CN110753712B - Acid group-containing (meth)acrylate resins and resin materials for solder resists - Google Patents

Abstract

The present invention provides: an acid group-containing (meth) acrylate resin characterized by containing an acid group or an acid anhydride group-containing amide imide resin (A), a (meth) acrylic acid hydroxy ester compound (B), a (meth) acryloyl group-containing epoxy compound (C) and a polycarboxylic acid anhydride (D) as essential reaction raw materials, a curable resin composition containing the same, an insulating material comprising the curable resin composition, a resin material for a solder resist, and a resist member. The acid group-containing (meth) acrylate resin can form a cured product having excellent heat resistance and elongation.

Description

Acid group-containing (meth)acrylate resins and resin materials for solder resists

technical field

The present invention relates to an acid group-containing (meth)acrylate resin having high heat resistance and elongation of a cured product, a curable resin composition containing the same, an insulating material containing the curable resin composition, and a solder resist Resin material and anti-corrosion member.

Background technique

The resin material for solder resists for printed wiring boards is widely used as an acid group-containing epoxy acrylate resin obtained by acrylated epoxy resin with acrylic acid and reacted with an acid anhydride. The required properties of the resin material for solder resists include: curing with a small amount of exposure; excellent alkali developability; heat resistance, strength, flexibility, elongation, dielectric properties, and substrate adhesion of the cured product Various properties such as excellent properties.

As a conventionally known resin material for solder resists, an acid group-containing epoxy acrylate resin obtained by reacting a novolak-type epoxy resin with acrylic acid and tetrahydrophthalic anhydride is known (refer to the following Patent Documents) 1). Although the acid group-containing epoxy acrylate resin described in Patent Document 1 has the characteristics of high heat resistance of a cured product derived from a novolak-type epoxy resin as a reaction raw material, it is not suitable for current market demands. full. In addition, since the elongation of the cured product is very low, cracks are easily generated in the cured product, and reliability is poor.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 61-243869

SUMMARY OF THE INVENTION

Invention to solve problem

Therefore, the subject to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin having high heat resistance and elongation of a cured product, a curable resin composition containing the same, and a curable resin composition containing the above-mentioned curable resin composition. Insulating materials, resin materials for solder resists, and corrosion-resistant members for objects.

solution to the problem

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result found that a (meth)acryloyl group is introduced by reacting an amideimide resin with a hydroxy (meth)acrylate and a (meth)acryloyl group-containing epoxy compound. , and further react with polycarboxylic acid anhydride to obtain an acid group-containing (meth)acrylate resin, and the cured product has very high heat resistance and elongation, thus completing the present invention.

That is, the present invention relates to an acid group-containing (meth)acrylate resin comprising an amideimide resin (A) having an acid group or an acid anhydride group, a hydroxy (meth)acrylate compound (B), a The epoxy compound (C) of the (meth)acryloyl group and the polycarboxylic acid anhydride (D) are necessary reaction raw materials.

The present invention further relates to a curable resin composition containing the acid group-containing (meth)acrylate resin and a photopolymerization initiator.

The present invention further relates to a cured product of the aforementioned curable resin composition.

The present invention further relates to an insulating material comprising the aforementioned curable resin composition.

The present invention further relates to a resin material for a solder resist comprising the aforementioned curable resin composition.

The present invention further relates to an anti-corrosion member comprising the aforementioned resin material for a solder resist.

effect of invention

According to the present invention, there can be provided an acid group-containing (meth)acrylate resin having high heat resistance and elongation of a cured product, a curable resin composition containing the same, an insulating material containing the above-mentioned curable resin composition, Resin material and corrosion-resistant member for solder resist.

Description of drawings

1 is a GPC spectrum of the acid group-containing (meth)acrylate resin (1) obtained in Example 1. FIG.

Detailed ways

Hereinafter, the present invention will be described in detail.

The acid group-containing (meth)acrylate resin of the present invention includes an acid group or acid anhydride group-containing amide imide resin (A), a (meth)acrylate hydroxyester compound (B), a (meth)acryloyl group-containing The epoxy compound (C) and polycarboxylic acid anhydride (D) are necessary reaction raw materials.

In the present invention, the (meth)acrylate resin refers to a resin having an acryloyl group, a methacryloyl group, or both in the molecule. In addition, a (meth)acryloyl group means one or both of an acryloyl group and a methacryloyl group, and (meth)acrylate is a general term for acrylate and methacrylate.

The amide-imide resin (A) which has the said acid group or an acid anhydride group may have only either one of an acid group or an acid anhydride group, and may have both. Among them, it is preferable to have an acid anhydride group, and it is preferable to have an acid group and acid anhydride group. The acid value of the amide-imide resin (A) is preferably in the range of 60 to 350 mgKOH/g as the measured value under neutral conditions, that is, conditions in which the acid anhydride group is not ring-opened. On the other hand, the measured value under conditions such as the presence of water and the ring-opening of the acid anhydride group is preferably in the range of 61 to 360 mgKOH/g.

The specific structure and manufacturing method of the said amide-imide resin (A) are not specifically limited, A general amide-imide resin etc. can be widely used. Specifically, what uses a polyisocyanate compound (a1) and a polycarboxylic acid or its acid anhydride (a2) as a reaction raw material is mentioned.

Examples of the polyisocyanate compound (a1) include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Alicyclic diisocyanate compounds such as methylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate; toluene diisocyanate, Xylene diisocyanate, tetramethylxylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, ortholink Aromatic diisocyanate compounds such as toluene diisocyanate; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following structural formula (1); their isocyanurate-modified products and biuret-modified products , Allophanate modified body, etc. These may be used independently, respectively, and may be used in combination of 2 or more types.

[In the formula, R ¹ is each independently any one of a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms. R ² is each independently an alkyl group having 1 to 4 carbon atoms, or a binding site connected to the structural site represented by the structural formula (1) via a methylene group denoted by the symbol *. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more. ]

Among them, the above-mentioned alicyclic diisocyanate compounds or modified products thereof are preferred, and alicyclic diisocyanates or their isocyanurates are preferred in terms of being an acid group-containing (meth)acrylate resin having high solvent solubility. Ester modification. In addition, in terms of being an acid group-containing (meth)acrylate resin having a very high elongation of the cured product, the aforementioned aliphatic diisocyanate compounds or modified products thereof are preferred, and aliphatic diisocyanates or their isocyanurates are preferred. Ester modification. Further, the ratio of the total mass of the alicyclic diisocyanate compound or its modified form and the aliphatic diisocyanate compound or its modified form to the total mass of the polyisocyanate compound (a1) is preferably 70% by mass or more, preferably 90% by mass or more. Moreover, when using the said alicyclic diisocyanate compound or its modified form and the said aliphatic diisocyanate compound or its modified form in combination, the range of 30/70 - 70/30 is preferable in the mass ratio of both.

As long as the said polycarboxylic acid or its acid anhydride (a2) is a compound which has a several carboxyl group in a molecular structure, or its acid anhydride, various compounds can be used irrespective of a specific structure. Moreover, a polycarboxylic acid or its acid anhydride (a2) may be used individually, respectively, and may be used in combination of 2 or more types. In addition, the amide-imide resin (A) has both an amide group and an imide group. Therefore, both a carboxyl group and an acid anhydride group must exist in the system. The compound having both a carboxyl group and an acid anhydride group may be used in combination with a compound having a carboxyl group and a compound having an acid anhydride group.

As an example of the said polycarboxylic acid or its acid anhydride (a2), an aliphatic polycarboxylic acid compound or its acid anhydride, an alicyclic polycarboxylic acid compound or its acid anhydride, an aromatic polycarboxylic acid compound or its acid anhydride, etc. are mentioned, for example. In the aforementioned aliphatic polycarboxylic acid compound or its acid anhydride, the aliphatic hydrocarbon group may be of a linear type or a branched type, and may have an unsaturated bond in the structure. Examples of the aforementioned aliphatic polycarboxylic acid compound or its acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. , maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaric acid, 1,2,3,4-butanetetracarboxylic acid, and their anhydrides, etc.

Regarding the aforementioned alicyclic polycarboxylic acid compound or its acid anhydride, in the present invention, a carboxyl group or an acid anhydride group is bonded to an alicyclic structure as an alicyclic polycarboxylic acid compound or its acid anhydride, regardless of other structural sites. whether there are aromatic rings in it. As an example of the said alicyclic polycarboxylic acid compound or its acid anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanedicarboxylic acid, Hexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dicarboxylic acid oxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, their acid anhydrides, and the like.

As an example of the said aromatic polycarboxylic acid compound or its acid anhydride, for example, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl Dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc.

Among them, the above-mentioned alicyclic polycarboxylic acid compound or its acid anhydride, or the above-mentioned aromatic polycarboxylic acid compound or its acid anhydride is preferable from the viewpoint of being an acid group-containing (meth)acrylate resin having particularly high heat resistance. In addition, since the aforementioned amide-imide resin (A) can be efficiently produced, it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in its molecular structure, and it is particularly preferable to use cyclohexanetricarboxylic acid anhydride or trimellitic acid anhydride. . Further, the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride to the total mass of the polycarboxylic acid or its acid anhydride (a2) is preferably 70% by mass or more, preferably 90% by mass or more.

When the amide-imide resin (A) uses the above-mentioned polyisocyanate compound (a1) and the above-mentioned polycarboxylic acid or its anhydride (a2) as reaction raw materials, other than these can be used in combination according to desired resin properties and the like. reaction raw materials. In the above-mentioned case, the total mass of the polyisocyanate compound (a1) and the polycarboxylic acid or its anhydride (a2) relative to the mass of the amideimide resin (A) is determined from the viewpoint that the effect obtained by the present invention can be sufficiently exhibited. The ratio of the total mass of the reaction raw materials is preferably 90% by mass or more, preferably 95% by mass or more.

When the said amide-imide resin (A) uses a polyisocyanate compound (a1) and a polycarboxylic acid or its acid anhydride (a2) as a reaction raw material, the manufacturing method is not specifically limited, It can manufacture by any method. For example, it can be manufactured by the same method as a general amide-imide resin. Specifically, a method of using 0.8 to 1.2 mol of the above-mentioned polycarboxylic acid or its anhydride (a2) with respect to 1 mol of the isocyanate group which the above-mentioned polyisocyanate compound (a1) has, at about 120 to 180° C. Stir and mix and react under the temperature conditions.

The reaction can be carried out in an organic solvent as necessary. The selection of the organic solvent to be used can be appropriately selected according to the solubility of the reaction raw materials and the acid group-containing (meth)acrylate resin as the product, the reaction temperature conditions, and the like, and examples thereof include methyl ethyl ketone, acetone, and dimethylformamide. , methyl isobutyl ketone, methoxy propanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate, etc. These may be used independently, respectively, and may be used as a mixed solvent of 2 or more types. The amount of the organic solvent to be used is preferably within a range of about 0.1 to 5 times the total mass of the reaction raw materials from the viewpoint of improving the reaction efficiency.

The above-mentioned hydroxy (meth)acrylate compound (B) is not particularly limited in other specific structures as long as it is a compound having a hydroxyl group and a (meth)acryloyl group in its molecular structure, and various compounds can be used. Moreover, the said hydroxy (meth)acrylate compound (B) may be used individually, respectively, and may be used in combination of 2 or more types. Among them, a (meth)acrylic acid monohydroxyester compound is preferable because the control of the reaction is easy. Examples thereof include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, di(meth)acrylate (Trimethylolpropane) tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and other (meth)acrylate hydroxyester compounds; in the molecular structure of the aforementioned various (meth)acrylate hydroxyester compounds (poly)oxyalkylene modified product obtained by introducing (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. (poly)oxyalkylene chain; Lactone-modified products obtained by introducing a (poly)lactone structure into the molecular structure of various hydroxy (meth)acrylate compounds. These may be used independently, respectively, and may be used in combination of 2 or more types. Among them, those having a molecular weight of 1,000 or less are preferable from the viewpoint of being an acid group-containing (meth)acrylate resin excellent in the balance between the heat resistance and elongation of the cured product. Moreover, when the said hydroxy (meth)acrylate compound (B) is the said oxyalkylene modified body or a lactone modified body, it is preferable that a weight average molecular weight (Mw) is 1000 or less.

The above-mentioned (meth)acryloyl group-containing epoxy compound (C) is not particularly limited to other specific structures as long as it has a (meth)acryloyl group and an epoxy group in the molecular structure, and various compounds can be used. Moreover, the said (meth)acryloyl group containing epoxy compound (C) may be used individually, respectively, and may be used in combination of 2 or more types. Among them, a monoepoxy compound is preferable because the control of the reaction is easy. As an example, glycidyl group-containing (meth)acrylates such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate can be mentioned. base) acrylate monomers; mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, bisphenol diglycidyl ether, etc. compounds, etc. Among them, the above-mentioned glycidyl group-containing (meth)acrylate monomer is preferable from the viewpoint of being an acid group-containing (meth)acrylate resin excellent in the balance between heat resistance and elongation of the cured product. In addition, the molecular weight thereof is preferably 500 or less. Further, the ratio of the glycidyl group-containing (meth)acrylate monomer with respect to the total mass of the (meth)acryloyl group-containing epoxy compound (C) is preferably 70% by mass or more, preferably 90% by mass or more .

As said polycarboxylic acid anhydride (D), the acid anhydride etc. in each compound exemplified as said polycarboxylic acid or its acid anhydride (a2) are mentioned, for example. Moreover, the said polycarboxylic acid anhydride (D) may be used individually, respectively, and may be used in combination of 2 or more types. Among them, the above-mentioned aliphatic polycarboxylic acid anhydride or the above-mentioned alicyclic type is preferable from the viewpoint of being an acid group-containing (meth)acrylate compound excellent in not only the heat resistance and elongation of the cured product but also the developability. The polycarboxylic acid anhydride is more preferably an aliphatic dicarboxylic acid anhydride or an alicyclic dicarboxylic acid anhydride.

Regarding the acid group-containing (meth)acrylate resin of the present invention, in addition to the aforementioned amide imide resin (A) having an acid group or an acid anhydride group, hydroxy (meth)acrylate compound ( B) In addition to the (meth)acryloyl group-containing epoxy compound (C) and the polycarboxylic acid anhydride (D), other reaction raw materials may be used in combination. In the above-mentioned case, the ratio of the total mass of the components (A) to (D) to the total mass of the reaction raw materials of the acid group-containing (meth)acrylate resin from the viewpoint that the effect obtained by the present invention can be sufficiently exhibited 80 mass % or more is preferable, and 90 mass % or more is preferable.

The manufacturing method of the said acid group-containing (meth)acrylate resin is not specifically limited, It can manufacture by any method. For example, it may be produced by a method of reacting all the reaction raw materials together, or it may be produced by a method of sequentially reacting the reaction raw materials. Among them, from the viewpoint of easy control of the reaction, it is preferable to manufacture by a method of reacting the aforementioned amide imide resin (A) with the aforementioned hydroxy (meth)acrylate compound (B) (Step 1), and then making Step 1 The product of step 2 is reacted with the aforementioned (meth)acryloyl group-containing epoxy compound (C) (step 2), and the product of step 2 is reacted with the aforementioned polycarboxylic acid anhydride (D).

In the above-mentioned step 1, in the reaction between the above-mentioned amide-imide resin (A) and the above-mentioned hydroxy (meth)acrylate compound (B), the acid group or acid anhydride group in the above-mentioned amide-imide resin (A) is mainly made to react with The hydroxyl group in the hydroxy (meth)acrylate compound (B) reacts. It is preferable that the said amide-imide resin (A) has an acid anhydride group from the point which is especially excellent in the reactivity of the said hydroxy (meth)acrylate compound (B) and an acid anhydride group as mentioned above. About the reaction ratio of the said amide-imide resin (A) and the said (meth)acrylic acid hydroxyester compound (B), it is preferable to be with respect to the sum total of the acid group and the acid anhydride group in the said amide-imide resin (A) The aforementioned hydroxy (meth)acrylate compound (B) is used in the range of 0.9 to 1.1 moles. It is especially preferable to use the said hydroxy (meth)acrylate compound (B) in the range of 0.9-1.1 mol with respect to the sum total of the acid anhydride group in the said amide-imide resin (A). The content of the acid anhydride group in the amide-imide resin (A) can be determined from the difference between the measured values of the above-mentioned two kinds of acid values, that is, the acid value under the condition that the acid anhydride group is ring-opened and the acid value that does not ring-open the acid anhydride group. The difference in acid value under the conditions was calculated.

The reaction between the amide imide resin (A) and the hydroxy (meth)acrylate compound (B) can be heated, for example, at a temperature of about 90 to 140° C. in the presence of a suitable esterification catalyst. It is carried out by stirring. Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine, 2-methylimidazole, Imidazole compounds such as 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, and the like. These may be used alone or in combination of two or more. The addition amount of the catalyst is preferably used in the range of 0.001 to 5 parts by mass with respect to the total mass of the reaction raw materials.

The reaction can be carried out in an organic solvent as necessary. The selection of the organic solvent to be used can be appropriately selected according to the solubility of the reaction raw material and the acid group-containing (meth)acrylate resin as the product, reaction temperature conditions, etc., for example, methyl ethyl ketone, acetone, dimethyl methyl ketone can be mentioned. Amide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate, and the like. These may be used independently, respectively, and may be used as a mixed solvent of 2 or more types. When the production of the amide-imide resin (A) and the step 1 are continuously performed, the reaction may be continued directly in the organic solvent used for the production of the amide-imide resin (A).

In the above-mentioned step 2, the (meth)acryloyl group-containing epoxy compound (C) mainly reacts with the carboxyl group in the product of the above-mentioned step 1. Regarding the reaction ratio, the above-mentioned (meth)acryloyl group-containing epoxy compound (C) is preferably used in a range of 0.5 to 1.2 mol, more preferably in a range of 0.9 to 1.1 mol, relative to the carboxyl group in the product of step 1. . The reaction of the step 2 can be carried out, for example, by heating and stirring in the presence of a suitable esterification catalyst under a temperature condition of about 90 to 140°C. When the step 1 and the step 2 are carried out continuously, the esterification catalyst may not be added, or the esterification catalyst may be appropriately added. In addition, the reaction can be carried out in an organic solvent as necessary.

In the aforementioned step 3, the aforementioned polycarboxylic acid anhydride (D) mainly reacts with the hydroxyl group in the product of the aforementioned step 2. In the product of the said process 2, the hydroxyl group etc. which generate|occur|produce by the ring-opening of the epoxy group in the said (meth)acryloyl group containing epoxy compound (C) exist, for example. The reaction ratio of the polycarboxylic acid anhydride (D) is preferably adjusted so that the acid value of the acid group-containing (meth)acrylate resin as a final product becomes about 50 to 100 mgKOH/g. The reaction of the step 3 can be carried out, for example, by heating and stirring in the presence of a suitable esterification catalyst under a temperature condition of about 90 to 140°C. When the step 2 and the step 3 are carried out continuously, the esterification catalyst may not be added, or the esterification catalyst may be appropriately added. In addition, the reaction can be carried out in an organic solvent as necessary.

The acid group-containing (meth)acrylate obtained in this way is preferable from the viewpoint of being an acid group-containing (meth)acrylate resin excellent not only in the heat resistance, elongation, developability, etc. of the cured product The acid value of the resin is in the range of 50 to 100 mgKOH/g, and more preferably in the range of 60 to 90 mgKOH/g. In addition, the acid value of the acid group-containing (meth)acrylate resin in this invention is the value measured by the neutralization titration method of JIS K 0070 (1992). In addition, the (meth)acryloyl equivalent of the acid group-containing (meth)acrylate resin is preferably in the range of 250 to 750 g/equivalent, and more preferably in the range of 300 to 700 g/equivalent. The mass average molecular weight (Mw) of the acid group-containing (meth)acrylate resin is preferably in the range of 1,000 to 10,000.

The molecular weight of the aforementioned acid group-containing (meth)acrylate resin is a value measured by GPC measured under the following conditions.

Measuring device: "HLC-8220GPC" manufactured by Tosoh Corporation,

Column: Tosoh Co., Ltd. guard column "HXL-L"

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC-8020model II version 4.10" manufactured by Tosoh Corporation

Measurement conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of the aforementioned "GPC-8020model II version 4.10".

(using polystyrene)

Tosoh Corporation "A-500"

Tosoh Corporation "A-1000"

Tosoh Corporation "A-2500"

Tosoh Corporation "A-5000"

Tosoh Corporation "F-1"

Tosoh Corporation "F-2"

Tosoh Corporation "F-4"

Tosoh Corporation "F-10"

Tosoh Corporation "F-20"

Tosoh Corporation "F-40"

Tosoh Corporation "F-80"

Tosoh Corporation "F-128"

Sample: A 1.0 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a microfilter (50 μl)

Since the acid group-containing (meth)acrylate resin of the present invention has a polymerizable (meth)acryloyl group in its molecular structure, it can be used as a curable resin composition by adding a photopolymerization initiator, for example.

The aforementioned photopolymerization initiator can be appropriately selected and used according to the type of active energy ray to be irradiated, and the like. In addition, it may be used in combination with photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)- 1-Butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Alkyl phenone-based photopolymerization initiators; acyl phosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; intramolecular hydrogen abstraction types such as benzophenone compounds Photopolymerization initiators, etc. These may be used independently, respectively, and may be used in combination of 2 or more types.

Commercially available products of the aforementioned photopolymerization initiators include, for example, "IRGACURE127", "IRGACURE184", "IRGACURE250", "IRGACURE270", "IRGACURE290", "IRGACURE369E", "IRGACURE379EG", "IRGACURE500", "IRGACURE379EG", "IRGACURE500", manufactured by BASF Corporation. "IRGACURE651", "IRGACURE754", "IRGACURE819", "IRGACURE907", "IRGACURE1173", "IRGACURE2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE OXE 01", "IRGACURE OXE 02", produced by IGM RESINS " "OMNIRAD184", "OMNIRAD250", "OMNIRAD369", "OMNIRAD369E", "OMNIRAD651", "OMNIRAD907FF", "OMNIRAD1173", etc.

For example, the amount of the photopolymerization initiator added is preferably in the range of 0.05 to 15 mass %, more preferably in the range of 0.1 to 10 mass %, relative to the total of the components other than the solvent of the curable resin composition.

The curable resin composition of the present invention may contain resin components other than the aforementioned acid group-containing (meth)acrylate resin of the present invention. Examples of the resin component include those obtained by reacting epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy resins with (meth)acrylic acid, dicarboxylic acid anhydrides, and optionally unsaturated monocarboxylic acid anhydrides, etc. Such resins having carboxyl groups and (meth)acryloyl groups in the resins; various (meth)acrylate monomers, etc.

Examples of the (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. Aliphatic mono(meth)acrylate compounds such as amyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate; cyclohexyl (meth)acrylate Alicyclic mono(meth)acrylate compounds such as isobornyl (meth)acrylate and adamantyl mono(meth)acrylate; heterocycles such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate type mono(meth)acrylate compound; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, (meth)acrylic acid phenoxyethyl ester, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, (meth)acrylate Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as benzyl benzyl acrylate and phenylphenoxyethyl (meth)acrylate; in the aforementioned various mono(meth)acrylate compounds (poly)oxyalkylene modified by introducing polyoxyalkylene chains such as (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain into the molecular structure of acrylate monomer Mono(meth)acrylate compounds; Lactone-modified mono(meth)acrylate compounds formed by introducing (poly)lactone structure into the molecular structure of the aforementioned various mono(meth)acrylate compounds;

Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate ) aliphatic di(meth)acrylate compounds such as acrylates; 1,4-cyclohexane dimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate Alicyclic di(meth)acrylate compounds such as meth)acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; biphenol di(methyl) ) Aromatic di(meth)acrylate compounds such as acrylates and bisphenol di(meth)acrylates; (poly)oxyethylene chains, (poly)oxyethylene chains, ( Polyoxyalkylene-modified di(meth)acrylate compounds formed from (poly)oxyalkylene chains such as poly)oxypropylene chains and (poly)oxytetramethylene chains; A lactone-modified di(meth)acrylate compound formed by introducing a (poly)lactone structure into the molecular structure of the acrylate compound;

Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerol tri(meth)acrylate; introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound (Poly)oxyalkylene-modified tri(meth)acrylic acid composed of (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. ester compound; lactone-modified tri(meth)acrylate compound obtained by introducing (poly)lactone structure into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound;

Aliphatic poly(meth)acrylate compounds with more than 4 functions such as pentaerythritol tetra(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. are introduced into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compounds to (poly)oxyalkylene-modified poly(meth)acrylate compound obtained from tetrafunctional or more; a (poly)lactone structure introduced into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compound A tetrafunctional or higher lactone-modified poly(meth)acrylate compound and the like.

The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity and the like. The type and addition amount can be appropriately adjusted according to the desired performance. Usually, it is used in the range of 10-90 mass % with respect to the total of curable resin composition. Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; methyl acetate, ethyl acetate, butyl acetate, and the like. Esters; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, etc. ; Glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether acetate, etc. These may be used independently, respectively, and may be used in combination of 2 or more types.

The curable resin composition of the present invention may further contain various additives such as inorganic fine particles, polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers.

The acid group-containing (meth)acrylate resin of the present invention is characterized in that the cured product has high heat resistance and high elongation. Furthermore, it has the characteristics of being excellent also in developability evaluated by photosensitivity, drying control width, etc., the substrate adhesiveness of a cured product, non-adhesion after temporary drying, and the like. Applications that utilize the various excellent properties of the acid group-containing (meth)acrylate resin of the present invention, such as applications related to semiconductor devices, can be used as solder resists, interlayer insulating materials, packaging materials, and underfill materials , the packaging adhesive layer of circuit components, etc., the adhesive layer of integrated circuit components and circuit substrates. In addition, as applications related to thin displays represented by LCD and OELD, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. . Among them, it is particularly suitable for solder resist applications. The resin material for a solder resist of the present invention contains, for example, a curing agent, a curing accelerator, an organic solvent, and the like in addition to the aforementioned acid group-containing (meth)acrylate resin, a photopolymerization initiator, and various additives. ingredients.

The said hardening|curing agent will not be specifically limited if it has the functional group which can react with the carboxyl group in the said acid group-containing (meth)acrylate resin, For example, an epoxy resin is mentioned. Examples of the epoxy resin used here include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthyl ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, and phenol. Novolac epoxy resin, cresol novolak epoxy resin, bisphenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-adol epoxy resin, naphthol- Cresol co-condensed novolac epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, etc. These may be used independently, respectively, and may be used in combination of 2 or more types. Among these epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol novolak type epoxy resins, and naphthol novolak type epoxy resins are preferable because the cured products are excellent in heat resistance. Novolak-type epoxy resins such as epoxy resins, naphthol-phenol co- novolak-type epoxy resins, and naphthol-cresol-co- novolak-type epoxy resins, particularly preferably those having a softening point in the range of 50 to 120°C .

The curing accelerator is used to accelerate the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, phosphorus-based compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complexes can be mentioned. salt etc. These may be used independently, respectively, and may be used in combination of 2 or more types. The addition amount of a hardening accelerator is used in the range of 1-10 mass parts with respect to 100 mass parts of said hardening|curing agents, for example.

The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth)acrylate resin and curing agent, and examples thereof include methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl. ketone, methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc.

As a method of obtaining a corrosion-resistant member using the resin material for a solder resist of the present invention, for example, a method of applying the resin material for a solder resist to a base material, and making organic After the solvent is evaporated and dried, it is exposed to ultraviolet rays, electron beams, etc. through a photomask having a desired pattern, and the unexposed portion is developed in an alkaline aqueous solution, and further heated and cured in a temperature range of about 140 to 180°C.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

The acid value of the acid group-containing (meth)acrylate resin in the examples of the present application was measured by the neutralization titration method of JIS K 0070 (1992).

The molecular weight of the acid group-containing (meth)acrylate resin in the examples of the present application was measured by GPC under the following conditions.

Measuring device: "HLC-8220GPC" manufactured by Tosoh Corporation,

Column: Tosoh Co., Ltd. guard column "HXL-L"

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC-8020model II version 4.10" manufactured by Tosoh Corporation

Measurement conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of the aforementioned "GPC-8020model II version 4.10".

(using polystyrene)

Tosoh Corporation "A-500"

Tosoh Corporation "A-1000"

Tosoh Corporation "A-2500"

Tosoh Corporation "A-5000"

Tosoh Corporation "F-1"

Tosoh Corporation "F-2"

Tosoh Corporation "F-4"

Tosoh Corporation "F-10"

Tosoh Corporation "F-20"

Tosoh Corporation "F-40"

Tosoh Corporation "F-80"

Tosoh Corporation "F-128"

Sample: A 1.0 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a microfilter (50 μl)

Example 1 Production of acid group-containing (meth)acrylate resin (1)

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 449.7 parts by mass of diethylene glycol monomethyl ether acetate and an isocyanurate modified product of isophorone diisocyanate (Evonik Co., Ltd.) were added. 175.5 mass parts of "VESTANAT T-1890/100", isocyanate group content 17.2 mass %), 142.6 mass parts of trimellitic anhydride, and 1.4 mass parts of dibutylhydroxytoluene were melt|dissolved. It was confirmed that the isocyanate group content was 0.1 mass % or less by reacting at 160° C. for 5 hours under a nitrogen atmosphere. Add 0.3 parts by mass of hydroquinone monomethyl ether (methoquinone), 31.1 parts by mass of a pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., content of pentaerythritol triacrylate about 67%, hydroxyl value 159.7 mgKOH/g) It reacted at 110 degreeC for 5 hours, blowing in air with 2.8 mass parts of triphenylphosphine. Next, 116.5 mass parts of glycidyl methacrylates were added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 116.3 mass parts of tetrahydrophthalic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the acid group containing (meth)acrylate resin (1) was obtained. The acid group-containing (meth)acrylate resin (1) had a solid content acid value of 80 mgKOH/g, an acryloyl equivalent of 485 g/equivalent, and a weight average molecular weight (Mw) of 5,200. The GPC spectrum of the acid group-containing (meth)acrylate resin (1) is shown in FIG. 1 .

Example 2 Production of acid group-containing (meth)acrylate resin (2)

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 449.9 parts by mass of diethylene glycol monomethyl ether acetate and an isocyanurate modified product of isophorone diisocyanate (Evonik Co., Ltd.) were added. Prepared "VESTANAT T-1890/100", isocyanate group content 17.2 mass %) 191.4 mass parts, trimellitic anhydride 155.5 mass parts, and 1.4 mass parts of dibutylhydroxytoluene were dissolved. It was confirmed that the isocyanate group content was 0.1 mass % or less by reacting at 160° C. for 5 hours under a nitrogen atmosphere. 0.3 parts by mass of hydroquinone monomethyl ether, 34.0 parts by mass of pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., content of pentaerythritol triacrylate about 67%, hydroxyl value 159.7 mgKOH/g) and triphenylene were added 2.8 parts by mass of phosphonium phosphine was reacted at 110° C. for 5 hours while blowing in air. Next, 127.1 mass parts of glycidyl methacrylates were added, and it was made to react at 120 degreeC for 10 hours. Further, 76.6 parts by mass of succinic anhydride was added, and the mixture was reacted at 110°C for 5 hours to obtain an acid group-containing (meth)acrylate resin (2). The acid group-containing (meth)acrylate resin (2) had a solid content acid value of 80 mgKOH/g, an acryloyl equivalent of 445 g/equivalent, and a weight average molecular weight (Mw) of 4700.

Example 3 Production of acid group-containing (meth)acrylate resin (3)

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 350.4 parts by mass of diethylene glycol monomethyl ether acetate and an isocyanurate modified product of isophorone diisocyanate (Evonik Co., Ltd.) were added. Manufactured "VESTANAT T-1890/100", isocyanate group content 17.2 mass %) 85.8 mass parts, urate modified product of hexamethylene diisocyanate (DIC Co., Ltd. "Burnock DN901S", isocyanate group content 23.5 mass %) %) 85.8 parts by mass, 209.4 parts by mass of trimellitic anhydride, and 1.6 parts by mass of dibutylhydroxytoluene were dissolved. It was confirmed that the isocyanate group content was 0.1 mass % or less by reacting at 160° C. for 5 hours under a nitrogen atmosphere. 0.3 parts by mass of hydroquinone monomethyl ether, 16.9 parts by mass of pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., content of pentaerythritol triacrylate about 67%, hydroxyl value 159.7 mgKOH/g) and triphenylene were added 3.3 parts by mass of the base phosphine was reacted at 110° C. for 5 hours while blowing in air. Next, 197.9 parts by mass of glycidyl methacrylate was added and reacted at 120° C. for 10 hours. Furthermore, 90.4 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the acid group containing (meth)acrylate resin (3) was obtained. The acid group-containing (meth)acrylate resin (3) had a solid content acid value of 80 mgKOH/g, an acryloyl equivalent of 415 g/equivalent, and a weight average molecular weight (Mw) of 4980.

Example 4 Production of acid group-containing (meth)acrylate resin (4)

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 300.2 parts by mass of diethylene glycol monomethyl ether acetate and a urate modified product of hexamethylene diisocyanate (“Burnock DN901S manufactured by DIC Corporation”) were added. ”, isocyanate group content 23.5 mass %) 197.9 mass parts, trimellitic anhydride 219.7 mass parts, and 1.8 mass parts of dibutylhydroxytoluene were dissolved. It was confirmed that the isocyanate group content was 0.1 mass % or less by reacting at 160° C. for 5 hours under a nitrogen atmosphere. 0.4 parts by mass of hydroquinone monomethyl ether, 11.9 parts by mass of pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., content of pentaerythritol triacrylate about 67%, hydroxyl value 159.7 mgKOH/g) and triphenyl 3.5 parts by mass of phosphine was reacted at 110° C. for 5 hours while blowing in air. Next, 221.7 parts by mass of glycidyl methacrylate was added and reacted at 120° C. for 10 hours. Furthermore, 97.3 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the acid group containing (meth)acrylate resin (4) was obtained. The acid group-containing (meth)acrylate resin (4) had a solid content acid value of 80 mgKOH/g, an acryloyl equivalent of 416 g/equivalent, and a weight average molecular weight (Mw) of 4350.

Example 5 Production of acid group-containing (meth)acrylate resin (5)

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 299.8 parts by mass of diethylene glycol monomethyl ether acetate, 232.8 parts by mass of isophorone diisocyanate, 302.0 parts by mass of trimellitic anhydride, and 1.8 parts by mass of dibutylhydroxytoluene were added. parts by mass to dissolve. It was confirmed that the isocyanate group content was 0.1 mass % or less by reacting at 160° C. for 5 hours under a nitrogen atmosphere. 0.4 parts by mass of hydroquinone monomethyl ether, 11.1 parts by mass of pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., content of pentaerythritol triacrylate about 67%, hydroxyl value 159.7 mgKOH/g) and triphenylene were added 3.5 parts by mass of phosphine was reacted at 110° C. for 5 hours while blowing in air. Next, 149.2 mass parts of glycidyl methacrylates were added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 97.4 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the acid group containing (meth)acrylate resin (5) was obtained. The acid group-containing (meth)acrylate resin (5) had a solid content acid value of 80 mgKOH/g, an acryloyl equivalent of 603 g/equivalent, and a weight average molecular weight (Mw) of 1780.

Example 6 Production of acid group-containing (meth)acrylate resin (6)

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 1,422.7 parts by mass of diethylene glycol monomethyl ether acetate and an isocyanurate modified product of isophorone diisocyanate (Evonik Co., Ltd. .Manufactured "VESTANATT-1890/100", isocyanate group content 17.2 mass %) 753.2 mass parts, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 644.2 mass parts, dibutylhydroxytoluene 6.5 parts by mass to dissolve. It was confirmed that the isocyanate group content was 0.1 mass % or less by reacting at 160° C. for 5 hours under a nitrogen atmosphere. Add 1.3 parts by mass of hydroquinone monomethyl ether, 189.2 parts by mass of pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., content of pentaerythritol triacrylate about 67%, hydroxyl value 159.7 mgKOH/g), triphenylene 12.9 parts by mass of the base phosphine was reacted at 110° C. for 5 hours while blowing in air. Next, 617.1 mass parts of glycidyl methacrylates were added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 546 mass parts of tetrahydrophthalic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the acid group containing (meth)acrylate resin (6) was obtained. The acid group-containing (meth)acrylate resin (6) had a solid content acid value of 80 mgKOH/g, an acryloyl equivalent of 434 g/equivalent, and a weight average molecular weight (Mw) of 5,600.

Example 7 Production of acid group-containing (meth)acrylate resin (7)

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 449.7 parts by mass of diethylene glycol monomethyl ether acetate and an isocyanurate modified product of isophorone diisocyanate (Evonik Co., Ltd. Prepared "VESTANAT T-1890/100", isocyanate group content 17.2 mass %) 170.5 mass parts, trimellitic anhydride 138.5 mass parts, and 1.4 mass parts of dibutylhydroxytoluene were dissolved. It was confirmed that the isocyanate group content was 0.1 mass % or less by reacting at 160° C. for 5 hours under a nitrogen atmosphere. 0.3 parts by mass of hydroquinone monomethyl ether, 30.3 parts by mass of pentaerythritol triacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., content of pentaerythritol triacrylate about 67%, hydroxyl value 159.7 mgKOH/g) and triphenylene were added 2.8 parts by mass of the phosphonium phosphine was reacted at 110° C. for 5 hours while blowing in air. Next, 165 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate (“CYCLOMER M100” manufactured by Daicel Corporation, epoxy group equivalent: 207 g/equivalent) was added and reacted at 120° C. for 10 hours. Furthermore, 76.7 parts by mass of succinic anhydride was added, and the reaction was carried out at 110°C for 5 hours to obtain an acid group-containing (meth)acrylate resin (7). The acid group-containing (meth)acrylate resin (7) had a solid content acid value of 80 mgKOH/g, an acryloyl equivalent of 500 g/equivalent, and a weight average molecular weight (Mw) of 4040.

Comparative Example 1 Production of acid group-containing (meth)acrylate resin (1')

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was placed, and an o-cresol novolak type epoxy resin (“EPICLON N-680 manufactured by DIC Corporation”) was prepared. ”, softening point 85°C, epoxy group equivalent 214 g/equivalent) 428 parts by mass dissolved. Furthermore, after adding 4 mass parts of dibutylhydroxytoluene and 0.4 mass part of hydroquinone monomethyl ether, 144 mass parts of acrylic acid and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 120 degreeC for 10 hours, blowing in air. Next, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 2.5 hours to obtain an acid group-containing (meth)acrylate resin (1′). ). The acid value of the solid content of the acid group-containing (meth)acrylate resin (1') was 85 mgKOH/g.

Examples 8 to 14 and Comparative Example 2

Curable resin compositions were prepared and various evaluation tests were performed in the following manner. The results are shown in Table 1.

·Preparation of curable resin composition

100 parts by mass of the acid group-containing (meth)acrylate resin (in terms of solid content) obtained above, 24 parts by mass of "EPICLON N-680" (cresol novolak type epoxy resin) manufactured by DIC Corporation, BASF Co., Ltd. "Irgacure907" [2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one] 5 parts by mass, diethylene glycol monomethyl ether acetate 13 parts by mass were blended to obtain a curable resin composition.

·Production of cured product

The curable resin composition was apply|coated to glass with the applicator of 50 micrometers, and it dried at 80 degreeC for 30 minutes. After irradiating ultraviolet rays of 1000 mJ/cm ² with a metal halide lamp, it was heated at 160° C. for 1 hour. The cured product is peeled off from the glass.

・Evaluation of heat resistance of cured products

A test piece of 6 mm × 40 mm was cut out from the cured product, and the elastic modulus was measured by a viscoelasticity measuring apparatus (DMA: Solid Viscoelasticity Measuring Apparatus "RSAII" manufactured by Rheometric Corporation, tensile method: frequency 1 Hz, heating rate 3°C/min). The temperature at which the amount change is the largest (the largest tan δ change rate) is evaluated as the glass transition temperature (Tg).

・Evaluation of the elongation of the cured product

A test piece of 10 mm × 80 mm was cut out from the cured product, and the elongation of the test piece was measured and evaluated using a tensile tester ("Confidential Universal Tester Autograph AG-IS" manufactured by Shimadzu Corporation) under the following conditions .

Temperature 23°C, humidity 50%, distance between marking lines 20mm, distance between fulcrums 20mm, stretching speed 10mm/min

[Table 1]

Claims (9)

1. An acid group-containing (meth)acrylate resin comprising an amideimide resin (A) having an acid group or an acid anhydride group, a (meth)acrylate hydroxyester compound (B), a (methyl) ) Epoxy compound (C) of acryloyl group and polycarboxylic acid anhydride (D) are necessary reaction raw materials, The amide-imide resin (A) having an acid group or an acid anhydride group uses a polyisocyanate compound (a1) and a polycarboxylic acid or its acid anhydride (a2) as necessary reaction raw materials, and the polyisocyanate compound (a1) is An alicyclic diisocyanate compound or a modified product thereof is an essential component, or an aliphatic diisocyanate compound or a modified product thereof is an essential component. 2 . The acid group-containing (meth)acrylate resin according to claim 1 , wherein the polycarboxylic acid or its acid anhydride (a2) has tricarboxylic acid anhydride as an essential component. 3 . 3 . The acid group-containing (meth)acrylate resin according to claim 1 , wherein the polycarboxylic acid anhydride (D) is an aliphatic polycarboxylic acid anhydride or an alicyclic polycarboxylic acid anhydride. 4 . 4 . The acid group-containing (meth)acrylate resin according to claim 1 , wherein the (meth)acryloyl equivalent is in the range of 250 to 750 g/equivalent. 5 . 5 . A curable resin composition comprising: the acid group-containing (meth)acrylate resin according to claim 1 , and a photopolymerization initiator. 6 . 6 . A cured product, which is a cured product of the curable resin composition according to claim 5 . 7 . An insulating material comprising the curable resin composition according to claim 5 . 8 . A resin material for a solder resist comprising the curable resin composition according to claim 5 . 9 . An anti-corrosion member formed using the resin material for a solder resist according to claim 8 .

Images