TWI491652B - Organic-inorganic hybrid material film and method for manufacturing the same - Google Patents

Description

Organic-inorganic hybrid material film and method of producing the same

The present invention relates to a method for producing an organic-inorganic hybrid material film, and more particularly to a method for producing a polymaleic anhydride-polyimine-ruthenium oxide mixed material film.

The composite material combines the characteristics of organic polymers and inorganic compounds, and can combine the advantages of various materials to have excellent properties. For example, polymers have the advantages of easy processing, toughness, elasticity, corrosion resistance, insulation and low cost, but their heat resistance and mechanical strength are poor; while ceramic materials have hard, low activity, excellent heat resistance and mechanical strength. Advantage, but heavy and fragile. If you can combine the advantages of various materials to make up for its shortcomings, you can get new materials with excellent properties. Some industrially widely used mixtures are known, from the following organic polymers such as polyethylene, polypropylene, polystyrene, polymethyl methacrylate, nylon, polyesters or polyimine; and inorganic compounds, for example Calcium carbonate, clay and strontium oxide. However, various developing mixed materials containing an organic-inorganic hybrid having organic polymer groups and inorganic oxide groups which are combined with each other and constitute a composite structure are known, exhibiting better characteristics than the above-described conventional composite materials.

The organic polymer in the organic-inorganic polymer mixture, for example, polyimide, has excellent heat resistance, mechanical properties, and chemical resistance, and is therefore widely used in the field of aerospace, electronic materials, and the like. At present, most of the users are mostly aromatic polyimine. Most aromatic polyimines are insoluble in solvents and non-thermoplastic, making them difficult to process. The precursor of polyimine is polylysine which is solvent-soluble, so a method in which a poly-proline solution is used in a desired shape and then ruthenium is obtained.

However, the hydrazine imidization reaction is accompanied by the detachment and evaporation of water, and the reaction temperature at the time of thermal imidization also reaches 300 ° C or more, which is far above the boiling point of water, and is formed when a thick film shaped article is formed. It is prone to bulging and other undesirable conditions related to surface properties. Therefore, it is difficult to appropriately select the operating conditions at the time of molding, such as temperature setting. The product of the polyaminic acid in which the oxime imidization reaction is omitted cannot have the heat resistance peculiar to polyimine. Further, since the polyaminic acid solution is easily hydrolyzed in the presence of water, the preservation method is difficult.

Polyimine is useful for applications in the electronics field and can be used as an insulating film or protective coating film on a semiconductor device. In particular, the wholly aromatic polyimine has a large contribution to high density, multi-function, and the like of a flexible circuit board or an integrated circuit due to its excellent heat resistance, mechanical properties, and electrical properties.

Therefore, when an interlayer insulating film or a protective coating film of a fine circuit is formed, a polyimide polyimide precursor solution has conventionally been used. Such a polyimide precursor solution is known as a polyacrylic acid (PAA) solution obtained by reacting a diamine compound with a tetracarboxylic dianhydride, or a polyglycinate or a polyamidite trihydrate. Various solutions such as sulfonate, poly(diethylguanamine). The polyimine precursor solutions are all polymer solutions having a high degree of polymerization. When the polyimide film is obtained from the polymer solution, the polymer solution is generally applied to copper, glass, etc. The substrate was heated and heated, and solvent removal and hydrazine imidation were carried out to obtain a polyimide film.

However, when a polymer solution having a high degree of polymerization is applied, since the degree of polymerization is high, in order to make the solution a coatable viscosity, there is a problem that it is necessary to lower the concentration of the solute. Moreover, if the solute concentration is increased in order to improve productivity, the viscosity of the solution will increase, and there is a problem that coating cannot be applied. Further, when the solute concentration is high and the polymer has a low viscosity in order to have a coatable viscosity, there is a problem that a coating film excellent in mechanical properties and heat resistance cannot be obtained. Further, it is extremely difficult for the polymer solution to be stored for a long period of time while maintaining the degree of polymerization.

An object of the present invention is to provide a polymaleic anhydride-polyimine-ruthenium oxide organic-inorganic hybrid material film having a polymaleic anhydride polyimide portion, a main chain of polymaleic anhydride, and a side chain. By grafting, the terminal has a crosslinkable reactive functional group, wherein the side chain contains a short-segment polyamine structure, the side chain is short to reduce the degree of polymerization, and the polymer solution is prevented from being too sticky and difficult to coat. The problem of film formation.

Another object of the present invention is to provide a method for producing a polymaleic anhydride-polyimine-iridium oxide organic-inorganic hybrid material film, which can avoid thick film using thermal cyclization method by using chemical cyclization method The surface of the molded article is prone to bulging.

Still another object of the present invention is to provide a film which has excellent heat resistance and mechanical properties and which can be applied to an insulating layer material of a copper foil substrate and a circuit board.

Still another object of the present invention is to provide a copper foil substrate which has excellent heat resistance and mechanical properties, and which is bonded to an electronic component and operated in a severe environment such as high temperature and high humidity without affecting the quality thereof.

In order to achieve the above object, the present invention is a polymaleic anhydride-polyimine-iridium oxide organic-inorganic hybrid material film, which is mainly composed of polymaleic anhydride, and side chains are grafted with polyimine and A cerium oxide group. The organic-inorganic hybrid material can be represented by structural formulas (9) and (10) in the second figure or structural formulas (19) and (20) in the third figure.

The invention relates to a method for producing a polymaleic anhydride-polyimine-iridium oxide organic-inorganic hybrid material film, comprising the steps of: (a) reacting a dianhydride with an aromatic diamine in a solvent to prepare a polyaminic acid solution; (b) reacting the polymaleic anhydride with the polyaminic acid solution obtained in the step (a) at a temperature lower than 80 ° C to prepare a side chain of the polymaleic anhydride -NH-CO a functional group and a carboxylic acid group-containing oligopolymer; (c) adding a decane coupling agent; (d) adding a catalyst to the solution prepared in the step (c) for chemical ring-closing reaction; (e) in the step (d) The obtained solution is added with an alkoxylated oxime monomer represented by the formula Si(R ³ ) ₄ (wherein R ³ may be the same or different from each other and represent a halogen, a C _1-6 alkoxy group, a C _2-6 alkenyloxy group and The aryloxy group is subjected to hydrolysis and condensation reaction in the presence of water and an acid catalyst or a base catalyst at a temperature ranging from 15 ° C to 100 ° C, whereby the decyl alcohol group in Si(R ³ ) ₄ is subjected to hydrolysis condensation reaction. After the decane coupling agent is covalently bonded to form a polymaleic anhydride-polyimine-ruthenium oxide mixed material solution; (f) polymaleic anhydride-polyimine- Hybrid material of the coating solution on a silicon substrate, is obtained by heating a cured polymaleic anhydride - Polyimide - silicon oxide film hybrid material.

The present invention provides a film obtained by impregnating a glass cloth of the above-mentioned polymaleic anhydride-polyimine-cerium oxide mixed material film.

The invention provides a copper foil substrate which is formed by pressing at least one copper foil with the aforementioned film.

S10~S20. . . step

The first figure is a flow chart of a method for producing a polymaleic anhydride-polyimine-iridium oxide organic-inorganic hybrid material film according to an embodiment of the present invention.

The second drawing is a flow chart of a method for producing a polymaleic anhydride-polyimine-iridium oxide organic-inorganic hybrid material film according to an embodiment of the present invention, wherein the decane coupling agent used is a formula H ₂ NR ¹ - An amine-based coupling agent represented by Si(R ² ) ₃ .

3 is a flow chart showing a method for producing a polymaleic anhydride-polyimine-ruthenium oxide organic-inorganic hybrid material film according to another embodiment of the present invention, wherein the decane coupling agent used is a formula OCN-R ¹ An isocyanate coupling agent represented by -Si(R ² ) ₃ .

The fourth figure is an IR spectrum of the polymaleic anhydride-polyimine-cerium oxide mixed material of the present invention.

The fifth picture is the analysis result of the fourth figure.

The sixth graph is a measure of the glass transition temperature of the polymaleic anhydride-polyimine-cerium oxide organic-inorganic hybrid material of the present invention.

The seventh graph is a measurement of the 5 wt% thermogravimetric loss temperature of the polymaleic anhydride-polyimine-cerium oxide organic-inorganic hybrid material of the present invention.

Referring to the first drawing, the first drawing is a flow chart of a method for producing a polymaleic anhydride-polyimide-cerium oxide organic-inorganic hybrid material film according to an embodiment of the present invention. As shown in the first figure, the method for producing a polymaleic anhydride-polyimine-iridium oxide organic-inorganic hybrid material film comprises the steps of: reacting a dianhydride with an aromatic diamine in a solvent to prepare a polyfluorene. An amine acid solution (S10); a polymaleic acid solution obtained by reacting polymaleic anhydride with the step (S10) at a temperature lower than 80 ° C to prepare a side chain of polymaleic anhydride having a -NH-CO-functionality And a carboxylic acid group-containing oligopolymer (S12); adding a decane coupling agent (S14); adding a catalyst to the solution prepared in the step (S14) to carry out a chemical ring-closing reaction (S16); and obtaining the step (S16) a solution of alkoxylated oxime monomer represented by the formula Si(R ³ ) ₄ (wherein R ³ may be the same or different from each other and represent a halogen, a C _1-6 alkoxy group, a C _2-6 alkenyloxy group, and an aryloxy group). Hydrolysis and condensation reaction in the presence of water and an acid catalyst or a base catalyst at a temperature ranging from 15 ° C to 100 ° C, whereby the stanol group in Si(R ³ ) ₄ is subjected to hydrolysis condensation reaction The decane coupling agent is covalently bonded to form a polymaleic anhydride-polyimine-ruthenium oxide mixed material solution (S18); polymaleic anhydride-polymerized Imine - silicon oxide hybrid material solution was coated on a substrate, cured by heating to obtain polymaleic anhydride - Polyimide - hybrid material, silicon oxide film (S20).

An example of a polyphthalic acid dianhydride prepared in step S10, such as but not limited to the following compounds, maleic anhydride, substituted maleic anhydride, tetrahydrophthalic anhydride, substituted tetrahydrophthalic anhydride , a phthalic anhydride, a substituted phthalic anhydride, an aromatic dianhydride such as pyromellitic dianhydride (PMDA), 4,4-diphthalic acid dianhydride (BPDA), 4 , 4-hexafluoroisopropylidene dicarboxylic acid dianhydride (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P3FDA), 1,4-double (trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P6GDA), 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylhydrazine Full-5,6-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindan-6,7-dicarboxylic dianhydride, 1 -(3',4'-dicarboxyphenyl)-3-methylindan-5,6-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methyl Indole-6,7-dicarboxylic dianhydride, 2,3,9,10-perylene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6- Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloro Naphthalene-2,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 3,3',4,4'-diphenyl Ketotetracarboxylic dianhydride, 1,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-isopropylidene dicarboxylic acid dianhydride, 3, 3'-isopropylidenediphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonyldicarboxylic acid dianhydride, 3,3'-oxydicdic acid Dihydride, 4,4'-methylene diruthenic acid dianhydride, 4,4'-thiodiphthalic acid dianhydride, 4,4'-ethylene dicarboxylic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, benzene-1,2,3,4-tetra a carboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, etc., among which pyromellitic dianhydride (PMDA), 4,4-diphthalic acid dianhydride (BPDA), 4,4-hexafluoroisopropylidene dicarboxylic acid dianhydride (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P3FDA), 1,4- Bis(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P6GDA).

Examples of the aromatic diamines for preparing polyamic acid in step S10 include, but are not limited to, for example, 4,4'-oxydiphenylamine (ODA), 5-amino-1-(4'-aminophenyl) -1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 4,4'-methylene Bis(o-chloroaniline), 3,3'-dichlorodiphenylamine, 3,3'-sulfonyldiphenylamine, 4,4'-diaminobenzophenone, 1,5-diaminonaphthalene , bis(4-aminophenyl)diethyldecane, bis(4-aminophenyl)diphenylnonane, bis(4-aminophenyl)ethylphosphine oxide, N-(double (4) -aminophenyl))-N-methylamine, N-(bis(4-aminophenyl))-N-phenylamine, 4,4'-methylenebis(2-methylaniline) , 4,4'-methylenebis(2-methoxyaniline), 5,5'-methylenebis(2-aminophenol), 4,4'-methylenebis(2-methyl Aniline), 4,4'-oxybis(2-methoxyaniline), 4,4'-oxybis(2-chloroaniline), 2,2'-bis(4-aminophenol), 5 , 5'-oxybis(2-aminophenol), 4,4'-thiobis(2-methylaniline), 4,4'-thiobis(2-methoxyaniline), 4, 4'-thiobis(2-chloroaniline), 4,4'-sulfonylbis(2-methylaniline), 4,4'-sulfonylbis(2-ethoxyaniline), 4, 4'-sulfonyl bis (2- Chloroaniline), 5,5'-sulfonylbis(2-aminophenol), 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethyl Oxy-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, m- Phenylenediamine, p-phenylenediamine, 4,4'-methylenediphenylamine, 4,4'-thiodiphenylamine, 4,4'-sulfonyldiphenylamine, 4,4'-isopropylidene Diphenylamine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dicarboxybenzidine, 2,4-tolyldiamine, 2,5- Tolyldiamine, 2,6-tolyldiamine, m-xylylenediamine, 2,4-diamino-5-chlorotoluene, 2,4-diamino-6-chlorotoluene, and the like. It is preferably 4,4'-oxydiphenylamine (ODA).

The solvent used in the step S10 is, for example, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, diethylene glycol monomethyl ether; Preferably, for example, N-methylpyrrolidone is combined with diethylene glycol monomethyl ether, N-methylpyrrolidone and methanol, N-methylpyrrolidone and 2-methoxyethanol.

The polymaleic anhydride used in the step S12 is a polymer having a structure of maleic anhydride in its main chain.

The decane coupling agent used in the step S14 may be an amine coupling agent represented by the formula H ₂ NR ¹ -Si(R ² ) ₃ (wherein R ¹ represents a C _1-6 alkylene group, an extended aryl group, and R ² each other The same or different and representing C _1-6 alkoxy), wherein the amine group is reacted with the acid anhydride group of the polymaleic anhydride obtained in the step (b) to obtain an amino coupling agent grafted polylysine, Wherein the number of moles of the amine coupling agent is less than the number of moles of the aromatic diamine. The amine coupling agent represented by the formula H ₂ NR ¹ -Si(R ² ) ₃ is selected from the group consisting of 3-aminopropyltrimethoxydecane (APrTMOS), 3-aminopropyltri Ethoxydecane (APrTEOS), 3-aminophenyltrimethoxydecane (APTMOS), 3-aminophenyltriethoxydecane (APTEOS), and combinations thereof.

Alternatively, the decane coupling agent of the step S14 may be an isocyanate coupling agent represented by the formula OCN-R ¹ -Si(R ² ) ₃ (wherein R ¹ represents a C _1-6 alkylene group, an extended aryl group, and R ² each other The same or different and representing a C _1-6 alkoxy group, wherein the isocyanato group is reacted with the hydroxyl group of the aromatic diamine on the side chain of the polymaleic anhydride obtained in the step (b).

The catalyst used in the step S16 may be pyridine or 3-picoline. The catalyst may also use a tertiary amine having a similar activity to the pyridine as well as betaheptylpyridine. These tertiary amines include 2-picoline (alpha picoline); 3,4-dimethylpyridine; 3,5-dimethylpyridine; 4-methylpyridine; 4-isopropylpyridine; N,N-dimethyl Benzylamine; isoquinoline; 4-benzylpyridine, N,N-dimethyldodecylamine, triethylamine and the like. Further, in step (d), a dehydrating agent such as acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride and a mixture thereof; an anhydride of an aromatic monocarboxylic acid; a mixture of an aliphatic anhydride and an aromatic anhydride; carbodiimide; Aliphatic ketene. The amount of catalyst and dehydrating agent is generally similar to the molar number of the anhydride dehydrating material, and lower or higher amounts may be used depending on the desired conversion rate and the catalyst used, which is often relative to the polylysine. The amide acid group is used in molar excess, typically from about 1.2 to 2.4 moles per equivalent of polyglycolic acid.

The alkoxylated oxime system of the formula Si(R ³ ) ₄ in the step S18 is selected from the group consisting of tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane and combinations thereof.

In addition, an intermolecular force coupler monomer represented by the formula R ⁴ Si(R ⁵ ) ₃ may be further added after the step S18 (wherein R ⁴ is a group having an epoxy group at the terminal, and R ⁵ may be the same or different from each other and The halogen, C _1-6 alkoxy group, C _2-6 alkenyloxy group and aryloxy group are subjected to a hydrolysis condensation reaction and are covalently bonded to the cerium oxide moiety. The intermolecular force coupler monomer of the formula R ⁴ Si(R ⁵ ) ₃ may be selected from the group consisting of γ -glycidoxypropyltrimethoxydecane (GTMOS), γ -glycidyloxy Propyltriethoxydecane (GTEOS) and combinations thereof.

The second drawing is a flow chart of a method for producing a polymaleic anhydride-polyimine-iridium oxide organic-inorganic hybrid material film according to an embodiment of the present invention, wherein the decane coupling agent used is a formula H ₂ NR ¹ - An amine-based coupling agent represented by Si(R ² ) ₃ . As shown in the second figure, the aromatic diamine represented by the structural formula (1) and the dianhydride represented by the structural formula (2) are first reacted in a solvent to produce a polymer represented by the structural formulas (3) and (4). Proline, wherein X in the structural formula (1) represents a structure consisting of a group consisting of C, O and a benzene ring; Y is H or CF ₃ . Next, the polymaleic anhydride is added and the polyamine acid solutions represented by the structural formulas (3) and (4) are reacted at a temperature lower than 80 ° C to prepare a side chain of polymaleic anhydride having -NH-CO. - an oligopolymer having a functional group and a carboxylic acid group, and further an amine coupling agent represented by the formula H ₂ NR ¹ -Si(R ² ) ₃ (wherein R ¹ represents a C _1-6 alkylene group, an aryl group, R ² may be the same or different from each other and represents a C _1-6 alkoxy group, and an amine group thereof is reacted with an acid anhydride group of polymaleic anhydride to obtain an amino group coupling agent represented by the formula (5). Polylysine and polylysine represented by structural formula (6). Next, a catalyst is added to carry out a chemical ring-closing reaction to obtain a polyimine imine grafted with an amine-based coupling agent represented by the structural formula (7) and a polyfluorene imine represented by the structural formula (8). Then, tetraethoxy decane (TEOS) is added, and hydrolysis and condensation reaction are carried out in the presence of water and an acid catalyst or a base catalyst at a temperature ranging from 15 ° C to 100 ° C, whereby the stanol group in TEOS is hydrolyzed. The amine coupling agent after the condensation reaction is covalently bonded to form a polymaleic anhydride-polyimine-cerium oxide mixed material represented by the structural formula (9) and a polyfluorene represented by the structural formula (10). amine. Since the side chain of the polymaleic anhydride contains a thermally crosslinkable reactive functional group, it is not possible to use a general direct heating to about 300 ° C to form a polyphosphite ring into a polymethyleneamine. Therefore, the present invention uses a chemical ring-closing method, selecting an appropriate base as a catalyst and selectively adding a dehydrating agent, and reacting at 100 ° C for about 4 hours to form an amine-based coupling agent as shown in the structural formula (7). The polyimine of the branch and the polyimine of the formula (8).

3 is a flow chart showing a method for producing a polymaleic anhydride-polyimine-ruthenium oxide organic-inorganic hybrid material film according to another embodiment of the present invention, wherein the decane coupling agent used is a formula OCN-R ¹ An isocyanate coupling agent represented by -Si(R ² ) ₃ . As shown in the third figure, the aromatic diamine represented by the structural formula (11) and the dianhydride represented by the structural formula (12) are first reacted in a solvent to produce a polymer represented by the structural formulas (13) and (14). Proline, wherein X in the structural formula (11) represents a structure consisting of a group consisting of C, O and a benzene ring; Y is H or CF ₃ . Next, the polymaleic anhydride is added and the polyamic acid solution represented by the structural formulas (13) and (14) is reacted at a temperature lower than 80 ° C to prepare a side chain of the polymaleic anhydride having -NH-CO. - an oligopolymer having a functional group and a carboxylic acid group, and further an isocyanate coupling agent represented by the formula OCN-R ¹ -Si(R ² ) ₃ (wherein R ¹ represents a C _1-6 alkylene group, an aryl group) , R ² may be the same or different from each other and represents a C _1-6 alkoxy group, and the isocyanate group thereof is reacted with the hydroxyl group of the aromatic diamine on the side chain of the polymaleic anhydride to obtain a structural formula (15). A polylysine having an isocyanate coupling agent and a poly-proline represented by the formula (16). Next, a catalyst is added to carry out a chemical ring-closing reaction to obtain a polyimine which has an isocyanate coupling agent as shown in the structural formula (17) and a polyimine which is represented by the structural formula (18). Then, tetraethoxy decane (TEOS) is added, and hydrolysis and condensation reaction are carried out in the presence of water and an acid catalyst or a base catalyst at a temperature ranging from 15 ° C to 100 ° C, whereby the stanol group in TEOS is hydrolyzed. The isocyanate coupling agent after the condensation reaction is covalently bonded to form a polymaleic anhydride-polyimine-ruthenium oxide mixed material represented by the structural formula (19) and a polyfluorene represented by the structural formula (20). Imine. Since the side chain of the polymaleic anhydride contains a thermally crosslinkable reactive functional group, it is not possible to use a general direct heating to about 300 ° C to form a polyphosphite ring into a polymethyleneamine. Therefore, the present invention uses a chemical ring-closing method, selecting an appropriate base as a catalyst and selectively adding a dehydrating agent, and reacting at 100 ° C for about 4 hours to form an isocyanate coupling agent as shown in Structural Formula (17). A bonded polyimine and a polyimine represented by the formula (18).

(Example)

The invention is further illustrated by the following examples, which are intended to illustrate and not to limit the scope of the invention. First, 1.602 g (8 mmol) of 4,4'-oxydiphenylamine (ODA) was dissolved in dimethylacetamide (DMAc), and after dissolution, 4.443 g (10 mmol) was slowly added. 4,4-hexafluoroisopropylidene dicarboxylic acid dianhydride (6FDA) was purged with nitrogen and vigorously stirred at room temperature for 24 hours to obtain a clear viscous polyamine acid (PAA) solution. At this time, 20 mmol of acetic anhydride and 20 mmol of pyridine were added to raise the temperature to 100 ° C for 4 hours to carry out chemical ring formation. After the solution was returned to room temperature, 886 mg (4 mmol) of 3-isocyanatotriethoxydecane was added, and the reaction was stirred at room temperature for 4 hours, and then attached to the polyimine end, followed by addition. 1.250 g of tetramethoxy decane (TMOS), stirred for 30 minutes, added 30 mg of deionized water and allowed to react at room temperature for 24 hours to obtain a polymaleic anhydride-polyimine-ruthenium oxide mixed material solution. .

Characterization of the obtained polymaleic anhydride-polyimine-ruthenium oxide mixed material, IR spectrum of polymaleic anhydride-polyimine-ruthenium oxide mixed material and analysis result thereof, Tg is about 150 ° C And the 5 wt% thermogravimetric loss temperature is about 288 ° C, as shown in the fourth to seventh figures. FIG fourth present invention based polymaleic anhydride - Polyimide - IR spectra of hybrid material of silicon oxide. The wave numbers 1538 cm-1 and 1650 cm-1 are absorption peaks of NH bending and C=O stretching in the structure of polyacrylic acid (PAA). After the formation of poly(imine) (PI) structure after PAA cyclization, the above two absorption peaks disappear, and a new absorption peak is formed, wherein the wave number of 1380 cm-1 is the absorption peak of the tertiary amine in the PI structure, and the wave number is 730 cm. -1 and 1770 cm-1 are absorption peaks of C=O in the PI structure.

Further, the present invention provides a film obtained by impregnating a glass cloth of the above-mentioned polymaleic anhydride-polyimine-ruthenium oxide mixed material film. This film has excellent heat resistance and mechanical properties, and can be applied to an insulating layer material of a copper foil substrate and a circuit board.

The invention provides a copper foil substrate which is formed by pressing a copper foil with the aforementioned film. The copper foil substrate has excellent heat resistance and mechanical properties, and is bonded to an electronic component and operated in a severe environment such as high temperature and high humidity without affecting the quality thereof.

The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the invention, and other equivalent variations of the patent spirit of the present invention are all within the scope of the invention.

S10~S20. . . step

Claims (14)

A method for producing an organic-inorganic hybrid material film, comprising the steps of:
(a) reacting a dianhydride with an aromatic diamine in a solvent to prepare a polyaminic acid solution;
(b) reacting the polymaleic anhydride with the polyamic acid solution obtained in the step (a) at a temperature lower than 80 ° C to prepare a side chain of the polymaleic anhydride having a -NH-CO-functional group and a carboxylic acid Oligomeric polymer;
(c) adding a decane coupling agent;
(d) adding a catalyst to the solution prepared in the step (c) for a chemical ring-closing reaction;
(e) adding, in the solution prepared in the step (d), an alkoxylated oxime monomer represented by the formula Si(R ³ ) ₄ (wherein R ³ may be the same or different from each other and represent a halogen, a C _1-6 alkoxy group, C _2-6 alkenyloxy group and aryloxy group), in the presence of water and an acid catalyst or a base catalyst, in a temperature range of 15 ° C to 100 ° C, hydrolysis and condensation reaction, and thus Si(R ³ ) ₄ The decyl alcohol group is covalently bonded to the decane coupling agent after the hydrolysis condensation reaction to form a polymaleic anhydride-polyimine-ruthenium oxide mixed material solution;
(f) Applying a solution of a polymaleic anhydride-polyimine-cerium oxide mixed material onto a substrate, and curing at elevated temperature to obtain a film of a polymaleic anhydride-polyimine-cerium oxide mixed material. The method for producing a film of an organic-inorganic hybrid material according to claim 1, wherein the decane coupling agent of the step (c) is an amine coupling agent represented by the formula H ₂ NR ¹ -Si(R ² ) ₃ (wherein R ¹ An acid anhydride which represents a C _1-6 alkylene group, an extended aryl group, and R ² which may be the same or different and represents a C _1-6 alkoxy group, and an amine group thereof and the polymaleic anhydride obtained in the step (b) The base reaction provides a poly-proline acid grafted with an amine-based coupling agent, wherein the number of moles of the amine-based coupling agent is less than the number of moles of the aromatic diamine. The method for producing an organic-inorganic hybrid material film according to claim 2, wherein the amine coupling agent represented by the formula H ₂ NR ¹ -Si(R ² ) ₃ is selected from the group consisting of: 3-amine Propyltrimethoxydecane (APrTMOS), 3-aminopropyltriethoxydecane (APrTEOS), 3-aminophenyltrimethoxydecane (APTMOS), 3-aminophenyltriethoxy Decane (APTEOS) and combinations thereof. The method for producing a film of an organic-inorganic hybrid material according to claim 1, wherein the decane coupling agent of the step (c) is an isocyanate coupling agent represented by the formula OCN-R ¹ -Si(R ² ) ₃ (wherein R ¹ represents a C _1-6 alkylene group, an aryl group, and R ² may be the same or different from each other and represents a C _1-6 alkoxy group, such that the isocyanate group and the polymalon obtained in the step (b) The hydroxyl group reaction of the aromatic diamine on the side chain of the anhydride. The method for producing an organic-inorganic hybrid material film according to claim 1, wherein the alkoxylated oxime system represented by the formula Si(R ³ ) ₄ in the step (e) is selected from the group consisting of: Methoxydecane, tetraethoxydecane, tetrapropoxydecane, and combinations thereof. The method for producing an organic-inorganic hybrid material film according to claim 1, wherein after the step (e), an intermolecular force coupler monomer represented by the formula R ⁴ Si(R ⁵ ) _{3 is} further added (wherein R ⁴ is a group having an epoxy group at the end, R ⁵ being the same or different from each other and representing a halogen, a C _1-6 alkoxy group, a C _2-6 alkenyloxy group and an aryloxy group) after undergoing a hydrolysis condensation reaction with a ruthenium oxide moiety The covalent bond is produced. The method for producing an organic-inorganic hybrid material film according to claim 6, wherein the intermolecular force coupler single system represented by the formula R ⁴ Si(R ⁵ ) _{3 is} selected from the group consisting of: γ - shrinkage Glyceroxypropyltrimethoxydecane (GTMOS), gamma -glycidoxypropyltriethoxydecane (GTEOS), and combinations thereof. The method for producing a film of an organic-inorganic hybrid material according to claim 1, wherein the solvent of the step (a) is N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethyl Acetamide, diethylene glycol monomethyl ether. The method for producing a film of an organic-inorganic hybrid material according to claim 1, wherein the catalyst of the step (d) is pyridine or 3-methylpyridine. The method for producing a film of an organic-inorganic hybrid material according to claim 1, wherein the step (d) further comprises a dehydrating agent. The method for producing an organic-inorganic hybrid material film according to claim 10, wherein the dehydrating agent is acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride and a mixture thereof; an aromatic monocarboxylic acid anhydride; an aliphatic anhydride and an aromatic group; a mixture of anhydrides; carbodiimides; and aliphatic ketenes. A polymaleic anhydride-polyimine-ruthenium oxide mixed material film produced by the method for producing an organic-inorganic hybrid material film according to claim 1, wherein polymaleic anhydride is used as a main chain, and side chains are connected The branches have polyimine and cerium oxide groups. A film obtained by impregnating a film of the polymaleic anhydride-polyimine-cerium oxide mixed material described in claim 12 with a glass cloth. A copper foil substrate formed by pressing at least one copper foil with the film of claim 13.