WO2018230428A1

WO2018230428A1 - Acid group-containing (meth)acrylate resin and resin material for solder resists

Info

Publication number: WO2018230428A1
Application number: PCT/JP2018/021824
Authority: WO
Inventors: 康介桑田; 高橋　誠治
Original assignee: Dic株式会社
Priority date: 2017-06-14
Filing date: 2018-06-07
Publication date: 2018-12-20
Also published as: JPWO2018230428A1; TW201905017A; JP6669311B2

Abstract

Provided are: an acid group-containing (meth)acrylate resin which provides a cured product that has high heat resistance, while exhibiting excellent developability and excellent solubility in a solvent; a curable resin composition which contains this acid group-containing (meth)acrylate resin; an insulating material which is composed of this curable resin composition; a resin material for solder resists; and a resist member. As the acid group-containing (meth)acrylate resin, the present invention more specifically provides an acid group-containing (meth)acrylate resin which uses an amide-imide resin having an acid group or an acid anhydride group and a hydroxy (meth)acrylate compound as essential reaction starting materials, and wherein: the amide-imide resin uses a polyisocyanate compound and a polycarboxylic acid or an acid anhydride thereof as essential reaction starting materials; and the polycarboxylic acid or an acid anhydride thereof contains an alicyclic polycarboxylic acid or an anhydride thereof as an essential component.

Description

Acid group-containing (meth) acrylate resin and solder resist resin material

The present invention provides an acid group-containing (meth) acrylate resin having high heat resistance in a cured product and excellent in developability and solvent solubility, a curable resin composition containing the acid group, and an insulating material comprising the curable resin composition The present invention relates to a solder resist resin material and a resist member.

As a resin material for a solder resist for a printed wiring board, an acid group-containing epoxy acrylate resin obtained by reacting an acid anhydride after an epoxy resin is acrylated with acrylic acid is widely used. Performance requirements for solder resist resin materials include curing with a small amount of exposure, excellent alkali developability, excellent heat resistance and strength, flexibility, elongation, dielectric properties, substrate adhesion, etc. in cured products, etc. There are various things.

As a conventionally known solder resist resin material, a branched polyimide resin obtained by reacting pentaerythritol triacrylate with a polyimide resin which is a reaction product of isocyanurate-modified isophorone diisocyanate and trimellitic anhydride is known. (See Patent Document 1 below). The branched polyimide resin described in Patent Document 1 has a feature that is excellent in heat resistance in a cured product, but has low alkali solubility, and does not sufficiently satisfy the required performance as a resin material for solder resist.

JP 2011-186042 A

Therefore, the problem to be solved by the present invention is an acid group-containing (meth) acrylate resin having high heat resistance in a cured product and excellent in developability and solvent solubility, a curable resin composition containing the acid group, and the curing It is in providing the insulating material which consists of a conductive resin composition, the resin material for solder resists, and a resist member.

As a result of intensive studies to solve the above problems, the present inventors have found that a (meth) acryloyl group-containing amideimide resin using an alicyclic polycarboxylic acid or its anhydride as a polycarboxylic acid raw material has a heat resistance in a cured product. The present invention has been completed by finding that it has both the property and developability.

That is, the present invention is an acid group-containing (meth) acrylate resin comprising an amideimide resin (A) having an acid group or an acid anhydride group and a hydroxy (meth) acrylate compound (B) as essential reaction raw materials, The amide-imide resin (A) uses a polyisocyanate compound (a1) and a polycarboxylic acid or acid anhydride (a2) as essential reaction raw materials, and the polycarboxylic acid or acid anhydride (a2) is alicyclic. The present invention relates to an acid group-containing (meth) acrylate resin characterized by comprising polycarboxylic acid or an anhydride thereof as an essential component.

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 curable resin composition.

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

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

The present invention further relates to a resist member made of the resin material for solder resist.

According to the present invention, the cured product comprises an acid group-containing (meth) acrylate resin having high heat resistance and excellent developability and solvent solubility, a curable resin composition containing the acid group, and the curable resin composition. An insulating material, a resin material for solder resist, and a resist member can be provided.

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

Hereinafter, the present invention will be described in detail.
The acid group-containing (meth) acrylate resin of the present invention is an acid group-containing (meta) group comprising an amideimide resin (A) having an acid group or an acid anhydride group and a hydroxy (meth) acrylate compound (B) as essential reaction materials. ) Acrylate resin, wherein the amide-imide resin (A) comprises a polyisocyanate compound (a1) and a polycarboxylic acid or acid anhydride (a2) as essential reaction raw materials, and the polycarboxylic acid or acid anhydride thereof. (A2) has alicyclic polycarboxylic acid or its anhydride as an essential component.

In the present invention, the (meth) acrylate resin refers to a resin having an acryloyl group, a methacryloyl group, or both in the molecule. The (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 amidoimide resin (A) having an acid group or an acid anhydride group may have only one of an acid group or an acid anhydride group, or may have both. Among them, it is preferable to have an acid anhydride group from the viewpoint of reactivity with the hydroxy (meth) acrylate compound (B) and reaction control, and it is preferable to have both an acid group and an acid anhydride group. . The acid value of the amideimide resin (A) is preferably in the range of 60 to 250 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not ring-opened. On the other hand, the measured value under the condition where the acid anhydride group is opened, such as in the presence of water, is preferably in the range of 61 to 300 mgKOH / g.

The amide-imide resin (A) uses a polyisocyanate compound (a1) and a polycarboxylic acid or an acid anhydride (a2) as essential reaction raw materials, and the polycarboxylic acid or an acid anhydride (a2) is alicyclic. A polycarboxylic acid or an anhydride thereof is an essential component.

Examples of the polyisocyanate compound (a1) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone Cycloaliphatic diisocyanate compounds such as diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato -Aromatic diisocyanate compounds such as 3,3'-dimethylbiphenyl; (1)

[In Formula (1), each R ¹ is independently a hydrogen atom or 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 bonding point linked to a structural site represented by the structural formula through a methylene group marked with *. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more. ] The polymethylene polyphenyl polyisocyanate which has the repeating structure represented by these; These isocyanurate modified bodies, biuret modified bodies, allophanate modified bodies, etc. are mentioned. These may be used alone or in combination of two or more.

Among these, the alicyclic diisocyanate compound or a modified product thereof is preferable because the acid group-containing (meth) acrylate resin is excellent in balance between developability and heat resistance in the cured product, and isocyanate of the alicyclic diisocyanate compound. Nurate modified products are preferred. Furthermore, it is preferable that the ratio of the said alicyclic diisocyanate compound or its modified body with respect to the total mass of the said polyisocyanate compound (a1) is 70 mass% or more, and it is preferable that it is 90 mass% or more.

For the polycarboxylic acid or acid anhydride (a2), in order for the amide-imide resin (A) to have both amide groups and imide groups, both carboxy groups and acid anhydride groups exist in the system. In the present invention, a compound having both a carboxy group and an acid anhydride group in the molecule may be used, or a compound having a carboxy group and a compound having an acid anhydride group are used in combination. May be.

Of the polycarboxylic acid or its acid anhydride (a2), a polycarboxylic acid having an alicyclic structure as an essential component of the present invention or an anhydride thereof (in the present invention, “alicyclic polycarboxylic acid or its anhydride” “)” Is not limited as long as the carboxy group or the acid anhydride group is bonded to the alicyclic structure, and other structures are not particularly limited, and a wide variety of compounds can be used. Moreover, you may have an aromatic ring in molecular structure. Examples of the alicyclic polycarboxylic acid compound or its anhydride include, for example, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, methylcyclohexanetricarboxylic acid, cyclohexytricarboxylic acid, methylcyclohexytricarboxylic acid. Acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dicarboxylic acid) And oxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, and acid anhydrides thereof.

In the present invention, an aliphatic polycarboxylic acid compound or an acid anhydride thereof, an aromatic polycarboxylic acid compound or an acid anhydride thereof may be used in combination with the alicyclic polycarboxylic acid or the anhydride thereof. Regarding the aliphatic polycarboxylic acid compound or the acid anhydride thereof, the aliphatic hydrocarbon group may be either a straight chain type or a branched type, and may have an unsaturated bond in the structure. Examples of the aliphatic polycarboxylic acid compound or its acid anhydride include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid. Examples thereof include acids, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and acid anhydrides thereof.

Examples of the aromatic polycarboxylic acid compound or acid anhydride thereof include, for example, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid , Biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and the like.

In the present invention, the polycarboxylic acid or its acid anhydride (a2) has the alicyclic polycarboxylic acid or its anhydride as an essential component, so that the cured product has high heat resistance, developability and solvent solubility. An acid group-containing (meth) acrylate resin having excellent properties can be obtained. Furthermore, since the said amide imide resin (A) can be manufactured efficiently, it is preferable to use an alicyclic tricarboxylic acid anhydride as said alicyclic polycarboxylic acid or its anhydride. Moreover, it is preferable that the ratio of alicyclic polycarboxylic acid or its anhydride with respect to the gross mass of the said polycarboxylic acid or its acid anhydride (a2) is 70 mass% or more, and it is preferable that it is 90 mass% or more. .

When the amide-imide resin (A) uses the polyisocyanate compound (a1) and the polycarboxylic acid or acid anhydride (a2) as essential reaction raw materials, other than these, depending on the desired resin performance, etc. These reaction raw materials may be used in combination. In this case, since the effect exhibited by the present invention is sufficiently exhibited, the polyisocyanate compound (a1) and the polycarboxylic acid or acid anhydride (a2) thereof with respect to the total reaction raw material mass of the amideimide resin (A) The ratio of the total mass is preferably 90% by mass or more, and preferably 95% by mass or more.

When the amide imide resin (A) is a polyisocyanate compound (a1) and a polycarboxylic acid or an acid anhydride (a2) as a reaction raw material, the production method is not particularly limited, and any method is used. It may be manufactured. For example, it can be produced by the same method as a general amideimide resin. Specifically, 0.6 to 1.1 mol of the polycarboxylic acid or its acid anhydride (a2) is used with respect to 1 mol of the isocyanate group of the polyisocyanate compound (a1), preferably 50 ° C. to Examples thereof include a method of stirring and mixing in a temperature range of 250 ° C., particularly preferably about 70 to 180 ° C.

The polyisocyanate (a1) and the polycarboxylic acid or acid anhydride (a2) are the number of moles (N) of the isocyanate group of the polyisocyanate (a1) and the polycarboxylic acid or acid anhydride (a2). ) Of the number of moles of carboxy groups (M1) and the number of moles of acid anhydride groups (M2) [((M1) + (M2)) / (N)] is 1.1 to 3. When the reaction is carried out, the polarity in the reaction system becomes high, the reaction proceeds to lubrication, the isocyanate group does not remain, and the resulting polyamideimide resin has good stability. Further, the polycarboxylic acid or its acid anhydride (a2) is preferably used for the reason that the residual amount is small and the problem of separation such as recrystallization hardly occurs, and among them, 1.2 to 2.5 is more preferable.

In the (amide) imidization reaction, one or more of the isocyanate compound (a1) and one or more of the polycarboxylic acid or acid anhydride (a2) thereof are mixed and stirred in a solvent or in the absence of a solvent. It is preferable to carry out the heating while performing. At that time, the polyisocyanate (a2) is added to the polycarboxylic acid or acid anhydride (a1) at least twice, more preferably 3 to 5 times, so that a polyamide having a sharp molecular weight distribution is added. It is preferable from the point that an imide resin is obtained. The (amide) imidization reaction is a reaction in which a hydroxyl group and an isocyanate group form an imide group with decarboxylation. The progress of the (amide) imidization reaction can be traced by an analytical means such as an infrared vector, acid value, or quantitative determination of an isocyanate group. The infrared spectrum, 2270 cm ^-1 which is the characteristic absorption of an isocyanate group was reduced as the reaction further acid anhydride group is reduced with a characteristic absorption at 1860 cm ^-1 and 850 cm ^-1. On the other hand, the absorption of imide groups increases at 1780 cm ⁻¹ and 1720 cm ⁻¹ . The (amide) imidation reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the (amide) imidization reaction until the isocyanate group disappears from the viewpoint of stability over time. Further, during or after the (amide) imidization reaction, a catalyst, an antioxidant, a surfactant, other solvents, and the like may be added as long as the physical properties of the synthesized resin are not impaired.

The (amide) imidation reaction may be performed in an organic solvent as necessary. The selection of the organic solvent to be used is appropriately selected depending on the reaction raw material and the solubility of the acid group-containing (meth) acrylate resin that is the product, reaction temperature conditions, etc., for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, Examples include methoxypropanol, cyclohexanone, methyl cellosolve, alkylene glycol monoalkyl ether acetate, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These may be used alone or as a mixed solvent of two or more. 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 because the reaction efficiency is good.

The polyamideimide resin (A1) used in the present invention thus obtained has an imide bond and an amide bond represented by the following structural formula (2), and at the molecular end, the following structural formula ( It has a structure represented by at least one selected from the group consisting of 3) to (5).

(In the formula, R ³ is a residue obtained by removing the acid anhydride group and the carboxy group from the polycarboxylic acid or its acid anhydride (a2).)

The polyamideimide resin of the present invention has the following structural formula (6)

(In the formula, n is a repeating unit of 0 to 30. Rb is an amide bond or an imide bond represented by the structural formula (2). Rc is the structural formula (3). ) To (5), wherein Rd is a residue obtained by removing an isocyanato group from polyisocyanate (a1). It is not limited to this.

Rd is, for example, the following structural formula (7)

(However, Ra represents a residue obtained by removing an isocyanato group from a divalent aliphatic diisocyanate, for example).

The hydroxy (meth) acrylate compound (B) is not particularly limited as long as it has a hydroxyl group and a (meth) acryloyl group in the molecular structure, and a wide variety of compounds can be used. Moreover, the said hydroxy (meth) acrylate compound (B) may be used independently, respectively and may use 2 or more types together. Among these, a monohydroxy (meth) acrylate compound is preferable because the reaction can be easily controlled. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol Hydroxy (meth) acrylate compounds such as penta (meth) acrylate; in the molecular structure of the various hydroxy (meth) acrylate compounds (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. (Poly) oxyalkylene-modified products in which (poly) oxyalkylene chains are introduced; lactone-modified products in which (poly) lactone structures are introduced into the molecular structures of the various hydroxy (meth) acrylate compounds, and the like. That. These may be used alone or in combination of two or more. Especially, since it becomes an acid group containing (meth) acrylate resin excellent in the balance of the heat resistance and elongation in hardened | cured material, a thing with a molecular weight of 1,000 or less is preferable. Moreover, when the said hydroxy (meth) acrylate compound (B) is the said oxyalkylene modified body and a lactone modified body, it is preferable that a mass mean molecular weight (Mw) is 1,000 or less.

The acid group-containing (meth) acrylate resin of the present invention includes the amide-imide resin (A) having the acid group or acid anhydride group and the hydroxy (meth) acrylate compound (B) depending on the desired resin performance and the like. Other reaction raw materials may be used in combination. In this case, since the effect exhibited by the present invention is sufficiently exhibited, the ratio of the total mass of the components (A) and (B) to the total mass of the reaction raw material of the acid group-containing (meth) acrylate resin is 80% by mass or more. It is preferable that it is 90 mass% or more.

The method for producing the acid group-containing (meth) acrylate resin is not particularly limited, and may be produced by any method. In the reaction between the amideimide resin (A) and the hydroxy (meth) acrylate compound (B), the acid group or acid anhydride group in the amideimide resin (A) and the hydroxy (meth) acrylate compound (B) are mainly used. The hydroxy (meth) acrylate compound (B) is particularly excellent in reactivity with an acid anhydride group, and as described above, the amideimide resin (A) is an acid anhydride group. It is preferable to have. The reaction ratio between the amideimide resin (A) and the hydroxy (meth) acrylate compound (B) is based on the total of acid groups and acid anhydride groups in the amideimide resin (A). (B) is preferably used in the range of 0.9 to 1.1 mol. In particular, it is preferable to use the hydroxy (meth) acrylate compound (B) in a range of 0.9 to 1.1 mol based on the total of acid anhydride groups in the amideimide resin (A).

More preferably, the reaction between the polyamideimide resin (A) and the hydroxy (meth) acrylate compound (B) is carried out by the number of moles of acid anhydride groups (M3) in the polyamideimide resin (A) and the hydroxy (meth). The ratio of the acrylate compound (B) to the number of moles of hydroxy groups (L) is preferably in the range of L / M3 = 1 to 5 because the resulting resin has high curability and heat resistance. / M3 = 1 to 2 is more preferable from the viewpoint of heat resistance.

In addition, the content of the acid anhydride group in the amideimide resin (A) is the difference between the two acid value measurement values described above, that is, the acid value under the condition where the acid anhydride group is ring-opened, Although it can be calculated from the difference from the acid value under conditions where the acid anhydride group is not ring-opened, more specifically, it can be determined by the following method.

That is, the number of moles of the acid anhydride group in the polyamideimide resin (A) is as follows because the polycarboxylic acid or the acid anhydride (a2) is consumed by the reaction with the polyisocyanate (a1): It can be calculated by (1) to (3).
(1) The polyamideimide resin (A) is diluted with a solvent or the like, and the acid value (a) is determined by titration with an aqueous KOH solution.
(2) The polyamideimide resin (A) is diluted with a solvent or the like, an excess amount of n-butanol is reacted with the acid anhydride group, and then the acid value (b) is determined by titration with a KOH aqueous solution. In (2), the reaction between the acid anhydride group and n-butanol is carried out at 117 ° C. The disappearance of the acid anhydride is confirmed by the complete disappearance of 1860 cm ^−1, which is the characteristic absorption of the acid anhydride group, in the infrared spectrum.
(3) From the difference between the acid value (a) and the acid value (b), the concentration of the acid anhydride group in the polyamideimide resin (A) used in the present invention is calculated and converted to the number of moles.

As the polyamideimide resin (A) used as a raw material, one produced by the above method can be used, but a side reaction of urethanization can be suppressed during the reaction with the hydroxy (meth) acrylate compound (B). It is preferable to use one in which the isocyanate group has completely disappeared. The disappearance of the isocyanate group can be confirmed by the disappearance of 2270 cm ^−1, which is the characteristic absorption of the isocyanate group in the infrared spectrum, for example.

The reaction of the amideimide resin (A) and the hydroxy (meth) acrylate compound (B) can be performed, for example, by heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of a suitable esterification catalyst. it can. Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, and amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine. These may be used alone or in combination of two or more. The addition amount of the catalyst is preferably in the range of 0.03 to 5% by mass with respect to the total mass of the reaction raw materials.

The reaction may be performed in an organic solvent as necessary. The selection of the organic solvent to be used is appropriately selected depending on the reaction raw material and the solubility of the acid group-containing (meth) acrylate resin that is the product, reaction temperature conditions, etc., for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, Examples include methoxypropanol, cyclohexanone, methyl cellosolve, alkylene glycol monoalkyl ether acetate, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These may be used alone or as a mixed solvent of two or more. When the production of the amideimide resin (A) and the production of the acid group-containing (meth) acrylate resin are carried out continuously, the reaction may be continued as it is in the organic solvent used in the production of the amideimide resin (A). Good.

The acid value of the acid group-containing (meth) acrylate resin thus obtained is an acid group-containing (meth) acrylate resin that is excellent in developability and the like in addition to heat resistance and elongation in the cured product. It is preferably in the range of ~ 200 mgKOH / g. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method of JIS K 0070 (1992). The (meth) acryloyl group equivalent of the acid group-containing (meth) acrylate resin is preferably in the range of 400 to 1,500 g / equivalent, and 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, and more preferably in the range of 1,000 to 6,000.

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

Measuring device: Tosoh Corporation HLC-8120GPC, UV8020
Column: TFKguardcolumnhxl-L, TFKgel (G1000HXL, G2000HXL, G3000HXL, G4000HXL) manufactured by Tosoh Corporation
Detector: RI (differential refractometer) and UV (254 nm)
Measurement conditions: Column temperature 40 ° C
Solvent THF
Flux 1.0ml / min
Standard: Calibration curve prepared with polystyrene standard sample Sample: 0.1% by mass THF solution in terms of resin solids filtered through microfilter (injection amount: 200 μl)

The acid group-containing (meth) acrylate resin of the present invention thus obtained has an imide bond and an amide bond represented by the following structural formula (2), and further has the following structural formula at the molecular end. A structure having an acid group represented by at least one selected from the group consisting of (3), (4), (4 ′) and (5), and the following structural formulas (3 ′), (4 ′) and And a structure having a (meth) acryloyl group represented by at least one selected from the group consisting of (4 ″).

(In the formula, R ³ is a residue obtained by removing an acid anhydride group and a carboxy group from polycarboxylic acid or acid anhydride (a2). R ⁴ is the hydroxy (meth) acrylate compound (B). It is a residue obtained by removing a hydroxy group from

The acid group-containing (meth) acrylate resin of the present invention has the following structural formula (8)

(In the formula, n is a repeating unit of 0 to 30. Rb is an amide bond or an imide bond represented by the above structural formula (2). Rc ′ is a molecular end, A structure having an acid group represented by at least one structural formula selected from the group consisting of formulas (3), (4), (4 ′) and (5), and the structural formulas (3 ′), (4 ′ ) And (4 ″) at least one of the structures having a (meth) acryloyl group represented by at least one structural formula. Rd has the same definition as described above. Although the thing of the said structural formula is an example, what is not limited to this.

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

The photopolymerization initiator may be selected and used according to the type of active energy ray to be irradiated. Moreover, you may use together with photosensitizers, such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) Alkylphenone photopolymerization initiators such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples include acylphosphine oxide photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.

Commercially available products of the photopolymerization initiator include, for example, “IRGACURE127”, “IRGACURE184”, “IRGACURE250”, “IRGACURE270”, “IRGACURE290”, “IRGACURE369E”, “IRGACURE379EG”, “IRGACURE500”, “IRGACURE500”, manufactured by BASF. , “IRGACURE 754”, “IRGACURE 819”, “IRGACURE 907”, “IRGACURE 1173”, “IRGACURE 2959”, “IRGACURE MBF”, “IRGACURE TPO”, “IRGACURE OXE 01”, “IRGACUREOX 4” , "OMNIRAD250", "OM IRAD369 "," OMNIRAD369E "," OMNIRAD651 "," OMNIRAD907FF "," OMNIRAD1173 ", and the like.

The addition amount of the photopolymerization initiator is preferably in the range of 0.05 to 15% by mass, for example, in the range of 0.1 to 10% by mass with respect to the total of components other than the solvent of the curable resin composition. It is more preferable that

The curable resin composition of the present invention may contain a resin component other than the acid group-containing (meth) acrylate resin of the present invention. The resin component is obtained, for example, by reacting an epoxy resin such as a bisphenol type epoxy resin or a novolak type epoxy resin with (meth) acrylic acid, dicarboxylic acid anhydride, and unsaturated monocarboxylic acid anhydride as required. Examples of such a resin include a resin having a carboxy group and a (meth) acryloyl group in the resin, and various (meth) acrylate monomers.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic mono (meth) acrylate compounds such as meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl ( Acrylate), phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as acrylate and phenylphenoxyethyl (meth) acrylate: (poly) oxyethylene chains in the molecular structure of the various mono (meth) acrylate monomers, ( (Poly) oxyalkylene-modified mono (meth) acrylate compound having a polyoxyalkylene chain such as poly) oxypropylene chain or (poly) oxytetramethylene chain introduced; In the molecular structure of the object (poly) lactone-modified mono introducing the lactone structure-containing (meth) acrylate compound;

Aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate Such as alicyclic di (meth) acrylate compounds; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; A polyoxyalkylene-modified di (meth) acrylate compound in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the compound; A lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of various di (meth) acrylate compounds;

Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; (poly) oxyethylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound, (poly) (Poly) oxyalkylene-modified tri (meth) acrylate compound introduced with (poly) oxyalkylene chain such as oxypropylene chain and (poly) oxytetramethylene chain; in the molecular structure of the aliphatic tri (meth) acrylate compound ( A lactone-modified tri (meth) acrylate compound having a poly) lactone structure;

Tetra- or higher functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; (Poly) oxyalkylene-modified poly (meth) having 4 or more functionalities in which (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, or other (poly) oxyalkylene chain is introduced into the molecular structure Acrylate compounds; tetrafunctional or higher functional lactone-modified poly (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound.

The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity. The kind and addition amount are appropriately adjusted according to the desired performance. Generally, it is used in the range of 10 to 90% by mass with respect to the total of the curable resin composition. Specific examples of the solvent include, for example, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate and butyl acetate; aromatics such as toluene and xylene. Solvents; cycloaliphatic, methylcyclohexane and other alicyclic solvents; carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohol solvents; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol mono Examples include glycol ether solvents such as alkyl ether acetates. These may be used alone or in combination of two or more.

In addition to this, the curable resin composition of the present invention may contain various additives such as inorganic fine particles and 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 by excellent developability evaluated by photosensitivity, drying control width, and the like, and heat resistance in a cured product. In addition, it also has excellent characteristics such as solvent solubility, substrate adhesion in a cured product, and non-adhesiveness after temporary drying. Examples of applications in which various characteristics of the acid group-containing (meth) acrylate resin according to the present invention are excellent, such as solder resists, interlayer insulating materials, package materials, underfill materials, circuit elements, etc. It can be used as a package adhesive layer or an adhesive layer between an integrated circuit element and a circuit board. In addition, thin film display applications such as LCD and OELD can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like. Among these, it can use suitably especially for a soldering resist use. The resin material for solder resist of the present invention includes, for example, each component such as a curing agent, a curing accelerator, and an organic solvent in addition to the acid group-containing (meth) acrylate resin, the photopolymerization initiator, and various additives. Become.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxy group in the acid group-containing (meth) acrylate resin, and examples thereof include an epoxy resin. Examples of the epoxy resin used here include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. Bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol Examples include addition reaction type epoxy resins. These may be used alone or in combination of two or more. Among these epoxy resins, phenolic novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin because of excellent heat resistance in cured products. Novolak type epoxy resins such as naphthol-cresol co-condensed novolak type epoxy resins are preferable, and those having a softening point in the range of 50 to 120 ° C. are particularly preferable.

The curing accelerator accelerates the curing reaction of the curing agent. When an epoxy resin is used as the curing agent, a phosphorus compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, Examples include amine complex salts. These may be used alone or in combination of two or more. The addition amount of the curing accelerator is, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

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 the curing agent. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, Examples include cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.

The method of obtaining a resist member using the solder resist resin material of the present invention is, for example, by applying the solder resist resin material on a substrate and evaporating and drying the organic solvent in a temperature range of about 60 to 100 ° C. Thereafter, there is a method in which a non-exposed portion is exposed with an ultraviolet solution or an electron beam through a photomask having a desired pattern formed, and an unexposed portion is developed with an alkaline aqueous solution, and further heated and cured in a temperature range of about 140 to 180 ° C. .

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

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

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

Example 1 Production of Acid Group-Containing (Meth) acrylate Resin (1) In a flask equipped with a stirrer, thermometer and condenser, 1102.8 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate (“VESTANAT” manufactured by EVONIK) T7.61 / 100 ”, isocyanate group content 17.2% by mass) 197.6 g and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 506.9 g were added. The temperature was raised to 140 ° C. over 2 hours, and the reaction was further continued for 2 hours at the same temperature. In the infrared spectrum, it was confirmed that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, completely disappeared. Subsequently, 197.6 g of an isocyanurate-modified form of isophorone diisocyanate (“VESTANAT T-1890 / 100” manufactured by EVONIK, isocyanate group content 17.2% by mass) was added, and the reaction was continued. It was confirmed that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption, was completely extinguished. Further, 197.6 g of an isocyanurate-modified form of isophorone diisocyanate (“VESTANAT T-1890 / 100” manufactured by EVONIK, isocyanate group content 17.2% by mass) was added, and the reaction was continued. It was confirmed that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption of, completely disappeared, and an amidoimide resin intermediate (1) solution was obtained. ^{1780 cm} -1 in the infrared spectra confirmed the characteristic absorption of an imide group at 1720 cm ^-1. The solid content acid value of the amidoimide resin intermediate (1) measured under acid anhydride group non-ring-opening conditions was 190 mgKOH / g.

Subsequently, the resulting amide-imide resin intermediate (1) solution was mixed with a pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toa Gosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH / g). ) 189.2 g, triphenylphosphine 3.8 g, and methoquinone 0.6 g were added and reacted at 120 ° C. for 7 hours. It was confirmed in the infrared spectrum that the absorption at 1860 cm ⁻¹ , which is the characteristic absorption of the acid anhydride group, completely disappeared, and an acid group-containing (meth) acrylate resin (1) solution was obtained. The solid content acid value of the acid group-containing (meth) acrylate resin (1) was 140 mgKOH / g, the (meth) acryloyl group equivalent was 727 g / equivalent, and the mass average molecular weight (Mw) was 2,353.

Example 2 Production of Acid Group-Containing (Meth) acrylate Resin (2) In a flask equipped with a stirrer, thermometer and condenser, 1422.7 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANAT" manufactured by EVONIK) T-2890 / 100 ", isocyanate group content 17.2% by mass) 753.2 g and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 644.2 g were added. After raising the temperature to 140 ° C. over 2 hours, the reaction was continued at the same temperature, and it was confirmed in the infrared spectrum that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, was completely eliminated. A resin intermediate (2) solution was obtained. ^{1780 cm} -1 in the infrared spectra confirmed the characteristic absorption of an imide group at 1720 cm ^-1. The solid content acid value of the amidoimide resin intermediate (2) measured under the acid anhydride group non-ring-opening condition was 197 mgKOH / g.
Subsequently, a pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toa Gosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH / g was added to the resulting amideimide resin intermediate (2) solution. ) 189.2 g, triphenylphosphine 3.8 g, and methoquinone 0.6 g were added and reacted at 120 ° C. for 7 hours. In the infrared spectrum, it was confirmed that the absorption at 1860 cm ⁻¹ , which is the characteristic absorption of the acid anhydride group, completely disappeared, and an acid group-containing (meth) acrylate resin (2) solution was obtained. The solid content acid value of the acid group-containing (meth) acrylate resin (2) was 147 mgKOH / g, the (meth) acryloyl group equivalent was 727 g / equivalent, and the mass average molecular weight (Mw) was 3,948.

Example 3 Production of Acid Group-Containing (Meth) acrylate Resin (3) In a flask equipped with a stirrer, thermometer and condenser, 1422.7 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate (“VESTANAT” manufactured by EVONIK) T-2890 / 100 ", isocyanate group content 17.2% by mass) 753.2 g and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 644.2 g were added. After raising the temperature to 140 ° C. over 2 hours, the reaction was continued at the same temperature, and it was confirmed in the infrared spectrum that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, was completely eliminated. A resin intermediate (3) solution was obtained. ^{1780 cm} -1 in the infrared spectra confirmed the characteristic absorption of an imide group at 1720 cm ^-1. The solid content acid value of the amidoimide resin intermediate (3) measured under acid anhydride group non-ring-opening conditions was 201 mgKOH / g.

Subsequently, 189.2 g of hydroxyethyl acrylate, 3.8 g of triphenylphosphine, and 0.6 g of methoquinone were added to the obtained amideimide resin intermediate (3) solution, and the mixture was reacted at 120 ° C. for 7 hours. In the infrared spectrum, it was confirmed that the absorption at 1860 cm ⁻¹ , which is the characteristic absorption of the acid anhydride group, completely disappeared, and an acid group-containing (meth) acrylate resin (3) solution was obtained. The solid content acid value of the acid group-containing (meth) acrylate resin (3) was 154 mgKOH / g, the (meth) acryloyl group equivalent was 889 g / equivalent, and the mass average molecular weight (Mw) was 3,443.

Example 4 Production of Acid Group-Containing (Meth) acrylate Resin (4) In a flask equipped with a stirrer, thermometer and condenser, 1422.7 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANAT" manufactured by EVONIK) T-2890 / 100 ", isocyanate group content 17.2% by mass) 753.2 g and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 644.2 g were added. After raising the temperature to 140 ° C. over 2 hours, the reaction was continued at the same temperature, and it was confirmed in the infrared spectrum that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, was completely eliminated. A resin intermediate (4) solution was obtained. ^{1780 cm} -1 in the infrared spectra confirmed the characteristic absorption of an imide group at 1720 cm ^-1. The solid content acid value of the amidoimide resin intermediate (4) measured under acid anhydride group non-ring-opening conditions was 201 mgKOH / g.

Subsequently, 189.2 g of hydroxypropyl acrylate, 3.8 g of triphenylphosphine, and 0.6 g of methoquinone were added to the obtained amideimide resin intermediate (4) solution, and the mixture was reacted at 120 ° C. for 7 hours. It was confirmed in the infrared spectrum that the absorption at 1860 cm −1, which is the characteristic absorption of the acid anhydride group, completely disappeared, and an acid group-containing (meth) acrylate resin (4) solution was obtained. The solid content acid value of the acid group-containing (meth) acrylate resin (4) was 164 mgKOH / g, the (meth) acryloyl group equivalent was 997 g / equivalent, and the mass average molecular weight (Mw) was 3,621.

Example 5 Production of Acid Group-Containing (Meth) acrylate Resin (5) In a flask equipped with a stirrer, thermometer and condenser, 1422.7 g of propylene glycol monomethyl ether acetate and isocyanurate modified form of isophorone diisocyanate (“VESTANAT” manufactured by EVONIK) T-2890 / 100 ", isocyanate group content 17.2% by mass) 753.2 g and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 644.2 g were added. After raising the temperature to 140 ° C. over 2 hours, the reaction was continued at the same temperature, and it was confirmed in the infrared spectrum that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, was completely eliminated. A resin intermediate (5) solution was obtained. ^{1780 cm} -1 in the infrared spectra confirmed the characteristic absorption of an imide group at 1720 cm ^-1. The solid content acid value of the amidoimide resin intermediate (5) measured under acid anhydride group non-ring-opening conditions was 201 mgKOH / g.

Subsequently, 189.2 g of 4-hydroxybutyl acrylate, 3.8 g of triphenylphosphine, and 0.6 g of methoquinone were added to the resulting amideimide resin intermediate (5) solution, and reacted at 120 ° C. for 7 hours. In the infrared spectrum, it was confirmed that the absorption at 1860 cm ⁻¹ , which is the characteristic absorption of the acid anhydride group, completely disappeared, and an acid group-containing (meth) acrylate resin (4) solution was obtained. The solid content acid value of the acid group-containing (meth) acrylate resin (4) was 149 mgKOH / g, the (meth) acryloyl group equivalent was 1,104 g / equivalent, and the mass average molecular weight (Mw) was 3,792.

Comparative Production Example 1 Production of Acid Group-Containing (Meth) acrylate Resin (1 ′) 276.4 g of Propylene Glycol Monomethyl Ether Acetate and Isocyanurate Modified Form of Isophorone Diisocyanate (EVONIK) “VESTANAT T-1890 / 100”, isocyanate group content 17.2% by mass) 146.4 g and trimellitic anhydride 121.0 g were added. After raising the temperature to 140 ° C. over 2 hours, the reaction was continued at the same temperature, and it was confirmed in the infrared spectrum that the absorption at 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, was completely eliminated. A resin intermediate (1 ′) solution was obtained. ^{1780 cm} -1 in the infrared spectra confirmed the characteristic absorption of an imide group at 1720 cm ^-1. The solid content acid value of the amidoimide resin intermediate (1 ′) measured under acid anhydride group non-ring-opening conditions was 212 mgKOH / g.

Subsequently, the resulting amide-imide resin intermediate (1 ′) solution was mixed with a pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toa Gosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value 159.7 mg KOH / g) 24.5 g was added and reacted at 120 ° C. for 2 hours. In the infrared spectrum, it was confirmed that absorption at 1860 cm ⁻¹ , which is the characteristic absorption of the acid anhydride group, completely disappeared, and an acid group-containing (meth) acrylate resin (1 ′) solution was obtained. The acid group-containing (meth) acrylate resin (1 ′) had a solid content acid value of 162 mg KOH / g, a (meth) acryloyl group equivalent of 567 g / equivalent, and a mass average molecular weight (Mw) of 3865.

Examples 6 to 10 and Comparative Example 1
Various evaluation tests were performed as follows. The results are shown in Table 1.

-Evaluation of solvent dilution The propylene glycol monomethyl ether acetate of 25 degreeC was added gradually to 10 g of acid group containing (meth) acrylate resins obtained previously, and the dilution rate until it became cloudy was measured.

-Preparation of curable resin composition 100 g of acid group-containing (meth) acrylate resin (solid content) obtained in the above, "EPICLON N-680" (cresol novolac type epoxy resin) manufactured by DIC Corporation, "Irgacure" manufactured by BASF Corporation 907 "(2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), 0.5 g of 2-ethyl-4-methylimidazole," LumiCure DPA-600T "manufactured by Toagosei Co., Ltd. "(Composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40/60) and 0.65 g of phthalocyanine green are added, and propylene glycol monomethyl ether acetate is added to add 50 mass of non-volatile matter. % To obtain a curable resin composition .

-Evaluation of photosensitivity The curable resin composition was apply | coated with the applicator of 50 micrometers on the glass base material, and it was made to dry at 80 degreeC for 30 minutes. Next, Step Tablet No. 2 was irradiated with 1,000 mJ / cm ² ultraviolet rays using a metal halide lamp. This was developed with a 5% aqueous sodium carbonate solution for 180 seconds and evaluated by the number of remaining steps. The greater the number of remaining stages, the higher the photosensitivity.

-Evaluation of drying control width A curable resin composition was applied onto a glass substrate with a 50 μm applicator, and samples with different drying times at 80 ° C. were prepared every 10 minutes from 30 minutes to 100 minutes. These were developed with a 5% by mass aqueous sodium carbonate solution for 180 seconds, and the drying time at 80 ° C. of the sample in which no residue remained was evaluated as the drying control width. The longer the drying control width, the better the alkali developability.

-Evaluation of heat resistance A curable resin composition was applied onto glass with a 50 µm applicator and dried at 80 ° C for 30 minutes. After irradiating 1,000 mJ / cm ² of ultraviolet rays using a metal halide lamp, it was heated at 170 ° C. for 1 hour.

The cured product is peeled off from the glass, and a 6 mm × 40 mm test piece is cut out, and viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., tension method: frequency 1 Hz, temperature rising rate 3 ° C./min. ) Was used to evaluate the glass transition temperature (Tg) at the temperature at which the elastic modulus change was maximum (the tan δ change rate was the largest).
A: Glass transition temperature (Tg) is 230 ° C. or higher B: Glass transition temperature (Tg) is lower than 230 ° C.

Claims

An acid group-containing (meth) acrylate resin comprising an amideimide resin (A) having an acid group or an acid anhydride group and a hydroxy (meth) acrylate compound (B) as essential reaction raw materials, the amideimide resin (A) However, the polyisocyanate compound (a1) and the polycarboxylic acid or acid anhydride (a2) are essential reaction raw materials, and the polycarboxylic acid or acid anhydride (a2) is an alicyclic polycarboxylic acid or anhydride thereof. An acid group-containing (meth) acrylate resin characterized by comprising a product as an essential component.
The acid group-containing (meth) acrylate resin has an imide bond and an amide bond represented by the following structural formula (2), and the following structural formulas (3), (4), ( 4 ') and a structure having at least one acid group selected from the group consisting of (5) and a group consisting of the following structural formulas (3'), (4 ') and (4 ") The acid group-containing (meth) acrylate resin according to claim 1, which has a structure having a (meth) acryloyl group represented by at least one kind.

(In the formula, R 3 is a residue obtained by removing an acid anhydride group and a carboxy group from polycarboxylic acid or acid anhydride (a2). R 4 is the hydroxy (meth) acrylate compound (B). It is a residue obtained by removing a hydroxy group from
The acid group-containing (meth) acrylate resin according to claim 1, wherein the polyisocyanate compound (a1) contains an aliphatic or alicyclic diisocyanate compound or a modified product thereof as an essential component.
2. The acid group-containing (meth) acrylate resin according to claim 1, wherein the polycarboxylic acid or its acid anhydride (a2) contains an alicyclic tricarboxylic acid anhydride as an essential component.
The acid group-containing (meth) acrylate resin according to claim 1, wherein the (meth) acryloyl group equivalent is in the range of 400 to 1,500 g / equivalent.
A curable resin composition comprising the modified (meth) acrylate resin according to any one of claims 1 to 4 and a photopolymerization initiator.
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 a solder resist comprising the curable resin composition according to claim 5.
A resist member comprising the resin material for solder resist according to claim 8.
A method for producing an acid group-containing (meth) acrylate resin, in which an amideimide resin (A) having an acid group or an acid anhydride group and a hydroxy (meth) acrylate compound (B) are reacted as essential reaction raw materials, Resin (A) uses polyisocyanate compound (a1) and polycarboxylic acid or acid anhydride (a2) as essential reaction raw materials, and the polycarboxylic acid or acid anhydride (a2) is alicyclic polycarboxylic acid. A method for producing an acid group-containing (meth) acrylate resin, which is obtained by reacting an acid or an anhydride thereof as an essential component.
The method for producing an acid group-containing (meth) acrylate resin according to claim 11, wherein the polyisocyanate compound (a1) comprises an aliphatic or alicyclic diisocyanate compound or a modified product thereof as an essential component.
The method for producing an acid group-containing (meth) acrylate resin according to claim 11 or 12, wherein the polycarboxylic acid or its acid anhydride (a2) contains an alicyclic tricarboxylic acid anhydride as an essential component.
The method for producing an acid group-containing (meth) acrylate resin according to any one of claims 11 to 13, wherein the (meth) acryloyl group equivalent is in the range of 400 to 1,500 g / equivalent.
A method for producing a curable resin composition, comprising mixing the acid group-containing (meth) acrylate resin obtained by the production method according to any one of claims 11 to 14 and a photopolymerization initiator.