 260 ° C. for 30 seconds in advance. After the substrate temperature has dropped to room temperature, the flux is applied again, and 30 ° C. in a solder bath at 260 ° C. Soaked for 2 seconds. After the solder was immersed once and twice, the flux was washed with isopropyl alcohol, and then a peel test using a cellophane adhesive tape was performed to evaluate the swelling, peeling and discoloration of the resist layer according to the following criteria.
○: No change at all △: Slight change in color, etc. ×: Resist layer swelling or peeling

<Storage stability>
After adjusting the photocurable thermosetting resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 6, the initial viscosity value at 25 ° C. was measured with an EHD viscometer (5 rpm value). Then, it was stored in a thermostatic bath at 25 ° C. for one week or one month, and the viscosity was measured in the same manner as the initial value after each period. From the viscosity increase rate, the following criteria were used for evaluation.
○: Thickening rate is less than 130% Δ: Thickening rate is within 130 to 200% ×: Gelation or thickening rate is over 200%

＊１８：感度が低く、現像後に塗膜が残らなかったため測定不可

* 18: Measurement is not possible due to low sensitivity and no coating film remaining after development.

As shown in the above table, in the compositions of Examples 1 to 6 including a carboxyl group-containing photosensitive organic-inorganic hybrid resin varnish obtained by a predetermined reaction, a photopolymerization initiator, and a thermosetting compound. As compared with Comparative Examples 1 to 6, it was confirmed that both were excellent in both sensitivity and solder heat resistance.

Claims (6)

  Unsaturated monocarboxylic acid (a2) is reacted with the epoxy group of polyfunctional epoxy resin (a1), and polybasic acid anhydride (a3) is added to the reaction product so that a part of the hydroxyl group remains. Compound obtained by hydrolytic condensation reaction of a silane compound containing at least one silane compound having a (meth) acryloyl group with respect to the hydroxyl group of the photosensitive resin (A-1) containing a carboxyl group obtained by the reaction ( A-2) a carboxyl group-containing photosensitive organic-inorganic hybrid resin varnish (A) obtained by partially reacting, a photopolymerization initiator (B), and an organic nitrogen compound (C). A photocurable thermosetting resin composition.   The photocurable thermosetting resin composition according to claim 1, wherein the polyfunctional epoxy resin (a1) is a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, or a cresol novolac type epoxy resin.   The photocurable thermosetting resin composition according to claim 1 or 2, wherein the unsaturated monocarboxylic acid (a2) is (meth) acrylic acid.   The photocurable thermosetting resin composition according to any one of claims 1 to 3, wherein the organic nitrogen compound (C) is at least one of dicyandiamide, melamine, and derivatives thereof. Cured product photocurable thermosetting resin composition according to any one of claims 1 to 4 and light cured, characterized in that it is obtained by. A printed wiring board comprising a cured coating film obtained by photocuring the photocurable thermosetting resin composition according to claim 1.