JP2004010664A - Material having resin layer thereon and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a resin layer (polyamic acid layer or polyimide layer) for coating the surface of a material uniformly with a very compact material that is strongly adhered to the surface. <P>SOLUTION: This method for manufacturing a material with a polyamic acid layer thereon, comprises (a) a step of forming a polyamic acid layer on the surface of a material by reacting a functional group on the surface of the material that is reactable with at least one of a tetracarboxylic anhydride and a diamine compound, with a tetracarboxylic anhydride and a diamine compound. The method for manufacturing a material with a polyimide layer thereon, comprises (a) a first step of forming a polyamic acid layer on the surface of the material, and (b) a second step of creating a polyimide layer by imidization of the polyamic acid layer. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel material having a resin layer on the surface and a method for producing the same.
[0002]
[Prior art]
Polyimide is excellent in heat resistance, chemical resistance, electric insulation and the like in addition to mechanical properties, and is widely used as an alternative material for electric and electronic materials, automobiles, and other metals and ceramics.
[0003]
Conventionally, a method for producing a polyimide thin film is a method in which a polyamide acid varnish is formed on a substrate using a method such as dipping, casting, or spin coating, and then imidized by heating or a catalyst; There is a method in which a certain diamine and tetracarboxylic anhydride are vacuum-deposited and then heated to imidize. However, the polyimide thin film obtained by the conventional method only physically adheres to the substrate, and can be coated only on a substrate having good adhesiveness. In addition, these methods do not allow nano-sized and controlled uniform coating on substrates having complicated shapes. Therefore, there is a need for a thin film that is more excellent in terms of adhesion to a substrate, denseness, uniformity, and the like.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel material having a resin layer (a polyamic acid layer or a polyimide layer) on the surface and a method for producing the same.
[0005]
[Means for Solving the Problems]
The present inventor has conducted intensive studies in view of the problems of the prior art, and as a result, using a material having a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound on the surface thereof, The inventors have found that the above object can be achieved by reacting a tetracarboxylic acid and a diamine compound to form a polyamic acid layer on the surface of the material, and then imidizing the polyamide layer to form a polyimide layer, and completed the present invention. I came to.
[0006]
That is, the present invention provides the inventions according to the following items.
Item 1. A method for producing a material having a polyamic acid layer on a surface,
(A) reacting a tetracarboxylic acid anhydride and a diamine compound with a functional group of a material having a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound to form a polyamide on the surface of the material; A production method, comprising a step of forming an acid layer.
Item 2 is a method for producing a material having a polyimide layer on the surface,
(A) reacting a tetracarboxylic acid anhydride and a diamine compound with a functional group of a material having a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound to form a polyamide on the surface of the material; A production method comprising: a first step of forming an acid layer; and (b) a second step of forming a polyimide layer by imidizing the polyamide layer.
Item 3. The method according to Item 1, wherein the reaction is performed in the presence of an organic solvent.
Item 4 The production method according to Item 2, wherein in the first step, the reaction is carried out in the presence of an organic solvent.
Item 5. The method according to Item 2 or 4, wherein in the second step, the imidization of the polyamic acid is performed by heating in an organic solvent.
Item 6 The method according to Item 2 or 4, wherein in the second step, the imidization of the polyamic acid is performed by heating in a gas phase.
Item 7. A material having a polyimide layer on the surface, wherein the polyimide layer is a layer formed of polyimide fine particles.
Item 8. The material according to item 7, wherein the polyimide layer is a layer formed on the surface of the material via a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound.
Item 9 is a material having a polyimide layer on the surface,
A material characterized in that the polyimide layer is a layer formed by a polyimide thin film formed on the surface of the material via a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound.
Item 10. The material according to item 7 or 8, wherein the material is a silicon wafer.
Item 11 The material according to item 9, wherein the material is a silicon wafer.
Item 12 The material according to Item 7, 8 or 10, wherein the thickness of the polyimide layer is 10 to 1000 nm.
Item 13 The material according to Item 9 or 11, wherein the thickness of the polyimide layer is 10 to 1000 nm.
Item 14. The material according to claim 7 or 8, which is a material for an interlayer insulating film.
Item 15. The material according to claim 9, which is a material for an interlayer insulating film.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present specification, “polyimide” includes “polyamideimide”.
[0008]
The method of the present invention is a method for producing a material having a polyimide layer on the surface, wherein (a) the functional group of the material having a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound on the surface. And a first step of forming a polyamic acid layer on the surface of the material by reacting a tetracarboxylic anhydride and a diamine compound, and (b) a second step of forming a polyimide layer by imidizing the polyamide layer. It is a method that includes a step.
[0009]
The present invention is a method comprising only the first step of the above-mentioned method, that is, a method for producing a material having a polyamic acid layer on the surface, wherein (a) reacting with at least one of tetracarboxylic anhydride and a diamine compound. A method including a step of forming a polyamic acid layer on the surface of the material by reacting the obtained functional group of the material having a functional group on the surface with a tetracarboxylic anhydride and a diamine compound is also included.
[0010]
Hereinafter, the first step (step (a)) and the second step (step (b)) will be described in detail.
[0011]
(1) First step In the first step, a material having on its surface a functional group capable of reacting with at least one of a tetracarboxylic anhydride and a diamine compound is used, and the functional group, tetracarboxylic anhydride and diamine are used. The compound is reacted to form a polyamic acid layer on the surface of the material.
[0012]
In the present invention, the material serving as the base material is not particularly limited as long as it has a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound on the surface. Can be appropriately selected from known materials.
[0013]
Examples of the functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, an acid chloride group, a carboxyl anhydride group, a thiol group, and an isocyanate group. The material serving as the base material has one or more functional groups.
[0014]
If the material does not have a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound on the surface, for example, the surface of the material is treated with a silane coupling agent having such a functional group according to a conventional method. By doing so, a functional group capable of reacting with at least one of the tetracarboxylic anhydride and the diamine compound can be provided. Examples of the silane coupling agent include 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Epoxy silane coupling agents such as triethoxysilane; N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3 -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-amino Amines such as propyltrimethoxysilane Urea-type silane coupling agent such as 3-ureidopropyltriethoxysilane; mercapto-type silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; 3-isocyanatepropyl Isocyanate-based silane coupling agents such as triethoxysilane and the like can be mentioned.
[0015]
Examples of the base material include plastics such as silicon wafer, polyimide, polyester resin, epoxy resin, phenol resin, melamine resin, acrylic resin, polycarbonate resin, polyurethane resin, polyether sulfone resin, polyacetal resin, and fluororesin. Examples include materials, glass, ceramics, and inorganic materials such as metals.
[0016]
The size of the material is not particularly limited and can be appropriately set according to the application. For example, in the case of a silicon wafer, the thickness is usually about 0.5 to 5 mm and the diameter is about 20 to 330 mm. is there.
[0017]
The tetracarboxylic anhydride is not particularly limited, and for example, those similar to those used in conventional polyimide synthesis can be used. Specifically, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′ , 4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxy Phenoxy) benzene dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3 3'-biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, anthracene-2, 3,6,7-tetracarboxylic acid , An aromatic tetracarboxylic dianhydride such as phenanthrene-1,8,9,10-tetracarboxylic dianhydride; butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1, Aliphatic tetracarboxylic dianhydrides such as 2,4,5-tetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride Use of heterocyclic tetracarboxylic dianhydrides such as thiophene-2,3,4,5-tetracarboxylic dianhydride and pyridine-2,3,5,6-tetracarboxylic dianhydride; Can be. One or two or more of these can be used. In the present invention, in particular, BTDA, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and the like are reactive, and the physical properties of the obtained thin film (heat resistance, mechanical strength, etc.) ), Which is preferable in terms of cost.
[0018]
Further, in the present invention, those obtained by partially replacing tetracarboxylic anhydride with acid chloride can be used. Substitution with an acid chloride has the effect of increasing the reaction rate depending on the conditions. As the acid chloride, for example, diethyl pyromellitate diacyl chloride or the like can be used.
[0019]
In the present specification, the polyimide also includes a polyamideimide. In order to produce polyamideimide, a known raw material may be used. For example, it can be produced by using a dicarboxylic acid chloride instead of a part of the tetracarboxylic anhydride. Specifically, (i) tetracarboxylic anhydrides such as aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, cycloaliphatic tetracarboxylic dianhydride, and heterocyclic tetracarboxylic dianhydride; An acid, (ii) a dicarboxylic acid chloride such as an aromatic dicarboxylic acid chloride, an aliphatic dicarboxylic acid chloride, a cycloaliphatic dicarboxylic acid chloride, or a heterocyclic dicarboxylic acid chloride; and (iii) an aromatic diamine, an aliphatic diamine, or a cyclic dicarboxylic acid. Using a diamine compound such as an aliphatic diamine as a raw material, a polyamide-polyamic acid layer is formed in the same manner as in the case of the polyamic acid layer as described above, and can be obtained by imidization according to a conventional method.
[0020]
The diamine compound is not particularly limited, and for example, those similar to those used in conventional polyimide synthesis can be used. For example, 4,4'-diaminodiphenyl sulfide (ASD), 4,4'-diaminodiphenylmethane (MDA), 4,4'-diaminodiphenyl ether (DPE), 4,4'-bis (4-aminophenoxy) biphenyl ( BAPB), 4,4'-bis (3-aminophenoxy) biphenyl, 1,4'-bis (4-aminophenoxy) benzene (TPE-Q), 1,3'-bis (4-aminophenoxy) benzene ( TPE-R), 1,3-bis (3-aminophenoxy) benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine (PPD), 3,4′-diaminodiphenyl ether, 4,4′-diamino Diphenylsulfone (ASN), 3,4-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone 4,4'-methylene-bis (2-chloroaniline), 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfide, 2,6'-diaminotoluene, 1,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobi Benzyl, R (+)-2,2'-diamino-1,1'-binaphthalene, S (+)-2,2'-diamino-1,1'-binaphthalene, 1,3-bis (4-aminophenoxy ) Alkanes, 1,4-bis (4-aminophenoxy) alkanes, 1,5-bis (4-aminophenoxy) alkanes and other 1, n-bis (4-aminophenoxy) alkanes Can (n is 3 to 10), 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 4,4'-diaminobenzanilide and the like 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminododecane Aliphatic diamines such as 1,4-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane and 4,4'-diaminodicyclohexylmethane Besides, 3,4-diaminopyridine, 1,4-diamino-2-butanone and the like can be used. One or two or more of these can be used. In the present invention, TPE-Q, ASD, DPE, TPE-R, MDA, BAPB and the like are particularly preferable in view of reactivity and physical properties (heat resistance, crystallinity) of the obtained fine particles.
[0021]
In addition to the diamine compound, other amine compounds (monoamine compound, polyamine compound, etc.) can also be used. Thus, the characteristics of the obtained material can be changed.
[0022]
Specific examples of the combination of the tetracarboxylic anhydride and the diamine compound include (1) a combination of p-phenylenediamine and pyromellitic dianhydride, (2) a combination of p-phenylenediamine and BTDA, and (3) ) A combination of o-phenylenediamine and pyromellitic dianhydride, (4) a combination of 4,4′-diaminodiphenyl sulfide and pyromellitic dianhydride, (5) a p-phenylenediamine and 3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride, (6) a combination of p-phenylenediamine and o-phenylenediamine with pyromellitic dianhydride, (7) a p-phenylenediamine and o- A combination of phenylenediamine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, (8) A combination of phenylenediamine and 4,4'-diaminodiphenyl sulfide with pyromellitic dianhydride, (9) p-phenylenediamine and 4,4'-diaminodiphenyl sulfide with 3,3 ', 4,4'- Combination with biphenyltetracarboxylic dianhydride, (10) Combination of p-phenylenediamine, o-phenylenediamine and 4,4'-diaminodiphenylsulfide with pyromellitic dianhydride, (11) p-phenylenediamine Combination of o-phenylenediamine, 4,4'-diaminodiphenyl sulfide and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, (12) p-phenylenediamine and pyromellitic dianhydride And combination with 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (13) a combination of o-phenylenediamine with pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, (14) 4,4′-diaminodiphenyl sulfide Combination with 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride, (15) 4,4'-diaminodiphenyl sulfide and p-phenylenediamine with pyromellitic dianhydride (16) 4,4'-diaminodiphenyl sulfide and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride. (17) 1,4'-bis (4-aminophenoxy) benzene and 3,3 ', 4,4'-benzophenonetetracarboxylic acid (18) Combination of DPE and BTDA, (19) Combination of ASD and BTDA, (20) Combination of p-phenylenediamine and BTDA, (21) DPE and 3,3 ′, 4, Combination with 4'-biphenyltetracarboxylic dianhydride, (22) combination of ASD with 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, (23) p-phenylenediamine and 3, A combination of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, (24) a combination of DPE and pyromellitic dianhydride, (25) a combination of ASD and pyromellitic dianhydride, ( 26) Combinations of p-phenylenediamine and pyromellitic dianhydride, and the like.
[0023]
In the first step, a tetracarboxylic anhydride and a diamine compound are reacted with a functional group on the surface of the material, and the reaction is preferably performed in the presence of an organic solvent. As a method of reacting in the presence of an organic solvent, specifically, (I) a method in which a material is immersed in an organic solvent in advance, and tetracarboxylic anhydride and a diamine compound are added to the solvent, and the surface of the material is functionalized (II) A solution in which tetracarboxylic anhydride and a diamine compound are dissolved in an organic solvent is separately prepared, and the solution is applied to the material by a method such as spray coating, dipping, spin coating, or casting. Then, a method of reacting a functional group on the material surface with a tetracarboxylic anhydride and a diamine compound is exemplified.
[0024]
In the production method of the present invention, (III) a substrate having a functional group capable of reacting with a tetracarboxylic anhydride and / or a diamine compound on a surface by dissolving a tetracarboxylic anhydride and a diamine compound in a solvent to form a solution; (Material) is alternately immersed in each solution at regular time intervals to react the functional group, tetracarboxylic anhydride and diamine compound to form a polyamic acid layer on the surface of the material, and the molecular order is reduced. Can form a thin film. In this case, the same tetracarboxylic anhydride solution or diamine compound solution may be used repeatedly, or different kinds of tetracarboxylic anhydride solutions or diamine compound solutions may be used.
[0025]
The ratio between the tetracarboxylic anhydride and the diamine compound used in the first step is usually about tetracarboxylic anhydride: diamine compound = 1: 0.5 to 1.5 (molar ratio), preferably 1: 0.9. It may be set so as to be about 1.1 (molar ratio).
[0026]
When using an organic solvent, the type of the solvent is substantially as long as it substantially dissolves tetracarboxylic anhydride and diamine and does not significantly affect the material serving as the base material chemically and physically. It is not limited.
[0027]
Such organic solvents include, for example, dimethylformamide (DMF), 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, acetanilide, methanol, ethanol , Isopropanol, N-methyl-2-pyrrolidone (NMP), methyl acetate and the like, and a solvent containing at least one of these can be used.
[0028]
When an organic solvent is used for the reaction, the ratio between the tetracarboxylic anhydride and the diamine compound and the organic solvent is not particularly limited as long as the reaction for obtaining the polyamic acid proceeds, and the type of the tetracarboxylic anhydride and the diamine For example, in the method (I), the concentration in the reaction mixture is usually about 0.01 to 2 mol / L, preferably 0.1 to 1 mol / L, respectively. It is an amount that will be about one liter.
[0029]
In the method (I), the tetracarboxylic anhydride and the diamine compound may be added to the solvent at the same time, or one of the compounds may be added first, and the other compound may be added after sufficient dissolution. For example, if the functional group on the surface of the material is an amino group, tetracarboxylic anhydride may be added first, and the diamine compound may be added after reacting the amino group with the carboxyl group, and when the functional group is a carbosyl group, , A diamine compound may be added first, and a carboxyl group and an amino group may be reacted, and then tetracarboxylic anhydride may be added.
[0030]
The tetracarboxylic anhydride and / or diamine compound may be added while stirring the solvent, and in that case, the stirring can be performed by a known stirring method (stirring device).
[0031]
In the method (III), the material may be immersed first in either the tetracarboxylic anhydride solution or the diamine compound solution. For example, if the functional group on the surface of the material is an amino group, first the tetracarboxylic anhydride solution is used. What is necessary is just to immerse in a diamine compound solution after immersing in an acid solution and reacting an amino group and a carboxyl group, and when a functional group is a carbosyl group, immerse in a diamine compound solution first and convert a carboxyl group and an amino group. After the reaction, it may be immersed in a tetracarboxylic anhydride solution.
[0032]
The reaction temperature in the first step is not particularly limited, and is usually about 0 to 130 ° C, preferably about 20 to 50 ° C. The reaction time is generally about 10 minutes to 48 hours, preferably about 4 to 24 hours.
[0033]
The first step forms a polyamic acid layer on the surface of the material.
[0034]
The material obtained in the first step may be collected by solid-liquid separation according to a known method, for example, if the substrate is a solid such as a plate or a lump, a known manual or electric supplementary device, It can be appropriately selected and used according to the size of the material (for example, tweezers, tongs, etc.). If it is a powder or a granular material, solid-liquid separation can be performed by a known method such as a centrifuge, decantation, or filtration.
[0035]
(2) Second step In the second step, a polyimide layer is generated by imidizing the polyamide layer obtained in the first step. The method of imidization is not particularly limited, but in the present invention, in particular, (i) a method of imidizing by heating in an organic solvent (thermal ring closure), and (ii) a method of imidizing by a chemical reaction in an organic solvent (chemical It is desirable to employ a method of (ring closure) or (iii) a method of imidization by heating in a gas phase (thermal ring closure).
[0036]
In the method by heating in the above (i), for example, a material having a polyamic acid layer may be immersed in an organic solvent and heated at a temperature of usually 130 ° C. or higher, preferably about 130 to 250 ° C. The organic solvent is not limited as long as it is a poor solvent for the polyamic acid and has a boiling point higher than the temperature required for the imidization reaction, and N, N-dimethylformamide (DMF), N, N-dimethyl Acetamide (DMAc), N-methyl-2-pyrrolidone (NMP), toluene and the like are exemplified. Alternatively, the organic solvent preferably contains a solvent capable of forming an azeotropic mixture with water (hereinafter, also referred to as an “azeotropic solvent”). That is, in the present invention, the azeotropic solvent may be used as part or all of the organic solvent. As the azeotropic solvent, for example, xylene, ethylbenzene, octane, cyclohexane, diphenyl ether, nonane, pyridine, dodecane and the like can be used. One or more of these can be used. In the present invention, the azeotropic solvent preferably contains at least 10% by volume of the organic solvent. By using an azeotropic solvent, particularly, by-produced water (mainly condensed water) can be azeotropically removed and removed outside the reaction system by reflux or the like. As a result of preventing a decrease in the molecular weight of the polyamic acid and the like, uniform polyimide fine particles or a thin film is formed on the surface of the substrate, which is preferable.
[0037]
The ratio of the material supporting the polyamic acid to be immersed in the organic solvent may be appropriately set according to the type of the organic solvent and the like, and may be such that the substrate is completely immersed.
[0038]
In the method based on the chemical reaction (ii), a known chemical ring closure method can be applied. For example, a material having a polyamic acid layer may be immersed in an organic solvent composed of pyridine and acetic anhydride, and heated at about 15 to 115 ° C. for about 24 hours while stirring. What is necessary is just to set the mixing ratio of both solvents suitably.
[0039]
In the method (iii) using heat in the gas phase, heating may be performed usually at a temperature of 130 ° C. or higher, preferably about 130 to 250 ° C., and if necessary, under reduced pressure for about 4 to 24 hours. More specifically, when a solvent is used in the first step, after the solvent on the surface of the base material is dried, the imidization may be performed by heating in a gas phase such as a hot-air circulation oven or an electric furnace. it can. The heating may be performed while the temperature is raised. Alternatively, the temperature may be raised after the temperature of the oven, the electric furnace, or the like is increased to a certain temperature, and then the material may be charged and the heating may be performed at a certain temperature for a certain time.
[0040]
The material obtained in the second step may be collected by a known method and, if necessary, washed with an organic solvent such as petroleum ether, methanol, acetone or the like.
[0041]
Thus, a material having a polyimide layer on the surface is obtained.
[0042]
For example, when imidization is performed in a solvent as in the above (i) and (ii), a polyimide fine particle layer having an average particle size of usually about 10 to 1000 nm, preferably about 10 to 50 nm is formed on the surface of the material. It is formed. In this case, the thickness of the polyimide layer is about the same as the particle size of the polyimide fine particles, and is usually about 10 to 1000 nm, preferably about 10 to 50 nm.
[0043]
Further, in this case, it is considered that the polyimide fine particles are formed on the surface of the material via a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound. And a layer formed on the surface of the material via the functional group. FIG. 1A shows a schematic diagram thereof.
[0044]
On the other hand, when imidization is performed in the gas phase as in (iii) above, a polyimide thin film having a thickness of usually about 10 to 1000 nm, preferably about 10 to 50 nm is formed on the surface of the material. It is considered that the polyimide thin film is formed on the surface of the material via a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound. FIG. 1B shows a schematic diagram thereof.
[0045]
The fact that the polyimide layer consisting of polyimide fine particles or polyimide thin film is formed on the surface of the material via the functional group is measured by measuring the chemical composition by FT-IR, EDX, ESCA, etc., and observing the form by SEM, AFM, etc. Can be confirmed.
[0046]
In this specification, the fact that the polyimide fine particles or the polyimide thin film is via a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound means that, for example, when the functional group is an amino group, -NH- When the functional group is a carboxyl group, the polyimide fine particle or polyimide thin film is formed on the material surface via -CO-.
[0047]
In the present invention, the first step and the second step can be repeated to form a multilayer structure having a plurality of polyimide layers.
[0048]
The present invention also includes a material having a polyimide layer on the surface, obtained by the first and second steps described above.
[0049]
The material of the present invention can be used as a carbon material, a carbon thin film, an interlayer insulating film, a laminate, a resist, a material for electronic devices (for example, LOC tape), and the like.
[0050]
【The invention's effect】
According to the method of the present invention, the surface of the material can be covered with the polyimide layer very densely and with good adhesion and uniformity. Further, according to the method for forming a polyimide layer of the present invention, the material surface can be coated with a polyimide thin film or a polyimide layer composed of polyimide fine particles controlled in nano-order.
[0051]
【Example】
Examples are shown below to further clarify the features of the present invention.
[0052]
Example 1
A silicon wafer whose surface is aminated by a silane coupling agent [a 5-inch silicon wafer cut to a size of about 3 cm × about 3 cm] is immersed in 100 ml of DMF, and tetracarboxylic anhydride 4,4 4.97 g of '-diaminobenzenesulfonic acid was added, and the mixture was completely dissolved and stirred for 1 hour. Then, 6.44 g of BTDA as a diamine was dissolved in 100 ml of DMF and added, followed by stirring for 24 hours to carry out an amidation polymerization reaction. Was. After the completion of the reaction, the silicon wafer was taken out of the solution, the polyamic acid physically adsorbed on the surface was washed with DMF, and then dried to obtain a silicon wafer whose surface was coated with a polyamic acid thin film.
[0053]
Next, the silicon wafer whose surface was coated with polyamic acid was heat-treated in an oven at 250 ° C. for 1 hour to be imidized, and the silicon wafer was coated with a polyimide thin film.
[0054]
Further, a silicon wafer whose surface was coated with polyamic acid was immersed in DMF, refluxed at 140 to 150 ° C. for 4 hours to imidize the polyamic acid, and the silicon wafer was coated with a nano-sized polyimide fine particle layer.
[0055]
FIGS. 2A and 2B show AMF images of a silicon wafer whose surface has been aminated by a silane coupling agent, a silicon wafer heated in an oven, and a silicon wafer heated in a solvent. And FIG. 2 (c).
[Brief description of the drawings]
FIGS. 1A and 1B are schematic diagrams of a material having a polyimide layer on the surface. FIG. 1A is a schematic diagram in the case where the polyimide layer is a layer formed by polyimide fine particles, and FIG. 1B is a diagram in which the polyimide layer includes at least one of tetracarboxylic anhydride and a diamine compound. FIG. 2 is a schematic diagram of a layer formed by a polyimide thin film formed on a surface of a material via a reactive functional group.
2 (a) is a silicon wafer subjected to amination treatment, FIG. 2 (b) is a silicon wafer heated in an oven in Example 1, and FIG. 2 (c) is a silicon wafer heated in a solvent. It is a figure showing an AMF image of a silicon wafer.

Claims (13)

A method for producing a material having a polyamic acid layer on the surface,
(A) reacting a tetracarboxylic acid anhydride and a diamine compound with a functional group of a material having a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound to form a polyamide on the surface of the material; A production method, comprising a step of forming an acid layer. A method for producing a material having a polyimide layer on the surface,
(A) reacting a tetracarboxylic acid anhydride and a diamine compound with a functional group of a material having a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound to form a polyamide on the surface of the material; A production method comprising: a first step of forming an acid layer; and (b) a second step of forming a polyimide layer by imidizing the polyamide layer. The method according to claim 1, wherein the reaction is performed in the presence of an organic solvent. The method according to claim 2, wherein in the first step, the reaction is performed in the presence of an organic solvent. The method according to claim 2, wherein in the second step, the imidization of the polyamic acid is performed by heating in an organic solvent. The method according to claim 2, wherein in the second step, the imidization of the polyamic acid is performed by heating in a gas phase. A material having a polyimide layer on its surface, wherein the polyimide layer is a layer formed of polyimide fine particles. The material according to claim 7, wherein the polyimide layer is a layer formed on the surface of the material via a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound. A material having a polyimide layer on the surface,
A material characterized in that the polyimide layer is a layer formed by a polyimide thin film formed on the surface of the material via a functional group capable of reacting with at least one of tetracarboxylic anhydride and a diamine compound. 9. The material according to claim 7, wherein the material is a silicon wafer. The material according to claim 9, wherein the material is a silicon wafer. The material according to claim 7, 8 or 10, wherein the thickness of the polyimide layer is 10 to 1000 nm. The material according to claim 9, wherein the thickness of the polyimide layer is 10 to 1000 nm.

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