Imide resin material, curable resin composition, adhesive film, temporary fixing material, and method for producing imide resin material

Abstract

The purpose of the present invention is to provide an imide resin material which, prior to curing, can exhibit high initial adhesive strength when applied and which exhibits excellent heat resistance and excellent ultraviolet radiation curability. Another purpose of the present invention is to provide a curable resin composition that contains said imide resin material. A further purpose of the present invention is to provide a curable resin composition which, prior to curing, can exhibit high initial adhesive strength when applied and which exhibits excellent heat resistance and excellent ultraviolet radiation curability. A further purpose of the present invention is to provide: an adhesive film having an adhesive layer that contains said curable resin composition; and a temporary fixing material that contains said curable resin composition. Another purpose of the present invention is to provide a method for producing said imide resin material. The present invention is an imide resin material which is constituted from an imide compound and which contains a compound represented by formula (1). The weight average molecular weight of the overall imide resin material, as measured by GPC, is 5000 or more. The content ratio of components having the weight average molecular weight of 500-3000 in the imide resin material is 5 mass% or more.

Description

Imide resin material, curable resin composition, adhesive film, temporary fixing material, and method for producing imide resin material

[0001] The present invention relates to an imide resin material. The present invention also relates to a curable resin composition. Furthermore, the present invention also relates to an adhesive film having an adhesive layer containing the curable resin composition and a temporary fixing material containing the curable resin composition. Additionally, the present invention also relates to a method for producing the imide resin material.

[0002] During processing of electronic components such as semiconductors, in order to facilitate handling of the electronic components and prevent breakage, the electronic components are protected by being fixed to a support plate via a pressure-sensitive adhesive composition or by being attached with a pressure-sensitive adhesive tape. For example, when a thick-film wafer cut from a high-purity silicon single crystal or the like is ground to a predetermined thickness to obtain a thin-film wafer, the thick-film wafer is adhered to a support plate via a pressure-sensitive adhesive composition.

[0003] Thus, processing materials such as pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes used for electronic components are required to have high enough adhesion to firmly fix the electronic components during processing, and also to be able to peel off the electronic components after processing without damaging them (hereinafter also referred to as "high adhesion and easy peeling"). As a means of achieving high adhesion and easy peeling, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet using a pressure-sensitive adhesive in which a polyfunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to the side chain or main chain of the polymer. By utilizing the fact that the polymer has a radiation-polymerizable functional group, which hardens when irradiated with ultraviolet light, the adhesive strength is reduced by irradiating with ultraviolet light during peeling, allowing peeling without leaving any adhesive residue.

[0004] Japanese Patent Application Publication No. 5-32946

[0005] In recent years, electronic components have become more highly functional, resulting in the development of various processing steps for electronic components. For example, in processes for forming metal thin films on the surfaces of electronic components by sputtering, processing at high temperatures of approximately 300 to 350°C allows for the formation of metal thin films with superior conductivity. Curable resin compositions containing imide resin materials that have excellent heat resistance and are cured by ultraviolet irradiation have been investigated as processing materials that can be used even when high-temperature processing is performed at 300°C or higher. However, imide resin materials have a rigid chemical structure with an imide skeleton as a repeating unit in the main chain, resulting in low tack (initial adhesive strength) before curing, making it difficult to attach them to substrates. Furthermore, imide resin materials often do not cure sufficiently even when irradiated with ultraviolet light.

[0006] The present invention provides an imide resin material that exhibits high initial adhesive strength when applied before curing and has excellent heat resistance and UV curability. Another object of the present invention is to provide a curable resin composition containing the imide resin material. A further object of the present invention is to provide a curable resin composition that exhibits high initial adhesive strength when applied before curing and has excellent heat resistance and UV curability. A further object of the present invention is to provide an adhesive film having an adhesive layer containing the curable resin composition, and a temporary fixing material containing the curable resin composition. Another object of the present invention is to provide a method for producing the imide resin material.

[0007] Disclosure 1 is an imide resin material composed of an imide compound, which contains a compound represented by the following formula (1), and in which the weight-average molecular weight of the entire imide resin material measured by GPC is 5,000 or more, and the content of components having a weight-average molecular weight of 500 or more and 3,000 or less in the imide resin material is 5 mass % or more. Disclosure 2 is an imide resin material composed of the following R ２１ and R ２２The imide resin material of Disclosure 1 is an imide resin material of Disclosure 1, wherein the aliphatic group derived from dimer diamine is at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4). The imide resin material of Disclosure 4 is an imide resin material of Disclosure 1, wherein the aliphatic group derived from dimer diamine is at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4). １ The imide resin material of Disclosure 1, 2, or 3 includes a compound having a weight average molecular weight of 0 or more and 3 or less. Disclosure 5 is the imide resin material of Disclosure 4, wherein the component having a weight average molecular weight of 500 or more and 3000 or less includes at least one compound selected from the group consisting of the following formulas (3-1), (3-2), and (3-3). Disclosure 6 is the imide resin material of Disclosure 4 or 5, wherein the component having a weight average molecular weight of 500 or more and 3000 or less includes at least one compound selected from the group consisting of the following formulas (4-1), (4-2), and (4-3). Disclosure 7 is a curable resin composition containing the imide resin material of Disclosure 1, 2, 3, 4, 5, or 6. Disclosure 8 is a curable resin composition containing a compound represented by the following formula (1) and a compound having a weight average molecular weight of 500 or more and 3000 or less as measured by GPC, wherein the compound represented by formula (1) has a weight average molecular weight of 500 or more and 3000 or less as measured by GPC, and the content of the compound having a weight average molecular weight of 500 or more and 3000 or less in the curable resin composition is 5.0 mass% or more. Disclosure 9 is a curable resin composition in which the compound having a weight average molecular weight of 500 or more and 3000 or less is a compound represented by formula (1) １The curable resin composition of the present disclosure 8 includes a compound having a molecular weight of 0 or more and a molecular weight of 3 or less. The present disclosure 10 is an adhesive film having an adhesive layer containing the curable resin composition of the present disclosure 7, 8, or 9. The present disclosure 11 is a temporary fixing material containing the curable resin composition of the present disclosure 7, 8, or 9. The present disclosure 12 is a method for producing an imide resin material of the present disclosure 1, 2, 3, 4, 5, or 6, comprising: Step I of preparing an imide intermediate by reacting a diamine compound with a difunctional or higher aromatic acid anhydride; and Step II of introducing a maleimide group to an end of the imide intermediate to prepare a compound represented by formula (1), wherein in Step I, the molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride (moles of diamine compound / moles of difunctional or higher aromatic acid anhydride) is 1.5 or more. Disclosure 13 is the method for producing an imide resin material according to Disclosure 12, wherein in Step I, the molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride (moles of diamine compound / moles of difunctional or higher aromatic acid anhydride) is 2.0 or less.

[0008]

[0009] In formula (1), R ２１ and R ２２ each independently represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group, or a substituted or unsubstituted aromatic group; R ２３ represents a substituted or unsubstituted aromatic group, m １ represents an integer of 1 or greater.

[0010] In formulas (2-1) to (2-4), R １ ~R １６ each independently represents a linear or branched hydrocarbon group. In addition, * represents a bond. The bond * is bonded to N in the above formula (1).

[0011] In formulas (3-1) to (3-3), R ３１ represents a substituted or unsubstituted, linear, branched or cyclic aliphatic group, or a substituted or unsubstituted aromatic group.

[0012] In formulas (4-1) to (4-3), R ４１and R ４２ each independently represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group, or a substituted or unsubstituted aromatic group; R ４３ represents a substituted or unsubstituted aromatic group; X １ and X ２ each independently represents a structure of either formula (5-1) or formula (5-2) below.

[0013]

[0014] The curable resin composition of Disclosure 7 is also referred to as the "curable resin composition of Invention 7," and the curable resin composition of Disclosure 8 is also referred to as the "curable resin composition of Invention 8." Furthermore, matters common to the curable resin composition of Invention 7 and the curable resin composition of Invention 8 will not be specified or will be described as the "curable resin composition of the present invention." The present inventors investigated the inclusion of a compound having a specific structure in an imide resin material composed of an imide compound, and further investigated the weight-average molecular weight of the entire imide resin material measured by GPC and the content ratio of low-molecular-weight components in the imide resin material, both of which are equal to or greater than specific values. As a result, the present inventors discovered that an imide resin material can be obtained that exhibits high initial adhesive strength when applied before curing and has excellent heat resistance and UV curability. This led to the completion of the present invention.

[0015] The imide resin material of the present invention is composed of an imide compound. Imide compounds have extremely excellent heat resistance and are unlikely to decompose even when subjected to high-temperature processing at 300°C or higher. Therefore, since the imide resin material of the present invention is composed of an imide compound, it can be easily peeled off after high-temperature processing, even when subjected to high-temperature processing at 300°C or higher.

[0016] The imide resin material of the present invention contains a compound represented by the above formula (1). Because the compound represented by the above formula (1) has a maleimide group, the imide resin material of the present invention, either alone or in combination with a polymerization initiator, undergoes curing by heating or light irradiation, thereby preventing adhesion enhancement even after high-temperature processing, and allowing for easy peeling. Furthermore, the compound represented by the above formula (1) has a maleimide group located at its terminal, which improves the reactivity of the maleimide group, resulting in the imide resin material of the present invention having excellent UV curability.

[0017] In formula (1), R ２１ and R ２２ each independently represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group, or a substituted or unsubstituted aromatic group; R ２３ represents a substituted or unsubstituted aromatic group. The substituted or unsubstituted linear, branched, or cyclic aliphatic group is not particularly limited, but is preferably an aliphatic group having 2 to 100 carbon atoms. The substituted or unsubstituted aromatic group is not particularly limited, but is preferably an aromatic group having 5 to 50 carbon atoms.

[0018] Also, R ２１ and R ２２ is preferably an aliphatic group or an aromatic group derived from a diamine compound. As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used. Among them, an aliphatic diamine compound is preferred from the viewpoints of solubility in a coating solvent and flexibility of the composition. These diamine compounds may be used alone or in combination of two or more.

[0019] Examples of the aliphatic diamine compound include 1,10-diaminodecane, 1,12-diaminododecane, dimer diamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane. These aliphatic diamine compounds may be used alone or in combination of two or more.

[0020] Examples of the aromatic diamine compound include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diamino Aminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methan fluorene, bis(4-amino-3,5-diethylphenyl)methane, 9,9'-bis(4-amino-3-ethylphenyl)fluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenyl sulfone, 3,3'-diaminophenyl sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenyl)phenyl)sulfone Bis(phenoxy)phenyl)sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, Bisaniline M, Bisaniline P, 9,9-bis(4-aminophenyl)fluorene, o-tolidine sulfone, 5,5'-methylenebis(anthranilic acid), 1,Examples of the aromatic diamine compounds include 3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylene diamines (e.g., Jeffamine D-230, D-400, D-2000, and D-4000 manufactured by Huntsman), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, and p-xylylenediamine. These aromatic diamine compounds may be used alone or in combination of two or more.

[0021] Among them, R ２１ and R ２２ is preferably an aliphatic group derived from dimer diamine, from the viewpoint of increasing the flexibility of the imide resin material and further improving initial adhesive strength, and from the viewpoint of increasing compatibility with the solvent and other components of the imide resin material. The dimer diamine is a diamine compound obtained by reducing and amminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples thereof include linear, monocyclic, and polycyclic dimer diamines. The dimer diamine may contain a carbon-carbon unsaturated double bond or may be a hydrogenated product to which hydrogen has been added. More specifically, the aliphatic group derived from the dimer diamine is preferably at least one selected from the group consisting of the group represented by formula (2-1), the group represented by formula (2-2), the group represented by formula (2-3), and the group represented by formula (2-4). Of these, the group represented by formula (2-2) is more preferred. The optical isomerism of these groups is not particularly limited, and includes any optical isomerism.

[0022] In the above formulas (2-1) to (2-4), R １ ~R １６The hydrocarbon group represented by R is not particularly limited, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In particular, from the viewpoint of increasing the flexibility of the imide resin material and further improving the initial adhesive strength, and from the viewpoint of increasing the compatibility of the imide resin material with the solvent and other components, １ and R ２ , R ３ and R ４ , R ５ and R ６ , R ７ and R ８ , R ９ and R １０ , R １１ and R １２ , R １３ and R １４ , and R １５ and R １６ The preferred lower limit of the total number of carbon atoms is 7, and the preferred upper limit is 50. The more preferred lower limit of the total number of carbon atoms is 9, and the more preferred upper limit is 35, and the even more preferred lower limit is 12, and the even more preferred upper limit is 25, and the even more preferred lower limit is 14, and the even more preferred upper limit is 18.

[0023] Also, R ２３is preferably an aromatic group derived from a difunctional or higher aromatic acid anhydride. Examples of the bifunctional or more aromatic acid anhydrides include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 1,1-bis(3,4-dicarboxyphenyl)ethane, bis(2,3 -dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid), and the like. Among these, pyromellitic acid is preferred. These difunctional or higher functional aromatic acid anhydrides may be used alone or in combination of two or more thereof. In this specification, the term "difunctional or higher functional aromatic acid anhydride" refers to a compound having an aromatic group and two or more acid anhydride groups.

[0024] The compound represented by formula (1) may have a maleimide group in a side chain. When the compound represented by formula (1) has a maleimide group in a side chain, the inter-crosslink distance is shortened, thereby further suppressing the adhesion enhancement of the imide resin material of the present invention and allowing it to be more easily peeled off.

[0025] The content of the compound represented by formula (1) in the imide resin material of the present invention preferably has a lower limit of 10% by mass. When the content of the compound represented by formula (1) is 10% by mass or more, the heat resistance and UV curability of the imide resin material of the present invention are further improved. A more preferred lower limit of the content of the compound represented by formula (1) is 15% by mass, and an even more preferred lower limit is 20% by mass. Furthermore, the content of the compound represented by formula (1) may be 100% by mass. That is, the imide resin material of the present invention may be composed solely of the compound represented by formula (1).

[0026] In the imide resin material of the present invention, the component having a weight average molecular weight of 500 or more and 3000 or less (hereinafter, sometimes simply referred to as "low molecular weight component") may be a compound represented by the above formula (1), or may be an imide compound other than the compound represented by the above formula (1). Examples of the other imide compounds include maleimide compounds that do not have an imide structure (excluding a maleimide group) in the main chain (for example, a maleimide compound represented by the above formula (1) １ = 0, etc.), polyimide resins not represented by the above formula (1) (for example, imide intermediates in the production of an imide resin material described later, etc.) are included. Among these, imide intermediates in the production of an imide resin material described later are preferred from the viewpoint of easily adjusting the content ratio of the low-molecular-weight component in the imide resin material of the present invention to within the range described later and from the viewpoint of controlling the elastic modulus and adhesive strength.

[0027] The low molecular weight component is m １ It is preferable that the low-molecular-weight component contains a compound in which m is 0 or more and 3 or less. １By including a compound in which m is 0 or more and 3 or less, it becomes easier to control the modulus of elasticity and adhesive strength of the imide resin material of the present invention. In particular, from the viewpoint of further improving the adhesive strength of the imide resin material of the present invention, the low-molecular-weight component is preferably a compound in which m is 0 or more and 3 or less in the above formula (1). １ It is more preferable that the low molecular weight component contains at least one compound selected from the group consisting of 0 to 2. In this specification, the identification of the compound species in the low molecular weight component can be carried out by the following method, etc. That is, the low molecular weight component is extracted using a separation column such as silica gel, １ By carrying out H-NMR measurement, the compound species in the low molecular weight component can be identified.

[0028] The low-molecular-weight component preferably contains a compound represented by at least one formula selected from the group consisting of the formula (3-1), the formula (3-2), and the formula (3-3) (hereinafter, sometimes simply referred to as "compound (3)"). When the low-molecular-weight component contains a compound represented by at least one formula selected from the group consisting of the formula (3-1), the formula (3-2), and the formula (3-3), adhesive strength and photoreactivity are further improved. In particular, from the viewpoint of excellent photoreactivity, it is preferable to contain a compound having the structure of the formula (3-1).

[0029] In the above formulas (3-1) to (3-3), R ３１ represents a substituted or unsubstituted, linear, branched or cyclic aliphatic group, or a substituted or unsubstituted aromatic group. ３１ is not particularly limited, but is preferably R in the above formula (1). ２１ A structure similar to the following is preferred.

[0030] The content of the compound (3) in the imide resin material of the present invention is preferably 1.0% by mass at its lower limit and 20% by mass at its upper limit. When the content of the compound (3) is 1.0% by mass or more, the content of low-molecular-weight components in the imide resin material of the present invention can be easily adjusted to the range described below. When the content of the compound (3) is 20% by mass or less, the cohesive strength of the imide resin material of the present invention is further improved, and the adhesive strength is improved. The content of the compound (3) is more preferably 2.0% by mass at its lower limit, more preferably 15% by mass at its upper limit, and even more preferably 10% by mass at its upper limit.

[0031] The low-molecular-weight component preferably contains a compound represented by at least one formula selected from the group consisting of the formula (4-1), the formula (4-2), and the formula (4-3) (hereinafter, sometimes simply referred to as "compound (4)"). When the low-molecular-weight component contains the compound (4), it becomes easier to control the elastic modulus and adhesive strength of the imide resin material of the present invention. In particular, from the viewpoint of further improving the elastic modulus of the imide resin material of the present invention, it is preferable that the low-molecular-weight component contains a compound having a structure of the formula (4-1).

[0032] In the above formulas (4-1) to (4-3), R ４１ and R ４２ Each of R independently represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, or a substituted or unsubstituted aromatic group. ４１ and R ４２ is not particularly limited, but is preferably R in the above formula (1). ２１ and R ２２ A structure similar to the following is preferred.

[0033] The content of the compound (4) in the imide resin material of the present invention is preferably 1% by mass at the lower limit and 20% by mass at the upper limit. When the content of the compound (4) is 1% by mass or more, the modulus of elasticity of the imide resin material of the present invention is further improved. When the content of the compound (4) is 20% by mass or less, the cohesive strength and adhesive strength of the imide resin material of the present invention are further improved. The content of the compound (4) is more preferably 2% by mass at the lower limit, more preferably 15% by mass at the upper limit, and even more preferably 10% by mass at the upper limit.

[0034] The lower limit of the content of low molecular weight components in the imide resin material of the present invention, as measured by GPC, is 5.0% by mass. By having a content of the low molecular weight components of 5.0% by mass or more, the imide resin material of the present invention can exhibit high initial adhesive strength when applied. Furthermore, the imide resin material of the present invention has excellent heat resistance, and therefore can be easily peeled off after high-temperature processing, even when subjected to high-temperature processing at 300°C or higher. Furthermore, the imide resin material of the present invention has excellent UV curing properties. The preferred lower limit of the content of the low molecular weight components is 10% by mass, and more preferably 15% by mass. The preferred upper limit of the content of the low molecular weight components is 60% by mass. By having a content of the low molecular weight components of 60% by mass or less, the cohesive strength and adhesive strength of the imide resin material of the present invention are further improved. The preferred upper limit of the content of the low molecular weight components in the imide resin material of the present invention is 50% by mass, and even more preferably 40% by mass.

[0035] The content of the other imide compounds in the imide resin material of the present invention is preferably 3.0% by mass at the lower limit and 90% by mass at the upper limit. By ensuring that the content of the other imide compounds is 3.0% by mass or more, the content of low-molecular-weight components in the imide resin material of the present invention can be easily adjusted to within the range described below. By ensuring that the content of the other imide compounds is 90% by mass or less, the cohesive strength and adhesive strength of the imide resin material of the present invention are further improved. The content of the other imide compounds is more preferably 5.0% by mass at the lower limit, more preferably 80% by mass at the upper limit, and even more preferably 10% by mass at the lower limit.

[0036] When the imide resin material of the present invention is measured by GPC, the lower limit of the weight-average molecular weight (Mw) of the entire imide resin material of the present invention is 5,000. When the weight-average molecular weight of the entire imide resin material of the present invention is 5,000 or more, the imide resin material of the present invention forms a self-supporting film and has improved cohesive strength, resulting in high initial adhesive strength upon application and excellent heat resistance. The lower limit of the weight-average molecular weight of the entire imide resin material of the present invention is preferably 6,000, more preferably 7,000. The upper limit of the weight-average molecular weight of the entire imide resin material of the present invention is not particularly limited, but a preferred upper limit is 30,000. When the weight-average molecular weight of the entire imide resin material of the present invention is 30,000 or less, the imide resin material of the present invention does not become too hard and can exhibit high initial adhesive strength upon application. The upper limit of the weight-average molecular weight of the entire imide resin material of the present invention is more preferably 20,000, even more preferably 10,000.

[0037] The preferred lower limit of the polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the entire imide resin material of the present invention is 1.6, and the preferred upper limit is 3.0. When the polydispersity of the entire imide resin material of the present invention is within the above range, the imide resin material of the present invention can have better UV curability. A more preferred lower limit of the polydispersity of the entire imide resin material of the present invention is 1.8, and a more preferred upper limit is 2.8. Note that if the polydispersity of the entire imide resin material of the present invention is too small, the imide resin material will become closer to a single substance (high purity) and will often be obtained as a powder.

[0038] In this specification, the weight-average molecular weight, polydispersity index, content ratio of compound (3), content ratio of compound (4), and content ratio of the low-molecular-weight component can be obtained by gel permeation chromatography (GPC). Specifically, for example, measurement is performed using an APC system (manufactured by Waters Corporation) and an HR-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) as a column under the conditions of a THF mobile phase, a flow rate of 1.0 mL / min, a column temperature of 40°C, a sample concentration of 0.2 wt%, and an RI-PDA detector, to obtain the weight-average molecular weight, number-average molecular weight, and polydispersity index in terms of polystyrene. Furthermore, the content ratios of compound (3), compound (4), and the low-molecular-weight component can be obtained by calculating the peak areas of compound (3), compound (4), and the low-molecular-weight component in the molecular weight distribution curve of the imide resin material in terms of polystyrene obtained by GPC measurement. The specific method for calculating the peak areas of the compounds (3) and (4) is as follows. That is, first, GPC measurement is performed in advance using compounds (3) and (4) that can be obtained by, for example, extracting low-molecular-weight components using a separation column such as silica gel, and the timing for detecting the peaks of compounds (3) and (4) is confirmed. Then, when GPC measurement is performed on the imide resin material, the peak areas of the peaks detected at the same timing as those of each compound whose peaks were previously confirmed in the GPC measurement are calculated, thereby obtaining the content ratios of compounds (3) and (4).

[0039] Examples of methods for adjusting the weight average molecular weight of the imide resin material of the present invention include methods for adjusting reaction conditions, dehydration conditions, purification conditions, reaction equivalents, etc. in the method for producing an imide resin material described below.

[0040] Examples of methods for adjusting the content ratio of the low-molecular-weight component include a method of adding another imide compound having a weight-average molecular weight of 500 or more and 3,000 or less to the imide resin material, a method of adjusting the reaction equivalent in the method for producing an imide resin material described below, a method of purifying the product by a purification method that does not use a solvent to wash the product, and a method of changing the type of solvent.

[0041] The uses of the imide resin material of the present invention are not particularly limited, but since it can exhibit high initial adhesive strength when applied before curing, it can be suitably used as a raw material for adhesive compositions. In particular, since it has excellent heat resistance, it can be more suitably used as a raw material for adhesive compositions for fixing parts exposed to high-temperature environments of 300°C or higher. Furthermore, since the imide resin material of the present invention has excellent UV curing properties, it can be particularly suitably used as a raw material for adhesive compositions used in processing materials. A curable resin composition containing the imide resin material of the present invention also constitutes one aspect of the present invention.

[0042] The present invention also provides a curable resin composition comprising a compound represented by formula (1) and a compound having a weight average molecular weight of 500 or more and 3000 or less as measured by GPC, wherein the compound represented by formula (1) has a weight average molecular weight of 5000 or more as measured by GPC, and the content of the compound having a weight average molecular weight of 500 or more and 3000 or less in the curable resin composition is 5.0 mass% or more. The curable resin composition of invention 8 can exhibit high initial adhesive strength when applied before curing, and has excellent heat resistance and excellent UV curability.

[0043] Examples of the compound represented by the formula (1) in the curable resin composition of invention 8 include the compound represented by the formula (1) in the imide resin material of the present invention described above.

[0044] In the curable resin composition of invention 8, when the compound represented by formula (1) is measured by GPC, the lower limit of the weight-average molecular weight (Mw) of the compound represented by formula (1) is 5,000. When the weight-average molecular weight of the compound represented by formula (1) in the curable resin composition of invention 8 is 5,000 or more, the curable resin composition of invention 8 has improved cohesive strength, thereby exhibiting high initial adhesive strength upon application and also having excellent heat resistance. In the curable resin composition of invention 8, the lower limit of the weight-average molecular weight of the compound represented by formula (1) is preferably 6,000, more preferably 7,000. In the curable resin composition of invention 8, the upper limit of the weight-average molecular weight of the compound represented by formula (1) is not particularly limited, but a preferred upper limit is 30,000. When the weight-average molecular weight of the compound represented by formula (1) in the curable resin composition of invention 8 is 30,000 or less, the curable resin composition of invention 8 does not become too hard and exhibits high initial adhesive strength upon application. In the curable resin composition of the eighth invention, the upper limit of the weight average molecular weight of the compound represented by the formula (1) is more preferably 20,000, and even more preferably 10,000.

[0045] Examples of the compound having a weight average molecular weight of 500 or more and 3000 or less in the curable resin composition of the present invention 8 include compounds contained as low molecular weight components in the imide resin material of the present invention. Among these, the compound having a weight average molecular weight of 500 or more and 3000 or less is a compound represented by the formula (1) m １ It is preferable that the compound contains a compound in which is 0 or more and 3 or less.

[0046] In the curable resin composition of the present invention 8, the lower limit of the content of the compound having a weight-average molecular weight of 500 or more and 3,000 or less in the curable resin composition is 5.0% by mass. By having the content of the low-molecular-weight component be 5.0% by mass or more, the curable resin composition of the present invention 8 can exhibit high initial adhesive strength when applied. Furthermore, the curable resin composition of the present invention 8 has excellent heat resistance, and therefore can be easily peeled off after high-temperature processing even when subjected to high-temperature processing at 300°C or more. Furthermore, the curable resin composition of the present invention 8 has excellent ultraviolet curability. The preferred lower limit of the content of the compound having a weight-average molecular weight of 500 or more and 3,000 or less is 10% by mass, and more preferably 15% by mass. The preferred upper limit of the content of the compound having a weight-average molecular weight of 500 or more and 3,000 or less is 60% by mass. By having the content of the compound having a weight-average molecular weight of 500 or more and 3,000 or less be 60% by mass or less, the cohesive strength and adhesive strength of the curable resin composition of the present invention 8 are further improved. The upper limit of the content of the low-molecular-weight component in the curable resin composition of invention 8 is more preferably 50% by mass, and even more preferably 40% by mass.

[0047] The curable resin composition of the present invention preferably further contains a polymerization initiator such as a thermal polymerization initiator, a photopolymerization initiator, etc. The content of the polymerization initiator in the curable resin composition of the present invention is not particularly limited and may be appropriately selected depending on the imide resin material of the present invention, but the lower limit is preferably 0.1 parts by mass, the upper limit is preferably 5.0 parts by mass, the lower limit is more preferably 0.5 parts by mass, and the upper limit is more preferably 2.0 parts by mass, relative to 100 parts by mass of the imide resin material of the present invention.

[0048] The curable resin composition of the present invention may contain, in addition to the imide resin material and polymerization initiator of the present invention, a solvent, an additive, etc., as long as the effects of the present invention are not impaired.

[0049] The curable resin composition of the present invention can exhibit high initial adhesive strength when applied before curing, and therefore can be suitably used as an adhesive that is liquid at room temperature or as an adhesive composition for an adhesive film having an adhesive layer. In particular, it can be more suitably used as an adhesive composition for an adhesive film having an adhesive layer, from the viewpoint of being able to fix electronic components to a substrate with high strength when the electronic components are subjected to various processing. In this specification, "room temperature" means 18°C ​​or higher and 25°C or lower.

[0050] Furthermore, since the curable resin composition of the present invention has excellent ultraviolet curability, the adhesive that is liquid at room temperature and the adhesive film having an adhesive layer described above are suitably used as temporary fixing materials, and further, since the curable resin composition of the present invention has excellent heat resistance, they are particularly suitably used as temporary fixing materials that can be applied even when high-temperature processing treatment is performed at 300°C or higher.

[0051] The present invention also relates to an adhesive film having an adhesive layer containing the curable resin composition of the present invention. As described above, the adhesive film having an adhesive layer containing the curable resin composition of the present invention is suitably used as a temporary fixing material, but depending on the application, it can also be used as a patch used to fix parts, etc.

[0052] A temporary fixing material containing the curable resin composition of the present invention also constitutes the present invention. The temporary fixing material of the present invention may be an adhesive that is liquid at room temperature, or may be an adhesive film having an adhesive layer that contains the curable resin composition of the present invention.

[0053] The method for producing the imide resin material of the present invention is not particularly limited, and can be obtained, for example, by reacting a diamine compound with an aromatic acid anhydride to prepare an imide intermediate, and then reacting the terminal of the imide intermediate with, for example, maleic anhydride. In this process, the weight average molecular weight (Mw) and polydispersity of the entire imide resin material, the content ratio of low molecular weight components in the imide resin material, and other factors can be adjusted by adjusting the reaction conditions, dehydration conditions, purification conditions, reaction equivalents, and the like.

[0054]

[0033] Furthermore, the method for producing the curable resin composition of the present invention is not particularly limited, and for example, a solution containing the curable resin composition of the present invention can be obtained by adding the obtained imide resin material of the present invention, and, if necessary, a polymerization initiator, a solvent, and an additive, and thoroughly stirring and mixing them, etc.

[0034] Furthermore, the method for producing the adhesive film of the present invention is not particularly limited, and for example, the adhesive film of the present invention can be obtained by applying a solution containing the curable resin composition of the present invention obtained by the above-mentioned method onto the release-treated surface of a release PET film, drying it to form an adhesive layer containing the curable resin composition of the present invention, and then overlapping the release-treated surface of a separately prepared release PET film so that it faces the formed adhesive layer, etc.

[0055] The present invention also provides a method for producing an imide resin material, which comprises Step I of reacting a diamine compound with a difunctional or higher aromatic acid anhydride to prepare an imide intermediate, and Step II of introducing a maleimide group into the terminal of the imide intermediate to prepare a compound represented by formula (1), wherein in Step I, the molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride (moles of diamine compound / moles of difunctional or higher aromatic acid anhydride) is 1.5 or greater. Note that, in this specification, the term "moles" refers to the amount (moles) of compounds at the time of their introduction as raw materials.

[0056] Examples of the diamine compound and the di- or higher functional aromatic acid anhydride used in the above step I include the same diamine compound and the di- or higher functional aromatic acid anhydride as described above.

[0057] In step I, the preferred lower limit of the molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride (moles of diamine compound / moles of difunctional or higher aromatic acid anhydride) is 1.5. By having a molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride of 1.5 or higher, the content of the low molecular weight component in the resulting imide resin material can be increased, making it easier to adjust the content within the above-mentioned range. A more preferred lower limit of the molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride is 1.6. Furthermore, a preferred upper limit of the molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride is 2.0. By having a molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride of 2.0 or less, the content of the low molecular weight component in the resulting imide resin material can be prevented from increasing too much, resulting in an imide resin material with high cohesive strength and excellent adhesiveness. The upper limit of the blending molar ratio of the diamine compound to the di- or higher functional aromatic acid anhydride is more preferably 1.9, and even more preferably 1.8.

[0058] In the above step I, the method for preparing the imide intermediate by reacting the diamine compound with the difunctional or higher aromatic acid anhydride is not particularly limited, and examples thereof include a method in which the diamine compound, the difunctional or higher aromatic acid anhydride, and a solvent are added and thoroughly stirred.

[0059] In the above step II, a method for introducing a maleimide group into the terminal of the imide intermediate may, for example, be a method in which maleic anhydride or the like is further added to the solution of the imide intermediate obtained in the above step I and reacted.

[0060] In the method for producing an imide resin material of the present invention, it is preferable to purify the product obtained in step II by a purification method that does not involve washing the product with a solvent. By purifying the imide resin material by a purification method that does not involve washing the product with a solvent, the content of the low-molecular-weight components in the imide resin material obtained after purification can be increased, making it easier to adjust the content within the above-mentioned range.

[0061] Examples of purification methods that do not use the solvent to wash the product include the following. First, the solution containing the product obtained in step II is transferred to a separatory funnel, pure water is added, the mixture is shaken, and the water is then allowed to stand to separate and remove. The solution remaining in the separatory funnel is then filtered through a glass-fritted funnel packed with silica gel, after which the solvent can be purified by vacuum removal. Examples of purification methods that do not use the solvent to wash the product include a method in which the solution containing the product obtained in step II is passed through an ion exchange resin, followed by filtration through a glass-fritted funnel packed with silica gel, followed by vacuum removal of the solvent; and a method in which a base is added to the solution containing the product obtained in step II, followed by filtration through a glass-fritted funnel packed with silica gel, followed by vacuum removal of the solvent.

[0062] In the method for producing an imide resin material of the present invention, it is preferable to prepare a polyimide resin by purifying the imide compound represented by formula (1) and then adding the other imide compounds described above. By adding the other imide compounds, the content of the low-molecular-weight components in the obtained imide resin material can be increased, making it easier to adjust the content within the above-mentioned range.

[0063] According to the present invention, an imide resin material can be provided that exhibits high initial adhesive strength when applied before curing, and has excellent heat resistance and UV curability. Furthermore, according to the present invention, a curable resin composition containing the imide resin material can be provided. Furthermore, according to the present invention, a curable resin composition can be provided that exhibits high initial adhesive strength when applied before curing, and has excellent heat resistance and UV curability. Furthermore, according to the present invention, an adhesive film having an adhesive layer containing the curable resin composition and a temporary fixing material containing the curable resin composition can be provided. Additionally, according to the present invention, a method for producing the imide resin material can be provided.

[0064] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0065] (Preparation of Imide Resin Material) (Example 1) 300 mL of toluene was placed in a 1000 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. Next, 75 g of N-methyl-2-pyrrolidone and 107 g (0.2 mol) of dimer diamine ("Priamine 1075" manufactured by Croda) were added and stirred for 5 minutes. 9.6 g (0.1 mol) of methanesulfonic anhydride was added and stirred for an additional 15 minutes. 21.8 g (0.1 mol) of pyromellitic anhydride was then added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 6 hours to obtain a solution containing an imide intermediate. After the solution containing the imide intermediate was cooled to below room temperature, 19.6 g (0.2 mol) of maleic anhydride was added. After refluxing the mixture for an additional 6 hours, the resulting reaction solution was cooled to room temperature and transferred to a 1 L separatory funnel. 150 mL of pure water was added to the separatory funnel, and the mixture was shaken and then allowed to stand to separate and remove the aqueous layer. The resulting solution was filtered through a glass fritted funnel filled with silica gel, and the solvent was then removed under vacuum to obtain an amber-colored wax-like compound A-1 having a structure represented by the following formula (6), which is represented as the compound of formula (1) above. Compound A-1 was used as an imide resin material. The resulting imide resin material was subjected to gel permeation chromatography (GPC) using an APC system (manufactured by Waters Corporation) under the following conditions: column HR-MB-M 6.0 x 150 mm (manufactured by Waters Corporation), mobile phase THF, flow rate 1.0 mL / min, column temperature 40°C, sample concentration 0.2% by mass, and RI-PDA detector. The overall weight-average molecular weight was 6,000. Furthermore, the content of low molecular weight components was calculated by calculating the peak area of ​​the low molecular weight components in the molecular weight distribution curve obtained in the GPC measurement, and the result was 60.4% by mass. Furthermore, the resulting imide resin material was subjected to separation of low molecular weight components using a silica gel column, and then １H-NMR measurement revealed that the imide resin material contained a compound represented by any one of the following formulas (7-1) to (7-3) as compound (3) (weight average molecular weight: 997), and a compound represented by any one of the following formulas (8-1) to (8-3) as compound (4) (weight average molecular weight: 2151). The peak areas of compound (3) and compound (4) in the molecular weight distribution curve obtained by GPC measurement were calculated to calculate the respective contents of compound (3) and compound (4). The results were as follows: the content of compound (3) was 20.3% by mass, and the content of compound (4) was 22.7% by mass. The results are shown in Table 2.

[0066]

[0067] In formula (6), n is an integer of 1 or more.

[0068]

[0069]

[0070] In formulas (8-1) to (8-3), X ３ and X ４ each independently represents a structure of either formula (5-1) or formula (5-2).

[0071] Example 2 Compound A-2 having a structure represented by the above formula (6) was obtained by the same method as in Example 1, except that the amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. Compound A-2 was used as an imide resin material. Furthermore, the weight-average molecular weight of the entire imide resin material and the content of low-molecular-weight components were measured by the same method as in Example 1. The overall weight-average molecular weight was 7,000, and the content of low-molecular-weight components was 45% by mass. Furthermore, by the same method as in Example 1, it was found that the obtained imide resin material contained a compound represented by any one of the above formulas (7-1) to (7-3) as compound (3) (weight-average molecular weight: 997), and a compound represented by any one of the above formulas (8-1) to (8-3) as compound (4) (weight-average molecular weight: 2,151). The contents of the compound (3) and the compound (4) were calculated in the same manner as in Example 1. The results were that the content of the compound (3) was 11.7% by mass and the content of the compound (4) was 15.4% by mass. The results are shown in Table 2.

[0072] Example 3 Compound A-3 having a structure represented by the above formula (6) was obtained by the same method as in Example 1, except that the amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. Compound A-3 was used as an imide resin material. Furthermore, the weight-average molecular weight of the entire imide resin material and the content of low molecular weight components were measured by the same method as in Example 1. The overall weight-average molecular weight was 8,000, and the content of low molecular weight components was 31.1% by mass. Furthermore, by the same method as in Example 1, it was found that the obtained imide resin material contained a compound represented by any one of the above formulas (7-1) to (7-3) as compound (3) (weight-average molecular weight: 997), and a compound represented by any one of the above formulas (8-1) to (8-3) as compound (4) (weight-average molecular weight: 2,151). The contents of the compound (3) and the compound (4) were calculated in the same manner as in Example 1. The results are shown in Table 2.

[0073] Example 4 Compound A-4 having a structure represented by the above formula (6) was obtained by the same method as in Example 1, except that the amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. Compound A-4 was used as an imide resin material. Furthermore, the weight-average molecular weight of the entire imide resin material and the content of low molecular weight components were measured by the same method as in Example 1. As a result, the overall weight-average molecular weight was 10,000, and the content of low molecular weight components was 18.0% by mass. Furthermore, by the same method as in Example 1, it was found that the obtained imide resin material contained a compound represented by any one of the above formulas (7-1) to (7-3) as compound (3) (weight-average molecular weight: 997), and a compound represented by any one of the above formulas (8-1) to (8-3) as compound (4) (weight-average molecular weight: 2151). The contents of the compound (3) and the compound (4) were calculated in the same manner as in Example 1. The results are shown in Table 2.

[0074] Example 5 Compound A-5 having a structure represented by the above formula (6) was obtained by the same method as in Example 1, except that the blending amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. The weight-average molecular weight and the content of low-molecular-weight components of the obtained compound A-5 were measured by the same method as in Example 1. As a result, the overall weight-average molecular weight was 20,000 and the content of low-molecular-weight components was 3.0% by mass. 30 parts by mass of a bismaleimide compound represented by the above formula (7-1) (manufactured by Designers Molecules, "BMI-689") was added to 70 parts by mass of the solid content of the obtained compound A-5, and the mixture was thoroughly stirred to prepare an imide resin material. Furthermore, the weight-average molecular weight and the content of low-molecular-weight components of the entire imide resin material were measured by the same method as in Example 1. As a result, the overall weight-average molecular weight was 15,000 and the content of low-molecular-weight components was 21% by mass. Furthermore, using a method similar to that used in Example 1, it was found that the obtained imide resin material contained, as the compound (3), a compound represented by the formula (7-1) above (including the bismaleimide compound described above) and a compound represented by any one of the following formulas (7-2) to (7-3) (weight average molecular weight: 997), and as the compound (4), a compound represented by any one of the formulas (8-1) to (8-3) (weight average molecular weight: 2151). The contents of the compound (3) and the compound (4) were calculated using the same method as in Example 1, and the results were that the content of the compound (3) was 4.5% by mass and the content of the compound (4) was 8.0% by mass. The results are shown in Table 2.

[0075] Example 6 Preparation of Compound B 431 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. Next, 107.0 g (0.2 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 104 g (0.2 mol) of isopropylidenediphenoxydiphthalic anhydride (BISDA-1000, manufactured by Sabic Corporation) were added in this order. A Dean-Stark trap and a condenser were attached to the flask, and the mixture was refluxed for 5 hours to synthesize Compound B having the structural unit shown in formula (9) below.

[0076] (Preparation of Imide Resin Material) Compound A-6 having a structure represented by the above formula (6) was obtained by the same method as in Example 1, except that the blending amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. The weight-average molecular weight and the content of low-molecular-weight components of the obtained Compound A-6 were measured by the same method as in Example 1. As a result, the overall weight-average molecular weight was 3,500 and the content of low-molecular-weight components was 75% by mass. An imide resin material was prepared by adding 10 parts by mass of the solid content of the obtained Compound B to 90 parts by mass of the solid content of the obtained Compound A-6 and thoroughly stirring. Furthermore, the weight-average molecular weight and the content of low-molecular-weight components of the entire imide resin material were measured by the same method as in Example 1. As a result, the overall weight-average molecular weight was 18,000 and the content of low-molecular-weight components was 8.0% by mass. Furthermore, using the same method as in Example 1, it was found that the obtained imide resin material contained a compound represented by any one of the formulas (7-1) to (7-3) above (weight average molecular weight: 997) as the compound (3), and a compound represented by any one of the formulas (8-1) to (8-3) above (weight average molecular weight: 2151) as the compound (4). The contents of the compound (3) and the compound (4) were calculated using the same method as in Example 1, and the results were that the content of the compound (3) was 1.4% by mass and the content of the compound (4) was 3.0% by mass. The results are shown in Table 2.

[0077]

[0078] Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that the amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. The resulting reaction mixture was cooled to room temperature, and then reprecipitation was carried out by adding an excess amount of ethanol to the reaction mixture and washing with stirring. The yellow precipitate was purified to obtain Compound A-7 having a structure represented by Formula (6) above. Compound A-7 was used as an imide resin material. Furthermore, the weight-average molecular weight of the entire imide resin material and the content of low-molecular-weight components were measured in the same manner as in Example 1. The overall weight-average molecular weight was 10,000, and the content of low-molecular-weight components was 2.0% by mass. Furthermore, using the same method as in Example 1, it was found that the resulting imide resin material contained a compound represented by any one of Formulas (7-1) to (7-3) above as Compound (3) (weight-average molecular weight: 997), and a compound represented by any one of Formulas (8-1) to (8-3) above as Compound (4) (weight-average molecular weight: 2151). The contents of the compound (3) and the compound (4) were calculated in the same manner as in Example 1. The results are shown in Table 2.

[0079] (Comparative Example 2) Compound A-8 having a structure represented by the above formula (6) was obtained by the same method as in Example 1, except that the blending amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. Compound A-8 was used as an imide resin material. Furthermore, the weight-average molecular weight of the entire imide resin material and the content of low molecular weight components were measured by the same method as in Example 1. As a result, the overall weight-average molecular weight was 20,000, and the content of low molecular weight components was 3.0% by mass. Furthermore, by the same method as in Example 1, it was found that the obtained imide resin material contained a compound represented by any one of the above formulas (7-1) to (7-3) as compound (3) (weight-average molecular weight: 997), and a compound represented by any one of the above formulas (8-1) to (8-3) as compound (4) (weight-average molecular weight: 2151). The contents of the compound (3) and the compound (4) were calculated in the same manner as in Example 1. The results are shown in Table 2.

[0080] (Comparative Example 3) Compound A-9 having a structure represented by the above formula (6) was obtained by the same method as in Comparative Example 1, except that the blending amounts of pyromellitic anhydride, dimer diamine, and maleic anhydride were changed as shown in Table 1. Compound A-9 was used as an imide resin material. Furthermore, the weight-average molecular weight of the entire imide resin material and the content of low molecular weight components were measured by the same method as in Example 1. As a result, the overall weight-average molecular weight was 3,500, and the content of low molecular weight components was 75% by mass. Furthermore, by the same method as in Example 1, it was found that the obtained imide resin material contained a compound represented by any one of the above formulas (7-1) to (7-3) as compound (3) (weight-average molecular weight: 997), and a compound represented by any one of the above formulas (8-1) to (8-3) as compound (4) (weight-average molecular weight: 2,151). The contents of the compound (3) and the compound (4) were calculated in the same manner as in Example 1. The results are shown in Table 2.

[0081]

[0082] <Evaluation> To 100 parts by mass of each imide resin material obtained in the Examples and Comparative Examples, 2 parts by mass of a photopolymerizable initiator ("Omnirad 819" manufactured by IGM Resins) was added, and toluene was added to a solids concentration of 50% to prepare a solution containing a curable resin composition. The obtained solution containing a curable resin composition was applied with a doctor knife to the release-treated surface of a 50 μm polyethylene terephthalate film with one side treated for release, so that the dry film thickness was 40 μm, and the film was dried by heating at 110°C for 5 minutes. The release-treated surface of a 25 μm thick polyethylene terephthalate film (separator film) with one side treated for release was bonded to the other side of the obtained film, yielding a film composed of the curable resin composition sandwiched between the separators. The obtained film composed of the curable resin composition was evaluated as follows. The results are shown in Table 2.

[0083] (1) UV curing: A film made of a curable resin composition is exposed to a 405 nm wavelength irradiation intensity of 100 mW / cm ２ UV rays of 6000mJ / cm ２ After the irradiation, the separator was removed from the film made of the curable resin composition, and the film was cut into a 50 mm x 100 mm flat rectangular shape to prepare a test piece. The test piece was immersed in toluene at 23°C for 24 hours, then removed from the toluene and dried at 110°C for 1 hour. The mass of the dried test piece was measured, and the gel fraction was calculated using the following formula (I): Gel fraction (mass%) = 100 x (W ２ -W ０ ) / (W １ -W ０ ) (I) (W ０ : Mass of the substrate, W １ : mass of test piece before immersion, W ２ (Wt: mass of test piece after immersion and drying) When the gel fraction after irradiation was 60 mass % or more, it was marked as "○", and when it was less than 60 mass %, it was marked as "×", and the UV curability was evaluated.

[0084] (2) Heat Resistance A film made of a curable resin composition was cut into a size of 50 mm wide x 50 mm long to prepare a test piece. The obtained test piece was irradiated with light of a wavelength of 405 nm from an ultra-high pressure mercury lamp at an integrated light intensity of 6000 mJ / cm. ２ The irradiation intensity was 100 mW / cm ２ The curable resin composition was cured by irradiating the cured resin composition for 60 seconds. A 4 mm diameter circle was cut out from the cured test piece, and the piece was weighed into an aluminum pan. The aluminum pan was placed in a differential thermal and thermogravimetric simultaneous measurement device (Hitachi High-Tech Science Corporation, "STA7200RV") and heated from 25°C to 300°C at a temperature increase rate of 10°C / min under a nitrogen atmosphere to perform differential thermal and thermogravimetric simultaneous measurement, and the residual weight ratio at 300°C was measured. Note that no separator was laminated on the test piece. Heat resistance was evaluated by assigning "○" when the measured residual weight ratio at 300°C was 95% or more and "×" when it was less than 95%.

[0085] (3) Initial adhesive strength before curing A film made of a curable resin composition was cut to a width of 1 inch, one separator was peeled off, and then the film was heat-laminated to a 1 mm thick glass (Matsunami Glass Industrial Co., Ltd., "Large Slide Glass White Edge Polished No. 2") using a laminator (Lamy Corporation, "Leon 13DX", speed memory 5) at 100 ° C. to prepare a measurement sample. The obtained measurement sample was subjected to a 180 ° peel test at 25 ° C. and a tensile speed of 300 mm / min using a tensile tester (Shimadzu Corporation, "AG-IS") to measure the peel strength from the glass at 25 ° C. The initial adhesive strength before curing was evaluated as follows: if the peel strength from the glass at 25 ° C. was 1 N / inch or more, it was marked "○", and if it was less than 1 N / inch, it was marked "X".

[0086] (4) Adhesion strength after curing A film made of a curable resin composition was cut to a width of 25 mm, one separator was peeled off, and then the film was heat-laminated to a 1 mm thick glass ("Large Slide Glass with White Polished Edge No. 2" manufactured by Matsunami Glass Industrial Co., Ltd.) using a laminator ("Leon 13DX" manufactured by Lamy Corporation, speed memory 5) at 100 ° C. to prepare a laminate. The prepared laminate was irradiated from the glass side with a wavelength of 405 nm and an irradiation intensity of 100 mW / cm using an ultra-high pressure mercury lamp. ２ UV rays of 6000mJ / cm ２ After irradiating the laminate, the other separator of the film was peeled off, and the glass side of the laminate was placed on a hot plate heated to 300°C and heated for 10 minutes to prepare a measurement sample. After air-cooling the measurement sample, a 180° peel test was performed on the measurement sample in accordance with JIS Z0237 using a tensile tester (Shimadzu Corporation, "AG-IS") at 25°C and a tensile speed of 300 mm / min, and the film was peeled from the glass. A peel force from the glass at 25°C of 0.3 N / inch or less was evaluated as "Good," a peel force greater than 0.3 N / inch but not greater than 3 N / inch was evaluated as "Fair," and a peel force greater than 3 N / inch was evaluated as "Poor." For Comparative Example 3, the wavelength was 405 nm and the irradiation intensity was 100 mW / cm. ２ UV rays of 6000mJ / cm ２ Immediately after irradiation, the film spontaneously peeled off from the glass, and the 180° peel test could not be carried out, so the evaluation was given as "-".

[0087]

[0088] According to the present invention, an imide resin material can be provided that exhibits high initial adhesive strength when applied before curing, and has excellent heat resistance and UV curability. Furthermore, according to the present invention, a curable resin composition containing the imide resin material can be provided. Furthermore, according to the present invention, a curable resin composition can be provided that exhibits high initial adhesive strength when applied before curing, and has excellent heat resistance and UV curability. Furthermore, according to the present invention, an adhesive film having an adhesive layer containing the curable resin composition and a temporary fixing material containing the curable resin composition can be provided. Additionally, according to the present invention, a method for producing the imide resin material can be provided.

Claims

1. An imide resin material composed of an imide compound, comprising a compound represented by the following formula (1), characterized in that the weight average molecular weight of the entire imide resin material is 5,000 or more, as measured by GPC, and the content of components having a weight average molecular weight of 500 or more and 3,000 or less in the imide resin material is 5 mass% or more. In formula (1), R ２１ and R ２２ each independently represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, or a substituted or unsubstituted aromatic group; R ２３ represents a substituted or unsubstituted aromatic group; m １ represents an integer of 1 or greater.

2. The above R ２１ and R ２２ 2. The imide resin material according to claim 1, wherein: is an aliphatic group derived from dimer diamine.

3. The imide resin material according to claim 1 or 2, wherein the aliphatic group derived from the dimer diamine includes at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4): In formulas (2-1) to (2-4), R １ ~R １６ each independently represents a linear or branched hydrocarbon group. In addition, * represents a bond. The bond * is bonded to N in the formula (1).

4. The component having a weight average molecular weight of 500 or more and 3000 or less is represented by the formula (1), m １ The imide resin material according to claim 1 , 2 or 3 , which contains a compound in which 5. The imide resin material according to claim 4, wherein the component having a weight average molecular weight of 500 or more and 3,000 or less includes at least one compound selected from the group consisting of the following formulas (3-1), (3-2), and (3-3): In formulas (3-1) to (3-3), R ３１ represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, or a substituted or unsubstituted aromatic group.

6. The imide resin material according to claim 4 or 5, wherein the component having a weight average molecular weight of 500 or more and 3,000 or less includes at least one compound selected from the group consisting of the following formulas (4-1), (4-2), and (4-3): In formulas (4-1) to (4-3), R ４１ represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, or a substituted or unsubstituted aromatic group; R ４３ represents a substituted or unsubstituted aromatic group; X １ and X ２ each independently represents a structure of the following formula (5-1) or (5-2).

7. A curable resin composition containing the imide resin material according to claim 1, 2, 3, 4, 5 or 6.

8. A curable resin composition comprising a compound represented by the following formula (1) and a compound having a weight average molecular weight of 500 or more and 3000 or less as measured by GPC, wherein the compound represented by formula (1) has a weight average molecular weight of 500 or more and 3000 or less as measured by GPC, and the content of the compound having a weight average molecular weight of 500 or more and 3000 or less in the curable resin composition is 5.0 mass% or more. In formula (1), R ２１ and R ２２ each independently represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, or a substituted or unsubstituted aromatic group; R ２３ represents a substituted or unsubstituted aromatic group; m １ represents an integer of 1 or greater.

9. The compound having a weight average molecular weight of 500 or more and 3000 or less is represented by the formula (1), m １ The curable resin composition according to claim 8 , comprising a compound in which 10. An adhesive film having an adhesive layer containing the curable resin composition according to claim 7, 8 or 9.

11. A temporary fixing material containing the curable resin composition according to claim 7, 8 or 9.

12. A method for producing an imide resin material according to claim 1, 2, 3, 4, 5 or 6, comprising: step I of reacting a diamine compound with a difunctional or higher aromatic acid anhydride to prepare an imide intermediate; and step II of introducing a maleimide group into the end of the imide intermediate to prepare a compound represented by formula (1), wherein in step I, the molar ratio of the diamine compound to the difunctional or higher aromatic acid anhydride (moles of diamine compound / moles of difunctional or higher aromatic acid anhydride) is 1.5 or more.

13. A method for producing an imide resin material as described in claim 12, wherein in step I, the molar ratio of the diamine compound to the di- or higher functional aromatic acid anhydride (moles of diamine compound / moles of di- or higher functional aromatic acid anhydride) is 2.0 or less.

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