TW202206485A - Resin, method for producing same, thermosetting resin composition, and cured product - Google Patents

Abstract

A resin according to one aspect of the present invention is obtained by linking a phenolic monomer by divalent crosslinking groups (X). The phenolic monomer includes at least one monomer (m1) selected from the group consisting of bisphenol imides and bisnaphthol imides. The divalent crosslinking groups (X) include a crosslinking group (X1) represented by -CH2-R1-CH2-. R1 represents a phenylene group optionally having a substituent, or a biphenylene group optionally having a substituent.

Description

Resin, method for producing the same, thermosetting resin composition, and cured product

The present invention relates to a resin, a method for producing the same, a thermosetting resin composition, and a cured product. This case claims priority based on Japanese Patent Application No. 2020-110089 filed in Japan on June 26, 2020, the content of which is incorporated herein by reference.

Conventionally, in order to form protective films, interlayer insulating films, planarizing films, etc. of electronic components, thermosetting resin compositions and photosensitive resin compositions have been used.

Patent Document 1 describes a thermosetting resin composition comprising: a copolymer comprising an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, and an unsaturated carboxylic acid having a hydroxyl group, and a solvent; Saturated compounds serve as copolymers of constituent monomers.

Patent Document 2 describes a positive-type photosensitive resin composition comprising: a resin, a compound that generates an acid by irradiation with an actinic light having a wavelength of 300 nm or more, a crosslinking agent, and an adhesion assistant, the resin having a specific acid dissociation It is alkali-insoluble or poorly soluble in alkali, and becomes soluble when the acid-dissociable group is dissociated.

[Prior Art Literature] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2009-215328 [Patent Document 2] Japanese Patent Laid-Open No. 2008-304902

[The problem to be solved by the invention] However, in the thermosetting resin composition of Patent Document 1, the hardness of the cured product is high. If the hardness is high, cracks are likely to occur, which is the main reason for the decrease in the yield of electronic equipment. The positive-type photosensitive resin composition of Patent Document 2 also has a high hardness of the cured product (after cross-linking with a cross-linking agent). In addition, depending on the type of the crosslinking agent, there is also a problem of poor chemical resistance.

The object of the present invention is to provide a resin capable of obtaining a cured product excellent in chemical resistance and flexibility, a method for producing the same, and a thermosetting resin composition capable of obtaining a cured product excellent in chemical resistance and flexibility material, and a hardened material excellent in chemical resistance and flexibility.

[MEANS TO SOLVE THE PROBLEM] This invention has the following aspects. [1] A resin in which a phenolic monomer is linked by a divalent crosslinking group (X); the phenolic monomer comprises a group selected from the group consisting of bisphenolimide and bisnaphtholimide At least one kind of monomer (m1) in the group, the above-mentioned divalent cross-linking group (X) includes a cross-linking group (X1) represented by -CH ₂ -R ¹ -CH ₂ -. However, R ¹ is a substituted phenyl group or a substituted biphenyl group. [2] The resin according to the aforementioned [1], wherein the monomer (m1) is at least one selected from the group consisting of a compound represented by the following formula (m11) and a compound represented by the following formula (m12) .

[Chemical formula 1]

However, R ² is a group represented by any one of the following formulae (21) to (26), R ³ is an alkyl group with 1 to 4 carbon atoms; b and c are each independently an integer of 1 to 2, and d and e are independently an integer from 0 to 2, b+d is an integer from 1 to 3, c+e is an integer from 1 to 3, and when d+e is 2 or more, (d+e) R ³ can be the same or different from each other; f and g Each independently is an integer from 1 to 2, h and i are each independently an integer from 0 to 2, f+h is an integer from 1 to 3, g+i is an integer from 1 to 3, and when h+i is 2 or more, each of (h+i) R ³ Can be the same or different.

[Chemical formula 2]

[3] The resin according to the aforementioned [1] or [2], wherein the aforementioned phenolic monomer further contains cresol. [4] The resin according to any one of the above [1] to [3], wherein the divalent crosslinking group (X) further comprises a crosslinking group (X2) represented by -CH ₂ -. [5] A method for producing a resin, comprising the step of reacting a phenolic monomer with a cross-linking base material; the phenolic monomer is selected from the group consisting of bisphenol imide and bisnaphtyl imide Among at least one monomer (m1), the aforementioned cross-linking base material includes a compound represented by Y ¹ -CH ₂ -R ¹ -CH ₂ -Y ² . However, R ¹ is a optionally substituted phenylene group or an optionally substituted biphenylene group, and Y ¹ and Y ² are each independently an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. [6] The method for producing a resin according to the aforementioned [5], wherein the monomer (m1) is selected from the group consisting of a compound represented by the following formula (m11) and a compound represented by the following formula (m12). at least one of them.

[Chemical formula 3]

However, R ² is a group represented by any one of the following formulae (21) to (26), R ³ is an alkyl group with 1 to 4 carbon atoms; b and c are each independently an integer of 1 to 2, and d and e are independently an integer from 0 to 2, b+d is an integer from 1 to 3, c+e is an integer from 1 to 3, and when d+e is 2 or more, (d+e) R ³ can be the same or different from each other; f and g Each independently is an integer from 1 to 2, h and i are each independently an integer from 0 to 2, f+h is an integer from 1 to 3, g+i is an integer from 1 to 3, and when h+i is 2 or more, each of (h+i) R ³ Can be the same or different.

[Chemical formula 4]

[7] The method for producing a resin according to the above [5] or [6], wherein the phenolic monomer further contains cresol. [8] The method for producing a resin according to any one of the above [5] to [7], wherein the crosslinking base material further contains formaldehyde. [9] A thermosetting resin composition comprising the resin according to any one of the above [1] to [4] and a curing agent. [10] The thermosetting resin composition according to the above [9], wherein the curing agent contains a polyfunctional alkoxymethyl compound. [11] A cured product, which is a cured product of the thermosetting resin composition of the aforementioned [9] or [10].

[Effect of invention] According to the present invention, there can be provided: a resin capable of obtaining a cured product excellent in chemical resistance and flexibility, a method for producing the same, a thermosetting resin composition capable of obtaining a cured product excellent in chemical resistance and flexibility, and a resistant Cured product with excellent medicinal properties and flexibility.

[Form for carrying out the invention] The "phenolic monomer" in the present invention is a compound having an aromatic ring having a hydroxyl group. As an aromatic ring, a benzene ring and a naphthalene ring are mentioned, for example.

[resin] The resin (hereinafter, also referred to as "resin (A)") of one aspect of the present invention is a phenolic monomer linked via a divalent crosslinking group (X). In other words, the resin (A) contains two or more phenolic monomer units and one or more divalent crosslinking groups (X), and the divalent crosslinking groups (X) are used for these two or more phenolic monomers. Two adjacent phenolic monomer units in the unit are linked to each other. The bivalent cross-linking group (X) typically couples aromatic rings having hydroxyl groups of adjacent phenolic monomers to each other. That is, one of the divalent cross-linking groups (X) is bonded to an aromatic ring having a hydroxyl group of one of the adjacent phenolic monomers, and the other is bonded to another phenol. It is an aromatic ring with a hydroxyl group of a monomer.

<Phenolic monomer> The phenolic monomer includes at least one monomer (m1) selected from the group consisting of bisphenolimide and bisnaphtholimide. When at least a part of the phenolic monomer is the monomer (m1), the cured product of the thermosetting resin composition containing the resin (A) has improved chemical resistance, flexibility, and heat resistance.

Bisphenol imide can be obtained by dehydrating and condensing an aminophenol compound and a carboxylic dianhydride (refer to JP 2011-173827 A). Examples of the aminophenol compound include: 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 2-amino-4-methylphenol, 3-aminophenol Amino-2-methylphenol, 5-amino-2-methylphenol, etc. Examples of the carboxylic dianhydride include: pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-biphthalic anhydride, 1,2 ,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-oxydiphthalic anhydride acid anhydride, etc.

Specific examples of bisphenolimide include N,N'-bis(2-hydroxyphenyl)-pyromellitic acid diimide, N,N'-bis(3-hydroxyphenyl)- Diimide of pyromellitic acid, N,N'-bis(4-hydroxyphenyl)-diimide of pyromellitic acid, N,N'-bis(2-hydroxyphenyl)-4,4'- Oxydiimide, N,N'-bis(3-hydroxyphenyl)-4,4'-oxydiphthalimide, N,N'-bis(4-hydroxybenzene) base)-4,4'-oxydiphthalimide, N,N'-bis(2-hydroxyphenyl)-3,3'-4,4'-benzophenonetetracarboxylic acid di Imide, N,N'-bis(3-hydroxyphenyl)-3,3'-4,4'-benzophenone tetracarboxylic acid diimide, N,N'-bis(4-hydroxy Phenyl)-3,3'-4,4'-benzophenone tetracarboxylic acid diimide, N,N'-bis(2-hydroxyphenyl)4,4'-biphthalic acid bis Imide, N,N'-bis(3-hydroxyphenyl)4,4'-biphthalate diimide, N,N'-bis(4-hydroxyphenyl)4,4'- Diimide diphthalate, N,N'-bis(2-hydroxyphenyl) 4,4'-sulfonyldiphthalimide, N,N'-bis(3-hydroxyl) Phenyl) 4,4'-sulfonyldiphthalimide, N,N'-bis(4-hydroxyphenyl) 4,4'-sulfonyldiphthalimide, etc. .

As bisphenol imide, a compound represented by the following formula (m11) is preferable from the viewpoint of the easiness of obtaining starting materials used for compound synthesis.

[Chemical formula 5]

However, R ² is a group represented by any one of the following formulae (21) to (26), R ³ is an alkyl group with 1 to 4 carbon atoms; b and c are each independently an integer of 1 to 2, and d and e are each independently an integer from 0 to 2, b+d is an integer from 1 to 3, c+e is an integer from 1 to 3, and when d+e is 2 or more, (d+e) R ³ may be the same or different from each other.

[Chemical formula 6]

R ² is preferably a group represented by formula (21), (22) or (23). R ³ may be linear or branched, and examples thereof include methyl, ethyl, isopropyl, and the like. b and c are each preferably 1. d and e are preferably 0 or 1 each.

The bisnaphthol imide can be obtained by dehydrating and condensing an aminonaphthol compound and a carboxylic dianhydride. As the aminonaphthol compound, 1-amino-2-naphthol, 3-amino-2-naphthol, 5-amino-1-naphthol, etc. are mentioned. As a carboxylic dianhydride, the thing similar to the above is mentioned.

The bisnaphtholimide is preferably a compound represented by the following formula (m12) from the viewpoint of the ease of obtaining the starting materials used for compound synthesis.

[Chemical formula 7]

However, each of R ² and R ³ is the same as above, f and g are each independently an integer from 1 to 2, h and i are each independently an integer from 0 to 2, f+h is an integer from 1 to 3, and g+i is an integer from 1 to 3. Integer, when h+i is 2 or more, each of (h+i) R ³ may be the same or different from each other. f and g are each preferably 1. h and i are each preferably 0 or 1.

The monomer (m1) is preferably at least one selected from the group consisting of the compound represented by the formula (m11) and the compound represented by the formula (m12). From the viewpoint of solvent solubility, the compound represented by the formula (m11) is preferred.

The phenolic monomer preferably further contains other phenolic monomers than the monomer (m1). The solvent solubility of resin (A) improves by containing another phenol type monomer. As other phenolic monomers, phenol, cresol, xylenol, etc. are mentioned, for example. Examples of cresols include o-cresol, m-cresol, and p-cresol. Examples of xylenol include 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, and 3,5-xylenol.

Among other phenolic monomers, the phenolic monomer preferably contains cresol, especially o-cresol. By containing cresol, especially o-cresol, the solvent solubility of resin (A) becomes more excellent. Furthermore, the time stability of the hardened product is improved, and it is difficult to become brittle with time. o-cresol and p-cresol can also be used in combination. The alkali solubility of resin (A) can be adjusted by the ratio of o-cresol and p-cresol. When the ratio of o-cresol increases, the alkali solubility of resin (A) tends to become high, and when the ratio of p-cresol increases, the alkali solubility of resin (A) tends to become low.

The ratio of the monomer (m1) to the total mass of the phenolic monomers is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass or more, and may be 100% by mass. When the ratio of the monomer (m1) is more than the aforementioned lower limit value, the heat resistance and flexibility of the cured product are further excellent. When the phenolic monomer contains other phenolic monomers, the ratio of the monomer (m1) to the total mass of the phenolic monomers is preferably 50 mass % or less, more preferably 40 mass % or less, and 35 mass % or less better. If the ratio of the monomer (m1) is below the above-mentioned upper limit value, the solvent solubility of the resin (A) is more excellent. When the phenol-based monomer contains other phenol-based monomers, the ratio of the monomer (m1) to the total mass of the phenol-based monomers may be, for example, 10 to 50% by mass, 20 to 40% by mass, or It is 25-35 mass %.

When the phenolic monomer contains cresol, the ratio of cresol to the total mass of the phenolic monomer is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and more preferably 45 to 85% by mass. When the ratio of cresol is within the aforementioned range, the solvent solubility of the resin (A) and the time stability of the cured product are more excellent.

When the phenolic monomer contains o-cresol, the ratio of the o-cresol to the total mass of the phenolic monomers is preferably 20 to 90 mass %, preferably 30 to 90 mass %, and 45 to 85 mass % % is better. When the ratio of o-cresol is within the aforementioned range, the solvent solubility of the resin (A) and the time stability of the cured product are more excellent.

When the phenolic monomer contains p-cresol, the ratio of p-cresol to the total mass of the phenolic monomers is preferably 5 to 60 mass %, preferably 10 to 50 mass %, and 20 to 40 mass % % is better.

In a preferred aspect, the phenolic monomer is composed of only the monomer (m1).

In another preferred aspect, the phenolic monomer is composed of the monomer (m1) and cresol, and the ratio of the monomer (m1) to the total mass of the phenolic monomer is 10 to 50% by mass (with 20-40 mass % is preferable, 25-35 mass % is preferable), and the ratio of cresol is 50-90 mass % (60-80 mass % is preferable, 65-75 mass % is preferable). However, the total of the ratio of the monomer (m1) and the ratio of cresol does not exceed 100 mass %.

In another preferred aspect, the phenolic monomer is composed of the monomer (m1) and о-cresol, and the ratio of the monomer (m1) is 10 to 50% by mass relative to the total mass of the phenolic monomer (20-40 mass % is preferable, 25-35 mass % is preferable), and the ratio of о-cresol is 50-90 mass % (60-80 mass % is preferable, 65-75 mass % is preferable). However, the total of the ratio of the monomer (m1) and the ratio of o-cresol does not exceed 100% by mass.

In another preferred aspect, the phenolic monomer is composed of the monomer (m1), o-cresol and p-cresol, and the ratio of the monomer (m1) to the total mass of the phenolic monomer is 10-50 mass % (preferably 20-40 mass %, preferably 25-35 mass %), the ratio of o-cresol is 20-70 mass % (preferably 30-60 mass %, 35-55 mass % % is preferred), and the ratio of p-cresol is 5 to 45 mass % (10 to 40 mass % is preferred, and 15 to 35 mass % is preferred). However, the total of the ratio of the monomer (m1), the ratio of o-cresol, and the ratio of p-cresol does not exceed 100 mass %.

<Divalent cross-linking group (X)> The divalent cross-linking group (X) includes a cross-linking group (X1) represented by -CH ₂ -R ¹ -CH ₂ -. Since the phenolic monomer is linked through the crosslinking group (X1), the flexibility of the cured product is improved. However, R ¹ is a substituted phenyl group or a substituted biphenyl group. Examples of phenylene groups include o-phenylene groups, m-phenylene groups, p-phenylene groups, and the like, and p-phenylene groups are preferred from the viewpoint of the ease of obtaining raw materials. Examples of the bi-extended phenyl group include 4,4'- bi-extended phenyl group, 2,4'- bi-extended phenyl group, etc. From the viewpoint of the availability of raw materials, 4,4'- bi-extended phenyl group better. As a substituent in a phenylene extended or a biextended phenyl group, a C1-C4 alkyl group, a hydroxyl group, and a C1-C4 alkoxy group are mentioned, for example. When the alkali solubility of resin (A) is sought, a hydroxyl group is preferable. The substituent which the phenylene group or the biphenylene group has may be one type or two or more types.

When resin (A) has two or more divalent crosslinking groups (X), it may further contain other crosslinking groups other than the crosslinking group (X1). As another crosslinking group, the crosslinking group (X2) represented by _-CH2- and the crosslinking group (X3) represented by ^-CHR4- are mentioned, for example. However, R ⁴ is a phenyl group which may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms.

As another crosslinking group, a crosslinking group (X2) is preferable. The crosslinking group (X2) can be formed by using formaldehyde as a crosslinking group material in the production method of the resin described later. When the crosslinking base material contains formaldehyde, the molecular weight and alkali solubility of the resin (A) can be easily controlled.

The ratio of the crosslinking groups (X1) is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, relative to the total mass of all bivalent crosslinking groups (X) in the resin (A), 100 mass % may be sufficient. When the ratio of the crosslinking group (X1) is at least the aforementioned lower limit value, the flexibility of the cured product is further excellent. When the bivalent crosslinking group (X) contains other crosslinking groups, the ratio of the crosslinking group (X1) is preferably 90 mass % or less with respect to the total mass of all the bivalent crosslinking groups (X), and 85 It is preferably not more than 80% by mass, more preferably not more than 80% by mass. When the bivalent crosslinking group (X) contains other crosslinking groups, the ratio of the crosslinking group (X1) may be, for example, 20 to 90 mass % with respect to the total mass of all the bivalent crosslinking groups (X). 30-85 mass % may be sufficient, and 40-80 mass % may be sufficient.

When the bivalent crosslinking group (X) contains the crosslinking group (X2), the ratio of the crosslinking group (X2) is 10 to 80 mass % with respect to the total mass of all the bivalent crosslinking groups (X). Preferably, 15-70 mass % is more preferable, 20-60 mass % is more preferable.

<Characteristics of resin (A)> The weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight is within the aforementioned range, the cured product is more excellent in chemical resistance and flexibility. The weight average molecular weight is a standard polystyrene conversion value measured by gel permeation chromatography (GPC).

The alkali dissolution rate of the resin (A) measured by the measurement method described in the following examples is preferably 5~4000Å/sec, preferably 10~2000Å/sec. If the alkali dissolution rate is within the above-mentioned range, it is useful for applications such as photosensitive insulating film materials.

<Production method of resin> The resin (A) can be produced, for example, by a production method including a step of reacting a phenolic monomer with a crosslinking-based material. By reacting the phenolic monomer with the crosslinking base material, the phenolic monomer is linked through the divalent crosslinking group (X) derived from the crosslinking base material. The phenolic monomer is as described above.

The crosslinking group material forms a divalent crosslinking group (X) by reacting with a phenolic monomer. The crosslinking-based material contains at least a compound represented by Y ¹ -CH ₂ -R ¹ -CH ₂ -Y ² (hereinafter, also referred to as "compound (1)"). The compound (1) forms a crosslinking group (X1) by reacting with a phenolic monomer. In the compound (1), R ¹ is the same as R ¹ in the cross-linking group (X1). Y ¹ and Y ² are each independently an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. The alkoxy group having 1 to 4 carbon atoms may be linear or branched. As a halogen atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of the compound (1) include p-xylene glycol dialkyl ethers such as p-xylene glycol dimethyl ether (hereinafter, also referred to as "PXDM"); m-xylene glycol dioxane Base ether, 1,4-bis(halogenated methyl)benzene, 2,6-dimethylol-4-methylphenol (hereinafter, also referred to as "DMLPC"); 4,4'-bis(methoxy) 4,4'-bis(alkoxymethyl)biphenyl such as methyl)biphenyl (hereinafter, also referred to as "BMMB"); 2,2'-bis(alkoxymethyl)biphenyl, 2,2'-bis(alkoxymethyl)biphenyl, 4'-bis(alkoxymethyl)biphenyl, 4,4'-bis(halogenated methyl)biphenyl, 2,2'-bis(halogenated methyl)biphenyl, 2,4'-bis(halogenated methyl)biphenyl methyl) biphenyl. These compounds may be used alone or in combination of two or more.

The cross-linking-based material may further include other cross-linking-based materials than compound (1). Examples of other crosslinking group materials include aldehydes such as formaldehyde, sulfalal, and p-hydroxybenzaldehyde. These aldehydes may be used alone or in combination of two or more. As other cross-linking base materials, formaldehyde is preferred. When the crosslinking base material contains formaldehyde, the molecular weight and alkali solubility of the resin (A) can be easily controlled.

The ratio of the compound (1) to the total mass of the crosslinking base material is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and may be 100% by mass. When the ratio of compound (1) is more than the said lower limit, the softness|flexibility of a hardened|cured material is more excellent. When the crosslinking base material contains other crosslinking base materials, the ratio of the compound (1) to the total mass of the crosslinking base material is preferably 90% by mass or less, more preferably 85% by mass or less, more preferably 80% by mass or less good. When the cross-linking base material contains other cross-linking base materials, the ratio of the compound (1) to the total mass of the cross-linking base materials may be, for example, 20 to 90 mass %, 30 to 85 mass %, or 40~80% by mass.

When the crosslinking base material contains formaldehyde, the ratio of formaldehyde to the total mass of the crosslinking base material is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and more preferably 20 to 60% by mass.

In the reaction between the phenolic monomer and the crosslinking base material, the molar ratio of the crosslinking base material to the phenolic monomer (crosslinking base material/phenolic monomer) is preferably 0.6~1.0, preferably 0.7~0.95 better. When the molar ratio of the crosslinking base material is within the aforementioned range, the balance between chemical resistance and flexibility of the cured product tends to be more excellent. If the molar ratio of the crosslinking-based material to the phenolic monomer is too low, it may be difficult to exhibit flexibility. If the molar ratio of the cross-linking base material to the phenolic monomer is too high, it may become easy to gel during the reaction, or the time stability may be lowered due to the residual cross-linking base material.

The reaction of the phenolic monomer and the cross-linking base material can also be carried out in the presence of an acid catalyst. When the reaction is performed in the presence of an acid catalyst, the reaction rate between the phenolic monomer and the crosslinking-based material increases. In particular, when Y ¹ and Y ² in compound (1) are alkoxy groups, the reaction is preferably carried out in the presence of an acid catalyst. When Y ¹ and Y ² are a hydroxyl group or a halogen atom, the reaction can also be carried out in the absence of an acid catalyst. When Y ¹ and Y ² are halogen atoms, the halogen atoms are removed by the heat of the reaction to generate acids (HY ¹ , HY ² ), and since the acids act as acid catalysts, even when the acid catalyst is not In the presence of the reaction, the reaction rate also becomes sufficiently fast.

The acid catalyst is not particularly limited as long as the reaction proceeds, and examples thereof include inorganic acids such as sulfuric acid and hydrochloric acid; and organic acids such as methanesulfonic acid and p-toluenesulfonic acid. The acid catalyst may be used alone or in combination of two or more. The usage-amount of an acid catalyst is 2-30 mass parts with respect to 100 mass parts of phenolic monomers, for example.

The reaction of the phenolic monomer and the crosslinking-based material can also be carried out in the presence of a solvent. The solvent (hereinafter, also referred to as "reaction solvent") used for the reaction between the phenolic monomer and the crosslinking group material is not particularly limited, but a solvent that dissolves the phenolic monomer is preferable. Examples of the reaction solvent include γ-butyrolactone (hereinafter also referred to as "GBL"), N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP"), dimethylacetamide , propylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc.

The reaction temperature of the phenolic monomer and the cross-linking base material is preferably 60-220°C, preferably 120-200°C. When the reaction temperature is too low, the reaction rate is slow, and when the reaction temperature is too high, gelation tends to occur during the reaction. The reaction time is, for example, 4 to 24 hours. At the end of the reaction, an alkali can be added to the reaction system to neutralize the acid catalyst as required.

As described above, a reaction product containing the resin (A) is obtained. The reaction product may also be subjected to the following treatments according to needs: removal of unreacted raw materials by distillation or the like, concentration, purification (precipitation, washing, column chromatography, etc.) and the like.

<Use of resin (A)> The resin (A) can be thermally hardened by blending with a hardener. The obtained hardened|cured material can be used for uses, such as an insulating film, a planarization film, and a sealing material of an electronic device. However, the application of resin (A) is not limited to these, For example, it can be used for the application of a bonding agent, such as a molding material, a plywood, and a stone.

[Thermosetting resin composition] A thermosetting resin composition (hereinafter, also referred to as "this composition") of one aspect of the present invention includes the above-mentioned resin (A) and a curing agent. The composition may further include a solvent according to requirements. The composition may further include other components than the above according to the needs.

As a hardening|curing agent, what is publicly known as a hardening|curing agent of polyvalent hydroxy resins, such as a phenol resin, can be mentioned, for example, a polyfunctional alkoxymethyl compound, an epoxy resin, etc. are mentioned.

The polyfunctional alkoxymethyl compound is a compound having two or more alkoxymethyl groups. The alkoxy group in the alkoxymethyl group may be linear or branched, and the carbon number of the alkoxy group is preferably 1-6. Examples of the polyfunctional alkoxymethyl compound include polyalkoxymethyl melamine, polyalkoxymethyl benzoguanamine, polyalkoxy methyl urea, polyalkoxy methyl acetylene urea, and Oxymethylphenols, etc. Examples of polyalkoxymethyl melamine and polyalkoxymethyl benzoguanamine include melamines of formula (1) and benzoguanamine of formula (2) described in JP-A No. 2008-304902 kind. As a polyalkoxy methyl urea and a polyalkoxy methyl acetylene urea, the compound represented by the formula (6), (7) or (8) described in Unexamined-Japanese-Patent No. 2009-215328 is mentioned, for example. Specific examples of the polyfunctional alkoxymethyl compound include hexamethoxymethyl melamine, tetramethoxymethyl acetylene carbamide, tetramethoxymethyl biphenol, hexamethoxymethyl bis(4-hydroxymethyl) phenyl) ethane, etc.

As the epoxy resin, known epoxy resins may be used, and examples thereof include phenol novolac epoxy resins, o-cresol novolac epoxy resins, bisphenol A epoxy resins, and bisphenol F epoxy resins. , biphenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthol type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, triphenyl epoxy resin Methane type epoxy resin, dicyclopentadiene type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, phosphorus atom-containing epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more.

As the curing agent, a polyfunctional alkoxymethyl compound is preferable because the cured product is more excellent in chemical resistance. Among the polyfunctional alkoxymethyl compounds, hexamethoxymethyl melamine is preferred. A hardener may be used individually by 1 type, or may be used in combination of 2 or more types.

The content of the hardener is preferably 5 to 30 parts by mass, preferably 10 to 20 parts by mass, relative to 100 parts by mass of the resin (A).

The solvent (hereinafter, also referred to as "diluent solvent") in the composition is preferably one that can dissolve the resin (A) and the curing agent. Examples of the dilution solvent include acetone, butanone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, N,N-dimethylformamide, NMP, butanol, ethyl lactate ( Hereinafter, also referred to as "EL"), ethyl acetate, butyl acetate, methylcellulose, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Tetrahydrofuran, etc. These dilution solvents may be used alone or in combination of two or more.

The boiling point of the dilution solvent is preferably 250°C or lower, more preferably 200°C or lower, and more preferably 160°C or lower. When the boiling point of the dilution solvent is below the aforementioned upper limit value, when the thermosetting resin composition is cured, the dilution solvent tends to volatilize, and the dilution solvent is less likely to remain in the cured product. The lower limit of the boiling point of the dilution solvent is not particularly limited, but is, for example, 60°C. The boiling point is the value at a pressure of 1 atm.

This composition can be prepared by blending resin (A), a hardener, a solvent according to needs, and other components according to needs.

The application of this composition is not particularly limited, and the application can be the same as that of a known thermosetting molding material. For example, a sealing material, a thin film material, a laminated material, a semiconductor insulating material, etc. are mentioned. Laminate materials are materials used to manufacture laminate boards.

[hardened material] The cured product of one aspect of the present invention is obtained by curing the composition, and includes a reactant of a resin (A) and a curing agent.

The cured product of this aspect can be produced by thermally curing this composition. The heating temperature when thermally hardening the composition is preferably 100 to 350°C, more preferably 150 to 250°C. The heating time varies depending on the heating temperature, but is, for example, 15 to 120 minutes.

[Example] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples at all. The following "parts" means "parts by mass".

[Measurement of weight average molecular weight (Mw)] The weight average molecular weight (hereinafter, referred to as "Mw") of the resin was measured using a gel permeation chromatograph HLC-8220 GPC manufactured by Tosoh Corporation. Mw is a value converted using standard polystyrene.

[Measurement of alkali dissolution rate] The resin was dissolved in a solvent to prepare a resin solution with a solid content of 20% by mass. The prepared resin solution was coated on a 3.5-inch silicon wafer by a spin coater, and then pre-baked at 110° C. for 1 minute using a hot plate to form a coating film. The film thickness of the coating film was measured using an optical interference type film thickness measuring apparatus AFT M5100 manufactured by Nanometrics. Next, the silicon wafer on which the coating film was formed was immersed in a 2.38 mass % tetramethylammonium hydroxide aqueous solution in an environment of 23° C., the time until the coating film was completely dissolved was measured, and the alkali dissolution was calculated by the following formula Speed (hereinafter, referred to as "ADR"). ADR (Å/sec) = film thickness of the coating film (Å) / time until the coating film is completely dissolved (sec) In addition, in this Example, as a solvent, NMP was used for resin A1-A12 type|system|group, and EL was used for resin A13-A26 type|system|group. When the resin was not dissolved in a 2.38 mass % tetramethylammonium hydroxide aqueous solution, it was referred to as "insoluble".

[Evaluation of chemical resistance] The thermosetting resin composition was coated on a 3.5-inch silicon wafer with a spin coater, then pre-baked at 120°C for 3 minutes using a hot plate, and thermally hardened by an oven at 200°C for 2 hours, and A cured film (cured product) is formed. The film thickness of the cured coating was measured using an optical interference type film thickness measuring apparatus AFT M5100 manufactured by Nanometrics. Next, the silicon wafer on which the cured film was formed was immersed in acetone at a temperature of 23° C. for 1 hour, and then the silicon wafer was pulled out and air-dried for 15 minutes. After air-drying, it was observed whether the cured film remained on the silicon wafer without peeling off, and when the cured film remained, the film thickness of the cured film was measured in the same manner as above, and the variation rate of the film thickness was calculated by the following formula. Change rate of film thickness (%) = (film thickness of cured film before acetone immersion (Å) - film thickness of cured film after acetone immersion (Å)) / film thickness of cured film before acetone immersion (Å) × 100 The chemical resistance was evaluated according to the following criteria from the variation rate of the film thickness of the cured film before and after the acetone immersion and the presence or absence of peeling. ⊚: The variation rate of the film thickness is less than ±5%. ○: The variation rate of the film thickness is ±5% or more and less than ±10%. △: The variation rate of the film thickness is ±10% or more and less than ±15%. ×: The variation rate of the film thickness is ±15% or more, or the cured film is peeled off.

[Evaluation of softness] The thermosetting resin composition was apply|coated to an aluminum plate by a bar coater, and it was made to thermoset by 200 degreeC in an oven for 2 hours, and the cured film with a film thickness of 1 micrometer was formed. The aluminum plate on which the cured film was formed was bent at an angle of 45° or 90° so that the cured film side was the outside. Then, the state of the cured film was visually observed, and the flexibility was evaluated according to the following criteria. ⊚: No cracks were found when bent at 90°. ○: Bending at 45° with no cracks, and bending at 90° with cracks. ×: There is a crack when it is bent at 45°.

[Synthesis Example 1] In a 0.5L 3-neck flask equipped with a Dean-Stark apparatus, add: 40.00 parts of N,N'-bis(3-hydroxyphenyl)-pyromellitic acid diimide as bisphenolimide ( Hereinafter, referred to as "BisPI-MAP"); 21.81 parts of 1,4-bis(methoxymethyl)biphenyl (hereinafter referred to as "BMMB") as a cross-linking base material; 123.70 parts of NMP as a reaction solvent 4.72 parts of p-toluenesulfonic acid (hereinafter, referred to as "PTS") as an acid catalyst, while stirring at 180 ° C to remove the methanol that is a by-product of the reaction, after 6 hours of reaction, at 40 ° C Cool down. The cooled reaction was dropped into 1 L of ion-exchanged water, and the precipitated resin was filtered out. The filtered resin was dried by a vacuum dryer at 80° C. for 12 hours to obtain resin A1. The Mw and ADR of the obtained resin are shown in Table 2.

[Synthesis Examples 2 to 26] Except having changed the raw materials to those shown in Table 1, the same operations as in Synthesis Example 1 were carried out to obtain resins A2 to A26. The Mw and ADR of the obtained resin are shown in Table 2.

[Table 1]

[Table 2]

The structures of the phenolic monomers and crosslinking base materials used are shown below.

[Chemical formula 8]

[Example 1] In a 50 mL polyethylene container, 10.0 parts of resin A1 obtained in Synthesis Example 1; 1.0 parts of hexamethoxymethyl melamine; 25.0 parts of NMP were added, and stirred and mixed to obtain a thermosetting resin composition.

[Examples 2 to 30] A thermosetting resin composition was obtained in the same manner as in Example 1 except that the resin, the curing agent, and the solvent were changed as shown in Table 3. As the bisphenol A epoxy resin, EPICLON850 from DIC was used. In addition, the boiling point of NMP is 202°C, and the boiling point of EL is 154°C.

[Synthesis Example 27] In a 1L 3-neck flask that has been nitrogen substituted, add: 88.2 parts of pt-butoxystyrene; 88.2 parts of propylene glycol monomethyl ether (PGME) as a reaction solvent; 10.3 parts of V-601 ( Fuji Film Wako Pure Chemical Industries Co., Ltd., trade name), was reacted at 80° C. for 8 hours with stirring. After the completion of the reaction, 10 parts of 35 mass % hydrochloric acid was added, and the reaction was performed under reflux for 6 hours to obtain a solution of poly-p-hydroxystyrene (hereinafter, referred to as "resin B1"). The obtained solution was added to 580 parts of pure water, and the precipitate was filtered out and dried at 60° C. for 8 hours with a vacuum dryer to obtain a powder of resin B1.

[Comparative Example 1] 10.0 parts of powders of resin B1 obtained in Synthesis Example 27 were dissolved in 25.0 parts of ethyl lactate, and 1.0 parts of hexamethoxymethyl melamine was added as a hardener to obtain a thermosetting resin composition.

[Comparative Examples 2 to 3] A thermosetting resin composition was produced in the same manner as in Comparative Example 1 except that the curing agent was changed as shown in Table 3.

The evaluation of chemical resistance and the evaluation of flexibility were performed with respect to the obtained thermosetting resin composition. The results are shown in Table 3.

[table 3]

The cured products of the thermosetting resin compositions of Examples 1 to 30 had chemical resistance and flexibility. On the other hand, the cured products of the thermosetting resin compositions of Comparative Examples 1 to 2 in which the resin B1 and hexamethoxymethyl melamine were combined were inferior in flexibility. The cured product of the thermosetting resin composition of Comparative Example 3 in which the resin B1 and the bisphenol A epoxy resin were combined was inferior in chemical resistance.

[Industrial Availability] According to the present invention, it is possible to provide a resin capable of obtaining a cured product excellent in chemical resistance and flexibility, a method for producing the same, a thermosetting resin composition capable of obtaining a cured product excellent in chemical resistance and flexibility, and chemical resistance A hardened product with excellent flexibility.

(without)

Claims (11)

A resin, which is a resin in which a phenolic monomer is linked by a divalent cross-linking group (X); the aforementioned phenolic monomer is selected from the group consisting of bisphenol imide and bisnaphtyl imide Among at least one monomer (m1), the aforementioned divalent cross-linking group (X) includes a cross-linking group (X1) represented by -CH ₂ -R ¹ -CH ₂ -; however, R ¹ may have a substituent The extended phenyl group or the extended biphenyl group which may have a substituent. The resin of claim 1, wherein the aforementioned monomer (m1) is at least one selected from the group consisting of a compound represented by the following formula (m11) and a compound represented by the following formula (m12); [chemical formula 1]

However, R ² is a group represented by any one of the following formulae (21) to (26), R ³ is an alkyl group with 1 to 4 carbon atoms; b and c are each independently an integer of 1 to 2, and d and e are independently an integer from 0 to 2, b+d is an integer from 1 to 3, c+e is an integer from 1 to 3, and when d+e is 2 or more, (d+e) R ³ can be the same or different from each other; f and g Each independently is an integer from 1 to 2, h and i are each independently an integer from 0 to 2, f+h is an integer from 1 to 3, g+i is an integer from 1 to 3, and when h+i is 2 or more, each of (h+i) R ³ Can be the same or different; [Chemical formula 2]

. The resin according to claim 1 or 2, wherein the aforementioned phenolic monomer further comprises cresol. The resin according to any one of claims 1 to 3, wherein the aforementioned divalent cross-linking group (X) further comprises a cross-linking group (X2) represented by -CH ₂ -. A method for manufacturing a resin, comprising the step of reacting a phenolic monomer with a cross-linking base material; the phenolic monomer comprises at least one selected from the group consisting of bisphenolimide and bisnaphtholimide 1 monomer (m1), the aforementioned cross-linking base material comprises a compound represented by Y ¹ -CH ₂ -R ¹ -CH ₂ -Y ² ; however, R ¹ is a substituted phenylene group or a substituted phenylene group In the biphenyl group of the group, Y ¹ and Y ² are each independently an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. The method for producing a resin according to claim 5, wherein the monomer (m1) is at least one selected from the group consisting of a compound represented by the following formula (m11) and a compound represented by the following formula (m12). ; [chemical formula 3]

However, R ² is a group represented by any one of the following formulae (21) to (26), R ³ is an alkyl group with 1 to 4 carbon atoms; b and c are each independently an integer of 1 to 2, and d and e are independently an integer from 0 to 2, b+d is an integer from 1 to 3, c+e is an integer from 1 to 3, and when d+e is 2 or more, (d+e) R ³ can be the same or different from each other; f and g Each independently is an integer from 1 to 2, h and i are each independently an integer from 0 to 2, f+h is an integer from 1 to 3, g+i is an integer from 1 to 3, and when h+i is 2 or more, each of (h+i) R ³ Can be the same or different; [Chemical formula 4]

. The method for producing a resin according to claim 5 or 6, wherein the phenolic monomer further contains cresol. The method for producing a resin according to any one of claims 5 to 7, wherein the aforementioned crosslinking-based material further comprises formaldehyde. A thermosetting resin composition comprising the resin according to any one of claims 1 to 4 and a hardener. The thermosetting resin composition according to claim 9, wherein the hardener contains a polyfunctional alkoxymethyl compound. A hardened product, which is the hardened product of the thermosetting resin composition according to claim 9 or 10.