WO2007119854A1 - 熱硬化性ポリイミド樹脂組成物及びその硬化物 - Google Patents
熱硬化性ポリイミド樹脂組成物及びその硬化物 Download PDFInfo
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- WO2007119854A1 WO2007119854A1 PCT/JP2007/058374 JP2007058374W WO2007119854A1 WO 2007119854 A1 WO2007119854 A1 WO 2007119854A1 JP 2007058374 W JP2007058374 W JP 2007058374W WO 2007119854 A1 WO2007119854 A1 WO 2007119854A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
Definitions
- thermosetting polyimide resin composition and a cured product thereof.
- This thermosetting polyimide resin composition is a one-component curing type, has a long pot life, such as not curing at room temperature, and the cured product has excellent flexibility and can be heated to 250 ° C. It has heat resistance such as not decomposing and has adhesiveness at high temperatures, so it can be applied to various industrial products.
- polyimide resin has been widely used as an engineering plastic having excellent heat resistance.
- a polyimide resin obtained by reacting a bismaleimide compound and an aromatic diamine as raw materials is widely used as an electrically insulating material as a thermosetting polyimide resin.
- thermosetting polyimide resin As a method for producing a thermosetting polyimide resin using the bismaleimide compound and aromatic diamine as raw materials, (1) without using a catalyst, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone (Patent Document 1), (2) A method of reacting a bismaleimide compound and an aromatic diamine using a carboxylic acid or a mineral acid as a catalyst ( Patent document 2) is known.
- the thermosetting polyimide resin obtained by the above-described production method using the conventional bismaleimide compound and aromatic diamine is suitable for use as a composite material such as a structural material, a laminated material, and a molding material.
- a composite material such as a structural material, a laminated material, and a molding material.
- thermosetting polyimide resin by reacting a bismaleimide compound and an aliphatic diamine as raw materials in an organic solvent (Patent Document 3).
- Patent Document 3 a method of obtaining a thermosetting polyimide resin by reacting a bismaleimide compound and an aliphatic diamine as raw materials in an organic solvent.
- aliphatic diamines are reacted in an organic solvent, which is more reactive than aromatic diamines, the molecular weight increases within a short time at low temperatures, and the reaction solution Hardens from liquid to solid, has a short pot life, and is difficult to handle.
- Patent Document 1 French Patent Invention No. 1555564
- Patent Document 2 JP-A-46-3845
- Patent Document 3 Japanese Patent Laid-Open No. 5-148360
- FIG. 1 is a chart showing viscoelasticity measurement results of a cured product (film) of a thermosetting polyimide resin composition synthesized in Example 1.
- FIG. 2 is a chart showing viscoelasticity measurement results of a cured product (film) of the thermosetting polyimide resin composition synthesized in Example 2.
- FIG. 3 is a chart showing viscoelasticity measurement results of a cured product (film) of the thermosetting polyimide resin composition synthesized in Example 3.
- FIG. 4 is a chart showing viscoelasticity measurement results of a cured product (film) of the thermosetting polyimide resin composition synthesized in Example 4.
- the present invention is a one-component curing type, a thermosetting polyimide resin composition having a long pot life, and excellent flexibility, and even when heated to 250 ° C. It is an object of the present invention to provide a cured product having heat resistance that does not decompose and adhesiveness at high temperatures. Means for solving the problem
- the present invention provides:
- thermosetting polyimide resin composition obtained from the following steps (1) to (3),
- Step (1) Tetracarboxylic acid dianhydride represented by the formula (1), tetracarboxylic acid represented by the formula (2), and derivative power of the tetracarboxylic acid Tetra composed of one or more selected compounds
- a carboxylic acid component and an aliphatic diamine represented by the formula (3) are blended so that the number of moles of the tetracarboxylic acid component is larger than the number of moles of the aliphatic diamine, and heated to react.
- Polyimide (A) The process of synthesizing Step (2): Step of synthesizing polyimide (B) by combining the polyimide (A) obtained in step (1) with the aromatic diamine represented by the formula (4) and heating.
- Step (3) Step of blending and mixing the polyimide (B) obtained in step (2) and the bismaleimide compound represented by formula (5)
- R is a tetravalent organic group
- Y to Y are independently hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.
- (X is a divalent group having 1 to 221 carbon atoms in which an aliphatic group or an alicyclic group is directly bonded to an amino group.
- the organic group may contain an aromatic group, an ether group, or other substituents in part of its structure.
- (X is a divalent organic group having 6 to 27 carbon atoms in which an aromatic ring is directly bonded to the amino group.
- an aliphatic group, an alicyclic group, and other substituents may be included in a part of the structure.
- thermosetting polyimide resin composition according to the above (1) which is a polyoxyalkylene diamine
- thermosetting polyimide resin composition according to (1) obtained by heating and curing the thermosetting polyimide resin composition according to (1) above at 150 to 250 ° C for 0.5 to LO time, and
- thermosetting polyimide resin composition described in (2) above at 150 to 250 ° C, 0.5 to 0.5: a cured product having adhesiveness obtained by heating and curing for LO time,
- the present invention is a one-component curable type, has a long pot life, a thermosetting polyimide resin composition, excellent flexibility, and heat resistance such as that it does not decompose even when heated to 250 ° C. And a cured product having adhesiveness at high temperature.
- the aliphatic diamine used in the production of the thermosetting polyimide resin composition is a polyoxyalkylene diamine
- the resulting cured product of the thermosetting polyimide resin composition exhibits adhesiveness. It has the feature to do.
- thermosetting polyimide resin composition which is a component of the thermosetting polyimide resin composition
- polyimide (A) which is a precursor thereof
- thermosetting polyimide resin composition of the present invention can obtain a solution with a high solid content in the production process, work by shortening the drying time when obtaining a cured product of the polyimide resin composition Excellent safety and health can be achieved by rationalizing the process and reducing the amount of solvent discharged during drying.
- tetracarboxylic acid is used as the starting tetracarboxylic acid component.
- an acid dianhydride is used.
- an ester of the tetracarboxylic acid or tetracarboxylic acid and an alcohol can be used.
- tetracarboxylic acid can be used as a raw material as it is, so that a practical polyimide resin composition can be produced advantageously in terms of production equipment and cost.
- thermosetting polyimide resin composition and the cured product thereof according to the present invention are obtained by a method including the following steps (1) to (4).
- Step (1) A tetracarboxylic acid component and an aliphatic diamine are blended so that the number of moles of the tetracarboxylic acid component is larger than the number of moles of the aliphatic diamine, and heated to react to synthesize polyimide (A).
- Step (2) Step of synthesizing polyimide (B) by blending polyimide (A) obtained in step (1) and aromatic diamine and reacting with heating.
- Step (3) Step of obtaining the thermosetting polyimide resin composition by blending the polyimide (B) obtained in step (2) and the bismaleimide compound and mixing at room temperature.
- Step (4) Step of obtaining a cured product by heating and curing the thermosetting polyimide resin composition obtained in step (3).
- the tetracarboxylic dianhydride used in the present invention is represented by the formula (1), and examples thereof include fatty acid tetraforce rubonic acid dianhydride and aromatic tetracarboxylic dianhydride.
- R 1 in the formula (1) is a tetravalent organic group.
- Examples of the aliphatic tetracarboxylic dianhydride include 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, 1, 2, 3, 4-butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentanetetracarboxylic Examples include acid dianhydride, bicyclo [2.2.2] otato 7-ene 2,3,5,6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, and the like.
- aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3, 3 ', 4, 4, -biphenyltetracarboxylic dianhydride, 2, 3, 3', 4 , -Biphenyl tetra-rubber rubonic acid dianhydride, 2, 2 bis (3,4 dicarboxyphenyl) propane dianhydride, 2, 2 bis (2,3 dicarboxyphenol) propane dianhydride, 2 , 2 Bis (3,4 dicarboxylphenyl) -1, 1, 1, 3, 3, 3 Hexafluoropropane dianhydride, 2, 2-bis (2, 3 dicarboxyphenyl) 1, 1, 1, 3, 3, 3 Hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Bis (2,3 dicarboxyphenol) ether dianhydride Bis (2,3
- the tetracarboxylic acid used in the present invention is represented by the formula (2), and examples thereof include aliphatic tetracarboxylic acids and aromatic tetracarboxylic acids.
- R in formula (2) is the same as R in formula (1)
- 1 1 is a tetravalent organic group
- Y to Y are independently hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.
- Examples of the aliphatic tetracarboxylic acid include 1, 2, 4, 5 cyclohexanetetracarboxylic acid, 1, 2, 3, 4 butanetetracarboxylic acid, 1, 2, 3, 4 cyclobutanetetracarboxylic acid.
- Acid, 1, 2, 3, 4 cyclopentanetetracarboxylic acid, bicyclo [2.2.2] oct 7 -2, 3, 5, 6-tetracarboxylic acid, dicyclohexyltetracarboxylic acid, etc., and derivatives thereof include esters of these aliphatic tetracarboxylic acids and alcohols having 1 to 8 carbon atoms. be able to.
- aromatic tetracarboxylic acid examples include pyromellitic acid, 3, 3, 4, 4, 4, 1-biphenyl tetracarboxylic acid, 2, 3, 3 ', 4, 1-biphenyl tetracarboxylic acid, 2 , 2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) ) — 1, 1, 1, 3, 3, 3—Hexafluoroproone, 2,2-bis (2,3-dicarboxyphenol) — 1, 1, 1, 3, 3, 3—Hexafluoro Mouth propane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, bis (2,3-dicarboxyphenyl) ether, 3, 3 ', 4 , 4, 1 Benzophenone tetracarboxylic acid, 2, 2 ', 3,
- 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic acid are preferred. These can be used alone or in combination of two or more.
- the aliphatic diamine used in the present invention is a diamine obtained by directly bonding an aliphatic group or an alicyclic group to an amino group represented by the formula (3).
- X of the aliphatic diamine represented by the formula (3) is a divalent organic group having 1 to 221 carbon atoms.
- a part of the structure contains an aromatic group, an ether group, and other substituents. It is preferable that the aliphatic diamine is a polyoxyalkylene diamine because a thermosetting polyimide resin composition having a flexible adhesive property is obtained.
- tackiness refers to the property of adhering by applying a little pressure at room temperature for a short time without using water, solvent, heat, etc. It refers to the force required to peel off the contacted body after applying a slight pressure to it.
- polyoxyalkylene diamine examples include a polyoxypropylene diamine represented by the formula (7), a polyoxyethylene diamine represented by the formula (8), and a formula (9). And polyoxybutylene diamine and copolymers thereof.
- propylene oxide represented by the formula (6) and polyoxyalkylene diamine containing a skeleton derived from ethylene oxide are preferably used for obtaining a cured product having good adhesiveness.
- n is the degree of polymerization of ethylene oxide units.
- the polyoxyalkylene diamines preferably have the following molecular weights in order to obtain a cured product having good adhesiveness!
- the molecular weight of the polyoxyalkylene diamine of formula (6) is preferably from 300 to 4000 (degree of polymerization of propylene oxide (a + c) from 1.0 to 9.4 (c is not 0), ethylene oxide (B) force of 7 to 79.8), more preferably 600 to 2000 (the degree of polymerization of propylene oxide (a + c) is 3.6 to 6.0 (c is not 0)), The degree of polymerization (b) of ethylene oxide is 9.0 to 38.7).
- the molecular weight of the polyoxypropylene diamine of formula (7) is preferably 230 to 4000 (degree of polymerization of propylene oxide n 2.6 to 68.0), more preferably 600 to 2000 (propylene
- the degree of polymerization of the oxide n is 8.7-33.0.
- the molecular weight of the polyoxyethylene diamine of formula (8) is preferably 300 to 4000 (the degree of polymerization n of ethylene oxide is 5.5 to 89.5), more preferably 600 to 2000 (ethylene oxide).
- the molecular weight of the polyoxybutylene diamine of formula (9) is preferably 200 to 4000 (degree of polymerization of butylene oxide n is 1.6 to 54.3), more preferably 600 to 2000 (butylene oxide).
- the degree of polymerization of the side n is 7.1 to 2.6.6).
- examples of diamines other than polyoxyalkylene diamines include, for example, 4,4'-diaminodicyclohexylenomethane, isophorone diamine, ethylene diamine, Tetramethylene diamine, norbornane diamine, norxylylene diamine, 1,3-bis (aminomethyl) cyclohexane, 1,3-diaminocyclo Examples thereof include hexane, hexamethylenediamine, metaxylylenediamine, 4,4′-methylenebis (cyclohexylamine), bicyclohexyldiamine, and siloxane diamines.
- diamines having an alicyclic structure such as 4,4'-diaminodicyclohexylenomethane, isophorone diamine, 1,3 diaminocyclohexane are used in terms of easy high molecular weight and excellent heat resistance. I prefer that. These diamines can be used alone or in combination of two or more.
- Polyimide (A) comprises the aliphatic diamine of step (1) and a tetracarboxylic dianhydride or tetracarboxylic acid or a tetracarboxylic acid component comprising one or more selected compounds of tetracarboxylic acid or a derivative of tetracarboxylic acid.
- the tetracarboxylic acid component is synthesized by a thermal imidization reaction in which the number of moles of the tetracarboxylic acid component is greater than the number of moles of the aliphatic diamine and heated.
- the tetracarboxylic dianhydride represented by the formula (1) or the tetracarboxylic acid represented by the formula (2) or the derivative power of the tetracarboxylic acid is selected.
- the amount of the tetracarboxylic acid component composed of one or more compounds must be greater than 1 mole per 1 mole of the aliphatic diamine represented by the formula (3). Less than 1 mol is preferred 1.5 to 2 mol is more preferred.
- both ends of the polyimide (A) will not become a group derived from the tetracarboxylic acid component. It is preferable in that it reacts with an aromatic diamine described later, and since a monomer component that does not leave much unreacted tetracarboxylic acid component does not remain, it is preferable without lowering heat resistance.
- the polyimide (A) can be obtained by performing a thermal imidization reaction in the absence of a solvent, but various organic solvents may be used.
- the solvent include N, N dimethylacetamide, N-methyl 2-pyrrolidone, N, N dimethylformamide, dimethyl sulfoxide, hexamethyl phosphoramide, tetramethylene sulfone, and the like. More than seeds can be used. Of these, N-methyl 2-pyrrolidone and N, N dimethylacetamide are preferable.
- xylene or toluene may be added. After the polyimide (A) is synthesized, it can be diluted with a low-boiling solvent such as tetrahydrofuran, acetone, or methanol.
- aliphatic diamine may be used by dissolving in an organic solvent as described above, if necessary.
- the reaction temperature of the thermal imidization reaction is preferably 150 to 200 ° C, particularly 180 to 200 ° C. If the reaction temperature is within the above range, a high molecular weight can be sufficiently obtained, so that a practical polyimide can be synthesized, which is economically preferable in terms of cost.
- the reaction time is preferably 1 to 12 hours, particularly 3 to 6 hours. When the reaction time is within the above range, a high molecular weight is sufficiently obtained, so that a practical polyimide can be synthesized, which is economically preferable in terms of cost.
- toluene or xylene may be added as an azeotropic solvent to carry out a thermal imidization reaction.
- the formation of polyimide can be confirmed by the characteristic absorption of the imide ring near 1770 and 1700 cm 1 by the IR ⁇ vector.
- Step (2) is a step of synthesizing polyimide (B) by thermal imidization reaction in which polyimide (A) obtained in step (1) and aromatic diamine are blended and reacted by heating.
- the aromatic diamine used in this step is a diamine represented by formula (4), in which an aromatic ring is directly bonded to the amino group, and was obtained in step (1) in step (2).
- Polyimide (B) is synthesized by heating reaction with polyimide (A).
- X is a divalent organic group having 6 to 27 carbon atoms, an aliphatic group in a part of its structure,
- aromatic diamines examples include 3,4, -diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl.
- the polyimide ( ⁇ ) is synthesized by a thermal imidization reaction in which the polyimide ( ⁇ ) obtained in step (1) of step (2) is reacted with an aromatic diamine.
- the amount of aromatic diamine represented by the formula (4) is 0 with respect to 1 mol of aliphatic diamine used in the production of polyimide ( ⁇ ). .02 mol or more and 2 mol or less is preferable 1 mol or more and 2 mol or less are more preferable.
- it is preferable to arrange an aromatic amino group at both ends of the polyimide ( ⁇ ). Amount of aromatic diamine added to 1 mol of aliphatic diamine If within the above range, the ratio of unreacted aromatic diamine is not increased, and the thermosetting resin composition obtained in the subsequent step is heated. The flexibility of the cured product obtained by curing does not decrease, which is preferable.
- Polyimide ( ⁇ ) is synthesized by performing a thermal imide reaction in the absence of a solvent, but various organic solvents may be used.
- Solvents include high boiling solvents such as ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylacetamide, ⁇ ⁇ ⁇ -methyl 2-pyrrolidone, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylformamide, dimethyl sulfoxide, hexamethyl phosphoramide, tetramethylene sulfone, tetrahydrofuran, acetone, etc.
- Examples include low-boiling solvents, and one or more of these can be used.
- ⁇ -methyl-2-pyrrolidone, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylacetamide is preferably used as a solvent.
- xylene or toluene may be added to perform azeotropic dehydration.
- aromatic diamine may be used by dissolving in an organic solvent as described above, if necessary.
- the reaction temperature of the thermal imidization reaction is preferably 150 200 ° C, particularly 180 200 ° C. If the reaction temperature is within the above range, high Since the molecular weight is sufficiently increased, a practical polyimide can be synthesized, which is economically preferable in terms of cost.
- the reaction time is preferably 1 to 12 hours, particularly 3 to 6 hours. When the reaction time is within the above range, a high molecular weight can be sufficiently obtained, so that a practical polyimide can be synthesized, which is economically preferable from the viewpoint of cost.
- heat or imido reaction may be carried out by adding toluene or xylene as an azeotropic solvent.
- Step (3) is a step in which the polyimide (B) obtained in step (2) and the bismaleimide compound are blended and mixed at room temperature to obtain a thermosetting polyimide resin composition.
- the bismaleimide compound is represented by the formula (5) and includes the following. N, N '-(4, 4, 1-diphenylmethane) bismaleimide, N, N,-(4, 4, 1-diphenyl) bismaleimide, N, N,-(4, 4, 1-diphenyl sulfone) ) Bismaleimide, N, N, 1 p-Phenylene balemaleimide, N, N, 1m-Phenylene bismaleimide, N, N, 1, 2, 4 Tolylene bismaleimide, N, N '-2, 6-tolylene bismaleimide, N, N, one ethylene bismaleimide, N, N, one hexamethylene bismaleimide, N, N, one ⁇ 4, 4, one [2, 2, one bis (4, , 4 "'-phenoxyphenyl) isopropylidene] ⁇ bismaleimide, N, N, one ⁇ 4, 4, one [2, 2, one bis (4, , 4 "'-phenoxyphenyl) isopropy
- both ends of polyoxyalkylenediamine are Bismaleimide compounds sealed with maleic anhydride can also be used, for example, bismaleimide compounds in which both ends of polyoxyethylenediamine are sealed with maleic anhydride, polyoxypropylene diamine Both ends of min are anhydrous Examples thereof include bismaleimide compounds sealed with acid and compounds in which both ends of polyoxybutylene diamine are sealed with hydrous maleic acid.
- N, N ' Preference is given to (4,4′-diphenylmethane) bismaleimide, N, N, 1 [4,4,1bis (3-methyl-5-ethylphenyl) methane] bismaleimide of the formula (11).
- the blending amount of the bis-maleimide compound represented by the formula (5) is determined when the polyimide (A) is produced. 0.25 mol or more and 4 mol or less are preferable with respect to 1 mol of the aliphatic diamine used, and 0.75 mol or more and 2 mol or less are more preferable. If the blending amount of the bismaleimide compound with respect to 1 mol of aliphatic diamine is within the above range, the crosslink density of the cured product obtained by heat curing the thermosetting polyimide resin composition is low and the strength is insufficient. A thermosetting polyimide resin composition is obtained which gives a flexible cured product.
- thermosetting polyimide resin composition of the present invention various organic solvents may be used in the step (3).
- the solvent include amide solvents such as N, N dimethylacetamide, N-methyl-2-pyrrolidone, N, N dimethylformamide and hexamethylphosphoramide, ketone solvents such as methyl ethyl ketone and acetone, Examples include cyclic ether solvents such as 1,4 dioxane and tetrahydrofuran, and acetonitrile, and one or more of these can be used.
- thermosetting polyimide resin composition and cured product thereof are preferred.
- amide solvents such as N, N dimethylacetamide, N-methyl-2-pyrrolidone, N, N dimethylformamide, and hexamethylphosphoramide are preferred.
- thermosetting polyimide resin composition of the present invention is obtained by the following method.
- the polyimide (B) obtained in step (2) and the bismaleimide compound are mixed in a solvent until a uniform solution is obtained.
- the amount of the solvent in the thermosetting polyimide resin composition is preferably an amount that provides a viscosity capable of casting.
- the mixing temperature is preferably 0 ° C to 80 ° C, more preferably 20 ° C to 60 ° C. If the mixing temperature is within the above range, the bismaleimide compound will not harden into a homogeneous liquid that is difficult to dissolve, and it will not harden from liquid to solid during mixing.
- the cured product of the thermosetting polyimide resin composition of the present invention is obtained by thermosetting the thermosetting polyimide resin composition obtained as described above. It can be obtained by casting the fat composition on a substrate such as glass, stainless steel, aluminum or the like to form a film and thermally curing.
- the curing temperature is preferably 150 to 250 ° C. If the curing temperature is within the above range, it is economically preferable from the viewpoint of cost that no uncured portion remains.
- the curing time is preferably 0.5 to 10 hours. If the curing time is within the above range, it is economically preferable from the viewpoint of cost that no uncured portion remains.
- the cured product of the present invention has adhesiveness, the uncured portion remains and the adhesive strength becomes too high, and cohesive failure occurs when the adherend is attached to the adhesive layer and then peeled off. Since no adhesive residue is generated, the above curing temperature and curing time are preferred.
- the cured product thermally cured on the substrate may be used as it is on the substrate, or may be used as a film after peeling off the substrate force.
- the cured product of the thermosetting polyimide resin composition of the present invention has excellent flexibility and heat resistance.
- the cured product of the thermosetting polyimide resin composition in which the aliphatic diamine used as a raw material is a polyoxyalkylene diamine has adhesiveness, and therefore requires flexibility and adhesiveness at high temperatures.
- the heat-resistant adhesive material used can be suitably used for a wide range of industrial products such as adhesive tape.
- IR spectrum was determined using JEOL's JIR—WINSPEC50 (infrared absorption spectrum).
- thermosetting polyimide resin composition with a solid content of 50 wt% at 25 ° C using a 1 ⁇ 20-type cone plate viscometer manufactured by Ding 01 ⁇ (solvent is N-methyl-2-pyrrolidone) The solution viscosity was determined.
- thermogravimetric analyzer (DTG-50) manufactured by Shimadzu Corporation, the temperature was raised from room temperature at a rate of 10 ° C Zmin in a nitrogen stream, held at 200 ° C for 30 min, and after removing moisture, 200 ° C The temperature was raised from C to 250 ° C at 5 ° C Zmin. After that, it was held at 250 ° C for 1 hour, and the weight loss% when holding at 250 ° C was determined.
- Laminate a Kapton 2000H type polyimide resin film (Toray 'DuPont, model number: 22M11P0860) with a width of 25mm, a length of 150mm, and a thickness of 50 / zm to a cured polyimide film (film) formed on an aluminum plate.
- polyimide resin film 90 degree peel adhesion (NZ25mm) was measured.
- IMAD A digital force gauge ZP-5N, IMADA sliding motorized stand MX-500 N, 90-degree peeling jig P90-200N were used.
- polyimide (A1) After 3 hours, it was confirmed that the distillation of water had stopped, and 3.60 g of water was recovered to obtain polyimide (A1).
- polyimide (A3) After 3 hours, it was confirmed that the distillation of water had stopped, 7.20 g of water was recovered, and allowed to cool to room temperature to obtain polyimide (A3).
- thermosetting polyimide resin composition ⁇ Manufacture of thermosetting polyimide resin composition>
- thermosetting polyimide resin composition does not cure at room temperature.
- this polyimide resin composition was applied to an aluminum plate having a size of 150 mm x 150 mm and a thickness of 1 mm at a coating thickness of 2.00 mm, and cured by placing it in a dryer at 240 ° C for 1 hour.
- a cured polyimide (film) having a rubber elasticity of 0.7 mm was obtained, and the cured polyimide (film) was peeled from the aluminum plate to confirm that it was a flexible film.
- the weight loss% of the cured polyimide (film) when held at 250 ° C for 1 hour was measured and found to be 0.08%. At 250 ° C, there was almost no weight loss, so it was heated to 250 ° C. Even though it was not decomposed, it had a heat resistance.
- thermosetting polyimide resin composition ⁇ Manufacture of thermosetting polyimide resin composition>
- Total amount of solution, N, N,-[4,4, -bis (3-methyl-5-ethylphenyl) methane] bismaleimide 22.27 g (0.050 mol), N-methyl-2-pyrodidone 70. 63 g Was added and stirred at room temperature for 1 hour to completely dissolve it to obtain a thermosetting polyimide resin composition.
- the solution viscosity of this thermosetting polyimide resin composition was measured and found to be 0.43 Pa's.
- this polyimide resin composition was applied to an aluminum plate having a size of 150 mm x 150 mm and a thickness of 1 mm at a coating thickness of 2.00 mm, and cured by placing it in a dryer at 240 ° C for 1 hour.
- a cured polyimide (film) having a rubber elasticity of 0.7 mm was obtained, and the cured polyimide (film) was peeled from the aluminum plate to confirm that it was a flexible film.
- the weight loss% of the cured polyimide (film) when held at 250 ° C for 1 hour was measured and found to be 0.12%. At 250 ° C, there was almost no weight loss, so it was heated to 250 ° C. Even though it was not decomposed, it had a heat resistance.
- the storage elastic modulus (G ') at 25 ° C was 2.03 X 10 7 Pa and the loss elastic modulus (G ") was 1. 99 X 10 7 Pa.
- the storage elastic modulus (G ') around 250 ° C does not change and is almost constant, so the region around 250 ° C is a rubber-like region, and it has rubber elasticity even when heated to 250 ° C. However, it was divided.
- the peak top force of the loss tangent (tan ⁇ ) was 32.0 ° C when the glass transition temperature was determined.
- thermosetting polyimide resin composition ⁇ Manufacture of thermosetting polyimide resin composition>
- thermosetting polyimide resin composition was measured and found to be 0.40 Pa's. Further, when the solution viscosity after measuring the solution at 23 ° C. and 50% RH for 1 month was measured, it was 0.51 Pa's, and the solution viscosity almost changed. It was found that this thermosetting polyimide resin composition does not cure at room temperature.
- this polyimide resin composition was applied to an aluminum plate having a size of 150 mm x 150 mm and a thickness of 1 mm at a coating thickness of 3.00 mm and cured by placing it in a dryer at 240 ° C for 1 hour.
- a cured polyimide (film) having a rubber-like elasticity of 26 mm was obtained, and the cured polyimide (film) was peeled off from the aluminum plate to confirm that it was a flexible film.
- the weight loss% of the cured polyimide (film) when held at 250 ° C for 1 hour was measured, it was 0.13%, and the weight was hardly reduced at 250 ° C, so it was heated to 250 ° C.
- the storage elastic modulus (G ') around 250 ° C does not change and is almost constant, so the region around 250 ° C is a rubber-like region, and it has rubber elasticity even when heated to 250 ° C. However, it was divided.
- the peak top force of the loss tangent (tan ⁇ ) was also -43.0 ° C when the glass transition temperature was determined.
- thermosetting polyimide resin composition ⁇ Manufacture of thermosetting polyimide resin composition>
- thermosetting polyimide resin composition Total reaction product solution containing polyimide (B3) obtained in Synthesis Example 3 in a 500 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, and condenser tube in a nitrogen stream , N, N,-(4, 4, 1-diphenylmethane) bismaleimide 38.43g (0.10 mol), N-methyl-2-pyrrolidone 56.55g was added and stirred at room temperature for 1 hour to complete To obtain a thermosetting polyimide resin composition. The solution viscosity of this thermosetting polyimide resin composition The measured value was 2. OOPa's. Furthermore, when this solution was allowed to stand at 23 ° C. and 50% RH for 1 month, the solution viscosity was measured to be 2.57 Pa's, and the solution viscosity almost changed! It was found that this thermosetting polyimide resin composition did not cure at room temperature.
- this polyimide resin composition was applied to an aluminum plate having a size of 150 mm x 150 mm and a thickness of 1 mm at a coating thickness of 1.30 mm, and cured by placing it in a dryer at 240 ° C for 1 hour.
- a cured polyimide (film) of 0.5 mm was obtained, and it was confirmed that the aluminum plate strength was a flexible film by peeling off the cured polyimide (film).
- the weight loss% of this polyimide cured product (film) when held at 250 ° CZl time was measured, it was 0.93%, and at 250 ° C there was almost no weight reduction. It was found that even when heated, it did not decompose and was heat resistant.
- the storage elastic modulus (G ') at 25 ° C was 5.08 X 10 8 Pa, and the loss elastic modulus (G ") was 1. was 90 X 10 7 Pa.
- the storage modulus around 250 ° C (G ') since no change is substantially constant, around 250 ° C is rubbery region, to 250 ° C Even when heated, it had a rubber elasticity, and the peak top force of loss tangent (tan ⁇ ) was 171.0 ° C when the glass transition temperature was determined.
- thermosetting polyimide resin composition obtained in Example 1 was applied to an aluminum plate having a size of 150 mm X 150 mm and a thickness of 1 mm at a coating thickness of 0.88 mm, and placed in a dryer at 230 ° C for 2 hours to harden. As a result, a cured polyimide (film) having a thickness of 0.44 mm was obtained.
- the polyimide cured product (film) formed on this aluminum plate was bonded with a “Kapton 200H” polyimide resin film with a width of 25 mm, a length of 150 mm, and a thickness of 50 m. When the peel strength (NZ25mm) was determined, it was 0.31 (NZ25mm). In addition, when measuring the 90 ° peel adhesive strength, it is visually inspected whether there is so-called adhesive residue that causes adhesive substances to adhere to the surface of the “Kapton 200H” polyimide resin film. It was confirmed that there was no remaining.
- thermosetting polyimide resin composition obtained in Example 2 was applied to an aluminum plate having a size of 150 mm X 150 mm and a thickness of 1 mm at a coating thickness of 0.80 mm, and placed in a dryer at 230 ° C for 2 hours to harden. As a result, a cured polyimide (film) having a thickness of 0.40 mm was obtained.
- the polyimide cured product (film) formed on this aluminum plate was bonded with a “Kapton 200H” polyimide resin film with a width of 25 mm, a length of 150 mm, and a thickness of 50 m. When the peel strength (NZ25mm) was determined, it was 0.13 (NZ25mm).
- thermosetting polyimide resin composition obtained in Example 3 was applied to an aluminum plate having a size of 150 mm X 150 mm and a thickness of 1 mm at a coating thickness of 0.84 mm, and placed in a dryer at 230 ° C for 2 hours to harden. As a result, a cured polyimide (film) having a thickness of 0.42 mm was obtained.
- the polyimide cured product (film) formed on this aluminum plate was bonded with a “Kapton 200H” polyimide resin film with a width of 25 mm, a length of 150 mm, and a thickness of 50 m.
- peel strength NZ25mm
- thermosetting polyimide resin composition ⁇ Manufacture of thermosetting polyimide resin composition>
- thermosetting polyimide resin composition ⁇ Manufacture of thermosetting polyimide resin composition>
- thermosetting polyimide resin composition was obtained.
- This thermosetting polyimide resin composition was applied to an aluminum plate with a size of 150 mm x 150 mm and a thickness of 1 mm at a coating thickness of 1.
- thermosetting polyimide resin composition of the present invention is a one-component curing type, gives a cured product having flexibility and adhesiveness, and has high heat resistance with a long pot life.
- the aliphatic diamine used in the production of the thermosetting polyimide resin composition is a polyoxyalkylene diamine
- the resulting cured product of the thermosetting polyimide resin composition is characterized by exhibiting tackiness.
- pressure-sensitive adhesive tapes as a heat-resistant adhesive material that requires flexibility and adhesiveness at high temperatures.
- thermosetting polyimide resin composition which is a component of the thermosetting polyimide resin composition
- polyimide (A) which is a precursor thereof
- thermosetting polyimide resin composition of the present invention can obtain a solution with a high solid content in the production process, work by shortening the drying time when obtaining a cured product of the polyimide resin composition Excellent safety and health can be achieved by rationalizing the process and reducing the amount of solvent discharged during drying.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US12/297,518 US20090306306A1 (en) | 2006-04-18 | 2007-04-17 | Thermosetting polyimide resin composition and cured product thereof |
CN2007800130304A CN101421356B (zh) | 2006-04-18 | 2007-04-17 | 热固性聚酰亚胺树脂组合物及其固化物 |
EP07741810A EP2009058B1 (en) | 2006-04-18 | 2007-04-17 | Thermosetting polyimide resin composition and cured product thereof |
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JP2006-114948 | 2006-04-18 | ||
JP2006114948 | 2006-04-18 | ||
JP2006248550A JP2007308676A (ja) | 2006-04-18 | 2006-09-13 | 熱硬化性ポリイミド樹脂組成物及びその硬化物 |
JP2006-248550 | 2006-09-13 |
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WO2007119854A1 true WO2007119854A1 (ja) | 2007-10-25 |
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PCT/JP2007/058374 WO2007119854A1 (ja) | 2006-04-18 | 2007-04-17 | 熱硬化性ポリイミド樹脂組成物及びその硬化物 |
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US (1) | US20090306306A1 (ja) |
EP (1) | EP2009058B1 (ja) |
JP (1) | JP2007308676A (ja) |
KR (1) | KR20090004930A (ja) |
CN (1) | CN101421356B (ja) |
TW (1) | TWI405794B (ja) |
WO (1) | WO2007119854A1 (ja) |
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WO2008041723A1 (fr) * | 2006-10-04 | 2008-04-10 | Mitsubishi Gas Chemical Company, Inc. | Composition de résine polyimide thermodurcissable en deux parties et produit durci à base de ladite composition |
WO2010128667A1 (ja) * | 2009-05-08 | 2010-11-11 | 三菱瓦斯化学株式会社 | 熱硬化性ポリイミド樹脂組成物、硬化物及び粘着剤 |
WO2012099133A1 (ja) * | 2011-01-18 | 2012-07-26 | 日立化成工業株式会社 | 変性シリコーン化合物、これを用いた熱硬化性樹脂組成物、プリプレグ、積層板及びプリント配線板 |
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CN108752928B (zh) * | 2018-05-03 | 2021-03-09 | 中国科学院宁波材料技术与工程研究所 | 一种含呋喃环的交联型聚酰亚胺树脂及其制备方法 |
CN114456378B (zh) * | 2020-11-09 | 2024-02-27 | 江苏三月科技股份有限公司 | 一种用于液晶取向剂的聚酰亚胺及其制备的液晶取向膜 |
JP2022097398A (ja) * | 2020-12-18 | 2022-06-30 | 信越化学工業株式会社 | 熱硬化性マレイミド樹脂組成物 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008041723A1 (fr) * | 2006-10-04 | 2008-04-10 | Mitsubishi Gas Chemical Company, Inc. | Composition de résine polyimide thermodurcissable en deux parties et produit durci à base de ladite composition |
US8273456B2 (en) | 2006-10-04 | 2012-09-25 | Mitsubishi Gas Chemical Company, Inc | Two-part thermocurable polyimide resin composition and cured product thereof |
WO2010128667A1 (ja) * | 2009-05-08 | 2010-11-11 | 三菱瓦斯化学株式会社 | 熱硬化性ポリイミド樹脂組成物、硬化物及び粘着剤 |
WO2012099133A1 (ja) * | 2011-01-18 | 2012-07-26 | 日立化成工業株式会社 | 変性シリコーン化合物、これを用いた熱硬化性樹脂組成物、プリプレグ、積層板及びプリント配線板 |
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Also Published As
Publication number | Publication date |
---|---|
TWI405794B (zh) | 2013-08-21 |
TW200804464A (en) | 2008-01-16 |
KR20090004930A (ko) | 2009-01-12 |
CN101421356A (zh) | 2009-04-29 |
US20090306306A1 (en) | 2009-12-10 |
EP2009058B1 (en) | 2012-07-18 |
CN101421356B (zh) | 2011-07-13 |
EP2009058A1 (en) | 2008-12-31 |
EP2009058A4 (en) | 2010-07-21 |
JP2007308676A (ja) | 2007-11-29 |
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