TWI782991B - (Meth)acrylate resins containing acid groups and resin materials for solder resist - Google Patents

Abstract

The present invention provides a kind of (meth)acrylic acid ester resin that contains acid group, it is characterized in that having acid group or acid anhydride group amidoimide resin (A), hydroxyl (meth)acrylate compound (B), containing (Meth) acrylic epoxy compound (C) and polycarboxylic acid anhydride (D) are used as necessary reaction raw materials; and a curable resin composition containing the (meth) acrylate resin containing acid groups is provided, including The insulating material of the curable resin composition, the resin material for solder resist, and the solder resist member. This acid group-containing (meth)acrylate resin can form a cured product excellent in heat resistance and elongation.

Description

(Meth)acrylate resin containing acid group and resin material for solder resist

The present invention relates to an acid group-containing (meth)acrylate resin with high heat resistance and elongation of the cured product, a curable resin composition containing the same, an insulating material containing the curable resin composition, and a solder resist resin materials and solder mask components.

Among solder resist resin materials for printed wiring boards, acid group-containing epoxy acrylate resins obtained by acrylated epoxy resins with acrylic acid and reacted with acid anhydrides are widely used. For the performance requirements of resin materials for solder resist, the following properties can be listed: hardening with a small amount of exposure, excellent alkali developability, heat resistance of hardened products, strength, flexibility, elongation, dielectric properties, substrate density, etc. Good adhesion and so on.

Among the conventionally known resin materials for solder resist, there is known an acid group-containing epoxy acrylate resin obtained by reacting a novolak-type epoxy resin with acrylic acid and tetrahydrophthalic anhydride (see Patent Document 1 below). . The acid-group-containing epoxy acrylate resin described in Patent Document 1 is derived from the novolac-type epoxy resin as the raw material for the reaction, and has the characteristics of high heat resistance of the hardened product, but it is still insufficient to meet the recent market requirements. Also, since the elongation of the cured product is very low, there is a problem that cracks are easily generated in the cured product, resulting in poor reliability.

prior art literature patent documents

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

Therefore, the problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin with high heat resistance and elongation of the cured product, a curable resin composition containing the same, and a composition comprising the aforementioned curable resin. Insulation materials for objects, resin materials for solder resist and solder resist components.

As a result of earnest investigations by the present inventors in order to solve the above-mentioned problems, it was found that by reacting an amidoimide resin with a hydroxy (meth)acrylate and an epoxy compound containing a (meth)acryl group, the introduction of (methyl) ) acryl group, further reaction with polycarboxylic acid anhydride to obtain (meth)acrylate resin containing acid groups, the heat resistance and elongation of the hardened product are very high, so the present invention has been completed.

That is, the present invention relates to the amidoimide resin (A) having an acid group or an acid anhydride group, a hydroxyl (meth)acrylate compound (B), an epoxy compound containing a (meth)acryl group ( C) and polycarboxylic acid anhydride (D) as an acid group-containing (meth)acrylate resin as necessary reaction raw materials.

Furthermore, the present invention relates to a curable resin composition comprising the above-mentioned acid group-containing (meth)acrylate resin and a photopolymerization initiator.

Furthermore, the present invention relates to a cured product of the aforementioned curable resin composition.

Furthermore, the present invention relates to an insulating material comprising the aforementioned curable resin composition.

Furthermore, this invention relates to the resin material for solder resists containing the said curable resin composition.

Furthermore, this invention relates to the solder resist member containing the said resin material for solder resists.

According to the present invention, it is possible to provide an acid group-containing (meth)acrylate resin having high heat resistance and elongation of the cured product, a curable resin composition containing the same, an insulating material including the curable resin composition, and a barrier material. Soldering resin materials and solder resist components.

Fig. 1 is the GPC graph of the (meth)acrylate resin (1) containing acid groups obtained in Example 1.

Mode for carrying out the invention

Hereinafter, the present invention will be described in detail.

The acid group-containing (meth)acrylate resin of the present invention is based on the amidoimide resin (A) with acid group or acid anhydride group, hydroxyl (meth)acrylate compound (B), containing (methyl) ) acryl-based epoxy compound (C) and polycarboxylic acid anhydride (D) as necessary reaction raw materials.

In the present invention, a (meth)acrylate resin means a resin having an acryl group, a methacryl group, or both in a molecule. In addition, (meth)acryl group means one or both of acryl group and methacryl group, and (meth)acrylate is a generic term for acrylate and methacrylate.

The aforementioned amidoimide resin (A) having an acid group or an acid anhydride group may have either only an acid group or an acid anhydride group, or may have both. Among them, from the viewpoint of reactivity or reaction control with the aforementioned hydroxy (meth)acrylate compound (B) or the aforementioned (meth)acryl group-containing epoxy compound (C), it is preferable to have an acid anhydride group. Preferably, it is more preferred to have both acid groups and acid anhydride groups. The acid value of the aforementioned amidoimide resin (A) is preferably in the range of 60 to 350 mgKOH/g under neutral conditions, that is, under the condition that the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measured value is in the range of 61 to 360 mgKOH/g under conditions such as the presence of water to open the acid anhydride group.

The specific structure or production method of the aforementioned amidoimide resin (A) is not particularly limited, and general amidoimide resins and the like can be widely used. Specifically, what uses a polyisocyanate compound (a1), a polycarboxylic acid, or its anhydride (a2) as a reaction raw material is mentioned.

The aforementioned polyisocyanate compound (a1) includes, for example, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic diisocyanate compounds such as methylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate; methylene diisocyanate Diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethyl Aromatic diisocyanate compounds such as biphenyl and bi-o-toluidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); modified isocyanates of these , biuret modified body, alloformate modified body, etc. These may be used individually or in combination of 2 or more types.

[In the formula, R ¹ are each independently a hydrogen atom or any one of a hydrocarbon group with 1 to 6 carbon atoms; R ² are each independently an alkyl group with 1 to 4 carbon atoms, or a methylene group marked with * Any of the bonding points where the group is connected to the structural site represented by the structural formula (1); l is 0 or an integer of 1 to 3, and m is an integer of 1 or more].

Among them, from the viewpoint of being an acid group-containing (meth)acrylate resin having high solvent solubility, the aforementioned alicyclic diisocyanate compound or a modified product thereof is preferable, and the alicyclic diisocyanate compound or its modified form is preferable. Diisocyanate or its modified form of isocyanate is preferable. Also, from the viewpoint of an acid group-containing (meth)acrylate resin having a very high elongation rate of the cured product, the aforementioned aliphatic diisocyanate compound or a modified product thereof is preferable, and the aliphatic diisocyanate or Its modified isocyanate is preferred. In addition, the ratio of the total mass of the aforementioned alicyclic diisocyanate compound or a modified product thereof to the aforementioned aliphatic diisocyanate compound or a modified product thereof relative to the total mass of the aforementioned polyisocyanate compound (a1) is 70% by mass. The above is more preferable, and more than 90 mass % is more preferable. Also, when the alicyclic diisocyanate compound or its modified product is used in combination with the aliphatic diisocyanate compound or its modified product, the mass ratio of the two is preferably in the range of 30/70 to 70/30. .

The aforementioned polycarboxylic acid or its anhydride (a2) does not matter the specific structure as long as it has a plurality of carboxyl groups in its molecular structure or its anhydride, and various compounds can be used. Moreover, polycarboxylic acid or its acid anhydride (a2) may be used individually, respectively, and may use 2 or more types together. Furthermore, since amidoimide resin (A) has both amido and imide groups, there must be both carboxyl and acid anhydride groups in the system, and in the present invention, it is possible to use molecules with carboxyl and acid anhydride groups. As for the compound of both acid anhydride groups, the compound which has a carboxyl group and the compound which has an acid anhydride group can also be used together.

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

Regarding the aforementioned alicyclic polycarboxylic acid compounds or their anhydrides, in the present invention, those with carboxyl or acid anhydride groups combined with an alicyclic structure are regarded as alicyclic polycarboxylic acid compounds or their anhydrides, regardless of whether there are aromatic rings in other structural parts. . As an example of the aforementioned alicyclic polycarboxylic acid compound or an anhydride thereof, for example, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylate methyl ester, 4-(2,5-dioxo-tetrahydrofuran -3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, and their anhydrides.

As an example of the aforementioned aromatic polycarboxylic acid compound or its anhydride, for example, phthalic acid, trimellitic acid, pyromelite, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl Dicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, diphenylketonetetracarboxylic acid, and the like.

Among them, the above-mentioned alicyclic polycarboxylic acid compound or its anhydride, or the above-mentioned aromatic polycarboxylic acid compound or its anhydride are preferable in terms of being an acid group-containing (meth)acrylate resin having particularly high heat resistance. . Also, from the viewpoint of efficiently producing the aforementioned amidoimide resin (A), it is preferable to use tricarboxylic anhydrides having both carboxyl and acid anhydride groups in the molecular structure, and to use cyclohexanetricarboxylic anhydride or Trimellitic anhydride is particularly preferred. Furthermore, the ratio of the total amount of the alicyclic tricarboxylic anhydride to the aromatic tricarboxylic anhydride is preferably 70% by mass or more, and 90% by mass or more with respect to the total mass of the polycarboxylic acid or its anhydride (a2). is better.

In the case where the aforementioned amidoimide resin (A) uses the aforementioned polyisocyanate compound (a1) and the aforementioned polycarboxylic acid or its anhydride (a2) as reaction raw materials, depending on desired resin properties, etc., other than these may be used. The reaction raw materials are used together. In this case, the effect achieved from the present invention can be fully brought into play, relative to the total mass of the reaction raw materials of the amidoimide resin (A), the aforementioned polyisocyanate compound (a1) and the aforementioned polycarboxylic acid or its anhydride (a2 ) is preferably at least 90% by mass, more preferably at least 95% by mass.

When the aforementioned amidoimide resin (A) uses polyisocyanate compound (a1) and polycarboxylic acid or its anhydride (a2) as reaction raw materials, its production method is not particularly limited, and can be produced by any method. For example, it can be manufactured by the same method as general amidoimide resin. Specifically, 0.8 to 1.2 mol of the aforementioned polycarboxylic acid or its anhydride (a2) is used with respect to 1 mol of the isocyanate group contained in the aforementioned polyisocyanate compound (a1), at about 120 to 180 The method of stirring and mixing at a temperature of ℃ to make it react.

The reaction may be carried out in an organic solvent if necessary. The selection of the organic solvent used can be appropriately selected according to the solubility of the reaction raw materials and the acid group-containing (meth)acrylate resin or the reaction temperature conditions of the product, for example, methyl ethyl ketone, acetone, etc. , Dimethylformamide, Methyl Isobutyl Ketone, Methoxypropanol, Cyclohexanone, Methyl Cellusu, Dialkylene Glycol Monoalkyl Ether Acetate, Dialkylene Di alcohol acetate etc. These may be used individually, or may form the mixed solvent of 2 or more types. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials in order to improve the reaction efficiency.

The above-mentioned hydroxy (meth)acrylate compound (B) is not particularly limited as long as it has a hydroxyl group and a (meth)acryl group in its molecular structure, and other specific structures can be used. Various compounds can be used. Moreover, the said hydroxy (meth)acrylate compound (B) may be used individually, respectively, and may use 2 or more types together. Among them, monohydroxy (meth)acrylate compounds are preferred in terms of easy control of the reaction. As an example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylthritol tri(methyl) Hydroxy (meth)acrylate compounds such as acrylates, di-trimethylolpropane tri(meth)acrylate, dipenteoerythritol penta(meth)acrylate; in the aforementioned various hydroxy(meth)acrylates A (poly)oxyalkylene group that introduces (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. (poly)oxyalkylene chains into the molecular structure of a compound Modifiers; lactone modifiers that introduce (poly)lactone structures into the molecular structures of the aforementioned various hydroxy (meth)acrylate compounds, etc. These may be used individually, respectively, and may use 2 or more types together. Among them, the acid group-containing (meth)acrylate resin having a good balance between heat resistance and elongation as a cured product preferably has a molecular weight of 1,000 or less. Moreover, when the said hydroxy (meth)acrylate compound (B) is the said oxyalkylene modified body or lactone modified body, it is preferable that a weight average molecular weight (Mw) is 1,000 or less.

The aforementioned epoxy compound (C) containing a (meth)acryl group, as long as it has a (meth)acryl group and an epoxy group in the molecular structure, other specific structures are not particularly limited, and various compounds can be used . Moreover, the said (meth)acryl group containing epoxy compound (C) may be used individually, respectively, and may use 2 or more types together. Among these, monoepoxides are preferred in terms of ease of reaction control. As an example, for example, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate, etc. containing ring Oxypropyl (meth)acrylate monomers; Dihydroxybenzene Diglycidyl Ether, Dihydroxynaphthalene Diglycidyl Ether, Biphenol Diglycidyl Ether, Bisphenol Diglycidyl Ether Diglycidyl ether compounds such as mono(meth)acrylate compounds, etc. Among them, the above-mentioned glycidyl group-containing (meth)acrylate monomer is preferable from the viewpoint of an acid group-containing (meth)acrylate resin having an excellent balance between heat resistance and elongation as a cured product. Also, its molecular weight is preferably 500 or less. Furthermore, with respect to the total mass of the epoxy compound (C) containing the (meth)acryl group, the ratio of the (meth)acrylate monomer containing the glycidyl group is preferably 70% by mass or more , preferably more than 90% by mass.

As said polycarboxylic acid anhydride (D), the acid anhydride etc. in each compound which were illustrated about the said polycarboxylic acid or its anhydride (a2) are mentioned, for example. Moreover, said polycarboxylic acid anhydride (D) may be used individually, respectively, and may use 2 or more types together. Among them, the aforementioned aliphatic polycarboxylic acid anhydride or the aforementioned alicyclic polycarboxylic acid anhydride is used as an acid group-containing (meth)acrylate compound having excellent developability in addition to the heat resistance and elongation of the cured product. Preferably, aliphatic dicarboxylic acid anhydride or alicyclic dicarboxylic acid anhydride is more preferred.

The acid group-containing (meth)acrylate resin of the present invention, according to desired resin properties, etc., except the aforementioned amidoimide resin (A) with acid group or acid anhydride group, hydroxyl (meth)acrylate compound ( B), besides (meth)acryl group-containing epoxy compound (C) and polycarboxylic acid anhydride (D), other reaction raw materials can also be used in combination. In this case, from the effect achieved by the present invention can be fully brought into play, relative to the total mass of the reaction raw materials of the acid group-containing (meth)acrylate resin, the total mass of the aforementioned (A) ~ (D) components The ratio is preferably at least 80% by mass, more preferably at least 90% by mass.

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 at once, or 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 produce by a method including the steps of: making the aforementioned amidoimide resin (A) and the aforementioned hydroxy (meth)acrylic acid Reaction of ester compound (B) (step 1), reaction of the product of step 1 with the aforementioned epoxy compound (C) containing (meth)acryl group (step 2), reaction of the product of step 2 with the aforementioned polycarboxylate Anhydride (D) reaction.

Regarding the aforementioned step 1, in the reaction between the aforementioned amidoimide resin (A) and the aforementioned hydroxy (meth)acrylate compound (B), the acid groups in the aforementioned amidoimide resin (A) are mainly Or the acid anhydride group reacts with the hydroxyl group in the hydroxy (meth)acrylate compound (B). Since the aforementioned hydroxy (meth)acrylate compound (B) has excellent reactivity with acid anhydride groups, as mentioned above, the aforementioned amidoimide resin (A) preferably has acid anhydride groups. The reaction ratio of the aforementioned amidoimide resin (A) and the aforementioned hydroxy (meth)acrylate compound (B), relative to the total of acid groups and acid anhydride groups in the aforementioned amidoimide resin (A), is It is preferable to use the said hydroxy (meth)acrylate compound (B) in the range of 0.9-1.1 mol. Especially, it is 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 amidoimide resin (A). The content of the acid anhydride group in the aforementioned amidoimide resin (A) can be determined from the difference in the measured value of the acid value of the aforementioned 2, that is, the acid value of the conditions under which the acid anhydride group is ring-opened, and the acid value without the acid anhydride group The difference in acid value for the conditions of ring opening was calculated.

The reaction between the aforementioned amidoimide resin (A) and the aforementioned hydroxy (meth)acrylate compound (B) can be, for example, heated at a temperature of about 90~140°C in the presence of an appropriate esterification catalyst While stirring. The aforementioned esterification catalysts, for example, phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine; 2- imidazole compounds such as methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, and the like. These may be used individually, respectively, and may use 2 or more types together. The amount of catalyst added is preferably within the range of 0.001 to 5 parts by mass relative to the total mass of the reaction raw materials.

The reaction may be carried out in an organic solvent if necessary. The selection of the organic solvent used can be appropriately selected according to the reaction raw materials and the solubility or reaction temperature conditions of the acid group-containing (meth)acrylate resin as the product, for example, methyl ethyl ketone, acetone, etc. , Dimethylformamide, Methyl Isobutyl Ketone, Methoxypropanol, Cyclohexanone, Methyl Cellusu, Dialkylene Glycol Monoalkyl Ether Acetate, Dialkylene Di alcohol acetate etc. These may be used individually, respectively, and may form the mixed solvent of 2 or more types. When the production of the aforementioned amidoimide resin (A) is performed continuously with step 1, the reaction may be continued as it is in the organic solvent used for the production of the aforementioned amidoimide resin (A).

Regarding the aforementioned step 2, the aforementioned (meth)acryl group-containing epoxy compound (C) mainly reacts with the carboxyl group in the product of the aforementioned step 1. Its reaction ratio, with respect to the carboxyl group in the product in step 1, it is better to use the above-mentioned epoxy compound (C) containing (meth)acryl group in the range of 0.5~1.2 moles, to use 0.9~1.1 Mole's range is better. The reaction in step 2 can be carried out, for example, by heating and stirring at a temperature of about 90-140° C. in the presence of an appropriate esterification catalyst. When performing step 1 and step 2 continuously, the esterification catalyst may not be added, but may be added appropriately. In addition, the reaction may be performed in an organic solvent if necessary.

Regarding 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 aforementioned step 2, for example, there are hydroxyl groups generated by ring-opening of the epoxy group in the aforementioned (meth)acryl group-containing epoxy compound (C), and the like. It is preferable to adjust the reaction ratio of the said polycarboxylic acid anhydride (D) so that the acid value of the acid group containing (meth)acrylate resin of the final product may become about 50-100 mgKOH/g. The reaction in step 3 can be carried out, for example, by heating and stirring at a temperature of about 90-140° C. in the presence of an appropriate esterification catalyst. When performing step 2 and step 3 continuously, the esterification catalyst may not be added, but may be added appropriately. In addition, the reaction may also be performed in an organic solvent if necessary.

The acid value of the acid group-containing (meth)acrylate resin obtained by this method becomes an acid group-containing (meth)acrylic acid that is excellent in heat resistance and elongation of the cured product, and is also excellent in developability, etc. For ester resin, the range of 50~100mgKOH/g is better, and the range of 60~90mgKOH/g is more preferable. In addition, in this invention, the acid value of the (meth)acrylate resin containing an acid group is the value measured based on the neutralization titration method of JISK0070 (1992). In addition, the (meth)acryl group equivalent weight of the (meth)acrylate resin containing acid groups is preferably in the range of 250-750 g/equivalent, more preferably in the range of 300-700 g/equivalent. The mass average molecular weight (Mw) of the aforementioned 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 under the following conditions.

Measuring device: Tosoh Co., Ltd. "HLC-8220 GPC", column: Tosoh Co., Ltd. guard column "HXL-L"

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Co., Ltd.

Measuring conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement operation manual of the aforementioned "GPC-8020 Model II Version 4.10", use the following monodisperse polystyrene with known molecular weight.

(using polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: 1.0% by mass (resin solid content conversion) tetrahydrofuran solution filtered through a microfilter (50 μl)

The acid group-containing (meth)acrylate resin of the present invention has a polymerizable (meth)acryl group in the molecular structure, for example, can be formed by adding a photopolymerization initiator to form a curable resin composition. use.

啉基苯基)-丁酮-1,2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮等烷基苯基酮系光聚合起始劑；2,4,6-三甲基苄醯基-二苯基-膦氧化物等醯基膦氧化物系光聚合起始劑；二苯基酮化合物等分子內奪氫型光聚合起始劑等。此等可分別單獨使用，亦可將2種以上併用。 The aforementioned photopolymerization initiator may be used by selecting an appropriate one according to the type of active energy rays to be irradiated, and the like. In addition, it can also 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 photopolymerization initiators include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Alkyl phenyl ketone photopolymerization initiators such as linyl)phenyl]-1-butanone; acylphosphine oxides such as 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide It is a photopolymerization initiator; intramolecular hydrogen abstraction photopolymerization initiators such as diphenyl ketone compounds, etc. These may be used individually, respectively, and may use 2 or more types together.

Commercially available products of the aforementioned photopolymerization initiator include, for example, "IRGACURE 127", "IRGACURE 184", "IRGACURE 250", "IRGACURE 270", "IRGACURE 290", "IRGACURE 369E", "IRGACURE 379EG", "IRGACURE 500" manufactured by BASF Corporation. "IRGACURE651", "IRGACURE754", "IRGACURE819", "IRGACURE907", "IRGACURE1173", "IRGACURE2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE OXE 01", "IRGACURE OXE 02", manufactured by IGM RESINS "OMNIRAD184", "OMNIRAD250", "OMNIRAD369", "OMNIRAD369E", "OMNIRAD651", "OMNIRAD907FF", "OMNIRAD1173", etc.

The amount of the above-mentioned photopolymerization initiator to be added is, for example, preferably in the range of 0.05 to 15% by mass, and more preferably in the range of 0.1 to 10% by mass, based on the total of 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. The resin component is, for example, one obtained by reacting an epoxy resin such as a bisphenol-type epoxy resin or a novolak-type epoxy resin with (meth)acrylic acid, a dicarboxylic acid anhydride, an unsaturated monocarboxylic acid anhydride, or the like if necessary. Among the obtained resins, there are resins having carboxyl groups and (meth)acryl groups, or various (meth)acrylate monomers.

The aforementioned (meth)acrylate monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Aliphatic mono(meth)acrylate compounds such as amyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, etc.; cyclohexyl (meth)acrylate alicyclic mono(meth)acrylate compounds such as ester, isocamphoryl (meth)acrylate, adamantyl mono(meth)acrylate; Cyclic mono(meth)acrylate compounds; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, (meth) Phenoxyethyl acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, ( Mono(meth)acrylate compounds such as benzylbenzyl methacrylate, phenylphenoxyethyl (meth)acrylate and other aromatic mono(meth)acrylate compounds; (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains and other polyoxyalkylene chains introduced into the molecular structure of acrylate monomers Modified mono(meth)acrylate compounds; lactone-modified mono(meth)acrylate compounds that introduce (poly)lactone structures into the molecular structures of the aforementioned various mono(meth)acrylate compounds;

Ethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, Butylene glycol di(meth)acrylate, Hexylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate ) acrylate and other aliphatic di(meth)acrylate compounds; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane dimethanol di(meth)acrylate, norbornane dimethanol di( Alicyclic di(meth)acrylate compounds such as meth)acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; biphenol di(meth)acrylate ) acrylate, bisphenol di(meth)acrylate and other aromatic di(meth)acrylate compounds; introducing (poly)oxyethylene chains, Polyoxyalkylene modified di(meth)acrylate compounds of (poly)oxypropylene chains, (poly)oxytetramethylene chains and other (poly)oxyalkylene chains; A lactone-modified di(meth)acrylate compound with a (poly)lactone structure introduced into the molecular structure of the acrylate compound;

Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compounds (Poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. (poly)oxyalkylene modified tri(methyl) ) acrylate compound; a lactone-modified tri(meth)acrylate compound in which a (poly)lactone structure is introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound;

Aliphatic poly(meth)acrylates with more than 4 functionalities such as neopentylthritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, and dipentynerythritol hexa(meth)acrylate ) acrylate compounds; introducing (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compounds The (poly)oxyalkylene modified poly(meth)acrylate compound with more than 4 functional groups in the (poly)oxyalkylene chain; ) lactone-structured tetrafunctional or higher lactone-modified poly(meth)acrylate compounds, etc.

The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting coating viscosity and the like. Its type and dosage can be adjusted appropriately according to the expected performance. Generally, it is used in the range of 10 to 90% by mass relative to the total of the curable resin composition. Specific examples of the aforementioned solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; methyl acetate, ethyl acetate, and the like; Esters such as esters and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, celuso, methanol, isopropanol, butanol, propylene glycol Alcohol solvents such as monomethyl ether; glycol ether-based solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These may be used individually, respectively, and may use 2 or more types together.

The curable resin composition of the present invention may also contain various additives such as inorganic fine particles or polymer fine particles, pigments, defoamers, viscosity regulators, leveling agents, flame retardants, storage stabilizers and the like.

The acid group-containing (meth)acrylate resin of the present invention has the characteristics of heat resistance and high elongation of the cured product. In addition, it has the characteristics of being excellent in developability evaluated by photosensitivity, drying control range, etc., substrate adhesion of cured products, and non-adhesiveness after temporary drying. In terms of applications utilizing the various excellent properties of the acid group-containing (meth)acrylate resin of the present invention, for example, in applications related to semiconductor devices, it can be used as solder resist, interlayer insulating materials, packaging materials, Underfill materials, circuit components, etc. are used as packaging adhesive layers or as adhesive layers between integrated circuit components and circuit substrates. In addition, for applications related to thin displays represented by LCDs and OELDs, it is suitable for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, and resists for black matrices. agents, spacers, etc. Among these, it can be used especially suitably for a solder resist application. The resin material for soldering resist of the present invention, for example, includes various components such as a hardener, a hardening accelerator, and an organic solvent in addition to the above-mentioned acid group-containing (meth)acrylate resin, photopolymerization initiator, and various additives.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the acid group-containing (meth)acrylate resin, for example, an epoxy resin is mentioned. The epoxy resins used here include, for example, bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthyl ether-type epoxy resins, biphenyl-type epoxy resins, and triphenylmethane-type epoxy resins. Oxygen resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol novolac epoxy resin, naphthol novolac epoxy resin, naphthol-phenol novolak epoxy resin , Naphthol-cresol co-condensed novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, etc. These may be used individually, respectively, and may use 2 or more types together. Among these epoxy resins, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin are used in view of the excellent heat resistance of the cured product. Epoxy resin, naphthol-phenol novolac type epoxy resin, naphthol-cresol novolac type epoxy resin and other novolac epoxy resins are preferred, with a softening point of 50~120°C The range is especially good.

The aforementioned hardening accelerator is one that accelerates the hardening reaction of the aforementioned hardening agent. In the case of using an epoxy resin as the aforementioned hardening agent, examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine zirconium salts, etc. . These may be used individually, respectively, and may use 2 or more types together. 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 agents, for example.

The above-mentioned organic solvent is not particularly limited as long as it can dissolve various components such as the above-mentioned acid group-containing (meth)acrylate resin or hardener, for example, methyl ethyl ketone, acetone, dimethylformamide, Methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl celuso, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc.

The method of using the solder resist resin material of the present invention to obtain a solder resist member includes, for example, coating the aforementioned solder resist resin material on a base material, and drying the organic solvent at a temperature range of about 60 to 100°C. A method in which a photomask with a desired pattern is formed, exposed to ultraviolet rays or electron rays, and the unexposed part is developed with an aqueous alkali solution, and then heated and hardened at a temperature range of about 140 to 180°C.

Example

Hereinafter, the present invention will be described in more detail with examples and comparative examples.

In this example, the acid value of the (meth)acrylate resin containing acid groups was measured according to the neutralization titration method of JIS K 0070 (1992).

In this example, the molecular weight of the (meth)acrylate resin containing acid groups was measured by GPC under the following conditions.

Measuring device: Tosoh Co., Ltd. "HLC-8220GPC", column: Tosoh Co., Ltd. guard column "HXL-L"

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Co., Ltd.

Measuring conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement operation manual of the aforementioned "GPC-8020 Model II Version 4.10", use the following monodisperse polystyrene with known molecular weight.

(using polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solids was filtered through a microfilter (50 μl)

Embodiment 1 The manufacture of (meth)acrylate resin (1) containing acid group

In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 449.7 parts by mass of diethylene glycol monomethyl ether acetate and 175.5 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK Co., Ltd., isocyanate group content 17.2% by mass), 142.6 parts by mass of trimellitic anhydride, and 1.4 parts by mass of dibutylhydroxytoluene were dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole (Methoquinone), 31.1 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Ya Gosei Co., Ltd., the content of neopentylthritol triacrylate is about 67 %, hydroxyl value 159.7mgKOH/g) and 2.8 parts by mass of triphenylphosphine, while blowing in air, react at 110°C for 5 hours. Then, 116.5 parts by mass of glycidyl methacrylate was 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 (meth)acrylate resin (1) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (1) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 485 g/equivalent, and a weight average molecular weight (Mw) of 5,200. The GPC chart of the acid group-containing (meth)acrylate resin (1) is shown in FIG. 1 .

Embodiment 2 Manufacture of (meth)acrylate resin (2) containing acid groups

In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 449.9 parts by mass of diethylene glycol monomethyl ether acetate and 191.4 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK Co., Ltd., isocyanate group content 17.2% by mass), 155.5 parts by mass of trimellitic anhydride, and 1.4 parts by mass of dibutylhydroxytoluene were dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole, 34.0 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl group Value 159.7 mgKOH/g) and 2.8 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 127.1 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 76.6 mass parts of succinic anhydrides were added, it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (2) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (2) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 445 g/equivalent, and a weight average molecular weight (Mw) of 4,700.

Embodiment 3 Manufacture of (meth)acrylate resin (3) containing acid groups

In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 350.4 parts by mass of diethylene glycol monomethyl ether acetate and 85.8 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK, the isocyanate group content is 17.2% by mass), 85.8 parts by mass of uric acid ester modified product of hexamethylene diisocyanate ("Burnock DN901S" manufactured by DIC Co., Ltd., The content of isocyanate group is 23.5% by mass), 209.4 parts by mass of trimellitic anhydride, and 1.6 parts by mass of dibutylhydroxytoluene are dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole and 16.9 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl value 159.7 mgKOH/g) and 3.3 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 197.9 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC 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 (meth)acrylate resin (3) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (3) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 415 g/equivalent, and a weight average molecular weight (Mw) of 4,980.

Embodiment 4 Production of (meth)acrylate resin (4) containing acid groups

In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add uric acid ester modified body ( "Burnock DN901S" manufactured by DIC Co., Ltd., isocyanate group content 23.5% by mass), 219.7 parts by mass of trimellitic anhydride, and 1.8 parts by mass of dibutylhydroxytoluene were dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.4 parts by mass of p-hydroxyanisole and 11.9 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl group Value 159.7 mgKOH/g) and 3.5 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 221.7 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC 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 (meth)acrylate resin (4) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (4) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 416 g/equivalent, and a weight average molecular weight (Mw) of 4,350.

Embodiment 5 The manufacture of (meth)acrylate resin (5) containing acid group

In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 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, 1.8 Parts by mass of dibutylhydroxytoluene to dissolve it. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.4 parts by mass of p-hydroxyanisole and 11.1 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Ya Gosei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl Value 159.7 mgKOH/g) and 3.5 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 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 (meth)acrylate resin (5) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (5) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 603 g/equivalent, and a weight average molecular weight (Mw) of 1,780.

Embodiment 6 Manufacture of (meth)acrylate resin (6) containing acid groups

In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 1422.7 parts by mass of diethylene glycol monomethyl ether acetate and 753.2 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK, the content of isocyanate group is 17.2% by mass), 644.2 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 6.5 parts by mass dibutylhydroxytoluene to dissolve it. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 1.3 parts by mass of p-hydroxyanisole and 189.2 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Ya Gosei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl value 159.7 mgKOH/g), 12.9 parts by mass of triphenylphosphine, and reacted at 110° C. for 5 hours while blowing in air. Then, 617.1 parts by mass of glycidyl methacrylate was 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 (meth)acrylate resin (6) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (6) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 434 g/equivalent, and a weight average molecular weight (Mw) of 5,600.

Example 7 Production of (meth)acrylate resin (7) containing acid groups

In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 449.7 parts by mass of diethylene glycol monomethyl ether acetate and 170.5 parts by mass of isophorone diisocyanate (EVONIK "VESTANAT T-1890/100" produced by the company, the content of isocyanate group is 17.2% by mass), 138.5 parts by mass of trimellitic anhydride, and 1.4 parts by mass of dibutylhydroxytoluene are dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole and 30.3 parts by mass of neopentylitol triacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl Value 159.7 mgKOH/g) and 2.8 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 165 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate ("Cyclomer M100" manufactured by Daicel Co., Ltd., 207 g/equivalent of epoxy group) was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 76.7 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (7) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (7) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 500 g/equivalent, and a weight average molecular weight (Mw) of 4,040.

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

In the flask equipped with thermometer, stirrer, and reflux cooler, add 101 mass parts of diethylene glycol monomethyl ether acetate to make 428 mass parts of o-cresol novolak type epoxy resin (DIC Co., Ltd. "EPICLON N-680" manufactured by the company, softening point 85°C, epoxy group equivalent weight 214g/equivalent) was dissolved. Furthermore, after adding 4 parts by mass of dibutylhydroxytoluene and 0.4 parts by mass of p-hydroxyanisole, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and air was blown in while reacting at 120°C for 10 Hour. Then, add 311 parts by mass of diethylene glycol monomethyl ether acetate, 160 parts by mass of tetrahydrophthalic anhydride, and react at 110° C. for 2.5 hours to obtain the (meth)acrylate resin containing acid groups (1 '). The solid content acid value of the acid group-containing (meth)acrylate resin (1') was 85 mgKOH/g.

Embodiment 8～14 and comparative example 2

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

‧Preparation of curable resin composition

啉基丙-1-酮]、13質量份之二乙二醇單甲基醚乙酸酯，得到硬化性樹脂組成物。 100 parts by mass of the previously obtained acid group-containing (meth)acrylate resin (in terms of solid content), 24 parts by mass of "EPICLON N-680" (cresol novolak type ring) manufactured by DIC Co., Ltd. oxygen resin), 5 parts by mass of "IRGACURE 907" [2-methyl-1-(4-methylthiophenyl)-2-

Linyl propan-1-one], 13 parts by mass of diethylene glycol monomethyl ether acetate to obtain a curable resin composition.

‧Manufacturing of hardened objects

On the glass, the curable resin composition was coated with a 50 μm applicator, and dried at 80° C. for 30 minutes. After irradiating 1000mJ/cm ² of ultraviolet rays using a metal halide lamp, it was heated at 160°C for 1 hour. Peel hardened material from glass.

‧Evaluation of heat resistance of cured products

Cut out a test piece of 6 mm x 40 mm from the cured product, and use a viscoelasticity measuring device (DMA: Rheometric Solid Viscoelasticity Measuring Device "RSAII", tensile method: frequency 1 Hz, heating rate 3 °C/min) to measure the elastic modulus The temperature at which the change becomes the largest (the rate of change in tan δ is the largest) was evaluated as the glass transition temperature (Tg).

‧Evaluation of elongation of hardened products

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

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

Claims (9)

A (meth)acrylic ester resin containing an acid group, which is based on an amidoimide resin (A) with an acid group or an anhydride group, a hydroxyl (meth)acrylate compound (B), and a (methyl) Acryl-based epoxy compound (C) and polycarboxylic acid anhydride (D) are the (meth)acrylic ester resin containing acid groups as necessary reaction raw materials, characterized in that: the amidoimide resin (A) is The polyisocyanate compound (a1) and polycarboxylic acid or its anhydride (a2) are used as the necessary reaction raw materials, and the polyisocyanate compound (a1) is an alicyclic diisocyanate compound or its modified body, or an aliphatic diisocyanate compound or Its modifier is an essential component. The acid group-containing (meth)acrylate resin according to Claim 1, wherein the polycarboxylic acid or its anhydride (a2) has tricarboxylic anhydride as an essential component. 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. The (meth)acrylate resin containing acid groups as claimed in claim 1, wherein the (meth)acryl group equivalent is in the range of 250~750g/equivalent. A curable resin composition, which contains the acid group-containing (meth)acrylate resin according to any one of claims 1 to 4, and a photopolymerization initiator. A cured product, which is a cured product of the curable resin composition according to claim 5. An insulating material comprising the curable resin composition according to claim 5. A resin material for solder resist, which includes the hardening tree as claimed in item 5 fat composition. A solder resist member formed using the resin material for solder resist according to Claim 8.

Images