Classifications

• • 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
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • 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
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • 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
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0346—Organic insulating material consisting of one material containing N
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0393—Flexible materials
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/0154—Polyimide

Definitions

• One embodiment of the present invention relates to a polyimide precursor, a polyimide, a resin composition, a polyimide molded body, a polyimide, and a flexible substrate.
• Polyimide has excellent heat resistance, mechanical strength, and high chemical resistance, so it is applied to various applications.
• polyimide is used as an insulating material in electronic parts or mechanical parts because it exhibits high insulating properties. Because of these characteristics, polyimide is used as a coating film for substrates, protective films, etc. in displays, solar cells, touch panels, organic EL lighting, millimeter-wave radar, and the like.
• Patent Document 1 proposes a solvent-insoluble polyimide film containing diaminediamine in an amount of more than 15 mol% and less than 50 mol% with respect to the total diamine component as a polyimide film having a low dielectric constant and a low dielectric loss tangent and exhibiting solvent insolubility.
• Patent Document 2 proposes a polyimide film containing diaminediamine in an amount of 5 mol% or more and 25 mol% or less with respect to the total diamine component as a polyimide film having a low dielectric constant and a low thermal expansion coefficient and excellent rigidity and toughness. ing.
• Patent Document 1 the dielectric property is improved when the compounding ratio of dimer diamine is high, but since the polyimide becomes solvent-soluble, the solvent-insoluble polyimide film is formed by limiting the upper limit of the compounding ratio of diamine diamine. Trying to get. Further, Patent Document 1 provides a laminated board in which a polyimide containing dimer diamine is sandwiched between polyimides containing no diamine diamine and having a low coefficient of thermal expansion from the viewpoint of a low coefficient of thermal expansion. Patent Document 2 discloses that the elongation of the polyimide film is preferably 50% or more and 90% or less in order to exhibit appropriate rigidity and toughness.
• a polyimide film having excellent toughness has an advantage that it has excellent coating film forming property and can easily form a coating film having a curved surface shape as a coating resin for electric wires or the like.
• dimer diamine when dimer diamine is used to improve the dielectric property, the obtained polyimide film is not sufficiently strong. In such a polyimide, it is difficult to further increase the strength due to the low dielectric constant and the low dielectric loss tangent, and there is a problem that the elongation at break cannot be sufficiently obtained.
• One object of the present disclosure is to provide a polyimide having excellent dielectric properties and strength, and a polyimide precursor for obtaining this polyimide.
• [6] Contains structural units derived from diamine and structural units derived from tetracarboxylic acid dianhydride, and contains 5 to 80 mol% of structural units derived from dimerdiamine with respect to all the structural units derived from the diamine.
• [7] A flexible substrate having the polyimide according to [6].
• the polyimide precursor according to one embodiment of the present disclosure is a polyimide precursor obtained by reacting diamine with a tetracarboxylic acid dianhydride, and is 5 to 80 mol% with respect to the diamine component contained in the polyimide precursor. It contains a diamine diamine and is characterized by having a weight average molecular weight of 15,000 to 130000. According to this polyimide precursor, it is possible to provide a polyimide having excellent dielectric properties and strength. This polyimide can be widely applied as a polyimide molded product, and is suitable for applications requiring high insulation.
• the polyimide formed by using this polyimide precursor is provided with a diamine diamine skeleton, so that the dielectric constant can be reduced by increasing the free volume. Further, in this polyimide, a low dielectric loss tangent can be obtained by introducing a long chain structure derived from dimer diamine, which reduces the concentration of imide groups and the relative decrease of polar groups.
• Polyimide having a low relative permittivity can be widely used as an insulating material.
• a low dielectric loss tangent As well as a low dielectric constant. Since the transmission loss tends to increase as the frequency increases, it is preferable to provide a low dielectric loss tangent even in the high frequency region.
• the polyimide obtained by using the polyimide precursor of one embodiment can have a low dielectric constant and a low dielectric loss tangent, and shows the tendency even in a high frequency region.
• Such polyimide can be used for various electronic parts and mechanical parts, and can be used, for example, for displays, solar cells, touch panels, organic EL lighting, millimeter-wave radars, and the like.
• the obtained polyimide has a high breaking elongation and can be molded into various applications such as a film, a substrate, and a molded body.
• This polyimide can be used, for example, for a flexible substrate. Since this polyimide has a high breaking elongation, even a polyimide single layer can be used as a base film for a flexible substrate. Further, when this polyimide is formed into a film on a base material, since the film has a high breaking elongation, it is possible to prevent the film from being damaged when the base material on which the film is formed is bent.
• polyimide precursor of one embodiment has a large weight average molecular weight, it is possible to improve the chemical resistance and water resistance of the obtained polyimide.
• Polyimide is a material with excellent heat resistance. For example, even in an application in which it comes into contact with chemicals or water in a high temperature environment, this polyimide can prevent decomposition due to hydrolysis and have excellent dielectric properties. Such characteristics are useful for parts that can withstand high temperatures, such as electronic parts installed near the engine of an automobile. For example, it is useful in applications where transmission loss in a high frequency region is a problem, such as in-vehicle millimeter-wave radar.
• this polyimide has flexibility, it can be used as a substrate for an in-vehicle millimeter-wave radar, a protective film, or a combination thereof, and has excellent dielectric properties, and the base material can be deformed and installed according to the shape of the vehicle body. be.
• the polyimide precursor according to one embodiment can be obtained by reacting a diamine compound with a tetracarboxylic acid dianhydride compound. This reaction can be carried out by mixing and polymerizing a diamine compound and a tetracarboxylic acid dianhydride compound in an organic solvent.
• the polyimide precursor can contain dimer diamine as a diamine component.
• Dimerdiamine is a compound derived from dimer acid, more specifically, a compound derived from dimer acid which is a dimer of unsaturated fatty acids such as oleic acid and linoleic acid.
• Dimerdiamine is, for example, a compound represented by the following general formulas (1) to (4). These dimer diamines may be used alone or in combination of two or more.
• the broken line indicates a single bond or a double bond, and all three broken lines may be a single bond, or a part or all of them may be a double bond.
• x is 2 when the broken line between CH x is a single bond and 1 when the broken line between CH x is a double bond.
• the diamine diamine is preferably a compound having a carbocyclic structure, and more preferably a compound represented by the general formula (4).
• the broken line on the carbon ring structure is a single bond, both the broken lines in the carbon chain shape are single bonds, or a combination thereof is preferable, and all the broken lines are. It is preferably a single bond.
• diamine diamines examples include "PRIAMINE 1075, PRIAMINE 1074" manufactured by Croda Japan Co., Ltd. (both are trade names).
• the polyimide precursor according to one embodiment can contain diamine diamine in an amount of 5 to 80 mol% with respect to the diamine component contained in the polyimide precursor.
• the diamine diamine is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, based on the diamine component contained in the polyimide precursor. Thereby, the relative permittivity and the dielectric loss tangent of the obtained polyimide can be lowered.
• the diamine diamine is preferably 80 mol% or less, more preferably 50 mol% or less, based on the diamine component contained in the polyimide precursor. This makes it possible to prevent a decrease in the heat resistance of the obtained polyimide. Further, it is possible to provide a polyimide suitable for an application having a high tensile strength or a high tensile elastic modulus.
• the proportion of the dimer diamine may be 40 mol% or less, and may be 30 mol% or less.
• the diamine diamine is preferably 5 to 80 mol%, 10 to 50 mol%, or 20 to 40 mol% with respect to the diamine component contained in the polyimide precursor. Within this range, the relative permittivity and dielectric loss tangent can be lowered while maintaining various characteristics.
• the polyimide precursor of one embodiment has a large weight average molecular weight, it is possible to prevent a decrease in the strength of the obtained polyimide even when the compounding ratio of the diamine diamine is large.
• a polyimide having a large blending ratio of dimer diamine and a lower dielectric constant and a low dielectric loss tangent can provide a high-strength molded product, and can be applied to, for example, a flexible substrate.
• the polyimide precursor polymerizes the tetracarboxylic acid dianhydride compound and the diamine compound in a molar equivalent of 1: 1, the tetracarboxylic acid dianhydride compound and the diamine compound are in a molar ratio of approximately 1: 1. Including by ratio.
• the two or more kinds of diamine compounds are introduced into the polyimide precursor while maintaining the molar ratio added to the synthetic system. From this, the amount of diamine diamine with respect to the diamine component contained in the polyimide precursor can be obtained from the following formula using the molar ratio of the diamine compound added to the synthetic system. ((Mole number of diamine diamine) / (total number of moles of diamine compound)) ⁇ 100 (mol%)
• the polyimide precursor may contain other diamines other than diamine diamine as the diamine component of the polyimide precursor.
• examples of other diamines include aromatic diamines, alicyclic diamines, aliphatic diamines, and the like, or a combination of two or more thereof.
• the aromatic ring may be either a monocyclic ring or a polycyclic ring.
• the polycycle may be a dicyclic ring, a tricyclic ring, a tetracyclic ring, or the like, and may be a condensed ring thereof.
• the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle.
• the aromatic diamine preferably has a monocyclic structure such as a benzene ring or a bicyclic structure such as biphenyl, diphenylmethane or diphenyl ether. Further, the aromatic diamine may have a nitrogen atom, a fluorine atom, a sulfonyl group, a sulfo group, an alkyl group or the like introduced therein.
• aromatic diamine examples include 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4.
• diamine having 2 to 4 benzene rings is preferable.
• diamines with a phenyl ether structure are preferred.
• 4,4'-diaminodiphenyl ether, 4,3'-diaminodiphenyl ether, 4,4'-bis (4-aminophenoxy) biphenyl, or a combination thereof is preferable, and 4,4'-diaminodiphenyl ether is preferable. More preferred.
• the alicyclic structure may be any of cycloalkane, cycloalkene, cycloalkyne, and any of polycyclic structures such as monocyclic, bicyclic, tricyclic, and tetracyclic. good.
• the number of carbon atoms in the alicyclic structure is preferably 3 to 20, more preferably 4 to 12, and even more preferably 6 to 10.
• the alicyclic structure is preferably cycloalkane, for example, cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, norbornan, and cycloalkanes thereof.
• examples thereof include a polycyclic structure having two or more.
• the alicyclic diamine may have a nitrogen atom, a fluorine atom, a sulfonyl group, a sulfo group, an alkyl group or the like introduced therein.
• Examples of the alicyclic diamine include 4,4'-methylenebis (cyclohexaneamine), 4,4'-methylenebis (2-methylcyclohexaneamine), 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis.
• Examples thereof include (aminomethyl) cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, norbornandiamine, bis (aminomethyl) norbornane, and hydrogenated m-xylylene diamine.
• Examples of the aliphatic diamine include hexamethylenediamine and 2,2,4-trimethylhexamethylenediamine.
• the above-mentioned other diamines may be used alone or in combination of two or more.
• the fluidity of the resin composition containing the polyimide precursor is improved and the coatability can be further improved. It is considered that this is because the formation of by-products such as sparingly soluble salts can be suppressed in the resin composition by mixing two or more kinds of diamine compounds.
• tetracarboxylic acid dianhydride component of the polyimide precursor examples include aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride, and two or more of these. Combinations can be mentioned.
• aromatic tetracarboxylic acid dianhydride as the tetracarboxylic acid dianhydride component, it is possible to further prevent the deterioration of heat resistance.
• the aromatic ring may be either a monocyclic ring or a polycyclic ring.
• the polycycle may be a dicyclic ring, a tricyclic ring, a tetracyclic ring, or the like, and may be a condensed ring thereof.
• the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle.
• the aromatic tetracarboxylic acid dianhydride preferably has a monocyclic structure such as a benzene ring or a bicyclic structure such as biphenyl, diphenylmethane or diphenyl ether.
• aromatic tetracarboxylic acid dianhydride may have a nitrogen atom, a fluorine atom, a sulfonyl group, a sulfo group, an alkyl group or the like introduced therein.
• aromatic tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetra.
• tetracarboxylic acid dianhydride having 1 to 2 benzene rings is preferable, for example, pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, and the like. Alternatively, a combination of these is preferable. Among them, when combined with a diamine component containing dimerdiamine, tetracarboxylic acid dianhydride having one benzene ring is preferable, and for example, pyromellitic acid dianhydride is preferable.
• the tetracarboxylic acid dianhydride having one benzene ring may be 30 mol% or more, preferably 50 mol% or more, and 80 to 100 mol% with respect to the tetracarboxylic acid dianhydride component. It's okay.
• the alicyclic structure may be any of cycloalkane, cycloalkene, and cycloalkyne, and has a polycyclic structure such as a monocyclic structure, a bicyclic, a tricyclic, and a tetracyclic. It may be either.
• the number of carbon atoms in the alicyclic structure is preferably 3 to 20, more preferably 4 to 12, and even more preferably 6 to 10.
• This alicyclic structure is, for example, a cycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and a polycyclic structure having two or more of these cycloalkanes. And so on.
• the alicyclic tetracarboxylic acid dianhydride may have a nitrogen atom, a fluorine atom, a sulfonyl group, a sulfo group, an alkyl group or the like introduced therein.
• Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2 and 4,5-cyclohexanetetracarboxylic acid dianhydride.
• Examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic acid dianhydride as the tetracarboxylic acid dianhydride.
• the above-mentioned tetracarboxylic acid dianhydride may be used alone or in combination of two or more.
• the weight average molecular weight of the polyimide precursor is preferably 15,000 to 130000.
• the weight average molecular weight of the polyimide precursor is preferably 15,000 or more, more preferably 30,000 or more, and even more preferably 60,000 or more.
• the weight average molecular weight of the polyimide precursor is preferably 130000 or less, more preferably 100,000 or less, still more preferably 80,000 or less. As a result, it is possible to suppress an increase in viscosity and further improve the coatability when forming a paint.
• the number average molecular weight of the polyimide precursor is preferably 10,000 to 80,000.
• the number average molecular weight of the polyimide precursor is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more.
• the number average molecular weight of the polyimide precursor is preferably 80,000 or less, more preferably 60,000 or less, still more preferably 50,000 or less. As a result, it is possible to suppress an increase in viscosity and further improve the coatability when forming a paint.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin are measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
• the calibration curve is approximated by a cubic equation using a 5-sample set of standard polystyrene (TSK standard POLYSTYRENE [manufactured by Tosoh Corporation, trade name]).
• TSK standard POLYSTYRENE manufactured by Tosoh Corporation, trade name
• GPC device High-speed GPC device HLC-8320GPC (manufactured by Tosoh Corporation, product name)
• Detector Ultraviolet absorption detector UV-8320 (manufactured by Tosoh Corporation, product name)
• Eluent: THF / DMF 1/1 (volume ratio) + LiBr (0.06 mol / L) + H 3 PO 4 (0.06 mol / L)
• Flow rate 1 mL / min
• Sample concentration 5 mg / 1 mL
• Injection volume 5 ⁇ L Measurement temperature: 40 ° C
• polyimide precursor is one containing 5 to 20 mol% of diamine diamine with respect to the diamine component contained in the polyimide precursor and having a weight average molecular weight of 60,000 or more.
• the polyimide obtained by using this polyimide precursor has a high elongation at break and can satisfy a relative permittivity of 3.3 or less, a dielectric loss tangent of 0.005 or less, or both.
• Another example of the polyimide precursor contains 20 mol% to 80% of diamine diamine with respect to the diamine component contained in the polyimide precursor, and has a weight average molecular weight of 60,000 or more.
• the polyimide obtained by using this polyimide precursor has a high elongation at break and can satisfy a relative permittivity of 2.9 or less, a dielectric loss tangent of 0.0015 or less, or both.
• Still another example of the polyimide precursor is one containing 30 mol% to 80% of diamine diamine with respect to the diamine component contained in the polyimide precursor and having a weight average molecular weight of 60,000 or more.
• the polyimide obtained by using this polyimide precursor has a high elongation at break, and can satisfy the dielectric constant of 2.7 or less, the dielectric loss tangent of 0.0015 or less, or both of them.
• Still another example of the polyimide precursor is one containing 50 mol% to 80% of diamine diamine with respect to the diamine component contained in the polyimide precursor and having a weight average molecular weight of 60,000 or more.
• the polyimide obtained by using this polyimide precursor has a high elongation at break, and can satisfy the dielectric constant of 2.7 or less, the dielectric loss tangent of 0.0015 or less, or both of them.
• the polyimide precursor according to one embodiment may have the above-mentioned configuration, and is not limited to the manufacturing method thereof.
• an example of a method for producing a polyimide precursor will be described, but the polyimide precursor according to one embodiment is not limited to the one produced by the following production method.
• One method for producing a polyimide precursor can include reacting a diamine compound with a tetracarboxylic acid dianhydride compound.
• the diamine compound can include dimer diamine.
• the diamine compound may contain other diamines such as aromatic diamines, alicyclic diamines and aliphatic diamines in addition to dimer diamines.
• the tetracarboxylic acid dianhydride compound can include aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride and the like. Details of the diamine compound and the tetracarboxylic acid dianhydride compound are as described above.
• the mixing ratio of the diamine compound and the tetracarboxylic acid dianhydride compound may be, for example, approximately 1: 1 in terms of molar ratio, and is adjusted in the range of 1.00: 0.95 to 1.00 to 1.05. It is preferable to do so.
• the reaction between the diamine compound and the tetracarboxylic acid dianhydride can be carried out by solution polymerization.
• the synthetic solvent include N-methyl-2-pyrrolidone, N, N'-dimethylformamide, ⁇ -butyrolactone, N, N'-dimethylpropylene urea [1,3-dimethyl-3,4,5,6- Tetrahydropyridimin-2 (1H) -one], dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, sulfolane, dimethylacetamide and other polar solvents, xylene, toluene and other aromatic hydrocarbon solvents, methyl ethyl ketone, methyl isobutyl ketone and the like.
• ketones include these may be used alone or in combination of two or more.
• the amount of the synthetic solvent used in the reaction is preferably 100 to 600 parts by mass, more preferably 200 to 400 parts by mass, based on 100 parts by mass of the total amount of diamine and tetracarboxylic acid dianhydride.
• the amount of the synthetic solvent used is 100 parts by mass or more, each component can be reacted homogeneously.
• the amount of the synthetic solvent used is 600 parts by mass or less, the polymerization reaction can be promoted. Further, since the amount of the synthetic solvent used is small, the resin concentration of the obtained resin composition can be increased, and the coating film can be made thicker at the time of coating.
• the polyimide precursor synthesized by the above method can have a weight average molecular weight in the above range.
• the weight average molecular weight can be adjusted by sampling the polyimide precursor during the synthesis and continuing the synthesis until the desired weight average molecular weight is reached.
• the number average molecular weight of the polyimide precursor can be adjusted in the same manner as the weight average molecular weight.
• the reaction temperature is not particularly limited, but the reaction can be allowed to proceed by mixing the raw materials in a synthetic solvent at room temperature, for example, 50 ° C. or lower, 40 ° C. or lower. It may be 10 ° C. or higher, and may be 20 ° C. or higher.
• the reaction time is preferably 3 hours or more, more preferably 5 hours or more, still more preferably 8 hours or more, from the viewpoint of obtaining a high molecular weight polyimide precursor.
• the end point of the reaction can be from sampling the reaction product to measuring the weight average molecular weight until the desired weight average molecular weight is reached.
• the present disclosure can provide a polyimide obtained by curing the above-mentioned polyimide precursor. Since this polyimide has a low dielectric constant and a low dielectric loss tangent, it can be preferably used for an insulating polyimide molded product. Since this polyimide is obtained by curing a high molecular weight polyimide precursor, it is possible to provide a polyimide molded body having excellent strength, particularly a polyimide molded body having high elongation. Such a polyimide molded body is useful for various applications that require insulation and strength, and is useful, for example, for application to a flexible substrate.
• Polyimide The present disclosure includes structural units derived from diamines and tetracarboxylic acid dianhydrides, including 5-80 mol% of structural units derived from dimerdiamine relative to all units of structural units derived from diamines. , A polyimide having a breaking elongation of 95% or more can be provided. This polyimide has a high elongation at break and can have a low dielectric constant and a low dielectric loss tangent. By using this polyimide, it is possible to provide a polyimide molded body having excellent dielectric properties and strength.
• the polyimide can contain a structural unit derived from a diamine and a structural unit derived from a tetracarboxylic acid dianhydride.
• the diamine-derived structural unit may be a diamine-derived structural unit that can be used for the above-mentioned polyimide precursor.
• the structural unit derived from tetracarboxylic acid dianhydride may be a structural unit derived from tetracarboxylic acid dianhydride that can be used for the above-mentioned polyimide precursor.
• the structural unit derived from diamine may be contained in one kind or a combination of two or more kinds, and the structural unit derived from tetracarboxylic acid dianhydride may be contained in one kind or a combination of two or more kinds. good.
• the structural unit derived from diamine can include a structural unit derived from dimer diamine.
• the structural unit derived from dimer diamine may be a structural unit derived from dimer diamine that can be used for the above-mentioned polyimide precursor.
• 5 to 80 mol% of the structural units derived from diamine diamine can be contained with respect to all the structural units derived from diamine.
• the unit derived from diamine diamine is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, based on all the structural units derived from diamine. Thereby, the relative permittivity and the dielectric loss tangent of the polyimide can be lowered.
• the unit derived from diamine diamine is preferably 80 mol% or less, more preferably 50 mol% or less, with respect to all the structural units derived from diamine. This makes it possible to prevent the heat resistance of the polyimide from being lowered. Further, it is possible to provide a polyimide suitable for an application having a high tensile strength or a high tensile elastic modulus. From the viewpoint of obtaining high heat resistance, high tensile strength or high tensile elastic modulus, the proportion of the dimer diamine may be 40 mol% or less, and may be 30 mol% or less.
• the unit derived from diamine diamine is preferably 5 to 80 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%, based on all the structural units derived from diamine.
• the relative permittivity and dielectric loss tangent can be lowered while maintaining various characteristics.
• the polyimide has a breaking elongation of 95% or more.
• the breaking elongation of the polyimide is preferably 95% or more, more preferably 100% or more, still more preferably 150% or more.
• a molded body having flexibility can be obtained, and for example, it can be usefully used for a molded body that requires bending stress, for example, a flexible substrate or the like.
• the breaking elongation of the polyimide is not particularly limited, but may be 500% or less, 400% or less, and further 350% or less.
• the breaking elongation of the polyimide is preferably 95 to 500%, may be 100 to 400%, and may be further 150 to 350%.
• the polyimide has a tensile strength of 10 to 400 MPa or more.
• the tensile strength of the polyimide is preferably 10 MPa or more, more preferably 50 MPa or more, from the viewpoint of material strength.
• the tensile strength of the polyimide is preferably 400 MPa or less, more preferably 300 MPa or less, and may be 200 MPa or less.
• the polyimide has a tensile elastic modulus of 0.1 to 5 GPa.
• the tensile elastic modulus of the polyimide is preferably 0.1 GPa or more, more preferably 0.3 GPa or more, and may be 0.5 GPa or more from the viewpoint of material strength.
• the tensile elastic modulus of the polyimide is preferably 5 GPa or less, more preferably 3 GPa or less, and even more preferably 2.0 GPa or less. This can improve problems such as mounting defects such as peeling and disconnection due to repulsive force when used for an in-vehicle millimeter-wave radar module, and an extra space is required because the radius at the time of bending becomes large.
• the tensile strength of the polyimide is such that a polyimide test piece having a width of 10 mm, a length of 60 mm, and a thickness of 25 ⁇ m is set in a tensile tester at a distance between chucks of 20 mm and pulled at a speed of 5 mm / min at 25 ° C.
• the maximum tensile stress applied during the tensile test is defined as the tensile strength.
• the breaking elongation is the breaking elongation calculated by dividing the elongation amount of the test piece until the test piece breaks by the distance between chucks of 20 mm in the test under the same conditions.
• the tensile elastic modulus is a tensile elastic modulus obtained by calculating Young's modulus (MPa) from the inclination of the elastic deformation region at the initial stage of stress rise in the test under the same conditions. Other detailed conditions and calculation methods conform to the international standard ISO527-1: 2019.
• MPa Young's modulus
• Other detailed conditions and calculation methods conform to the international standard ISO527-1: 2019.
• As the tensile test apparatus for example, "Autograph AGS-100NG” manufactured by Shimadzu Corporation can be used.
• polyimide contains 5 to 20 mol% of structural units derived from diamine diamine with respect to all the structural units derived from diamine, and has an elongation at break of 95% or more. This polyimide can satisfy a relative permittivity of 3.3 or less, a dielectric loss tangent of 0.005 or less, or both.
• Another example of polyimide contains 20 mol% to 80% of structural units derived from diamine diamine with respect to all the structural units derived from diamine, and has an elongation at break of 95% or more, preferably 150% or more. Is. This polyimide can satisfy a relative permittivity of 2.9 or less, a dielectric loss tangent of 0.0015 or less, or both.
• polyimide contains 30 mol% -80% of structural units derived from diamine diamine with respect to all units of structural units derived from diamine, and has an elongation at break of 95% or more, preferably 150% or more, further. It is preferably 300% or more. This polyimide can satisfy the dielectric constant of 2.7 or less, the dielectric loss tangent of 0.0015 or less, or both of them. Yet another example of polyimide contains 50 mol% -80% of structural units derived from diamine diamine with respect to all units of structural units derived from diamine, and has an elongation at break of 95% or more, preferably 150% or more, further. It is preferably 300% or more. This polyimide can satisfy the dielectric constant of 2.7 or less, the dielectric loss tangent of 0.0015 or less, or both of them.
• the polyimide has a glass transition temperature (Tg) of preferably 200 to 500 ° C, more preferably 300 to 500 ° C. Thereby, a polyimide molded body having sufficient heat resistance can be obtained.
• Tg glass transition temperature
• the glass transition temperature is set to 10 ° C./ It is a value obtained by measuring the temperature rise in min and determining the temperature corresponding to the turning point as the glass transition temperature (° C.).
• the polyimide has a 5% thermogravimetric reduction temperature (T d5 ) of preferably 200 to 600 ° C, more preferably 300 to 500 ° C. Thereby, a polyimide molded body having sufficient heat resistance can be obtained.
• T d5 is a temperature measured in the range of 50 ° C. to 500 ° C. at a heating rate of 10 ° C. per minute under an inert atmosphere, and the weight is reduced by 5% from the initial stage.
• the relative permittivity of the polyimide is preferably 2.00 to 3.30.
• the polyimide relative permittivity is preferably 3.30 or less, more preferably 3.20 or less, still more preferably 2.80 or less, and may be 2.60 or less. This makes it possible to provide a polyimide molded body having high insulating properties.
• the polyimide relative permittivity is not particularly limited, but may be 2.00 or more from the viewpoint of preventing deterioration of heat resistance and strength.
• the dielectric loss tangent of the polyimide is preferably 0.0150 or less, more preferably 0.0100 or less, still more preferably 0.0050 or less. Thereby, it is possible to provide a polyimide molded body having a small transmission loss. Further, for applications with higher insulating properties, the dielectric loss tangent of the polyimide is preferably 0.0030 or less, more preferably 0.0015 or less. The dielectric loss tangent of the polyimide is not particularly limited, but may be 0.0001 or more, and may be 0.0005 or more. The relative permittivity and the dielectric loss tangent of the polyimide can be obtained from the value and thickness of the capacitance of the sample piece according to the cavity resonator perturbation method.
• the relative permittivity and the dielectric loss tangent can be measured by the cavity resonator method (TE mode) using a sample piece obtained by cutting polyimide into 60 mm ⁇ 60 mm and a thickness of 25 ⁇ m.
• the measurement conditions are a frequency of 10 GHz and a measurement temperature of 25 ° C.
• the polyimide having the above-mentioned characteristics can be obtained by curing the above-mentioned polyimide precursor, but is not limited to that obtained by this method.
• a polyimide having the above-mentioned elongation at break can be obtained.
• the present disclosure is a resin composition containing a polyimide precursor, which is a polyimide precursor obtained by reacting a diamine with a tetracarboxylic acid dianhydride, and is a diamine component contained in the polyimide precursor.
• a resin composition containing 5 to 80 mol% of diamine diamine and having a weight average molecular weight of 15,000 to 130000.
• This resin composition preferably contains the above-mentioned polyimide precursor.
• This resin composition can contain a solvent together with the polyimide precursor.
• the solvent those listed as synthetic solvents in the above-mentioned method for producing a polyimide precursor can be used.
• the mixture of the obtained polyimide precursor and the synthetic solvent may be used as it is. Further, the mixture may be obtained by removing excess synthetic solvent, or may be obtained by further adding a diluting solvent.
• the resin content of this resin composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. Within this range, the viscosity can be adjusted to a more preferable range for the paint.
• This resin composition can be preferably used as a paint for a flexible substrate.
• the viscosity of the resin composition is preferably 1 to 10 Pa ⁇ s, more preferably 1 to 5 Pa ⁇ s at 30 ° C.
• the viscosity is No. 1 at 30 ° C. in a rotary B-type viscometer. It is a numerical value measured using 3 rotors.
• This resin composition may contain additives, if necessary.
• the additive include pigments, colorants such as dyes, inorganic fillers, organic fillers, lubricants and the like.
• the resin composition contains a filler such as an inorganic filler or an organic filler
• the obtained polyimide molded product contains a filler having a low dielectric constant, and the molded product can have a low dielectric constant.
• the polyimide according to one embodiment exhibits a low dielectric constant by itself, it can be preferably applied to applications in which the polyimide molded body does not contain a filler from the viewpoint of flexibility.
• the present disclosure can provide a polyimide molded body formed by using the above-mentioned resin composition.
• the polyimide molded body may be a plate-shaped substrate, a coating film applied to the base material, various shapes that can be molded by a molding die, or the like.
• the present disclosure can provide a flexible substrate having a polyimide formed by using the above-mentioned resin composition. Since the polyimide formed by using the polyimide precursor or the resin composition of one embodiment has a low dielectric constant and a low dielectric loss tangent, it can be used as a flexible substrate to provide a substrate having high insulating properties. can.
• this polyimide has high heat resistance and flexibility, it can be preferably applied to a flexible substrate. Since such a flexible substrate is excellent in dielectric characteristics, heat resistance, and strength, it is useful for application to an in-vehicle pressure sensor, an angle sensor, a flexible substrate for inverter wiring (FPC), an in-vehicle millimeter-wave radar substrate, and the like. ..
• the flexible substrate comprises a base film.
• the base film may be a single layer or a laminated body.
• the polyimide of one embodiment can be used for the base film.
• the polyimide resin layer of one embodiment and another resin layer can be used for the base film, or at least two layers of the base film have two or more different compositions.
• Polyimide can be used.
• the other resin layer is formed of, for example, polyethylene terephthalate, liquid crystal polymer, polyamide-imide, or other polyimide other than the polyimide of one embodiment. Since the polyimide according to one embodiment has a high elongation at break, a base film can also be provided by a polyimide single layer.
• the flexible substrate may be a single-sided flexible substrate in which a conductive layer such as copper foil is formed on one side of the base film, or a double-sided flexible substrate in which conductive layers such as copper foil are formed on both sides of the base film. May be good.
• the flexible substrate may include a base film and a coating film layer.
• the coating film layer may be formed as a protective layer after a conductive layer such as a copper foil is applied to the base film.
• the base film having the polyimide of one embodiment is as described above.
• the coating layer preferably comprises the polyimide of one embodiment. Both the base film and the coating film layer may contain the polyimide of one embodiment.
• the present disclosure is a molded body or a flexible substrate having a polyimide, wherein the polyimide contains a structural unit derived from a diamine and a structural unit derived from a tetracarboxylic acid dianhydride, and is 5 with respect to the total amount of the structural unit derived from a diamine. It is possible to provide a molded body or a flexible substrate containing ⁇ 80 mol% of a structural unit derived from diamine diamine and having an elongation at break of 95% or more. The details of the polyimide are as described above.
• the molded body or the flexible substrate may be formed by using the resin composition containing the above-mentioned polyimide precursor, but is not limited to the one produced by this method.
• a resin composition containing a polyimide precursor and a solvent may be applied and heated.
• the above-mentioned ones can be used as the polyimide precursor, the solvent and the resin composition.
• the polyimide molded product in the form of a coating film can be obtained by applying a resin composition to a base material and heating it.
• the base material may be a rigid base material such as glass or metal, a flexible base material such as resin, or the like.
• the polyimide of one embodiment may be used.
• the substrate-shaped polyimide molded body can be obtained by applying a resin composition to a temporary fixing base material and heating it to form a polyimide resin layer, and peeling the polyimide resin layer from the temporary fixing base material.
• This substrate-shaped polyimide molded body can be used as a flexible base material.
• the polyimide molded body can be molded into various shapes by filling a molding die with a resin composition and heating the molded body.
• the method of applying the resin composition to the base material may be a method of applying the resin composition to the surface of the base material, a method of immersing the base material in the resin composition, or the like.
• a method of applying the resin composition to the surface of the base material a method of immersing the base material in the resin composition, or the like.
• the resin composition applied to the base material can be cured by heating to form a polyimide molded body.
• the heating temperature is preferably 260 ° C to 520 ° C.
• the solvent can be removed from the molded product so that no residual solvent remains, and the curing of the molded product can be promoted to further improve the characteristics.
• the resin component may be dissolved or swollen in the polar solvent, and the characteristics of the molded product may be deteriorated.
• the heating time is preferably 1 second to 1 hour. Within this range, the residual solvent can be prevented from remaining on the molded product. Further, by preventing the heating time from becoming excessively long, it is possible to prevent deterioration of the molded product under heating.
• the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
• the upper or lower limit of the numerical range at one stage may be optionally combined with the upper or lower limit of the numerical range at another stage.
• the materials exemplified in the present specification may be used alone or in combination of two or more.
• the content of each component in the composition is the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means.
• the term "process” is included in this term not only in an independent process but also in the case where the intended action of the process is achieved even if it cannot be clearly distinguished from other processes.
• Table 1 shows the formulation and evaluation results of the examples.
• Example 1 Dimerdiamine (trade name “PRIAMINE 1075", Claude Japan Co., Ltd., hereinafter referred to as "DDA") 79.9 g (0.15 mol) as a diamine component, and 4,4'-diaminodiphenyl ether (hereinafter referred to as "ODA”).
• ODA 4,4'-diaminodiphenyl ether
• 29.9 g (0.15 mol) is dissolved in 700.0 g of N-methyl-2-pyrrolidone, and 63.9 g (0) of pyromellitic acid dianhydride (hereinafter referred to as "PMDA”) is used as an acid anhydride component. .29 mol) was added and reacted.
• PMDA pyromellitic acid dianhydride
• This reaction was carried out by stirring at 50 ° C. or lower for 8 hours or more. After stirring for 8 hours or more, the reaction product was sampled to measure the weight average molecular weight and the number average molecular weight, and the reaction was stopped when the reaction proceeded sufficiently. After the reaction was stopped, a resin composition containing a polyimide precursor having a structure derived from dimer diamine at the resin concentration shown in the table was obtained. When the appearance of this resin composition was visually observed, it was uniform and transparent.
• Example 2 46.6 g (0.087 mol) of DDA and 52.4 g (0.26 mol) of ODA were dissolved in 700.0 g of N-methyl-2-pyrrolidone as a diamine component, and 74.5 g (0) of PMDA as an acid anhydride component was dissolved therein. .34 mol) was added and reacted. This reaction was carried out by stirring at 50 ° C. or lower for 8 hours or more. After stirring for 8 hours or more, the reaction product was sampled to measure the weight average molecular weight and the number average molecular weight, and the reaction was stopped when the reaction proceeded sufficiently. After the reaction was stopped, a resin composition containing a polyimide precursor having a structure derived from dimer diamine was obtained at the resin concentration shown in the table. When the appearance of this resin composition was visually observed, it was uniform and transparent.
• Example 3 20.7 g (0.039 mol) of DDA and 69.8 g (0.35 mol) of ODA were dissolved in 700.0 g of N-methyl-2-pyrrolidone as a diamine component, and 82.8 g (0) of PMDA as an acid anhydride component was dissolved therein. .38 mol) was added and reacted.
• This reaction was carried out by stirring at 50 ° C. or lower for 8 hours or more. After stirring for 8 hours or more, the reaction product was sampled to measure the weight average molecular weight and the number average molecular weight, and the reaction was stopped when the reaction proceeded sufficiently. After the reaction was stopped, a resin composition containing a polyimide precursor having a structure derived from dimer diamine was obtained at the resin concentration shown in the table. When the appearance of this resin composition was visually observed, it was uniform and transparent.
• Example 4 10.8 g (0.020 mol) of DDA and 76.5 g (0.38 mol) of ODA were dissolved in 700.0 g of N-methyl-2-pyrrolidone as a diamine component, and 86.0 g (0) of PMDA as an acid anhydride component was dissolved therein. .40 mol) was added and reacted. This reaction was carried out by stirring at 50 ° C. or lower for 8 hours or more. After stirring for 8 hours or more, the reaction product was sampled to measure the weight average molecular weight and the number average molecular weight, and the reaction was stopped when the reaction proceeded sufficiently. After the reaction was stopped, a resin composition containing a polyimide precursor having a structure derived from dimer diamine was obtained at the resin concentration shown in the table. When the appearance of this resin composition was visually observed, it was uniform and transparent.
• Example 5 83.8 g (0.42 mol) of ODA as a diamine component was dissolved in 700.0 g of N-methyl-2-pyrrolidone, and 89.4 g (0.41 mol) of PMDA as an acid anhydride component was added thereto for reaction. This reaction was carried out by stirring at 50 ° C. or lower for 3 hours or more. After stirring for 3 hours or more, the reaction product was sampled to measure the weight average molecular weight and the number average molecular weight, and the reaction was stopped when the reaction proceeded sufficiently. After the reaction was stopped, a resin composition containing a polyimide precursor having a structure derived from dimer diamine was obtained at the resin concentration shown in the table. When the appearance of this resin composition was visually observed, it was uniform and transparent.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
• the calibration curve is approximated by a cubic equation using a 5-sample set of standard polystyrene (TSK standard POLYSTYRENE [manufactured by Tosoh Corporation, trade name]).
• TSK standard POLYSTYRENE manufactured by Tosoh Corporation, trade name
• GPC device High-speed GPC device HLC-8320GPC (manufactured by Tosoh Corporation, product name)
• Detector Ultraviolet absorption detector UV-8320 (manufactured by Tosoh Corporation, product name)
• Eluent: THF / DMF 1/1 (volume ratio) + LiBr (0.06 mol / L) + H 3 PO 4 (0.06 mol / L)
• Flow rate 1 mL / min
• Sample concentration 5 mg / 1 mL
• Injection volume 5 ⁇ L Measurement temperature: 40 ° C
• a film was prepared according to the following procedure using the obtained resin composition containing the polyimide precursor.
• the surface of a commercially available glass substrate is degreased with acetone, a resin composition is applied using a film applicator with a film thickness adjustment function so that the film thickness after curing is 25 ⁇ m, and the temperature is 80 ° C. using a hot plate. Pre-dried for 60 minutes. Next, the temperature was raised to 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes using an inert gas oven, and then baked at 350 ° C. for 1 hour to obtain a polyimide cured film. The cured film was immersed in warm water for about 15 minutes and peeled off from the glass substrate.
• the cured film obtained above is cut into a size of 60 mm ⁇ 60 mm, dried at 120 ° C. for 15 minutes, and then the dielectric properties (dielectric constant Dk and dielectric loss tangent Df) are determined by the cavity resonator method (TE mode). It was measured.
• the device used was "MS46122B" manufactured by Anritsu Co., Ltd. The conditions were a frequency of 10 GHz and a measurement temperature of 25 ° C.
• the tensile strength, tensile elastic modulus, and breaking elongation of the film were measured by the following procedure.
• the cured film obtained above was cut into a size of 10 mm in width and 60 mm in length, and used as a test sample.
• the tensile test was performed under the following measurement conditions, and the maximum tensile stress applied during the tensile test was taken as the tensile strength.
• the breaking elongation was calculated by dividing the elongation amount of the film until breaking by the distance between chucks of 20 mm.
• Young's modulus was calculated from the slope of the elastic deformation region at the initial stage of stress rise, and this was used as the tensile elastic modulus. Other detailed conditions and calculation methods were carried out in accordance with the international standard ISO527-1: 2019.
• Device name "Autograph AGS-100NG” manufactured by Shimadzu Corporation (trade name) Test speed: 5 mm / min Distance between chucks: 20 mm Specimen size: width 10 mm, length 60 mm Set temperature: Room temperature (25 ° C)
• the cured film obtained above was cut into a width of 4 mm and a length of 25 mm to prepare a sample piece.
• a thermomechanical analyzer (“TMA7100”, manufactured by Hitachi High-Tech Science Co., Ltd., trade name)
• the temperature between chucks was 10 mm, and the temperature was measured from 20 ° C to 500 ° C by the tensile method at 10 ° C / min.
• the temperature corresponding to the above was defined as the glass transition temperature (° C.).
• Example 1 a film having a low dielectric constant and a low dielectric loss tangent could be obtained by using a polyimide precursor containing dimerdiamine (DDA). It can be seen that the polyimide films of Examples 1 to 4 have a low dielectric constant and a low dielectric loss tangent, and have a high elongation at break. Since the polyimide precursors contained in the resin compositions of Examples 1 to 4 have a large weight average molecular weight and a number average molecular weight, it can be seen that a molded product having high elongation can be produced.
• Example 5 is a polyimide precursor containing no dimer diamine, and has a high relative permittivity and dielectric loss tangent, and sufficient dielectric properties cannot be obtained.

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