Polyamide-imide resins, polyamide-imide resin compositions, adhesives, and semiconductors

Abstract

The present invention provides a polyamide-imide resin, a polyamide-imide resin composition, an adhesive, and a semiconductor that exhibit excellent adhesive properties when used as an adhesive. [Solution] A polyamide-imide resin comprising structural units derived from at least one type (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives, structural units derived from polyester polyol (B), and structural units derived from at least one type (C) selected from the group consisting of polyisocyanate compounds and polyamine compounds, wherein the ratio of structural units derived from polyester polyol (B) to the total number of moles of structural units derived from at least one type (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives and structural units derived from polyester polyol (B) is 5 mol% or more.

Description

[Technical Field]

[0001] This disclosure relates to polyamide-imide resins, polyamide-imide resin compositions, adhesives, and semiconductors. [Background technology]

[0002] Polyamide-imide resins are used in a variety of applications, including insulating materials, protective films, nonwoven fabrics, adhesives, and battery electrodes, due to their excellent heat resistance, electrical insulation, chemical resistance, solvent resistance, and strength when made into films.

[0003] As an example of a polyamide-imide resin, Patent Document 1 describes a polyamide-imide resin obtained by copolymerizing poly(acrylonitrile-butadiene) with dimer acid or polyester, which has a glass transition temperature of 120°C or higher, a logarithmic viscosity of 0.1 dl / g or higher, and a tensile modulus of 1,500 MPa or lower. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-208295 [Overview of the project] [Problems that the invention aims to solve]

[0005] One of the objectives of this disclosure is to provide a polyamide-imide resin, a polyamide-imide resin composition, an adhesive, and a semiconductor that exhibit excellent adhesion when used as an adhesive. [Means for solving the problem]

[0006] This disclosure includes the following embodiments. This disclosure is not limited to the following embodiments. One embodiment relates to a polyamide-imide resin comprising structural units derived from at least one (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives, structural units derived from polyester polyol (B), and structural units derived from at least one (C) selected from the group consisting of polyisocyanate compounds and polyamine compounds, wherein the ratio of structural units derived from polyester polyol (B) to the total number of moles of structural units derived from at least one (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives and structural units derived from polyester polyol (B) is 5 mol% or more. [Effects of the Invention]

[0007] This disclosure provides a polyamide-imide resin, a polyamide-imide resin composition, an adhesive, and a semiconductor that exhibit excellent adhesion when used in adhesives. [Modes for carrying out the invention]

[0008] The embodiments of the present invention will be described in detail below. The present invention is not limited to the embodiments described below.

[0009] In this disclosure, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, the upper or lower limits of numerical ranges described in this disclosure may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain one or more of the applicable substances unless otherwise specified. In this disclosure, the content of each component in the resin composition means the total amount of multiple substances present in the resin composition, unless otherwise specified, if there are multiple substances corresponding to each component in the resin composition.

[0010] In this disclosure, unless otherwise specified, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) are values ​​obtained by gel permeation chromatography (GPC) under the following conditions and converted using a calibration curve based on standard polystyrene.

[0011] [Method for measuring molecular weight] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured by gel permeation chromatography (GPC) under the following conditions and converted using a calibration curve based on standard polystyrene. The calibration curve was approximated by a cubic equation using a set of five standard polystyrene samples ("TSK standard POLYSTYRENE," manufactured by Tosoh Corporation). The GPC conditions are shown below.

[0012] Model: High-speed GPC system "HLC-8320GPC" (manufactured by Tosoh Corporation) Detector: UV-8320 ultraviolet absorption detector (manufactured by Tosoh Corporation) Wavelength: 270nm Column: "Shodex KF-806L+806L" (manufactured by Resonac Corporation) Column size: 8mm diameter x 300mm Solvent: DMF / THF = 1 / 1 liter + 0.06 M phosphoric acid + 0.06 M lithium bromide Sample concentration: 5 mg / 1 ml Injection volume: 5μl Flow rate: 1.0ml / min

[0013] A polyamide-imide resin according to an embodiment includes a structural unit derived from at least one type (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives, a structural unit derived from a polyester polyol (B), and a structural unit derived from at least one type (C) selected from the group consisting of polyisocyanate compounds and polyamine compounds. The proportion of the structural unit derived from the polyester polyol (B) with respect to the total number of moles of the structural unit derived from at least one type (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives and the structural unit derived from the polyester polyol (B) is 5 mol% or more.

[0014] At least one type (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives (hereinafter also referred to as "acid component (A)") is not particularly limited as long as it is a trivalent carboxylic acid having an acid anhydride group that reacts with an isocyanate group or an amino group, including its derivatives. The acid component (A) may be used alone or in combination of two or more. In terms of excellent heat resistance of the resin, the acid component (A) may be a compound having an aromatic ring group. Specific examples of the acid component (A) include compounds represented by the following general formula (2) or (3). The acid component (A) may be trimellitic anhydride.

[0015] [Chemical formula]

[0016] [In general formula (3), Y is a methylene group, a carbonyl group, a sulfonyl group, or an oxygen atom.]

[0017] The polyester polyol (B) may be a condensation reaction product of a polyol compound and a polycarboxylic acid compound. The polyol compound is, for example, a diol compound such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; a polyol compound with three or more functional groups such as glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol; and (poly)oxyalkylene modified products obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains into their molecular structures, etc. The polyol compound may be used alone or in combination of two or more kinds.

[0018] The polycarboxylic acid compound is, for example, an aliphatic dicarboxylic acid compound such as oxalic acid, malonic acid, succinic acid, maleic acid (anhydride), fumaric acid, citraconic acid (anhydride), glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; an alicyclic dicarboxylic acid such as tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), 1,4-cyclohexanedicarboxylic acid; an aromatic dicarboxylic acid compound such as phthalic acid (anhydride), isophthalic acid, terephthalic acid, etc. The polycarboxylic acid compound may be used alone or in combination of two or more kinds.

[0019] Among these, polyester diols using a diol compound and a dicarboxylic acid compound are preferred because they exhibit superior adhesive properties when used as adhesives. Furthermore, the dicarboxylic acid compound may also contain an aliphatic dicarboxylic acid compound. The proportion of the aliphatic dicarboxylic acid compound in the dicarboxylic acid compound may be 40 mol% or more, 60 mol% or more, 80 mol% or more, or 100 mol%. It may also be 90 mol% or less, 70 mol% or less, or 60 mol% or less. The proportion of the aliphatic dicarboxylic acid compound in the dicarboxylic acid compound may be in the range of 40 to 100 mol%.

[0020] The molecular weight of polyester polyol (B) is adjusted as appropriate depending on the application of the polyamide-imide resin and the desired performance. However, for superior adhesion when used as an adhesive, the number average molecular weight (Mn) may be 500 or more, 1,000 or more, or 1,500 or more. It may also be 5,000 or less, 4,000 or less, or 3,000 or less. The number average molecular weight (Mn) of polyester polyol (B) may be in the range of 500 to 5,000.

[0021] At least one compound (C) selected from the group consisting of polyisocyanate compounds and polyamine compounds (hereinafter also referred to as "polyisocyanate / polyamine (C)"), specific examples include, for example, aliphatic diisocyanate compounds such as butanediisocyanate, hexamethylenediisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, and 2,4,4-trimethylhexamethylenediisocyanate; and aliphatic diamine compounds such as hexamethylenediamine and 2,2,4-trimethylhexamethylenediamine.

[0022] Alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; alicyclic diamine compounds such as diaminoisophorone, bis(4-aminocyclohexyl)methane, 1,4-diaminotranscyclohexane, and hydrogenated m-xylylenediamine;

[0023] Tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4′-diisocyanatodiphenylmethane, 4,4′-diisocyanatobiphenyl, 3,3′-diisocyanatobiphenyl, 3,4′-diisocyanatobiphenyl, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 4,4′-diisocyanato-2,2′-dimethylbiphenyl, 4,4′-diisocyanato-3,3′-diethylbiphenyl, 4,4′-diisocyanato-2,2′-diethylbiphenyl, 4,4′-diisocyanato-3,3′-dimethoxybiphenyl, 4,4′-diisocyanato-2,2′-dimethoxybiphenyl, 1,5-diisocyanatonaphthalene, 2,6-diisocyanatonaphthalene, 4,4′-diisocyanatodiphenyl Examples include aromatic diisocyanate compounds such as nyl ethers, 2,2-bis[4-(4′-isocyanatophenoxy)phenyl]propane, and polymethylene polyphenyl polyisocyanates; and aromatic diamine compounds such as 4,4′-diaminodiphenylmethane, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diamino-3,3′-dimethylbiphenyl, 4,4′-diamino-2,2′-dimethylbiphenyl, 4,4′-diamino-3,3′-diethylbiphenyl, 4,4′-diamino-2,2′-diethylbiphenyl, 4,4′-diamino-3,3′-dimethoxybiphenyl, 4,4′-diamino-2,2′-dimethoxybiphenyl, 1,5-diaminonaphthalene, and 2,6-diaminonaphthalene.

[0024] The polyisocyanate may be an isocyanurate modified compound, a biuret modified compound, an allophanate modified compound, etc. If necessary to avoid changes over time, a compound in which the isocyanate group has been stabilized with a blocking agent may be used. Examples of blocking agents include alcohols, phenols, and oximes, but there are no particular restrictions. In addition, one type of polyisocyanate / polyamine(C) may be used alone, or two or more types may be used in combination.

[0025] In particular, regarding the excellent heat resistance of the resin, the polyisocyanate / polyamine(C) may contain one or more compounds selected from aromatic polyisocyanate compounds and aromatic polyamine compounds. The proportion of aromatic polyisocyanate compounds and aromatic polyamine compounds in the polyisocyanate / polyamine(C) may be 80% by mass or more, 90% by mass or more, or 100% by mass.

[0026] Furthermore, in terms of having an excellent balance between heat resistance and adhesive properties when used as an adhesive, it is preferable that the polyisocyanate / polyamine (C) contains a compound (C1) represented by the following general formula (1).

[0027] [ka]

[0028] [In general formula (1), X is a -NCO group or an -NH2 group. R 1 R is either an aliphatic hydrocarbon group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms. 1 If there are multiple elements, they may all be different, or some or all of them may be the same. 2 R is one of the following: a direct bond, an alkylene group with 1 to 3 carbon atoms, or an oxygen atom. 2 If there are multiple values, they may all be different, or some or all of them may be the same. m is 0, 1, or 2, and n is an integer greater than or equal to 1.

[0029] R in general formula (1) 1m is either an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl. Examples of alkoxy groups having 1 to 4 carbon atoms include those represented as -OR, where R is one of the above alkyl groups having 1 to 4 carbon atoms. m is 0, 1, or 2. m may also be 0.

[0030] R in general formula (1) 2 R2 is either a direct bond, an alkylene group with 1 to 3 carbon atoms, or an oxygen atom. Examples of alkylene groups with 1 to 3 carbon atoms include methylene, ethylene, propylene, and isopropylidene groups. R2 may be a direct bond, a methylene group, or an isopropylidene group, and may be either a direct bond or a methylene group. In general formula (1), n ​​is an integer of 1 or more. n may be 1.

[0031] The proportion of compound (C1) in the polyisocyanate / polyamine (C) may be 80% by mass or more, 90% by mass or more, or 100% by mass.

[0032] The polyamide-imide resin may contain structural units derived from other compounds, in addition to structural units derived from the acid component (A), the polyester polyol (B), and the polyisocyanate / polyamine (C). The total mass ratio of structural units derived from the acid component (A), the polyester polyol (B), and the polyisocyanate / polyamine (C) in the polyamide-imide resin may be 80% by mass or more, 90% by mass or more, or 100% by mass.

[0033] In polyamide-imide resins, the ratio of structural units derived from polyester polyol (B) to the total number of moles of structural units derived from acid component (A) and structural units derived from polyester polyol (B) is 5 mol% or more. This value of 5 mol% or more results in a polyamide-imide resin with excellent heat resistance and adhesion when used as an adhesive. The ratio of structural units derived from polyester polyol (B) to the total number of moles of structural units derived from acid component (A) and structural units derived from polyester polyol (B) may be 10 mol% or more, or 20 mol% or more. It may also be 80 mol% or less, 70 mol% or less, or 60 mol% or less. The ratio of structural units derived from polyester polyol (B) to the total number of moles of structural units derived from acid component (A) and structural units derived from polyester polyol (B) may be in the range of 5 to 80 mol%.

[0034] Furthermore, the ratio of structural units derived from polyester polyol (B) to the total mass of structural units derived from the acid component (A), the polyester polyol (B), and the polyisocyanate / polyamine (C) in the polyamide-imide resin may be 20% by mass or more, 30% by mass or more, or 40% by mass or more. It may also be 80% by mass or less, 70% by mass or less, or 60% by mass or less. The ratio of structural units derived from polyester polyol (B) to the total mass of structural units derived from the acid component (A), the polyester polyol (B), and the polyisocyanate / polyamine (C) in the polyamide-imide resin may be in the range of 20 to 80% by mass.

[0035] There are no particular restrictions on the method for producing polyamide-imide resin, but for example, it can be produced using an acid component (A), a polyester polyol (B), and a polyisocyanate / polyamine (C) as reaction raw materials. The ratio of the total mass of the acid component (A), polyester polyol (B), and polyisocyanate / polyamine (C) to the total mass of the polyamide-imide resin reaction raw materials may be 80% by mass or more, 90% by mass or more, or 100% by mass.

[0036] The ratio of the total number of moles of isocyanate groups and amino groups contained in the polyisocyanate / polyamine (C) to the total number of moles of carboxyl groups, acid anhydride groups, and hydroxyl groups contained in the acid component (A) and polyester polyol (B) may be in the range of 0.8 to 2.5 moles.

[0037] The reaction order of the acid component (A), polyester polyol (B), and polyisocyanate / polyamine (C) is not particularly limited. For example, they may be reacted together, or the polyester polyol (B) and polyisocyanate / polyamine (C) may be reacted to obtain an intermediate, which may then be reacted with the acid component (A). The reaction temperature is not particularly limited, but may be in the range of 80 to 180°C, for example. A catalyst may be used if desired. The reaction may also be carried out in a solvent. The amount of solvent used is not particularly limited, but may be in the range of 100 to 300 parts by mass per 100 parts by mass of the total reactant materials.

[0038] Examples of solvents used in the reaction include aromatic hydrocarbon solvents such as xylene and toluene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate, butyl butyrate, benzyl acetate, and γ-butyrolactone; ether solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; N-methyl-2-pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylpropylene urea [1,3-dimethyl-3,4,5,6-tetrahydropyridimine-2(1H)-one], dimethyl sulfoxide, and sulfolane. These may be used individually or in combination of two or more.

[0039] The molecular weight of the polyamide-imide resin is adjusted as appropriate depending on the application of the polyamide-imide resin, the desired performance, etc. For example, the number average molecular weight (Mn) may be 3,000 or more, 5,000 or more, 8,000 or more, 15,000 or more, or 20,000 or more. It may also be 100,000 or less, 80,000 or less, 50,000 or less, or 30,000 or less. The number average molecular weight (Mn) of the polyamide-imide resin may be in the range of 3,000 to 100,000.

[0040] The weight-average molecular weight (Mw) of the polyamide-imide resin may be 3,000 or more, 5,000 or more, 8,000 or more, 15,000 or more, or 20,000 or more. It may also be 300,000 or less, 200,000 or less, 100,000 or less, or 50,000 or less. The weight-average molecular weight (Mw) of the polyamide-imide resin may be in the range of 3,000 to 300,000.

[0041] The degree of dispersion (Mw / Mn) of the polyamide-imide resin may be 3 or less, 2.8 or less, or 2.5 or less. Its lower limit is not particularly limited, but may be 1 or more, 1.1 or more, or 1.2 or more. The degree of dispersion of the polyamide-imide resin may be in the range of 1 to 3.

[0042] The polyamide-imide resin composition may contain other components besides the polyamide-imide resin, depending on the application. Examples of other components include, for example, polyester resins, polyamide resins, polyurethane resins, acrylic resins, epoxy compounds, isocyanate compounds, melamine compounds, polyethersulfones and other resin components, pigments, fillers, defoamers, preservatives, surfactants, and the like.

[0043] The polyamide-imide resins and polyamide-imide resin compositions disclosed herein are not particularly limited in their applications and can be used in a wide variety of applications. Some specific examples include their excellent heat resistance, electrical insulation properties, chemical resistance, solvent resistance, and strength when made into films, making them suitable for use as insulating materials, protective films, nonwoven fabrics, adhesives, battery electrodes, and the like. The polyamide-imide resins and polyamide-imide resin compositions disclosed herein are particularly suitable for use in adhesive applications.

[0044] [glue] The present invention includes an adhesive or polyamide-imide resin according to one embodiment. The form of the adhesive is not limited and may be liquid or sheet-like. Specifically, a resin composition containing polyamide-imide resin and a solvent can be used as a liquid adhesive. Alternatively, a resin composition containing polyamide-imide resin and a solvent can be applied to an easily peelable substrate, and the resulting sheet can be obtained by peeling it off. The specific applications of the adhesive are not particularly limited, but taking advantage of the excellent heat resistance, solvent resistance, etc., properties of polyamide-imide resin, examples include semiconductor manufacturing applications.

[0045] Examples of embodiments are listed below. This disclosure is not limited to the following embodiments. <1>At least one structural unit (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives, a structural unit (B) derived from a polyester polyol, and at least one structural unit (C) selected from the group consisting of polyisocyanate compounds and polyamine compounds, wherein the proportion of the structural unit (B) derived from the polyester polyol to the total number of moles of the structural unit (A) selected from the group consisting of the tricarboxylic acid anhydrides and their derivatives and the structural unit (B) derived from the polyester polyol is 5 mol% or more, a polyamide-imide resin.

[0046] <2>The polyamide-imide resin according to <1>, wherein the polyester polyol (B) is a polyester diol.

[0047] <3>The polyamide-imide resin according to <1> or <2>, wherein at least one type (C) selected from the group consisting of the polyisocyanate compound and the polyamine compound includes one or more selected from the group consisting of aromatic polyisocyanate compounds and aromatic polyamine compounds.

[0048] <4>The polyamide-imide resin according to <1> or <2>, wherein at least one type (C) selected from the group consisting of the polyisocyanate compound and the polyamine compound includes a compound (C1) represented by the following general formula (1).

[0049] [Chemical formula]

[0050] [In general formula (1), X is an -NCO group or an -NH2 group. R 1 is either an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. When there are a plurality of Rs 1 in the formula, they may all be different, or some or all of them may be the same. R 2 is either a direct bond, an alkylene group having 1 to 3 carbon atoms, or an oxygen atom. When there is an R in the formula2 If there are multiple values, they may all be different, or some or all of them may be the same. m is 0, 1, or 2, and n is an integer greater than or equal to 1.

[0051] <5> <1> ~ <4> A resin composition comprising the polyamide-imide resin described in any one of the following.

[0052] <6> <1> ~ <4> An adhesive containing a polyamide-imide resin as described in any one of the following.

[0053] <7> For semiconductor manufacturing <6> The adhesive described above.

[0054] <8> <7> A semiconductor manufactured using the adhesive described above. [Examples]

[0055] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0056] [Method for measuring molecular weight] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured by gel permeation chromatography (GPC) under the following conditions and converted using a calibration curve based on standard polystyrene. The calibration curve was approximated by a cubic equation using a set of five standard polystyrene samples ("TSK standard POLYSTYRENE," manufactured by Tosoh Corporation). The GPC conditions are shown below.

[0057] Model: High-speed GPC system "HLC-8320GPC" (manufactured by Tosoh Corporation) Detector: UV-8320 ultraviolet absorption detector (manufactured by Tosoh Corporation) Wavelength: 270nm Column: "Shodex KF-806L+806L" (manufactured by Resonac Corporation) Column size: 8mm diameter x 300mm Solvent: DMF / THF = 1 / 1 liter + 0.06 M phosphoric acid + 0.06 M lithium bromide Sample concentration: 5 mg / 1 ml Injection volume: 5μl Flow rate: 1.0ml / min

[0058] [Example 1: Production of polyamide-imide resin (1)] In a flask equipped with a thermometer, stirrer, and condenser, 15.6 g (0.06 mol) of 4,4'-diphenylmethane diisocyanate, 62.1 g (0.03 mol) of polyol (1) (*1), and 51.8 g of N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") were charged. The mixture was heated to 120°C while stirring under a stream of dry nitrogen and reacted for 1 hour to obtain an NMP solution (non-volatile content 60% by mass) of the composition containing the urethane prepolymer. Subsequently, 136.4 g of NMP was added to dilute the solution to 40% non-volatile content, and then 24.0 g (0.13 mol) of trimellitic anhydride and 23.8 g (0.10 mol) of 4,4'-diphenylmethane diisocyanate were added at 40°C. The temperature was gradually raised to 140°C over 2 hours, and while taking care to avoid the rapid foaming of carbon dioxide gas due to the reaction, the temperature was maintained at 140°C. After continuing heating for 4 hours, the reaction was stopped to obtain an NMP solution of polyamide-imide resin (1) (40% by mass of non-volatile content).

[0059] (*1) Polyol (1): Amorphous polyester polyol with adipic acid, propylene glycol, and neopentyl glycol as the main reactive components, 2 hydroxyl groups per molecule, number average molecular weight (Mn) 2,000

[0060] [Example 2: Production of polyamide-imide resin (2)] In a flask equipped with a thermometer, stirrer, and condenser, 16.3 g (0.07 mol) of 4,4'-diphenylmethane diisocyanate, 64.0 g (0.03 mol) of polyol(2)(*2), and 53.5 g of NMP were charged. The mixture was heated to 120°C while stirring under a stream of dry nitrogen and reacted for 1 hour to obtain an NMP solution (non-volatile content 60% by mass) of the composition containing the urethane prepolymer. Subsequently, 141.4 g of NMP was added to dilute the solution to 40% non-volatile content, and then 25.0 g (0.13 mol) of trimellitic anhydride and 24.7 g (0.10 mol) of 4,4'-diphenylmethane diisocyanate were added at 40°C. The temperature was gradually raised to 140°C over 1 hour, and while taking care to avoid the rapid foaming of carbon dioxide gas due to the reaction, the temperature was maintained at 140°C. After continuing heating for 3 hours, the reaction was stopped to obtain an NMP solution of polyamide-imide resin (2) (40% by mass of non-volatile content).

[0061] (*2) Polyol(2): Amorphous polyester polyol with adipic acid, isophthalic acid, ethylene glycol, and neopentyl glycol as the main reactive components, 2 hydroxyl groups per molecule, number average molecular weight (Mn) 2,000

[0062] [Comparative Example 1: Production of Polyamide-Imide Resin (1')] In a flask equipped with a thermometer, stirrer, and condenser, 48.0 g (0.30 mol) of trimellitic anhydride, 63.5 g (0.30 mol) of 4,4'-diphenylmethane diisocyanate, and 167.3 g of NMP were charged. The mixture was gradually heated to 140°C over 2 hours while stirring under a stream of dry nitrogen. The mixture was then maintained at 140°C, taking care to avoid the rapid effervescence of carbon dioxide due to the reaction, and heating was continued for another 2 hours. After that, the reaction was stopped to obtain an NMP solution of polyamideimide (1') (40% by mass of non-volatile content).

[0063] [Evaluation of adhesion] NMP was added to the polyamide-imide resin solutions obtained in Examples 1 and 2 and Comparative Example 1 to achieve a non-volatile content of 10% by mass. These solutions were then applied to aluminum plates, and the solvent was dried on an 80°C hot plate for 30 minutes to obtain a 5 μm thick coating. The temperature was further increased to 200°C, a Kapton film was placed on the coating, and a roller was used to press it into place to obtain an adhesive sample. After storing the adhesive samples at room temperature for 1 hour, they were visually inspected for peeling, lifting, etc. No peeling or lifting occurred in the adhesive samples using polyamide-imide resins (1) and (2) from Examples 1 and 2. However, in the adhesive sample using polyamide-imide resin (1') from Comparative Example 1, the adhesion was insufficient in some areas, and lifting occurred in some areas.

Claims

1. A polyamide-imide resin comprising structural units derived from at least one (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives, structural units derived from polyester polyols (B), and structural units derived from at least one (C) selected from the group consisting of polyisocyanate compounds and polyamine compounds, wherein the ratio of structural units derived from polyester polyols (B) to the total number of moles of structural units derived from at least one (A) selected from the group consisting of tricarboxylic acid anhydrides and their derivatives and structural units derived from polyester polyols (B) is 5 mol% or more.

2. The polyamide-imide resin according to claim 1, wherein the polyester polyol (B) is a polyester diol.

3. The polyamide-imide resin according to claim 1, wherein at least one (C) selected from the group consisting of polyisocyanate compounds and polyamine compounds includes at least one selected from the group consisting of aromatic polyisocyanate compounds and aromatic polyamine compounds.

4. The polyamide-imide resin according to claim 1, wherein at least one (C) selected from the group consisting of the polyisocyanate compound and the polyamine compound comprises a compound (C1) represented by the following general formula (1). 【Chemistry 1】 [In general formula (1), X is a -NCO group or -NH ２ It is the basis. R １ R is either an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. １ If there are multiple elements, they may all be different, or some or all of them may be identical. ２ R is one of the following: a direct bond, an alkylene group with 1 to 3 carbon atoms, or an oxygen atom. ２ If there are multiple elements, they may all be different, or some or all of them may be the same. m is 0, 1, or 2, and n is an integer greater than or equal to 1.

5. A resin composition comprising the polyamide-imide resin according to any one of claims 1 to 4.

6. An adhesive comprising the polyamide-imide resin according to any one of claims 1 to 4.

7. The adhesive according to claim 6, for use in semiconductor manufacturing.

8. A semiconductor manufactured using the adhesive described in claim 7.

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