JP5147137B2 - Composition for polyimide resin - Google Patents

Description

  The present invention relates to a composition for polyimide resin. More specifically, a polyimide resin composition having high transparency, yellowing suppression, excellent heat resistance, and excellent mechanical strength and adhesion when formed into a thin film, obtained by reacting the composition. The present invention relates to a polyimide resin composition, a polyimide film which is a sheet-like molded product of the resin composition, an adhesive comprising the film, a photosensitive substrate, and a method for producing the resin composition.

  Polyimide is a polymer excellent in heat resistance, light resistance, and mechanical strength. As a synthesis method thereof, for example, polycarboxylic acid dianhydride and a diamine derivative are polycondensated to produce a polyamic acid (polyamic acid) which is a polyimide precursor, and the obtained polyamic acid is heated or a catalyst. The method of imidizing using is mentioned.

  However, the polyimide obtained in this way is a linear (straight) polymer, has a poor three-dimensional network in the polymer, and has a problem in alkali resistance and film strength when formed into a thin film. In addition, since the linear polymer has weak interaction between the polymers, the adhesive force to the substrate such as glass or metal is weak, and it is necessary to treat the substrate surface with a primer in advance when bonding to the substrate. .

  On the other hand, for example, Patent Document 1 discloses a polyimide having many voids in which a multi-branched structure is formed in a molecule using a triamine derivative capable of three-dimensional crosslinking. In addition, a method of forming a resin composite by adding metal oxide fine particles such as silica treated with a specific surface treatment agent has been reported (see Patent Document 2).

JP 2006-131706 A Japanese Patent Laid-Open No. 7-304886

  However, when a polyimide is prepared using a triamine derivative, depending on the amount of use, there is a problem that crosslinking occurs excessively at the time of polyamic acid generation, and the resulting resin is gelled and difficult to imidize.

  In addition, the metal oxide fine particles treated with the conventional surface treatment agent disperse well in the polyamic acid, but the dispersibility to the low-polarity polyimide is not yet sufficient, and during the conversion from polyamic acid to polyimide, Aggregation is likely to occur.

  Furthermore, when the polyamic acid is heated to imidize, the resulting resin tends to yellow.

  An object of the present invention is to provide a polyimide resin composition having high transparency, yellowing suppression, excellent heat resistance, and excellent mechanical strength and adhesiveness when formed into a thin film, and reacting the composition. It is in providing the polyimide resin composition obtained by this, the polyimide film which is a sheet-like molding of this resin composition, the adhesive agent which consists of this film, a photosensitive base material, and the manufacturing method of the said resin composition.

The present invention
[1] Carboxylic acid compound anhydride, diamine compound, and formula (I):

(In the formula, R ¹ represents an epoxy structure-containing substituent, R ² , R ³ and R ⁴ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
It is a composition for polyimide resin containing the metal oxide fine particle processed with the surface treating agent containing trifunctional alkoxysilane represented by these, Comprising: The average particle of the metal oxide fine particle after the said surface treatment A polyimide resin composition having a diameter of 1 to 20 nm ,
[2] A polymer obtained by polymerizing an anhydride of a carboxylic acid compound and a diamine compound is converted into a compound of formula (I):

(In the formula, R ¹ represents an epoxy structure-containing substituent, R ² , R ³ and R ⁴ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
A polyimide resin composition obtained by reacting a metal oxide fine particle treated with a surface treatment agent containing a trifunctional alkoxysilane represented by the formula at 100 ° C. or higher, the metal oxide after the surface treatment A polyimide resin composition having an average particle diameter of 1 to 20 nm of fine particles ,
[3] A polyimide film comprising the polyimide resin composition according to [2],
[4] An adhesive comprising the polyimide film according to [3],
[5] A photosensitive substrate comprising the polyimide film of [3], and [6] Formula (I):

(In the formula, R ¹ represents an epoxy structure-containing substituent, R ² , R ³ and R ⁴ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
A step of polymerizing an anhydride of a carboxylic acid compound and a diamine compound at 23 to 80 ° C. in the presence of metal oxide fine particles treated with a surface treatment agent containing a trifunctional alkoxysilane represented by: A method for producing a polyimide resin composition comprising a step of reacting at 100 ° C. or higher after molding the reaction product obtained in the step , wherein the average particle size of the metal oxide fine particles after the surface treatment is 1 to 20 nm The present invention relates to a method for producing a polyimide resin composition .

  The composition for polyimide resin of the present invention provides a polyimide resin composition having high transparency, yellowing suppression, excellent heat resistance, and excellent mechanical strength and adhesiveness when formed into a thin film. Can do.

  The polyimide resin composition of the present invention contains an anhydride of a carboxylic acid compound, a diamine compound, and metal oxide fine particles, and the metal oxide fine particles are represented by the formula (I):

(In the formula, R ¹ represents an epoxy structure-containing substituent, R ² , R ³ and R ⁴ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
It has the big characteristic in having been processed by the surface treating agent containing trifunctional alkoxysilane represented by these.

Polyamide acid, which is a precursor of polyimide, is soluble in amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. On the other hand, polyimide is obtained by dehydration condensation (imidization) of polyamic acid and is insoluble in the solvent. Since the polarities of the two are greatly different in this way, even if the metal oxide fine particles are well dispersed in the polyamic acid, when the polyimide is formed, the metal oxide fine particles are not dispersed in the polyimide and cause aggregation. Therefore, in the present invention, it is possible to suppress the aggregation of the fine particles by binding the metal oxide fine particles obtained by the treatment with the surface treatment agent containing the compound represented by the above formula (I) to the resin. It became. That is, the compound represented by the formula (I) is present by bonding the —SiR ¹ group to the surface of the metal oxide fine particles by the surface treatment of the metal oxide fine particles. The R ¹ group is an epoxy structure-containing substituent, and the epoxy structure is opened upon reaction with the surface of the metal oxide fine particles or upon imidization to produce a hydroxy group. Such hydroxy groups can be dehydrated with the carboxy groups of the polyamic acid to bond the metal oxide fine particles to the resin through SiR ¹ groups. Since the metal oxide fine particles bonded in this way are well dispersed without agglomerating in the resin, high transparency can be maintained and light transmittance can be improved. Moreover, yellowing can be suppressed by combining the metal oxide fine particles and the resin. Furthermore, although the resin bond due to imidization is reduced, a three-dimensional network is formed, the interaction between the resins is strengthened, and the resin strength is imparted by the metal oxide fine particles. However, it has sufficient mechanical strength and has good adhesion to substrates such as glass and metal.

R ¹ in the formula (I) represents an epoxy structure-containing substituent. The epoxy structure-containing substituent is not particularly limited as long as it is an organic group containing at least one epoxy structure in the substituent. The epoxy structure may be present at any position of the substituent, but from the viewpoint of reactivity with the polyamic acid, it is located farthest from the terminal portion of the substituent, that is, the silicon atom to which R ¹ is bonded. It is preferable. In addition, the substituent preferably has 1 to 6 carbon atoms.

  Specific examples of such a substituent include an epoxyethyl group, an epoxycyclohexyl group, and a glycidoxypropyl group, and among them, an epoxycyclohexyl group and a glycidoxypropyl group are preferable.

R ² , R ³ and R ⁴ in the formula (I) each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Among these, a methyl group, an ethyl group, and a propyl group are preferable, and R ² , R ^3, and R ⁴ are all preferably a methyl group, an ethyl group, or a propyl group.

  Examples of the trifunctional alkoxysilane represented by the formula (I) include 2-[(3,4) -epoxycyclohexyl] ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. A triethoxysilane etc. are mentioned, These can be used individually or in combination of 2 or more types.

  The trifunctional alkoxysilane represented by the formula (I) can be synthesized according to a known method. Commercially available products include 2-[(3,4) -epoxycyclohexyl] ethyltrimethoxysilane as `` KBM-303 '' (manufactured by Shin-Etsu Silicone), 3-glycidoxypropyltriethoxysilane as `` KBM-403 (Shin-Etsu Silicone Co., Ltd.) is preferably used.

  The content of the trifunctional alkoxysilane represented by the formula (I) in the surface modifier is preferably 20% by weight or more, more preferably 30% by weight or more, from the viewpoint of the amount of crosslinking sites introduced into the resin. 50 to 100% by weight is more preferable.

  In the present invention, from the viewpoint of dispersibility of the metal oxide fine particles, other surface modifiers other than the trifunctional alkoxysilane represented by the formula (I) can be used. Other surface modifiers include methyl (trimethoxy) silane, ethyl (trimethoxy) silane, hexyl (trimethoxy) silane, decyl (trimethoxy) silane, vinyl (trimethoxy) silane, 2-[(3,4) -epoxycyclohexyl] Examples include ethyl (trimethoxy) silane, 3-glycidoxypropyl (trimethoxy) silane, 3-methacryloxypropyl (trimethoxy) silane, and 3-acryloxypropyl (trimethoxy) silane.

  The metal oxide fine particles to be surface-treated in the present invention are preferably at least one selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, silica, and alumina, and more preferably silica. In addition, the average particle diameter of the metal oxide fine particles to be surface-treated is preferably 1 to 100 nm from the viewpoint of transparency. In the present specification, the average particle diameter of the metal oxide fine particles can be measured according to the method described in Examples described later.

  The surface treatment method is not particularly limited and may be a known method. For example, a method (wet method) of stirring the metal oxide fine particles and the surface modifier in a solvent at 10 to 100 ° C. for 0.1 to 72 hours is exemplified.

  The amount of the surface modifier used is preferably 30 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the metal oxide fine particles to be surface treated.

  Thus, metal oxide fine particles surface-treated with a specific surface modifier can be obtained. The average particle diameter of the metal oxide fine particles after the surface treatment is preferably 1 to 100 nm, and more preferably 1 to 20 nm from the viewpoint of transparency of the polyimide resin composition obtained by reacting the fine particles. In addition, since the average particle diameter of the metal oxide fine particles is hardly changed by the surface treatment by the above method, in order to obtain the surface-treated metal oxide fine particles having a desired average particle diameter, the surface treatment is performed. What is necessary is just to adjust beforehand the average particle diameter of the metal oxide fine particle to be provided according to a well-known method.

  The content of the metal oxide fine particles after the surface treatment is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, and further preferably 1 to 10% by weight in the resin composition.

  The anhydride of the carboxylic acid compound in the present invention may be an anhydride of a divalent or higher carboxylic acid compound, but a dianhydride of a tetracarboxylic acid compound is preferable. Tetracarboxylic acid compound dianhydrides include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2 -Bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 4,4'-hexafluoroisopropylidene The dianhydride of aromatic tetracarboxylic acid compounds, such as a phthalic anhydride, is mentioned, These can be used individually or in combination of 2 or more types.

  Examples of the diamine compound in the present invention include m-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) Sulfide, bis (3-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) Sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 1, 3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) , 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4 -Aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, Bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-amino Phenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3 -(4-Aminophenoxy) benzoyl] diphenyl ether 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxy Benzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4 -Phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3 , 4'-Diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4- Biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-a No-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, bis (Trifluoromethyl) -1,1′-biphenyl-4,4′-diamine and the like can be mentioned, and these can be used alone or in combination of two or more.

  In the polyimide resin composition of the present invention, the molar ratio of carboxylic acid compound anhydride to diamine compound (carboxylic acid compound anhydride / diamine compound) is preferably 1.0 / 1.2 to 1.2 / 1.0, and 1.0 / 1.1 to 1.1. /1.0 is more preferable, and substantially equimolar (1.0 / 1.0) is more preferable.

  Moreover, in addition to the anhydride of the carboxylic acid compound, the diamine compound and the metal oxide fine particles, the resin composition of the present invention is an anti-aging agent, a modifier, a surfactant, as long as the effects of the present invention are not impaired. You may contain additives, such as dye, a pigment, a discoloration prevention agent, and an ultraviolet absorber.

  The polyimide resin composition of the present invention can be obtained by polymerizing the polyimide resin composition of the present invention. For example, a surface treatment is performed on a polymer obtained by polymerizing an anhydride of a carboxylic acid compound and a diamine compound. It can be prepared by reacting the subsequent metal oxide fine particles at 100 ° C. or higher.

  The polymerization reaction between the anhydride of the carboxylic acid compound and the diamine compound (hereinafter, also referred to as the polymerization reaction of the polyamic acid) can be carried out according to a known method. Preferably, the polymerization reaction of the carboxylic acid compound is performed in the presence of an organic solvent. An anhydride and a diamine compound are mixed. The anhydride of the carboxylic acid compound may be used after drying at a temperature of preferably 100 ° C. or higher, more preferably 100 to 150 ° C. before being subjected to the reaction.

  Organic solvents include N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolid Non, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, Tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphonamide, phenol, o-cresol, m-cresol, p-cresol, m-cresolic acid , P-chlorophenol, anisole, benzene, toluene, xylene, etc., and these may be used alone or in combination of two or more. It can be used Te. Among these, N, N-dimethylacetamide is preferable because of its solubility and a small degree of coloring upon heating during imidization.

  The polyamic acid polymerization reaction is carried out under normal pressure (101.3 kPa), if necessary under pressure or under reduced pressure, preferably at a temperature of less than 100 ° C., more preferably 23-80 ° C. The reaction time is not generally determined by the type of anhydride of the carboxylic acid compound and the diamine compound, the type of the organic solvent, and the reaction temperature, but usually 1 to 24 hours is preferable.

  In the reaction, in order to adjust the solution viscosity, the organic solvent may be added while being added as appropriate.

  Next, the polymer oxide obtained above is reacted by heating the metal oxide fine particles after the surface treatment (hereinafter also referred to as thermal imidization reaction). The heating temperature is 100 ° C. or higher, preferably 100 to 300 ° C., more preferably 150 to 300 ° C. The heating time is preferably 1 to 5 hours. The heating may be carried out at a constant temperature for a fixed time, for example, at 100 to 150 ° C. for 1 to 2 hours, 150 to 200 ° C. for 1 to 2 hours, 200 to 300 ° C. for 1 to 2 hours. And may be performed in multiple stages.

  The metal oxide fine particles after the surface treatment can be reacted by adding and mixing after preparing a polyamic acid polymer. Further, from the viewpoint of dispersibility of the metal oxide fine particles in the obtained resin composition, the metal oxide fine particles after the surface treatment are added in advance at the start of the polymerization of the polyamic acid, and the polyamic acid polymerization reaction is performed on the metal oxide fine particles. The thermal imidization reaction may be performed after the metal oxide fine particles are uniformly dispersed in the polymerized product.

  In addition, after the thermal imidization reaction, a polymer of an anhydride of a carboxylic acid compound and a diamine compound, that is, a mixture of a polyamic acid polymer and metal oxide fine particles after surface treatment is formed in advance. Can be subjected to reaction. Specifically, for example, after coating the mixture to an appropriate thickness by a method such as casting, spin coating, roll coating, etc. on a Kapton film, 100 ° C or higher, preferably 100-300 ° C, more preferably 150 The sheet-like polyimide resin composition can be obtained by heating at ˜300 ° C. to simultaneously remove the solvent and imidize. Therefore, this invention provides the polyimide film by which the polyimide resin composition of this invention was shape | molded in the sheet form. Examples of the film include those having a thickness of about 10 to 200 μm, preferably 30 to 120 μm. The heating time varies depending on the type of resin and solvent and the heating temperature, and cannot be determined unconditionally, but 1 to 6 hours are preferable.

  The polyimide film is a sheet of the polyimide resin composition of the present invention, which has high transparency, suppressed yellowing, excellent heat resistance, and mechanical strength and adhesion when formed into a thin film. It is also excellent in properties. Therefore, it is suitably used as an adhesive or a photosensitive substrate.

  If the polyimide film of this invention is used, an adhesive agent and a photosensitive base material can be prepared according to a well-known method.

  Moreover, this invention provides the manufacturing method of the polyimide resin composition of invention. The method is not particularly limited as long as it includes a step of reacting the metal oxide fine particles after the surface treatment with the polymer obtained by polymerizing the anhydride of the carboxylic acid compound and the diamine compound. Specifically, from the viewpoint of dispersibility of the metal oxide fine particles in the resin composition to be obtained, in the presence of the metal oxide fine particles after the surface treatment, the anhydride of the carboxylic acid compound and the diamine compound are added at 23 to 80 ° C. A method comprising a step of carrying out a polymerization reaction (hereinafter also referred to as step (A)) and a step of reacting at 100 ° C. or higher after forming the reaction product obtained in the step (hereinafter also referred to as step (B)) is preferred. .

  Specific examples of the step (A) include, for example, a diamine compound such as dimethylacetamide in the presence of fine metal oxide particles treated with a surface treatment agent containing a trifunctional alkoxysilane represented by the formula (I). To the liquid prepared so as to have a concentration of 20 to 40% by weight in an organic solvent, preferably an anhydride of a carboxylic acid compound dried at 100 ° C. or higher, more preferably 100 to 150 ° C., preferably Examples include a step of reacting at 23 to 80 ° C., more preferably 23 to 60 ° C., and preferably 1 to 24 hours.

  As a specific example of the step (B), for example, the polymer obtained in the step (A) is coated to an appropriate thickness by a method such as casting, spin coating, roll coating, etc., and then 100 ° C. or higher, preferably 100 The process of making it react at -300 degreeC, More preferably, 150-300 degreeC is illustrated. The reaction time is preferably 1 to 12 hours, more preferably 1 to 6 hours.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited at all by these Examples.

[Average particle diameter of metal oxide fine particles]
The average particle size of the metal oxide fine particles is the average particle size of the primary particles of the metal oxide fine particles. The transmission electron microscope TEM is used to measure the diameter of 100 particles in the image. Let the average value be the average particle size.

Surface treatment example 1 of metal oxide fine particles
In a container equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 10.0 g of a colloidal silica aqueous dispersion having an average particle size of 15 nm (trade name: Snowtex OS, manufactured by Nissan Chemical Co., Ltd., solid concentration 20 wt%), and 15.0 g of methanol was added. As a surface treatment agent, 2-[(3,4) -epoxycyclohexyl] ethyltrimethoxysilane [trade name: KBM-303, manufactured by Shin-Etsu Silicone Co., Ltd., R ¹ in the formula (I) is 3,4-epoxy Cyclohexyl group, R ² , R ³ and R ⁴ are methyl groups] A solution obtained by dissolving 2.0 g (100 parts by weight with respect to 100 parts by weight of metal oxide fine particles) in 5.0 g of methanol was added for 1 second using a dropping funnel. The mixture was dropped and mixed at a dropping speed so as to drop one drop at a time, and stirred at 60 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, 3 g of dimethylacetamide was added, methanol and water were then distilled off using a rotary evaporator to adjust the solid concentration to 20% by weight, and a dimethylacetamide dispersion of surface-treated silica ( Silica dispersion A) was obtained.

Example 2 of surface treatment of metal oxide fine particles
Using the same equipment as in Surface Treatment Example 1, instead of using 10.0 g of colloidal silica aqueous dispersion (Snowtex OS) and 15.0 g of methanol, a colloidal silica aqueous dispersion (trade name: Snowtex OSX with an average particle size of 5 nm) Surface treatment silica dimethylacetamide dispersion (silica dispersion B) in the same manner as in surface treatment example 1 except that 20.0 g of solid chemical concentration, manufactured by Nissan Chemical Co., Ltd. and 20.0 g of methanol were used. )

Surface treatment example 3 of metal oxide fine particles
Instead of using 2.0 g of KBM-303 as the surface treatment agent, using the same apparatus as in Surface Treatment Example 1, 3-glycidoxypropyltriethoxysilane [trade name: KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd. Except for the use of 2.0 g (100 parts by weight with respect to 100 parts by weight of metal oxide fine particles)] in which R ¹ in I) is 3-glycidoxypropyl group, R ² , R ³ and R ⁴ are ethyl groups In the same manner as in Treatment Example 1, a surface-treated dimethylacetamide dispersion of silica (silica dispersion C) was obtained.

Surface treatment example 4 of metal oxide fine particles
Using the same equipment as in Surface Treatment Example 1, instead of using 2.0 g of KBM-303 as the surface treatment agent, 1.5 g of KBM-303 and hexyltrimethoxysilane [trade name: KBM-3063, manufactured by Shin-Etsu Silicone Co., Ltd. In the formula (I), R ¹ is a hexyl group, R ² , R ³ and R ⁴ are methyl groups] 0.5 g (total amount used is 100 parts by weight with respect to 100 parts by weight of metal oxide fine particles) Produced surface-treated dimethylacetamide dispersion (silica dispersion D) in the same manner as in surface treatment example 1.

Surface treatment example 5 of metal oxide fine particles
Instead of using 2.0 g of KBM-303 as the surface treatment agent, using the same apparatus as in Surface Treatment Example 1, methyltrimethoxysilane [trade name: KBM-13, manufactured by Shin-Etsu Silicone, R ¹ in formula (I) Is a methyl group, R ² , R ^3, and R ⁴ are methyl groups], except that 2.0 g (100 parts by weight with respect to 100 parts by weight of metal oxide fine particles) is used. A silica dimethylacetamide dispersion (silica dispersion E) was obtained.

Example 1
In a container equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 10.81 g of bis [4- (3-aminophenoxy) phenyl] sulfone (trade name: m-BAPS, manufactured by Wakayama Seika Co., Ltd.) as a diamine derivative, And 20 g of anhydrous dimethylacetamide were added to dissolve the diamine derivative. Thereto, 0.75 g of silica dispersion A at room temperature (25 ° C.) and 8.97 g of oxydiphthalic anhydride (trade name: ODPA, Manac) previously dried at 150 ° C. for 3 hours are added, and the viscosity is adjusted. Therefore, a total amount of 8 g of anhydrous dimethylacetamide was appropriately added and stirred for 3 hours to obtain a polyamic acid solution. The obtained polyamic acid solution was applied to a Kapton film so as to have a film thickness of 100 μm, and heated successively at 100 ° C. for 1 hour, 150 ° C. for 1 hour, and 250 ° C. for 1 hour to obtain 2.5 wt% silica particles. A polyimide film containing was obtained.

Example 2
Using the same apparatus as in Example 1, instead of using 0.75 g of silica dispersion A and 8 g of anhydrous dimethylacetamide for adjusting viscosity, 3.75 g of silica dispersion A and 7.25 g of anhydrous dimethylacetamide for adjusting viscosity are used. A polyimide film containing 10% by weight of silica particles was obtained in the same manner as in Example 1 except that.

Example 3
In the same manner as in Example 1, except that 0.75 g of silica dispersion B was used instead of 0.75 g of silica dispersion A using the same apparatus as in Example 1, 2.5 wt% silica particles were contained. A polyimide film was obtained.

Example 4
Using the same apparatus as in Example 1, instead of using 8.97 g of oxydiphthalic anhydride (ODPA), except that 7.25 g of biphenyltetracarboxylic dianhydride (trade name: BPDA, manufactured by JFE Chemical) was used, In the same manner as in Example 1, a polyimide film containing 2.5% by weight of silica particles was obtained.

Example 5
Using the same apparatus as in Example 1, instead of using 10.81 g of the diamine derivative (m-BAPS) and 8.97 g of oxydiphthalic anhydride (ODPA), 2,2′-bis (trifluoromethyl) -1,1 '-Biphenyl-4,4'-diamine (trade name: m-TBFA, manufactured by Wakayama Seika Co., Ltd.) 6.40 g, 4,4'-hexafluoroisopropylidenediphthalic anhydride (trade name: 6FDA, manufactured by Clariant) ) A polyimide film containing 2.5% by weight of silica particles was obtained in the same manner as in Example 1 except that 8.88 g was used.

Example 6
In the same manner as in Example 1, except that 0.75 g of silica dispersion C was used instead of 0.75 g of silica dispersion A, 2.5 wt% silica particles were contained. A polyimide film was obtained.

Example 7
In the same manner as in Example 1, except that 0.75 g of silica dispersion D was used instead of 0.75 g of silica dispersion A using the same apparatus as in Example 1, 2.5 wt% silica particles were contained. A polyimide film was obtained.

Comparative Example 1
Using the same apparatus as in Example 1, instead of using 0.75 g of silica dispersion A, a commercially available organosilica sol (trade name: DMAC-ST, manufactured by Nissan Chemical Industries, dimethylacetamide solvent, silica concentration 20 wt%) 0.75 g A polyimide film containing 2.5% by weight of silica particles was obtained in the same manner as in Example 1 except that was used.

Comparative Example 2
Using the same apparatus as in Example 1, instead of using 0.75 g of silica dispersion A, a commercially available organosilica sol (trade name: DMAC-ST, manufactured by Nissan Chemical Industries, dimethylacetamide solvent, silica concentration 20 wt%) 0.75 g A polyimide film containing 2.5% by weight of silica particles was obtained in the same manner as in Example 4 except that was used.

Comparative Example 3
In the same manner as in Example 1, except that 0.75 g of silica dispersion E was used instead of 0.75 g of silica dispersion A using the same apparatus as in Example 1, 2.5 wt% silica particles were contained. A polyimide film was obtained.

Reference example 1
A polyimide film containing no silica particles was obtained in the same manner as in Example 1, except that the same apparatus as in Example 1 was used and 0.75 g of silica dispersion A was not used. The polyamic acid solution was applied on a glass plate to obtain a polyimide film.

Reference example 2
A polyimide film containing no silica particles was obtained in the same manner as in Example 4 except that the same apparatus as in Example 1 was used and 0.75 g of silica dispersion A was not used. The polyamic acid solution was applied on a glass plate to obtain a polyimide film.

Reference example 3
A polyimide film containing no silica particles was obtained in the same manner as in Example 5 except that the same apparatus as in Example 1 was used and 0.75 g of silica dispersion A was not used. The polyamic acid solution was applied on a glass plate to obtain a polyimide film.

  About the obtained polyimide film, it evaluated according to the method of the following test examples 1-5. The results are shown in Table 1. In Test Example 5, the polyimide film separately prepared by the method described in Test Example 5 was evaluated.

Test Example 1 [Haze]
The haze value of the film was measured using a haze meter (HR-100, manufactured by Murakami Color Co., Ltd.). A haze value of 3.0% or less means excellent transparency.

Test Example 2 [Light transmittance]
The light transmittance of the film with respect to a wavelength of 430 nm was measured using an ultraviolet-visible spectrum measuring instrument (U4100, manufactured by Hitachi). The numerical values in parentheses in the table are Examples 1, 2, 3, 6, 7 and Comparative Examples 1 and 3, the rate of increase / decrease relative to Reference Example 1, and Example 4 and Comparative Example 2 are Reference Examples. Example 5 shows the rate of increase / decrease relative to 2 and Example 5 shows the rate of increase / decrease relative to Reference Example 3. It means that the larger the increase rate, the less the coloring during the thermal imidization with respect to the film containing no metal oxide fine particles.

Test Example 3 [Heat resistance]
The light transmittance after the film was treated at 400 ° C. for 24 hours was measured in the same manner as in Test Example 2.

Test Example 4 [Elastic modulus]
The elastic modulus of the film was measured using an autograph (AGS-J, manufactured by Shimadzu Corporation). If the elastic modulus is 710 N / cm ² or more, it means excellent mechanical strength. The numerical values in parentheses in the table are Examples 1, 2, 3, 6, 7 and Comparative Examples 1 and 3, the rate of increase / decrease relative to Reference Example 1, and Example 4 and Comparative Example 2 are Reference Examples. Example 5 shows the rate of increase / decrease relative to 2 and Example 5 shows the rate of increase / decrease relative to Reference Example 3. It means that it is excellent in mechanical strength with respect to the film which does not contain metal oxide microparticles, so that an increase rate is large.

Test Example 5 [Adhesiveness]
After coating the polyamic acid solution on a Kapton film (length 10 cm, width 2 cm) to a film thickness of 100 μm, a glass plate was bonded on top of it, and 100 ° C. for 1 hour, 150 ° C. for 1 hour, An adhesive film obtained by imidization by sequential heating at 250 ° C. for 1 hour was obtained. Using the autograph (AGS-J, manufactured by Shimadzu Corporation), the peel strength (adhesive strength) was measured when the obtained adhesive film was peeled 90 degrees at a speed of 300 mm / min at room temperature (25 ° C). The adhesiveness was evaluated. If the peel strength is 200 N / cm ² or more, it means excellent adhesion.

  As a result, it can be seen that the compositions of the examples have lower haze, higher light transmittance, and better mechanical strength than the comparative examples. Moreover, while containing metal oxide fine particles, it was excellent in heat resistance and had very high peel strength. On the other hand, the composition of the comparative example was improved in mechanical strength by containing silica, but the dispersibility of silica was lowered by imidization, and the resin composition was weak and clouded.

Photosensitive base material 27 g of the polyamic acid solution (containing silica after the surface treatment) in Example 1 and 0.32 g of a photobase generator (1,4-dihydroxypyridine derivative, manufactured by Aldrich) (based on 100 parts by weight of polyamic acid) 4 parts by weight), and varnish added with UNIOX (MM-500, NOF Corporation) 2.43 g (30 parts by weight with respect to 100 parts by weight of polyamic acid) was applied to a film thickness of 30 μm using a spin coater. Then, pre-baking was performed at 90 ° C. for 15 minutes, and after placing a photomask (line / space = 200 μm / 50 μm, manufactured by Mitani Micronics), I-line 40 mJ was exposed. After exposure, heat (PEB) at 165 ° C for 10 minutes and immerse in undeveloped part for 6 minutes in developer (10% -TMAH aqueous solution / Echinen = 50/50 (weight ratio)) heated to 40 ° C. After complete removal, the remaining part was heat-cured on a hot plate in steps of 200 ° C for 33 minutes, 250 ° C for 33 minutes, 300 ° C for 33 minutes, and 385 ° C for 2 hours. By microscopic observation of the obtained cured product, it was confirmed that patterning was possible.

  The polyimide resin composition of the present invention is suitably used, for example, when producing electronic materials for semiconductors, coating materials, paints, separation membranes and the like.

Claims (7)

Carboxylic acid anhydrides, diamine compounds, and formula (I):

(In the formula, R ¹ represents an epoxy structure-containing substituent, R ² , R ³ and R ⁴ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
It is a composition for polyimide resin containing the metal oxide fine particle processed with the surface treating agent containing trifunctional alkoxysilane represented by these, Comprising: The average particle of the metal oxide fine particle after the said surface treatment A composition for polyimide resin having a diameter of 1 to 20 nm . A polymer obtained by polymerizing an anhydride of a carboxylic acid compound and a diamine compound is converted into a compound represented by the formula (I):

(In the formula, R ¹ represents an epoxy structure-containing substituent, R ² , R ³ and R ⁴ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
A polyimide resin composition obtained by reacting a metal oxide fine particle treated with a surface treatment agent containing a trifunctional alkoxysilane represented by the formula at 100 ° C. or higher, the metal oxide after the surface treatment A polyimide resin composition having an average particle diameter of 1 to 20 nm . 3. The polyimide resin composition according to claim 2 , wherein in the reaction, a mixture of a polymer of an anhydride of a carboxylic acid compound and a diamine compound and a metal oxide fine particle treated with a surface treatment agent is molded, and then subjected to the reaction. object. A polyimide film comprising the polyimide resin composition according to claim 3 . An adhesive comprising the polyimide film according to claim 4 . A photosensitive substrate comprising the polyimide film according to claim 4 . Formula (I):

(In the formula, R ¹ represents an epoxy structure-containing substituent, R ² , R ³ and R ⁴ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
A step of polymerizing an anhydride of a carboxylic acid compound and a diamine compound at 23 to 80 ° C. in the presence of metal oxide fine particles treated with a surface treatment agent containing a trifunctional alkoxysilane represented by: A method for producing a polyimide resin composition comprising a step of reacting at 100 ° C. or higher after molding the reaction product obtained in the step , wherein the average particle size of the metal oxide fine particles after the surface treatment is 1 to 20 nm The manufacturing method of the polyimide resin composition which is .